CN1257902A - Adhesive for paint coating paper and its preparing process - Google Patents
Adhesive for paint coating paper and its preparing process Download PDFInfo
- Publication number
- CN1257902A CN1257902A CN 99112595 CN99112595A CN1257902A CN 1257902 A CN1257902 A CN 1257902A CN 99112595 CN99112595 CN 99112595 CN 99112595 A CN99112595 A CN 99112595A CN 1257902 A CN1257902 A CN 1257902A
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- Prior art keywords
- adhesive
- acid
- ester
- vinyl monomer
- temperature
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 18
- 238000000576 coating method Methods 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 title claims abstract description 14
- 239000003973 paint Substances 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 6
- 230000008569 process Effects 0.000 title description 3
- 239000000839 emulsion Substances 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 39
- -1 acrylic ester Chemical class 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229920000570 polyether Polymers 0.000 claims description 19
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004159 Potassium persulphate Substances 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 235000019394 potassium persulphate Nutrition 0.000 claims description 11
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 11
- 239000001488 sodium phosphate Substances 0.000 claims description 11
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 11
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 11
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 8
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 238000011017 operating method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- DBRRMIJQAZXJLO-UHFFFAOYSA-N (2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)methanol Chemical compound OC[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C DBRRMIJQAZXJLO-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 238000011161 development Methods 0.000 description 4
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 3
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及涂布纸涂料用粘合剂及其制备方法,属于化工粘合剂技术领域。有机硅改性丙烯酸酯乳液L1重量百分比40～60%,聚氨酯水分散体L2重量百分比40～60%,所述L1中聚合物分子含醛或酮羰基活性基团,L2中聚合物分子含酰肼基活性基团。本发明的粘合剂是含有聚氨酯、丙烯酸酯、有机硅成份的乳液,光泽度、平滑度、印刷表面强度及油墨吸收性等方面综合性能优于现有公开报道。The invention relates to an adhesive for coated paper coating and a preparation method thereof, belonging to the technical field of chemical adhesives. Silicone-modified acrylate emulsion L1 is 40-60% by weight, polyurethane aqueous dispersion L2 is 40-60% by weight, the polymer molecules in L1 contain aldehyde or ketone carbonyl active groups, and the polymer molecules in L2 are polymerized The molecule contains a hydrazide active group. The adhesive of the present invention is an emulsion containing polyurethane, acrylate, and silicone components, and its comprehensive performance in terms of gloss, smoothness, printing surface strength, ink absorption, etc. is better than existing public reports.
Description
The present invention relates to adhesive for paint coating paper and preparation method thereof, belong to the chemical industry technical field of adhesive.
By protein-based, natural glues such as cellulose family change to composite adhesives adhesive for paint coating paper.At three big composite adhesiveses promptly: in carboxyl styrene-butadiene emulsion, aqueous polyvinyl acetate emulsion and the acrylic ester emulsion, acrylic ester emulsion has better performance: have superior bond strengths rendering, ink absorption, print gloss, surface smoothing are useless etc.; Its printability is subjected to the influence of glue spread hardly; Have very strong characteristics such as heat-resisting, fast light and anti-oxidant degraded.Along with the development of petrochemical complex, the cost of acrylic ester monomer descends gradually, and this makes the development of acrylic ester emulsion very fast, and the trend that replaces at present general carboxyl styrene-butadiene emulsion is arranged greatly.But above-mentioned tackiness agent still is difficult to satisfy the requirements at the higher level of White Board development, and the used a large amount of dependence on import of high grade coated paper of China are studied and exploitation high grade coated paper tackiness agent at present, have been trend of the times.Therefore the development and the application of this tackiness agent are put into State Scientific and Technological Commission " 95 " brainstorm subject.
Although acrylic ester emulsion has many advantages, but still exist shortcomings such as not low temperature resistant, hot sticky cold crisp, water tolerance be relatively poor.People are doing number of research projects aspect the modification of acrylic ester emulsion for this reason, and are wherein more to the research of polyurethane-modified acrylic acid ester emulsion and organosilicon-modified acrylate emulsion.Organosilicon-modified acrylate emulsion can improve the not low temperature resistant shortcoming of acrylic ester emulsion significantly, and in addition, because organosilicon material polarity is little, hydrophobicity is strong, can improve the water tolerance of acrylate again.As the coated paper coatings tackiness agent, the glossiness of White Board obviously improves with organic-silicon-modified acrylic ester emulsion, but print surface intensity descends greatly.Polyurethane aqueous dispersion body is the very strong tackiness agent of a kind of bounding force, has superior elasticity, the performance that wear resistance and cold resistance etc. are excellent is carried out the copolymerzation with cross-linking modification with urethane to acrylic ester emulsion, has greatly improved the cohesive force of acrylic ester emulsion and the mechanical property of film.This tackiness agent is used for White Board, has improved the print surface intensity of White Board widely, shortcoming is that glossiness descends obviously.
The objective of the invention is to, overcome the shortcoming of prior art, adhesive for paint coating paper of a kind of excellent combination property and preparation method thereof is provided.
Adhesive for paint coating paper of the present invention is made up of following component, and proportioning is weight percentage.
Organosilicon-modified acrylate emulsion L
140～60%
Polyurethane aqueous dispersion body L
240～60%
Above-mentioned L
1Middle polymer molecule contains aldehydes or ketones carbonyl active group, L
2Middle polymer molecule contains the hydrazide group active group.
Above-mentioned L
1The organosilicon-modified acrylate emulsion that contains active group is obtained by following method:
The vinyl monomer of hydroxyl, the vinyl monomer that contains the aldehydes or ketones carbonyl, octamethylcyclotetrasiloxane (D
4) with after acrylic ester monomer etc. mixes, carry out letex polymerization, promptly obtain L
2The vinyl monomer that contains the aldehydes or ketones carbonyl is as the functional monomer, can introduce the aldehydes or ketones carbonyl in the acrylic ester polymer molecule, the vinyl monomer that contains the aldehydes or ketones carbonyl can be diacetone-acryloamide(DAA) (DAAM), propenal, methyl vinyl ketone, methacrylic acid etheric acid glycol ester (AAEM) or vinylformic acid etheric acid glycol ester etc.The vinyl monomer of hydroxyl is as grafting agent, can make octamethylcyclotetrasiloxane and acrylic ester polymer generation graft reaction, the vinyl monomer of hydroxyl can be propenoic acid beta-hydroxy ethyl ester (HEA), propenoic acid beta-hydroxy propyl ester (HPA), Jia Jibingxisuanβ-Qiang Yizhi or methacrylic acid β-hydroxypropyl acrylate.L
1Reaction formula is as follows:
N is an integer, and R is-H-CH
3,-C
2H
5,-C
4H
9-n,
Above-mentioned L
2The polyurethane aqueous dispersion body that contains active group is that the aqueous solution that will contain hydrazine is distributed in the base polyurethane prepolymer for use as, introduces hydrazide group at the end of polyurethane molecular.The reaction skeleton symbol is as follows:
L
1With L
2Composition mixture in proportion, when practical application, along with the volatilization of moisture, crosslinking reaction takes place between two kinds of polymkeric substance in aldehydes or ketones carbonyl and hydrazide group dehydrating condensation in film process, and this reaction at room temperature just can be carried out.
Adhesive for paint coating paper preparation method of the present invention is at L
1Preparation in except that aforesaid each composition, also need add low quantity of surfactant, as sodium lauryl sulphate, polyoxyethylene nonylphenol ether, the PH conditioning agent is as trisodium phosphate, and radical initiator, as Potassium Persulphate.
Concrete preparation method is as follows:
One, L
1Preparation
Proportioning raw materials (weight part) A component distillation water 20～60
Polyoxyethylene nonylphenol ether (OP-10) 0.4～2.0
Sodium lauryl sulphate 0.1～0.8
Trisodium phosphate 0.05～0.2
Potassium Persulphate 0.1～0.5B part acrylic butyl ester (BA) 10～30
Isooctyl acrylate monomer (EHA) 10～30
Methyl methacrylate (MMA) 1～5
Vinylformic acid (AA) 1～5
Vinylbenzene (ST) 20～60
The vinyl monomer 1～6 that contains hydroxyl
Octamethylcyclotetrasiloxane (D
4) 1～6
Vinyl monomer 2～10C component distillation the water 30～80 that contains the aldehydes or ketones carbonyl
Polyoxyethylene nonylphenol ether (OP-10) 1.5～7
Sodium lauryl sulphate 0.05～0.2
Potassium Persulphate 0.15～0.6
Trisodium phosphate 0.1～0.5
More than the raw materials used technical pure that is, be the industry code name in the bracket.
The vinyl monomer that contains hydroxyl in the above-mentioned B component is propenoic acid beta-hydroxy ethyl ester (HEA), propenoic acid beta-hydroxy propyl ester (HPA), Jia Jibingxisuanβ-Qiang Yizhi or methacrylic acid β-hydroxypropyl acrylate.
The vinyl monomer that contains the aldehydes or ketones carbonyl in the above-mentioned B component is diacetone-acryloamide(DAA) (DAAM), propenal, methyl vinyl ketone, methacrylic acid etheric acid glycol ester (AAEM) or vinylformic acid etheric acid glycol ester etc.Operating procedure is: (1) joins the A component and is equipped with in the churned mechanically reactor, starts stirring, is warming up to 75～95 ℃.(2) stirring drips B component and C component down simultaneously in reactor in header tank, maintains the temperature between 75～95 ℃, drips off in 1～3 hour.(3) start stirring, logical cold water is cooled to below 60 ℃, filters, and obtains L
1Product.
Two, L
2Contain the preparation of the polyurethane aqueous dispersion body of hydrazide group
Composition of raw materials:
Material name consumption (weight part)
Polyethers 8～17
Ethylene glycol is or/and Diethylene Glycol 0.5～2
Tolylene diisocyanate (TDI) 5～12
Dimethylol propionic acid (DMPA) 0.5～2.5
Above raw material is the industrial goods top grade, and concentration is more than 98%, with before to dewater; Following raw material is a technical pure.
Triethylamine 0.5～2
Hydrazine hydrate 1～2
Acetone 10～20
Distilled water 43～73 concrete steps are as follows: (1) polyethers, ethylene glycol, Diethylene Glycol vacuum hydro-extraction respectively.Vacuum tightness:＜50mmHg; Temperature: 105～120 ℃; Time: 4～6 hours.(2) prepolymerization reaction: with polyethers and tolylene diisocyanate (TDI) hybrid reaction, temperature: 50～90 ℃, the time: 1～4 hour.(3) chain extending reaction: with dimethylol propionic acid (DMPA), ethylene glycol, Diethylene Glycol add in the above-mentioned reactive system, temperature: 70～90 ℃, and the time: 1～2 hour.(4) dilution neutralization: acetone is added in the above-mentioned reactive system, stir evenly, put into the triethylamine neutralization, temperature: 30～50 ℃, the time: 1～2 hour.(5) hydrazine hydrate and water are put into above-mentioned reactive system, high-speed stirring makes it to disperse room temperature, 1～3 hour time.(6) vacuum is removed acetone solvent: 30～60 ℃ of temperature, vacuum tightness:＜50mmHg time: 1～3 hour.(7) filter to such an extent that contain the polyurethane aqueous dispersion body product of hydrazide group.
Tackiness agent of the present invention is the composition emulsion that contains urethane, acrylate, organosilicon composition, active group generation crosslinking reaction in film process, use excellent combination property on White Board, aspect over-all propertieies such as glossiness, smoothness, print surface intensity and ink absorption are better than existing open report.Following table has listed the embodiment of the invention 1 product and the other products performance compares: emulsion glossiness smoothness print surface intensity ink absorption
(%) (S) (m/s) (%) embodiment 1 58.9 1,852 4.3 28.6 B
0J
439.6 1,868 2.08 37.6 B
060.2 1,326 1.80 40.7 carboxyl styrene-butadiene emulsion, 46.4 3.03 39.0 benzene-acrylic emulsion 49.3 2.33 36.2 polyurethane aqueous dispersion bodies 45.1 4.5 40.6
Wherein, B
0For not containing the organosilicon-modified acrylate emulsion of carbonyl active group, J
4For containing the polyurethane aqueous dispersion body of hydrazide group, B
0J
4Be the mixture of the two.Embodiment 1:
L
1Contained active group is the ketone carbonyl, L
2Contained active group is a hydrazide group.L
1?55％，L
2?45％。
L
1Preparation
Proportioning raw materials (weight part) A component distillation water 40
Nonyl phenol polyvinyl chloride ether (OP-10) 0.8
Sodium lauryl sulphate 0.4
Trisodium phosphate 0.12
Potassium Persulphate 0.2B part acrylic butyl ester (BA) 18
Isooctyl acrylate monomer (EHA) 18
Methyl methacrylate (MMA) 3
Vinylformic acid (AA) 3
Vinylbenzene (ST) 40
Diacetone-acryloamide(DAA) (DAAM) 6
Propenoic acid beta-hydroxy propyl ester (HPA) 3
Eight methoxyl group cyclotetrasiloxane (D
4) 3C component distillation water 55
Polyoxyethylene nonylphenol ether (OP-10) 4
Sodium lauryl sulphate 0.1
Potassium Persulphate 0.4
Trisodium phosphate 0.2
More than the raw materials used technical pure that is.Operating procedure is: (1) joins the A component and is equipped with in the churned mechanically reactor, starts stirring, is warmed up to 80 ℃.(2) stirring drips B component and C component down simultaneously in reactor in header tank, maintains the temperature at 80 ℃ ± 2 ℃, drips off in 3 hours.(3) start stirring, logical cold water is cooled to below 60 ℃, filters with 120 mesh filter screens, obtains L
1Product.
L
2Preparation
Material name consumption (weight part)
Polyethers 210 (molecular weight 1000) 6
Polyethers 220 (molecular weight 2000) 5
Ethylene glycol 0.7
Diethylene Glycol 0.6
Tolylene diisocyanate (TDI) 8
Dimethylol propionic acid (DMPA) 1.5
Above raw material is the industrial goods top grade, and following raw material is a technical pure.
Triethylamine 1.5
Hydrazine hydrate 1.5
Acetone 15
Distilled water 58 concrete steps are as follows: (1) polyethers 210, polyethers 220, ethylene glycol, Diethylene Glycol vacuum hydro-extraction respectively.Vacuum tightness: 45mmHg; Temperature: 110 ± 2 ℃; Time: 5 hours.(2) prepolymerization reaction: with polyethers 210, polyethers 220 and tolylene diisocyanate (TDI) hybrid reaction, temperature: 75 ± 2 ℃, the time: 3 hours.(3) chain extending reaction: with dimethylol propionic acid (DMPA), ethylene glycol, Diethylene Glycol add in the above-mentioned reactive system, temperature: 80 ± 2 ℃, and the time: 1.5 hours.(4) dilution neutralization: acetone is added in the above-mentioned reactive system, stir evenly, put into the triethylamine neutralization, temperature: 40 ℃, the time: 1.5 hours.(5) hydrazine hydrate and water are put into above-mentioned reactive system, high-speed stirring makes it to disperse room temperature, 2 hours time.(6) vacuum is removed acetone solvent: 40 ℃ of temperature, vacuum tightness: 45mmHg, time: 2 hours.(7) 120 mesh filter screens filter to such an extent that contain the polyurethane aqueous dispersion body product L of hydrazide group
2Embodiment 2.L
1Contained active group is the ketone carbonyl, L
2Contained active group is a hydrazide group.L
1 60％，L
2 40％。
L
1Preparation
Proportioning raw materials (weight part) A component distillation water 20
Polyoxyethylene nonylphenol ether (OP-10) 0.5
Sodium lauryl sulphate 0.2
Trisodium phosphate 0.06
Potassium Persulphate 0.15 B part acrylic butyl ester (BA) 15
Isooctyl acrylate monomer (EHA) 15
Methyl methacrylate (MMA) 1.5
Vinylformic acid (AA) 1.5
Vinylbenzene (ST) 25
Propenoic acid beta-hydroxy propyl ester (HPA) 1
Eight methoxyl group cyclotetrasiloxane (D
4) 1
Methacrylic acid etheric acid glycol ester (AAEM) 2.5C component distillation water 40
Polyoxyethylene nonylphenol ether (OP-10) 1.5
Sodium lauryl sulphate 0.06
Potassium Persulphate 0.2
Trisodium phosphate 0.1
More than the raw materials used technical pure that is.Operating procedure is: (1) joins the A component and is equipped with in the churned mechanically reactor, starts stirring, is warmed up to 75 ℃.(2) stirring drips B component and C component down simultaneously in reactor in header tank, maintains the temperature at 75 ℃ ± 2 ℃, drips off in 2 hours.(3) start stirring, logical cold water is cooled to below 60 ℃, filters with 120 mesh filter screens, obtains L
1Product.
L
2Preparation
Material name consumption (weight part)
Polyethers 220 (molecular weight 2000) 7
Polyethers 204 (molecular weight 400) 1.7
Ethylene glycol 0.5
Diethylene Glycol 0.7
Tolylene diisocyanate (TDI) 5
Dimethylol propionic acid (DMPA) 0.7
Above raw material is the industrial goods top grade, and following raw material is a technical pure.
Triethylamine 1
Hydrazine hydrate 1
Acetone 10
Distilled water 45 concrete steps are as follows: (1) polyethers 220, polyethers 204, ethylene glycol, Diethylene Glycol vacuum hydro-extraction respectively.Vacuum tightness: 45mmHg; Temperature: 112 ± 2 ℃; Time: 4 hours.(2) prepolymerization reaction: polyethers 220, polyethers 204 and tolylene diisocyanate (TDI) hybrid reaction, temperature: 85 ± 2 ℃, the time: 2 hours.(3) chain extending reaction: with dimethylol propionic acid (DMPA), ethylene glycol, Diethylene Glycol add in the above-mentioned reactive system, temperature: 85 ± 2 ℃, and the time: 1 hour.(4) dilution neutralization: acetone is added in the above-mentioned reactive system, stir evenly, put into the triethylamine neutralization, temperature: 45 ℃, the time: 2 hours.(5) hydrazine hydrate and water are put into above-mentioned reactive system, high-speed stirring makes it to disperse room temperature, 1 hour time.(6) vacuum is removed acetone solvent: 35 ℃ of temperature, vacuum tightness: 45mmHg, time: 3 hours.(7) 120 mesh filter screens filter to such an extent that contain the polyurethane aqueous dispersion body product L of hydrazide group
2Embodiment 3: as described in embodiment 1, that different is L
140%, L
260%, proportioning raw materials is as follows:
L
1Preparation
Proportioning raw materials (weight part) A component distillation water 60
Polyoxyethylene nonylphenol ether (OP-10) 1.6
Sodium lauryl sulphate 0.7
Trisodium phosphate 0.18
Potassium Persulphate 0.5B part acrylic butyl ester (BA) 26
Isooctyl acrylate monomer (EHA) 26
Methyl methacrylate (MMA) 4.5
Vinylformic acid (AA) 4.5
Vinylbenzene (ST) 55
Diacetone-acryloamide(DAA) (DAAM) 9
Propenoic acid beta-hydroxy propyl ester (HPA) 4
Octamethylcyclotetrasiloxane (D
4) 4C component distillation water 80
Polyoxyethylene nonylphenol ether (OP-10) 6
Sodium lauryl sulphate 0.2
Potassium Persulphate 0.5
Trisodium phosphate 0.4
L
2Preparation
Material name consumption (weight part)
Polyethers 220 (molecular weight 2000) 15
Ethylene glycol 1
Diethylene Glycol 0.8
Tolylene diisocyanate (TDI) 11
Dimethylol propionic acid (DMPA) 2.5
Triethylamine 2
Hydrazine hydrate 2
Acetone 20
Distilled water 70
Claims (6)
1. adhesive for paint coating paper is characterized in that, organosilicon-modified acrylate emulsion L
1Weight percent 40～60%, polyurethane aqueous dispersion body L
2Weight percent 40～60%, described L
1Middle polymer molecule contains aldehydes or ketones carbonyl active group, L
2Middle polymer molecule contains the hydrazide group active group.
2. adhesive for paint coating paper as claimed in claim 1 is characterized in that, described L
1The organosilicon-modified acrylate emulsion that contains active group is obtained by following method:
The vinyl monomer of hydroxyl, the vinyl monomer that contains the aldehydes or ketones carbonyl, octamethylcyclotetrasiloxane (D
4) with after acrylic ester monomer etc. mixes, carry out letex polymerization, promptly obtain L
1, reaction formula is as follows:
N is an integer, and R is-H-CH
3,-C
2H
5,-C
4H
9-n,
3. adhesive for paint coating paper composition as claimed in claim 1, it is characterized in that the vinyl monomer of hydroxyl is propenoic acid beta-hydroxy ethyl ester, propenoic acid beta-hydroxy propyl ester, Jia Jibingxisuanβ-Qiang Yizhi or methacrylic acid β-hydroxypropyl acrylate as grafting agent.
4. adhesive for paint coating paper composition as claimed in claim 1, it is characterized in that the vinyl monomer that contains the aldehydes or ketones carbonyl is diacetone-acryloamide(DAA), propenal, methyl vinyl ketone, methacrylic acid etheric acid glycol ester or vinylformic acid etheric acid glycol ester.
5. adhesive for paint coating paper composition as claimed in claim 1 is characterized in that, described L
2The polyurethane aqueous dispersion body that contains active group is that the aqueous solution that will contain hydrazine is distributed in the base polyurethane prepolymer for use as, introduces hydrazide group at the end of polyurethane molecular, and the reaction skeleton symbol is as follows:
6. the adhesive for paint coating paper preparation of compositions method of claim 1 is as follows:
The organosilicon-modified acrylate emulsion L that contains active group
1Preparation
Proportioning raw materials (weight part) A component distillation water 20～60
Polyoxyethylene nonylphenol ether 0.4～2.0
Sodium lauryl sulphate 0.1～0.8
Trisodium phosphate 0.05～0.2
Potassium Persulphate 0.1～0.5B part acrylic butyl ester 10～30
Isooctyl acrylate monomer 10～30
Methyl methacrylate 1～5
Vinylformic acid 1～5
Vinylbenzene 20～60
The vinyl monomer 1～6 that contains hydroxyl
Octamethylcyclotetrasiloxane 1～6
Vinyl monomer 2～10C component distillation the water 30～80 that contains the aldehydes or ketones carbonyl
Polyoxyethylene nonylphenol ether 1.5～7
Sodium lauryl sulphate 0.05～0.2
Potassium Persulphate 0.15～0.6
Trisodium phosphate 0.1～0.5
The vinyl monomer that contains hydroxyl in the above-mentioned B component is propenoic acid beta-hydroxy ethyl ester, propenoic acid beta-hydroxy propyl ester, Jia Jibingxisuanβ-Qiang Yizhi or methacrylic acid β-hydroxypropyl acrylate;
The vinyl monomer that contains the aldehydes or ketones carbonyl in the above-mentioned B component is diacetone-acryloamide(DAA), propenal, methyl vinyl ketone, methacrylic acid etheric acid glycol ester or vinylformic acid etheric acid glycol ester; Operating procedure is: (1) joins the A component and is equipped with in the churned mechanically reactor, starts stirring, is warming up to 75～95 ℃; (2) stirring drips B component and C component down simultaneously in reactor in header tank, maintains the temperature between 75～95 ℃, drips off in 1～3 hour; (3) start stirring, logical cold water is cooled to below 60 ℃, filters, and obtains L
1Product;
L
2Contain the preparation of the polyurethane aqueous dispersion body of hydrazide group
Composition of raw materials:
Material name consumption (weight part)
Polyethers 8～17
Ethylene glycol is or/and Diethylene Glycol 0.5～2
Tolylene diisocyanate 5～12
Dimethylol propionic acid 0.5～2.5
Triethylamine 0.5～2
Hydrazine hydrate 1～2
Acetone 10～20
Distilled water 43～73 concrete steps are as follows: (1) polyethers, ethylene glycol, Diethylene Glycol vacuum hydro-extraction respectively; Vacuum tightness:＜50mmHg; Temperature: 105～120 ℃; Time: 4～6 hours; (2) prepolymerization reaction: with polyethers and tolylene diisocyanate (TDI) hybrid reaction, temperature: 50～90 ℃, the time: 1～4 hour; (3) chain extending reaction: with dimethylol propionic acid (DMPA), ethylene glycol, Diethylene Glycol add in the above-mentioned reactive system, temperature: 70～90 ℃, and the time: 1～2 hour; (4) dilution neutralization: acetone is added in the above-mentioned reactive system, stir evenly, put into the triethylamine neutralization, temperature: 30～50 ℃, the time: 1～2 hour; (5) hydrazine hydrate and water are put into above-mentioned reactive system, high-speed stirring makes it to disperse room temperature, 1～3 hour time; (6) vacuum is removed acetone solvent: 30～60 ℃ of temperature, vacuum tightness:＜50mmHg time: 1～3 hour; (7) filter to such an extent that contain the polyurethane aqueous dispersion body product of hydrazide group;
L with 40～60%
1With 40～60%L
2Mix and promptly get product of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112595A CN1098325C (en) | 1999-12-07 | 1999-12-07 | Adhesive for paint coating paper and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112595A CN1098325C (en) | 1999-12-07 | 1999-12-07 | Adhesive for paint coating paper and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1257902A true CN1257902A (en) | 2000-06-28 |
| CN1098325C CN1098325C (en) | 2003-01-08 |
Family
ID=5275883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99112595A Expired - Fee Related CN1098325C (en) | 1999-12-07 | 1999-12-07 | Adhesive for paint coating paper and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1098325C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101057034B (en) * | 2004-11-12 | 2011-07-06 | 巴斯福股份公司 | Aqueous paper coating slurry containing pigment-polymer hybrid |
| CN101516950B (en) * | 2006-07-31 | 2012-07-04 | 路博润高级材料公司 | Aqueous dispersions of polyurethane compositions with ketone-hydrazide |
| CN102702729A (en) * | 2012-06-21 | 2012-10-03 | 东莞市方振塑胶电子制品有限公司 | A kind of endothermic cooling material composition and preparation method thereof |
| CN101952384B (en) * | 2008-02-21 | 2014-01-29 | 3M创新有限公司 | Temporarily Repositionable Pressure Sensitive Adhesive Blends |
| CN113431275A (en) * | 2021-07-05 | 2021-09-24 | 广东省水利水电第三工程局有限公司 | Construction method of interior wall coating |
| CN115698427A (en) * | 2020-06-16 | 2023-02-03 | 日本制纸株式会社 | coated paper |
| CN118126568A (en) * | 2024-03-05 | 2024-06-04 | 丽水海维特新材料有限公司 | A boiling-resistant water-based ink binder suitable for high-speed printing and its application |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54138092A (en) * | 1978-04-18 | 1979-10-26 | Asahi Chem Ind Co Ltd | Elastomer emulsion conposition |
| DE3829587A1 (en) * | 1988-09-01 | 1990-03-15 | Bayer Ag | COATING AGENT, A PROCESS FOR THE PRODUCTION THEREOF, AND THE USE OF SELECTED TWO-COMPONENT POLYURETHANE SYSTEMS AS BINDER FOR SUCH COATING AGENTS |
| JPH03227387A (en) * | 1990-01-31 | 1991-10-08 | Sekisui Chem Co Ltd | Aqueous pressure-sensitive adhesive composition |
| JP2771018B2 (en) * | 1990-07-25 | 1998-07-02 | 三菱化学ビーエーエスエフ株式会社 | Method for producing resin aqueous emulsion |
| CN1045971C (en) * | 1993-01-19 | 1999-10-27 | 江苏石油化工学院 | Method for preparation of polyurethane acrylic ester copolymerized emulsion |
| CN1046952C (en) * | 1995-10-27 | 1999-12-01 | 王南 | Polyurethane-polyacrylate composite leather finishing agent |
-
1999
- 1999-12-07 CN CN99112595A patent/CN1098325C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101057034B (en) * | 2004-11-12 | 2011-07-06 | 巴斯福股份公司 | Aqueous paper coating slurry containing pigment-polymer hybrid |
| CN101516950B (en) * | 2006-07-31 | 2012-07-04 | 路博润高级材料公司 | Aqueous dispersions of polyurethane compositions with ketone-hydrazide |
| CN101952384B (en) * | 2008-02-21 | 2014-01-29 | 3M创新有限公司 | Temporarily Repositionable Pressure Sensitive Adhesive Blends |
| US9359531B2 (en) | 2008-02-21 | 2016-06-07 | 3M Innovative Properties Company | Temporarily repositionable pressure sensitive adhesive blends |
| CN102702729A (en) * | 2012-06-21 | 2012-10-03 | 东莞市方振塑胶电子制品有限公司 | A kind of endothermic cooling material composition and preparation method thereof |
| CN102702729B (en) * | 2012-06-21 | 2013-09-18 | 东莞市方振塑胶电子制品有限公司 | Heat-absorbing cooling material composition and preparation method thereof |
| CN115698427A (en) * | 2020-06-16 | 2023-02-03 | 日本制纸株式会社 | coated paper |
| CN113431275A (en) * | 2021-07-05 | 2021-09-24 | 广东省水利水电第三工程局有限公司 | Construction method of interior wall coating |
| CN118126568A (en) * | 2024-03-05 | 2024-06-04 | 丽水海维特新材料有限公司 | A boiling-resistant water-based ink binder suitable for high-speed printing and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1098325C (en) | 2003-01-08 |
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