CN106916503A

CN106916503A - A kind of single component varnish composition, preparation method and its usage

Info

Publication number: CN106916503A
Application number: CN201710226719.0A
Authority: CN
Inventors: 张萌; 夏天渊; 果建军; 梅鹏; 张景斌
Original assignee: NIPPON PAINT (GUANGZHOU) CO Ltd; Langfang Nippon Paint Co Ltd; Nippon Paint China Co Ltd
Current assignee: NIPPON PAINT (GUANGZHOU) CO Ltd; Langfang Nippon Paint Co Ltd; Nippon Paint China Co Ltd
Priority date: 2017-04-09
Filing date: 2017-04-09
Publication date: 2017-07-04
Anticipated expiration: 2037-04-09
Also published as: CN106916503B

Abstract

It is the invention discloses a kind of single component varnish composition including at least one with hyperbranched or tree polymer；At least one Hydroxylated acrylic resin or hydroxy resin；At least one organosilicon modified crylic acid resin；At least one crosslinking and curing agent；At least one acid catalyst；At least one rheology control agent；At least one auxiliary agent, and at least one solvent；The single component varnish composition is the single component varnish composition of scratch-resistant high and high durable.Scratch-resistant high and the single component varnish composition of high durable that the present invention is provided, can effectively improve the slipping of clear coat composition film coated surface, so as to increase the rub resistance of film；Additionally, the introducing of organosilicon modified crylic acid resin can further improve the weatherability of clear coat composition film.

Description

A kind of single component varnish composition, preparation method and its usage

Technical field

The invention belongs to technical field of paint preparation, it is related to clear coat composition, preparation method and its usage, more particularly to one Single component varnish composition of scratch-resistant kind high and high durable and preparation method thereof, and the scratch-resistant high and high durable list Component varnish composition is coated on ground according to different construction and forms solidify coating or prepare multicoat Finish Application process.

Background technology

At present, automobile is gradually deep into huge numbers of families as the daily most common walking-replacing tool of people.With People are continuously increased to automobile demand amount, and the thing followed is also being improved constantly for the requirement of automobile appearance and performance.Vapour Car vehicle body can assign vehicle body excellent outward appearance by spray car coating, it is also possible to improve the properties of body of a motor car.Day Often in life, automobile is often placed on outdoor and carries out exposure by car owner, or automobile is delivered into cleaning shop is scrubbed, and this will Seeking the coating for being coated in body of a motor car surface can have excellent a weatherability and rub resistance, usual these performances be mainly by What car paint film most external protected decorative coveringn to determine.It is applied on finish paint and forms the varnish system of most external protection decorative coveringn Referred to as coating varnish, is characterized in that lightness is high, gloss is high, adhesive force good, hardness is high and richness is good, while also having excellent The performance such as water-fast, resistance to gasoline, chemicals-resistant, wear-resisting and weather-proof, thus be widely used in medium-to-high grade automobile, palace car and The top finishing of the advanced vehicles such as station wagon.

Organosilicon is that a class is main chain with the Si-O-Si keys for repeating, and the polymer of organic group is directly connected on silicon atom, It is difficult to be decomposed by ultraviolet light and ozone so that organosilicon has preferably resistance to irradiation and weather-proof energy than other macromolecular materials Power；On the other hand, the main chain of organosilicon is very submissive, and intermolecular force ratio hydrocarbon wants much weaker so that have The features such as machine silicon has weak surface tension, surface energy small and strong film forming ability, therefore when organosilicon modified crylic acid resin addition After in paint film, can assign paint film good scratch resistance and stain resistance, while so that there is paint film good feel to slide May just as well.

World patent WO0198393 discloses a kind of preparation method of double-component clear coat composition.The clear coat composition by Base-material containing polyhydric alcohol polymer and containing part isocyanate groups by alkoxysilane-modified polyisocyanate curing agent Composition, its colored paint/varnish system that can be used in car paint as original factory of vehicle finishing varnish and repairing finishing varnish, but the patent In weatherability and rub resistance not with regard to the clear coat composition optimize explanation.

European patent EP 994117 discloses a kind of composition that can be solidified by moisture.Said composition is by containing more The base-material of first alkoxide polymer and contain the modified PIC solidification of part isocyanate groups coverlet alkoxysilane group amine Agent is constituted.The coating prepared using said composition has special hardness of paint film, but for weathering stability and rub resistance, Also there is limitation in the application that automobile covers with paint, lacquer, colour wash, etc. field in said composition.

The one kind that United States Patent (USP) US20060217472 discloses contains hydroxy acrylic acid, low molecular weight polyols component, gathers different The coating composition of cyanate and amine alkoxysilanes components.The coating composition can be used for colored paint/varnish as automobile varnish System, assigns varnish coat rub resistance, but the storage stability of the coating composition is bad, particularly in dry and wet alternation ring Under border, there is poor weathering stability for UV ray.

World patent WO2006042585 discloses a kind of clear coat composition covered with paint, lacquer, colour wash, etc. suitable for automobile.The clear coat composition Main base component in contain silane-modified PIC, more than 90% isocyanates wherein in the PIC Group is reacted with bis-alkoxy silicon substrate amine.The clear coat composition has excellent rub resistance and chemically-resistant high and resistance to concurrently Hou Xing, but the clear coat composition still needs to further improve and lifted its weathering stability, especially under dry and wet alternation environment, For the weathering stability of UV ray.

European patent EP 1273640 discloses a kind of double-component clear coat composition covered with paint, lacquer, colour wash, etc. suitable for automobile.Said composition Constituted by polyhydric alcohol polymer component and by the curing agent component that aliphatic and/or alicyclic polymeric isocyanate are constituted, wherein：Should 0.1%~95% isocyanate groups are reacted with bis-alkoxy silicon substrate amine in curing agent component.But the varnish is combined When thing is covered with paint, lacquer, colour wash, etc. for automobile, the film fully after solidification has good rub resistance concurrently under extraneous ambient influnence.However, this is clear Coating compositions have very strong post-crosslinking trend, and the trend can be negatively affected to weathering stability.

United States Patent (USP) US8569438 discloses a kind of with high friction resistance and weathering stability clear coat composition.This is clear Component A of the coating compositions by hydroxyl, the B component containing NCO and can be used for be catalyzed silane group be crosslinked it is phosphorous Catalytic component constitute.

It is analyzed by above-mentioned document, is referred to organosilicon for improving clear coat composition film rub resistance, And it is used to improve the alkyl silane containing response type group of the silicone ingredients mainly small molecule of film performance.By in silane Contained response type group, for example：Amino and hydroxyl, are reacted so as to obtain partially enclosed or all closings with isocyanates Silane-modified isocyanates, and the isocyanates is used to as curing agent component to prepare double-component varnish or single group is distinguished Paint；Be hydrolyzed the poly-organosilicon structure being cross-linked to form containing Si-O-Si repeat units using the Si-O-R groups in silane, from And improve the rub resistance of paint film.But, while improving rub resistance using silane, the negative shadow of correlation is also brought to paint film Ring.Si-O-R groups can also be hydrolyzed and reacted with the hydroxyl in resin, and this is conducive to increasing crosslink density raising rub resistance Property, but newly-generated Si-O-C groups are easily hydrolyzed, therefore under wet heat condition, with poor weathering stability.

In view of this, it is necessary to which a kind of scratch-resistant high with good rub resistance and weathering stability and Gao Nai are provided The single component varnish composition of time.

The content of the invention

For defect present in above-mentioned prior art, it is an object of the invention to provide a kind of with good rub resistance With scratch-resistant weathering stability, high and the single component varnish composition of high durable.

It is a further object to provide the single component varnish composition of a kind of scratch-resistant high and high durable Preparation method, particular by specific preparation method, by with hyperbranched or tree polymer, hydroxy acrylic acid, Organosilicon modified crylic acid resin, crosslinking agent, rheology control agent and other components are prepared into the described of scratch-resistant high and high durable The preparation method of single component varnish composition.

A further object of the present invention is to provide a kind of single component varnish using scratch-resistant high and high durable and combines , specifically according to different construction be coated in the single component varnish composition of scratch-resistant high and high durable by the purposes of thing On ground, form cured varnish coating and prepare the application process of multicoat Finish.

To achieve these goals, the technical solution adopted by the present invention is as follows：

One aspect of the present invention provides the single component varnish composition of a kind of scratch-resistant high and high durable, including：

It is at least one with hyperbranched or tree polymer；

At least one Hydroxylated acrylic resin or hydroxy resin；

At least one organosilicon modified crylic acid resin；

At least one crosslinking and curing agent；

At least one acid catalyst；

At least one rheology control agent；

At least one auxiliary agent,

And

At least one solvent.

Preferably, one aspect of the present invention provides the single component varnish composition of a kind of scratch-resistant high and high durable, Component including following weight portion：

Preferably, described is a kind of with hyperbranched or tree height with hyperbranched or tree polymer Molecule polyester, average described each high molecular polymer chain contains 8~80 oh groups, its hydroxyl value between 150~ Between 600mgKOH/g, glass transition temperature (Tg) is between -25 DEG C to+30 DEG C.For the present invention, it is described with over-expense Change or the polymer of tree may be selected from Singapore Science and Technology Ltd. and NIPPON PAINT immediatelyBB600 resins,BB900 resins andBB400 resins；Wherein, Containing admittedly for BB600 resins is 61~63%, and acid number is 5~6mgKOH/g, and solid hydroxyl value is 209mgKOH/g； Containing admittedly for BB900 resins is 54~58%, and acid number is 2~8mgKOH/g, and solid hydroxyl value is 279mgKOH/g； Containing admittedly for BB400 resins is 65~68%, and acid number is 3~6mgKOH/g, and solid hydroxyl value is 280mgKOH/g.

The hydroxyl with hyperbranched or tree polymer is optionally by epoxide group and closing fat The modified substitution of fat race isocyanate groups, becomes epoxide modified Hyperbranched Polyester Resin, blocked isocyanate modified ultra-branching Polyester resin；And the number of the functional groups after the substitution that is modified, that is, the number of the hydroxyl being substituted, account for former hyperbranched or tree The 1%~50% of hydroxy number in the polymer of shape structure.

The epoxide modified Hyperbranched Polyester Resin is carried out by raw material of hyperbranched hydroxyl polyester, acid anhydrides and epoxy resin Prepare, with following structural：

In formula, m and n is positive integer, m+n≤80；Wherein,It is the skeleton of hyperbranched hydroxyl polyester, the skeleton knot Structure has been described in the prior art document【Specifically see：《Aliphatic hyper-branched polyester based on 2,2- dihydromethyl propionic acids Structure, solution and overall performance determine》,《Polymer science is in progress》36 phases, P in 2011st_53~88；And《Hyperbranched copolymerization Thing micelle is used as the adriamycin carrier in breast cancer cell》,《Polymer science magazine：Polymer chemistry》, the 2012nd the 50th Phase, P_280~288.(Aliphatic hyperbranched polyesters based on 2,2-bis (methylol) Propionic acid-Determination of structure, solution and bulk properties " .Progress in Polymer Science,2011,36：53~88. " Hyperbranched copolymer micelles as delivery vehicles of doxorubicin in breast cancer cells"Journal of Polymer Science Part A:Polymer Chemistry,2012,50：280~288)】, will not be repeated here；R₁It is anhydride molecule Remaining alkyl group after middle removing anhydride group, wherein, acid anhydrides is hexahydrophthalic anhydride, methylhexahydrophthaacid acid Acid anhydride, tetrabydrophthalic anhydride, methyl tetrahydro phthalic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, At least one in adipic anhydride, dodecenylsuccinic acid acid anhydride, trimellitic anhydride；R₂To remove epoxy radicals in epoxy molecule Remaining alkyl group after group, wherein, epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy Resin, bisphenol-A D-ring oxygen tree fat, ethylene glycol diglycidylether, diethylene glycol diglycidyl ether, three contracting diethyls two Alcohol diglycidyl ether, polyethyleneglycol diglycidylether, 1,2- propylene glycol diglycidylethers, polypropylene glycol diglycidyl Ether, 1,4- butanediol diglycidyl ethers, 1,6 hexanediol diglycidyl ethers, neopentylglycol diglycidyl ether, O-phthalic Sour 2-glycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, tetrahydrophthalic acid two At least one in ethylene oxidic ester.

The blocked isocyanate modified ultra-branching polyester resin is with hyperbranched hydroxyl polyester, isocyanates and sealer For raw material is prepared, with following structural：

In formula, x and y is positive integer, total functional group's number of 2≤x+y≤hyperbranched hydroxyl polyester；For hyperbranched The skeleton of hydroxyl polyester, R₃It is remaining alkyl group after removing isocyanate groups in isocyanate molecule, wherein, isocyanic acid Ester is toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, polymethylene polyphenyl diisocyanate, the isocyanide of hexa-methylene two Acid esters, XDI, IPDI, dicyclohexyl methyl hydride isocyanates, trimethyl six are sub- At least one in methyl diisocyanate, HTDI；R₄To be remained after active hydrogen is removed in capping reagent molecule Remaining alkyl group, wherein：Sealer be methyl alcohol, ethanol, propyl alcohol, butanol, hexanol, octanol, phenmethylol, glycol monoethyl ether, Ethylene glycol monobutyl ether, ethylene glycol monohexylether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol list Butyl ether, diethylene glycol monomethyl ether, methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, diisopropylamine, 3,5- dimethyl pyrazoles, the tertiary fourths of N- At least one in base benzylamine, caprolactam, dimethyl malenate, diethyl malonate.

When the usage amount with hyperbranched or tree polymer is 1~20 part, preferably 3~10 parts.Work as tool Have hyperbranched or tree polymer addition be less than 1 part when, system viscosity reduction, cure response, film crosslink density and Reduction film shrinkage factor does not reach level ideally；And when the addition with hyperbranched or tree polymer During more than 20 parts, the functional group of remained unreacted can weaken coating dry film toughness and chemical resistance in system.

The hydroxyl value of the Hydroxylated acrylic resin or hydroxy resin between 110~250mg KOH/g, Between -10 DEG C to+35 DEG C, between 2000~4000, solid content is more than number-average molecular weight glass transition temperature (Tg) Equal to 80%.For the present invention, Hydroxylated acrylic resin or hydroxy resin are with acrylate and/or methyl The derivative of acrylate monomer, the derivative of the acrylate of hydroxyl and/or methacrylate monomers, carboxylic third The derivative and carbon-carbon double bonds of olefin(e) acid and/or methacrylic acid and the monomer of copolyreaction can be carried out for raw material, triggered Obtained by radical polymerization under agent effect.

The structure of the organosilicon modified crylic acid resin is as shown in formula I：

Wherein：

In formula I：

R₁Selected from containing 1~20 aliphatic of carbon atom, alicyclic, aromatic alkyl, alkoxy, acyloxy, hydroxyl alkane Base, hydroxyl alkylidene；

R₂、R₃、R₄、R₅Be each independently selected from hydrogen atom, containing 1~20 aliphatic of carbon atom, alicyclic, aromatic series Alkyl, hydroxyalkyl, hydroxyl alkylidene；

R₆Structure be selected from Formula II in one kind：

CH₂CH₂CH₂OH CH₂CH₂CH₂CH2OH CH₂CH₂CH₂CH₂CH₂OH

CH₂CH₂CH₂CH₂CH₂CH₂OH CH₂CH₂CH₂OCH₂CH(OH)CH₂OCH₃

(II)；

R₇Structure be selected from formula III in one kind：

CH₃CH₂CH₂CH₂ CH₃CH(CH₃)CH₂ (CH₃)₃C (CH₃)₃SiO

(III)；

m>0, n>0, o>0, p>0, q>0, x>0, y>0.

Signified alkyl includes straight or branched alkyl in formula I.Aliphatic, alicyclic, aromatic series in following mutual-through type I Alkyl, alkoxy, acyloxy, hydroxyalkyl, hydroxyl alkylidene be illustrated：Alkyl is that ethyl belongs to aliphatic alkyl；Alkane Base is that phenyl belongs to aromatic alkyl；Alkyl is that cyclohexyl belongs to alicyclic alkyl group.Similarly, alkoxy is that ethyoxyl belongs to fat Fat race alkoxy；Alkoxy is that phenoxy group belongs to aromatic series alkoxy；Alkoxy is that hexamethylene alkoxy belongs to alicyclic alkoxy.

The hydroxyl value of the organosilicon modified crylic acid resin is between 50~250mgKOH/g；Acid number is between 0~20mg Between KOH/g；Glass transition temperature (Tg) is between -30 DEG C to+50 DEG C；Number-average molecular weight between 500~20000, It is preferred that 1500~5000；Solid content between 70%~100%, preferably 75%~90%；Type B rotary viscosity between 0.5~ Between 200Pas (25 DEG C), preferably 2~25Pas.

The organosilicon modified crylic acid resin includes the component of following weight portion：

The solvent be selected from aliphatic ester, unary alcohol, ketone, di-alcohols, dihydroxylic alcohols ethers, dihydroxylic alcohols esters, At least one in aromatic series carbon varsol, including but not limited to following compound known to those skilled in the art：Toluene, Dimethylbenzene, S-100# solvent naphthas, trimethylbenzene solvent naphtha, S-150# solvent naphthas, durol solvent naphtha, butanone, methyl-isobutyl Ketone, cyclohexanone, ethyl acetate, butyl acetate, butyl glycol ether acetic acid esters, pentyl acetate, ethylene glycol ethyl ether propionic ester, ethylene glycol Butyl ether, ethylene glycol, normal propyl alcohol, isopropanol, n-butanol, propylene glycol methyl ether acetate.

The carbon-carbon double bonds and the monomer of copolyreaction can be carried out include but is not limited to following those skilled in the art institute The compound known：Styrene, methyl-prop ethene, allyl alcohol, tertiary ethylene carbonate, monomethyl maleate, ethyl maleate, horse Come sour single n-propyl, maleic acid list isopropyl ester, maleic acid list N-butyl, the secondary butyl ester of maleic acid list, the maleic acid list tert-butyl ester, Malaysia Sour list pentyl ester, the own ester of maleic acid list, maleic acid list Octyl Nitrite, the double methyl esters of maleic acid, the double ethyl esters of maleic acid, maleic acid double positive third The double N-butyls of the double isopropyl esters of ester, maleic acid, maleic acid, the double secondary butyl esters of maleic acid, the double tert-butyl esters of maleic acid, the double pentyl esters of maleic acid, The double own esters of maleic acid, the double Octyl Nitrites of maleic acid.

The derivative of the acrylate and/or methacrylate monomers is selected from alkyl acrylate, methacrylic acid At least one in Arrcostab, acrylate base ester, cycloalkyl methacrylate, including but not limited to following this area skill Compound known to art personnel：Methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, acrylic acid The positive fourth of propyl ester, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methacrylic acid Ester, isobutyl acrylate, Isobutyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate, amyl acrylate, first Base amyl acrylate, Hexyl 2-propenoate, hexyl methacrylate, EHA, ethylhexyl methacrylate, propylene The sour own ester of 3,3,5- trimethyls, the own ester of methacrylic acid 3,3,5- trimethyls, octadecyl acrylate, methacrylic acid 18 Arrcostab, dodecylacrylate, lauryl methacrylate, acrylic acid cyclopentyl ester, methacrylic acid cyclopenta Ester, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid shrink Glyceride, GMA.

The acrylate of the hydroxyl and/or the derivative of methacrylate monomers be selected from acrylic acid hydroxy alkyl ester, At least one in hydroxyalkyl methacrylate, including but not limited to following compound known to those skilled in the art：Third Olefin(e) acid 2- hydroxyethyl esters, HEMA, acrylic acid 2- hydroxypropyl esters, methacrylic acid 2- hydroxypropyl esters, third Olefin(e) acid 3- hydroxypropyl esters, methacrylic acid 3- hydroxypropyl esters, acrylic acid 3- hydroxyls butyl ester, methacrylic acid 3- hydroxyls butyl ester, third Olefin(e) acid 4- hydroxyls butyl ester, methacrylic acid 4- hydroxyls butyl ester, acrylic acid and tertiary carbonic acid glycidyl ester condensation product, metering system Acid and tertiary carbonic acid glycidyl ester condensation product.

The derivative of the carboxylic acrylic acid and/or methacrylic acid is selected from acrylic acid and/or methacrylic acid.

The initiator is selected from least one in azo-initiator or peroxide initiator, including but not limited to following Compound known to those skilled in the art：Azodiisobutyronitrile, ABVN, benzoyl peroxide, peroxidating 2- second Base double (t-amyl peroxy) the ring group alkane of tert-butyl acrylate, peroxidating 2- ethyl acids tert-pentyl ester, 1,1-, the double (tertiary pentyls of 1,1- Peroxide) -3,3,5- trimethyls thiacyclohexane, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxidating acetic acid uncle penta Ester, peroxidating 3,5, double (t-butyl peroxy) ethyl butyrates of tert-butyl acrylate, 3,3-, 3,3- are double (t-amyl peroxy) for-trimethyl Ethyl butyrate, cumyl peroxide, t-amyl peroxy hydrogen, TBHP, di-t-butyl peroxide, peroxidating two Tertiary pentyl.

The preparation method of the silicone macromolecule monomer is comprised the following steps：

1) HMDS is added drop-wise in unsaturated monohydric alcohol A, system is warming up to 90~120 DEG C, and herein At a temperature of continue react 4~8h, trimethylsiloxy group unsaturated compound B is obtained by hydroxyl protection；

2) toward catalyst is added in trimethylsiloxy group unsaturated compound B, protected with nitrogen, reaction temperature is： 80~110 DEG C, the reaction time is：4~12h, is then added dropwise trimethyl cyclotrisiloxaneTrimethyl is obtained after reaction completely Siloxyalkyl is modified cyclotrisiloxane

3) by the alkyl-modified cyclotrisiloxane of trimethylsiloxy groupHexamethyl cyclotrisiloxane D₃With nonpolar organic molten Agent and polar solvent are dissolved, and add alkyl lithium initiator, are protected with argon gas in course of reaction, reaction temperature：-70 DEG C~50 DEG C, reaction time：4-12h, is eventually adding dimethyl silicane hydroxide and is blocked, and obtains side chain with hydroxyl protecting group Group, the single-ended silicone macromolecule E with silicon hydrogen group；

4) side chain is carried into hydroxy-protective group, single-ended silicone macromolecule E, polymerization inhibitor, catalysis with silicon hydrogen group Agent mixes, and allyl methacrylate is added dropwise, and is protected with nitrogen in course of reaction, and reaction temperature is：80~110 DEG C, instead It is between seasonable：4~12h, obtains side chain with hydroxy-protective group, the single-ended silicone macromolecule list with methacrylic acid group Body F；

5) side chain is added with hydroxy-protective group, the single-ended silicone macromolecule monomer F with methacrylic acid group To in alcohols solvent, with weak acid as catalyst reaction, reaction temperature is：65 DEG C~100 DEG C, the reaction time is：4~12h, decompression Distillation removal alcohol compound and low-boiling-point substance, obtain side chain big with hydroxyl alkyl, the single-ended organosilicon with methacrylic acid group Molecule monomer G.

The mol ratio of the unsaturated monohydric alcohol A and HMDS is 2:(1~2), preferably 2:(1~1.1).

The unsaturated monohydric alcohol A is selected from the one kind in following structure：

A₁)CH₂=CHCH₂OH A₂)CH₂=CHCH₂CH₂OH A₃)CH₂=CHCH₂CH₂CH₂OH

A₄)CH₂=CHCH₂CH₂CH₂CH₂OH A₅)CH₂=CHCH₂OCH₂CH(OH)CH₂OCH₃。

The trimethylsiloxy group unsaturated compound B is selected from the one kind in following structure：

B₁)CH₂=CHCH₂OSi(CH₃)₃ B₂)CH₂=CHCH₂CH₂OSi(CH₃)₃ B₃)CH₂=CHCH₂CH₂CH₂OSi (CH₃)₃

B₄)CH₂=CHCH₂CH₂CH₂CH₂OSi(CH₃)₃ B₅)CH₂=CHCH₂OCH₂CH[OSi(CH₃)₃]CH₂OCH₃。

The catalyst is chloroplatinic acid.

The trimethylsiloxy group unsaturated compound B and trimethyl cyclotrisiloxaneMol ratio be 3:1~6:1, It is preferred that 3:1~3.3:1.

The quality of the catalyst accounts for the 0.05%~1% of trimethyl cyclotrisiloxane quality.

The alkyl-modified cyclotrisiloxane of trimethylsiloxy groupStructure it is as follows：

T₁)CH₂CH₂CH₂OSi(CH₃)₃ T₂)CH₂CH₂CH₂CH₂OSi(CH₃)₃ T₃)CH₂CH₂CH₂CH₂CH₂OSi(CH₃)₃

T₄)CH₂CH₂CH₂CH₂CH₂CH₂OSi(CH₃)₃ T₅)CH₂CH₂CH₂OCH₂CH[OSi(CH₃)₃]CH₂OCH₃。

The mass ratio of the non-polar organic solvent and polar solvent is 1:1~1:5, non-polar organic solvent and polarity are molten The gross mass of agent and the alkyl-modified cyclotrisiloxane of trimethylsiloxy groupHexamethyl cyclotrisiloxane D₃, lithium alkylide total matter Amount is than being 1:4~4:1.

The alkyl lithium initiator is 1 with the molar ratio range of dimethyl silicane hydroxide:1~1:1.2；Three in preparation process Methyl siloxyalkyl is modified cyclotrisiloxaneHexamethyl cyclotrisiloxane D₃This 3 kinds of feeding intake for reactant are rubbed with lithium alkylide That ratio is depending on the size of final product molecular weight.

With reference to the molecular structure in embodiment 9, (with n-BuLi as initiator, consumption is 1mol to molecular weight design formula As a example by) as follows：

Molecular weight (57)+D of the design molecular weight=normal-butyl of silicone macromolecule E^T ₃Molecular weight × D^T ₃Material amount (n=x/3)+D₃Molecular weight × D₃Material amount (m=y/3)+(CH3)₂The molecular weight (59) of SiH, i.e. M=57+60y+ 190x+59。

If design molecular weight is 1000 or so, x and y are respectively 1 and 12 in above-mentioned reaction equation, then n and m respectively may be about 1/ 3 and 4, that is, the silicone macromolecule E that molecular weight is 1000 or so is prepared, about need initiator, the D of 1/3mol of 1mol^T ₃And 4mol D₃。

The side chain carries hydroxy-protective group, the design molecular weight of the single-ended silicone macromolecule E with silicon hydrogen group =M_{Alkyl lithium initiator removes the molecular weight of lithium}+D^T ₃Molecular weight × D^T ₃Material amount+D₃Molecular weight × D₃Material amount+M_{Dimethyl silicane hydroxide}。

The non-polar organic solvent is selected from aliphatic carbon varsol, alicyclic carbon varsol, aromatic series carbon hydro carbons At least one in solvent, including but not limited to following compound known to those skilled in the art：Isopentane, pentane, stone Oily ether, n-hexane, hexamethylene, isooctane, pentamethylene, trimethylpentane, pentamethylene, heptane, toluene, benzene, dimethylbenzene.

The alkyl lithium initiator be selected from n-BuLi, s-butyl lithium, tert-butyl lithium, trimethylsiloxy group lithium at least It is a kind of.

The polar solvent be selected from aliphatic ketone, alicyclic ketones, aromatic series ketone, amide-type, sulfoxide type, nitrile, At least one in heterocyclic solvent, including but not limited to following compound known to those skilled in the art：Tetrahydrofuran, first Acid amides, acetonitrile, N,N-dimethylformamide, hexamethyl phosphoramide, butanone, dimethyl sulfoxide, acetone, 1,4- dioxane, pyridine.

The dimethyl silicane hydroxide is chlorodimethyl silane.

The side chain carries hydroxy-protective group, the number-average molecular weight of the single-ended silicone macromolecule E with silicon hydrogen group Between 500~4500, and with following structure：

Wherein：y>0, x>0.

The quality of the polymerization inhibitor accounts for the 0.1%~5% of allyl methacrylate quality.

The quality of the catalyst accounts for side chain with hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group The 0.05%~1% of the quality of E.

The side chain carries hydroxy-protective group, single-ended silicone macromolecule E and methacrylic acid with silicon hydrogen group Mol ratio Primary Reference side chain between allyl ester carries hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group In E in Si -- H and allyl methacrylate C=C groups mol ratio, i.e., described allyl methacrylate and side chain With between hydroxy-protective group, silicon hydrogen group (Si-H) contained by the single-ended silicone macromolecule E with silicon hydrogen group mole Than being 1:1~2:1, preferably 1.01:1~1.05:1.

The polymerization inhibitor is selected from phenols and quinones polymerization inhibitor, including but not limited to following change known to those skilled in the art Compound：Hydroquinones, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2- TBHQs, 2,5- di-t-butyls are to benzene Diphenol.

The catalyst is selected from chloroplatinic acid.

The side chain has with hydroxy-protective group, the single-ended silicone macromolecule monomer F with methacrylic acid group Following structure：

Wherein, y>0, x>0.

The side chain carries hydroxy-protective group, single-ended silicone macromolecule monomer F and alcohol with methacrylic acid group The mass ratio of class solvent is 1:1~1:4.

The quality of the weak acid accounts for side chain and divides greatly with hydroxy-protective group, the single-ended organosilicon with methacrylic acid group The 0.5%~5% of sub- monomer F mass.

The alcohols solvent is selected from least one in methyl alcohol, ethanol, normal propyl alcohol, isopropanol.

The weak acid is selected from least in formic acid, acetic acid, propionic acid, lactic acid, dihydromethyl propionic acid, dimethylolpropionic acid Kind.

Another aspect of the present invention provides a kind of preparation of the organosilicon modified crylic acid resin of the high-solid lower-viscosity Method, comprises the following steps：

By 25~200 parts of carbon-carbon double bonds and the monomer of copolyreaction, 200~500 parts of acrylate and/or first can be carried out The derivative of the derivative of base acrylate monomer, the acrylate of 150~250 parts of hydroxyls and/or methacrylate monomers Thing, the derivative of 1~20 part of carboxylic acrylic acid and/or methacrylic acid, 25~100 parts of silicone macromolecule monomers, 14 ~70 parts of initiator mixing, are added to reaction in 100~200 parts of solvents, and reaction temperature is 80~200 DEG C, and the time is 4~20h, Obtain the organosilicon modified crylic acid resin of the high-solid lower-viscosity.

The crosslinking and curing agent is 10~40 parts of melamine resins of alkylation；

Or, the melamine resin of 10~40 parts of alkylation and 0.1~10 part have carbamate-functional Amino resins；

Or, the melamine resin of 10~40 parts of alkylation, 0.1~20 part of enclosed type aliphatic isocyanates；

Or, the melamine resin of 10~40 parts of alkylation, 0.1~10 part there is carbamate-functional Amino resins, 0.1~20 part of enclosed type aliphatic isocyanates.

The crosslinking and curing agent be alkylation melamine resin when, preferably butyl ether type, containing imido grpup, with The melamine resin that polymer form is present, equivalent between 200~280, the scratch-resistant high and high durable The number of crosslinking and curing agent is 10~40 parts in single component varnish composition；Can also select complex etherified type, containing imido grpup, With oligomer form exist melamine resin and/or complex etherified type, all it is etherification modified, with monomeric form exist Melamine resin matched use.When using the complex etherified type, containing imido grpup, deposit in oligomer form Melamine resin and/or complex etherified type, all it is etherification modified, with monomeric form exist melamino-formaldehyde During resin, its usage amount should be no more than the 50% of the melamine resin total weight parts of alkylation.

The crosslinking and curing agent can also further include it is containing alkoxycarbonylamino-triazines structure, have The amino resins of carbamate-functional, has described in the single component varnish composition of the scratch-resistant high and high durable The number of the amino resins of carbamate-functional is 0.1~10 part；The crosslinking and curing agent can also further select envelope Closed form aliphatic isocyanates, the enclosed type aliphatic described in the single component varnish composition of the scratch-resistant high and high durable The number of isocyanates is 0.1~20 part.

In the present invention, the melamine resin of the alkylation may be selected from Niu Peisi resins (Suzhou) limited public affairs The commercialization of all related trade mark that department, BASF China produce to Zhan Xin resins (Shanghai) Co., Ltd. is produced Product, for example：Setalux US138BB70 and the Setalux US146BB72 of Niu Peisi resins (Suzhou) Co., Ltd, BASF The Luwipol 072 and Luwipol 052 of (China) Co., Ltd, the Cymel 325 of profound new resin (Suzhou) Co., Ltd, Cymel 1168 and Cymel 303.The amino resins with carbamate-functional may be selected from BASF (China) to be had The commercially produced product of all related trade mark that limit company produces to profound new resin (Suzhou) Co., Ltd, for example：BASF (in State) Co., Ltd Larotact 150, the Cymel NF2000 of profound new resin (Suzhou) Co., Ltd.The enclosed type fat Race's isocyanates may be selected from the commercially produced product of all related trade mark of Bayer's production, for example： Desmodur BL3575, Desmodur BL3475 and Desmodur BL3175.

The acid catalyst is sulfonic acid type catalyst, and it contains free and closing sulfonic acid group；In the scratch-resistant high In the single component varnish composition of high durable, the number of the acid catalyst is 0.1~3 part.For the present invention, the acid Catalyst may be selected from the business of all related trade mark that Jin Shi industrial groups of the U.S. produce to profound new resin (Suzhou) Co., Ltd Change product, for example：The Nacure 2500 of Jin Shi industrial groups, Nacure 5225, Nacure 3525 and Nacure5414, it is profound The Cycat 4040, Cycat 500 and Cycat 600 of new resin (Suzhou) Co., Ltd.

The rheology control agent may be selected the compound containing urea bond, polymer and its related derivatives, and/or with crosslinking The macromolecule fine particle of structure, and/or the treated fine silica particle in surface；Prioritizing selection is with polyester or poly- third Olefin(e) acid resin is modified the polyureas and its derivative of preparation for main body, in the scratch-resistant high of the invention and the list of high durable In component varnish composition, the number of the rheology control agent is 5~30 parts.For the present invention, the rheology control agent can The commercially produced product of all related trade mark produced selected from Niu Peisi resins (Suzhou) Co., Ltd, for example：Niu Peisi resins (Soviet Union State) Co., Ltd Setalux 61767, Setalux 91757 and Setalux 91760, also may be selected other companies production Similar products.

The auxiliary agent is generally selected from least in levelling controlling agent, ultra-violet absorber and hindered amine as light stabilizer Kind.

Preferably, the levelling controlling agent may be selected from the institute that German Bi Ke chemical technologies seek advice from 's production There is the commercially produced product of the related trade mark, for example：BYK 310、BYK 315、BYK 320、BYK 325、BYK 331、BYK 358N、 BYK 3550 and BYK 3560, also may be selected the similar products of other companies production.

Preferably, for ultraviolet absorber and the reagent of hindered amine as light stabilizer, refer to have selected from BASF (China) The commercially produced product of all related trade mark of limit company production, for example：Tinuvin 292、Tinuvin 1130、Tinuvin 123, the similar products of other companies production also may be selected.

Preferably, the auxiliary agent can further include antioxidant and antisettling agent；The antioxidant and anti-settling Shallow lake agent, refers to the commercially produced product of all related trade mark selected from BASF China's production, for example： Irgafos168 and963S；Also the similar products of other companies production may be selected.Wherein, it is described anti-oxidant The consumption of agent is depending on the resin of different purposes, and the consumption of antisettling agent is depending on the consumption of pigment.It is foregoing when needing to use When antioxidant and antisettling agent, need also exist for being well mixed them with other components in auxiliary agent.

The solvent is aliphatic ester, ketone, di-alcohols, dihydroxylic alcohols ethers, dihydroxylic alcohols esters, aromatic series carbon hydro carbons At least one in solvent etc.；Including but not limited to following compound known to those skilled in the art：Toluene, dimethylbenzene, S- 100# solvent naphthas, trimethylbenzene solvent naphtha, S-150# solvent naphthas, durol solvent naphtha, acetone, butanone, methyl iso-butyl ketone (MIBK), ring Hexanone, ethyl acetate, butyl acetate, butyl glycol ether acetic acid esters, pentyl acetate, ethylene glycol ethyl ether propionic ester, butyl glycol ether, Ethylene glycol.

Another aspect of the present invention provides the single component varnish composition of a kind of scratch-resistant high and high durable Preparation method, particular by by with hyperbranched or tree polymer, Hydroxylated acrylic resin or hydroxymethyl third Olefin(e) acid resin, crosslinking and curing agent, rheology control agent and other components are prepared into the preparation method of large arch dam varnish, including following step Suddenly (as a example by preparing 1kg varnish samples)：

The first step, with 1~20 part there is the stirring of hyperbranched or tree polymer to mix 0.5~10 part of solvent It is even；

Second step, adds 5~50 parts of Hydroxylated acrylic resins or hydroxy resin and 1~20 part of organosilicon to change Property acrylic resin is uniformly mixed；

3rd step, be kept stirring for speed it is constant in the case of, sequentially add 1~10 part of auxiliary agent, 5~30 parts of rheology controls Agent and 10~70 parts of crosslinking and curing agents are uniformly mixed；

4th step, be kept stirring for speed it is constant in the case of, add 0.1~3 part of acid catalyst and 0.5~32 part it is molten Agent, is uniformly mixed the acquisition single component varnish composition.

It is described be uniformly mixed refer to stirring speed for 400~1000 revs/min (r/min), mixing time is 10 ~60min.

The time interval that auxiliary agent, rheology control agent and crosslinking and curing agent are sequentially added in 3rd step is 5~8min.

Another aspect of the invention provides a kind of scratch-resistant high and the single component varnish composition of high durable is used Make the purposes of finishing varnish.The single component varnish composition of the scratch-resistant high and high durable is used as the purposes of finishing varnish including following Step：The single component varnish composition of the scratch-resistant high and high durable is coated on pre- coated ground, at 80-180 DEG C At a temperature of solidify to form varnish coat.

The ground is the body of a motor car of standard or the component component of body of a motor car, by passing through chemical pre-treatment and covering electricity The cold-reduced sheet of swimming coating is prepared from.

An additional aspect of the present invention provides a kind of scratch-resistant high and the single component varnish composition of high durable is used In the purposes for preparing multicoat Finish；The multicoat Finish includes at least one colored paint coating and at least one is clear Lacquer coat, wherein the varnish coat is the outermost coating of multicoat Finish, and by the single component varnish group Compound is prepared from.

Preferably, the single component varnish composition of the scratch-resistant high and high durable is used to prepare multicoat Finish Purposes, it is further comprising the steps：

On priming paint or floating coating application and construction to ground and will first be solidified, by colored paint application and construction to priming paint or middle painting On the ground that coating has cured, then by the single component varnish composition application and construction to uncured colored paint table Face, finally solidifies two parts coating simultaneously, and to obtain the multicoat Finish, the multicoat Finish can be used for Three apply two dries system；

Or,

First by priming paint or middle painting application and construction to ground, then by colored paint application and construction to uncured priming paint or middle painting Coating surface, then by the single component varnish composition application and construction to uncured colored paint coating surface, finally by three parts Coating solidifies simultaneously, to obtain the multicoat Finish, the multicoat Finish can be used for the baking system of three painting one or Integrated form spraying coating process system；

Or,

Two-layer colored paint is constructed onto the ground without priming paint and middle painting, then single described in second layer colored paint surface spraying The clear coat composition of component, scratch-resistant high and high durable, and three partial coatings are solidified simultaneously, covered with paint, lacquer, colour wash, etc. with obtaining the multicoat System, the multicoat Finish can be used for deflation formula spraying coating process system；

Or,

On priming paint or floating coating application and construction to ground and will first be solidified, then by solid-shade paint application and construction to priming paint Or on the ground that has cured of middle coating layer, then by metallic coatings construction to uncured solid-shade paint coating surface, then By the single component varnish composition application and construction of the scratch-resistant high and high durable to uncured metallic coatings surface, finally will Three partial coatings solidify simultaneously, and to obtain the multicoat Finish, the multicoat Finish can be used for the baking of four painting two System；

Or,

First by priming paint or middle painting application and construction to ground, then by solid-shade paint application and construction to uncured priming paint or in Coating layer surface, then by metallic coatings construction to uncured solid-shade paint coating surface, then by the scratch-resistant high and Gao Nai The single component varnish composition application and construction of time finally solidifies four partial coatings to uncured metallic coatings surface simultaneously, To obtain the multicoat Finish, the multicoat Finish can be used for the baking system of four painting one.

Three painting two is dried, three apply a baking or integrated form spraying coating process, deflation formula spraying coating process, four paintings two are dried and four apply one The priming paint and/or colored paint used in baking system be water paint or solvent based coating, the priming paint and/or colored paint construction solid content Between 25%~55%；The colored paint is at least one in solid-shade paint, metallic paint or metallic finishe, is water colour paint or molten Formulation colored paint, thickness is 5~40 μm after solidification, is further 5~30 μm.

The priming paint or floating coating are aqueous or solvent borne priming paint or floating coating；Thickness is 10~50 μm after solidification, is entered One step is 15~40 μm.

The thickness of dry film of the multicoat Finish is 10 μm~80 μm, preferably 20 μm~70 μm, further preferred 30 μ M~60 μm；The temperature being heating and curing is 100~180 DEG C, preferably 120~160 DEG C；The time being heating and curing is 10 ~40min.

There is advantages below and beneficial effect due to using above-mentioned technical proposal, the present invention：

The main chain of organosilicon is Si-O-Si keys in organosilicon modified crylic acid resin of the invention, be difficult by ultraviolet light and Ozone is decomposed so that organosilicon has preferably resistance to irradiation and weather-proof ability than other macromolecular materials, therefore, work as organosilicon It is acrylic resin modified to be added in clear coat composition as coating composition, can further lift the weatherability and paint of film Guarantor's color gloss retention of film；Further, since without easily hydrolysis in organosilicon modified crylic acid resin used in the present invention Si-O-C keys, therefore, the stabilization of resinous molecular structure can be kept under humid tropical condition, especially under dry and wet alternation environment, pin There is excellent weathering stability to UV ray.

Organosilicon has that surface tension is weak, surface can small and film forming ability in organosilicon modified crylic acid resin of the invention Strong the features such as, therefore after organosilicon modified crylic acid resin is added in paint film, can assign paint film good scratch resistance And stain resistance, while so that paint film has good feel slipping.

Force ratio hydrocarbon in organosilicon modified crylic acid resin of the invention between silicone molecules is wanted weak and is obtained It is many, therefore compared with the hydrocarbon with molecular weight, organosilicon has the advantages that viscosity is low, so forged when organosilicon chain introducing After in acrylic resin molecule, can effectively lower the viscosity of acrylic resin.By a certain amount of organic-silicon-modified propylene After acid resin is incorporated into clear coat composition, while raising clear coat composition construction contains admittedly, varnish can be further reduced The working viscosity of composition.

The main chain of organosilicon is very submissive in organosilicon modified crylic acid resin of the invention, works as organosilicon-modified acrylic After resin is incorporated into clear coat composition, the pliability of paint film can be adjusted so that paint film has good impact；Additionally, Containing the hydroxyl that can be reacted with curing agent on the side chain of silicone molecules, when being recoated, will not be because of silicone segments Introducing also results in the bad negative effect of recoating adhesive force.

Scratch-resistant high and the single component varnish composition of high durable that the present invention is provided, the shelf-stable phase is 3~6 months (depending on storage condition).

The present invention provide scratch-resistant high and high durable single component varnish composition, it is also an option that property be respectively cooperating with Colored pigment, metallic pigments and flitter, use as solid-shade paint, metallic paint or metallic finishe.

Scratch-resistant high and the single component varnish composition of high durable that the present invention is provided, can effectively improve varnish combination The slipping of thing film coated surface, so as to increase the rub resistance of film；Additionally, the introducing of organosilicon modified crylic acid resin can be with Further improve the weatherability of clear coat composition film.

Specific embodiment

In order that creation characteristic of the invention, technological means and reached purpose are readily apparent from understanding, below in conjunction with specific reality Apply example and the present invention is expanded on further.It will be appreciated by those skilled in the art that below specifically described content be it is illustrative and It is nonrestrictive, should not be limited the scope of the invention with this.

In the case of being clear to the purpose of the present invention by following examples, being explained, the component of the composition Released bright by the universal standard of weight portion.In the case of without special instruction, for simplicity, institute in the embodiment of the present invention " weight portion " and " part " stated has identical meaning.

Embodiment 1

Preparing has hyperbranched or tree polymer

354.8g Boltorn H40 and 74g HHPAs are added to equipped with agitator, thermometer, nitrogen conduit and returned In the 1L reactors of flow condenser, reaction system is then warming up to 130 DEG C.After reaction temperature is constant, at this temperature after Continuation of insurance 4~5h of temperature, period every 1h sampling and measuring acid values, when acid value measured value (63mgKOH/g) reaches theoretical value When (62.8mgKOH/g), it is 240 tertiary carbonic acid glycidyl ester and the N of 0.5g, N- dimethylbenzyls to add 115.2g epoxide equivalents Amine, and continue to be incubated 4~5h at this temperature.In insulating process, acid value change is persistently monitored, when acid value is less than 2mgKOH/g Stop reaction.Butyl acetate is added after reaction temperature is down to 110 DEG C to carry out viscosity reduction and adjusts to contain admittedly, finally gives 804g and contains admittedly Measure as 65% with hyperbranched or tree polymer.

Embodiment 2

Preparing has hyperbranched or tree polymer

By 354.8g Boltorn H40 and 98.6g HHPAs be added to equipped with agitator, thermometer, nitrogen conduit and In the 1L reactors of reflux condenser, reaction system is then warming up to 130 DEG C.After reaction temperature is constant, at this temperature Continue be incubated 4~5h, period every 1h sampling and measuring acid values, when acid value measured value (79mgKOH/g) reaches theoretical value When (79.2mgKOH/g), it is 240 tertiary carbonic acid glycidyl ester and the N of 0.5g, N- dimethylbenzyls to add 153.6g epoxide equivalents Amine, and continue to be incubated 4~5h at this temperature.In insulating process, acid value change is persistently monitored, when acid value is less than 2mgKOH/g Stop reaction.Butyl acetate is added after reaction temperature is down to 110 DEG C to carry out viscosity reduction and adjusts to contain admittedly, finally gives 912g and contains admittedly Measure as 65% with hyperbranched or tree polymer.

Embodiment 3

Prepare epoxide modified Hyperbranched Polyester Resin

Synthetic method with reference to described in patent CN104628995 embodiments one is prepared, and specific synthesis step is as follows： 354.8g Boltorn H40 and 74g HHPAs are added to equipped with agitator, thermometer, nitrogen conduit and reflux condenser 1L reactors in, reaction system is then warming up to 130 DEG C.After reaction temperature is constant, at this temperature continue be incubated 4~ 5h, period every 1h sampling and measuring acid values, when acid value measured value (63mgKOH/g) reaches theoretical value (62.8mgKOH/g), plus Enter BDDE and 0.6g triphenylphosphines that 134.4g epoxide equivalents are 140, and continue at this temperature 4~5h of insulation.In insulating process, acid value and epoxide equivalent change are persistently monitored, when acid value is less than 2mgKOH/g and epoxide equivalent Close to stopping reaction when 1200.Butyl acetate is added after reaction temperature is down to 110 DEG C to carry out viscosity reduction and adjusts to contain admittedly, finally Obtain the epoxide modified Hyperbranched Polyester Resin that 845g solid contents are 65%.

Embodiment 4

Prepare epoxide modified Hyperbranched Polyester Resin

Synthetic method with reference to described in patent CN104628995 embodiments one is prepared, and specific synthesis step is as follows： 354.8g Boltorn H40 and 98.6g HHPAs are added to equipped with agitator, thermometer, nitrogen conduit and reflux condensation mode In the 1L reactors of device, reaction system is then warming up to 130 DEG C.After reaction temperature is constant, continue to be incubated 4 at this temperature ~5h, period every 1h sampling and measuring acid values, when acid value measured value (79mgKOH/g) reaches theoretical value (79.2mgKOH/g), 1,6- hexanediol diglycidyl ethers and 0.6g triphenylphosphines that 204.8g epoxide equivalents are 160 are added, and is continued in this temperature 4~5h of lower insulation.In insulating process, acid value and epoxide equivalent change are persistently monitored, when acid value is worked as less than 2mgKOH/g with epoxy Amount is reacted close to stopping when 1000.Butyl acetate is added after reaction temperature is down to 110 DEG C to carry out viscosity reduction and adjusts to contain admittedly, most The epoxide modified Hyperbranched Polyester Resin that 983g solid contents are 65% is obtained eventually.

Embodiment 5

Prepare blocked isocyanate modified ultra-branching polyester resin

Synthetic method with reference to described in patent CN104893533 embodiments one is prepared, and specific synthesis step is as follows：

Capping：444g IPDIs are added to equipped with agitator, thermometer, nitrogen conduit and returned In the 2L reactors of flow condenser, reaction system is then warming up to 70 DEG C.After temperature is constant, it is slowly added dropwise 235.04g Caprolactam is dissolved in the mixed solution after 200g cyclohexanone, controlling reaction temperature during dropwise addition, and keeping temperature is no more than 80 ℃.Completion of dropping continues to react 4~5h in this temperature, remaining isocyanate group content in analytical reactions system.When remaining isocyanide When acid groups content reaches theoretical value 9.17%, stopping is reacted and is discharged and obtains the caprolactam that 860g solid contents are 77% and partly seal different Cyanate.

Blocked isocyanate is modified：354.8g Boltorn H40 and 250g cyclohexanone is added to equipped with agitator, temperature In the 2L reactors of degree meter, nitrogen conduit and reflux condenser, and reaction system is warming up to 110 DEG C, treats that Boltorn H40 are complete After CL, reaction system is cooled to 80 DEG C.When temperature of reaction system is when stabilization is kept for 80 DEG C, 366g solid contents are added dropwise is The 77% semiclosed isocyanates of caprolactam, keeping temperature is no more than 80 DEG C during dropwise addition.Completion of dropping is in this temperature Continue to react 4~5h, period samples every 1h, wave number is observed about in 2200cm with infrared spectrum^-1The isocyanate groups at place Whether infrared signature absorption peak disappears, and after the characteristic absorption peak is wholly absent, stops heating, and obtaining 940g solid contents is 65.5% blocked isocyanate modified ultra-branching polyester resin.

Embodiment 6

Prepare blocked isocyanate modified ultra-branching polyester resin

Capping：444g IPDIs are added to equipped with agitator, thermometer, nitrogen conduit and returned In the 2L reactors of flow condenser, reaction system is then warming up to 70 DEG C.After temperature is constant, it is slowly added dropwise 181g first and second Ketoxime, controlling reaction temperature during dropwise addition, keeping temperature is no more than 80 DEG C.Completion of dropping continue in this temperature reaction 4~ 5h, remaining isocyanate group content in analytical reactions system.When remaining isocyanate group content reaches theoretical value 12.9%, stop anti- Butyl acetate viscosity reduction should be simultaneously used, discharging obtains the semiclosed isocyanates of methyl ethyl ketoxime that 775g solid contents are 80%.

Blocked isocyanate is modified：354.8g Boltorn H40 and 250g cyclohexanone is added to equipped with agitator, temperature In the 2L reactors of degree meter, nitrogen conduit and reflux condenser, and reaction system is warming up to 110 DEG C, treats that Boltorn H40 are complete After CL, reaction system is cooled to 80 DEG C.When temperature of reaction system is when stabilization is kept for 80 DEG C, 250g solid contents are added dropwise is The 80% semiclosed isocyanates of caprolactam, keeping temperature is no more than 80 DEG C during dropwise addition.Completion of dropping is in this temperature Continue to react 4~5h, period samples every 1h, wave number is observed about in 2200cm with infrared spectrum^-1The isocyanate groups at place Whether infrared signature absorption peak disappears, and after the characteristic absorption peak is wholly absent, stops heating, and obtaining 833g solid contents is 64.9% blocked isocyanate modified ultra-branching polyester resin.

Embodiment 7

Prepare hydroxyl (methyl) acrylic resin

First, by 1250g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:1) mixed solvent is added to and is equipped with In the 10L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C. After reaction temperature stabilization, will be by 500g styrene, 2250g n-butyl acrylates, 1750g hydroxyethyl methacrylates, 50g third The reactant mixture of olefin(e) acid, 450g methyl methacrylates and the 310g peroxidating 2- ethyl acids tert-butyl ester composition, by wriggling Pump is added drop-wise in reactor, and maintenance reaction temperature controls drop rate, it is ensured that 2 between 130~140 DEG C during dropwise addition By reactant mixture completion of dropping in~4h.After completion of dropping, continue to be incubated 2~4h between 130~140 DEG C, terminating reaction, Obtain solid content for 80%, hydroxyl value be 150mgKOH/g, glass transition temperature (Tg) be 0 DEG C, number-average molecular weight be 3500 or so Hydroxylated acrylic resin.

Embodiment 8

Prepare hydroxyl (methyl) acrylic resin

First, by 1250g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:1) mixed solvent, is added to dress In there are a 10L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 ℃.When reaction temperature stabilization after, will by 500g styrene, 1750g n-butyl acrylates, 1750g hydroxyethyl methacrylates, The reactant mixture of 50g acrylic acid, 950g methyl methacrylates and the 432g peroxidating 2- ethyl acids tert-butyl ester composition, passes through Peristaltic pump is added drop-wise in reactor, and maintenance reaction temperature controls drop rate between 130~140 DEG C during dropwise addition, it is ensured that By reactant mixture completion of dropping in 2~4h.After completion of dropping, continue to be incubated 2~4h between 130~140 DEG C, terminate anti- Should, obtain solid content for 80%, hydroxyl value be 150mgKOH/g, glass transition temperature (Tg) be 15 DEG C, number-average molecular weight be 2500 The Hydroxylated acrylic resin of left and right.

Embodiment 9

Hydroxyl protection：In the reactor of 1L, 338.1g (2.1mol) HMDS is slowly added dropwise at room temperature To in 232g (4mol) allyl alcohol.After completion of dropping, reaction system is warming up to 100 DEG C, and it is small to continue reaction 6 in this temperature When after stop reaction.Normal pressure collects 98-100 DEG C of cut, obtains allyloxy trimethyl silane 473.2g, yield 91%.

Si―H addition reaction：In the reactor of 1L, 393.9g (3.03mol) allyloxy trimethyl silane is sequentially added With 0.5g chloroplatinic acid catalysts (0.5/180=0.27%), after being passed through nitrogen 20min, reaction system is warming up to 100 DEG C, 180g (1mol) trimethyl cyclotrisiloxane, terminating reaction after reaction 8h are added dropwise at a temperature of this.Vacuum distillation removes low-boiling-point substance, obtains To the alkyl-modified cyclotrisiloxane of 553g trimethylsiloxy groups, yield 97.0%.

Anionic polymerisation：In the 2L reactors after being processed by anhydrous and oxygen-free, sequentially add 1mol n-BuLi, 740g (3.333mol) hexamethyl cyclotrisiloxane, the alkyl-modified cyclotrisiloxane of 190g (0.333mol) trimethylsiloxy group, (mass ratio is 1 for 500g n-hexanes and tetrahydrofuran:1), after stirring reaction 8h at 25 DEG C, the chlorine silicon of 1.1mol dimethyl one is added Alkane terminating reaction.Reacting liquid filtering is removed the lithium chloride of generation, after vacuum distillation removal low-boiling-point substance, the equal molecule of 987g numbers is obtained The side chain measured as 1026 or so carries hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group, yield 96.2%.

Secondary Si―H addition reaction：In the reactor of 1L, 615.6g (0.6mol Si -- Hs) side chain is sequentially added with hydroxyl Base blocking group, the single-ended silicone macromolecule with silicon hydrogen group, 0.38g MEHQs polymerization inhibitor and 1g chloroplatinic acids are urged Agent, after being passed through nitrogen 20min, 100 DEG C is warming up to by reaction system, and 74.4g is added dropwise at this temperature, and (0.6mol C=C are double Key group) allyl methacrylate, terminating reaction after reaction 5h.Vacuum distillation removes low-boiling-point substance, obtains the equal molecule of 662g numbers The side chain for 1150 or so is measured with hydroxy-protective group, the single-ended silicone macromolecule monomer with methacrylic acid group, is received Rate 95.9%.In above-mentioned reaction, the mol ratio between allyl methacrylate and silicon hydrogen group (Si-H) is 1:1.

Alcoholysis reaction：In the reactor of 1L, 345g side chains are sequentially added with hydroxy-protective group, single-ended with methyl The silicone macromolecule monomer of acrylic, 500g methyl alcohol and 3g acetic acid.Under 65 DEG C of heated reflux conditions, stop after reaction 9h Reaction.Vacuum distillation removal acetic acid, excessive methyl alcohol and low-boiling-point substance, obtain the side chain band that 320g number-average molecular weights are 1078 or so There are hydroxyl alkyl, the single-ended silicone macromolecule monomer with methacrylic acid group, yield 98.9%.

Embodiment 10

Hydroxyl protection：In the reactor of 1L, 338.1g (2.1mol) HMDS is slowly added dropwise at room temperature To in 288g (4mol) 3- butene-1-ols.After completion of dropping, reaction system is warming up to 100 DEG C, and continued in this temperature anti- Stop reaction after answering 6 hours.Normal pressure collects 110-115 DEG C of cut, obtains alkene butoxy trimethyl silane 558g, yield 96.9%.

Si―H addition reaction：In the reactor of 1L, 436.3g (3.03mol) alkene butoxy trimethyl silane is sequentially added With 0.5g chloroplatinic acid catalysts, after being passed through nitrogen 20min, reaction system is warming up to 100 DEG C, 180g is added dropwise at this temperature (1mol) trimethyl cyclotrisiloxane, terminating reaction after reaction 8h.Vacuum distillation removes low-boiling-point substance, obtains 601g trimethyl silica The alkyl-modified cyclotrisiloxane of base, yield 98.2%.

Anionic polymerisation：In the 2L reactors after being processed by anhydrous and oxygen-free, sequentially add 1mol n-BuLi, 518g (2.333mol) hexamethyl cyclotrisiloxane, the alkyl-modified cyclotrisiloxane of 408g (0.666mol) trimethylsiloxy group, (mass ratio is 1 for 500g n-hexanes and tetrahydrofuran:1), after stirring reaction 8h at 25 DEG C, 1.1mol terminating reactions are added.Will Reacting liquid filtering removes the lithium chloride of generation, and after vacuum distillation removal low-boiling-point substance, it is 1022 or so to obtain 975g number-average molecular weights Side chain carry hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group, yield 95.4%.

Secondary Si―H addition reaction：In the reactor of 1L, 600g (0.6mol Si -- Hs) side chain is sequentially added with hydroxyl Blocking group, the single-ended silicone macromolecule with silicon hydrogen group, 0.38g 1,4-benzoquinone polymerization inhibitor and 1g chloroplatinic acid catalysts, lead to After entering nitrogen 20min, reaction system is warming up to 100 DEG C, 74.4g (0.6mol C=C double bonds group) is added dropwise at this temperature Allyl methacrylate, terminating reaction after reaction 5h.Vacuum distillation removes low-boiling-point substance, and it is 1146 to obtain 640g number-average molecular weights The side chain of left and right carries hydroxy-protective group, the single-ended silicone macromolecule monomer with methacrylic acid group, yield 94.9%. Allyl methacrylate and side chain are siliceous with hydroxy-protective group, the single-ended silicone macromolecule E institutes with silicon hydrogen group Mol ratio between hydrogen group (Si-H) is 1:1.

Alcoholysis reaction：In the reactor of 2L, 458.4g side chains are sequentially added with hydroxy-protective group, single-ended with first The silicone macromolecule monomer of base acrylic, 800g methyl alcohol and 5g acetic acid.Under 65 DEG C of heated reflux conditions, stop after reaction 9h Only react.Vacuum distillation removal acetic acid, excessive methyl alcohol and low-boiling-point substance, obtain the side chain that 410g number-average molecular weights are 1074 or so With hydroxyl alkyl, the single-ended silicone macromolecule monomer with methacrylic acid group, yield 95.3%.

Embodiment 11

First, by 125g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:1) mixed solvent is added to and is equipped with In the 1L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C. After reaction temperature stabilization, will be by 50g styrene, 225g n-butyl acrylates, 175g HEMAs, 5g third Olefin(e) acid, 45g methyl methacrylates, the silicone macromolecule monomer of the preparation of 26.3g embodiments 9 and 38g peroxidating 2- ethyls are The reactant mixture of tert-butyl acrylate composition, is added drop-wise in reactor by peristaltic pump, and maintenance reaction temperature is 130 during dropwise addition Between~140 DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue 2~4h is incubated between 130~140 DEG C, terminating reaction obtains solid content for 80.8%, hydroxyl value is 143mg KOH/g, organosilicon Content is that 5%, Type B rotary viscosity is 25Pas, the organosilicon modified crylic acid resin that number-average molecular weight is 3000 or so, acid It is 7.4mg KOH/g to be worth；Glass transition temperature (Tg) is -7.6 DEG C.

Embodiment 12

First, by 125g butyl acetates, dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:3:4) mixed solvent It is added in the 1L reactors equipped with agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.After reaction temperature stabilization, will be by 100g styrene, 200g n-butyl acrylates, 150g methacrylic acids 2- Hydroxyethyl ester, 8g acrylic acid, 42g ethylhexyl methacrylates, 55.5g embodiments 10 prepare silicone macromolecule monomer and The reactant mixture of 48g peroxidating 2- ethyl acids tert-butyl ester composition, is added drop-wise in reactor, during dropwise addition by peristaltic pump Maintenance reaction temperature controls drop rate, it is ensured that by reactant mixture completion of dropping in 2~4h between 120~140 DEG C. After completion of dropping, continue to be incubated 2~4h between 120~140 DEG C, terminating reaction, obtain solid content for 81.6%, hydroxyl value is 116mg KOH/g, silicone content be 10%, Type B rotary viscosity for 7.4Pas, number-average molecular weight be 2500 or so it is organic Fluorine-silicon modified acrylic resin, acid number is 11.2mg KOH/g；Glass transition temperature (Tg) is -12 DEG C.

13~21 concrete examples illustrate the single component varnish of scratch-resistant high of the invention and high durable by the following examples The component of composition, preparation method, and combine and its concrete application the present invention is further elucidated：

What embodiment 13~21 was referred in the present invention can be used for automobile covering with paint and the scratch-resistant high and height of other association areas Weather-proof single component varnish composition is prepared in the following manner, i.e., according to the different resins component set in Tables 1 and 2 Consumption, they and catalyst, auxiliary agent and solvent are mixed into preparation by dispersal device.

To ensure the single component varnish composition quality and the homogeneity of performance of the scratch-resistant high and high durable, the system Each component should be stirred mixing (to prepare 1kg by Preparation Method according to following specific charging sequence under atmospheric pressure at room state As a example by the single component varnish composition sample)：

The first step, there is hyperbranched or tree polymer to be added to dispersion 0.5~10 part of solvent and 1~20 part In kettle, and 10~60 minutes (min) is stirred with the stir speed (S.S.) of 400~1000 revs/min (r/min)；

Second step, added in Scattered Kettle 5~50 parts of Hydroxylated acrylic resins or hydroxy resin and 1~ 20 parts of organosilicon modified crylic acid resins, and stirred 10~15 minutes under identical stirring；

3rd step, be kept stirring for speed it is constant in the case of, successively by 1~10 part of auxiliary agent, 5~30 parts of rheology control agents It is added in Scattered Kettle with 10~70 parts of crosslinking and curing agents, wherein, spaced 5~8 minutes of the addition time of each component, before treating One component adds next component after being thoroughly mixed completely；

4th step, continues to keep the stir speed (S.S.) of 400~1000r/m, finally by 0.1~3 part of acid catalyst and 0.5~32 Part solvent is added in Scattered Kettle, and dispersed with stirring stops stirring after 30 minutes, obtains the single component varnish composition.

Embodiment 13~16 prepares the component of the single component varnish composition of the scratch-resistant high and high durable and matches somebody with somebody Side is as shown in table 1：

Table 1

Note：

^aEmbodiment 1 prepare with hyperbranched or tree polymer, solid content is：65%；

^bHydroxyl (methyl) acrylic resin prepared by embodiment 7, solid content is：80%；

^cOrganosilicon modified crylic acid resin prepared by embodiment 11；

^dNiu Peisi resins (Suzhou) Co., Ltd product, the trade mark is：Setalux US138BB70, solid content is：70%；

^eBASF China's product, the trade mark is：Larotact 150, solid content is：50%；

^fNiu Peisi resins (Suzhou) Co., Ltd product, the trade mark is：Setalux 61767, solid content is：60%；

^gJin Shi industrial groups product, the trade mark is：Nacure 2500；

^hGerman Bi Ke chemical technologies seek advice from (Shanghai) Co., Ltd. and BASF China's product, the trade mark point It is not：BYK 315, BYK358N, Tinuvin 292 and Tinuvin 1130；The mass ratio of this several material is 1:1:1:1.

ⁱThe mass ratio of butyl acetate, the first step and the 4th step solvent for use is 1:2.

^jFilm crocking resistance after solidification is surveyed by using the sand paper of model P2400 on Friction tester Examination, investigates 20 ° of retention of gloss of film after 15 circulations of friction.

The preparation method of comparative example 1 need not simply be added with the preparation method of embodiment 13~16 in second step in table 1 Organosilicon modified crylic acid resin.

Embodiment 17~21 prepares the component of the single component varnish composition of the scratch-resistant high and high durable and matches somebody with somebody Side is as shown in table 2：

Table 2

Note：

^aEmbodiment 2 prepare with hyperbranched or tree polymer, solid content is：65%；

^bEpoxide modified Hyperbranched Polyester Resin prepared by embodiment 3, solid content is：65%；

^cBlocked isocyanate modified ultra-branching polyester resin prepared by embodiment 5, solid content is：65%；

^dHydroxyl (methyl) acrylic resin prepared by embodiment 8, solid content is：80%；

^eOrganosilicon modified crylic acid resin prepared by embodiment 12, solid content is：81.6%；

^fNiu Peisi Products, the trade mark is：Setalux US138BB70, solid content is：70%；

^gProfound new company's product, the trade mark is：Cymel 303, solid content is：98%；

^hBASF AG's product, the trade mark is：Larotact 150, solid content is：50%；

ⁱNiu Peisi Products, the trade mark is：Setalux 61767, solid content is：60%；

^jJin Shi industrial groups product, the trade mark is：Nacure 2500；

^kGerman Bi Ke companies and BASF AG's product, the trade mark are respectively：BYK 315、BYK358N、Tinuvin 292 With Tinuvin 1130；The mass ratio of this several material is 1:1:1:1；

^lThe mass ratio of butyl acetate, the first step and the 4th step solvent for use is 1:2.

The scratch-resistant described high and the single component varnish composition of high durable prepared to embodiment 13~16 carry out performance survey Examination, wherein involved compelx coating (3C1B systems) is prepared in the following manner.First, from by chemical pre-treatment And the cold rolling test board of electrophoretic coating is covered, the test board is that the processing technology according to standard on automotive OEM production line is carried out Prepare；Then, according to wet on wet technique spray respectively the trade mark be AR800N2 aqueous dark-grey middle painting (ippon product) and the trade mark be The aqueous black colored paint (ippon product) of AR3500 731P, and by the film after spraying at 85 DEG C preliminary drying 8min；Then, exist Uncured colored paint surface is again according to the clear coat composition of the present invention under wet on wet technique spraying application state；Finally will Above-mentioned composite coating, i.e., the multiple coating being made up of aqueous middle painting, water colour paint and clear coat composition of the present invention, 145 The compelx coating being made up of multiple coating is formed after toasting 25min at DEG C together；Wherein, the thickness of each coating divides in compelx coating It is not：Middle 20 ± 2 μm of painting, 12 ± 1 μm of colored paint, 45 ± 5 μm of varnish.

Be can be seen that by data in table 1 and compared with comparative example 1, with organosilicon modified crylic acid resin usage amount Increase, the Erichsen test of paint film and resistance to dry friction data are improved, illustrate to be added to organosilicon modified crylic acid resin clearly In coating compositions, it is possible to increase the pliability and rub resistance of paint film.Additionally, the varnish described in embodiment 13 and embodiment 14 Composition and the clear coat composition in comparative example have a similar working viscosity, and now described in embodiment 13 and embodiment 14 The construction of clear coat composition solid contain admittedly containing the construction for being above clear coat composition in comparative example；On the other hand, the He of embodiment 15 Clear coat composition described in embodiment 16 with the clear coat composition in comparative example there is identical construction to contain admittedly, and now implement The construction that clear coat composition its working viscosity described in example 15 and embodiment 16 is below clear coat composition in comparative example 1 is glued Degree.Illustrated by the above results, organosilicon modified crylic acid resin is added in clear coat composition, can aid in reduction varnish The working viscosity of composition and improve construction contain admittedly.

Embodiment 22

First, by 125g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:1) mixed solvent is added to and is equipped with In the 1L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C. After reaction temperature stabilization, will be by 50g styrene, 225g n-butyl acrylates, 175g HEMAs, 5g third Olefin(e) acid, 45g methyl methacrylates, the silicone macromolecule monomer of the preparation of 26.3g embodiments 1 and 38g peroxidating 2- ethyls are The reactant mixture of tert-butyl acrylate composition, is added drop-wise in reactor by peristaltic pump, and maintenance reaction temperature is 130 during dropwise addition Between~140 DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue 2~4h is incubated between 130~140 DEG C, terminating reaction obtains solid content for 80.8%, hydroxyl value is 143mg KOH/g, organosilicon Content is that 5%, Type B rotary viscosity is 25Pas, the organosilicon modified crylic acid resin that number-average molecular weight is 3000 or so, acid It is 7.4KOH/g to be worth；Glass transition temperature (Tg) is -7.6 DEG C.

Embodiment 23

First, by 125g butyl acetates, dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:3:4) mixed solvent It is added in the 1L reactors equipped with agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.After reaction temperature stabilization, will be by 100g styrene, 200g n-butyl acrylates, 150g methacrylic acids 2- Hydroxyethyl ester, 8g acrylic acid, 42g ethylhexyl methacrylates, 55.5g embodiments 2 prepare silicone macromolecule monomer and The reactant mixture of 48g peroxidating 2- ethyl acids tert-butyl ester composition, is added drop-wise in reactor, during dropwise addition by peristaltic pump Maintenance reaction temperature controls drop rate, it is ensured that by reactant mixture completion of dropping in 2~4h between 120~140 DEG C. After completion of dropping, continue to be incubated 2~4h between 120~140 DEG C, terminating reaction, obtain solid content for 81.6%, hydroxyl value is 116mg KOH/g, silicone content be 10%, Type B rotary viscosity for 7.4Pas, number-average molecular weight be 2500 or so it is organic Fluorine-silicon modified acrylic resin, acid number is 11.2mg KOH/g；Glass transition temperature (Tg) is -12 DEG C.

Embodiment 24

First, by 156g butyl acetates and dimethylbenzene, (mass ratio is 7:2) mixed solvent is added to equipped with agitator, temperature In the 1L reactors of degree meter, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.Work as reaction temperature After stabilization, will be by 80g styrene, 220g n-butyl acrylates, 180g HEMAs, 2g acrylic acid, 18g first Silicone macromolecule monomer and 53.4g peroxidating 2- ethyl acids prepared by base dodecylacrylate, 43.5g embodiments 3 The reactant mixture of tert-butyl ester composition, is added drop-wise in reactor by peristaltic pump, during dropwise addition maintenance reaction temperature 120~ Between 130 DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue 120 2~4h is incubated between~130 DEG C, terminating reaction obtains solid content for 77.7%, hydroxyl value is 143mg KOH/g, silicone content For 8%, Type B rotary viscosity is 8.7Pas, the organosilicon modified crylic acid resin that number-average molecular weight is 2200 or so, acid number is 2.9mg KOH/g；Glass transition temperature (Tg) is -9.5 DEG C.

Embodiment 25

First, by 125g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:1) mixed solvent is added to and is equipped with In the 1L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C. After reaction temperature stabilization, will be by 53g styrene, 220g n-butyl acrylates, 175g HEMAs, 7g third Olefin(e) acid, 45g methyl methacrylates, the silicone macromolecule monomer of the preparation of 26.3g embodiments 4 and 35g peroxidating 2- ethyls are The reactant mixture of sour tert-pentyl ester composition, is added drop-wise in reactor by peristaltic pump, and maintenance reaction temperature is 130 during dropwise addition Between~140 DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue 2~4h is incubated between 130~140 DEG C, terminating reaction obtains solid content for 80.8%, hydroxyl value is 143mg KOH/g, organosilicon It is 27.4Pas, the organosilicon modified crylic acid resin that number-average molecular weight is 3500 or so that content is 5%, Type B rotary viscosity, Acid number is between 10.4mg KOH/g；Glass transition temperature (Tg) is -7.1 DEG C.

Embodiment 26

First, by 125g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 2:1) mixed solvent, is added to and is equipped with In the 1L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C. After reaction temperature stabilization, will be by 50g styrene, 175g n-butyl acrylates, 175g HEMAs, 5g third Silicone macromolecule monomer and 61g perbenzoic acids uncle penta prepared by olefin(e) acid, 95g methyl methacrylates, 88g embodiments 1 The reactant mixture of ester composition, is added drop-wise in reactor by peristaltic pump, and maintenance reaction temperature is 130~140 during dropwise addition Between DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue 130~ Be incubated 2~4h between 140 DEG C, terminating reaction, obtain solid content for 82.5%, hydroxyl value be that 128mg KOH/g, silicone content are 15%th, Type B rotary viscosity is 5.4Pas, the organosilicon modified crylic acid resin that number-average molecular weight is 2000 or so, and acid number is Between 6.6mg KOH/g；Glass transition temperature (Tg) is -16.2 DEG C.

Embodiment 27

First, by 100g butyl acetates and S-100# solvent naphthas, (mass ratio is 1:4) mixed solvent, is added to be equipped with and stirs In mixing the 1L reactors of device, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.When After reaction temperature stabilization, will be by 30g styrene, 70g n-butyl acrylates, 70g Tert-butyl Methacrylates, 50g versatic acid second Prepared by alkene ester, 100g methacrylic acid 2- hydroxypropyl esters, 6g acrylic acid, 74g isobornyl methacrylates, 20g embodiments 1 The reactant mixture of silicone macromolecule monomer and 14g di-t-butyl peroxides composition, is added drop-wise in reactor by peristaltic pump, Maintenance reaction temperature controls drop rate, it is ensured that by reactant mixture in 2~4h between 130~140 DEG C during dropwise addition Completion of dropping.After completion of dropping, continue to be incubated 2~4h between 130~140 DEG C, terminating reaction, obtaining solid content is 80.8%th, hydroxyl value is that 92mg KOH/g, silicone content are that 4.7%, Type B rotary viscosity is that 7.7Pas, number-average molecular weight are 2200 or so organosilicon modified crylic acid resin, acid number is 11mgKOH/g, Tg=-3.1 DEG C.

Embodiment 28

First, by 200g butyl acetates, dimethylbenzene and pentyl acetate, (mass ratio is 1:4:5) mixed solvent, is added to In 1L reactors equipped with agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 ℃.When reaction temperature stabilization after, will by 100g styrene, 150g n-butyl acrylates, 100g ethylhexyl methacrylates, 100g HEMAs, 75g methacrylic acid 2- hydroxypropyl esters, 10g acrylic acid, 10g methacrylic acids, 100g Prepared by the double N-butyls of dodecylacrylate, 55g isobornyl methacrylates, 100g maleic acids, 50g embodiments 2 has The reactant mixture of machine silicon macromonomer and 33g di-t-butyl peroxides composition, is added drop-wise in reactor by peristaltic pump, is dripped Plus during maintenance reaction temperature between 130~140 DEG C, control drop rate, it is ensured that reactant mixture is dripped in 2~4h Add complete.After completion of dropping, continue to be incubated 2~4h between 130~140 DEG C, terminating reaction, obtain solid content for 80.9%, Hydroxyl value is 88mg KOH/g, silicone content is 2.4%, Type B rotary viscosity is 3.3Pas, number-average molecular weight is 1800 or so Organosilicon modified crylic acid resin, acid number is 17.5mgKOH/g, Tg=-2.7 DEG C.

Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description To make other changes in different forms, the embodiment that the present invention is enumerated cannot give all of implementation method thoroughly To the greatest extent, it is every to belong to obvious change or variation that technical scheme extends out still in protection model of the invention The row for enclosing.The all documents for referring in the present invention are all incorporated as reference in this application, independent just as a document It is cited as with reference to such.

Claims

1. a kind of single component varnish composition, it is characterised in that：Including：

It is at least one with hyperbranched or tree polymer；

At least one Hydroxylated acrylic resin or hydroxy resin；

At least one organosilicon modified crylic acid resin；

At least one crosslinking and curing agent；

At least one acid catalyst；

At least one rheology control agent；

At least one auxiliary agent；And

At least one solvent；

The single component varnish composition is the single component varnish composition of scratch-resistant high and high durable.

2. single component varnish composition according to claim 1, it is characterised in that：Component including following weight portion：

3. single component varnish composition according to claim 1 and 2, it is characterised in that：It is described with hyperbranched or tree-shaped The polymer of structure is a kind of with hyperbranched or tree macromolecule polyester, average described each high molecular polymer chain Containing 8~80 oh groups, between 150~600mgKOH/g, glass transition temperature is between -25 DEG C to+30 for its hydroxyl value Between DEG C；

The hydroxyl with hyperbranched or tree polymer is optionally by epoxide group and closing aliphatic The modified substitution of isocyanate groups, becomes epoxide modified Hyperbranched Polyester Resin, blocked isocyanate modified ultra-branching polyester Resin；And the number of the functional groups after the substitution that is modified, that is, the number of the hydroxyl being substituted, account for former hyperbranched or tree-shaped knot The 1%~50% of hydroxy number in the polymer of structure.

4. single component varnish composition according to claim 3, it is characterised in that：The epoxide modified hyper-branched polyester tree Fat is prepared by raw material of hyperbranched hydroxyl polyester, acid anhydrides and epoxy resin, with following structural：

In formula, m and n is positive integer, m+n≤80；Wherein,It is the skeleton of hyperbranched hydroxyl polyester, R₁For in anhydride molecule Remaining alkyl group after anhydride group is removed, wherein, acid anhydrides is hexahydrophthalic anhydride, methylhexahydrophthaacid acid Acid anhydride, tetrabydrophthalic anhydride, methyl tetrahydro phthalic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, At least one in adipic anhydride, dodecenylsuccinic acid acid anhydride, trimellitic anhydride；R₂To remove epoxy radicals in epoxy molecule Remaining alkyl group after group, wherein, epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy Resin, bisphenol-A D-ring oxygen tree fat, ethylene glycol diglycidylether, diethylene glycol diglycidyl ether, three contracting diethyls two Alcohol diglycidyl ether, polyethyleneglycol diglycidylether, 1,2- propylene glycol diglycidylethers, polypropylene glycol diglycidyl Ether, 1,4- butanediol diglycidyl ethers, 1,6 hexanediol diglycidyl ethers, neopentylglycol diglycidyl ether, O-phthalic Sour 2-glycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, tetrahydrophthalic acid two At least one in ethylene oxidic ester.

5. single component varnish composition according to claim 3, it is characterised in that：The modified over-expense of the blocked isocyanate Change polyester resin to be prepared by raw material of hyperbranched hydroxyl polyester, isocyanates and sealer, with following structural：

In formula, x and y is positive integer, total functional group's number of 2≤x+y≤hyperbranched hydroxyl polyester；It is hyperbranched hydroxyl The skeleton of polyester, R₃It is remaining alkyl group after removing isocyanate groups in isocyanate molecule, wherein, isocyanates is Toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, polymethylene polyphenyl diisocyanate, the isocyanic acid of hexa-methylene two Ester, XDI, IPDI, dicyclohexyl methyl hydride isocyanates, the methylene of trimethyl six At least one in group diisocyanate, HTDI；R₄It is residue after removing active hydrogen in capping reagent molecule Alkyl group, wherein：Sealer is methyl alcohol, ethanol, propyl alcohol, butanol, hexanol, octanol, phenmethylol, glycol monoethyl ether, second Glycol monobutyl ether, ethylene glycol monohexylether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono butyl Ether, diethylene glycol monomethyl ether, methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, diisopropylamine, 3,5- dimethyl pyrazoles, the N- tert-butyl groups At least one in benzylamine, caprolactam, dimethyl malenate, diethyl malonate.

6. single component varnish composition according to claim 1 and 2, it is characterised in that：The Hydroxylated acrylic resin or Between 110~250mg KOH/g, glass transition temperature is between -10 DEG C to+35 DEG C for the hydroxyl value of hydroxy resin Between, between 2000~4000, solid content is more than or equal to 80% to number-average molecular weight.

7. single component varnish composition according to claim 1 and 2, it is characterised in that：The organosilicon-modified acrylic The structure of resin is as shown in formula I：

Wherein：

In formula I：

R₁Selected from containing 1~20 aliphatic of carbon atom, alicyclic, aromatic alkyl, alkoxy, acyloxy, hydroxyalkyl, hydroxyl Alkylidene；

R₂、R₃、R₄、R₅Be each independently selected from hydrogen atom, containing 1~20 aliphatic of carbon atom, alicyclic, aromatic alkane Base, hydroxyalkyl, hydroxyl alkylidene；

R₆Structure be selected from Formula II in one kind：

CH₂CH₂CH₂OH CH₂CH₂CH₂CH₂OH CH₂CH₂CH₂CH₂CH₂OH

CH₂CH₂CH₂CH₂CH₂CH₂OH CH₂CH₂CH₂OCH₂CH(OH)CH₂OCH₃

(II)；

R₇Structure be selected from formula III in one kind：

CH₃CH₂CH₂CH₂ CH₃CH(CH₃)CH₂ (CH₃)₃C (CH₃)₃SiO

(III)；

m>0, n>0, o>0, p>0, q>0, x>0, y>0.

8. single component varnish composition according to claim 1 and 2, it is characterised in that：The organosilicon-modified acrylic The hydroxyl value of resin is between 50~250mgKOH/g；Acid number is between 0~20mg KOH/g；Glass transition temperature between- Between 30 DEG C Dao+50 DEG C；Number-average molecular weight is between 500~20000；Between 70%~100%, Type B revolves solid content Turn viscosity between 0.5~200Pas.

9. single component varnish composition according to claim 1 and 2, it is characterised in that：The organosilicon-modified acrylic Resin includes the component of following weight portion：

10. single component varnish composition according to claim 9, it is characterised in that：The solvent be selected from aliphatic ester, At least one in unary alcohol, ketone, di-alcohols, dihydroxylic alcohols ethers, dihydroxylic alcohols esters, aromatic series carbon varsol；

The derivative of the acrylate and/or methacrylate monomers is selected from alkyl acrylate, methacrylate At least one in ester, acrylate base ester, cycloalkyl methacrylate；

The acrylate of the hydroxyl and/or the derivative of methacrylate monomers are selected from acrylic acid hydroxy alkyl ester, methyl At least one in acrylic acid hydroxy alkyl ester；

The initiator is selected from least one in azo-initiator or peroxide initiator.

11. single component varnish compositions according to claim 10, it is characterised in that：The solvent be toluene, dimethylbenzene, S-100# solvent naphthas, trimethylbenzene solvent naphtha, S-150# solvent naphthas, durol solvent naphtha, butanone, methyl iso-butyl ketone (MIBK), hexamethylene Ketone, ethyl acetate, butyl acetate, butyl glycol ether acetic acid esters, pentyl acetate, ethylene glycol ethyl ether propionic ester, butyl glycol ether, second At least one in glycol, normal propyl alcohol, isopropanol, n-butanol, propylene glycol methyl ether acetate；

The carbon-carbon double bonds and can carry out copolyreaction monomer be styrene, methyl-prop ethene, allyl alcohol, versatic acid ethene Ester, monomethyl maleate, ethyl maleate, maleic acid list n-propyl, maleic acid list isopropyl ester, maleic acid list N-butyl, horse Come the sour secondary butyl ester of list, the maleic acid list tert-butyl ester, maleic acid list pentyl ester, the own ester of maleic acid list, maleic acid list Octyl Nitrite, maleic acid The double ethyl esters of double methyl esters, maleic acid, the double n-propyls of maleic acid, the double isopropyl esters of maleic acid, the double N-butyls of maleic acid, the double Zhong Ding of maleic acid At least one in the double tert-butyl esters of ester, maleic acid, the double pentyl esters of maleic acid, the double own esters of maleic acid, the double Octyl Nitrites of maleic acid；

The derivative of the acrylate and/or methacrylate monomers is methyl acrylate, methyl methacrylate, propylene Acetoacetic ester, EMA, propyl acrylate, propyl methacrylate, isopropyl acrylate, methacrylic acid isopropyl Ester, n-butyl acrylate, n-BMA, isobutyl acrylate, Isobutyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate, amyl acrylate, pentylmethacrylate, Hexyl 2-propenoate, hexyl methacrylate, acrylic acid second The own ester of base, ethylhexyl methacrylate, the own ester of acrylic acid 3,3,5- trimethyls, the own ester of methacrylic acid 3,3,5- trimethyls, Octadecyl acrylate, octadecyl methacrylate, dodecylacrylate, lauryl methacrylate, Acrylic acid cyclopentyl ester, methacrylic acid cyclopentyl ester, isobornyl acrylate, isobornyl methacrylate, acrylic acid ring At least one in own ester, cyclohexyl methacrylate, glycidyl acrylate, GMA；

The acrylate of the hydroxyl and/or the derivative of methacrylate monomers are HEA, methyl HEA, acrylic acid 2- hydroxypropyl esters, methacrylic acid 2- hydroxypropyl esters, acrylic acid 3- hydroxypropyl esters, methyl Acrylic acid 3- hydroxypropyl esters, acrylic acid 3- hydroxyls butyl ester, methacrylic acid 3- hydroxyls butyl ester, acrylic acid 4- hydroxyls butyl ester, methyl Acrylic acid 4- hydroxyls butyl ester, acrylic acid and tertiary carbonic acid glycidyl ester condensation product, methacrylic acid and tertiary carbonic acid glycidyl At least one in ester condensation products；

The derivative of the carboxylic acrylic acid and/or methacrylic acid is selected from acrylic acid and/or methacrylic acid；

The initiator is azodiisobutyronitrile, ABVN, benzoyl peroxide, the tertiary fourth of peroxidating 2- ethyl acids Double (t-amyl peroxy) the ring group alkane of ester, peroxidating 2- ethyl acids tert-pentyl ester, 1,1-, double (t-amyl peroxy) -3,3 of 1,1-, 5- trimethyls thiacyclohexane, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxidating acetic acid tert-pentyl ester, peroxidating 3,5 ,-trimethyl double (t-amyl peroxy) ethyl butyrates of double (t-butyl peroxy) ethyl butyrates of tert-butyl acrylate, 3,3-, 3,3-, In cumyl peroxide, t-amyl peroxy hydrogen, TBHP, di-t-butyl peroxide, di t-amyl peroxide At least one.

12. single component varnish compositions according to claim 9, it is characterised in that：The silicone macromolecule monomer Preparation method is comprised the following steps：

1) HMDS is added drop-wise in unsaturated monohydric alcohol A, system is warming up to 90~120 DEG C, and in this temperature It is lower to continue to react 4~8h, trimethylsiloxy group unsaturated compound B is obtained by hydroxyl protection；

2) toward catalyst is added in trimethylsiloxy group unsaturated compound B, protected with nitrogen, reaction temperature is：80~ 110 DEG C, the reaction time is：4~12h, is then added dropwise trimethyl cyclotrisiloxaneTrimethyl silica is obtained after reaction completely The alkyl-modified cyclotrisiloxane of base

3) by the alkyl-modified cyclotrisiloxane of trimethylsiloxy groupHexamethyl cyclotrisiloxane D₃With non-polar organic solvent and Polar solvent is dissolved, and adds alkyl lithium initiator, is protected with argon gas in course of reaction, reaction temperature：- 70 DEG C~ 50 DEG C, reaction time：4-12h, is eventually adding dimethyl silicane hydroxide and is blocked, obtain side chain with hydroxy-protective group, The single-ended silicone macromolecule E with silicon hydrogen group；

4) side chain is mixed with hydroxy-protective group, the single-ended silicone macromolecule E with silicon hydrogen group, polymerization inhibitor, catalyst Close, allyl methacrylate is added dropwise, protected with nitrogen in course of reaction, reaction temperature is：80~110 DEG C, during reaction Between be：4~12h, obtains side chain with hydroxy-protective group, the single-ended silicone macromolecule monomer F with methacrylic acid group；

5) side chain is added to alcohol with hydroxy-protective group, the single-ended silicone macromolecule monomer F with methacrylic acid group In class solvent, with weak acid as catalyst reaction, reaction temperature is：65 DEG C~100 DEG C, the reaction time is：4~12h, vacuum distillation Removal alcohol compound and low-boiling-point substance, obtain side chain with hydroxyl alkyl, the single-ended silicone macromolecule with methacrylic acid group Monomer G.

13. single component varnish compositions according to claim 12, it is characterised in that：The unsaturated monohydric alcohol A and six The mol ratio of methyl disilazane is 2:(1~2)；

A₁)CH₂=CHCH₂OH A₂)CH₂=CHCH₂CH₂OH A₃)CH₂=CHCH₂CH₂CH₂OH

14. single component varnish compositions according to claim 12, it is characterised in that：The catalyst is chloroplatinic acid；

The trimethylsiloxy group unsaturated compound B and trimethyl cyclotrisiloxaneMol ratio be 3:1~6:1；

15. single component varnish compositions according to claim 12, it is characterised in that：The non-polar organic solvent and pole Property solvent mass ratio be 1:1~1:5, the gross mass of non-polar organic solvent and polar solvent changes with trimethylsiloxy group alkyl Property cyclotrisiloxaneHexamethyl cyclotrisiloxane D₃, lithium alkylide total mass ratio be 1:4~4:1；

The alkyl lithium initiator is 1 with the molar ratio range of dimethyl silicane hydroxide:1~1:1.2；

The side chain with hydroxy-protective group, the single-ended silicone macromolecule E with silicon hydrogen group design molecular weight= M_{Alkyl lithium initiator removes the molecular weight of lithium}+D^T ₃Molecular weight × D^T ₃Material amount+D₃Molecular weight × D₃Material amount+M_{Dimethyl silicane hydroxide}。

16. single component varnish compositions according to claim 12, it is characterised in that：The non-polar organic solvent is selected from At least one in aliphatic carbon varsol, alicyclic carbon varsol, aromatic series carbon varsol；

The polar solvent is selected from aliphatic ketone, alicyclic ketones, aromatic series ketone, amide-type, sulfoxide type, nitrile, heterocycle At least one in class solvent.

17. single component varnish compositions according to claim 16, it is characterised in that：The non-polar organic solvent is different Pentane, pentane, petroleum ether, n-hexane, hexamethylene, isooctane, pentamethylene, trimethylpentane, pentamethylene, heptane, toluene, At least one in benzene, dimethylbenzene；

The alkyl lithium initiator is selected from least in n-BuLi, s-butyl lithium, tert-butyl lithium, trimethylsiloxy group lithium Kind；

The polar solvent is tetrahydrofuran, formamide, acetonitrile, N,N-dimethylformamide, hexamethyl phosphoramide, butanone, two At least one in first sulfoxide, acetone, 1,4- dioxane, pyridine；

The dimethyl silicane hydroxide is chlorodimethyl silane.

18. single component varnish compositions according to claim 12, it is characterised in that：The quality of the polymerization inhibitor accounts for methyl The 0.1%~5% of allyl acrylate quality；

The quality of the catalyst accounts for side chain with hydroxy-protective group, the single-ended silicone macromolecule E with silicon hydrogen group The 0.05%~1% of quality；

The allyl methacrylate carries hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group with side chain Mol ratio between silicon hydrogen group contained by E is 1:1~2:1；

The polymerization inhibitor is selected from phenols and quinones polymerization inhibitor.

19. single component varnish compositions according to claim 18, it is characterised in that：The polymerization inhibitor be hydroquinones, In 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2- TBHQs, 2,5 di tert butyl hydroquinone at least one Kind；

The catalyst is chloroplatinic acid.

20. single component varnish compositions according to claim 12, it is characterised in that：The side chain carries hydroxyl protecting group Group, the mass ratio of single-ended silicone macromolecule monomer F and alcohols solvent with methacrylic acid group are 1:1~1:4；

The quality of the weak acid accounts for side chain with hydroxy-protective group, the single-ended silicone macromolecule list with methacrylic acid group The 0.5%~5% of body F mass；

The alcohols solvent is selected from least one in methyl alcohol, ethanol, normal propyl alcohol, isopropanol；

The weak acid is selected from least one in formic acid, acetic acid, propionic acid, lactic acid, dihydromethyl propionic acid, dimethylolpropionic acid.

21. single component varnish compositions according to claim 1, it is characterised in that：The crosslinking and curing agent is 10~40 The melamine resin of part alkylation；

Or, the melamine resin of 10~40 parts of alkylation and 0.1~10 part of ammonia with carbamate-functional Base resin；

Or, the melamine resin of 10~40 parts of alkylation, 0.1~10 part of amino with carbamate-functional Resin, 0.1~20 part of enclosed type aliphatic isocyanates.

22. single component varnish compositions according to claim 1 and 2, it is characterised in that：The acid catalyst is sulfonic acid type Catalyst, it contains free and closing sulfonic acid group；

Compound of the rheology control agent selection containing urea bond, polymer and its related derivatives, and/or with cross-linked structure Macromolecule fine particle, and/or the treated fine silica particle in surface；

The auxiliary agent is selected from least one in levelling controlling agent, ultra-violet absorber and hindered amine as light stabilizer.

23. single component varnish compositions according to claim 22, it is characterised in that：The auxiliary agent still further comprises anti- Oxidant and antisettling agent.

24. single component varnish compositions according to claim 1 and 2, it is characterised in that：The solvent is aliphatic ester At least one in class, ketone, di-alcohols, dihydroxylic alcohols ethers, dihydroxylic alcohols esters, aromatic series carbon varsol.

25. single component varnish compositions according to claim 24, it is characterised in that：The solvent be toluene, dimethylbenzene, S-100# solvent naphthas, trimethylbenzene solvent naphtha, S-150# solvent naphthas, durol solvent naphtha, acetone, butanone, methyl iso-butyl ketone (MIBK), Cyclohexanone, ethyl acetate, butyl acetate, butyl glycol ether acetic acid esters, pentyl acetate, ethylene glycol ethyl ether propionic ester, ethylene glycol fourth At least one in ether, ethylene glycol.

A kind of preparation method of any described single component varnish composition of 26. claims 1 to 25, it is characterised in that：Including Following steps：

The first step, with 1~20 part there is hyperbranched or tree polymer to be uniformly mixed 0.5~10 part of solvent；

Second step, adds 5~50 parts of Hydroxylated acrylic resins or hydroxy resin and 1~20 part organic-silicon-modified third Olefin(e) acid resin agitating is well mixed；

3rd step, be kept stirring for speed it is constant in the case of, sequentially add 1~10 part of auxiliary agent, 5~30 parts of rheology control agents and 10~70 parts of crosslinking and curing agents are uniformly mixed；

4th step, be kept stirring for speed it is constant in the case of, add 0.1~3 part of acid catalyst and 0.5~32 part of solvent, stir Mix the single component varnish composition described in well mixed acquisition.

The preparation method of 27. single component varnish compositions according to claim 26, it is characterised in that：The stirring mixing Uniform refers to that the speed of stirring is 400~1000 revs/min (r/min), and mixing time is 10~60min；

A kind of any described single component varnish composition of 28. claims 1 to 25 is used as the purposes of finishing varnish, and its feature exists In：Comprise the following steps：

The single group clear coat composition is coated on pre- coated ground, varnish painting is solidify to form at a temperature of 80-180 DEG C Layer.

A kind of any described single component varnish composition of 29. claims 1 to 25 is used to prepare the use of multicoat Finish On the way, it is characterised in that：The multicoat Finish includes at least one colored paint coating and at least one varnish coat, wherein institute Varnish coat is stated for the outermost coating of multicoat Finish, and is prepared from by the single component varnish composition； Wherein, the single component varnish composition is the single component varnish composition of scratch-resistant high and high durable.

30. single component varnish compositions according to claim 29 are used to prepare the purposes of multicoat Finish, and it is special Levy and be：Comprise the following steps：

On priming paint or floating coating application and construction to ground and will first be solidified, by colored paint application and construction to priming paint or middle coating layer On the ground having cured, then by the single component varnish composition application and construction to uncured colored paint surface, most Two parts coating is solidified simultaneously afterwards, to obtain the multicoat Finish, the multicoat Finish can be used for three paintings Two dry system；

Or,

First by priming paint or middle painting application and construction to ground, then by colored paint application and construction to uncured priming paint or middle coating layer Surface, then by the single component varnish composition application and construction to uncured colored paint coating surface, finally by three partial coatings Solidify simultaneously, to obtain the multicoat Finish, the multicoat Finish can be used for the baking system or integrated of three painting one Formula spraying coating process system；

Or,

Two-layer colored paint is constructed onto the ground without priming paint and middle painting, then in one pack system described in second layer colored paint surface spraying Clear coat composition, and three partial coatings are solidified simultaneously, to obtain the multicoat Finish, the multicoat Finish Can be used for deflation formula spraying coating process system；

Or,

On priming paint or floating coating application and construction to ground and will first be solidified, then by solid-shade paint application and construction to priming paint or in On the ground that coating layer has cured, then by metallic coatings construction to uncured solid-shade paint coating surface, then by institute Single component varnish composition application and construction to uncured metallic coatings surface is stated, finally solidifies three partial coatings simultaneously, with The multicoat Finish is obtained, the multicoat Finish can be used for the baking system of four painting two；

Or,

First by priming paint or middle painting application and construction to ground, then solid-shade paint application and construction to uncured priming paint or middle painting are applied Layer surface, then by metallic coatings construction to uncured solid-shade paint coating surface, then should by the single component varnish composition With construction to uncured metallic coatings surface, finally four partial coatings are solidified simultaneously, to obtain the multicoat coating decoration material System, the multicoat Finish can be used for the baking system of four painting one.

31. single component varnish compositions according to claim 30 are used to prepare the purposes of multicoat Finish, and it is special Levy and be：Three painting two is dried, three apply a baking or integrated form spraying coating process, deflation formula spraying coating process, four paintings two are dried and four apply one The priming paint and/or colored paint used in baking process system are water paint or solvent based coating, and the priming paint and/or colored paint construction are solid Content is between 25%~55%；The colored paint is at least one in solid-shade paint, metallic paint or metallic finishe, thickness after solidification It is 5~40 μm；

The priming paint or floating coating are aqueous or solvent borne priming paint or floating coating；Thickness is 10~50 μm after solidification；

The thickness of dry film of the multicoat Finish is 10 μm~80 μm；The temperature being heating and curing is 100~180 DEG C； The time being heating and curing is 10~40min.