CN100575382C - Contain polynary isocyanate composition of aqueous dispersion type of urea and/or biuret and uses thereof - Google Patents
Contain polynary isocyanate composition of aqueous dispersion type of urea and/or biuret and uses thereof Download PDFInfo
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- CN100575382C CN100575382C CN03155957A CN03155957A CN100575382C CN 100575382 C CN100575382 C CN 100575382C CN 03155957 A CN03155957 A CN 03155957A CN 03155957 A CN03155957 A CN 03155957A CN 100575382 C CN100575382 C CN 100575382C
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- aqueous dispersion
- urea
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- polynary isocyanate
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- 239000000203 mixture Substances 0.000 title claims abstract description 204
- 239000012948 isocyanate Substances 0.000 title claims abstract description 176
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 176
- 239000006185 dispersion Substances 0.000 title claims abstract description 102
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000004202 carbamide Substances 0.000 title claims abstract description 50
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 150000003672 ureas Chemical class 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 33
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims description 60
- 235000013877 carbamide Nutrition 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000004814 polyurethane Substances 0.000 claims description 26
- 150000004985 diamines Chemical class 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- 150000002334 glycols Chemical class 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 7
- -1 urethane ester Chemical class 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical class NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000007973 cyanuric acids Chemical class 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- WNVQBUHCOYRLPA-UHFFFAOYSA-N triuret Chemical compound NC(=O)NC(=O)NC(N)=O WNVQBUHCOYRLPA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000004135 Bone phosphate Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- 229960004042 diazoxide Drugs 0.000 claims description 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- PVNFUHRSPUCTEN-UHFFFAOYSA-N isocyanic acid;1,2-xylene Chemical compound N=C=O.CC1=CC=CC=C1C PVNFUHRSPUCTEN-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 4
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 52
- 238000012360 testing method Methods 0.000 description 50
- 239000000047 product Substances 0.000 description 18
- 229920001971 elastomer Polymers 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 230000006872 improvement Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 125000003368 amide group Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001289 polyvinyl ether Polymers 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- XEVKRTIYWSUXHP-UHFFFAOYSA-N (3-ethyloxiran-2-yl)methanol Chemical compound CCC1OC1CO XEVKRTIYWSUXHP-UHFFFAOYSA-N 0.000 description 1
- PLFFHJWXOGYWPR-HEDMGYOXSA-N (4r)-4-[(3r,3as,5ar,5br,7as,11as,11br,13ar,13bs)-5a,5b,8,8,11a,13b-hexamethyl-1,2,3,3a,4,5,6,7,7a,9,10,11,11b,12,13,13a-hexadecahydrocyclopenta[a]chrysen-3-yl]pentan-1-ol Chemical compound C([C@]1(C)[C@H]2CC[C@H]34)CCC(C)(C)[C@@H]1CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@@H]1[C@@H](CCCO)C PLFFHJWXOGYWPR-HEDMGYOXSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- XOMPUFACNHSNPC-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1C XOMPUFACNHSNPC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to the polynary isocyanate composition of a kind of urea-containing aqueous dispersion type, it comprises the mixture of polynary isocyanate of (a) aliphatics or the polynary isocyanate of aliphatics or the mixture of the polynary isocyanate of aliphatics and other polynary isocyanate; And (b) reaction product of the mixture of composition (a) and composition (c) polyetheramine or polyetheramine and Aethoxy Sklerol; Wherein, said composition system by, in said composition weight, about 99.5% to about 92% composition (a) and about 0.5% to about 8% composition (c) prepared in reaction.The present invention also provides a kind of polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative; The polynary isocyanate composition of a kind of aqueous dispersion type of biuret-containing; And a kind of water-base resin tackiness agent, it comprises the water-base resin of polynary isocyanate composition of aqueous dispersion type of the present invention and active hydrogen containing reactant group.
Description
Technical field
The present invention relates to the polynary isocyanate composition of a kind of aqueous dispersion type, the polynary isocyanate composition of aqueous dispersion type that particularly contains urea or biuret, and a kind of water-base resin tackiness agent that comprises the polynary isocyanate composition of this aqueous dispersion type as the water-base resin of linking agent and active hydrogen containing reactant group.
Background technology
It is as linking agent in the tackiness agent of matrix that the polynary isocyanate of aqueous dispersion type is generally used for the water-base resin.Particular words it, this isocyanate presents highly reactive for the compound with active hydrogen base, formed such as amido ethyl formate, urea, vinegar amine, allophanate, reach product such as biuret.Therefore, polynary isocyanate system helps the molecular weight of resin to grow up with crosslinked, thus clinging power, thermotolerance and mechanical property when significantly improving resin as tackiness agent.The characteristic of polynary isocyanate hyperergy makes it become the excellent linking agent that is used for water-base resin.
Polynary preparation of isocyanates of aqueous dispersion type and application be known and teaching in prior art.Say it for example, United States Patent (USP) the 4th, 663, disclose for No. 377 and use the polynary isocyanate of one or more blended aliphatics, has about 2.0 to 3.5 average N CO functional number, with wetting ability raw material polyethers monohydroxy-alcohol (polyether monols), as the illustrated polyvinyl ether monohydroxy-alcohol of embodiment (poly ethoxylated ether monol) reaction, the NCO% of the polynary isocyanate formulation of aqueous dispersion type that obtains is 18.4%, viscosity is 2500cps/23 ℃.The polynary isocyanate formulation of aqueous dispersion type of taking 2 weight % to 10 weight % again adds in the aqueous binder, promotes adhesive performance.
United States Patent (USP) the 5th, 200, relate to for No. 489 and use the polyethers monohydroxy-alcohol to come modification with 1, own diisocyanate of 6-(HDI) or HDI and be the polynary isocyanate of matrix up to the mixture of the another kind of diisocyanate of 70 weight % (in diisocyanate weight), with the polynary isocyanate composition of aqueous dispersion type of acquisition tool 2 to 6 average N CO functional number, and further provide a kind of method of testing polynary isocyanate composition water dispersible.Its test result shows, adds about 10 weight % and has 200 to 1000 gram/molar polyethers monohydroxy-alcohols, is beneficial to the water dispersible that improves polynary isocyanate composition.
United States Patent (USP) the 5th, 252, No. 696 polynary isocyanate mixtures of a kind of aqueous dispersion type of teaching, it is by the polynary isocyanate of the aliphatics that will have about 2.1 to 4.4NCO functional number, HDI trimer for example, with contain the unitary polyethers monohydroxy-alcohol of 5 to 9.9 oxyethane (EO), under 4: 1 to 120: 1 NCO/OH equivalence ratio the reaction and get.One of them synthetic example is that the polyvinyl ether monohydroxy-alcohol is added in the HDI tripolymer, and reaction obtains having the product of the viscosity of 17.3% NCO% and 3050cps/23 ℃.The polynary isocyanate mixture of gained aqueous dispersion type is added to water soluble acrylic acid (acryl) dispersion liquid that has hydroxyl again can provide surface of good glossiness and solvent resistance.
United States Patent (USP) the 6th, 221, No. 995 a kind of polynary isocyanate of announcement through modification, it has high emulsification/dispersion in aqueous resin composition, and is beneficial to as solidifying or linking agent.See through with HDI is that the reaction of matrix and the polynary isocyanate that contains isocyanuric acid salt group and nonionic emulsifier polyvinyl ether monohydroxy-alcohol makes through the modified multicomponent isocyanate.Propose to represent the hydrophilic structure of polyethers monohydroxy-alcohol in the literary composition with hydrophile-lyophile balance number (HLB), and think that the polyethers monohydroxy-alcohol is 17 or when (about 5 to 17) institute polynary isocyanate of synthetic aqueous dispersion type is applied in water-borne coatings, ink and tackiness agent when lower having the HLB value, can provide preferable performance.
In view of known techniques, the polynary isocyanate of aqueous dispersion type is usually via being the polynary isocyanate of aliphatics of matrix with the HDI trimer and having low-molecular-weight non-ionic type polyethers monohydroxy-alcohol prepared in reaction.Only, the speed of reaction between Aethoxy Sklerol and polynary isocyanate is slower, generally needs to add catalyst and carries out with accelerated reaction.Moreover, when it is applied to bonding between rubber substrate, can't in time promote the initial stage clinging power of rubber and rubber.
The inventor finds that the mixture of polyetheramine and polyetheramine and Aethoxy Sklerol and the reaction of polynary isocyanate are rapider, helps preparing the polynary isocyanate composition of aqueous dispersion type, particularly contains the polynary isocyanate composition of aqueous dispersion type of urea or biuret.Simultaneously, compared to the obtained person of known techniques, the polynary isocyanate composition of aqueous dispersion type of the present invention is more conducive to the linking agent as water-base resin.Particular words it, the water-base resin tackiness agent crosslinked with the polynary isocyanate composition of aqueous dispersion type of the present invention has the mechanical characteristics of raising, such as clinging power (comprising initial stage and later stage clinging power) and thermotolerance etc.
Summary of the invention
The present invention relates to the polynary isocyanate composition of a kind of urea-containing aqueous dispersion type, it comprises
(a) mixture of the mixture of polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics and other polynary isocyanate; And
(b) reaction product of the mixture of composition (a) and composition (c) polyetheramine or polyetheramine and Aethoxy Sklerol;
Wherein, said composition system by, in said composition weight, about 99.5% to about 92% composition (a) is with the reaction of about 0.5% to about 8% composition (c) and make.
The present invention is also about a kind of polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative, it is heated up to continue to react to promote isocyanate official energy radix in the said composition by above-mentioned urea-containing composition reheat to make, wherein urea derivative comprise biuret, the contract triuret and four ureas that contract, and be mainly biuret.
The present invention is more about the polynary isocyanate composition of a kind of aqueous dispersion type of biuret-containing, its be by above-mentioned contain the urea composition reheat heated up continue reaction can radix and make to promote in the said composition isocyanate official.
The present invention provides a kind of water-base resin tackiness agent in addition, and it comprises the water-base resin of polynary isocyanate composition of aqueous dispersion type of the present invention and active hydrogen containing reactant group.
Polynary isocyanate
Being used for polynary isocyanate of the present invention is the mixture of the polynary isocyanate of aliphatics or the polynary isocyanate mixture of aliphatics or the polynary isocyanate of aliphatics and other polynary isocyanate, this polynary isocyanate cording has an appointment 2 to about 6, preferable about 2.5 to about 4, average N CO functional number, and about 5% to about 30%, preferable about 10 to about 25%, NCO content.
In the present invention, the polynary isocyanate of suitable aliphatics comprises, but be not limited to, the isocyanate of the following derivative of tool, for example isocyanuric acid salt, biuret, urea diketone ring (uretdione), urethanum, allophanates, carbonyl diimine, Evil diazoxide triketone (oxadiazonetrione) derivative, and composition thereof.Polynary isocyanate of these aliphatics and its preparation method be known and have been described in the Prior Art, such as United States Patent (USP) the 4th, 518, No. 522 with No. the 4th, 663,377, United States Patent (USP), they disclose and are and for reference in this.The polynary isocyanate of preferable aliphatics is the polynary isocyanate of ring system, for example isocyanuric acid salt derivative, biuret derivatives or its mixture; Preferable is HDI trimer, isophorone diisocyanate (isophoronediisocyanate, IPDI) trimer or HDI/IPDI trimer or its mixture.
Can be used for other polynary isocyanate of the present invention and can be any known and tradition and be used for this skill person, for example the polynary isocyanate of aromatic series.The polynary isocyanate of suitable aromatic series comprises, but is not limited to, the diphenyl-methyl diisocyanate (4,4-diphenylmethane diisocyanate, MDI), aggretion type MDI, toluene di isocyanate, and the dimethylbenzene diisocyanate, and composition thereof.Polynary isocyanate of aromatic series and preparation method thereof also is known and is described in the Prior Art, and as United States Patent (USP) the 4th, 939, No. 191, it discloses and is and for reference in this.
Polyetheramine
Being used for polyetheramine of the present invention can be via any currently known methods preparation, and for example mixture and the capable alkoxide effect of initiator with oxyethane (EO) or oxyethane and propylene oxide (PO) makes Aethoxy Sklerol, again its terminal hydroxyl is converted into amido thereafter.Suitable starter comprises, but be not limited to methyl alcohol, ethanol, propyl carbinol, n-propyl alcohol, Virahol, hexalin, phenol, water, ethylene glycol, Diethylene Glycol (DEG), propylene glycol, glycerine, 2-Ding Tong Evil (2-butone oxime), aniline, trihydroxymethyl propane, and 3-methyl-hydroxymethyl propylene oxide.
According to the present invention, the general system of polyetheramine selects for use the oxyethane (EO) that has greater than about 50: 50 scopes to propylene oxide (PO) weight ratio person, and preferable boundary was in about 60: 40 to about 95: 5, and more Jia Jie was in about 70: 30 and about 90: 10.If the too strong words of wetting ability of contained remaining hydrophilic radical in the water-base resin tackiness agent that forms, the water-base resin tackiness agent will easily make its hydrophilic radical adsorb too many moisture, and easily cause the hydrolysis of groups such as contiguous urea, amido ethyl formate, biuret, allophanate, and reduce its adhesive performance.Therefore, in the present invention, importing corresponding to greater than the hydrophobic group (being propylene oxide) of the ratio of about 50: 50 hydrophilic radical/hydrophobic group ratio to the polyetheramine that is used for preparing the polynary isocyanate composition of aqueous dispersion type, preferable boundary was in about 60: 40 to about 95: 5, more Jia Jie was in about 70: 30 and about 90: 10, it can be during mixing polynary isocyanate and water-base resin, suitably avoid the undue consumption of isocyanate group, and promote initial clinging power via amido, hydroxyl and/or the carboxyl binding of hydrophobic group and water-base resin simultaneously.
Being used for polyetheramine of the present invention can be selected from, but is not limited to, polyethers monoamine, polyethers diamine, polyethers tertiary amine, and composition thereof; Preferable system is selected from polyethers monoamine and polyethers diamine.Wherein, the molecular weight of polyethers monoamine and polyethers diamine is about 500 to about 3000 gram/moles, and preferable about 600 to about 2500 gram/moles, and better about 800 to about 2000 gram/moles.
The specific examples that can be used for polyethers monoamine of the present invention comprises, but is not limited to,
M-1000 reaches
M-2070.The specific examples that can be used for polyethers diamine of the present invention comprises, but is not limited to,
ED-600,
ED-900,
ED-2001, and
ED-2003.Above-mentioned
Series is the product of US business Heng Ziman international corporation (HUNTSMAN INTERNATIONAL LLC).
Aethoxy Sklerol
Being used for Aethoxy Sklerol of the present invention can be via any currently known methods preparation, and for example mixture and the capable alkoxide effect of initiator with oxyethane or oxyethane and propylene oxide makes, and suitable starter as mentioned above.
As the explanation of above-listed polyetheramine part, in the present invention, Aethoxy Sklerol generally also selects for use the oxyethane that has greater than about 50: 50 scopes to propylene oxide weight ratio person, and preferable boundary was in about 60: 40 to about 95: 5, and more Jia Jie was in about 70: 30 and about 90: 10.
Being used for Aethoxy Sklerol of the present invention can be selected from, but is not limited to, polyethers monohydroxy-alcohol, polyether Glycols, polyether-tribasic alcohol, and composition thereof; Preferable system is selected from polyether Glycols.The molecular weight that is used for polyethers monohydroxy-alcohol of the present invention, polyether Glycols and polyether-tribasic alcohol is distinctly for about 150 to about 800 gram/moles, preferable about 300 to 500 gram/moles; 300 to 1600 gram/moles, preferable about 500 to 1000 gram/moles, better about 600 to 800 gram/moles; And about 450 to 2400 gram/moles, preferable about 600 to 1800 gram/moles, better about 900 to 1200 gram/moles.
The polynary isocyanate composition of aqueous dispersion type
Preparing the polynary isocyanate composition of aqueous dispersion type of the present invention can any known method preparation.According to the present invention, the manufacturing of reaction product (b) can be via with the mixture reaction of the mixture of the mixture of polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics and other polynary isocyanate and polyetheramine or polyetheramine and Aethoxy Sklerol and carry out.Generally speaking, reaction product (b) can the step through separating prepare, promptly pass through mixture or the mixture of the polynary isocyanate of aliphatics and other polynary isocyanate and the mixture reaction of polyetheramine or polyetheramine and Aethoxy Sklerol of polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics, and then mix to form the polynary isocyanate composition of aqueous dispersion type with composition (a); Or can make on the spot.The polynary isocyanate of aliphatics that is used for preparation feedback product (b) can be identical or different kind with composition (a).
Dividing (a) is identical or different kind.
According to the present invention, preferably reaction product (b) prepares on the spot, and in other words, the polynary isocyanate composition of aqueous dispersion type is to make through a step method, wherein uses the contained NCO base and composition (c) reaction of composition (a) of more amount.Reaction product (b) can be by separation steps or preparation on the spot, and its technology is known in this area, for example sees U.S. Pat 4,663, and 377 and U.S. Pat 5,200,489, and can not change material of the present invention.
In one embodiment, can under room temperature, make composition (a) and composition (c) reaction about 2 to about 4 hours, and need not can react under the catalyst existence.Also have, in this specific embodiments, said composition system by, with composition weight meter, about 99.5% to about 92% composition (a) with about 0.5% to about 8% composition (c), preferable be about 99% to about 96% composition (a) with about 1% to about 4% composition (c), reaction and making.When composition (c) is the mixture of polyetheramine, polyetheramine can by polyethers monoamine, polyethers diamine, and the polyethers tertiary amine mix with any suitable proportion, the ratio that is preferably polyethers monoamine and polyethers diamine is 1: 4 to 13: 1 former.When composition (c) is polyetheramine and Aethoxy Sklerol mixture, the general system of said composition by, with composition weight meter, about 99% to about 92% composition (a) with about 0.5% to about 4% polyetheramine and about 0.5% to the reaction of about 4% Aethoxy Sklerol and make, the preferably is that the ratio of polyetheramine and Aethoxy Sklerol is about 1: 3 to about 2: 3.
When only with polyetheramine and the reaction of polynary isocyanate, the polynary isocyanate of gained aqueous dispersion type has urea functional group structure.And when using the reaction of polyetheramine and Aethoxy Sklerol mixture and isocyanate, the polynary isocyanate of gained aqueous dispersion type then has urea and amido ethyl formate functional group structure.With the reaction of low molecular polyether alcohol with polynary isocyanate, use polyetheramine person can significantly shorten the time of reaction, the carrying out that does not need to add any catalyst assisted reaction compared to known.
The polynary isocyanate composition of aqueous dispersion type of above-mentioned gained tool urea functional group structure can give heat temperature raising again to about 100 to about 150 ℃, and reaction about 2 to about 8 hours continues.Know all that generally the reaction times looks closely temperature of reaction and decides.In the present invention, preferable system is warming up to about 110 ℃ of about 5 hours of reactions that continue.See through this heat treated, impel contained urea functional group structure in the polynary isocyanate composition of aqueous dispersion type, reaction generates urea and urea derivative functional group structure.Most even almost be urea derivative in the resultant of reaction after the heat treated, and urea derivative comprises biuret, the contract triuret and four ureas that contract, and be mainly biuret.
Thereby, a kind of polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative is provided among the present invention, be preferably a kind of polynary isocyanate composition of aqueous dispersion type that contains urea derivative, be more preferred from a kind of polynary isocyanate composition of aqueous dispersion type that contains urea and biuret, and a kind of polynary isocyanate composition of aqueous dispersion type of biuret-containing, its feature all is the reaction that continues that heated up by the polynary isocyanate composition reheat of above-mentioned urea-containing aqueous dispersion type, makes to promote isocyanate official energy radix in the said composition.
The polynary isocyanate composition of aqueous dispersion type about above-mentioned gained tool urea and amido ethyl formate functional group structure, can give heat temperature raising in the same manner again to about 100 to about 150 ℃, reaction about 2 to about 8 hours continues, preferable system is warming up to about 110 ℃ of about 5 hours of reactions that continue, to impel contained urea and urethanum functional group structure in the polynary isocyanate composition of aqueous dispersion type, reaction generates urea and urea derivative and carbamate functional group structure.And most even almost be urea derivative and allophanate in the resultant of reaction after the heat treated, urea derivative comprises biuret, the contract triuret and four ureas that contract, and is mainly biuret.Therefore, in one embodiment, the invention provides a kind of polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative and allophanate, be preferably a kind of polynary isocyanate composition of aqueous dispersion type that contains urea derivative and carbamate, be more preferred from a kind of polynary isocyanate composition of aqueous dispersion type that contains urea and biuret and allophanate, and the polynary isocyanate composition of aqueous dispersion type of a kind of biuret-containing and carbamate.The viscosity of the polynary isocyanate composition of gained aqueous dispersion type and the add amount of polyetheramine and kind thereof and molecular weight have significant relation.In specific words, because the urea functional group easily forms hydrogen-bond phenomenon to each other, be with, then will have the urea functional group of higher concentration by the polynary isocyanate composition of aqueous dispersion type of the low-molecular-weight tool urea of the prepared tool of low-molecular-weight polyetheramine functional group structure, that is intermolecularly contain more vacation-bond (pseudo-bondings) and produce higher viscosity.But when seeing through heat treated, after this urea functional group is converted into the biuret functional group, can reduce hydrogen-bond phenomenon, thereby reduce the viscosity of the polynary isocyanate composition of aqueous dispersion type, the reduction amplitude can reach 25% to 300%, and when using the polyethers diamine even can reduce viscosity and reach 3000%, this reduction amplitude is generally also decided on the kind of used polyetheramine and molecular weight thereof and addition.
In one embodiment, be the further viscosity of the polynary isocyanate composition of control aqueous dispersion type, can be before polynary isocyanate composition uses the lower boiling inert organic solvents of interpolation in wherein.This organic solvent can be, but is not limited to, ethyl acetate, acetone, dimethyl ethylene glycol or methyl ethyl ketone or its mixture; Preferable series ethyl acetate.In addition, can be via adjusting its addition, control final moisture loose the polynary isocyanate composition of type desire viscosity.
The water-base resin tackiness agent
According to the present invention, can utilize any known mixer means, mechanical stirring for example is in conjunction with polynary isocyanate composition of aqueous dispersion type of the present invention and water-base resin.
The example that is applicable to the water-base resin of production water-base resin tackiness agent of the present invention comprises active hydrogen containing reactant group person, for example hydroxyl, amido, carboxyl and similar group thereof etc., particularly hydroxyl and amido person.According to the present invention, preferable water-base resin be water-based polyurethane (PUs), water-based polyvinyl acetate (PVACs), watersoluble polyvinyl alcohol (PVOHs), and the water-based hydroxyl polyacrylic ester, and composition thereof, preferable is water-based PUs.As for mixing of the polynary isocyanate composition of aqueous dispersion type and water-base resin, the consumption of the polynary isocyanate composition of aqueous dispersion type in the weight of water-base resin, is about 1 to about 5 weight %, and preferable about 2 to about 4 weight %.
System is applicable to the material that engages selected identical or different kind according to water-base resin tackiness agent of the present invention, for example timber, paper, plastics, fabric, leather, and inorganic materials, especially PUs, PVACs and rubber.
Compared to present business-like product, the polynary isocyanate composition of aqueous dispersion type that interpolation the present invention contains urea or biuret can be improved on using to water-base resin, especially clinging power, thermotolerance aspect.And compared to by Aethoxy Sklerol and the polynary isocyanate composition of the formed aqueous dispersion type of polynary isocyanate, the present invention more has remarkable efficacy in the initial stage of rubber substrate adhesion strength.
The following example is to set forth the present invention in more detail, removes to particularly point out, and all per-cents mean weight percent.
Embodiment
Embodiment 1: utilize polyethers monoamine or diamine to prepare the polynary isocyanate composition of aqueous dispersion type
(it is through trimerizing HDI gained and has about 3000cps/25 ℃ viscosity and about NCO% of 21 to 22% with the HDI trimer, can buy from Bayer Corp., Rhodia Chimie or BASFAktiengesellschafi) be added in the loam cake separate type reactor, and stir with mechanical stirrer with the not imperial rod of iron.At room temperature slowly will add at leisure in the reactor, last about 30 minutes available from polyethers monoamine or the diamine (as listed in the table 1) of Heng Ziman (Huntsman) with feed-pipe.A part of (about 300 grams) were heated to about 110 ℃ of thermotonuses about 5 hours, were cooled to room temperature again.
Table 1
| Material modified | The EO/PO ratio | MW (gram/mole) |
| Polyethers monoamine monoamine-1 monoamine-2 polyethers diamine diamine-1 diamine-2 | 32/10 19/3 39.5/5 5.5/2.5 | 2000 1000 2000 900 |
Be used to prepare the HDI trimer of the polynary isocyanate composition of aqueous dispersion type and the consumption of polyether monoamine, and the NCO% and the viscosity of the polynary isocyanate composition of gained aqueous dispersion type are as shown in table 2.
Table 2
| Sample number into spectrum | Parent material | Weight % | Equivalence ratio | Addition (g) | Temperature of reaction | NCO％ | Viscosity (cps/ ℃) |
| 1A | HDI trimer monoamine-1 | 93.13 6.87 | 138.83 1 | 279.4 20.6 | Room temperature | 19.55 | 2600/ 31.1 |
| 1B | HDI trimer monoamine-1 | 93.13 6.87 | 138.83 1 | 279.4 20.6 | 110℃ | 19.36 | 3100/ 31.2 |
| 2A | HDI trimer monoamine-2 | 93.13 6.87 | 69.42 1 | 279.4 20.6 | Room temperature | 18.38 | 53360/ 27.5 |
| 2B | HDI trimer monoamine-2 | 93.13 6.87 | 69.42 1 | 279.4 20.6 | 110℃ | 17.57 | 4950/ 27.5 |
| 3A | HDI trimer monoamine-2 | 94 6 | 80.56 1 | 282 18 | Room temperature | 19.11 | 17110/ 27.5 |
| 3B | HDI trimer monoamine-2 | 94 6 | 80.56 1 | 282 18 | 110℃ | 18.9 | 4170/ 27.5 |
| 4A | HDI trimer monoamine-2 | 95 5 | 97.33 1 | 285 15 | Room temperature | 19.15 | 7000/ 27.5 |
| 4B | HDI trimer monoamine-2 | 95 5 | 97.33 1 | 285 15 | 110℃ | 18.94 | 2338/ 27.5 |
| 5A | HDI trimer monoamine-2 | 96 4 | 123.33 1 | 288 12 | Room temperature | 21 | 28440/ 27.5 |
| 5B | HDI trimer monoamine-2 | 96 4 | 123.33 1 | 288 12 | 110℃ | 18.98 | 4464/ 27.5 |
| 6A | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | Room temperature | 19.76 | 26850/ 27.5 |
| 6B | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | 110℃ | 19.02 | 5640/ 24.7 |
| 7A | HDI trimer diamine-1 | 97 3 | 165.56 1 | 291 9 | Room temperature | 21.61 | 120000/ 27 |
| 7B | HDI trimer diamine-1 | 97 3 | 165.56 1 | 291 9 | 110℃ | 19.19 | 4122/ 27 |
| 8A | HDI trimer diamine-1 | 98 2 | 251.67 1 | 294 6 | Room temperature | 21.91 | 107600/ 27 |
| 8B | HDI trimer diamine-1 | 98 2 | 251.67 1 | 294 6 | 110℃ | 21.68 | 3932/ 27 |
| 9A | HDI trimer diamine-2 | 98 2 | 113.53 1 | 294 6 | Room temperature | 20.79 | 7400/ 26.5 |
| 9B | HDI trimer diamine-2 | 98 2 | 113.53 1 | 294 6 | 110℃ | 20.38 | 4080/ 26.5 |
Embodiment 2: utilize polyethers monoamine and polyethers diamine to prepare the polynary isocyanate composition of aqueous dispersion type
Preparation process is person as described in Example 1, and removing is that the mixture of monoamine-1 with diamine-1 reacted with the HDI trimer.Be used to prepare the consumption of HDI trimer, monoamine-1 and the diamine-1 of the polynary isocyanate composition of aqueous dispersion type, and the NCO% and the viscosity of the polynary isocyanate composition of gained aqueous dispersion type are as shown in table 3.
Table 3
| Sample number into spectrum | Parent material | Weight % | Equivalence ratio | Addition (g) | Temperature of reaction | NCO％ | Viscosity (cps/) |
| 10A | HDI trimer monoamine-1 diamine-1 | 93.13 6.183 0.687 | 694.17 4.5 1 | 279.4 18.54 2.06 | Room temperature | 19.18 | 2940/ 29.4 |
| 10B | HDI trimer monoamine-1 diamine-1 | 93.13 6.183 0.687 | 694.17 4.5 1 | 279.4 18.54 2.06 | 110℃ | 18.95 | 4060/ 29.5 |
| 11A | HDI trimer monoamine-1 diamine-1 | 93.13 5.496 1.374 | 347.09 2 1 | 279.4 16.48 4.12 | Room temperature | 19.93 | 3720/ 29.5 |
| 11B | HDI trimer monoamine-1 diamine-1 | 93.13 5.496 1.374 | 347.09 2 1 | 279.4 16.48 4.12 | 110℃ | 18.55 | 4440/ 29.6 |
| 12A | HDI trimer monoamine-1 diamine-1 | 93.13 6.183 0.687 | 694.17 9 1 | 279.4 18.54 2.06 | Room temperature | 20.34 | 22680/ 27.5 |
| 12B | HDI trimer monoamine-1 diamine-1 | 93.13 6.183 0.687 | 694.17 9 1 | 279.4 18.54 2.06 | 110℃ | 17.17 | 4890/ 27.5 |
Embodiment 3: utilize polyethers monoamine or polyethers diamine and polyether Glycols to prepare the polynary isocyanate composition of aqueous dispersion type
Preparation process is person as described in Example 1, and removing is that monoamine-2 or diamine-1 mixture with dibasic alcohol-1 is reacted with the HDI trimer.Wherein, dibasic alcohol-1 is that (Eu Hou Polymer Chemical Industry Co. Ltd), and has about 80/20 the EO/PO ratio and the molecular weight of about 700 gram/moles available from the steady good polymer chemistry in Taiwan Industrial Co., Ltd.Be used to prepare the consumption of HDI trimer, monoamine-2, diamine-1 and the dibasic alcohol-1 of the polynary isocyanate composition of aqueous dispersion type, and the NCO% and the viscosity of the polynary isocyanate composition of gained aqueous dispersion type are as shown in table 4.
Table 4
| Sample number into spectrum | Parent material | Weight % | Equivalence ratio | Addition (g) | Temperature of reaction | NCO％ | Viscosity (cps/) |
| 13A | HDI trimer monoamine-2 dibasic alcohol-1 | 96 1 3 | 493.33 1 8.57 | 288 3 9 | Room temperature | 20.34 | 2780/ 27.5 |
| 13B | HDI trimer monoamine-2 dibasic alcohol-1 | 96 1 3 | 493.33 1 8.57 | 288 3 9 | 110℃ | 19.93 | 3672/ 27.5 |
| 14A | HDI trimer monoamine-2 dibasic alcohol-1 | 95 2 3 | 243.33 1 4.28 | 285 6 9 | Room temperature | 20.13 | 2720/ 27.5 |
| 14B | HDI trimer monoamine-2 dibasic alcohol-1 | 95 2 3 | 243.33 1 4.28 | 285 6 9 | 110℃ | 19.56 | 2920/ 27.5 |
| 15A | HDI trimer diamine-1 dibasic alcohol-1 | 96 1 3 | 493.33 1 8.57 | 288 3 9 | Room temperature | 19.66 | 3120/ 28.5 |
| 15B | HDI trimer diamine-1 dibasic alcohol-1 | 96 1 3 | 493.33 1 8.57 | 288 3 9 | 110℃ | 19.38 | 4722/ 28.5 |
| 16A | HDI trimer diamine-1 dibasic alcohol-1 | 95 2 3 | 243.33 1 4.28 | 285 6 9 | Room temperature | 19.88 | 5400/ 28.5 |
| 16B | HDI trimer diamine-1 dibasic alcohol-1 | 95 2 3 | 243.33 1 4.28 | 285 6 9 | 110℃ | 18.78 | 4278/ 28.5 |
Embodiment 4: the clinging power of water-based PU tackiness agent and the thermotolerance test of adhesion back
According to the polynary isocyanate composition of aqueous dispersion type of the 1.5g of the obtained sample of the foregoing description and commerical prod (the sample C of 1.5g, it is a kind of anhydrous and by HDI trimer and the polynary isocyanate of polyethers monohydroxy-alcohol synthetic aliphatics, the NCO% and 3 of its tool 18.5% to 20.5%, 000mPa s/23 ℃ viscosity), be added into respectively that (commodity are called GE-6608 among the water-based PU of 48.5g, make by Dadong Resin Chemical Co., Ltd.), with preparation water-based PU tackiness agent.Because the used water-based PUs of each test is prepared by different batches, so test result system is a benchmark with the measured person of sample C.Change speech, the gained data are comparison clinging power or stable on heating purpose, but not an absolute figure.The clinging power of water-based PU tackiness agent and adhesion back stable on heating operational condition such as following contained between the testing rubber base material:
1. (10cm * 2.5cm) surface is beaten slightly with the rubber substrate desiring to be adhered with making thick machine.
2. handle the rubber substrate surface with bottom layer treatment agent (commodity are called GE-001AB, are made by Dadong Resin Chemical Co., Ltd.).
3. the rubber substrate that will handle is in 60 ℃ of baking ovens dry 3 minutes.
4. the dry rubber substrate system of crossing evenly applies with the water-based PU tackiness agent that contains the polynary isocyanate composition of aqueous dispersion type.
5. the system of the rubber substrate through applying is further in 60 ℃ of baking ovens dry 5 minutes.
6. get two rubber substrates and adhered through coated surface, thereafter 10 seconds of 30kg pressure laminated with this from step 5 gained.
7. leaving standstill this after 10 minutes, utilizes the omnipotent test machine of computer type to test its early strength through laminated rubber substrate.
8. leaving standstill this after 1 hour, utilizes the omnipotent test machine of computer type to test its clinging power through laminated rubber substrate again.
9. leaving standstill this after 24 hours, utilizes the omnipotent test machine of computer type to test its later stage clinging power through laminated rubber substrate again.
10. leave standstill this through laminated rubber substrate after 72 hours, be placed on again in 70 ℃ the baking oven and hung 60 hours, to test its later stage thermotolerance so that the 1.5kg weights is resuspended.
Test (A)
Carry out the test of clinging power with sample 1B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 5.
Table 5
According to above-mentioned test result, sample 1B of the present invention surmounts sample C person, i.e. commercially produced product in the performance of the clinging power of improvement water-based PU tackiness agent.
Test (B)
Carry out clinging power and stable on heating test with sample 6B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 6.
Table 6
According to above-mentioned test result, sample 6B of the present invention all surmounts sample C person, i.e. commercially produced product in the clinging power of improvement water-based PU tackiness agent with the stable on heating performance in adhesion back.
Test (C)
Carry out clinging power and the adhesion stable on heating test in back with sample 7B, 8B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 7.
Table 7
According to above-mentioned test result, sample 7B and 8B all surmount sample C person, i.e. commercially produced product in the clinging power and the stable on heating performance of improvement water-based PU tackiness agent.
Test (D)
Carry out the test of clinging power with sample 9B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 8.
Table 8
According to above-mentioned test result, sample 9B surmounts sample C person, i.e. commercially produced product in the performance of the clinging power of improvement water-based PU tackiness agent.
Test (E)
Carry out the test of clinging power with sample 12B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 9.
Table 9
According to above-mentioned test result, sample 12B surmounts sample C person, i.e. commercially produced product in the performance of the clinging power of improvement water-based PU tackiness agent.
Test (F)
Carry out clinging power and the adhesion stable on heating test in back with sample 13B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 10.
Table 10
According to above-mentioned test result, sample 13B surmounts sample C person, i.e. commercially produced product in the clinging power of improvement water-based PU tackiness agent all significantly with the stable on heating performance in adhesion back.
Test (G)
Carry out clinging power and the adhesion stable on heating test in back with sample 14B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 11.
Table 11
According to above-mentioned test result, sample 14B surmounts sample C person, i.e. commercially produced product in the clinging power of improvement water-based PU tackiness agent all significantly with the stable on heating performance in adhesion back.
Test (H)
Carry out the test of clinging power with sample 15B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 12.
Table 12
According to above-mentioned test result, sample 15B of the present invention surmounts sample C person, i.e. commercially produced product in the clinging power of improvement water-based PU tackiness agent.
Test (I)
Carry out clinging power and the adhesion stable on heating test in back with sample 16B or the crosslinked water-based PU tackiness agent system of C according to abovementioned steps, listed in test result such as the table 13.
Table 13
According to above-mentioned test result, sample 16B all surmounts sample C person, i.e. commercially produced product in the clinging power and the stable on heating performance of improvement water-based PU tackiness agent.
Clear as can be known by above-mentioned data, with the water-base resin tackiness agent of the polynary isocyanate composition modification of the aqueous dispersion type of biuret-containing of the present invention, the modification person of commercially produced product institute provides preferable clinging power and thermotolerance at present really.Particularly, utilize the ratio of polyethers diamine and polyether Glycols to be about 2: 3 water-base resin tackiness agents that the polynary isocyanate composition of synthetic water-dispersion is crosslinked, have best adhesion effect, especially on later stage adhesion strength and adhesion back thermotolerance, significant lifting is arranged all.
Embodiment 5: use the polyethers monoamine to prepare the influence to composition viscosity of the polynary isocyanate composition of aqueous dispersion type and test reaction time
Preparation process is person as described in Example 1, and removing is with monoamine-2 and the reaction of HDI trimer.Wherein, the viscosity that listed each reaction times is tested the polynary isocyanate composition of gained aqueous dispersion type respectively in table 14.Be used to prepare the HDI trimer of the polynary isocyanate composition of aqueous dispersion type and the consumption of monoamine-2, and the viscosity of the polynary isocyanate composition of gained aqueous dispersion type is as shown in table 14.
Table 14
| Sample number into spectrum | Parent material | Weight % | Equivalence ratio | Addition (g) | Temperature of reaction and time | Viscosity (cps/ ℃) |
| 17A1 | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | Room temperature/1hr | 4680/ 28.5 |
| 17A2 | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | Room temperature/2hr | 6350/ 28.5 |
| 17A3 | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | Room temperature/3hr | 6700/ 28.5 |
| 17B1 | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | 110℃/1hr | 2840/ 28.5 |
| 17B2 | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | 110℃/2hr | 3056/ 28.5 |
| 17B3 | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | 110℃/3hr | 3240/ 28.5 |
| 17B4 | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | 110℃/4hr | 3400/ 28.5 |
| 17B5 | HDI trimer monoamine-2 | 97 3 | 165.56 1 | 291 9 | 110℃/5hr | 3712/ 28.5 |
According to above-mentioned test result, sample 17A1 to 17A3 product, viscosity increases along with the reaction times and strengthens.Only through being heated to 110 ℃ and heated 1 hour, the viscosity degradation of sample 17B1 product is to 2840cps/28.5 ℃, and along with the increase in reaction times, the viscosity of sample 17B2 to 17B5 product also increases.
Though the present invention system is described in detail in above to reach illustrative purpose, only when will be appreciated that, these detail content only are the illustration purpose, and the variation of the present invention that those who familiarize themselves with the technology does not depart from spirit and scope still surely belong to this case claim can the person of containing.
Claims (30)
1. polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative, it comprises
(a) mixture of the mixture of polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics and other polynary isocyanate; And
(b) reaction product of the mixture of composition (a) and composition (c) polyetheramine or polyetheramine and Aethoxy Sklerol;
Wherein, this combination be by, in said composition weight, 99.5% to 92% composition (a) and the reaction of 0.5% to 8% composition (c), and continue reaction via heating can radix and make to promote in the said composition isocyanate official.
2. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein the polynary isocyanate of this aliphatics be selected from isocyanuric acid salt derivative, biuret derivatives, urea diketone ring derivatives, urethane ester derivative, allophanic acid salt derivative, carbonyl diimine derivative, Evil diazoxide triketone derivative, and composition thereof isocyanate.
3. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 2, wherein the polynary isocyanate of this aliphatics be selected from isocyanuric acid salt derivative, biuret derivatives, and composition thereof polynary isocyanate.
4. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 3, wherein the polynary isocyanate of this aliphatics is to be selected from 1, the own diisocyanate trimer of 6-, isophorone diisocyanate trimer, and 1, the own diisocyanate of 6-/isophorone diisocyanate trimer, and composition thereof.
5. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 4, wherein the polynary isocyanate of this aliphatics is 1, the own diisocyanate trimer of 6-.
6. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 5, wherein this other polynary isocyanate is to be selected from 4,4-diphenyl-methyl diisocyanate, aggretion type 4,4-diphenyl-methyl diisocyanate, toluene di-isocyanate (T, and isocyanic acid dimethylbenzene, and composition thereof the polynary isocyanate of aromatic series.
7. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein this polyetheramine be selected from polyethers monoamine, polyethers diamine, polyethers tertiary amine, and composition thereof, and this Aethoxy Sklerol be selected from polyethers monohydroxy-alcohol, polyether Glycols, polyether-tribasic alcohol, and composition thereof.
8. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein this polyetheramine be selected from polyethers monoamine, polyethers diamine, and composition thereof, and this Aethoxy Sklerol is to be selected from polyether Glycols.
9. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 7, wherein this polyethers monoamine and polyethers diamine have the molecular weight of 500 to 3000 gram/moles, and this polyether Glycols has the molecular weight of 300 to 1600 gram/moles.
10. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 9, wherein this polyethers monoamine and polyethers diamine have the molecular weight of 600 to 2500 gram/moles, and this polyether Glycols has the molecular weight of 500 to 1000 gram/moles.
11. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 10, wherein this polyethers monoamine and polyethers diamine have the molecular weight of 800 to 2000 gram/moles, and this polyether Glycols has the molecular weight of 600 to 800 gram/moles.
12. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein oxyethane is greater than 50: 50 to the weight ratio of propylene oxide in this polyetheramine and the Aethoxy Sklerol.
13. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 12, wherein oxyethane is between 60: 40 to 95: 5 to the weight ratio of propylene oxide in this polyetheramine and the Aethoxy Sklerol.
14. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 13, wherein oxyethane is between 70: 30 and 90: 10 to the weight ratio of propylene oxide in this polyetheramine and the Aethoxy Sklerol.
15. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein said composition be by, in said composition weight, 98% to 96% composition (a) and 2% to 4% composition (c) reaction and making.
16. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein said composition be by, in said composition weight, 99% to 92% composition (a) reacts with 0.5 to 4% polyetheramine and 0.5 to 4% Aethoxy Sklerol and makes.
17. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, it further comprises lower boiling inert organic solvents.
18. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 17, wherein this solvent be selected from ethyl acetate, acetone, dimethyl ethylene glycol, and composition thereof.
19. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein composition (a) reacts prior to room temperature with composition (c).
20. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 19, wherein this reaction need not be carried out under catalyst exists.
21. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1 wherein is to be warming up to 100 to 150 ℃ to react 2 to 8 hours down.
22. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 21 wherein is to be warming up to 110 ℃ to react 5 hours down.
23. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein urea derivative comprise biuret, contract triuret and contract four ureas one of them.
24. the polynary isocyanate composition of aqueous dispersion type that contains urea and urea derivative according to claim 1, wherein urea derivative is a biuret.
25. the polynary isocyanate composition of the aqueous dispersion type of a biuret-containing, it comprises
(a) mixture of the mixture of polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics or the polynary isocyanate of aliphatics and other polynary isocyanate; And
(b) reaction product of the mixture of composition (a) and composition (c) polyetheramine or polyetheramine and Aethoxy Sklerol; Wherein, said composition be by, in said composition weight, 99.5% to 92% composition (a) and the reaction of 0.5% to 8% composition (c), and continue reaction via heating can radix and make to promote in the said composition isocyanate official.
26. a water-base resin tackiness agent, it comprises water-base resin and claim 1 or the polynary isocyanate composition of 25 described aqueous dispersion types.
27. water-base resin tackiness agent according to claim 26, wherein in this water-base resin weight, the amount of the polynary isocyanate composition of this aqueous dispersion type is 1 to 5%.
28. water-base resin tackiness agent according to claim 27, wherein in this water-base resin weight, the amount of the polynary isocyanate composition of this aqueous dispersion type is 2 to 4%.
29. water-base resin tackiness agent according to claim 26, wherein this water-base resin be selected from polyurethane, polyvinyl acetate, polyvinyl alcohol, alkyl polyacrylic ester, and composition thereof.
30. water-base resin tackiness agent according to claim 29, wherein this water-base resin is the water-based polyurethane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN03155957A CN100575382C (en) | 2003-08-27 | 2003-08-27 | Contain polynary isocyanate composition of aqueous dispersion type of urea and/or biuret and uses thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03155957A CN100575382C (en) | 2003-08-27 | 2003-08-27 | Contain polynary isocyanate composition of aqueous dispersion type of urea and/or biuret and uses thereof |
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| CN100575382C true CN100575382C (en) | 2009-12-30 |
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