CN104693407B - A kind of waterborne polyurethane resin for film printing varnish and preparation method thereof - Google Patents
A kind of waterborne polyurethane resin for film printing varnish and preparation method thereof Download PDFInfo
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- CN104693407B CN104693407B CN201510143713.8A CN201510143713A CN104693407B CN 104693407 B CN104693407 B CN 104693407B CN 201510143713 A CN201510143713 A CN 201510143713A CN 104693407 B CN104693407 B CN 104693407B
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Abstract
The invention provides a kind of waterborne polyurethane resin for film printing varnish and preparation method thereof.This waterborne polyurethane resin comprises each composition of following parts by weight: polymer polyatomic alcohol 90-110 part, dimethylol propionic acid 6-8 part, TriMethylolPropane(TMP) 0-0.5 part, isophorone diisocyanate 30-40 part, triethylamine 0.4-0.6 part, water 300-350 part.Its preparation method is reacted at polymer polyatomic alcohol, dimethylol propionic acid and TriMethylolPropane(TMP) and isophorone diisocyanate, and add the waterborne polyurethane resin that triethylamine and water-dispersion obtain.Prepared urethane resin and PE, PET film has similar snappiness, and coating has higher sticking power simultaneously.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of waterborne polyurethane resin for film printing varnish and preparation method thereof.
Background technology
Urethane (PU) refers to the abbreviation of the superpolymer polyurethane(s) (Polyurethane) containing a large amount of carbamate groups (-NHCOO-) on main chain.By feed change kind and composition, product form and performance thereof can be changed significantly, obtain from softness to hard the finished product.Line style and build two kinds can be divided into by its molecular structure.Because cross-linking density is different in three dimensional structure, hard, soft or Jie's performance between the two can be presented, there is the features such as high strength, high abrasion and solvent resistant.
Urethane resin is mainly divided into oiliness urethane resin and waterborne polyurethane resin.Oiliness urethane resin is that superpolymer polyurethane(s) is dissolved in dimethylformamide (DMF), organic solvents such as toluene and obtaining.Superpolymer polyurethane(s) is scattered in water by waterborne polyurethane resin to be made.In current leather-making enterprises, more than 90% still uses oiliness urethane resin, is only using waterborne polyurethane resin less than the enterprise of 10%.
Oiliness urethane resin contains a large amount of dimethylformamides (DMF), the organic solvents such as toluene, causes very major injury in the fabrication process to surrounding environment and the healthy of site operation personnel.Because chemical solvents is most of inflammable and explosive, hold fire hazardous, therefore oleoresin becomes the No.1 threat of leather industry " three is high ".In addition, the product that oiliness urethane resin makes, when not adding fire retardant, does not have fire-retardant performance yet.
Aqueous polyurethane is the new polyurethane system using water to replace organic solvent as dispersion medium, also claims water dispersible polyurethane, aqueous polyurethane or waterbased urethane.Aqueous polyurethane take water as solvent, have pollution-free, safe and reliable, good mechanical performance, consistency are good, be easy to the advantages such as modification, are widely used in coating, tackiness agent, fabric coating and finishing composition, hide finishes, sheet surface treating agent and Fiber strength agent.
The adhesion layer be currently used on metallized film mainly uses solvent-based varnishes, can cause a large amount of VOC discharges in production and application.And the sticking power of existing water varnish in PET film is poor, being difficult to especially on PE film adheres to.And use a large amount of auxiliary agents that the compactness of coating can be made to decline to increase sticking power, easily punctured by aluminium atom in follow-up vacuum plating operation and cause the glossiness of aluminium coated to decline, becoming mute, affect sticking power, affect the decorative effect of coating.
Summary of the invention
The object of the invention is for prior art Problems existing, a kind of snappiness, high strength, high adhesive force are provided and are easy to disperse, for the waterborne polyurethane resin and preparation method thereof of film printing varnish.
For a waterborne polyurethane resin for film printing varnish, comprise each composition of following parts by weight:
Polymer polyatomic alcohol 90-110 part
Dimethylol propionic acid 6-8 part
TriMethylolPropane(TMP) 0-0.5 part
Isophorone diisocyanate 30-40 part
Triethylamine 0.4-0.6 part
Water 300-350 part
Wherein, polymer polyatomic alcohol is one or more in polyneopentyl glycol adipate glycol, poly-diethylene glycol adipate glycol, polycarbonate diol, polycaprolactone glycol and polytetrahydrofuran diol.
Preferably, the molecular weight of described polymer polyatomic alcohol is 800 ~ 1200.
Preferably, the molecular weight of described polymer polyatomic alcohol is 1000.
Preferably, the hydroxyl value of described polymer polyatomic alcohol is 50 ~ 80mgKOH/g.
The mol ratio of-the NCO in described polymer polyatomic alcohol and isophorone diisocyanate is 1:1.2-1.4.
Preferably, described waterborne polyurethane resin comprises each composition of following parts by weight:
Polymer polyatomic alcohol 102 parts
Dimethylol propionic acid 6.9 parts
TriMethylolPropane(TMP) 0.26 part
Isophorone diisocyanate 35 parts
Triethylamine 0.5 part
330 parts, water
For a preparation method for the waterborne polyurethane resin of film printing varnish, this preparation method comprises the following steps:
(1) by proportioning by polymer polyatomic alcohol, dimethylol propionic acid and TriMethylolPropane(TMP), drop in dry reactor, 110 DEG C of vacuum hydro-extraction 1 hour, is then incubated 1-2 hour under 110 ° of C;
(2) cool to 90 DEG C, add isophorone diisocyanate, under 20-50rpm speed, react 3-6 hour;
(3) cool to 35 ° of C, add triethylamine, under 1500-2500rpm speed, disperse 0.5-1.5 minute;
(4) then add 300-350 part water fast, be uniformly dispersed under 1500-2500rpm speed and can obtain waterborne polyurethane resin.
Wherein, the molecular weight of prepared waterborne polyurethane resin is 15-21 ten thousand.
Use alcohol dilution solid content to 20% described waterborne polyurethane resin, use coating machine to be rolled onto on PE film, use 250 object anilox roll, machine speed 30m/min, tension force 5kgf, drying tunnel temperature 65-110 DEG C, time is about 25-30 second, goes out drying tunnel rolling, requires not roll banding.Film after being coated with enters in vacuum aluminum-plating machine aluminizes 2 μm, obtains aluminium plating film product.
The present invention program is by a kind of hydroxy polymer with high crystalline of urethane building-up reactions synthesis, this polyether polyols with reduced unsaturation has good snappiness and intensity, with PE, PET film has similar snappiness, high strength, to ensure that coating is not easily breakdown in vacuum plating process, has ensured the sticking power of coating simultaneously.Employ more dimethylol propionic acid and contain more hydroxyl, make particle diameter less, film clarity is high, and the effect luminance brightness of institute's coating is high.In synthesis, add TriMethylolPropane(TMP), improve cross-linking density, the crosslinked polymer degree after film forming is large, and crystallinity is high, finer and close, improves resistance to sparking energy.Meanwhile, obtain the different polyether polyols with reduced unsaturation of film forming polarity by the formula changing polyether polyols with reduced unsaturation, and then obtain the more excellent polymkeric substance of performance.In synthesis, introduce oh group, make polymkeric substance also be easy to be dispersed in water when higher molecular weight, obtain the water dispersion of high-clarity.Meanwhile, the introducing of oh group adds the sticking power of itself and aluminium lamination.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and wherein said each number is parts by weight.
Embodiment 1
(1) by the polyneopentyl glycol adipate glycol of 90 part of 800 molecular weight, 6 parts of dimethylol propionic acids, drop in dry reactor, and 110 DEG C of vacuum hydro-extraction 1 hour, is then incubated 1-2 hour under 110 ° of C;
(2) cool to 90 DEG C, add 30 parts of isophorone diisocyanates, under 20-50rpm speed, react 3-6 hour;
(3) cool to 35 DEG C, add 0.4 part of triethylamine, under 1500-2500rpm speed, disperse 0.5-1.5 minute;
(4) then add 300 parts of water fast, be uniformly dispersed under 1500-2500rpm speed and can obtain waterborne polyurethane resin.
The proportioning molecular weight about 150,000 calculated, carries out performance test to prepared waterborne polyurethane resin.
Adhesion test method: use 3M610 adhesive tape, fit tightly after in coating, pulled open by adhesive tape, coating is complete is 0 grade without any coming off, and a small amount of trickle disengaging is 1 grade, and a small amount of point-like comes off 2 grades, comes off 3 grades in a large number, comes off 4 grades completely.
The molecular weight about 150,000 of the waterborne polyurethane resin prepared by the present embodiment, its performance test results is: the upper sticking power of PE 0 grade, the upper sticking power of PET 0 grade, aluminium lamination adhesion 1 grade after aluminizing; Snappiness is high, and on PE, PET, positive inverse folding does not ftracture for 15 times; After application, slight roll banding, does not glue after need increasing the process that cools.
Embodiment 2
(1) by the polyneopentyl glycol adipate glycol of 102 part of 1000 molecular weight, 6.9 parts of dimethylol propionic acids, 0.26 part of TriMethylolPropane(TMP), drops in dry reactor, and 110 DEG C of vacuum hydro-extraction 1 hour, is then incubated 1-2 hour under 110 ° of C;
(2) cool to 90 DEG C, add 35 parts of isophorone diisocyanates, under 20-50rpm speed, react 3-6 hour;
(3) cool to 35 DEG C, add 0.5 part of triethylamine, under 1500-2500rpm speed, disperse 0.5-1.5 minute;
(4) then add 330 parts of water fast, be uniformly dispersed under 1500-2500rpm speed and can obtain waterborne polyurethane resin.
Compare embodiment 1, this example improves the polymerization degree, the crystallinity of prepared polymkeric substance, more resistance toly punctures, the molecular weight about 210,000 of waterborne polyurethane resin.Its performance test results is: sticking power 0 grade on PE, PET, postadhesion power of aluminizing 0 grade; Snappiness is high, and on PE, positive inverse folding does not ftracture for 20 times, and on PET, positive inverse folding does not ftracture for 22 times; Apply not roll banding.
Embodiment 3
(1) by the polyneopentyl glycol adipate glycol of 110 part of 1200 molecular weight, 8 parts of dimethylol propionic acids, 0.5 part of TriMethylolPropane(TMP), drops in dry reactor, and 110 DEG C of vacuum hydro-extraction 1 hour, is then incubated 1-2 hour under 110 ° of C;
(2) cool to 90 DEG C, add 40 parts of isophorone diisocyanates, under 20-50rpm speed, react 3-6 hour;
(3) cool to 35 DEG C, add 0.6 part of triethylamine, under 1500-2500rpm speed, disperse 0.5-1.5 minute;
(4) then add 350 parts of water fast, be uniformly dispersed under 1500-2500rpm speed and can obtain waterborne polyurethane resin.
The molecular weight about 190,000 of the waterborne polyurethane resin prepared by the present embodiment.Its performance test results is: sticking power 0 grade on PE, the upper adhesion 1 grade of PET, aluminium lamination sticking power 0 grade after aluminizing; Snappiness is high, and on PE, positive inverse folding does not ftracture for 16 times, and on PET, positive inverse folding does not ftracture for 19 times; Apply not roll banding.
Embodiment 4
(1) by the poly-diethylene glycol adipate glycol of 102 part of 1000 molecular weight, 6.9 parts of dimethylol propionic acids, 0.26 part of TriMethylolPropane(TMP), drops in dry reactor, and 110 DEG C of vacuum hydro-extraction 1 hour, is then incubated 1-2 hour under 110 ° of C;
(2) cool to 90 DEG C, add 35 parts of isophorone diisocyanates, under 20-50rpm speed, react 3-6 hour;
(3) cool to 35 DEG C, add 0.5 part of triethylamine, under 1500-2500rpm speed, disperse 0.5-1.5 minute;
(4) then add 330 parts of water fast, be uniformly dispersed under 1500-2500rpm speed and can obtain waterborne polyurethane resin.
Change the type of polyvalent alcohol, the polarity of polymkeric substance is changed, and the performances such as the sticking power of polymkeric substance also change thereupon.The molecular weight about 160,000 of waterborne polyurethane resin, its performance test results is: sticking power 0 grade on PET, but on PE adhesion 1 grade, sticking power weak effect, postadhesion power of aluminizing 1 grade; Snappiness is good, and PE folds and does not ftracture for 17 times, the upper positive inverse folding of PET does not ftracture for 14 times; Rate of drying is slightly slow, can not parch completely, slight roll banding under application conditions.
Embodiment 5
(1) by 102 parts, hydroxyl value is the polyvalent alcohol of the polyneopentyl glycol adipate glycol of 50 ~ 80mgKOH/g, polycaprolactone glycol and polytetrahydrofuran diol composition, 6.9 parts of dimethylol propionic acids, 0.26 part of TriMethylolPropane(TMP), drop in dry reactor, 110 DEG C of vacuum hydro-extraction 1 hour, is then incubated 1-2 hour under 110 ° of C;
(2) cool to 90 DEG C, add 35 parts of isophorone diisocyanates, under 20-50rpm speed, react 3-6 hour;
(3) cool to 35 DEG C, add 0.5 part of triethylamine, under 1500-2500rpm speed, disperse 0.5-1.5 minute;
(4) then add 330 parts of water fast, be uniformly dispersed under 1500-2500rpm speed and can obtain waterborne polyurethane resin.
The molecular weight about 190,000 of property urethane resin.Its performance test results is: adhesion 1 grade on PE, the upper sticking power of PET 0 grade, aluminium lamination sticking power 0 grade after aluminizing; Snappiness is high, and on PE, positive inverse folding does not ftracture for 18 times, and on PET, positive inverse folding does not ftracture for 22 times; Apply not roll banding.
Embodiment 6
(1) by 102 parts of hydroxyl values be the polyvalent alcohol of the polyneopentyl glycol adipate glycol of 50 ~ 80mgKOH/g, polycaprolactone glycol and polytetrahydrofuran diol composition, 6.9 parts of dimethylol propionic acids, 0.26 part of TriMethylolPropane(TMP), drop in dry reactor, 110 DEG C of vacuum hydro-extraction 1 hour, is then incubated 1-2 hour under 110 ° of C;
(2) cool to 90 DEG C, add 30-40 part isophorone diisocyanate, make the mol ratio of-NCO in polymer polyatomic alcohol and isophorone diisocyanate be 1:1.2-1.4, then, under 20-50rpm speed, react 3-6 hour;
(3) cool to 35 DEG C, add 0.5 part of triethylamine, under 1500-2500rpm speed, disperse 0.5-1.5 minute;
(4) then add 330 parts of water fast, be uniformly dispersed under 1500-2500rpm speed and can obtain waterborne polyurethane resin.
The molecular weight about 200,000 of property urethane resin.Its performance test results is: sticking power 0 grade on PE, the upper sticking power of PET 0 grade, aluminium lamination sticking power 0 grade after aluminizing; Snappiness is high, and on PE, positive inverse folding does not ftracture for 21 times, and on PET, positive inverse folding does not ftracture for 18 times; Apply not roll banding.
Above to waterborne polyurethane resin for film printing varnish that the embodiment of the present invention provides and preparation method thereof, be described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (7)
1. for a preparation method for the waterborne polyurethane resin of film printing varnish, it is characterized in that, described waterborne polyurethane resin is grouped into by each one-tenth of following parts by weight:
Polymer polyatomic alcohol 90-110 part
Dimethylol propionic acid 6-8 part
TriMethylolPropane(TMP) 0-0.5 part
Isophorone diisocyanate 30-40 part
Triethylamine 0.4-0.6 part
Water 300-350 part;
Wherein, the hydroxyl value of described polymer polyatomic alcohol is 50 ~ 80mgKOH/g;
The preparation method of described urethane resin comprises the following steps:
(1) by proportioning by polymer polyatomic alcohol, dimethylol propionic acid and TriMethylolPropane(TMP), drop in dry reactor, 110 DEG C of vacuum hydro-extraction 1 hour, is then incubated 1-2 hour under 110 ° of C;
(2) cool to 90 DEG C, add isophorone diisocyanate, under 20-50rpm speed, react 3-6 hour;
(3) cool to 35 ° of C, add triethylamine, under 1500-2500rpm speed, disperse 0.5-1.5 minute;
(4) then add 300-350 part water fast, be uniformly dispersed under 1500-2500rpm speed and can obtain waterborne polyurethane resin.
2. the preparation method of the waterborne polyurethane resin for film printing varnish according to claim 1, it is characterized in that, described polymer polyatomic alcohol is one or more in polyneopentyl glycol adipate glycol, poly-diethylene glycol adipate glycol, polycarbonate diol, polycaprolactone glycol and polytetrahydrofuran diol.
3. the preparation method of the waterborne polyurethane resin for film printing varnish according to claim 1, is characterized in that, the molecular weight of described polymer polyatomic alcohol is 800 ~ 1200.
4. the preparation method of the waterborne polyurethane resin for film printing varnish according to claim 3, is characterized in that, the molecular weight of described polymer polyatomic alcohol is 1000.
5. the preparation method of the waterborne polyurethane resin for film printing varnish according to claim 1, is characterized in that, the mol ratio of-NCO in described polymer polyatomic alcohol and isophorone diisocyanate is 1:1.2-1.4.
6. the preparation method of the waterborne polyurethane resin for film printing varnish according to claim 1, is characterized in that, described waterborne polyurethane resin comprises each composition of following parts by weight:
Polymer polyatomic alcohol 102 parts
Dimethylol propionic acid 6.9 parts
TriMethylolPropane(TMP) 0.26 part
Isophorone diisocyanate 35 parts
Triethylamine 0.5 part
330 parts, water.
7. the preparation method of the waterborne polyurethane resin for film printing varnish according to claim 1, is characterized in that, the molecular weight of described waterborne polyurethane resin is 15-21 ten thousand.
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| CN105440244A (en) * | 2016-01-08 | 2016-03-30 | 广东邦固化学科技有限公司 | High-film-forming-property aqueous polyurethane resin as well as preparation method and use method of high-film-forming-property aqueous polyurethane resin |
| CN105968313A (en) * | 2016-07-02 | 2016-09-28 | 安徽中恩化工有限公司 | Preparation method of high-bonding waterborne polyurethane resin applied to PET film |
| CN112251138A (en) * | 2018-05-25 | 2021-01-22 | 广东尚联新材料科技有限公司 | Nano fireproof heat-insulating coating and preparation method thereof |
| CN108834388B (en) * | 2018-05-30 | 2020-03-10 | 海宁卓泰电子材料有限公司 | Electromagnetic shielding film and preparation method thereof |
| CN109776752A (en) * | 2019-01-22 | 2019-05-21 | 华大化学(安徽)有限公司 | A kind of ultra-soft matter skin sense dry method surface layer resin and its preparation method and application |
| CN114276706A (en) * | 2020-03-30 | 2022-04-05 | 欧朋(深圳)环保涂料有限公司 | Water-based varnish for vehicle |
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