CN108659775A - A kind of bi-component solvent-free reaction type polyurethane hot melt adhesive and its application method applied to electronic appliance industry - Google Patents

A kind of bi-component solvent-free reaction type polyurethane hot melt adhesive and its application method applied to electronic appliance industry Download PDF

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Publication number
CN108659775A
CN108659775A CN201810316880.1A CN201810316880A CN108659775A CN 108659775 A CN108659775 A CN 108659775A CN 201810316880 A CN201810316880 A CN 201810316880A CN 108659775 A CN108659775 A CN 108659775A
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component
anhydride
polyol
type polyurethane
reaction type
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Inventor
黄世斌
吴义强
刘立华
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Guangdong Zhong Yan New Mstar Technology Ltd
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Guangdong Zhong Yan New Mstar Technology Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • C09J175/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • C09J175/06Polyurethanes from polyesters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a kind of bi-component solvent-free reaction type polyurethane hot melt adhesive applied to electronic appliance industry, polyurethane adhesive in the present invention is bi-component reaction-type polyurethane hot melt, not only contain hydroxyl in component, also contain epoxy construction, Ju oxazolidones can be generated with end NCO prepolymer reactions, the high temperature resistance after hot melt adhesive curing is increased, reaction is not mainly that humidity is limited by environment, and final Young's modulus can reach 1000Mpa or more.

Description

A kind of bi-component solvent-free reaction type polyurethane applied to electronic appliance industry heats Glue and its application method
Technical field
The present invention relates to a kind of bi-component solvent-free reaction type polyurethane hot melt adhesive and its application methods, more particularly to one kind Bi-component solvent-free reaction type polyurethane hot melt adhesive and its application method applied to electronic appliance industry.
Background technology
The PUR for being traditionally used for electronic appliance industry is usually one-component reaction type polyurethane hot-melt adhesive, is designed by connector Relatively long with the hardening time of the influence of moisture content in environment, PUR, adhesion strength rises slowly, and Young's modulus is relatively low, heat-resisting Property is poor.In this way, in the production of electronic appliance industry such as electronics and automobile lamp, seriously affect the production technology efficiency and How quality can both improve the efficiency of production, it is also ensured that required bond quality, be the technical staff of the industry urgently It solves the problems, such as.
Invention content
The present invention is intended to overcome the deficiencies of existing technologies, and it is an object of the present invention to provide a kind of applied to electronic appliance industry Bi-component solvent-free reaction type polyurethane hot melt adhesive, can both improve the efficiency of production, it is also ensured that required bond quality.
The technical solution adopted by the present invention to solve the technical problems is:A kind of bi-component applied to electronic appliance industry Solvent-free reaction type polyurethane hot melt adhesive, including component A and component B:
--- the component A includes performed polymer, auxiliary agent, the first catalyst that side chain or main chain carry isocyanato; Wherein performed polymer degree of functionality is more than or equal to 1, isocyano-content 0.1%-30%;Performed polymer in the component A is Polyisocyanates polymerize generation with polyol b, wherein polyisocyanates be isophorone diisocyanate (IPDI) and Methyl diphenylene diisocyanate (MDI) (IPDI by a certain percentage:MDI=0.2-1 composition), and account for the total matter of component A The 30-80% of amount;The polyol b is one or more compositions that side chain or main chain carry hydroxyl group, including Polyether polyol, polyester polyol, hydroxyl value ranging from 60-220mgKOH/g, molecular weight are 50-2000 dalton, preferably 400- 1000 dalton;Wherein polyol b accounts for the 20-70% of component A gross masses.It is water-fast after IPDI increase glue curings Solution property and adhesion strength, polyol b ratios are higher, and glue curing speed is slower, and oligomer molecules amount is bigger, and viscosity is got over It is high;
Auxiliary agent in the component A includes antifoaming agent, levelling agent, antioxidant, and additive amount is the 0.1- of component A total weights 5%;The antifoaming agent is non-silicone high molecular polymer, and the levelling agent is Siloxane-Oxyalkylene Copolymers compound, described anti- Oxygen agent is Hinered phenols.
First catalyst includes triethylenediamine, bis- (dimethylaminoethyl) ethers and dibutyl tin laurate, carboxylic The sour one or more compositions of bismuth, preferably bismuth carboxylate, content are the 0.01-0.5% of component A gross masses;First catalyst improves Reaction speed shortens the reaction time;
The synthesis technology of the component A is:Polyol b, MDI, IPDI and the first catalysis is added to reaction kettle Agent, control material temperature react 1-2h at 40-50 DEG C;60-70 DEG C, react 1-2h;80-100 DEG C, 1-4h is reacted, finger is reached Determine viscosity (2000-20000cps/120 DEG C, preferably 5000-10000cps/120 DEG C), then auxiliary agent is added into reaction kettle, 80- It is cooled to 40 DEG C after 100 DEG C of stirring 0.5-1h and terminates reaction, and 400 mesh filter screen filtering and dischargings form component A finished products.
--- the component B includes polyol a, anhydride modified polyalcohol, bisphenol A epoxide resin, chain extender, amine Class catalyst;
Polyol a in the component B is one or more compositions that side chain or main chain carry hydroxyl group, Including polyether polyol, polyester polyol, molecular weight is 500-4000 dalton, preferably 500-2000 dalton, hydroxyl value range For 10-250mgKOH/g, the 10-70% of component B total weights is accounted for.(after the higher glue curing of ratio of polyol (1) Modulus is lower, and adhesion strength is lower;Viscosity is lower after AB mixing, is conducive to improve production line coating speed)
Anhydride modified polyalcohol accounts for the 5-60% of component B total weights in the component B, anhydride modified more in the component B First alcohol synthesis signal:
R ', R1, R2For alkyl, aryl;Or alkyl, the aryl replaced with methacryloxy or vinyl;Or Alkoxy, phenoxy group;Optimizing alkyl (carbon atom number 1-5) or aryl (carbon atom number 6-10);X is NH3-, OH-, SH- Deng;R is alkyl (carbon atom number 1-20) or aryl (carbon atom number 6-20).
Acid anhydrides in the anhydride modified polyalcohol is phthalic anhydride, maleic anhydride, tetrabydrophthalic anhydride, six Hydrogen phthalic anhydride, 3- methyl and 4- methylhexahydrophthalic anhydrides, 3- methyl and 4- ethyl hexahydrophthalic acids Acid anhydride, itaconic anhydride, succinic anhydride, the eleventh of the twelve Earthly Branches dicarboxylic anhydride, adipic anhydride, carbic anhydride, methylnadic anhydride, hydrogenating methyl receive enlightening Gram acid anhydrides, poly- azelaic acid acid anhydride, poly sebacic polyanhydride, poly- icosane diacid anhydride, trimellitic anhydride, pyromellitic acid anhydride, Any one in 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides.
Further, the anhydride modified polyalcohol synthesis preparation method:By chemical compounds I and II and second catalyst Reactor is added, temperature is controlled at 80-120 DEG C, reacts 1-4h, and interval half an hour measures acid value, after acid value is stablized, is continued Compound III is added to reactor, control temperature measures acid value in 80 DEG C of -140 DEG C of reaction 1-6h, when acid value is less than 10mg It is considered as reaction end when KOH/g, preferably smaller than 5mg KOH/g;
Second catalyst is triethylamine, trimethyl benzyl ammonia chloride, N, N- dimethyl benzylamines, N, N- dimethylbenzyl benzene Amine, trimethyl benzyl ammonia chloride, triphenylphosphine, antimony triphenyl, acetylacetone metal complex, tetraethylammonium bromide, pyridine or Any one in dimethylamino naphthyridine or several mixture.
The bisphenol A epoxide resin, epoxy-ester 0.2-0.6 account for the 5-60% of component B total weights.(epoxy resin ratio Modulus is higher after higher glue curing, and adhesion strength is higher, and heat-resisting water resistance is better after solidification)
The chain extender is 4,4'- diamino -3,3'- dichloro diphenyl methanes, 2,4- diamino -3,5- dimethyl sulphur-based first Benzene, glycerine, hydroquinone two hydroxy ethyl ether, one or more compositions in resorcinol two (2- ethoxys) ether account for component B The 0.1-10% of gross mass, preferably 1-5%.Chain extender is for improving glue curing reaction speed and final glue after AB is mixed Molecular weight, modulus is higher after the higher glue curing of content, and adhesion strength is higher)
The amines catalyst includes N, N- dimethyl cyclohexyl amines, N, and one kind in N- dimethyl benzylamines or composition account for The 0.01-1% of component B gross masses.
The each component of said components B is uniformly mixed stirring 1-2 hours at normal temperatures, is then allowed to stand 1-2 hours and is consolidated The component B of body state.
In addition, the invention further relates to bi-component solvent-free reaction type polyurethane hot melt adhesive to be applied to electronic appliance industry Application method includes the following steps:
(1) before use, component A and component B are packed with independent sealing container respectively, the sealing container include but It is not limited to tinplate bucket, PET/Al/Nylon/PP films etc. or combinations thereof.
(2) process is used, component A and B component are not put into glue-smelting machine and are heated to 80-120 DEG C of melting, passes through metering pump In proportion (100:30~100:100) being output to static mixing tube mixing or mechanical mixture makes two kinds of components be uniformly mixed, and obtains The bi-component solvent-free reaction type polyurethane glue.
(3) reach 40-50 DEG C to applying gum base materials and carrying out being preheated to substrate surface;
(4) after uniformly mixed polyurethane adhesive being heated to 80-120 DEG C, pass through the modes such as spraying, roller coating, showering, squeezing and coating Substrate surface is glued.
(5) another base material being bonded will be needed to be bonded by mechanical force realization with gum base materials are applied.
Further, the ratio of the component A and component B is 1:0.3~1:0.5
Further, bi-component solvent-free reaction type polyurethane hot melt adhesive modulus after mixing for 24 hours reaches 200- 1500Mpa。
The bi-component solvent-free reaction type polyurethane hot melt adhesive be applied to electronic appliance industry, the present invention in bi-component without Not only contain hydroxyl in the component of solvent reaction type polyurethane hot melt adhesive, also contains epoxy construction, it can be with end NCO prepolymer reactions Poly- oxazolidone is generated, increases the high temperature resistance after hot melt adhesive curing, reaction is not mainly that humidity is limited by environment, finally Young's modulus can reach 1000Mpa or more.Both the efficiency of production had been improved, it is also ensured that required bond quality has wide Market prospects.
Specific implementation mode
Embodiment 1
A kind of bi-component solvent-free reaction type polyurethane applied to electronic appliance industry described in the embodiment of the present invention 1 Hot melt adhesive, including component A and component B:
--- the component A includes performed polymer, auxiliary agent, the first catalyst that side chain carries isocyanato;It is wherein pre- Aggressiveness degree of functionality is more than or equal to 1, isocyano-content 20%;
Performed polymer in the component A is that polyisocyanates polymerize generation, wherein polyisocyanic acid with polyol b Ester is isophorone diisocyanate (IPDI) and methyl diphenylene diisocyanate (MDI) (IPDI in proportion:MDI=0.6) Made of composition, and account for the 60% of component A gross masses;The polyol b is polyether polyol, selects day Winsization Work limited liability company P-2707 hydroxyl value of polyester polyol ranging from 150-180mgKOH/g, molecular weight are 700 dalton;Its Middle polyol b accounts for the 50% of component A gross masses.
Auxiliary agent in the component A includes antifoaming agent, levelling agent, antioxidant, and additive amount is the 3% of component A total weights; The antifoaming agent is non-silicone high molecular polymer, and the levelling agent is Siloxane-Oxyalkylene Copolymers compound, the antioxidant For Hinered phenols.
First catalyst is bismuth carboxylate, and content is the 0.25% of component A gross masses.
The synthesis technology of the component A is:To P-2707 polyester polyol is added in reaction kettle, MDI, IPDI and first are urged Agent, control material temperature react 2h at 50 DEG C;70 DEG C, react 2h;100 DEG C, 1h is reacted, specified viscosity is reached (9000cps/120 DEG C), then auxiliary agent is added into reaction kettle, being cooled to 40 DEG C after 100 DEG C of stirring 1h terminates reaction, and 400 mesh Strainer filtering discharging forms component A finished products.
--- the component B includes anhydride modified polyalcohol, polyol a, bisphenol A epoxide resin, chain extender, amine Class catalyst;
Polyol a in the component B is polyether polyol, selects day Wins chemical inc P-2715 Hydroxyl value of polyester polyol ranging from molecular weight is 1500 dalton, hydroxyl value ranging from 72-78mgKOH/g;Account for component B total weights 40%.
Anhydride modified polyalcohol accounts for the 30% of component B total weights in the component B, anhydride modified polynary in the component B Alcohol synthesis signal:
R ', R1, R2 are alkyl (carbon atom number 4);X is OH-;R is alkyl (carbon atom number 4).It is described anhydride modified more Acid anhydrides in first alcohol is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides;
The anhydride modified polyalcohol synthesis preparation method:By chemical compounds I and II and second catalyst be added reaction Device, temperature are controlled at 120 DEG C, react 2h, and interval half an hour measures acid value, after acid value is stablized, continue to be added to reactor Compound III, control temperature react 4h at 120 DEG C, measure acid value, are considered as reaction end when acid value is less than 5mg KOH/g;Institute It is tetraethylammonium bromide to state the second catalyst.
The bisphenol A epoxide resin, epoxy-ester 0.4 account for the 40% of component B total weights.
The chain extender is resorcinol two (2- ethoxys) ether, accounts for the 0.1-10% of component B gross masses, preferably 3%.
Described to urge the first agent for bismuth carboxylate, content is the 0.25% of component A gross masses.
The each component of said components B is uniformly mixed stirring 1 hour at normal temperatures, is then allowed to stand 1 hour and obtains solid-like The component B of state.
Embodiment 2
The embodiment of the present invention 2 is described, and the invention further relates to bi-component solvent-free reaction type polyurethane hot melt adhesive to be used for The application method of plastic film industry, includes the following steps:
(1) before use, component A and component B are packed with independent foil laminated film sealing container respectively;
(2) process is used, component A and B component are not put into glue-smelting machine and are heated to 100 DEG C of meltings, is pressed by metering pump Ratio (100:50) being output to static mixing tube mixing or mechanical mixture makes two kinds of components be uniformly mixed, and obtains the bi-component Solvent-free reaction type polyurethane glue.
(3) 50 DEG C of preheating is carried out to applying gum base materials.
(4) after uniformly mixed polyurethane adhesive being heated to 100 DEG C, pass through the modes pair such as spraying, roller coating, showering, squeezing and coating Substrate surface is glued.
(5) another base material being bonded will be needed to be bonded by mechanical force realization with gum base materials are applied.
Above-mentioned bi-component solvent-free reaction type polyurethane hot melt adhesive modulus after mixing for 24 hours reaches 1300Mpa.
The above described is only a preferred embodiment of the present invention, not making any form to the technology contents of the present invention On limitation.It is every according to the technical essence of the invention to any simple modification made by above example, equivalent variations and repair Decorations, in the range of still falling within technical scheme of the present invention.

Claims (7)

1. a kind of bi-component solvent-free reaction type polyurethane hot melt adhesive applied to electronic appliance industry, which is characterized in that including Component A and component B:
--- the component A includes performed polymer, auxiliary agent, the first catalyst that side chain or main chain carry isocyanato;Wherein Performed polymer degree of functionality is more than or equal to 1, isocyano-content 0.1%-30%;
Performed polymer in the component A is that polyisocyanates polymerize generation with polyol b, and wherein polyisocyanates is Isophorone diisocyanate (IPDI) and methyl diphenylene diisocyanate (MDI) (IPDI by a certain percentage:MDI=0.2- 1) composition, and account for the 30-80% of component A gross masses;The polyol b is that side chain or main chain carry hydroxyl base One or more compositions of group, including polyether polyol, polyester polyol, hydroxyl value ranging from 60-220mgKOH/g, molecular weight For 50-2000 dalton, preferably 400-1000 dalton;Wherein polyol b accounts for the 20-70% of component A gross masses;
Auxiliary agent in the component A includes antifoaming agent, levelling agent, antioxidant, and additive amount is the 0.1-5% of component A total weights;Institute It is non-silicone high molecular polymer to state antifoaming agent, and the levelling agent is Siloxane-Oxyalkylene Copolymers compound, and the antioxidant is Hinered phenols;
First catalyst includes triethylenediamine, bis- (dimethylaminoethyl) ethers and dibutyl tin laurate, bismuth carboxylate One or more compositions, preferably bismuth carboxylate, content are the 0.01-0.5% of component A gross masses;
The synthesis technology of the component A is:Polyol b, MDI, IPDI and the first catalyst, control is added to reaction kettle Temperature of charge reacts 1-2h at 40-50 DEG C;60-70 DEG C, react 1-2h;80-100 DEG C, 1-4h is reacted, specified viscosity is reached (2000-20000cps/120 DEG C, preferably 5000-10000cps/120 DEG C), then auxiliary agent is added into reaction kettle, 80-100 DEG C is stirred 40 DEG C of termination reactions are cooled to after mixing 0.5-1h, and 400 mesh filter screen filtering and dischargings are to form the component A finished products of solid state;
--- the component B is urged comprising anhydride modified polyalcohol, polyol a, bisphenol A epoxide resin, chain extender, amine Agent, uniform stirring mixes each component at normal temperatures;
Anhydride modified polyalcohol accounts for the 5-60% of component B total weights in the component B;
Polyol a in the component B is one or more compositions that side chain or main chain carry hydroxyl group, including Polyether polyol, polyester polyol, molecular weight are 500-4000 dalton, preferably 500-2000 dalton, hydroxyl value ranging from 10- 250mgKOH/g accounts for the 10-70% of component B total weights;
The bisphenol A epoxide resin, epoxy-ester 0.2-0.6 account for the 5-60% of component B total weights;
The chain extender is 4,4'- diamino -3,3'- dichloro diphenyl methanes, and 2,4- diamino -3,5- dimethyl sulphur-based toluene are sweet Oil, hydroquinone two hydroxy ethyl ether, one or more compositions in resorcinol two (2- ethoxys) ether account for the total matter of component B The 0.1-10% of amount, preferably 1-5%;
The amines catalyst includes N, N- dimethyl cyclohexyl amines, N, and one kind in N- dimethyl benzylamines or composition account for component B The 0.01-1% of gross mass.
2. a kind of bi-component solvent-free reaction type polyurethane applied to electronic appliance industry heats according to claim 1 Glue, it is characterised in that:Shown in anhydride modified polyalcohol synthesis schematically as follows in the component B:
R ', R1, R2For alkyl, aryl;Or alkyl, the aryl replaced with methacryloxy or vinyl;Or alcoxyl Base, phenoxy group;Optimizing alkyl (carbon atom number 1-5) or aryl (carbon atom number 6-10);X is NH3-, OH-, SH- etc.;R For alkyl (carbon atom number 1-20) or aryl (carbon atom number 6-20).
3. a kind of bi-component solvent-free reaction type polyurethane applied to electronic appliance industry heats according to claim 1 Glue, it is characterised in that:Acid anhydrides used in the anhydride modified polyalcohol is phthalic anhydride, maleic anhydride, tetrahydrochysene O-phthalic Acid anhydrides, hexahydrophthalic anhydride, 3- methyl and 4- methylhexahydrophthalic anhydrides, 3- methyl and 4- ethyl hexahydro neighbours benzene two Formic anhydride, itaconic anhydride, succinic anhydride, the eleventh of the twelve Earthly Branches dicarboxylic anhydride, adipic anhydride, carbic anhydride, methylnadic anhydride, hydrogenating methyl Carbic anhydride, poly- azelaic acid acid anhydride, poly sebacic polyanhydride, poly- icosane diacid anhydride, trimellitic anhydride, Pyromellitic Acid two Acid anhydride, 3,3 ', any one in 4,4 '-benzophenone tetracarboxylic dianhydrides.
4. a kind of bi-component solvent-free reaction type polyurethane applied to electronic appliance industry heats according to claim 2 Glue, it is characterised in that:The anhydride modified polyalcohol synthesis preparation method is:By chemical compounds I and II and second catalyst add Enter reactor, temperature is controlled at 80-120 DEG C, reacts 1-4h, and interval half an hour measures acid value, after acid value is stablized, continue to Composition III is added in reactor, and control temperature measures acid value in 80 DEG C of -140 DEG C of reaction 1-6h, when acid value is less than 10mg KOH/ It is considered as reaction end when g, preferably smaller than 5mg KOH/g;Second catalyst be triethylamine, trimethyl benzyl ammonia chloride, N, N- dimethyl benzylamines, N, N- dimethylbenzyls aniline, trimethyl benzyl ammonia chloride, triphenylphosphine, antimony triphenyl, cetylacetone metallic Any one in complex compound, tetraethylammonium bromide, pyridine or dimethylamino naphthyridine or several mixture.
5. a kind of bi-component solvent-free reaction type polyurethane adhesive is applied to the application method of woodworking, it is characterised in that: Include the following steps:
(1) before use, component A and component B are packed with independent sealing container respectively, the sealing container includes but unlimited In tinplate bucket, PET/Al/Nylon/PP films etc. or combinations thereof;
(2) use process, component A and B component are not put into glue-smelting machine be heated to 80-120 DEG C melting, by metering pump press than Example, which is output to static mixing tube mixing or mechanical mixture, makes two kinds of components be uniformly mixed, and obtains the bi-component solvent-free reaction Type polyurethane glue;
(3) reach 40-50 DEG C to applying gum base materials and carrying out being preheated to substrate surface;
(4) after uniformly mixed polyurethane adhesive being heated to 80-120 DEG C, by modes such as spraying, roller coating, showering, squeezing and coating to base Material surface is glued;
(5) another base material being bonded will be needed to be bonded by mechanical force realization with gum base materials are applied.
6. the application method according to claim 5, it is characterised in that:The ratio of the component A and component B is 1:0.3~ 1:0.5.
7. the application method according to claim 5, it is characterised in that:The bi-component solvent-free reaction type polyurethane hot melt Glue modulus after mixing for 24 hours reaches 200-1500Mpa.
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
WO2020097900A1 (en) 2018-11-16 2020-05-22 Dow Global Technologies Llc Solventless adhesive composition process and laminate with same
CN113166620A (en) * 2018-11-16 2021-07-23 陶氏环球技术有限责任公司 Solvent-free adhesive composition method and laminates thereof
JP2022518657A (en) * 2018-11-16 2022-03-16 ダウ グローバル テクノロジーズ エルエルシー Solvent-free adhesive compositions, processes, and laminates thereof
EP3880767A4 (en) * 2018-11-16 2022-06-29 Dow Global Technologies LLC Solventless adhesive composition process and laminate with same
JP7275265B2 (en) 2018-11-16 2023-05-17 ダウ グローバル テクノロジーズ エルエルシー Solventless Adhesive Compositions, Processes, and Laminates Thereof
CN113166620B (en) * 2018-11-16 2024-03-08 陶氏环球技术有限责任公司 Solvent-free adhesive composition method and laminates thereof
TWI696638B (en) * 2018-12-06 2020-06-21 財團法人工業技術研究院 Resin and hot melt adhesive
EP4083158A4 (en) * 2019-12-25 2024-01-24 Mitsui Chemicals Inc Polyurethane structural adhesive

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