CN1942549A - Coating agent aqueous compositions for flexible backgrounds - Google Patents
Coating agent aqueous compositions for flexible backgrounds Download PDFInfo
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- CN1942549A CN1942549A CNA2006800000096A CN200680000009A CN1942549A CN 1942549 A CN1942549 A CN 1942549A CN A2006800000096 A CNA2006800000096 A CN A2006800000096A CN 200680000009 A CN200680000009 A CN 200680000009A CN 1942549 A CN1942549 A CN 1942549A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/02—Condensation polymers of aldehydes or ketones only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/02—Condensation polymers of aldehydes or ketones only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
Abstract
The invention relates to aqueous compositions of adhesive and coating agents for flexible backgrounds consisting of at least one type of binder, modified ketone/aldehyde resin and, optionally, of auxiliary agents and additives.
Description
Technical field
The present invention relates to by at least a base-material, a kind of modification ketone resin and auxiliary agent and additive are formed when wishing aqueous binder and coating composition.
This tackiness agent and coating composition are used for the various flexible parent metals of bonding, lamination and coating, plastics film and/or layered product for example foam materials and synthetic leather etc. of metallized film, textiles, fiber, weaving material, leather, metal, mill bristol, paper, paper layered product and/or synthetic materials for example for example, this coating does not have formaldehyde to a great extent.This tackiness agent and coating composition are applicable to all usual method of application, for example inject, spraying, roller coat, brushing, dip-coating, film color, roller coating, curtain coating and printing.
This tackiness agent and coating composition merit attention because of dried speed of extra high beginning, excellent water tolerance and high hardness and extraordinary elasticity.
Background technology
Flexible articles usually is equipped with an organic coating (seeing " R mpp Lexikon; Lacke undDruckfarben; Dr.Ulrich Zorll compiles; Georg Thieme Verlag; Stuttgart; 1998 "), on the one hand-because of the use field different-be intended to protect this material (for example, protect that these article avoid wearing out, time effect, physical disturbance, make dirty etc.).On the other hand, this organic coating is being born the decoration function.For example, in order to prevent that the timeization effect from flooding the dry goods article usually.
For example, the printing of paper and film is information (brochure, wrapping material) service on the one hand; On the other hand, by means of topological design, make this information change into can be noticeable form.Except that performances such as dried speed of maximum beginning, such as not only excellent bonds and elastic performance but also excellent abrasive resistance also are important.
Coating is after it is used, in order to ensure further processing rapidly and preventing that it is desirable beginning dried rapidly such as the pollutent defective that causes such as dust and dirt for example.
Based on the known hardness that can improve coating of hardened resin of ketone and aldehyde, but elastic performance reduces.
The reaction product that the water of ketone and aldehyde or derivatives thereof can disperse condensation product and may contain such product is described in EP 0 617 103 A1, EP 0838485, EP 0838486 (DE19643704), DE 25 42 090, DE-A 31 44 673 and DE-A 3406474 (EP0154835).
DE-A 25 42 090 described have sulfonic and-depart from the inventive method-can be at the water-soluble cpds that from the associating condensation reaction of naphthenone, formaldehyde and basic metal hydrosulphite, obtains.
DE-A 31 44 673 has introduced equally by ketone, aldehyde and can import the water-soluble condensation product that the association response of the compound of acidic group obtains.The latter's example is sulphite and amide group sulfonate, Glycinates and phosphite.
Obtain containing the product of ionogen (for example Na ion) according to DE-A 25 42 090 and DE-A 31 44 673.Yet one of effect of such resin is the water tolerance of infringement vanish system.
EP 0 617 103 A1 have described and have not contained the group (for example carboxyl) that can change into ionic groups but contain for example reaction of ester group or polyisocyanates ether, molecular weight 500～5000 (a) and dihydroxy compound (b) of other functional group (seeing p.3 the 17th～21 row).The urethane that obtains so further with compound (c) reaction that except that the NCO reactive group, also contains the group that can change into ionic groups, and when wishing with the glycol that does not have further functional group, molecular weight 60～500 or many alcohol (d) reaction (seeing p.4 the 5th～15 row).This reaction product is subsequently with the reaction of a kind of condensation resins and transfer to aqueous phase.
DE 3406474 (EP 0154835) has described and has used aqueous liquid dispersion organic protective colloid, ketone resin or ketone/urea formaldehyde.Protective colloid is stayed in the coating subsequently and may be influenced some performances nocuously and for example the shortcoming of the tolerance of water and moisture hindered their purposes in the high value coating composition.
EP 0838485 has described esterification products.Thereby hydrolysis can take place known ester group causes polymer degradation, and influences package stability nocuously.And then, the acidic group that can freely touch also may induce reaction and/or with the non-compatibility of pigment.
EP 0838486 has described the aqueous resin dispersion that can obtain by the reaction or the partial reaction of following ingredients:
I. contain ketone resin, ketone/urea formaldehyde and/or the urea/urea formaldehyde of hydroxyl or its hydroderivating thing and
II. at least a have at least one free NCO group, can be by making the reaction of at least a isocyanic ester and/or polyisocyanates and some compounds the hydrophilic modifying isocyanic ester and/or the polyisocyanates that obtain, described compound except that containing hydrophilic radical or potential hydrophilic radical, also have at least one can be with the functional group of isocyanic ester radical reaction, have when testing active hydrogen and have at least one hydrophilic radical and/or a potential hydrophilic radical with Zerewitinoff
With in this and the combination subsequently of resin and water.
Summary of the invention
An object of the present invention is to find the aqueous binder and the coating composition that are used for various flexible parent metals, being intended that this coating should not have formaldehyde on very big degree.This coating composition should have dried speed of high beginning, and should positive influence be arranged to hardness, water tolerance and elastic performance.
The purpose of institute of the present invention foundation is to reach by the following use of special coating composition in greater detail surprisingly.
The invention provides the aqueous binder and the coating composition that are used for various flexible parent metals, comprise in fact
A) at least a water-based base-material of 20wt%～95wt% and
B) 5wt%～80wt% hydrophilization ketone/urea formaldehyde and/or a kind of hydrophilization hydrogenation ketone/urea formaldehyde and
C) at least a additive of 0wt%～75wt%,
Composition A)～C) weight amount sum is 100wt%.
Have been found that the following stated and comprise composition A)～combination of C) coating composition meets whole needed benchmark.
Embodiment
Composition A)
The substantial water-based base material A of the present invention) be to use with the quantity of 20wt%～95wt%, better 30wt%～80wt%.
Give preferential one group the water-based base-material that is selected from following composition that is to use: urethane, polyacrylic ester, polyethers, polyester, Synolac, ether of cellulose, derivatived cellulose, polyvinyl alcohol and derivative, rubber, maleic acid ester resinoid, phenol/urea-formaldehyde resin, aminoresin (for example melamine resin, benzo guanamine resin), epoxy acrylate, Resins, epoxy, silicon ester and alkalimetal silicate (for example water glass) and/or silicone resin and/or fluoropolymer.This water-based base-material can be external crosslinking and/or self-crosslinking, air-dry (physical dryness) and/or oxidative cure.
Composition B)
The substantial composition B of the present invention) be to use with the quantity of 5wt%～80wt%, better 10wt%～60wt%.
The composition B that is suitable for) comprise the aqueous resin dispersion that can obtain by the reaction or the partial reaction of following ingredients:
I. contain the ketone/urea formaldehyde of hydroxyl or its hydroderivating thing and
II. at least a have at least one free NCO group, can be by making the reaction of at least a isocyanic ester and/or polyisocyanates and some compounds the hydrophilic modifying isocyanic ester and/or the polyisocyanates that obtain, described compound except that containing hydrophilic radical or potential hydrophilic radical, also have at least one can with the functional group of isocyanic ester radical reaction
After the reaction with resin-neutralize when needing-make up with water.
The ketone that is applicable to preparation ketone/urea formaldehyde (composition I) comprises all ketone, especially acetone, phenyl methyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclododecanone, 2,2,4-and 2,4,4-trimethylammonium cyclopentanone, suberone and cyclooctanone, pimelinketone and one or more mixtures that the alkyl substituted cyclohexanone is arranged that contain the alkyl that adds up to 1～8 carbon atom are all arranged are separately or form of mixtures.There is the possible example of alkyl substituted cyclohexanone to comprise 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.
Also can use for example ketone of amino and/or acidic group of further functional group in principle, although not so good.
Yet, in general, can use report on the document, be applicable to ketone resin and ketone/all ketone of urea formaldehyde synthetic; In general, the acid ketone of all C-H-.Give preferential phenyl methyl ketone, pimelinketone, the 4-tertiary butyl pimelinketone, 3,3 of being based on, 5-trimethylcyclohexanone and heptanone are separately or form of mixtures.
As the aldehyde composition of ketone/urea formaldehyde (composition I), what have suitability in principle is the aldehyde of no branching or branching, for example formaldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and 12 (alkane) aldehyde.In general, can use bibliographical information to be applicable to ketone/all aldehyde of urea formaldehyde synthetic.Yet, give preferentially to be individually or to mix ground and use formaldehyde.
Needed formaldehyde normally as concentration for the aqueous solution of about 20wt%～40wt% or the use of alcohol (for example methyl alcohol or butanols) solution.Other type of service of formaldehyde comprises such as the use of paraformaldehyde or three alkane, is fine equally.Aromatic aldehyde for example phenyl aldehyde may reside among the mixture with formaldehyde equally.
The good especially initial compounds that is used for ketone/urea formaldehyde of composition I is phenyl methyl ketone, pimelinketone, 4-tertiary butyl pimelinketone, 3,3, and 5-trimethylcyclohexanone and heptanone are separately or form of mixtures, and formaldehyde.
The resin that generates from ketone and aldehyde also can be in the presence of suitable catalyzer, can be up to the pressure of 300bar hydrogen hydrogenation.In the process of this hydrogenation, some carbonyls of ketone/urea formaldehyde change into secondary hydroxyl.But from aldehyde and ketogenetic, except that the carbonyl segment, also have further hydrogenation official for example under the situation of the resin of aromatic structure, these further structures also can transform by suitable hydrogenation.Under situation, obtained cyclo-aliphatic structure such as aromatic structure.
Hydrophilic modifying that may be necessary is such as realizing by resin I and composition II are reacted, the latter is made up of at least a hydrophilic modifying isocyanic ester and/or polyisocyanates by at least one free NCO group, can obtain by making the reaction of at least a isocyanic ester and/or polyisocyanates and some compounds, this compound removes hydrophilic radical or potential hydrophilic radical-the hydrophilic group that promptly just becomes after neutralization-in addition at least one to the group of responding property of isocyanate group for example hydroxyl or amino etc.
This being used for, the examples for compounds of (many) isocyanic ester hydrophilic modifying was amino acid, hydroxyl sulfoacid, thionamic acid and hydroxycarboxylic acid.Give preferential two (methylol) propionic acid or derivatives thereof that is to use.This hydrophilic modifying also can carry out with non-ionic type group (for example using polyethers) or with neutral compound.
Hydroxycarboxylic acid, especially for example two (methylol) propionic acid is good especially, this is due to the following facts: when with volatile alkali for example in the amine etc. and the time, they demonstrate strong hydrophilic effects, but, this effect rapidly disappears after this volatile alkali evaporation.Therefore, coating can be owing to not losing its defencive function, because any initial stage swelling does not take place such as humidity exposure.
Because it carries out the ability of (potential) hydrophilic modifying of two hydrophobic polyisocyanates by two hydroxyl, two (methylol) propionic acid also is good especially.
The polyisocyanates that is applicable to prepared composition II better is the functional polyisocyanates of two senses to four.The example is a cyclohexyl diisocyanate, methylcyclohexane diisocyanate, the ethylcyclohexane vulcabond, the propyl cyclohexane vulcabond, methyl diethyl cyclohexane vulcabond, phenylene diisocyanate, tolylene diisocyanate, two (isocyanato-phenyl) methane, the propane vulcabond, the butane vulcabond, the pentane vulcabond, hexane diisocyanate is hexamethylene diisocyanate (HDI) or 1 for example, 5-two isocyanato-s-2-methylpentane (MPDI), the heptane vulcabond, the octane vulcabond, nonane vulcabond for example 1,6-two isocyanato-s-2,4,4-trimethyl cyclohexane or 1,6-two isocyanato-s-2,2,4-trimethyl cyclohexane (TMDI), nonane triisocyanate is 4-isocyanato-methyloctane-1 for example, 8-vulcabond (TIN), decane vulcabond and triisocyanate, undecane vulcabond and triisocyanate, dodecane two isocyanide ester and triisocyanates, isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride-4,4 '-vulcabond (H
12MDI), isocyanato-methyl cyclohexyl isocyanate, 2,5 (2,6)-two (isocyanato-methyl) dicyclos [2.2.1] heptane (NBDI), 1,3-two (isocyanato-methyl) hexanaphthene (1,3-H
6-XDI) or 1, and 4-two (isocyanato-methyl) hexanaphthene (1,4-H
6-XDI), independent or its mixture.
Another kind of polyisocyanates preferably has the compound of more than 2 isocyanate group by making simple vulcabond dimerization or trimerization, allophanic acid esterification, biuretized and/or polyurethane-reinforcement preparation, per molecule, and example is for example IPDI, HDI and/or H of these simple vulcabond
12The reaction product of MDI etc. and polyvalent alcohol (for example glycerine, TriMethylolPropane(TMP), tetramethylolmethane) and/or multifunctional polyamines maybe can be by making simple vulcabond for example IPDI, HDI and H
12The triisocyanate that trimerizations such as MDI obtain.
Giving preferential especially is from two (methylol) propionic acid or derivatives thereof and IPDI and/or TMDI and/or H
12MDI and/or HDI are with the hydrophilically modified polyisocyanates (II) of 1: 2 mol ratio generation.
Composition B) be that this solvent can be separated with distillation method after preparation when wishing with melt or the formulations prepared from solutions in being suitable for organic solvent.
Under the situation with solution reaction, solids content is 30wt%～95wt%, better 60wt%～80wt% preferably.
Employed suitable secondary solvent is an inert, this solvent does not form the compatibility gap, under atmospheric pressure the boiling point that is lower than 100 ℃ thereby can easily separate with distillation method is arranged with water in broad range at least, be reduced to the final dispersion liquid or the aqueous solution be benchmark be lower than 2wt%, especially be lower than 0.5wt% residual level, and utilize once more.The example of this kind solvent that is suitable for comprises acetone, methylethylketone and tetrahydrofuran (THF).What also be suitable in principle is the more for example positive butyleneglycol of high boiling solvent, two positive butyleneglycols and N-Methyl pyrrolidone etc., and they are stayed in the dispersion liquid subsequently.
Yet, specifically, composition B) advantage be the following fact: in final aqueous resin dispersion, can not have organic solvent fully, and can also obtain stable high solid and disperse liquid.
On the reaction of I and II better can proceed to so a bit: residual NCO content (measuring according to DIN 53185) was lower than 1%NCO; Preferential especially is on reaching so a bit: the residual NCO content of the product that generates from I and II is in 0.1%～0.5%NCO scope.According to current state of the art, still the NCO function of unreacted can be used to increase chain reaction by adding polyamines or water etc. in the reaction of I and II, otherwise, when wishing, can cause chain termination by the compound (for example monohydroxy-alcohol, monoamine) that adds NCO group simple function.
Under the situation of potential hydrophilic radical, the neutralizing agent that is suitable for can be added in the product of the present invention, thereby provide water-dilutable, water can disperse or the product of water dissolvable.
Potential hydrophilic radical according to the resin of the present invention preparation can use organic bases and/or mineral alkali for example organic amine or ammonia neutralization.Give preferential primary amine, secondary amine and/or the tertiary amine of being to use, for example ethamine, propylamine, dimethylamine, dibutylamine, hexahydroaniline, benzylamine, morpholine, piperidines and trolamine.Under the situation of the potential group of anionic, giving preferential especially is volatility tertiary amine, especially dimethylethanolamine, diethylethanolamine, 2-dimethylin-2-methyl-4-propyl alcohol, triethylamine, tripropyl amine and Tributylamine.Cationic potential ionic groups can use for example neutralizations such as acetate, formic acid, phosphoric acid, hydrochloric acid of organic acid and/or mineral acid.
The neutral degree better be in the stoichiometric quantity and required dosis neutralisata 50%～130%.
Neutral hydrophilic resin or resin solution are imported in the water, otherwise water is added to wherein, stirring is better arranged.Before adding water, the reaction product of I and II can be merged with the further resin that does not carry out hydrophilic modifying as yet or with other composition when wishing, these compositions are disperseed together.As the result of this measure, can obtain in this dispersion liquid more than the 45wt%, technical favourable highly filled.This solid fraction is positioned at 20wt%～70wt%, better 25wt%～60wt% scope in principle.
After the dispersion, this organic secondary solvent can remove, better under reduced pressure remove, and can reprocess when wishing.
Composition C)
Composition C) be to use with the quantity of 0～75wt%, better 5～70wt%.
The composition C that is suitable for) be auxiliary agent and additive, for example, inhibitor, organic solvent, surfactant, oxygen scavenqer and/or free-radical scavengers, catalyzer, photostabilizer, the color brightener, photosensitizer and light trigger, the additive that influences rheologic behavio(u)r is thixotropic agent and/or thickening material for example, flow control agent, anti, defoamer, antistatic agent, lubricant, wetting agent, dispersion agent, softening agent, sanitas comprises mycocide and/or biocide etc., thermoplastic additive, dyestuff, pigment, matting agent, fire retardant, in release agent, filler, isocyanate curing agent and/or whipping agent.
From composition A)～C) preparation tackiness agent and coating composition
This tackiness agent and coating composition are by making (" the Lehrbuch der Lacktechnologie " of each composition 20～80 ℃ temperature intense mixing preparation, Th.Brock, M.Groteklaes, P.Mischke, V.Zorll compiles, Vincentz Verlag, Hannover, 1998, the 229ff pages or leaves).
The composition that is not liquid form is made into the solution in the appropriate solvent or in the water earlier before mixing when wishing, under agitation add remaining component then.Under the situation of pigment and/or filler etc., disperse.
The formaldehyde content of this tackiness agent and coating composition be lower than 100ppm, better be lower than 20ppm, better be lower than 10ppm.
Aqueous binder required for protection and coating composition are suitable for being coated with the article made by various materials for example plastics film and/or layered product such as metallized film, textiles, fiber, weaving material, leather, mill bristol, paper, paper layered product and/or synthetic materials, and this coating does not have formaldehyde on very big degree.This coating composition is applicable to all usual method of application.
Good elasticity merits attention because of dried speed of extra high beginning, excellent water tolerance and high hardness have both very for this tackiness agent and coating composition.
Drying, curing and crosslinked film have good adhesion property to undercoat; In addition, contraposition coating thereon is coated with that interlayer is bonding to be subjected to favourable influence.
Aqueous binder required for protection and coating composition be zero defect ground levelling on employed base material, and does not have surface imperfection for example paint face and wetting defective etc.
Aqueous binder required for protection and coating composition have 10%～80%, better 20%～60% solids content.
Tackiness agent of the present invention and coating composition be as for example single coating finishing paint such as finish paint and transparent coating material, dipping systems, and the undercoat material of painted, surperficial, priming paint and multiple tracks layer of lacquer system, and also be used as printing-ink and adhesives system.
Embodiment subsequently is intended to further specify the present invention but does not limit its range of application.
Embodiment
Composition A)
Use a kind of polyurethane dispersions W-PT 532 of Degussa AG company, its feature is as follows: solids content 35.5%, and pH=7.6, viscosity is 77mPas.
Composition B) preparation
1. the preparation of adducts
The mixture of 134g two (methylol) propionic acid, 380g acetone and 6g 10wt% concentration dibutyl tin laurate acetone soln under agitation with the 444g isophorone diisocyanate with the blending of speed so so that this thermopositive reaction still can be managed at leisure.With this mixture heating up to 60 ℃ and to keep this temperature be 9.2% until nco value.
After cool to room temperature, this solution under agitation with 2300g 55wt% concentration hydrogenation phenyl methyl ketone/formaldehyde resin (Kunstharz SK, available from Degussa AG) acetone soln and the blending of 12g10wt% concentration DBTL acetone soln, this mixture heating up is arrived about 60 ℃ reflux temperature., be reduced to below the 0.1%NCO its further stirring in this temperature until the nco value of this solution.
2. shift to aqueous phase
Replacement scheme A:
1) solution of the hydrophilic modifying resin of preparation neutralizes by add the 89g dimethylamino-ethanol under stirring at room in, and this solution is by adding the full softening water dispersed with stirring of 4200g then.Secondary solvent, acetone, under reduced pressure remove, provide solids content and be resin dispersion liquid about 33wt%, shelf-stable, fine, shallow lacteous together with the water of a certain ratio.
Replacement scheme B:
1) in the preparation solution under agitation with 3300g 55wt% concentration hydrogenation phenyl methyl ketone/formaldehyde resin (Kunstharz SK, available from Degussa AG) the acetone soln blending, with the neutralization of 89g dimethylamino-ethanol, this solution under agitation disperses by importing the full softening water of 4400g product under stirring at room.Secondary solvent, acetone, under reduced pressure remove together with the water of a certain ratio, provide solids content and be about 50wt%, shelf-stable, albescent dispersion liquid.
The dispersion liquid performance
Package stability
To saving 2) dispersion liquid A and B carry out shelf-stable sex investigation about the change of pH, viscosity and visual appearance.
| Performance | A | B |
| pH | ||
| Initially | 8.9 | 8.8 |
| After 6 months | 8.9 | 8.8 |
| 23 ℃ of viscosity * | ||
| Initially | 375-714mPa·s | 69-138mPa·s |
| After 6 months | 335-563mPa·s | 67-135mPa·s |
| Outward appearance | ||
| Post precipitation | Shallow lacteous | White |
| After 6 months | Shallow lacteous | White |
*Rotational viscosimeter; D:100 to 900s
-1
Coating composition embodiment:
| Relatively | Varnish I | Varnish II | Varnish III | |
| Composition | Quality/g | Quality/g | Quality/g | Quality/g |
| W-PT 532 | 100.0 | 90.0 | 80.0 | 70.0 |
| Composition B as each example | - | 10.0 | 20.0 | 30.0 |
| Each composition under agitation merges (600rpm) by described order | ||||
With on the above-mentioned varnish paint aluminium sheet and 80 ℃ of dryings 30 minutes.Use aluminium sheet,, therefore can record hardness and can improve and can not damage its flexibility because measure pendulum hardness and cupping cup-drawing test value in this case easily.
| Performance: | Relatively | Varnish I | Varnish II | Varnish III |
| Thickness (μ m) | 41-48 | 40-47 | 49-54 | 43-48 |
| K nig pendulum hardness (s) | 43 | 56 | 72 | 95 |
| The mark signature tack | 3 | 0 | 0 | 0 |
| Cupping deep-draw value | ＞8.0 | ＞8.0 | ＞8.0 | ＞8.0 |
| 20 °/60 ° of gloss | 78/88 | 80/90 | 81/91 | 83/92 |
| The Peugeot test | ++ | ++ | ++ | ++ |
The interpolation of composition B has improved hardness, clinging power and the gloss of coating, and can not damage its flexibility.
Claims (34)
1. an aqueous binder or a coating composition that is used for flexible parent metal comprises in fact
A) at least a water-based base-material of 20wt%～95wt% and
B) 5wt%～80wt% hydrophilization ketone/urea formaldehyde and/or a kind of hydrophilization hydrogenation ketone/urea formaldehyde and
C) at least a additive of 0wt%～75wt%,
Composition A)～C) weight amount sum is 100wt%.
2. claim 1 aqueous binder required for protection or coating composition; wherein; the solids content of this tackiness agent or coating composition is 10wt%～80wt%, better 20wt%～60wt%; the formaldehyde content of this coating composition be lower than 100ppm, better be lower than 50ppm, better be lower than 10ppm, and organic solvent content be lower than 20wt%, better be lower than 10wt%, better be lower than 2wt%.
3. claim 1 or 2 aqueous binder required for protection or coating compositions; wherein; use is selected from following one group water-based base-material as composition A): urethane; polyacrylic ester; polyethers; polyester; Synolac; ether of cellulose; derivatived cellulose; polyvinyl alcohol and derivative; rubber; the maleic acid ester resinoid; phenol/urea-formaldehyde resin; aminoresin (melamine resin for example; the benzo guanamine resin); epoxy acrylate; Resins, epoxy; silicon ester; and alkalimetal silicate (for example water glass) and/or silicone resin and/or fluoropolymer, independent or its mixture.
4. claim 3 aqueous binder required for protection or coating composition are wherein, as composition A) preferably the water-based base material be external crosslinking and/or self-crosslinking, air-dry (physical dryness) and/or oxidative cure.
5. any one aqueous binder required for protection or coating composition in the above claim, wherein, the aqueous resin dispersion that use can obtain by the reaction or the partial reaction of following ingredients is as composition B):
I. contain the ketone/urea formaldehyde of hydroxyl or its hydroderivating thing and
II. at least a have at least one free NCO group, can be by making the reaction of at least a isocyanic ester and/or polyisocyanates and some compounds the hydrophilic modifying isocyanic ester and/or the polyisocyanates that obtain, described compound except that containing hydrophilic radical or potential hydrophilic radical, also have at least one can with the functional group of isocyanate groups reaction
After the reaction with resin-neutralize when needing-make up with water.
6. claim 5 aqueous binder required for protection or coating composition wherein, use the resin that comprises the acid ketone of C-H as prepared composition B) composition I.
7. claim 6 aqueous binder required for protection or coating composition; wherein; use is selected from the acid ketone of following C-H: acetone, phenyl methyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclododecanone, 2; 2; 4-and 2; 4; the mixture of mixture, suberone and the cyclooctanone of 4-trimethylammonium cyclopentanone, pimelinketone and one or more mixtures that the alkyl substituted cyclohexanone is arranged that contain the alkyl that adds up to 1～8 carbon atom are all arranged are separately or form of mixtures.
8. claim 7 aqueous binder required for protection or coating composition; wherein; the pimelinketone that uses following conduct to have alkyl to replace: 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3; 3; the 5-trimethylcyclohexanone, independent or its mixture.
9. claim 5 aqueous binder required for protection or coating composition wherein, use to comprise the resin of aldehyde as prepared composition B) composition I.
10. any one aqueous binder required for protection or coating composition in the above claim; wherein; use following as prepared composition B) the aldehyde composition of composition I: formaldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and 12 (alkane) aldehyde, separately or its mixture.
11. any one aqueous binder required for protection or coating composition in the above claim; wherein; use is from phenyl methyl ketone, pimelinketone, 4-tertiary butyl pimelinketone, 3; 3,5-trimethylcyclohexanone and heptanone, separately or the hydrogenation products of the resin made of its mixture and formaldehyde as composition I.
12. any one aqueous binder required for protection or coating composition in the above claim, wherein, composition B) composition II is to use tertiary amine groups alcohol, aminocarboxylic acid, hydroxyl sulfoacid, thionamic acid and/or hydroxycarboxylic acid preparation.
13. any one aqueous binder required for protection or coating composition in the above claim, wherein, composition B) composition II is to use the preparation of two (methylol) propionic acid.
14. any one aqueous binder required for protection or coating composition in the above claim, wherein, composition B) composition II with composition I reaction before neutralize.
15. any one aqueous binder required for protection or coating composition in the above claim wherein, use the functional polyisocyanates prepared composition of two senses to four B) II.
16. any one aqueous binder required for protection or coating composition in the above claim, wherein, use aromatic series is arranged, the polyisocyanates of isocyanate groups that aliphatics and/or cyclic aliphatic connect or these mixture prepared composition B) II.
17. any one aqueous binder required for protection or coating composition in the above claim wherein, use 1-isocyanato--3,3,5-trimethylammonium-5-isocyanato-methylcyclohexane (isophorone diisocyanate; IPDI), trimethyl hexamethylene diisocyanate (TMDI), 1,6-two isocyanato-hexanes (HDI) and two (4-isocyanato-hexyl) methane (H
12MDI), independent or its mixture.
18. any one aqueous binder required for protection or coating composition in the above claim wherein, use the polyisocyanates prepared composition B that biuret, uretdione (uretdione) or isocyanurate structure are arranged) II.
19. any one aqueous binder required for protection or coating composition in the above claim wherein, use from polyvalent alcohol and/or amine and react the polyisocyanates prepared composition B that obtains with monomeric diisocyanate) II.
20. any one aqueous binder required for protection or coating composition in the above claim; wherein; use two (methylol) propionic acid and isophorone diisocyanate, trimethyl hexamethylene diisocyanate, 1,6-two isocyanato-hexanes and/or two (4-isocyanato-hexyl) methane was with 1: 2 mol ratio prepared composition B) II.
21. any one aqueous binder required for protection or coating composition in the above claim, wherein, composition B) I and the reaction of II and being dispersed in the body (solvent-free) or in the presence of secondary solvent are subsequently carried out.
22. aqueous binder required for protection or coating composition in the above claim, wherein, employed secondary solvent has at 1013hPa and is lower than 100 ℃ boiling point.
23. aqueous binder required for protection or coating composition in the above claim, wherein, employed secondary solvent is acetone and/or methylethylketone and/or tetrahydrofuran (THF).
24. any one aqueous binder required for protection or coating composition in the above claim, wherein, composition B) be with organic bases or mineral alkali neutral.
25. aqueous binder required for protection or coating composition in the above claim, wherein, neutralization is to use dimethylethanolamine and/or diethylethanolamine and/or 2-dimethylin-2-methyl isophthalic acid-propyl alcohol to carry out.
26. any one aqueous binder required for protection or coating composition in the above claim, wherein, neutralization is to use in the stoichiometric quantity and 50%～130% the carrying out of needed dosis neutralisata.
27. any one aqueous binder required for protection or coating composition in the above claim wherein, before adding water, add one or more compositions water-insoluble or water-dilutable.
28. any one aqueous binder required for protection or coating composition in the above claim wherein, make used additives and additive as composition C).
29. any one aqueous binder required for protection or coating composition in the above claim; wherein, use be selected from following one group; separately or the auxiliary agent of mixture and additive as composition C): inhibitor; organic solvent; surfactant; oxygen scavenqer and/or free-radical scavengers; catalyzer; photostabilizer; the color brightener; photosensitizer and light trigger; the additive that influences rheologic behavio(u)r is thixotropic agent and/or thickening material for example; flow control agent; anti; defoamer; softening agent; antistatic agent; lubricant; wetting agent; dispersion agent; sanitas comprises mycocide and/or biocide etc.; thermoplastic additive; dyestuff; pigment; matting agent; fire retardant; in release agent; filler; isocyanate curing agent and/or whipping agent.
30. the preparation method of aqueous binder or coating composition, said composition comprises in fact
A) at least a water-based base-material of 20wt%～95wt% and
B) the hydrogenation ketone/urea formaldehyde of the ketone/urea formaldehyde of 5wt%～80wt% hydrophilization and/or a kind of hydrophilization and
C) at least a additive of 0～75wt%,
Composition A)～C) weight amount sum is 100wt%,
This method is included in+and 20～+ 80 ℃ temperature stirs and/or disperses each thorough mixing that becomes to assign to.
31. the purposes of at least one item aqueous binder required for protection or coating composition is used to strengthen Flexible articles in the above claim.
32. the purposes of at least one aqueous binder required for protection or coating composition in the above claim is used to strengthen for example for example metallized film, textiles, fiber, weaving material, leather, metal, mill bristol, paper, paper layered product and/or synthetic materials of plastics film and/or layered product of Flexible articles.
33. the purposes of at least one item aqueous binder required for protection or coating composition in the above claim; single coating finishing paint such as finish paint and transparent coating material as flexible parent metal; dipping systems; the undercoat material of painted, surperficial, priming paint and multiple tracks layer of lacquer system, and also as printing-ink and adhesives system.
34. a coated article is with at least one tackiness agent required for protection or coating composition production and/or reinforcement in the above claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005010963.2 | 2005-03-10 | ||
| DE102005010963A DE102005010963A1 (en) | 2005-03-10 | 2005-03-10 | Aqueous coating compositions for flexible substrates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1942549A true CN1942549A (en) | 2007-04-04 |
Family
ID=36050740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800000096A Pending CN1942549A (en) | 2005-03-10 | 2006-01-17 | Coating agent aqueous compositions for flexible backgrounds |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1942549A (en) |
| DE (1) | DE102005010963A1 (en) |
| WO (1) | WO2006094851A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104342003A (en) * | 2014-10-14 | 2015-02-11 | 凤阳徽亨商贸有限公司 | Dustproof and bactericidal type aqueous coating material for glass doors and preparation method thereof |
| CN106457787A (en) * | 2014-05-15 | 2017-02-22 | 凸版印刷株式会社 | Gas-barrier packaging material |
| CN109111559A (en) * | 2018-07-25 | 2019-01-01 | 禾丰新材料科技有限公司 | Aqueous polyketone resin lotion and its preparation method and application |
| CN110003757A (en) * | 2019-03-28 | 2019-07-12 | 广东绿色大地化工有限公司 | A kind of aqueous one-component nano modification self-cross linking type anti-corrosion primer |
| TWI750240B (en) * | 2016-10-20 | 2021-12-21 | 德商巴斯夫塗料有限責任公司 | Method for producing a coating |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118730A (en) * | 2017-05-27 | 2017-09-01 | 江苏省江南新型复合研磨材料及制品工程技术研究中心有限公司 | A kind of blinds abrasive disk adhesive and preparation method thereof |
| CN114149556B (en) * | 2021-11-18 | 2023-10-27 | 广东西顿新材料科技有限公司 | Aldehyde ketone modified self-extinction aqueous polyurethane dispersion and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3075935A (en) * | 1959-12-17 | 1963-01-29 | Shawinigan Resins Corp | Coating compositions of aqueous vinyl acetate polymer emulsions modified with ketone-aldehyde resins |
| IT1087205B (en) * | 1977-10-24 | 1985-06-04 | Moplefan Spa | POLYALEFINECHE FILMS COATED WITH A HEAT-SEALING LACQUER BASED ON A KETONIC RESIN |
| JPH083082B2 (en) * | 1987-09-09 | 1996-01-17 | 荒川化学工業株式会社 | Aqueous emulsion type adhesive composition |
| DE4309079A1 (en) * | 1993-03-20 | 1994-09-22 | Basf Ag | Aqueous dispersion of a polyurethane and a condensation resin |
| JPH1060260A (en) * | 1996-08-22 | 1998-03-03 | Sakata Corp | Cold-curable water-based polyurethane resin composition and its use |
| DE19643704A1 (en) * | 1996-10-23 | 1998-04-30 | Huels Chemische Werke Ag | Aqueous resin dispersions |
| US5977227A (en) * | 1997-09-30 | 1999-11-02 | Ncr Corporation | Method for forming aqueous dispersions of ketone resins |
| AT407253B (en) * | 1997-10-06 | 2001-02-26 | Vianova Kunstharz Ag | WATER-THINNABLE RESINS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| ES2216764T3 (en) * | 1999-06-21 | 2004-11-01 | Surface Specialties Austria Gmbh | DILUABLE RESINS WITH WATER, PROCEDURE FOR ITS PREPARATION AND ITS USE. |
| DE10354394B4 (en) * | 2003-11-20 | 2005-12-08 | Dynea Erkner Gmbh | Binders for the production and bonding of wood-based materials and / or fibrous materials and use thereof |
-
2005
- 2005-03-10 DE DE102005010963A patent/DE102005010963A1/en not_active Withdrawn
-
2006
- 2006-01-17 CN CNA2006800000096A patent/CN1942549A/en active Pending
- 2006-01-17 WO PCT/EP2006/050246 patent/WO2006094851A1/en not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106457787A (en) * | 2014-05-15 | 2017-02-22 | 凸版印刷株式会社 | Gas-barrier packaging material |
| US10155365B2 (en) | 2014-05-15 | 2018-12-18 | Toppan Printing Co., Ltd. | Gas barrier packaging material |
| CN104342003A (en) * | 2014-10-14 | 2015-02-11 | 凤阳徽亨商贸有限公司 | Dustproof and bactericidal type aqueous coating material for glass doors and preparation method thereof |
| TWI750240B (en) * | 2016-10-20 | 2021-12-21 | 德商巴斯夫塗料有限責任公司 | Method for producing a coating |
| CN109111559A (en) * | 2018-07-25 | 2019-01-01 | 禾丰新材料科技有限公司 | Aqueous polyketone resin lotion and its preparation method and application |
| CN110003757A (en) * | 2019-03-28 | 2019-07-12 | 广东绿色大地化工有限公司 | A kind of aqueous one-component nano modification self-cross linking type anti-corrosion primer |
| CN110003757B (en) * | 2019-03-28 | 2021-06-15 | 广东绿色大地化工有限公司 | Water-based single-component nano modified self-crosslinking anticorrosive primer |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102005010963A1 (en) | 2006-09-14 |
| WO2006094851A1 (en) | 2006-09-14 |
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Open date: 20070404 |