CN101423723A

CN101423723A - Coating material compositions

Info

Publication number: CN101423723A
Application number: CNA2008101887341A
Authority: CN
Inventors: P·格洛克纳; A·温宁
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2007-10-05
Filing date: 2008-09-28
Publication date: 2009-05-06
Also published as: WO2009047102A1; DE102007047586A1

Abstract

The present invention relates to a coating composition which is composed of at least one adhesive, carbonyl ketone-aldehyde hydride resin without formaldehyde, a colorant, auxiliary material and additive according to requirement. The carbonyl ketone-aldehyde hydride resin is manufactured based on formaldehyde and has low viscosity, low chromatic number and extraordinarily high heat resistance and light resistance. The invention also relates to the preparing and usage.

Description

Coating composition

Technical field

The present invention relates to coating composition, it is made up of at least a tackiness agent, the carbonyl hydrogenated ketone-urea formaldehyde that does not contain formaldehyde, tinting material and auxiliary substance optionally and additive; Described carbonyl hydrogenated ketone-urea formaldehyde is that make on the basis with formaldehyde, has low viscosity, extremely low face number and high thermotolerance and photostabilization; The invention still further relates to its preparation and purposes.

Background technology

Coating composition is used to different base materials is applied, described base material for example is metal, plastics, paper, laminated paper, strawboard, cardboard, inorganic materials, for example pottery, stone material, concrete, gypsum and/or glass, fabric, fiber, weaving material, leather and synthetic materials, the film made of leatheroid, timber, plastics and matrix material for example, for example cover the aluminium film, wherein said coating is substantially free of formaldehyde.

After applying coating, total wish dryly rapidly, can continue fast to handle guaranteeing, and avoid the flaw that causes as dust and spot or the like such as dirty.In addition, importantly high scratch resistance is so that obtain a kind of to the insensitive coating of mechanical load.

The mixture of known ketone or ketone and aldehyde can react under the condition of basic catalyst or acid existence and generate the arborescens product.Can use pimelinketone and methyl cyclohexane alcohol/ketone mixtures to prepare resin (the 12nd of Ullmann, the 551st page).The reaction of ketone and aldehyde in most cases can form the hardened resin of often using in the paint industry.In most cases all use formaldehyde to prepare ketone-urea formaldehyde (Keton-Aldehydharze) now.

Ketone-formaldehyde resin is known already.For example at DE 33 24 287, US 2,540,885, US2,540,886, all described relevant preparation method in DE 11 55 909, DD 12 433, DE 13 00 256 and DE 12 56 898 patent documentations.

Usually making ketone and formaldehyde react to each other under the condition that alkali exists is prepared.

For example, in coating, can use ketone-urea formaldehyde as the film for additive composition, in order to improve some characteristic, as rate of drying, gloss, hardness or scratch resistance.Because its molecular weight is less, common ketone-urea formaldehyde has low melt viscosity and soltion viscosity, therefore in coating especially as the film forming function filler.

The carbonyl of ketone-urea formaldehyde is for example being used such as under the solar radiation typical DeR, for example Norrish I type or II type DeR [Laue, Plagens taking place, Namen und Schlagwort-Reaktionen, Teubner Studienb ü cher, Stuttgart, 1995].

Therefore ketone-the urea formaldehyde or the ketone resin of non-modified can't be used for the very high application of specification of quality, for example need especially climate change (Bewitterung) and heat are had the applications of height endurability.Can improve these shortcomings by carbonyl hydrogenated method.Early existing people adopts ketone-urea formaldehyde is carried out the hydrogenant method, and carbonyl is transformed into secondary alcohol (DE 826 974, and DE 870 022, and JP 11012338, and US 6,222,009).

To contain the ketone of aryl, equally also can prepare carbonyl and aromatic ring (kern) hydrogenant ketone-urea formaldehyde.In DE 33 34 631, this resinoid is described to some extent.

Find to prove that all these hydrogenated products generally contain the free formaldehyde of high level as a large amount of specialties.Although the described method for hydrogenation of prior art can still leave the tangible free formaldehyde of quantity so that the content of free formaldehyde is less than non-hydrogenation ketone-urea formaldehyde among hydrogenated products.Temperature higher during the hydrogenation can further reduce formaldehyde content, but may form disadvantageous effect to other characteristic of resin such as color, melting range, OH number or the like like this.

Formaldehyde may cause Health cost.But still do not carry out precise classification at present." international cancer research institution (International Agency for Reserch on Cancer) " under the The World Health Organization (WHO) (IARC) not long ago a result of study shows: formaldehyde can make the people suffer from rare sudden nasopharyngeal carcinoma (Nasenrachenraumkrebs (nasopharyngeal cancer)).

Although the sheerly scientific research character of assessment of IARC, do not cause any direct legal consequence as yet, but, definitely be necessary to provide the product that does not contain formaldehyde from " Sustainable development (nachhaltigen Entwicklung) " and " disposing chemical substance (verantwortlichen Umgang mit chemischen Stoff) " aspect to be responsible for attitude.In addition, on market, will only there be the product that does not contain formaldehyde mid-term.

At US 5,247, the method that reduces the formaldehyde content of non-hydrogenization acetone-formaldehyde resin under the situation that does not reduce carbonyl has been described in 066.Here can realize being lower than 0.4% free formaldehyde content, but still obviously too high according to current yardstick.Existing carbonyl can influence above-mentioned characteristic.

Patent DE 826 974, DE 870 022, JP 11012338, US 6,222,009 and DE 33 34631 described methods obtain such product, and this product has than original material (Ausgangsprodukt) better color, light and heat stability.According to current viewpoint, improve although these products are existing, abundant not enough.

That DE 10 2,006 00 9079.9 describes is the preparation method who does not contain the carbonyl hydrogenated ketone-urea formaldehyde of formaldehyde.But be not described in the purposes in the coating.

Ketone-urea formaldehyde always is used to improve the content of involatile constituent in the coating.Under the mandatory provision of new criteria, for example European Union is about the instruction 1999/13/EG[derRichtlinie 1999/13/EG des Rates der EU ü ber die Begrenzung von Emissionen of restriction volatile organic compounds discharging], must further improve these characteristics.

Summary of the invention

Task of the present invention is, finds out the coating composition that is used to apply different substrate materials and does not contain free formaldehyde.These coating compositions should have high rate of drying (Antrocknungsgeschwindigkeit), water tolerance and scratch resistance, and have low soltion viscosity and high solids content.In addition, film also should have good adhesion to base material, low mist degree (Glanzschleier), high color stability and high light and heat stability.

By using the following special coating composition that will describe in detail, can solve task of the present invention surprisingly.

Theme of the present invention is the coating composition that free formaldehyde content is lower than 100ppm, and (imWesentlich) comprises necessarily

A) weight percent is at least a carbonyl hydrogenated ketone-urea formaldehyde based on formaldehyde of 5～75%, and the content of free formaldehyde is lower than 3ppm, and this resin comprises the structure unit shown in the formula I (Strukturelement) necessarily

Wherein

R=has the aromatics of 6-14 carbon atom, has fat (ring) family of 1～12 carbon atom,

R′＝H，CH ₂OH，

K=2～15, preferred 3～12, be preferably 4～12 especially;

M=0～13 are preferably 0～9,

1＝0～2，

The k+l+m sum is 5～15, and k〉m, be preferably 5～12, these three kinds of structure units can be alternately distributed or stochastic distribution; And these structure units can pass through CH ₂The group straight chain connects, and perhaps connects by the CH group branched chain.

With

B) weight percent is 20～90% at least a tackiness agent,

With

C) weight percent is 0～50% at least a tinting material and/or filler

With

D) weight percent is 5～75% at least a additive,

And weight data sum composition A)～D) is 100 weight %.

Found by composition A)～the following coating composition combination D) formed can satisfy all required standards.

Composition A)

Carbonyl hydrogenated ketone-urea formaldehyde the A of necessity of the present invention) weight percent quantity is 5～75%, is preferably 5～50%.Be suitable as composition A) be carbonyl hydrogenated ketone-urea formaldehyde based on formaldehyde, free formaldehyde content is lower than 3ppm, these resins comprise the structure unit shown in the formula I necessarily

R′＝H，CH ₂OH，

K=2～15 are preferably 3～12, are preferably 4～12 especially,

M=0～13 are preferably 0～9,

1＝0～2，

The k+l+m sum is 5～15, and k〉m, be preferably 5～12, these three kinds of structure units can be alternately distributed or stochastic distribution; And these structure units can pass through CH ₂The group straight chain connects, and/or connects by the CH group branched chain.

Particularly preferably be wherein carbonyl hydrogenated ketone-urea formaldehyde A) based on formaldehyde

Have following characteristics,

Free formaldehyde content is lower than 3ppm, preferably is lower than 2.5ppm, especially preferably is lower than 2.0ppm,

The carbonyl number is 0～100mg KOH/g, is preferably 0～50mg KOH/g, is preferably 0～25mg KOH/g especially,

Hydroxyl value (Hydroxylzahl) is 50～450mg KOH/g, is preferably 150～400mgKOH/g, is preferably 200～375mg KOH/g especially,

Gardner's chromatic number (Farbzahl) (50% (50%in Ethylacetat) in ethyl acetate) is lower than 1.5, preferably is lower than 1.0, especially preferably is lower than 0.75,

After resin bears thermal load (24 hours, 150 ℃), Gardner's chromatic number (in ethyl acetate 50%) is lower than 2.0, preferably is lower than 1.5, especially preferably is lower than 1.0,

The polymolecularity of resin (Mw/Mn) is 1.35～1.6, is preferably 1.4～1.58 especially,

Under the 40% concentration situation, soltion viscosity is 5000～12000mPa-s, is preferably 6000～10000mPa-s especially in Phenoxyethanol,

Fusing point/melting range is 50～150 ℃, is preferably 75～140 ℃, is preferably 100～130 ℃ especially,

Through after the thermal treatment in 24 hours, involatile constituent content is higher than 97.0%, preferably is higher than 97.5% under 150 ℃ of conditions.

The carbonyl hydrogenated ketone-urea formaldehyde A that does not contain formaldehyde based on formaldehyde of preparation necessity of the present invention) preferably carry out in the following way, this resin comprises the structure unit shown in the formula I necessarily,

I. under the condition that has at least a kind of basic catalyst and optionally at least a phase-transfer catalyst to exist, do not use solvent or use can with water blended organic solvent, make at least a ketone and at least a aldehyde carry out condensation reaction, thereby prepare base resin (Grundharze)

Then

II. under the condition that catalyzer exists, in the solution of melt or appropriate solvent, make the carbonyl of ketone-urea formaldehyde and hydrogen carry out continuous, semicontinuous or discontinuous hydrogenation; Pressure is 50～350 crust, is preferably 100～300 crust, is preferably 150～300 crust especially; And temperature is 40～140 ℃, is preferably 50～140 ℃.

Can significantly reduce the formaldehyde content that impairs one's health by this way.What is called does not contain formaldehyde, and the contained free formaldehyde of (erfindungswesentlich) carbonyl hydrogenated ketone-urea formaldehyde that refers to necessity of the present invention is lower than 3ppm, preferably is lower than 2.5ppm, especially preferably is lower than 2.0ppm.

Found that if carbonyl number (Carbonylzahl) very little (I-c 1＜2) then chromatic number is very little and thermotolerance is very high.Carbonyl hydrogenated ketone-urea formaldehyde the A of necessity of the present invention) carbonyl number is being 0～100mg KOH/g, be preferably 0～50mg KOH/g, be preferably 0～25mg KOH/g especially, thereby make Gardner's chromatic number (in ethyl acetate 50%) of carbonyl hydrogenated ketone-urea formaldehyde of necessity of the present invention be lower than 1.5, preferably be lower than 1.0, especially preferably be lower than 0.75; And after bearing thermal load (24 hours, 150 ℃), Gardner's chromatic number (in ethyl acetate 50%) is lower than 2.0, preferably is lower than 1.5, especially preferably is lower than 1.0.

Wish that soltion viscosity is low as far as possible, thereby make organic solvent content the least possible that this is that described organic solvent is mainly used to soltion viscosity is reduced to required process range for the not only purpose of economy but also environmental protection.When the carbonyl hydrogenated ketone-urea formaldehyde of necessity of the present invention was 40% concentration in Phenoxyethanol, its soltion viscosity was 5000～12000mPa-s, is preferably 6000～10000mPa-s especially.

Under the situation of given molecular weight (Mn), institute's dissolved polymers inconsistent (uneinheitlicher) (polymolecularity height), then soltion viscosity is high more.The carbonyl hydrogenated ketone resin A of necessity of the present invention) having low polymolecularity (Mw/Mn), is 1.35～1.6, is preferably 14～1.58 especially.

Wish the carbonyl hydrogenated ketone-urea formaldehyde A of necessity of the present invention) have high as far as possible melting range, so that the hardness of the rate of drying of feasible for example coating and coating is high as far as possible.

Can obtain high-melting-point/melting range by bigger molecular weight (the k+l+m sum among the formula I).But molecular weight is big more, and then soltion viscosity is high more.Therefore wish under the situation that does not increase molecular weight, to improve fusing point/melting range.K among the formula I is occupied the majority all the time, and the high as far as possible value of preferred selection, just can reach this purpose.The value of k is 2～15, is preferably 3～12, especially is preferably 4～12.Carbonyl hydrogenated ketone-urea formaldehyde the A of necessity of the present invention) fusing point/melting range is 50～150 ℃, is preferably 75～140 ℃, is preferably 100～130 ℃ especially.

In addition, bigger k value helps the carbonyl hydrogenated ketone-urea formaldehyde A of necessity of the present invention among the formula I) solubleness among polar solvent (for example alcohols), this is even more important for coating because normally used here be alcohols (for example ethanol).So also can improve consistency with polarity tackiness agent (for example nitrocotton).Therefore should suitably select the k value, make k, and hydroxyl value (Hydroxylzahl) is 50～450mg KOH/g, be preferably 150～400mg KO greater than m _H/ g is preferably 200～375mg KOH/g especially.

Can pass through the ratio of k, l and m and regulate solvability.For example, high more and m of k value and l are more little, then the carbonyl hydrogenated ketone-urea formaldehyde A of necessity of the present invention) be more prone to be dissolved among the polar solvent (for example alcohols), and better with the consistency of polarity tackiness agent (for example nitrocotton).And on the other hand, must suitably select the ratio of k, l and m, make other characteristic (for example water tolerance) not be subjected to negative impact.

The value of k, l and m and the summation of these values can be integer (for example 2), but also can be intermediate value (for example 2.4).

With the composition of the base resin that contains carbonyl of drying Preparation Method step I,

Ketone and aldehyde

All ketone all are suitable as the carbonyl hydrogenated ketone-urea formaldehyde A of preparation based on formaldehyde) ketone, especially do not have response capacity or very all Alpha-Methyl ketone of low reactivity are only arranged in α ' position in the α '-position that connects carbonyl, for example methyl phenyl ketone, acetophenone derivs, alkyl substituted benzene ethanone derivatives, methoxyacetophenone, 3 that 1～8 carbon atom is for example arranged on hydroxy acetophenone, the phenyl ring, 3-dimethyl-2-butanone, methyl iso-butyl ketone (MIBK), but also can use Propiophenone, separately or with form of mixtures.These ketones (especially Alpha-Methyl ketone) are present in the resin of the present invention, are 70～100mol-% with respect to the molar percentage of ketone composition.Preferably use with methyl phenyl ketone, 3,3-dimethyl-2-butanone and methyl iso-butyl ketone (MIBK) are the carbonyl hydrogenated ketone-urea formaldehyde A on basis), individually or with form of mixtures.

In addition, in being mixed into the process of above-mentioned ketone, also can use other CH acid ketone on a small quantity, be at most 30mol-%, preferred 15mol-% at the most with respect to the molar percentage of ketone composition, acetone for example, methyl ethyl ketone, 2-heptanone, propione, cyclopentanone, cyclododecanone, 2,2,4-and 2,4,4-trimethylammonium cyclopentanone mixture, suberone and cyclooctanone mixture, pimelinketone and contain all alkyl substituted cyclohexanones that one or more total carbon atom numbers are 1～8 alkyl is individually or with form of mixtures.For example, the alkyl substituted cyclohexanone can be a 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.Preferred pimelinketone, methyl ethyl ketone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone and 3,3, the 5-trimethylcyclohexanone.

Except formaldehyde, non-branching or branching aldehydes, for example acetaldehyde, butyraldehyde-n and/or different-butyraldehyde, valeral and lauric aldehyde all are suitable as the carbonyl hydrogenated ketone-urea formaldehyde A based on formaldehyde in principle) extra aldehyde composition.Being fit to be used for all aldehydes of synthetic ketone resin described in the pertinent literature all can use usually.But the preferred formaldehyde that uses separately.Can use other aldehydes, be 0～75mol-% with respect to the molar percentage of aldehyde composition, is preferably 0～50mol-%, especially is preferably 0～25mol-%.In containing the mixture of formaldehyde, equally also can there be the aromatic aldehyde of 10mol%, for example phenyl aldehyde at the most.

Required formaldehyde is about 20～40% the aqueous solution or the use of alcohol (for example methyl alcohol or butanols) solution usually as weight percent.Other type of service of formaldehyde provides the compound of formaldehyde, for example paraformaldehyde (para-Formaldehyd) and/or trioxane (Trioxan).

Very particularly preferably, precursor compound as carbonyl hydrogenated ketone-urea formaldehyde, use methyl phenyl ketone, 3,3-dimethyl-2-butanone and methyl iso-butyl ketone (MIBK) and acid ketone of CH optionally and formaldehyde, wherein said Ch acid ketone is selected from pimelinketone, methyl ethyl ketone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone and 3,3, the 5-trimethylcyclohexanone is individually or with form of mixtures.Also can use different ketone-urea formaldehyde A) mixture.

Mol ratio between ketone and the aldehyde composition is 1:0.25 to 1:15, is preferably 1:0.9 to 1:5, is preferably 1:0.95 to 1:4 especially.

The method that is used for the base resin that contains carbonyl of preparation method's step I

Usually exist under the condition of at least a basic catalyst, making the mixture of ketone or various ketone and formaldehyde or react, making the base resin I that contains carbonyl with the mixture of formaldehyde and other aldehyde.Especially when using formalin and water-soluble limited ketone, then can advantageously use can with water blended organic solvent.Mix mutually owing to particularly bring so better, therefore the reaction conversion more rapidly, fully.In addition, optionally can also add and use at least a phase-transfer catalyst, for example just can reduce the amount of basic cpd like this.After reaction finishes, water and resin are separated.Use sour water washing crude product, until the clear bath sample that resin occurs.Make resin drying by distillation then.

Preparing being reflected in the alkaline environment of base resin by ketone and aldehyde carries out.Being fit to be used for all basic catalysts of synthetic ketone resin described in the pertinent literature all can use usually, for example alkali metal compound (Alkaliverbindung).The preferred NH that uses ₄, NR ₄, Li, Na, K oxyhydroxide.Very particularly preferably use NH ₄, NR ₄, Li, Na oxyhydroxide.

The reaction that is prepared base resin by ketone and aldehyde can be carried out under the situation of using certain secondary solvent.The alcohol that formaldehyde for example or ethanol and so on are arranged that be fit to use.Also can use and to enter water-soluble ketone among the resin as secondary solvent by reaction.

Must remove employed basic catalyst, with purification base resin I.Use acid to neutralize, and water is washed, just can purify at an easy rate.All organic acids and/or mineral acid all are fit to be used for neutralizing usually.The preferred organic acid that contains 1～6 carbon atom that uses, the preferred especially organic acid that contains 1～4 carbon atom that uses.

Prepare by ketone and aldehyde in the polycondensation mixture of base resin and can also randomly use phase-transfer catalyst.

When using certain phase-transfer catalyst, but operating weight per-cent is the phase-transfer catalyst of the general formula (II) of 0.01～15% (with respect to ketone)

Wherein

X: nitrogen-atoms or phosphorus atom

R ₁, R ₂, R ₃, R ₄: can be identical or different, have the alkyl of 1～22 carbon atom in the expression carbochain, perhaps phenyl or benzyl

With

Y: expression (inorganic) organic acid negatively charged ion or hydroxide ion.

If quaternary ammonium salt has 1～22 carbon atom in the then preferred carbochain, especially has the alkyl (R of 1～12 carbon atom _1-4), and phenyl and/or phenmethyl, and/or both mixtures.As anionic can be the negatively charged ion of (inorganic) organic acid, for example Cl ^-, Br ^-, J ^-(iodine), but also can be the negatively charged ion of oxyhydroxide, methylate or acetate.Quaternary ammonium salt for example is: hexadecyldimethyl benzyl ammonium phenmethyl ammonium chloride, tributyl phenmethyl ammonium chloride, Three methyl Benzene ammonio methacrylate, Three methyl Benzene methyl ammonium iodide, triethylbenzene ammonio methacrylate or triethylbenzene methyl ammonium iodide, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride.Preferred phenmethyl tributyl ammonium chloride, hexadecyldimethyl benzyl ammonium phenmethyl ammonium chloride and/or the triethylbenzene ammonio methacrylate of using.

For quaternary alkylphosphonium salt (Phosphoniumsalze), the alkyl, phenyl or benzyl that preferably have 1～22 carbon atom are as R _1-4As anionic can be the negatively charged ion of (inorganic) organic acid, for example Cl ^-, Br ^-, J ^-, but also can be the negatively charged ion of oxyhydroxide, methylate or acetate.

For example can use triphenyl phenmethyl phosphonium chloride or triphenylbenzene methyl phosphonium iodide as quaternary alkylphosphonium salt.Can certainly use mixture.

Optionally can use phase-transfer catalyst in polycondensation mixing process, be 0.01～15% with respect to the weight percent quantity of used ketone, is preferably 0.1～10.0%, especially is preferably 0.1～5.0%.

Particularly preferred embodiment

According to a kind of particularly preferred embodiment, at first preparation contains the base resin I of carbonyl.At first add 10mol ketone in 50～90% methanol solutions, the phase-transfer catalyst of 0～5 quality % and 1～5mol formalin stir then for this reason.Add 0.1～5mol aqueous sodium hydroxide solution in the whipping process.Adding 4～10mol formalin at 70～115 ℃ then stirred 30～120 minutes.After continuing to stir 0.5～5 hour, when reaching reflux temperature, close agitator.Randomly, can after through 1/3rd reaction times, additionally add 0.1～1mol formalin.Water and resin are separated.Under use organic acid situation, wash crude product with water, until the clear bath sample that resin occurs.Make resin drying by distillation then.

Be used to prepare method according to the ketone-urea formaldehyde of necessity of the present invention of method steps II

Under the condition that catalyzer exists, the resin that uses hydrogen hydrogenation to obtain by ketone and aldehyde.At this moment the carbonyl of ketone resin is converted into secondary hydroxyl.Visual response condition and deciding, part of hydroxyl may be sloughed, and the result produces methylene radical.Suitably the selective reaction condition makes that the composition of reducing carbonyl is not few.Below describe with rough schematic view:

Can catalysis of carbonyl and hydrogen carry out hydrogenation and free formaldehyde and hydrogen and carry out all compounds that hydrogenation generates methyl alcohol and all can be used as catalyzer in principle and use.Can use homogeneous phase or heterogeneous catalyst, especially preferably use heterogeneous catalyst.

In order to obtain the product that does not contain formaldehyde of the present invention, verified suitable be to be used alone or as a mixture the metal catalyst that is selected from nickel, copper, copper-chromium, palladium, platinum, ruthenium and rhodium, particularly preferably be nickel, copper-chromium and ruthenium catalyst.

In order to improve activity, selectivity and/or work-ing life, can also comprise doping metals or other properties-correcting agent in the catalyzer.Typical doping metals for example has molybdenum, iron, silver, chromium, nickel, vanadium, gallium, indium, bismuth, titanium, zirconium and manganese and rare earth element.Typical properties-correcting agent for example is the properties-correcting agent that can be used to change the soda acid characteristic of catalyzer, for example basic metal and alkaline-earth metal or its compound, phosphoric acid or sulfuric acid and compound thereof.Can use the catalyzer of powder or formed body form, for example extrudate or compressing powder.Can use type catalyzer or carried catalyst in full catalyst (Vollkontakt), the Ruan.Type catalyzer and carried catalyst in preferred Ruan.The solid support material that is suitable for for example has diatomite, silicon-dioxide, aluminum oxide, silico-aluminate, titanium dioxide, zirconium dioxide, aluminium-titanium-silicon mixed oxide, magnesium oxide and gac.Can reactive metal be applied on the solid support material according to method known to those skilled in the art, for example can adopt dipping, spraying or the precipitator method.Decide on the Preparation of catalysts mode, also need preparation process well known by persons skilled in the art, for example drying, calcining, moulding and activation.Can randomly add other subsidiary material and carry out moulding, for example graphite or Magnesium Stearate.

Catalytic hydrogenation can be in melt, carry out in the solution of appropriate solvent, perhaps carries out as in the hydrogenated products of " solvent " at self.If necessary, also can after finishing reaction, separate employed solvent.The solvent of separating can turn back in the technology, decides on used solvent, might also need some additional purification steps to remove easy volatile or difficult volatile byproducts, for example first alcohol and water wholly or in part.The solvent that is suitable for is that charging thing and product can be dissolved in wherein and can keep the inert solvent under selected hydrogenation conditions with capacity.These solvents for example are alcohols, and preferred propyl carbinol and isopropylcarbinol, cyclic ether, preferred tetrahydrofuran (THF) and dioxane, alkyl oxide, aromatic substance be dimethylbenzene for example, and ester, for example ethyl acetate and butylacetate.Also can use the mixture of these solvents.The concentration of resin in solvent can be 1～99%, preferably change in 10～50% scopes.

Preferred use high relatively pressure, so as to obtain higher transformation efficiency and the residence time in reactor short as far as possible.Total pressure in the reactor is 50～350 crust, is preferably 100～300 crust.Best hydrogenation temperature depends on employed hydrogenation catalyst.For example temperature is 40～75 ℃ for rhodium catalyst, be preferably 40～60 ℃ just enough; Copper catalyst or copper/chrome catalysts then need higher temperature, and representative temperature is 100～140 ℃.

Can adopt discontinuous or the operate continuously mode comes hydrogenation to obtain resin of the present invention.Also can adopt the semi continuous operation mode, promptly in batch reactor, add resin and/or solvent continuously, and/or remove one or more reaction product and/or solvent continuously.

Catalyst loading is per hour 0.05～4 ton of resin of every cubic metre of catalyzer, is preferably per hour 0.1～2 ton of resin of every cubic metre of catalyzer.

The whole bag of tricks well known by persons skilled in the art all is fit to be used for temperature variation, especially limited maximum temperature in the controlling reactor.For example when enough hour of resin concentration, can operate under the extra refrigerative situation reactor not being carried out fully, at this moment reaction medium will absorb the energy that discharges fully, and with convection type from reactor with its discharge.In addition, suitable is the column plate reactor (Hordenreaktor) with intercooler unit, use air cooled hydrogen recycle loop, recycle a part through cooled reaction product (loop reactor), use the external coolant circulation loop, especially when using bundled tube reactor.

Carbonyl hydrogenated ketone-urea formaldehyde the A of preparation necessity of the present invention) preferred embodiment

For hydrogenation (method steps II.) according to the prepared resin that contains carbonyl of method steps I, in the continous way fixed-bed reactor, operate.Shaft furnace and tube bank with the work of trickle bed mode are particularly useful for making resin of the present invention.At the top of reactor with hydrogen with treat that the hydrogenant resin joins on the catalyst bed, optionally is dissolved in resin among the solvent.Also can send into hydrogen with reflux type from the bottom up.If necessary, then contained separated from solvent is come out.

In order to improve rate of drying, ketone resin (composition A) and vulcabond and/or polyisocyanates are reacted.So the product of the urethane that obtains has the rate of drying and the water tolerance (Wasserfestigkeit) of improvement.

What be suitable as isocyanic ester is aromatics, aliphatic series and/or alicyclic diisocyanate and/or polyisocyanates.Vulcabond for example is: separately or the cyclohexyl diisocyanate of form of mixtures, methylcyclohexane diisocyanate, the ethylcyclohexane vulcabond, phenylene diisocyanate, the propyl cyclohexane vulcabond, methyl diethyl cyclohexane vulcabond, tolylene diisocyanate, two (isocyanato-phenyl) methane, the propane vulcabond, the butane vulcabond, the pentane vulcabond, hexane diisocyanate, hexamethylene diisocyanate (HDI) or 1 for example, 5-two isocyanato-s-2-methylpentane (MPDI), the heptane vulcabond, the octane vulcabond, the 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, 4-isocyanato-methyl isophthalic acid for example, 8-octane vulcabond (TIN), decane vulcabond and triisocyanate, undecane vulcabond and triisocyanate, dodecane vulcabond and triisocyanate, isophorone diisocyanate (IPDI), separately or form of mixtures 2,2 '-and 2,4 '-and 4.4 '-dicyclohexyl methane diisocyanate (H ₁₂MDI), H ₁₂MDI preferably contains 4,4 of at least 80 weight % '-H ₁₂MDI, more preferably 85-95 weight %; 2,5 (2,6)-two (isocyanato-methyl), two ring [2.2.1] heptane (NBDI), 1, and two (isocyanato-methyl) hexanaphthenes of 3-(1,3-H ₆-XDI) or 1, and two (isocyanato-methyl) hexanaphthenes of 4-(1,4-H ₆-XDI).Preferred H ₁₂MDI, IPDI, HDI, TMDI, very particularly preferably H ₁₂MDI, IPDI.

Preferably as composition B) another kind of polyisocyanates be that simple (einfach) vulcabond is carried out dimerization, trimerizing, allophanic acid esterification, biuretized and/or urethane and each molecule of making contains the compound more than two isocyanate groups, for example IPDI, TMDI, HDI and/or H ₁₂The reaction product of the simple vulcabond of MDI and so on and polyvalent alcohol (for example glycerine, TriMethylolPropane(TMP), tetramethylolmethane) or polynary polyamine.Equally preferably select for use for example IPDI, HDI and H ₁₂The simple vulcabond of MDI and so on carries out trimerizing and the isocyanuric acid ester that obtains.Very particularly preferably be isocyanuric acid ester and IPDI, TMDI, HDI and/or the H of IPDI ₁₂MDI and TriMethylolPropane(TMP) and or the reaction product of tetramethylolmethane.

Composition B)

Tackiness agent B of the present invention) weight percent quantity is 20～90%, is preferably 30～75%.

The preferred tackiness agent that uses is: urethane, the polypropylene ester, polyethers, saturated and/or undersaturated polyester and copolyesters, Synolac, polymeric amide, casein, polyureas, derivatived cellulose is nitrocellulose for example, ether of cellulose and/or acetobutyric acid Mierocrystalline cellulose, polyvinyl alcohol and derivative, polyvinyl acetate (PVA), polyvinylpyrrolidone, (cyclisation) rubber, natural resin, hydrocarbon resin is coumarone resin for example, indene resin, cyclopentadiene resin, terpine resin, maleic ester resin, phenol resins, resol, urea-formaldehyde resin, ketone-urea formaldehyde, ketone resin, aminoplastics (trimeric cyanamide for example, benzoguanamine resin), polyolefine, the acrylated polyester, the acrylated polyethers, acrylated Resins, epoxy, urethane acrylate, Resins, epoxy, resole, Gum Rosin, resinate/ester (Resinate), silicon ester and alkalimetal silicate (for example water glass), silicone resin, chlorine-containing polymer and/or fluoropolymer be polyvinyl chloride and derivative thereof for example, chlorinated rubber, chlorinated polyester, PVDF.Also can use mixture.These tackiness agents can be outside cross-linking type or self-cross linking type, dry air (physical dryness) and/or oxidative cure.The preferred use separately or the urethane of mixed form, the polypropylene ester, polyethers, saturated and/or undersaturated polyester and copolyesters, Synolac, polyureas, derivatived cellulose, nitrocellulose for example, ether of cellulose and/or acetobutyric acid Mierocrystalline cellulose, polyvinyl alcohol and derivative, polyvinyl acetate (PVA), polyvinylpyrrolidone, natural resin, hydrocarbon resin, coumarone resin for example, indene resin, cyclopentadiene resin, terpine resin, maleic ester resin, phenol resins, resol, urea-formaldehyde resin, ketone-urea formaldehyde, ketone resin, aminoplastics (Aminoplaste) is melamine resin for example, benzoguanamine resin, resole, Gum Rosin, resinate/ester.

These tackiness agents dissolve among the organic solvent, but also dissolve in reactive diluent among (Reaktivverd ü nner), and/or can dissolve in water, mix or disperse.

What be suitable in principle is employed all tackiness agents of paint industry.

Composition C)

Composition C) weight percent quantity is 0～50%, is preferably 10～40%.Be suitable for employed all tinting materials of paint industry and/or filler in principle.Can require to select according to color, for example tone, colour strength, brightness, saturation ratio, transparency, covering power, photostabilization, bleeding resistance, consistency or the like can require to select hardness, elasticity or the like according to mechanicalness.Can use mineral dye and filler, rice beautiful indigo plant, titanium dioxide, ferric oxide, the metallic pigment (spinel for example that falls for example, pucherite, NiTi, chromic oxide), carbon black and carbonate (Wingdale for example, limestone powder, calcite, rhombspar, barium carbonate), vitriol (barite for example, barium white, calcium sulfate), silicate (for example talcum, pyrophyllite), chlorite, mica, kaolin, slate flour, feldspar, sedimentary Calucium Silicate powder, pure aluminium silicate, Calucium Silicate powder/aluminium, water glass/aluminium, silica ( ), for example quartz, fused quartz, cristobalite, diatomite, precipitated silica or fumed silica, glass powder and oxide compound, for example magnesium and aluminum oxide and oxyhydroxide, and pigment dyestuff (for example isoindoline pigment, azo pigment, quinacridone pigment, perylene dye, triazine dioxin pigment, phthalocyanine pigment).Also can use metal effect pigments in addition, for example aluminium, copper, copper/zinc pigment and zinc pigment, gold bronze (

), ferric oxide-aluminium pigment, coated interference pigment or pearly pigment, for example metal oxide-pigments, mica, pearl white, basic lead white, pearl essence (Fischsilber) or micronized titanium dioxide, flake graphite, flake ferric oxide, use PVD film or the multi-layer effect pigment of making according to the CVD method (chemical vapour deposition) and liquid crystal (polymkeric substance) pigment.In addition, can also use dyestuff.The tabulation of used pigment, filler and/or dyestuff can consult "

Lexikon, Paints And Oil China ink (Lacke undDruckfarben), Ulrich doctor Zorll of publisher, Georg Thieme press, Stuttgart, 1998 " or " pigment and filler table (Pigment-und F ü llstofftabell), the Olaf L ü ckert of publisher, Vincentz press, Hanover, 2002 ".

Components D)

Components D of the present invention) weight percent quantity is 5～75%, is preferably 5～45%.

Be suitable for all auxiliary substances and the additive that paint industry is suitable in principle.

Be particularly suitable as components D) auxiliary substance and additive for example have: inhibitor, organic solvent, water, surfactant, oxygen and/or free-radical scavengers, catalyzer, photostabilizer, the color brightener, photosensitizers and light trigger, the additive that is used to influence rheological characteristics is thixotropic agent and/or thickening material for example, flowing agent, anti, defoamer and degasifier, static inhibitor, lubricant, wetting agent and dispersion agent, linking agent is melamino-formaldehyde resin for example, sealing and/or untight (many) isocyanic ester, (gathering) amine and/or (many) carboxylic acids, sanitas is mycocide and/or biocide for example, thermoplastic additive, softening agent, matting agent, fire retardant, internal mold release and/or whipping agent.

Be suitable as solvent D) be the employed solvent of paint industry.For example can preferably be used alone or as a mixture alcohol, acetic ester, ketone, ether, glycol ethers, aliphatic cpd, aromatic substance.But also can use in the radiation-curable coating reactive diluent commonly used, for example also can be through oxyalkylated simple function, difunctionality or more polyfunctional acrylate monomer, and/or vinyl ether.

Use composition A)～D) prepare coating composition:

By at 20～80 ℃ of these compositions of thorough mixing, make coating composition (" paint technology textbook (Lehrbuch der Lacktechnologie) ", Th.Brock, M.Groteklaes, P.Mischke, the V.Zorll of publisher, Vincentz press, the Hanover, 1998, the 229th page was risen).

Optionally can before mixing, at first non-liquid parts be dissolved among appropriate solvent or the water, stir the remaining composition of adding then.If for example pigment and/or filler are arranged, then can use proper device (for example similar machine such as dissolver, three-roller, ball mill, ball mill) to make its dispersion.

The formaldehyde content of coating composition is lower than 100ppm, preferably is lower than 50ppm, and especially preferably is lower than 10ppm.

Coating composition required for protection can be used to different base materials is applied; for example metal, plastics, paper, laminated paper, strawboard, cardboard, inorganic materials; for example pottery, stone material, concrete, gypsum, glass, fabric, fiber, weaving material, leather, synthetic materials; for example leatheroid, timber, plastics film or matrix material for example cover the aluminium film.

These coating compositions both can be used for indoor; also can be used for outdoor; for example as building protection colorant/paint, road mark paint, automobile finish (OEM, renovation), coil coating, can lacquer, textile finishing, timber lacquer, plastic paint, and be used for decorative applications or the like.These compositions also are suitable among the tackiness agent, for example are used for fabric, leather, paper, plastics, metal and the analogous material of boning.

Can use all known methods to apply coating of the present invention, for example roller coating, brushing, dip-coating, flow coat, spraying, flow coat, roller coat, spraying, printing, obliterating, washcoated, rotary drum coating, centrifugal coating.

The characteristics of coating composition of the present invention are extra high rate of drying, resistance to marring and water tolerance.

Film has that very high gloss, low turbidity, color stability are very high, thermostability and light stability are high.

Drying, sclerosis or crosslinked after film have good adhesion property; Also help the middle layer tack.

Coating composition required for protection ideally flows on the use base material, and does not have the flaw such as pit and moistening defective.

Decide on applying method, the viscosity of coating composition is adjusted.When given soltion viscosity, it is 10～100% that coating composition required for protection has weight percent, be preferably 25～100% involatile constituent.

Theme of the present invention also is the goods that use coating composition to handle.

Embodiment

The following example is tackled detailed explanation of the present invention, but does not limit its range of application:

Embodiment

Neccessary composition A of the present invention) analytical procedure

Measure the content of free formaldehyde

Utilize HPLC to measure formaldehyde content (the research method official according to § 64LFGB K 84.00 7 (EG) includes: " detection of free formaldehyde and quantitative assay (Nachweis und quantitative Bestimmung des freien Formaldehyds) ") according to lutidine method (Lutidin-Method)

Equipment: the HPLC system that is furnished with two degree such as grade (isokratisch) pump, isothermal reactor, variable UV/VIS detector and analytical unit (for example Hewlett-Packard HP 1100, have the analysis software ChemStation that PC supports).

Stationary phase C18-is anti-phase, 5 μ m, 250 x 4.0mm

Moving phase ultrapure water (Milli-Q-Water)

Sample size 20 μ l

Post-column derivation methyl ethyl diketone solution

Flow 1.0ml/ minute

Detect UV-and detect wavelength 420nm

The sample preparation is dissolved in 250mg among the 3ml THF, and water is filled it up with to 25ml then

Calibration solution 100mg formaldehyde solution/100ml water

1:1000 dilutes in water

Dissecting needle is to external standard

Measure hydroxyl value

Measure the composition A of necessity of the present invention according to the guide of DIN53240-2 " measure hydroxyl value (Bestimmung der Hydroxylzahl) ") hydroxyl value.Should note: strictly observe 3 hours acetylize time.

Measure carbonyl value

In the sodium-chlor cuvette, use after the 2-ethyl cyclohexanone be dissolved among the THF calibrates, utilize the FT-IR spectroscopic analysis to measure the composition A of necessity of the present invention) carbonyl value.

Measure before the thermal load and afterwards Gardner's chromatic number (Farbzahl nach Gardner)

According to the guide of DIN ISO 4630, resin is dissolved in makes 50% solution in the ethyl acetate, measure the composition A of necessity of the present invention) Gardner's chromatic number.Equally in this way measure the composition A of necessity of the present invention) chromatic number after thermal load.For this reason at first at 150 ℃ with the 5g Resin A) in air atmosphere, deposited 24 hours.According to the guide of DIN ISO 4630, will be dissolved in through the resin that thermal load is handled and make 50% solution in the ethyl acetate then, measure Gardner's chromatic number.

Mensuration composition A) soltion viscosity

Measure soltion viscosity according to DIN EN ISO 3219.Solid resin is dissolved in (for example Phenoxyethanol) among the appropriate solvent, and solid matter content for example is 40%.Under 23 ℃ of temperature condition, utilize plate/coning to change viscometer determining viscosity (1/40s).

Measure polymolecularity

Utilizing gel permeation chromatography, is solvent with the tetrahydrofuran (THF), is standard specimen with the polystyrene, measures the composition A of necessity of the present invention) molecular weight distribution.According to the ratio calculating polymolecularity (Mw/Mn) of weight-average molecular weight (Mw) with number-average molecular weight (Mn).

Measure melting range

According to the guide of DIN 53181, use capillary melting point determination instrument (B ü chi B-545) to measure the composition A of necessity of the present invention) fusing point/melting range.

The calculating multipolymer distributes

Composition A according to calculating as described below necessity of the present invention) k, l and m value.

Calculate embodiment(having used integer) in order to explain:

R=phenyl wherein

Suppose:

Molecular weight (Mn) is 1000g/mol, and hydroxyl value is 300mg KOH/g, and carbonyl value is 10mgKOH/g.

Because of the OH value is 300mg KOH/g, drawing (300/56110 * 1000) every 1000g/mol has 5.35 oh groups.K=5.35 just.

Because of the C=O value is 10mg KOH/g, drawing (10/56110 * 1000) every 1000g/mol has 0.18 C=O group.1=0.18 just.

Calculating m:(1000g/mol-(5.35mol * 134g/mol)-(0.18mol * 132g/mol))/118g/mol=259/118=2.2

The k+m+l sum is 5.35+2.2+0.18=7.73

The analytical procedure of coating composition of the present invention

Measure yellowing resistance, light stability and thermostability

When measuring yellowing resistance, light stability and thermostability, apply coating composition, remove solvent, be placed on then and carry out weathering test under the 1200-Test xenon lamp, perhaps it was deposited 24 hours under 100 ℃ of temperature.According to DIN6174/DIN5033, use the control film and the composition A that contains necessity of the present invention of survey meter x-rite 8200 spectrophotometers (measuring parameter: D65/10 ° of tarnish/diaphragm 12.7mm/ light type), do not having the composition A of necessity of the present invention)) film between measure load before with afterwards CIE-Lab aberration.

Measure the soltion viscosity of coating

According to the soltion viscosity of DIN53211 mensuration coating, 4mm flow cup (Auslaufbecher).

Measure base material wettability and flowability (Verlauf)

The base material wettability and the flowability of coating composition determined in range estimation.If the coating composition that is applied forms the closing membrane that does not have defective (for example pit), then wettability is good.If the closing membrane that is applied has few inherent structure (for example tangerine peel excessively infiltrates among the base materials such as paper), then good fluidity.

Measure adhesive power

Before bearing load,, utilize cross cut test to check the adhesive power (DIN EN ISO2409) of coating with afterwards.

Load test/water tolerance

Hot-weather trial: under 40 ℃ and 95% air humidity conditions, place the film that is applied

Soaked: DIN EN ISO 2812-2 (40 ℃ sample board is positioned over deionized water among)

Measure glossiness/mist degree

Measure according to DIN EN ISO 2813.

Rate of drying

Coating is applied on the base material to be detected.After 5 minutes, 1 hour and 24 hours, carry out nail delineation test (referring to scratch resistance intensity).

Scratch resistance intensity (nail delineation test)

Forefinger is streaked coating, with the naked eye estimate the extent of damage of coating then.

Measure the content (nfA) of involatile constituent

With the content of involatile constituent mean value as twice mensuration.The about 2g sample of weighing (coating) on analytical balance puts it into (tare weight m among the aluminum ship after the purification ₁) (the quality m of material ₂).Then aluminum ship is put into circulated air oven, under 150 ℃ of temperature, placed 2 hours.With the aluminum ship cool to room temperature, be accurate to 0.1mg weighing (m again then ₃).Calculate involatile constituent (nfA) according to following formula:

Measure the content of free formaldehyde

Utilize HPLC to measure formaldehyde content (the research method official according to § 64LFGB K 84.007 (EG) includes: " detection of free formaldehyde and quantitative assay (Nachweis und quantitative Bestimmung des freien Formaldehyds) ") according to lutidine method (Lutidin-Method)

Stationary phase C18-is anti-phase, 5 μ m, 250 x 4.0mm

Moving phase ultrapure water (Milli-Q-Water)

Sample size 20 μ l

Post-column derivation methyl ethyl diketone solution

Flow 1.0ml/ minute

Detect UV-and detect wavelength 420nm

Calibration solution 100mg formaldehyde solution/100ml water

1:1000 dilutes in water

Dissecting needle is to external perimysium reference

Embodiment:

Non-comparative example of the present invention

It is DE 33 34 631 A1 that description of the Prior Art gets the most excellent patent documentation.Here employed methyl phenyl ketone/formaldehyde resin obtains according to DE 892 974 described embodiment 2.

Embodiment A: repeat DE 892 974 described embodiment 2

Add 240g 50% potassium hydroxide aqueous solution and 400g methyl alcohol and join after the 1200g methyl phenyl ketone, in 2 hours, 1000g 30% formaldehyde solution violent stirring is added.At this moment temperature will be elevated to 90 ℃.This temperature was kept 10 hours.Carry out acidification with sulfuric acid,, will in decompression, remove moisture after its fusion then with the condensation product that hot wash generated.

Obtain the yellow resin of 1260g.This resin is transparence and fragility is arranged, and fusing point is 67 ℃.Gardner's chromatic number is 3.8 (50% in ethyl acetate).Dissolve among the acetic ester of for example N-BUTYL ACETATE and vinyl acetic monomer and so on, dissolve among the aromatic substance of toluene and dimethylbenzene and so on.Be insoluble to ethanol.Formaldehyde content is 255ppm.

Embodiment B: repeat the described embodiment 3 of DE 33 34 631 A1

According to the described embodiment 3 of DE 33 34 631 A1,, make the resin that obtains according to embodiment A in trickle-bed reactor, carry out hydrogenation 300 bar pressures and 180 ℃.In reactor, add 100mL Harshaw-Ni-5124 catalyst (can order) by Engelhard company.Per hour 50mL 30% resin solution is added among the isopropylcarbinol, replenish the hydrogen that is consumed, make that the pressure in the reactor keeps 300 crust constant.

Embodiments of the invention

Embodiments of the invention I)

Preparation is based on the base resin that is used to proceed hydrogenation of methyl phenyl ketone and formaldehyde

Add 1200g methyl phenyl ketone, 220g methyl alcohol, 0.3g phenmethyl tributyl ammonium chloride and 360g 30% formalin, and stir.Stir then and add 32g 25% aqueous sodium hydroxide solution.Adding 655g 30% formalin then under 80～85 ℃ of temperature stirred 90 minutes.Stirred when reaching reflux temperature afterwards in 5 hours, close agitator, then water and resin are separated.Use acetic acid water washing crude product, until the clear bath sample that resin occurs.Make resin drying by distillation then.

Obtain the light yellow resin of 1270g.This resin is transparence and fragility is arranged, and fusing point is 72 ℃.Gardner's chromatic number is 0.8 (50% in ethyl acetate).Dissolve among the acetic ester of for example N-BUTYL ACETATE and vinyl acetic monomer and so on, dissolve among the aromatic substance of toluene and dimethylbenzene and so on.Be insoluble to ethanol.Formaldehyde content is 35ppm.

To according to example I) resin based on methyl phenyl ketone and formaldehyde that obtains carries out hydrogenation

Embodiments of the invention 1:

Will be according to example I) be dissolved among the 700g isopropylcarbinol after the 300g resin heating that obtains.Under 260 bar pressures and 120 ℃, in the autoclave of being furnished with the catalyzer basket (Parr company), carry out hydrogenation then, be added with type nickel catalyzator in Ruan 100mL in the catalyzer basket.After 8 hours, in reactor, emit reaction mixture by strainer.

Embodiments of the invention 2:

Will be according to example I) the 300g resin that obtains is dissolved in (water-content is about 7%) among the 700g tetrahydrofuran (THF).Under 260 bar pressures and 120 ℃ of temperature condition, in the autoclave of being furnished with the catalyzer basket (Parr company), carry out hydrogenation then, be added with the common on the market ruthenium catalyst of 100mL (3% ruthenium on aluminum oxide) in the catalyzer frame.After 20 hours, in reactor, emit reaction mixture by strainer.

Embodiments of the invention 3:

Will be according to example I) the resin heating back that obtains is dissolved among the isopropylcarbinol according to 30% ratio.In the continous way fixed-bed reactor, carry out hydrogenation, be added with the common on the market silica supported copper-chromium catalyst of 400mL in the reactor.Under 300 bar pressures and 130 ℃, per hour make the 500mL reaction mixture pass through reactor (drip mode) from top to down.Make pressure remain unchanged by hydrogen make-up.

Embodiments of the invention 4:

Will be according to example I) the resin heating back that obtains is dissolved among the isopropylcarbinol according to 30% ratio.In the continous way fixed-bed reactor, carry out hydrogenation, be added with type nickel catalyzator in common on the market Ruan of 400mL in the reactor.Under 300 bar pressures and 130 ℃ of temperature condition, per hour make the 400mL reaction mixture pass through reactor (drip mode) from top to down.Make pressure remain unchanged by hydrogen make-up.

To place decompression to remove solvent according to the resin solution that embodiment 1～4 and comparative example B obtain.The characteristic of the resin that is produced is as shown in table 1.

Table 1: the characteristic of the hydrogenated resin that obtains according to embodiment 1～4

	The comparative example	Resin 1	Resin 2	Resin 3	Resin 4
	The comparative example	Resin 1	Resin 2	Resin 3	Resin 4	Free formaldehyde content [ppm]	6.0	1.2	1.1	<1	1.3
Carbonyl value [mg KOH/g]	24.3	14.9	58	2.5	5.2	Free formaldehyde content [ppm]	6.0	1.2	1.1	<1	1.3
Carbonyl value [mg KOH/g]	24.3	14.9	58	2.5	5.2	Hydroxyl value [mg KOH/g]	210	295	315	335	317
Fusing point [℃]	92	109	114	124	118	Hydroxyl value [mg KOH/g]	210	295	315	335	317
Fusing point [℃]	92	109	114	124	118	Gardner's chromatic number (50% in ethyl acetate)	2.2	0.4	0.2	0.1	0.1
Gardner's chromatic number is (at 150 ℃ through after 24 hours thermal loads; 50% in ethyl acetate)	3.1	0.6	0.3	0.2	0.2	Gardner's chromatic number (50% in ethyl acetate)	2.2	0.4	0.2	0.1	0.1
	3.1	0.6	0.3	0.2	0.2	Viscosity (40% in Phenoxyethanol)	6800	6600	7300	8600	7900
Mn (GPC is with respect to PS)	910	980	1000	1070	1040	Viscosity (40% in Phenoxyethanol)	6800	6600	7300	8600	7900
Mn (GPC is with respect to PS)	910	980	1000	1070	1040	Mw (GPC is with respect to PS)	1570	1490	1430	1550	1530
Polymolecularity	1.73	1.52	1，43	1，45	1，47	Mw (GPC is with respect to PS)	1570	1490	1430	1550	1530
Polymolecularity	1.73	1.52	1，43	1，45	1，47	K	3.4	5.2	5.6	6.4	5.9
1	0.4	0.3	0.1	0.1	0.1	K	3.4	5.2	5.6	6.4	5.9
1	0.4	0.3	0.1	0.1	0.1	M	3.4	2.2	1.2	1.8	2.0
k+l+m	7.2	7.6	7.7	8.2	8.0	M	3.4	2.2	1.2	1.8	2.0

All resins all dissolve among the common paint solvent.With example I) difference of described base resin is that these resins dissolve among the alcohols polar solvent.For example, these resins dissolve in methylene dichloride, ethyl acetate, butylacetate, Virahol, acetone and diethyl ether.

Embodiment 1～4 described resin can be dissolved among the ethanol according to any ratio.In contrast to this, comparative example B) described resin can't be dissolved under the concentration situation of 10% solid matter (bei Konzentrationunter 10% Feststoff) among the ethanol smoothly being lower than.

Compare with non-resin of the present invention in the Embodiment B, the resin 1～4 of necessity of the present invention has formaldehyde content still less.Because carbonyl value is lower, chromatic number and all lower through the chromatic number after the thermal load.Although the fusing point of these resins exceeds 35% than the fusing point of non-resin of the present invention in the Embodiment B, the described resin of viscosity and Embodiment B is suitable.Its reason may have than higher polymolecularity by right and wrong resin of the present invention.

Application Example 1: plastic paint

Composition shown in the following table all can be processed into plastic paint.Resin (comparative example B, embodiment 2 and 3), Degalan and SER-AD stirring are dissolved among the solvent mixture.Adding after the pigment, make paint by dispersion method, add methyl iso-butyl ketone (MIBK)/propyl carbinol/isopropanol solvent mixture (2:1:1) and measure viscosity in the DIN4mm cup, is 18s at 23 ℃.

Buying source of goods example:

Test method	Blank sample V1	Comparative Example V 2	Embodiment A 1	Embodiment A 2
Test method	Blank sample V1	Comparative Example V 2	Embodiment A 1	Embodiment A 2	Free formaldehyde content [ppm]	<10	<10	<10	<10
Involatile constituent content [%]	42.2	44.1	45.6	46.0	Free formaldehyde content [ppm]	<10	<10	<10	<10
Involatile constituent content [%]	42.2	44.1	45.6	46.0	Soltion viscosity [s, DIN4mm-cup]	16	17	17	18

Base material wettability/flowability

With the film thickness of about 30 μ m with paint application on the polystyrene base material.Blank sample mobile defective.Can see tangible inherent structure (tangerine peel).Pin hole can be seen in the part.Use prescription can obtain better result as the comparative resin B of V2.Paint according to embodiment A 1 of the present invention and A2 preparation can be realized optimum fluidity and optimal wet lubricant nature.

Rate of drying

Film thickness with about 30 μ m is assessed rate of drying with paint application on the polystyrene base material.After 5 minutes, 1 hour and 24 hours, carry out nail delineation test, check then whether scuffing is arranged on the film.

Time	Blank sample V1	Comparative Example V 2	Embodiment A 1	Embodiment A 2
Time	Blank sample V1	Comparative Example V 2	Embodiment A 1	Embodiment A 2	5 minutes	5	4	2	2
1 hour	4	3	1-2	1-2	5 minutes	5	4	2	2
1 hour	4	3	1-2	1-2	24 is little	3	1-2	1	1

1 is fine, and 6 is very poor

Under the situation of not adding hydrogenation ketone-urea formaldehyde, rate of drying very poor (V1).Use the comparative resin B of prescription V2 can obtain better result; But only just can reach good adhesive power after through 24 hours, reason may be that the fusing point of V2 resin is lower.Then different therewith according to embodiment A 1 of the present invention with the paint of A2 preparation, after 5 minutes, just have fabulous value.This shows that resin of the present invention has improved rate of drying.

Measure adhesive power

Film thickness with about 30 μ m is assessed adhesive power with paint application on the polystyrene base material.After 24 hours, sheet material at standard climate, tropical climate and deposited 24 hours, is carried out cross cut test under water then, and check adhesive power.

Load type	Blank sample V1	Comparative Example V 2	Embodiment A 1	Embodiment A 2
Load type	Blank sample V1	Comparative Example V 2	Embodiment A 1	Embodiment A 2	Standard climate	5	1	0	0-1
Tropical climate	5	1-2	0	0-1	Standard climate	5	1	0	0-1
Tropical climate	5	1-2	0	0-1	Soaked	5	2	0-1	1

0 is fine, and 5 is very poor

Generally speaking, under the situation of not adding hydrogenation ketone-urea formaldehyde, adhesive power very poor all the time (V1).Use prescription can obtain reasonable result as the comparative resin B of V2.Use the paint of embodiment A 1 of the present invention and A2 preparation can obtain optimum.Therefore as seen: even the resin of necessity of the present invention under critical condition, also can improve adhesive power and water tolerance.

Measure yellowing resistance, light stability and thermostability

Film thickness with about 30 μ m is measured yellowing resistance, light stability and thermostability with paint application on the polystyrene base material.After 24 hours, sheet material is placed on carries out 24 hours weathering tests under the 1200-Test xenon lamp.Under 100 ℃ of temperature, sample was placed 24 hours, measured thermotolerance.

According to DIN 6174/DIN5033, use the control film and the composition A that contains necessity of the present invention of survey meter x-rite 8200 spectrophotometers (measuring parameter: D65/10 ° of tarnish/diaphragm 12.7mm/ light type), do not having the composition A of necessity of the present invention)) film between measure load before with afterwards CIE-Lab aberration.

Test recipe is that the comparative resin B of V2 can cause serious tone variation, and reason may be the carbonyl value height.And different therewith, then have extraordinary stability according to the paint of embodiment A 1 of the present invention and A2 preparation.

Measure glossiness/mist degree

Film thickness with about 30 μ m is measured glossiness and mist degree (Haze) with paint application on the polystyrene base material.Placement was measured after 24 hours under the standard climate condition.

	Blank sample V1	Comparative Example V 2	Embodiment A 1	Embodiment A 2
	Blank sample V1	Comparative Example V 2	Embodiment A 1	Embodiment A 2	20°	72	83	93	92
60°	87	92	96	97	20°	72	83	93	92
60°	87	92	96	97	Mist degree	34	29	8	13

Under the situation of not using hydrogenation ketone-urea formaldehyde (V1), glossiness is low relatively, and the mist degree height.Reason may be to lack hardened resin to cause wet pigments/bad stability.Use prescription can obtain reasonable result as the comparative resin B of V2.But at this moment mist degree is high equally.Use the paint of embodiment A 1 of the present invention and A2 can obtain optimum.This shows that the resin of necessity of the present invention can improve glossiness and mist degree.

Application Example 2: timber lacquer (Holzlack)

Composition shown in the following table all is processed into the timber lacquer.Resin (according to comparative example B, embodiment 2 and 3) and the stirring of other composition are dissolved among the solvent mixture.

Buying source of goods example:

Test method	Blank sample V3	Comparative Example V 4	Embodiment A 3	Embodiment A 4
Test method	Blank sample V3	Comparative Example V 4	Embodiment A 3	Embodiment A 4	Free formaldehyde content [ppm]	<10	<10	<10	<10
Involatile constituent content [%]	234	298	30.1	30.3	Free formaldehyde content [ppm]	<10	<10	<10	<10

Base material wettability/flowability

With the film thickness of about 50 μ m with paint application on pine.Under the situation of the paint of blank sample V3, paint is strong to infiltrate among the base material (do not have sag resistance (

)).The paint that adds the hydrogenation ketone resin can reach best finish paint visual appearance and optimal wet lubricant nature.

Measure glossiness/mist degree

Film thickness with about 50 μ m is measured glossiness with paint application on pine.Placement was measured after 24 hours under the standard climate condition.

	Blank sample V3	Comparative Example V 4	Embodiment A 3	Embodiment A 4
	Blank sample V3	Comparative Example V 4	Embodiment A 3	Embodiment A 4	20°	15	48	65	61
60°	35	65	78	81	20°	15	48	65	61

Under the situation of not adding hydrogenation ketone-urea formaldehyde (V3), glossiness is smaller.Use prescription can obtain reasonable result as the comparative resin B of V4.Use the paint of embodiment A 3 of the present invention and A4 can obtain optimum.This shows that the resin of necessity of the present invention can improve glossiness.

Application Example 3: ultraviolet light polymerization lacquer

Listed composition stirring and processing in the table is become the ultraviolet light polymerization lacquer.

Measure adhesive power

Use 50 μ m scraper plates with corresponding paint application on polyester sheet.Use the adhesive power of cross-hatching inspection paint then.

Blank sample V5	Comparative Example V 6	Embodiment A 5	Embodiment A 6
Blank sample V5	Comparative Example V 6	Embodiment A 5	Embodiment A 6	3-4	2-3	1	1

0 is fine, and 5 is very poor

Under the situation of not adding hydrogenation ketone-urea formaldehyde, adhesive power is not optimum (V5).Use prescription can obtain better result as the comparative resin B of V6.Use the paint of embodiment A 5 of the present invention and A6 preparation can obtain optimum.Therefore as seen: the resin of necessity of the present invention also can improve the adhesive power of ultraviolet light polymerization lacquer.

Claims

1. free formaldehyde content is lower than the coating composition of 100ppm,

Comprise necessarily:

A) weight percent is at least a carbonyl hydrogenated ketone-urea formaldehyde based on formaldehyde of 5～75%, and the content of free formaldehyde is lower than 3ppm, and this resin comprises the structure unit shown in the formula I necessarily

Wherein

R′＝H，CH ₂OH，

K=2～15, preferred 3～12, be preferably 4～12 especially;

M=0～13 are preferably 0～9,

1＝0～2，

Wherein the k+1+m sum is 5～15, and k〉m, be preferably 5～12, these three kinds of structure units can be alternately distributed or stochastic distribution; And wherein these structure units can pass through CH ₂The group straight chain connects, and perhaps connects by the CH group branched chain.

With

B) weight percent is 20～90% at least a tackiness agent,

With

C) weight percent is 0～50% at least a tinting material and/or filler

With

D) weight percent is 5～75% at least a additive, and composition A)～D) weight data sum is 100 weight %.

2. coating composition according to claim 1 is characterized in that, carbonyl hydrogenated ketone-urea formaldehyde A) comprise the structure unit of formula I necessarily

Wherein

R′＝H，CH ₂OH，

K=2～15 are preferably 3～12, are preferably 4～12 especially,

M=0～13 are preferably 0～9,

1＝0～2，

The k+1+m sum is 5～15, and k〉m, be preferably 5～12, these three kinds of structure units can be alternately distributed or stochastic distribution; And these structure units can pass through CH ₂The group straight chain connects, and/or connects by the CH group branched chain,

Obtain in the following way:

I. under the condition that has at least a kind of basic catalyst and optionally at least a phase-transfer catalyst to exist, do not use solvent or use can with water blended organic solvent, make at least a ketone and at least a aldehyde carry out condensation reaction, thereby prepare base resin

Then

II. under the condition that catalyzer exists, in the solution of melt or appropriate solvent, make the carbonyl of ketone-urea formaldehyde (A) and hydrogen carry out continuous, semicontinuous or discontinuous hydrogenation; Pressure is 50～350 crust, is preferably 100～300 crust, is preferably 150～300 crust especially; And temperature is 40～140 ℃, is preferably 50～140 ℃.

3. coating composition according to claim 1 and 2, wherein carbonyl hydrogenated ketone resin has following feature

Hydroxyl value is 50～450mg KOH/g, is preferably 150～400mg KOH/g, is preferably 200～375mg KOH/g especially,

Gardner's chromatic number (in ethyl acetate 50%) is lower than 1.5, preferably is lower than 1.0, especially preferably is lower than 0.75,

Under 40% concentration, soltion viscosity is 5000～12000mPa-s, is preferably 6000～10000mPa-s especially in Phenoxyethanol,

4. at least one described coating composition in requiring according to aforesaid right is characterized in that, is used for preparing ketone-urea formaldehyde A) Alpha-Methyl ketone in the α '-position that connects carbonyl, do not have response capacity, very low reactivity is perhaps only arranged in α '-position.

5. at least one described coating composition in requiring according to aforesaid right, it is characterized in that, be used alone or as a mixture methyl phenyl ketone, acetophenone derivs, alkyl substituted benzene ethanone derivatives, methoxyacetophenone, 3 that 1～8 carbon atom is for example arranged on hydroxy acetophenone, the phenyl ring, 3-dimethyl-2-butanone, methyl iso-butyl ketone (MIBK) or Propiophenone, as being used to prepare ketone-urea formaldehyde A) precursor compound, be 70～100mol-% with respect to the molar percentage quantity of ketone composition.

6. at least one described coating composition in requiring according to aforesaid right, it is characterized in that, be used alone or as a mixture C-H acid ketone as being used to prepare ketone-urea formaldehyde A) precursor compound, with respect to the molar percentage quantity of ketone composition 30mol-% at the most, preferred 15mol-% at the most, described C-H acid ketone is selected from acetone, methyl ethyl ketone, 2-heptanone, propione, cyclopentanone, cyclododecanone, 2,2,4-and 2,4, the mixture of 4-trimethylammonium cyclopentanone, suberone, cyclooctanone, pimelinketone, contain one or more total carbon numbers of hydrogen atoms and be all alkyl substituted cyclohexanones of 1～8 alkyl.

7. at least one described coating composition in requiring according to aforesaid right, it is characterized in that, use C-H acid ketone as being used to prepare ketone-urea formaldehyde A) precursor compound, molar percentage quantity with respect to the ketone composition is at most 30mol-%, preferably be at most 15mol-%, described C-H acid ketone is selected from pimelinketone, methyl ethyl ketone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone and/or 3,3,5-trimethylcyclohexanone.

8. at least one described coating composition in requiring according to aforesaid right is characterized in that, the compound that uses formaldehyde and/or formaldehyde is provided is as being used to prepare aldehyde-ketone resin A) precursor compound.

9. at least one described coating composition in requiring according to aforesaid right is characterized in that, uses formaldehyde and/or paraformaldehyde and/or trioxane as being used to prepare aldehyde-ketone resin A) precursor compound.

10. at least one described coating composition in requiring according to aforesaid right, it is characterized in that, except formaldehyde, also can use separately or mix and use the aldehyde be selected from acetaldehyde, butyraldehyde-n, isobutyric aldehyde, valeral, lauric aldehyde as being used to prepare ketone-urea formaldehyde A) precursor compound, with respect to the molar percentage quantity of aldehyde composition 75mol-% at the most, preferred 50mol% at the most, especially preferably 25mol-% at the most.

11. according at least one described coating composition in the aforesaid right requirement, it is characterized in that, be used alone or as a mixture methyl phenyl ketone, 3.3-dimethyl-2-butanone and/or methyl iso-butyl ketone (MIBK) and optionally be selected from pimelinketone, methyl ethyl ketone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone and 3,3, the CH of 5-trimethylcyclohexanone acid ketone is used to prepare ketone-urea formaldehyde A with the formaldehyde conduct) precursor compound.

12., it is characterized in that the mol ratio between ketone and the aldehyde composition is 1:0.25 to 1:15, is preferably 1:0.9 to 1:5, and is preferably 1:0.95 to 1:4 especially according at least one described coating composition in the aforesaid right requirement.

13. according at least one described coating composition in the aforesaid right requirement, it is characterized in that, contain separately or the following tackiness agent B of mixed form): urethane, the polypropylene ester, polyethers, saturated and/or undersaturated polyester and copolyesters, Synolac, polymeric amide, casein, polyureas, derivatived cellulose, polyvinyl alcohol and derivative, polyvinyl acetate (PVA), polyvinylpyrrolidone, (cyclisation) rubber, natural resin, hydrocarbon resin, terpine resin, maleic ester resin, phenol resins, resol, urea-formaldehyde resin, ketone-urea formaldehyde, ketone resin, aminoplastics, polyolefine, the acrylated polyester, the acrylated polyethers, acrylated Resins, epoxy, urethane acrylate, Resins, epoxy, resole, Gum Rosin, resinate/ester, silicon ester and alkalimetal silicate, silicone resin, fluoropolymer, chlorinated rubber, chlorinated polyester, PVDF.

14. according at least one described coating composition in the aforesaid right requirement, it is characterized in that, the following material that contains independent or mixed form is as tackiness agent B): urethane, the polypropylene ester, polyethers, saturated and/or undersaturated polyester and copolyesters, Synolac, polyureas, derivatived cellulose, nitrocellulose for example, ether of cellulose and/or acetobutyric acid Mierocrystalline cellulose, polyvinyl alcohol and derivative, polyvinyl acetate (PVA), polyvinylpyrrolidone, natural resin, hydrocarbon resin, coumarone resin for example, indene resin, cyclopentadiene resin, terpine resin, maleic ester resin, phenol resins, resol, urea-formaldehyde resin, ketone-urea formaldehyde, ketone resin, aminoplastics is melamine resin for example, benzoguanamine resin, resole, Gum Rosin, resinate/ester.

15. according at least one described coating composition in the aforesaid right requirement, it is characterized in that, contain separately or the following mineral dye of mixed form and filler as composition C): milori blue, titanium dioxide, ferric oxide, metallic pigment, pigment carbon black, carbonate, vitriol, silicate, pyrophyllite, chlorite, mica, kaolin, slate flour, feldspar, sedimentary Calucium Silicate powder, pure aluminium silicate, Calucium Silicate powder/aluminium, water glass/aluminium, silica, diatomite, precipitated silica or fumed silica, glass powder, oxide compound.

16. according at least one described coating composition in the aforesaid right requirement, it is characterized in that, contain separately or the following pigment dyestuff of mixed form as composition C): for example isoindoline pigment, azo pigment, quinacridone pigment, perylene dye, triazine dioxin pigment, phthalocyanine pigment.

17. according at least one described coating composition in the aforesaid right requirement, it is characterized in that, contain separately or the inhibitor of mixed form, organic solvent, water, surfactant, oxygen and/or free-radical scavengers, catalyzer, photostabilizer, the color brightener, photosensitizers and light trigger, be used to influence the additive of rheological characteristics, flowing agent, anti, defoamer, degasifier, static inhibitor, lubricant, wetting agent and dispersion agent, linking agent, sanitas, mycocide, biocide, thermoplastic additive, softening agent, matting agent, fire retardant, internal mold release or whipping agent are as components D).

18. at least one described coating composition in requiring according to aforesaid right is characterized in that, contain separately or the alcohol of form of mixtures, acetic ester, ketone, ether, glycol ethers, aliphatic cpd, aromatic substance as components D) organic solvent.

19. according at least one described coating composition in the aforesaid right requirement, it is characterized in that, also make composition A) react with vulcabond and/or polyisocyanates.

20. coating composition according to claim 19, it is characterized in that, use following material to come prepared composition A as vulcabond and/or polyisocyanates): separately or the cyclohexyl diisocyanate of form of mixtures, methylcyclohexane diisocyanate, the ethylcyclohexane vulcabond, phenylene diisocyanate, the propyl cyclohexane vulcabond, methyl diethyl cyclohexane vulcabond, tolylene diisocyanate, two (isocyanato-phenyl) methane, the propane vulcabond, the butane vulcabond, the pentane vulcabond, hexane diisocyanate, hexamethylene diisocyanate (HDI) or 1 for example, 5-two isocyanato-s-2-methylpentane (MPDI), the heptane vulcabond, the octane vulcabond, the 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, 4-isocyanato-methyl isophthalic acid for example, 8-octane vulcabond (TIN), decane vulcabond and triisocyanate, undecane vulcabond and triisocyanate, dodecane vulcabond and triisocyanate, isophorone diisocyanate (IPDI), separately or form of mixtures 2,2 '-and 2,4 '-and 4.4 '-dicyclohexyl methane diisocyanate (H ₁₂MDI), H ₁₂MDI preferably contains 4,4 of at least 80 weight % '-H ₁₂MDI, more preferably 85-95 weight %; 2,5 (2,6)-two (isocyanato-methyl), two ring [2.2.1] heptane (NBDI), 1, and two (isocyanato-methyl) hexanaphthenes of 3-(1,3-H ₆-XDI) or 1, and two (isocyanato-methyl) hexanaphthenes of 4-(1,4-H ₆-XDI).

21. coating composition according to claim 19, it is characterized in that, use dimerization, trimerizing, allophanic acid esterification, polyisocyanates biuretized and/or that urethane obtains to come prepared composition A) by simple vulcabond with independent or form of mixtures.

22. coating composition according to claim 19 is characterized in that, uses based on IPDI, TMDI, H with independent or form of mixtures ₁₂The isocyanic ester of MDI and/or HDI comes prepared composition A).

23. coating composition according to claim 19 is characterized in that, uses vulcabond IPDI, HDI and/or H with independent or form of mixtures ₁₂The isocyanuric acid ester of MDI comes prepared composition A).

24. coating composition according to claim 19 is characterized in that, uses IPDI, TMDI, HDI and/or H with independent or form of mixtures ₁₂The reaction product of MDI and TriMethylolPropane(TMP) and/or tetramethylolmethane is come prepared composition A).

25. be used for preparation method, undertaken by under 20～80 ℃ of temperature condition, making described composition thorough mixing according at least one described coating composition of aforesaid right requirement.

26. at least one described coating composition is used for for example pottery of metallizing, plastics, paper, laminated paper, strawboard, cardboard, inorganic materials in the claim 1～25, stone material, concrete, gypsum, glass, fabric, fiber, weaving material, leather, synthetic materials be the purposes of leatheroid, timber, plastics film or matrix material for example.

27. the described coating composition of at least one item is as the purposes of building protection colorant/paint, road mark paint, automobile finish (OEM, renovation), coil coating, can lacquer, textile finishing, timber lacquer, plastic paint in the aforesaid right requirement 1～25.

28. aforesaid right requires in 1～25 at least one described coating composition be used to the to bond purposes of fabric, leather, paper, plastics, metal.

29. utilize at least one goods that described coating composition applies in the claim 1～25.