CN108192488A - Solvent-type double-component, the clear coat composition of high slipping, Preparation method and use - Google Patents

Abstract

The invention discloses a kind of solvent-type double-component, the clear coat composition of high slipping, including：Component A includes：Hydroxylated acrylic resin or hydroxy resin, hydroxy polyester resin, amino resins, rheology control agent, Polycaprolactone modified polysiloxanes, auxiliary agent and the first solvent；Component B includes：It is that polyfunctionality aliphatic isocyanates, and/or polyfunctionality alicyclic isocyanate, and/or part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for polyfunctionality aliphatic and or alicyclic isocyanate；Wherein, curing reaction is participated in baking process for the sealer of blocked isocyanate group or sealer for blocked isocyanate group is sloughed in baking process and releases isocyanate groups, the second solvent again.The solvent-type double-component of the present invention, the clear coat composition of high slipping can effectively improve the slipping of clear coat composition film coated surface, so as to increase the rub resistance of film.

Description

Solvent-type double-component, the clear coat composition of high slipping, Preparation method and use

Technical field

The invention belongs to technical field of paint preparation, are related to clear coat composition, preparation method and its usage more particularly to one Kind of solvent-type double-component, the clear coat composition and preparation method thereof of high slipping and the solvent-type double-component, high slipping Clear coat composition according to different construction be coated in ground on formed solidify coating or prepare multicoat Finish should Use method.

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 Automobile demand amount is continuously increased, the thing followed is also being continuously improved for the requirement of automobile appearance and performance.Automobile Vehicle body can assign vehicle body excellent appearance by spray car coating, can also improve the properties of body of a motor car.In order to Vehicle body cleaning is kept, automobile can usually be sent to cleaning shop and be scrubbed in daily life.In scrubbing process, hard hair brush and The cleaning agent of unlike material can be applied to varnish film coated surface, and more or less varnish appearance of film can be impacted, such as：Firmly Matter hairbrush is being scrubbed in friction process, cut can be caused to varnish film coated surface, so as to influence the lustrous surface of varnish film And flatness.In order to improve the rub resistance of varnish film, it will usually by adjusting the usage amount of curing agent in clear coat composition, So that the crosslink density and hardness of film increase, so as to improve the rub resistance of film；But if the friendship of film is improved simply Join density and hardness, some counter productives will certainly be brought, such as：With being continuously increased for hardness of paint film, the flexibility of paint film It is gradually reduced, the impact resistance of paint film and cupping degradation.In recent years, it is referred in some reports, when in clear coat composition After adding in nano-particle, under the premise of film performance is not influenced, it can help to improve the rub resistance of varnish film, still, The high cost of nano-particle also constrains its application in clear coat composition.

Organosilicon is a kind of containing a large amount of organic polymers for repeating Si-O-Si units, and main chain is very submissive, and molecule Between force ratio hydrocarbon want much weaker so that organosilicon have surface tension is weak, surface can small and film forming ability it is strong The features such as, therefore, after organosilicon macromolecule is added in clear coat composition, it can aid in the cunning for improving varnish film coated surface May just as well, film coated surface tension and frictional property are reduced, so as to assign film good rub resistance.

United States Patent (USP) US6387519, US6803408, US2003207985 and world patent WO0109261 disclose one kind The preparation method of the curable clear coat composition of rub resistance can be improved.The clear coat composition contains what is prepared by organosilicon Nano-particle when it is applied on multicoat Finish, after prolonged weathering Erosion, remains to possess good rub resistance Property.

United States Patent (USP) US8569438, US8679589 and US8808805 disclose a kind of with high friction resistance and weather-proof Stability clear coat composition.Component A of the clear coat composition by hydroxyl, the B component containing isocyanate group and available for being catalyzed Silane group carries out crosslinked phosphorous catalytic component and forms.

United States Patent (USP) US2002042471 discloses one kind and has both good rub resistance and acid rain resistance, by polyhydroxy polycarboxylic Two-component solvent type, the heat cure clear coat composition that polymer component and curing agent component are formed.It is different used in the composition Cyanate curing agent contains the aliphatic and/or alicyclic polymeric isocyanate of at least 2~6 isocyanate functionalities, these are different The isocyanate groups of about 0.1%-95% and N- alkyl -3- amine propyl trialkoxy silane and/or N- acyl groups in cyanate - 3- amine propyl trialkoxy silanes are reacted.

United States Patent (USP) US20060217472 disclose it is a kind of containing hydroxy acrylic acid, it is low molecular weight polyols component, poly- different The coating composition of cyanate and amine alkoxysilanes components.The coating composition can be used as automobile varnish to be used for colored paint/varnish System assigns varnish coat rub resistance.

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 containing silane-modified polyisocyanate, wherein：More than 90% isocyanic acid in the polyisocyanate Ester group is reacted with bis-alkoxy silicon substrate amine, the clear coat composition have both excellent rub resistance and high chemically-resistant and Weatherability.

European patent EP 1273640 discloses a kind of two-component clear coat composition covered with paint, lacquer, colour wash, etc. suitable for automobile.The composition It is formed by polyhydric alcohol polymer component and by the curing agent component that aliphatic and/or alicyclic polymeric isocyanate form, wherein：It should 0.1%~95% isocyanate groups are reacted with bis-alkoxy silicon substrate amine in curing agent component.But the varnish combines When object is covered with paint, lacquer, colour wash, etc. for automobile, the film fully after curing has both good rub resistance under the influence of external environment.

Above patent document is referred to the film rub resistance that organosilicon is used to improve to clear coat composition, and is used to improve The silicone ingredients of film performance are mainly the alkyl silane of the group containing response type of small molecule.Pass through reaction contained in silane Type group, such as：Amino and hydroxyl are reacted to obtain partially enclosed or all close silane-modified with isocyanates Isocyanates, and it is used to prepare two-component varnish using the isocyanates as curing agent component.

United States Patent (USP) US4663413 discloses a kind of preparation method of polycaprolactone-polysiloxane block copolymers.According to Associated description in embodiment, 6-caprolactone and linear α, the siloxanes of ω-modification are used to prepare relevant block copolymer, The copolymer is used as the surface modifier of other polymer.

United States Patent (USP) US8729207 discloses a kind of preparation method of novel polycaprolactone-polysiloxane block copolymers. The copolymer contains polysubstituted lactones monomeric unit, additive can be used as to be used for paint field.

United States Patent (USP) US2008255317 discloses a kind of preparation method of polyester-polysiloxane copolymers.According to explanation Associated description in book, when the key component of copolymer is polyester block, which can be used for the centre or surface of vehicle Coating, it can also be used to the additive of various coating, to enhance surface property, such as：Weatherability, gas permeability, rub resistance and cunning May just as well etc..

Yilgor et al. has delivered a kind of preparation of-oxazoline ternary block polymer of novel polycaprolactone-polysiloxanes Method.The ternary block polymer can be used as auxiliary agent for surface modification and modification.Particular content description refers to：[《Novel three First block silicone copolymer：Synthesis, characterization and the application as surface modified additive》,《Polymer science magazine：High score Sub- chemistry》, the 27th phase in the 1989th, P_3673~3690。(“Novel TriblockSiloxane Copolymers:Synthesis, Characterization,and Their Use asSurface Modifying Additives.”Journal of Polymer Science:Part A:Polymer Chemistry,1989,Vol.27,3673-3690.)]

Ekin et al. has delivered a kind of novel hydroxyalkyl and double hydroxyalkyl carbonic ester sealing end dimethyl silicone polymer oligomer The preparation method of copolymer is prepared with them and polycaprolactone.Above-mentioned copolymer can be used as surface modification auxiliary agent, such as handle It is added in thermosetting resin system, can assign low viscous, high flexible, the good impact resistance of system and adhesive force.In specific Hold description to refer to：[《The synthesis of novel hydroxyalkyl and double hydroxyalkyl carbonic ester sealing end dimethyl silicone polymer oligomer and characterization with And their copolymers with polycaprolactone》,《Macromolecular》, the 39th phase in the 2006th, P_8659~8668。(“Synthesis and Characterization of Novel HydroxyalkylCarbamate andDihydroxyalkylCarbamate Terminated Poly(dimethylsiloxane)Oligomers and Their Block Copolymers with Poly(ε-caprolactone).”Macromolecular,2006,Vol.39,8659-8668.)]

Above patent document is referred to a variety of methods for preparing polycaprolactone-polysiloxane block copolymers, these modifications Block copolymer afterwards can be used as potential surface modifier to be used for paint field.

By analyzing above-mentioned document, do not find that there is block and the polycaprolactone of graft modification-poly- silicon simultaneously Siloxane copolymers are used for the example of coating application field as surface slip agent.

In view of this, it is necessary to which a kind of coating with high slipping and high friction resistance, especially a kind of film are provided The varnish of solvent-type double-component with rub resistance, high slipping.

Invention content

For defect in the prior art, it is an object of the present invention to provide a kind of solvent-type double-component, height are sliding Clear coat composition may just as well, the film of the clear coat composition have rub resistance.

It is a further object to provide the systems of a kind of solvent-type double-component, the clear coat composition of high slipping Preparation Method particular by specific preparation method, will have Hydroxylated acrylic resin or hydroxy resin, hydroxyl It is double that polyester resin, amino resins, rheology control agent, Polycaprolactone modified polysiloxanes slipping agent and curing agent are prepared into solvent type Component, high slipping clear coat composition method.

It is also another object of the present invention to provide the use of a kind of solvent-type double-component, the clear coat composition of high slipping On the way, specifically the clear coat composition of the solvent-type double-component, high slipping is coated according to different construction on ground, It forms cured varnish coating and prepares the application process of multicoat Finish.

In order to achieve the above objectives, the technical solution adopted by the present invention is as follows：

One aspect of the present invention provide a kind of solvent-type double-component, high slipping clear coat composition, including：

Component A, including：

At least one Hydroxylated acrylic resin or hydroxy resin；

At least one hydroxy polyester resin；

At least one amino resins；

At least one rheology control agent；

At least one Polycaprolactone modified polysiloxanes；

At least one auxiliary agent；And

At least one first solvent；

Component B, including：

At least one polyfunctionality aliphatic isocyanates；

And/or at least one polyfunctionality alicyclic isocyanate；

And/or at least one part isocyanate groups be closed but still have free isocyanate groups roll into a ball existing for it is more Degree of functionality aliphatic and or alicyclic isocyanate；Wherein, for the sealer of blocked isocyanate group in baking process It participates in curing reaction or the sealer for blocked isocyanate group is sloughed in baking process and releases isocyanates again Group；And

At least one second solvent.

Preferably, one aspect of the present invention provide a kind of solvent-type double-component, high slipping clear coat composition, packet Include the component of following parts by weight：

Component A, including：

20~50 parts of at least one Hydroxylated acrylic resin or hydroxy resin；

At least one 10~30 parts of hydroxy polyester resin；

At least one 10~20 parts of amino resins；

At least one 5~30 parts of rheology control agent；

At least one Polycaprolactone modified 0.1~5 part of polysiloxanes；

At least one 0.1~7 part of auxiliary agent；And

At least one 1~40 part of first solvent；

Component B, including：

At least one 10~50 parts of polyfunctionality aliphatic isocyanates；

And/or at least one 0~20 part of polyfunctionality alicyclic isocyanate；

And/or at least one part isocyanate groups be closed but still have free isocyanate groups roll into a ball existing for it is more Degree of functionality aliphatic and or 0~10 part of alicyclic isocyanate；Wherein, it is being dried for the sealer of blocked isocyanate group Curing reaction is participated in during roasting or the sealer for blocked isocyanate group is sloughed in baking process and released again Isocyanate groups；And

At least one 5~50 parts of second solvent.

The component A and component B is using the ratio that parts by weight are counted as (1~18)：3.

The solvent-type double-component, high slipping clear coat composition in, the solid content of component A between 40%~70% it Between, the solid content of component B is between 50%~90%；In construction, in component A the amount of the substance of hydroxyl with it is different in component B The ratio of the amount of the substance of cyanate group is 1：(0.2~5).

The number-average molecular weight of the Hydroxylated acrylic resin or hydroxy resin is between 2000~20000g/ Between mol, hydroxyl value is between 60~250mg KOH/g, and glass transition temperature (Tg) is between -40 DEG C~+60 DEG C, admittedly contain Amount is between 50%~90%.

The hydroxy functionality of the hydroxy polyester resin is between 2~5, and number-average molecular weight is between 500~8000g/mol Between, hydroxyl value is between 60~250mg KOH/g, and solid content is between 70%~90%.

The amino resins for butyl ether type, containing imido grpup, with melamine resin existing for polymer form, And/or complex etherified type, containing imido grpup, melamine resin existing in the form of oligomer and/or complex etherified Type, whole are etherification modified, with melamine resin existing for monomeric form and/or with carbamate-functional Amino resins；In the present invention, the butyl ether type, containing imido grpup, with melamino-formaldehyde tree existing for polymer form Fat and/or complex etherified type, containing imido grpup, melamine resin and/or compound ether existing in the form of oligomer Change type, whole is etherification modified, may be selected from Niu Pei with melamine resin melamine resin existing for monomeric form The quotient of all related trades mark that this resin (Suzhou) Co., Ltd, BASF AG produce to Zhan Xin resins (Shanghai) Co., Ltd. Industry product, including but not limited to following product known to those skilled in the art：Niu Peisi resins (Suzhou) Co., Ltd Setalux US138 BB70 and Setalux US146 BB72, the Luwipol 072 of BASF AG and Luwipol 052, The Cymel 325, CYMEL 1158, Cymel 1168 and Cymel 303 of Zhan Xin resins (Shanghai) Co., Ltd.；It is described that there is ammonia The amino resins of Carbamate functional groups may be selected from all phases of BASF AG and the production of Zhan Xin resins (Shanghai) Co., Ltd. The commercially produced product of the trade mark is closed, including but not limited to following product known to those skilled in the art：BASF AG The Cymel NF2000 of Larotact 150, Zhan Xin resin (Shanghai) Co., Ltd..

The rheology control agent is the compound containing urea bond, polymer and its derivative；And/or the height with cross-linked structure Molecule fine particle；And/or the treated fine silica particle in surface, preferential selection is with polyester or polyacrylic resin Based on be modified the polyureas and its derivative of preparation.For the present invention, the rheology control agent may be selected from Niu Peisi trees The commercially produced product of all related trades mark of fat (Suzhou) Co., Ltd production, such as：Niu Peisi resins (Suzhou) Co., Ltd Setalux 61767, Setalux 91796, Setalux 91757 and Setalux 91760, also may be selected other companies life The similar products of production.

The Polycaprolactone modified polysiloxanes has the structure as shown in formula (I) or (II)：

In formula (I), R₁With at least one of structure as shown in formula (III)：

In formula (II), R₅With at least one of structure as shown in formula (IV)：

R₂、R₃And R₄It can be identical group or different groups, be respectively provided in the structure as shown in formula (V) At least one：

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

The auxiliary agent is levelling controlling agent, ultra-violet absorber, hindered amine light stabilizer are at least one.

The levelling controlling agent may be selected from the commercially produced product of all related trades mark of German Bi Ke chemical companies production, example Such as：BYK 310, BYK 315, BYK 320, BYK 325, BYK 331, BYK 358N, BYK 3550 and BYK 3560, it is also optional Select the similar products of other companies production.

The ultra-violet absorber can refer to the commercially produced product of all related trades mark produced selected from BASF AG, example Such as：The similar products of other companies production also may be selected in Tinuvin 292, Tinuvin 1130.

The hindered amine light stabilizer can refer to the commercially produced product of all related trades mark produced selected from BASF AG, Such as：The similar products of other companies production also may be selected in Tinuvin 384-2, Tinuvin 123.

The auxiliary agent can further include antioxidant and/or antisettling agent.

The antioxidant and/or antisettling agent can refer to the quotient of all related trades mark produced selected from BASF AG Industry product, such as：Irgafos168 and963S；Also the similar products of other companies production may be selected.Its In, the dosage of the antioxidant is depending on the resin of different purposes, and the dosage of antisettling agent is depending on the dosage of pigment.When When needing using aforementioned antioxidant and antisettling agent, also need they being uniformly mixed with other components in auxiliary agent.

First solvent is aliphatic ester, ketone, dihydric alcohol ethers, dihydric alcohol esters, aromatic series carbon hydrocarbon solvent At least one of, including but not limited to following compound known to those skilled in the art：Toluene, dimethylbenzene, S-100# are molten Agent oil, 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, propylene glycol monomethyl ether acetic acid Ester.

The degree of functionality of isocyanate groups is at least 2, specially Isosorbide-5-Nitrae-two in the polyfunctionality aliphatic isocyanates Isocyanate group butane, 1,6- diisocyanate bases hexane (HDI, hexamethylene diisocyanate), 2- methyl-1s, 5- diisocyanate bases Pentane, 1,5- diisocyanate base -2,2- dimethyl-pentane, 2,2,4- trimethyl -1,6- diisocyanate bases hexane, 2,4,4- tri- Methyl-1,6- diisocyanate bases hexane, 1,10- diisocyanate base decane and/or by above-mentioned aliphatic diisocyanate monomer shape Into tripolymer, pentamer and polymer.

The degree of functionality of isocyanate groups is at least 2 in the polyfunctionality alicyclic isocyanate, specially 1,3- bis- Isocyanate group hexamethylene, 1,4- diisocyanates butylcyclohexane, 2,6- diisocyanate base -1- hexahydrotoluenes, 2,4- diisocyanates Base -1- hexahydrotoluenes, 1,3- be bis--and (isocyanatometyl) hexamethylene, 1,4- be bis--(isocyanatometyl) hexamethylene, different Buddhist Your ketone diisocyanate (IPDI), 2,4 '-diisocyanate base dicyclohexyl methyl hydride, 4,4 '-diisocyanate base dicyclohexyl methyl hydride, - 4 (3) isocyanato methylcyclohexane of 1- isocyanate group -1- methyl, bis- (isocyanatometyl)-norbornanes and/or by upper State tripolymer, pentamer and the polymer of alicyclic diisocyanate monomer formation.

It is that the part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for polyfunctionality fat Race and or the degrees of functionality of alicyclic isocyanate middle reaches free isocyanate groups be at least 1.

Second solvent is aliphatic ester, ketone, dihydric alcohol ethers, dihydric alcohol esters, aromatic series carbon hydrocarbon solvent At least one of, including but not limited to following compound known to those skilled in the art：Toluene, dimethylbenzene, S-100# are molten Agent oil, 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, propylene glycol monomethyl ether acetic acid Ester.

Another aspect of the present invention provide a kind of solvent-type double-component, high slipping clear coat composition system Preparation Method, particular by first by Hydroxylated acrylic resin or hydroxy resin, hydroxy polyester resin, amino tree Component A is made in fat, rheology control agent, Polycaprolactone modified polysiloxanes, auxiliary agent and solvent, then carries out component A and component B Be prepared by mixing into solvent-type double-component, high slipping clear coat composition, include the following steps (using prepare 1kg varnish sample as Example)：

The first step gathers the first solvent of first part, Hydroxylated acrylic resin or hydroxy resin and hydroxyl Ester resin agitating is uniformly mixed；

Second step, be kept stirring rate it is constant in the case of, sequentially add amino resins, rheology control agent, gather oneself in The first solvent of ester modified polysiloxanes, auxiliary agent and second part is uniformly mixed and obtains the component A；

Third walk, be kept stirring rate it is constant in the case of, by polyfunctionality aliphatic isocyanates, and/or more officials It is that energy degree alicyclic isocyanate, and/or part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for Polyfunctionality aliphatic and or alicyclic isocyanate；Wherein, for the sealer of blocked isocyanate group in baking process Middle participation curing reaction or the sealer for blocked isocyanate group are sloughed in baking process and release isocyanic acid again Ester group；And second solvent mixing, obtain the component B；

Component B is added in component A by the 4th step, and the solvent-type double-component, high slipping are obtained after stirring evenly Clear coat composition.

The rate for referring to stirring that is uniformly mixed is 400~1000 revs/min (r/min), mixing time 10 ~60min.

Amino resins, rheology control agent, Polycaprolactone modified polysiloxanes, auxiliary agent and are sequentially added in the second step The time interval of two the first solvents of part is 5~10min.

The preparation method of the Polycaprolactone modified polysiloxanes includes the following steps：

Unsaturated monohydric alcohol and hexamethyldisilazane are mixed temperature reaction by the first step, and front three is obtained after the reaction was complete Base siloxy unsaturated compound；

Under nitrogen protection, catalyst is added in the trimethylsiloxy group unsaturated compound that the first step is obtained for second step Trimethyl cyclotrisiloxane is added dropwise in mixing, temperature reactionThe alkyl-modified ring three of trimethylsiloxy group is obtained after reaction Siloxanes

Third walks, under the conditions of anhydrous and oxygen-free, by monofunctional alkyl lithium or difunctional alkyl's lithium, the front three of second step acquisition Base siloxyalkyl is modified cyclotrisiloxaneHexamethyl cyclotrisiloxane D₃It is mixed with solvent, temperature reaction, adds in diformazan Base silicane hydroxide terminates reaction, and obtain side chain by post processing carries silicon hydrogen group with hydroxy-protective group, single-ended or both-end Polysiloxanes；

The side chain that third step obtains under nitrogen protection, is carried silicon by the 4th step with hydroxy-protective group, single-ended or both-end The polysiloxanes of hydrogen group is mixed with catalyst, temperature reaction, and the trimethylsiloxy group unsaturation chemical combination that the first step obtains is added dropwise Object reacts, and side chain, single-ended or the both-end polysiloxanes with hydroxy-protective group are obtained by post processing；

5th step, the side chain that the 4th step is obtained, single-ended or both-end carry polysiloxanes, the alcohols of hydroxy-protective group Solvent and weak acid catalyst mixing, temperature reaction obtain the polysiloxanes that side chain, single-ended or both-end carry hydroxyl alkyl；

6th step by the side chain of the 5th step acquisition, single-ended or the both-end polysiloxanes with hydroxyl alkyl, caprolactone and has Machine tin catalyst mixes, and heating is reacted, and Polycaprolactone modified polysiloxanes is obtained by post processing.

The temperature of temperature reaction is 90~120 DEG C in the first step, and the time is 4~8h.

The molar ratio of unsaturated monohydric alcohol and hexamethyldisilazane is 2 in the first step:(1~2), preferably 2:(1~ 1.1)。

Unsaturated monohydric alcohol is at least one of lower structure in the first step：

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

A₄)CH₂=CHCH₂CH₂CH₂CH₂OH A₅)CH₂=CHCH₂NHC(O)OCH₂CH₂OH。

Trimethylsiloxy group unsaturated compound is at least one of lower structure in the first step：

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

B₄)CH₂=CHCH₂CH₂CH₂CH₂OSi(CH₃)₃ B₅)CH₂=CHCH₂NHC(O)OCH₂CH₂OSi(CH₃)₃。

The temperature of temperature reaction is 80~110 DEG C in the second step, and the time is 4~12h.

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

Trimethylsiloxy group unsaturated compound and trimethyl cyclotrisiloxane in the second stepMolar ratio be (3 ~6):1, preferably (3~3.3):1.

Catalyst is chloroplatinic acid in the second step.

The alkyl-modified cyclotrisiloxane of trimethylsiloxy group in the second stepFor at least one of lower structure：

The temperature of temperature reaction is -70 DEG C~50 DEG C in the third step, time 4-12h.

Monofunctional alkyl lithium or the molar ratio of difunctional alkyl's lithium and dimethyl silicane hydroxide are 1 in the third step:(1 ~2.2).

Solvent includes non-polar organic solvent and polar organic solvent in third step, the non-polar organic solvent and Mass ratio between polar organic solvent is 1:(1~5).

Solvent and the alkyl-modified cyclotrisiloxane of trimethylsiloxy group in the third stepHexamethyl cyclotrisiloxane D₃, monofunctional alkyl lithium or difunctional alkyl's lithium total mass ratio be (0.25~4):1.

The alkyl-modified cyclotrisiloxane of trimethylsiloxy group in third stepHexamethyl cyclotrisiloxane D₃With simple function alkane The molar ratio of these three reactants of base lithium or difunctional alkyl's lithium regards the size of products therefrom molecular weight after anionic polymerisation Depending on.

Hydroxy-protective group is carried with reference to the side chain obtained after anionic polymerisation in embodiment 7, single-ended with silicon hydrogen group Polysiloxanes, molecular weight design formula (using n-BuLi as initiator, dosage be 1mol for) it is as follows：

Molecular weight (57)+D of design molecular weight=normal-butyl of the polysiloxanes^T ₃Molecular weight × D^T ₃Substance amount (n/ 3)+D₃Molecular weight × D₃Substance amount (m/3)+(CH₃)₂The molecular weight (59) of SiH, i.e. M=57+60m+190n+59.

If it is 1000 or so to design molecular weight, n and m is respectively 1 and 12 in above-mentioned reaction equation, that is, preparing molecular weight is 1000 or so side chain about needs the n-BuLi of 1mol with hydroxy-protective group, the single-ended polysiloxanes with silicon hydrogen group The D of initiator, 1/3mol^T ₃With the D of 4mol₃。

The side chain with hydroxy-protective group, the single-ended polysiloxanes with silicon hydrogen group design molecular weight= M_{The molecular weight of monofunctional alkyl lithium or difunctional alkyl's lithium removal lithium}+D^T ₃Molecular weight × D^T ₃Substance amount+D₃Molecular weight × D₃Substance amount+ M_{Dimethyl silicane hydroxide}。

With reference to the side chain obtained after anionic polymerisation in embodiment 8 silicon hydrogen group is carried with hydroxy-protective group, both-end Polysiloxanes, molecular weight design formula (using dimethylsilyl bis lithium as initiator, dosage be 1mol for) it is as follows：

Molecular weight (90)+D of design molecular weight=dimethylsilyl bis of the polysiloxanes^T ₃Molecular weight × D^T ₃Substance Amount ((p+q)/3)+D₃Molecular weight × D₃Substance amount ((o+r)/3)+2 × (CH₃)₂The molecular weight (118) of SiH, i.e. M + 204 (p+q)+118 of=57+60 (o+r).

If design molecular weight is 1000 or so, (p+q) and (o+r) is respectively 1 and 10 in above-mentioned reaction equation, that is, is prepared point Son amount carries the polysiloxanes of hydroxy-protective group, both-end with silicon hydrogen group for 1000 or so side chain, about needs the two of 1mol The D of methyl siloxy lithium initiator, 1/3mol^T ₃With the D of 10/3mol₃。

Design molecular weight of the side chain with the polysiloxanes of hydroxy-protective group, both-end with silicon hydrogen group= M_{The molecular weight of monofunctional alkyl lithium or difunctional alkyl's lithium removal lithium}+D^T ₃Molecular weight × D^T ₃Substance amount+D₃Molecular weight × D₃Substance amount+2 × M_{Dimethyl silicane hydroxide}。

Monofunctional alkyl lithium or difunctional alkyl's lithium are at least one of lower structure in the third step：

In the third step non-polar organic solvent in aliphatic, alicyclic, aromatic series carbon hydrocarbon solvent at least One kind, including but not limited to following compound known to those skilled in the art：Isopentane, pentane, petroleum ether, n-hexane, Hexamethylene, isooctane, pentamethylene, trimethylpentane, pentamethylene, heptane, toluene, benzene, dimethylbenzene.

In the third step polar organic solvent be selected from aliphatic ketone, alicyclic ketones, aromatic ketones, amides, At least one of sulfoxide type, nitrile, heterocyclic solvent, including but not limited to following chemical combination known to those skilled in the art Object：Tetrahydrofuran, formamide, acetonitrile, N,N-dimethylformamide, hexamethyl phosphoramide, butanone, dimethyl sulfoxide, acetone, 1,4- Dioxane, pyridine.

Dimethyl silicane hydroxide is dimethylchlorosilane in the third step.

Number of the side chain with the polysiloxanes of hydroxy-protective group, single-ended or both-end with silicon hydrogen group in the third step Average molecular weight (Mn) is between 200~10000, and preferably 500~3000；Degree of polymerization index (PDI) is between 1~1.2；Tool Have at least one of lower structure,

Wherein：m>0, n>0, o>0, p>0, q>0, r>0；

R₁With at least one of structure as shown in formula (III)：

R₂With at least one of structure as shown in formula (V)：

R₅With at least one of structure as shown in formula (IV)：

The temperature reacted in 4th step is 80~110 DEG C, and the time is 4~12h.

Catalyst is chloroplatinic acid in 4th step.

Catalyst quality accounts for side chain and carries silicon hydrogen group with hydroxy-protective group, single-ended or both-end in 4th step The 0.05%~1% of polysiloxanes quality.

Trimethylsiloxy group unsaturated compound carries hydroxy-protective group, single-ended or both-end with side chain in 4th step Molar ratio between silicon hydrogen group contained by polysiloxanes with silicon hydrogen group (Si-H) is (1~2):1, preferably (1.01~ 1.05):1。

Side chain, single-ended or the both-end polysiloxanes with hydroxy-protective group have following structure in 4th step At least one：

Wherein：m>0, n>0, o>0, p>0, q>0, r>0；

R₁With at least one of structure as shown in formula (III)：

R₅With at least one of structure as shown in formula (IV)：

R₂、R₃And R₄It can be identical group or different groups, be respectively provided in the structure as shown in formula (V) At least one：

The temperature of temperature reaction is 65 DEG C~100 DEG C in 5th step, and the reaction time is 4~12h.

Alcohols solvent is at least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol in 5th step.

Weak acid catalyst is formic acid, acetic acid, propionic acid, lactic acid, dihydromethyl propionic acid, dimethylolpropionic acid in 5th step At least one of.

Side chain, single-ended or both-end are between polysiloxanes and alcohols solvent with hydroxy-protective group in 5th step Mass ratio be 1:(1~4).

The quality of weak acid catalyst accounts for the poly- silicon that side chain, single-ended or both-end carry hydroxy-protective group in 5th step The 0.5%~5% of oxygen alkane quality.

During side chain, single-ended or the both-end polysiloxanes with hydroxyl alkyl have following structure in 5th step at least It is a kind of：

Wherein：m>0, n>0, o>0, p>0, q>0, r>0；

R₁With at least one of structure as shown in formula (III)：

R₅With at least one of structure as shown in formula (IV)：

R₂、R₃And R₄It can be identical group or different groups, be respectively provided in the structure as shown in formula (V) At least one：

The temperature reacted that heats up in 6th step is 80 DEG C~140 DEG C, and the time is 5~20h.

In 6th step in Polycaprolactone modified polysiloxanes the number-average molecular weight (Mn) of polycaprolactone segment between 200 Between~5000, preferably 500~3500.

Organotin catalysts are stannous iso caprylate, dibutyl tin laurate, dioctyl tin oxide, two in 6th step At least one of butyl tin oxide, tributyl tin, dibutyltin diacetate.

Organotin catalysts quality accounts for the 0.01%~5% of caprolactone quality in 6th step.

The side chain, single-ended or the both-end molar ratio of polysiloxanes and caprolactone with hydroxyl alkyl between the two Depending on the size of polycaprolactone chain segment molecular weight, wherein：The molecular weight of each polycaprolactone segment between 200~5000 it Between.

With reference to the polycaprolactone modified polyorganosiloxane in embodiment 7 with structure formula (I), point of each polycaprolactone segment Son is measured：The molecular weight (114) of molecular weight (114) and y × own lactones of n × x × own lactones, wherein：200<n×x×114< 5000,200<114y<5000, the total molecular weight of polycaprolactone segment is：400<(3x+y)×114<10000.

If in final product structural formula, n, x and y are respectively 1,1.8 and 1.9, then the molecule of each polycaprolactone segment It measures and is：205.2 and 216.6.

There is the polycaprolactone modified polyorganosiloxane of structure formula (II) in reference embodiment 8, each polycaprolactone segment Molecular weight is：(p+q) molecular weight (114) of the molecular weight (114) of × x × own lactones and (y+z) × own lactones, wherein：200< (p+q)×x×114<5000,200<114(y+z)<5000, the total molecular weight of polycaprolactone segment is：400<[(p+q)×x+ (y+z)]×114<10000。

If in final product structural formula, (p+q), x, y and z are respectively 1,2.7,2 and 2, then each polycaprolactone segment Molecular weight be：307.8th, 228 and 228.

It is that the part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for polyfunctionality fat Race and or the preparation method of alicyclic isocyanate include the following steps：

Polyfunctionality aliphatic isocyanates and/or polyfunctionality alicyclic isocyanate are mixed with catalyst, then Reaction system is warming up to 60~80 DEG C, after constant temperature, the mixed solution of sealer and solvent is slowly added dropwise, during dropwise addition Controlling reaction temperature keeps temperature to be no more than 80 DEG C, the 4~5h that is added dropwise in this temperature that the reaction was continued, controls remaining isocyanide Acid groups content stops reacting and discharges, obtain that part isocyanate groups are closed but still have free isocyanate groups group to deposit Polyfunctionality aliphatic and or alicyclic isocyanate.

The catalyst is organo-tin compound or organo-alkali compound.

The organo-tin compound is stannous iso caprylate, dibutyltin dilaurate, dioctyl tin oxide, dibutyl oxygen Change at least one of tin, tributyl tin, dibutyltin diacetate.

The organo-alkali compound is at least one of sodium methoxide, sodium ethoxide.

The sealer has one of structure as shown in formula (VI), (VII) or (VIII)：

Wherein, R₆And R₇It can be identical group or different groups, be respectively selected from containing 1~8 carbon original The aliphatic alkane base of son；

R₈(CH₂)_aSi(OR₉)(OR₁₀)(OR₁₁)

(VII)

HN[(CH₂)_aSi(OR₉)(OR₁₀)(OR₁₁)]

(VIII)

Wherein, R₈For at least one of primary amino group, hydroxyl, sulfydryl, a is the integer more than or equal to 1, R₉、R₁₀And R₁₁It can To be identical group or different groups, be respectively selected from the aliphatic alkane base containing 1~8 carbon atom and/or The aliphatic acyl radical of 1~8 carbon atom；

Or, sealer is the compound containing reactive hydrogen, specially unary alcohol, monosubstituted alcohol ethers, ketoxime class, unitary At least one of amine, pyrazoles, alicyclic ring amides, including but not limited to following chemical combination known to those skilled in the art Object：Methanol, ethyl alcohol, propyl alcohol, n-butanol, isobutanol, n-hexyl alcohol, n-octyl alcohol, isooctanol, benzyl alcohol, benzyl carbinol, ethylene glycol list first Ether, ethylene glycol monobutyl ether, ethylene glycol monohexylether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl two Alcohol monobutyl ether, diethylene glycol monohexyl ether, methyl ethyl ketoxime, acetoxime, cyclohexanone ketoxime, diisopropylamine, N- tert-butyl benzyl amines, 3, 5- dimethyl pyrazoles, caprolactam.

The solvent is aliphatic ester, in ketone, dihydric alcohol ethers, dihydric alcohol esters, aromatic series carbon hydrocarbon solvent At least one, 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), cyclohexanone, acetic acid second Ester, butyl acetate, butyl glycol ether acetic acid esters, pentyl acetate, ethylene glycol ethyl ether propionic ester, propylene glycol methyl ether acetate.

The degree of functionality of isocyanate groups is at least 2, specially Isosorbide-5-Nitrae-two in the polyfunctionality aliphatic isocyanates Isocyanate group butane, 1,6- diisocyanate bases hexane (HDI, hexamethylene diisocyanate), 2- methyl-1s, 5- diisocyanate bases Pentane, 1,5- diisocyanate base -2,2- dimethyl-pentane, 2,2,4- and/or 2,4,4- trimethyl -1,6- diisocyanates base oneself Alkane, 1,10- diisocyanate base decane and/or the tripolymer formed by above-mentioned aliphatic diisocyanate monomer, pentamer and more Aggressiveness.

The degree of functionality of isocyanate groups is at least 2 in the polyfunctionality alicyclic isocyanate, specially 1,3- bis- Isocyanate group hexamethylene, 1,4- diisocyanates butylcyclohexane, 2,6- diisocyanate base -1- hexahydrotoluenes, 2,4- diisocyanates Base -1- hexahydrotoluenes, 1,3- be bis--and (isocyanatometyl) hexamethylene, 1,4- be bis--(isocyanatometyl) hexamethylene, different Buddhist Your ketone diisocyanate (IPDI), 2,4 '-diisocyanate base dicyclohexyl methyl hydride, 4,4 '-diisocyanate base dicyclohexyl methyl hydride, - 4 (3) isocyanato methylcyclohexane of 1- isocyanate group -1- methyl, bis- (isocyanatometyl)-norbornanes and/or by upper State tripolymer, pentamer and the polymer of alicyclic diisocyanate monomer formation.

The quality of the catalyst accounts for the polyfunctionality aliphatic isocyanates and/or the alicyclic isocyanic acid of polyfunctionality The 0.01~1% of the quality of ester.

The quality of the sealer accounts for the polyfunctionality aliphatic isocyanates and/or the alicyclic isocyanic acid of polyfunctionality The 20~50% of the quality of ester.

The quality of the solvent accounts for the polyfunctionality aliphatic isocyanates and/or polyfunctionality alicyclic isocyanate Quality 40~50%.

Another aspect of the invention provide a kind of solvent-type double-component, high slipping clear coat composition use On the way, specially described solvent-type double-component, high slipping clear coat composition for forming solidify coating on ground；Including with Lower step：

On priming paint or floating coating application and construction to ground and it will first be cured, by colored paint application and construction to priming paint or middle painting On the ground that coating has been cured, then by the solvent-type double-component, high slipping clear coat composition application and construction to not Cured colored paint surface, finally cures two parts coating simultaneously, and to obtain the multicoat Finish, the multicoat applies Decorations system can be used for three to apply two baking systems；

Alternatively,

First by priming paint or it is middle painting application and construction to ground on, then by colored paint application and construction to uncured priming paint or middle painting Coating surface, then by the solvent-type double-component, high slipping clear coat composition application and construction to uncured colored paint coating Surface finally cures three parts coating simultaneously, and to obtain the multicoat Finish, the multicoat Finish can be used One, which is applied, in three dries system or integrated form spraying process (IPP) system；

Alternatively,

Two layers of colored paint is constructed onto no priming paint and the ground of middle painting, then molten described in second layer colored paint surface spraying The clear coat composition of dosage form bi-component, high slipping, and three parts coating is cured simultaneously, to obtain the multicoat coating decoration material System, the multicoat Finish can be used for deflation formula spraying process (CCT) system；

Alternatively,

On priming paint or floating coating application and construction to ground and it will first be cured, then by solid-shade paint application and construction to priming paint Or on the ground that has been cured of middle coating layer, then metallic coatings are constructed to uncured solid-shade paint coating surface, then by institute State solvent-type double-component, high slipping clear coat composition application and construction to uncured metallic coatings surface, finally by three Coating is divided to cure simultaneously, to obtain the multicoat Finish, the multicoat Finish can be used for four to apply two baking systems；

Alternatively,

First by priming paint or it is middle painting application and construction to ground on, then by solid-shade paint application and construction to uncured priming paint or in Coating layer surface, then metallic coatings are constructed to uncured solid-shade paint coating surface, then by the solvent-type double-component, height The clear coat composition application and construction of slipping finally cures four partial coatings simultaneously to uncured metallic coatings surface, with The multicoat Finish is obtained, the multicoat Finish can be used for four to apply a baking system.

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；The cured temperature is 100~180 DEG C；The cured time is 10~40min.

Three paintings, two baking, integrated form spraying process, tightens formula spraying process, four paintings, two baking, four paintings, one baking at three one bakings of painting Priming paint and colored paint used in system are water paint, the construction solid content of the priming paint between 35%~55%, Gu Film thickness after change is between 10~50 μm, and between 20%~40%, the film thickness after curing is situated between the construction solid content of the colored paint Between 6~20 μm.

The outermost coating of multicoat Finish is by the solvent-type double-component, the clear coat composition of high slipping It is prepared；The thickness of dry film of the multicoat Finish be 10 μm~80 μm, preferably 20 μm~70 μm, further preferred 30 μm~60 μm；The cured temperature is 100~180 DEG C, preferably 120~160 DEG C；The cured time is 10~40min.

The solvent-type double-component, high slipping clear coat composition can be used as finishing varnish, for automobile cover with paint, lacquer, colour wash, etc..

Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effect：

The solvent-type double-component of the present invention, the clear coat composition of high slipping have used gathering in oneself with special construction Ester modified polysiloxanes when it is added in solvent based coating, particularly in solvent-based varnishes, can improve the superficiality of film Can, increase slipping, improve rub resistance.

The clear coat composition of solvent-type double-component provided by the invention, high slipping can effectively improve varnish combination The slipping of object film coated surface, so as to increase the rub resistance of film.

Solvent-type double-component provided by the invention, high slipping clear coat composition in, Polycaprolactone modified polysiloxanes Middle polycaprolactone is simultaneously modified polysiloxanes by block and grafting, can have the block modified poly- silica of polycaprolactone concurrently The advantages of alkyl copolymer and polycaprolactone graft modification graft polysiloxane copolymer.

Solvent-type double-component provided by the invention, high slipping clear coat composition in, Polycaprolactone modified polysiloxanes Can be used as solvent based coating auxiliary agent, when being added in solvent based coating, particularly in solvent-based varnishes when, film can be improved Surface property, increase slipping, improve rub resistance.

Solvent-type double-component provided by the invention, high slipping clear coat composition in, Polycaprolactone modified polysiloxanes It is made of special polysiloxanes segment and polycaprolactone segment, there is excellent compatibility between solvent based coating, it can As coating additive, can especially be used as surface slip agent；It is slided Polycaprolactone modified polysiloxanes as surface After refreshing agent is added in solvent based coating, coating surface tension can be reduced, so as to provide good wetability and good anti- Shrinkage cavity；It is particularly added in solvent-based varnishes, will not generate varnish muddy, moreover it is possible to further enhance varnish paint Surface slip and scratch resistance.

Specific embodiment

In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection domain of invention.

In the case of being clear from, being explained to the purpose of the present invention by following embodiment, the component of the composition It is released using parts by weight as the universal standard bright.In the case of no special instruction, for simplicity, institute in the embodiment of the present invention " parts by weight " and " part " stated have identical meaning.

Embodiment 1

Hydroxyl (methyl) acrylic resin

First, by 3000g dimethylbenzene and propylene glycol methyl ether acetate (mass ratio 1:1) mixed solvent, which is added to, to be equipped with Blender, thermometer, nitrogen conduit and reflux condenser 10L reaction kettles in, and reaction system is warming up to 130~140 DEG C. It, will be by 500g styrene, 2250g n-butyl acrylates, 1750g hydroxyethyl methacrylates, 50g third after reaction temperature is stablized The reaction mixture of olefin(e) acid, 450g methyl methacrylates and 310g peroxidating 2- ethyl acids tert-butyl ester composition passes through peristaltic pump It is added drop-wise in reaction kettle, reaction temperature is maintained to control drop rate between 130~140 DEG C during being added dropwise, it is ensured that 2~ Reaction mixture is added dropwise in 4h.After being added dropwise, continue to keep the temperature 2~4h between 130~140 DEG C, terminate reaction, obtain To solid content be 62.5%, hydroxyl value 150mgKOH/g, glass transition temperature (Tg) for 0 DEG C, number-average molecular weight be 3500 or so Hydroxylated acrylic resin.

Embodiment 2

Hydroxyl (methyl) acrylic resin

First, by 3000g dimethylbenzene and propylene glycol methyl ether acetate (mass ratio 1:1) mixed solvent is added to dress Have in the 10L reaction kettles of blender, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 ℃.After reaction temperature is stablized, will by 500g styrene, 1750g n-butyl acrylates, 1750g hydroxyethyl methacrylates, The reaction mixture of 50g acrylic acid, 950g methyl methacrylates and 432g peroxidating 2- ethyl acids tert-butyl ester composition passes through Peristaltic pump is added drop-wise in reaction kettle, reaction temperature is maintained to control drop rate between 130~140 DEG C during being added dropwise, it is ensured that Reaction mixture is added dropwise in 2~4h.After being added dropwise, continue to keep the temperature 2~4h between 130~140 DEG C, terminate anti- Should, obtain solid content be 62.5%, hydroxyl value 150mgKOH/g, glass transition temperature (Tg) for 15 DEG C, number-average molecular weight be 2500 or so Hydroxylated acrylic resin.

Embodiment 3

Hydroxy polyester resin

In the reaction kettle of 5L, sequentially add 708g 1,6- hexylene glycols (M=118), 312g neopentyl glycols (M=104), 804g trimethylolpropanes (M=134), 216g 1,4 cyclohexane dimethanols (M=144), 1752g adipic acids (M=146), 516g1,6- cyclohexane diacids (M=172) and 2.5g Dibutyltin oxides.It opens and stirs and reaction kettle is to slowly warm up to 120 DEG C, And 15~30min is kept the temperature at this temperature.After material all dissolving, reaction kettle is warming up to 150 DEG C and is protected at this temperature Then reaction kettle is warming up to 180 DEG C and continues 2~2.5h of heat preservation at this temperature, finally reaction kettle heats up by 2~2.5h of temperature To 220 DEG C.Reaction kettle is persistently kept the temperature at 220 DEG C, when still temperature drops to 80 DEG C, adds in refluxing xylene band water, And every 3h sampling and measuring acid values.When acid value is less than 3, stops heating and reaction system is cooled to 110 DEG C, then add in 1572g butyl acetates are diluted, and are obtained solid content and are 70%, hydroxyl value 134mgKOH/g, hydroxy functionality 3, count and divide equally The hydroxy polyester resin that son amount is 2500 or so.

Embodiment 4

Hydroxy polyester resin

In the reaction kettle of 5L, sequentially add 708g 1,6- hexylene glycols (M=118), 312g neopentyl glycols (M=104), 804g trimethylolpropanes (M=134), 216g 1,4 cyclohexane dimethanols (M=144), 1752g adipic acids (M=146), 567.6g1,6- cyclohexane diacid (M=172) and 2.5g Dibutyltin oxides.It opens and stirs and reaction kettle is to slowly warm up to 120 DEG C, and 15~30min is kept the temperature at this temperature.After material all dissolving, reaction kettle is warming up to 150 DEG C and at this temperature 2~2.5h is kept the temperature, reaction kettle is then warming up to 180 DEG C and continues 2~2.5h of heat preservation at this temperature, finally by reaction kettle liter Temperature is to 220 DEG C.Reaction kettle is persistently kept the temperature at 220 DEG C, when still temperature drops to 80 DEG C, adds in refluxing xylene band Water, and every 3h sampling and measuring acid values.When acid value is less than 3, stops heating and reaction system is cooled to 110 DEG C, Ran Houjia Enter 1230g butyl acetates to be diluted, obtain solid content and be 75%, hydroxyl value 82mgKOH/g, hydroxy functionality 3.25, count Average molecular weight is 3000 or so hydroxy polyester resin.

Embodiment 5

It is that part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for polyfunctionality aliphatic With or alicyclic isocyanate, wherein, slough in baking process and discharge again for the sealer of blocked isocyanate group Go out isocyanate groups；

By 964g hexamethylene diisocyanate trimers (the Desmodur N 3300 of product designation Beyer Co., Ltd) and 1g dibutyltin dilaurates are added in the 2L reaction kettles equipped with blender, thermometer, nitrogen conduit and reflux condenser, Then reaction system is warming up to 70 DEG C.After constant temperature, 288g 3 is slowly added dropwise, 5- dimethyl pyrazoles are dissolved in 410g second The mixed solution of acid butyl ester, controlling reaction temperature during dropwise addition keep temperature to be no more than 80 DEG C.It is added dropwise in this temperature The reaction was continued 4~5h when remaining isocyanate group content reaches theoretical value 5.05%, stops reacting simultaneously discharging, obtains solid content For 75%, part isocyanate groups be closed but still have free isocyanate groups roll into a ball existing for polyfunctionality aliphatic and Or alicyclic isocyanate.

Embodiment 6

It is that part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for polyfunctionality aliphatic With or alicyclic isocyanate, wherein, for the sealer of blocked isocyanate group, that curing is participated in baking process is anti- It should；

By 964g hexamethylene diisocyanate trimers (the Desmodur N 3300 of product designation Beyer Co., Ltd), 222g isophorone diisocyanate and 1g dibutyltin dilaurates are added to equipped with blender, thermometer, nitrogen conduit In the 2L reaction kettles of reflux condenser, reaction system is then warming up to 70 DEG C.After constant temperature, 270g hydroxyls are slowly added dropwise Propyl trimethoxy silicane and 261g methyl ethyl ketoximes, controlling reaction temperature during dropwise addition keep temperature to be no more than 80 DEG C.It is added dropwise 4~the 5h that finishes in this temperature that the reaction was continued, when remaining isocyanate group content reaches theoretical value 7.34%, stop reacting simultaneously plus Enter 570g butyl acetates, obtain solid content for 75%, part isocyanate groups are closed but still have free isocyanate groups Group existing for polyfunctionality aliphatic and or alicyclic isocyanate.

Embodiment 7

Polycaprolactone modified polysiloxanes with structure formula (I), R₁For CH₃CH₂CH₂CH₂, R₂And R₃It is CH₂CH₂CH₂, n=1, m=12, x=1.8, y=1.9；

The reaction equation of Polycaprolactone modified polysiloxanes with structure formula (I) is as follows：

The first step, hydroxyl protection：In the reaction kettle of 1L, 338.1g (2.1mol) hexamethyldisilazane is delayed at room temperature Slowly it is added drop-wise to 232g (4mol) allyl alcohols A₁In (molar ratio of unsaturated monohydric alcohol and hexamethyldisilazane be 2:1.05).Drop After adding, reaction system is warming up to 100 DEG C, and stops reaction after the reaction was continued 6 hours in this temperature.Normal pressure is collected 98-100 DEG C of fraction obtains allyloxy trimethyl silane 473.2g, yield 91%.

Second step, a Si―H addition reaction：In the reaction kettle of 1L, the acquisition of 393.9g (3.03mol) first step is sequentially added Allyloxy trimethyl silane and 0.5g chloroplatinic acid catalysts (quality of catalyst accounts for trimethyl cyclotrisiloxane quality 0.28%) after, being passed through nitrogen 20min, reaction system is warming up to 100 DEG C, 180g (1mol) trimethyl is added dropwise at this temperature (molar ratio of trimethylsiloxy group unsaturated compound and trimethyl cyclotrisiloxane is 3.03 to cyclotrisiloxane:1) 8h, is reacted Reaction is terminated afterwards.Vacuum distillation removal low-boiling-point substance, obtains the alkyl-modified cyclotrisiloxane of 553g trimethylsiloxy groups, yield 97.0%.

Third walks, anionic polymerisation：In by anhydrous and oxygen-free treated 2L reaction kettles, 64g (1mol) is sequentially added The alkyl-modified cyclotrisiloxane of trimethylsiloxy group that n-BuLi, 740g hexamethyl cyclotrisiloxanes, 190g second steps obtain With 500g n-hexanes and tetrahydrofuran (mass ratio 1:1) mixed solution (solvent and the alkyl-modified ring three of trimethylsiloxy group Siloxanes, hexamethyl cyclotrisiloxane, monofunctional alkyl lithium or difunctional alkyl's lithium total mass ratio be 0.33:1), at 25 DEG C Under be stirred to react 8h after, adding in 1.1mol dimethylchlorosilanes, (molar ratio of n-BuLi and dimethylchlorosilane is 1:1.1) Terminate reaction.Reaction solution is filtered to remove to the lithium chloride of generation, after vacuum distillation removes low-boiling-point substance, obtains 987g number-average molecular weights Hydroxy-protective group and single-ended gathering with silicon hydrogen group are carried for 1026 or so the, side chain that degree of polymerization index (PDI) is 1.12 Siloxanes, yield 96.2%.

The alkyl-modified cyclotrisiloxane of trimethylsiloxy group in preparation processHexamethyl cyclotrisiloxane D₃And simple function The molar ratio of these three reactants of lithium alkylide or difunctional alkyl's lithium regard anionic polymerisation after products therefrom molecular weight it is big Depending on small.

The side chain obtained after anionic polymerisation in the present embodiment is with hydroxy-protective group, single-ended gathering with silicon hydrogen group Siloxanes, molecular weight design formula are as follows (using n-BuLi as initiator, for dosage is 1mol)：

Molecular weight (57)+D of design molecular weight=normal-butyl of the polysiloxanes^T ₃Molecular weight × D^T ₃Substance amount (n/ 3)+D₃Molecular weight × D₃Substance amount (m/3)+(CH₃)₂The molecular weight (59) of SiH, i.e. M=57+60m+190n+59.

If it is 1000 or so to design molecular weight, n and m is respectively 1 and 12 in above-mentioned reaction equation, that is, preparing molecular weight is 1000 or so side chain about needs the n-BuLi of 1mol with hydroxy-protective group, the single-ended polysiloxanes with silicon hydrogen group The D of initiator, 1/3mol^T ₃With the D of 4mol₃。

4th step, secondary Si―H addition reaction：In the reaction kettle of 1L, sequentially add what 615.6g (0.6mol) third step obtained With hydroxy-protective group and single-ended polysiloxanes and 1g chloroplatinic acid catalysts with silicon hydrogen group, (catalyst quality accounts for side chain Side chain carries the 0.16% of hydroxy-protective group and the single-ended polysiloxanes quality with silicon hydrogen group.), it is passed through nitrogen 20min Afterwards, reaction system is warming up to 100 DEG C, the allyloxy trimethyl that 78g (0.6mol) first step obtains is added dropwise at this temperature (trimethylsiloxy group unsaturated compound carries hydroxy-protective group and the single-ended poly- silica with silicon hydrogen group to silane with side chain Molar ratio between silicon hydrogen group contained by alkane (Si-H) is 1:1) reaction is terminated after, reacting 5h.Vacuum distillation removal low-boiling-point substance, obtains To the side chain and the single-ended polysiloxanes for carrying hydroxy-protective group that 657g number-average molecular weights are 1156 or so, yield 94.8%.

5th step, alcoholysis reaction：In the reaction kettle of 1L, the side chain of the 4th steps of 345g acquisition and single-ended equal band are sequentially added There are polysiloxanes, 500g methanol (side chain and the single-ended polysiloxanes and alcohol for carrying hydroxy-protective group of hydroxy-protective group Mass ratio between class solvent is 1:1.45) (quality of weak acid catalyst accounts for side chain and the single-ended hydroxyl that carries is protected with 3g acetic acid Protect the 0.87% of the polysiloxanes quality of group), under 65 DEG C of heated reflux conditions, stop reaction after reacting 9h.Vacuum distillation Acetic acid, excessive methanol and low-boiling-point substance are removed, obtain side chain that 320g number-average molecular weights are 1000 or so and single-ended carries hydroxyl The polysiloxanes of alkyl, yield 92.7%.

6th step, ring-opening polymerisation：It is primary to add in side chain and the single-ended equal band that the 5th steps of 300g obtain in the reaction kettle of 1L Having the polysiloxanes, 228g caprolactones and 0.3g stannous iso caprylates of hydroxyl alkyl, (organotin catalysts quality accounts for caprolactone quality 0.13%.), under stirring, reaction system is warming up to 80 DEG C and reacts 6h at this temperature, then reaction system heats up To 120 DEG C, and reaction is terminated after the reaction was continued 6 hours, obtain the Polycaprolactone modified polysiloxanes with structure formula (I).

Side chain, single-ended or the both-end molar ratio of polysiloxanes and caprolactone with hydroxyl alkyl between the two regard poly- Depending on the size of caprolactone chain segment molecular weight, wherein：The molecular weight of each polycaprolactone segment is between 200~5000.

There is the polycaprolactone modified polyorganosiloxane of structure formula (I) in reference the present embodiment, each polycaprolactone segment Molecular weight is：The molecular weight (114) of molecular weight (114) and y × own lactones of n × x × own lactones, wherein：200<n×x×114 <5000,200<114y<5000, the total molecular weight of polycaprolactone segment is：400<(3x+y)×114<10000.

In final product structural formula, n, x and y are respectively 1,1.8 and 1.9, then the molecular weight of each polycaprolactone segment For：205.2 and 216.6.

Embodiment 8

Polycaprolactone modified polysiloxanes with structure formula (II)：R₅For OSi (CH₃)₂O, R₂、R₃And R₄It is CH₂CH₂CH₂CH₂, (p+q)=1, (o+r)=10, x=2.7, y=2, z=2；

o>0, p>0, q>0, r>0, x>0, y>0, z>0.

The first step, hydroxyl protection：In the reaction kettle of 1L, 338.1g (2.1mol) hexamethyldisilazane is delayed at room temperature Slowly it is added drop-wise to 288g 3- butene-1-ols (4mol) A₃In (molar ratio of unsaturated monohydric alcohol and hexamethyldisilazane be 2: 1.05).After being added dropwise, reaction system is warming up to 100 DEG C, and stops reaction after the reaction was continued 6 hours in this temperature.Often Pressure collects 110-115 DEG C of fraction, obtains alkene butoxy trimethyl silane 558g, yield 96.9%.

Second step, a Si―H addition reaction：In the reaction kettle of 1L, the alkene of 436.3g (3mol) first step acquisition is sequentially added (quality of catalyst accounts for trimethyl cyclotrisiloxane quality for butoxy trimethyl silane and 0.2g chloroplatinic acid catalysts 0.11%) after, being passed through nitrogen 20min, reaction system is warming up to 100 DEG C, 180g (1mol) trimethyl is added dropwise at this temperature (molar ratio of trimethylsiloxy group unsaturated compound and trimethyl cyclotrisiloxane is 3 to cyclotrisiloxane:1) after, reacting 8h Terminate reaction.Vacuum distillation removes low-boiling-point substance, obtains the alkyl-modified cyclotrisiloxane of 601g trimethylsiloxy groups, yield 98.2%.

Third walks, anionic polymerisation：In by anhydrous and oxygen-free treated 2L reaction kettles, 104g (1mol) is sequentially added The alkyl-modified ring three of trimethylsiloxy group that dimethylsilyl bis lithium, 592g hexamethyl cyclotrisiloxanes and 204g second steps obtain Siloxanes, 500g n-hexanes and tetrahydrofuran (mass ratio 1:1) (solvent is alkyl-modified with trimethylsiloxy group for mixed solution Cyclotrisiloxane, hexamethyl cyclotrisiloxane, monofunctional alkyl lithium or difunctional alkyl's lithium total mass ratio be 0.56:1), exist After being stirred to react 8h at 25 DEG C, adding in the dimethylchlorosilane of 2.1mol, (dimethylsilyl bis lithium and dimethylchlorosilane rub You are than being 1:2.1) reaction is terminated.Reaction solution is filtered to remove to the lithium chloride of generation, after vacuum distillation removes low-boiling-point substance, is obtained 961g number-average molecular weights are 1004 or so, the side chain of PDI=1.15 carries silicon hydrogen group with hydroxy-protective group and both-end Polysiloxanes, yield 95.7%.

With reference to the side chain obtained after anionic polymerisation in the present embodiment silicon hydrogen-based is carried with hydroxy-protective group and both-end The polysiloxanes of group, molecular weight design formula are as follows (using dimethylsilyl bis lithium as initiator, for dosage is 1mol)：

Molecular weight (90)+D of design molecular weight=dimethylsilyl bis of the polysiloxanes^T ₃Molecular weight × D^T ₃Substance Amount ((p+q)/3)+D₃Molecular weight × D₃Substance amount ((o+r)/3)+2 × (CH₃)₂The molecular weight (118) of SiH, i.e. M + 204 (p+q)+118 of=57+60 (o+r).

If design molecular weight is 1000 or so, (p+q) and (o+r) is respectively 1 and 10 in above-mentioned reaction equation, that is, is prepared point Son amount carries hydroxy-protective group for 1000 or so side chain and both-end carries the polysiloxanes of silicon hydrogen group, about needs the two of 1mol The D of methyl siloxy lithium initiator, 1/3mol^T ₃With the D of 10/3mol₃。

Design molecular weight of the side chain with the polysiloxanes of hydroxy-protective group and both-end with silicon hydrogen group= M_{The molecular weight of monofunctional alkyl lithium or difunctional alkyl's lithium removal lithium}+D^T ₃Molecular weight × D^T ₃Substance amount+D₃Molecular weight × D₃Substance amount+2 × M_{Dimethyl silicane hydroxide}。

4th step, secondary Si―H addition reaction：In the reaction kettle of 1L, 500g (1mol Si -- Hs) third step is sequentially added The side chain of acquisition is with the polysiloxanes of hydroxy-protective group and both-end with silicon hydrogen group and the (catalysis of 0.5g chloroplatinic acid catalysts Agent quality accounts for 0.1% of side chain with the polysiloxanes quality of hydroxy-protective group and both-end with silicon hydrogen group.), it is passed through nitrogen After gas 20min, reaction system is warming up to 100 DEG C, the alkene fourth oxygen that 150g (1.04mol) first step obtains is added dropwise at this temperature (trimethylsiloxy group unsaturated compound carries silicon to base trimethyl silane with side chain with hydroxy-protective group, single-ended or both-end Molar ratio between silicon hydrogen group (Si-H) contained by the polysiloxanes of hydrogen group is 1.04:1) reaction is terminated after, reacting 5h.Decompression Distillation removal low-boiling-point substance obtains side chain and both-end the gathering with hydroxy-protective group that 621g number-average molecular weights are 1292 or so Siloxanes, yield 96.4%.

5th step, alcoholysis reaction：In the reaction kettle of 1L, side chain and the both-end for sequentially adding the acquisition of the 4th steps of 581.4g are equal Polysiloxanes with hydroxy-protective group, 600g methanol (polysiloxanes of side chain and both-end with hydroxy-protective group with Mass ratio between alcohols solvent is 1:1.03) (quality of weak acid catalyst accounts for side chain and both-end and carries hydroxyl with 3.6g acetic acid The 0.62% of the polysiloxanes quality of base blocking group).Under 65 DEG C of heated reflux conditions, stop reaction after reacting 9h.Decompression Distillation removal acetic acid, excessive methanol and low-boiling-point substance obtain the side chain and the equal band of both-end that 479g number-average molecular weights are 1124 or so There are the polysiloxanes of hydroxyl alkyl, yield 94.7%.

6th step, ring-opening polymerisation：In the reaction kettle of 1L, the primary side chain for adding in the acquisition of the 5th steps of 337.2g and both-end are equal (organotin catalysts quality accounts for caprolactone quality for polysiloxanes with hydroxyl alkyl, 228g caprolactones and 0.3g stannous iso caprylates 0.13%.).Under stirring, reaction system is warming up to 80 DEG C and reacts 6h at this temperature, then by reaction system liter Temperature terminates reaction to 120 DEG C after the reaction was continued 6 hours, obtains the Polycaprolactone modified polysiloxanes with structure formula (II).

Side chain, single-ended or the both-end molar ratio of polysiloxanes and caprolactone with hydroxyl alkyl between the two regard poly- Depending on the size of caprolactone chain segment molecular weight, wherein：The molecular weight of each polycaprolactone segment is between 200~5000.

There is the polycaprolactone modified polyorganosiloxane of structure formula (II) in reference the present embodiment, each polycaprolactone segment Molecular weight is：(p+q) molecular weight (114) of the molecular weight (114) of × x × own lactones and (y+z) × own lactones, wherein：200< (p+q)×x×114<5000,200<114(y+z)<5000, the total molecular weight of polycaprolactone segment is：400<[(p+q)×x+ (y+z)]×114<10000。

When in final product structural formula, (p+q), x, y and z are respectively 1,2.7,2 and 2, then each polycaprolactone segment Molecular weight is：307.8th, 228 and 228.

By the following examples 9~18 concrete examples illustrate the present invention solvent-type double-component, high slipping varnish group Component, the preparation method of object are closed, and the present invention is furtherd elucidate with reference to its concrete application.

In the present invention embodiment 9~18 refer to can be used for automobile cover with paint, lacquer, colour wash, etc. and other related fields solvent-type double-component, The clear coat composition of high slipping is prepared in the following manner, i.e., according to the different resins component set in Tables 1 and 2 Dosage by Hydroxylated acrylic resin or hydroxy resin, hydroxy polyester resin, amino resins, rheology control agent, is gathered Component A is made in caprolactone modification polysiloxanes, auxiliary agent and solvent, is then mixed with component A and the curing agent of component B Into solvent-type double-component, the clear coat composition of high slipping.

To ensure the solvent-type double-component, the clear coat composition quality of high slipping and the homogeneity of performance, the system Each component under atmospheric pressure at room state should be stirred mixing (to prepare 1kg by Preparation Method according to following specific charging sequence The solvent-type double-component, high slipping clear coat composition sample for)：

The first step, by 0.5~30 part of first solvent, 20~50 Hydroxylated acrylic resins or hydroxy resin and 10~30 parts of hydroxy polyester resins are uniformly mixed；

Second step, be kept stirring rate it is constant in the case of, sequentially add 10~20 parts of amino resins, 5~30 parts stream Become controlling agent, 0.1~5 part of Polycaprolactone modified polysiloxanes, 0.1~7 part of auxiliary agent and 0.5~10 part of first stirring solvent mixing Uniformly obtain the component A；

Third walk, be kept stirring rate it is constant in the case of, by 10~50 parts of polyfunctionality aliphatic isocyanates, And/or 0~20 part of polyfunctionality alicyclic isocyanate, and/or 0~10 part of part isocyanate groups be closed but still Have free isocyanate groups roll into a ball existing for polyfunctionality aliphatic and or alicyclic isocyanate；Wherein, for closing isocyanic acid The sealer of ester group participates in curing reaction in baking process or was being toasted for the sealer of blocked isocyanate group It is sloughed in journey and releases isocyanate groups again；And 5~50 part of second solvent mixing, obtain the component B；

Component B is added in component A by the 4th step, and the solvent-type double-component, high slipping are obtained after stirring evenly Clear coat composition；

Component A and component B is using the ratio that parts by weight are counted as (1~18)：3.

The clear coat composition of the solvent-type double-component, high slipping is tested for the property below, wherein involved Compelx coating (3C1B systems) is prepared in the following manner.First, it selects by chemical pre-treatment and covers electrophoretic coating Cold rolling test board, which is to be prepared on automotive OEM production line according to the processing technology of standard；Then, according to It is AR3500 731P's that wet on wet technique sprays aqueous dark-grey middle (the ippon product) and the trade mark of applying that the trade mark is AR800N2 respectively Aqueous black colored paint (ippon product), and by the film after spraying at 85 DEG C preliminary drying 8min；Then, in uncured colored paint table Face is again according to the clear coat composition of the present invention under wet on wet technique spraying application state；Finally by above-mentioned composite coating, The multiple coating being made of aqueous middle painting, water colour paint and clear coat composition of the present invention, is toasted together at 145 DEG C The compelx coating being made of multiple coating is formed after 25min；Wherein, the film thickness of each coating is respectively in compelx coating：It is middle to apply 20 ± 2 μm, 12 ± 1 μm of colored paint, 45 ± 5 μm of varnish.

The solvent-type double-component, the component of the clear coat composition of high slipping and formula prepared by embodiment 9~18 is such as Shown in Tables 1 and 2 (in terms of parts by weight)：

Table 1

* the film crocking resistance after curing is surveyed by using the sand paper of model P2400 on Friction tester The retention of 20 ° of gloss of film after 15 cycles of friction is investigated in examination.

In embodiment 9~13, in component A in preparation method the solvent of the first step for 3 parts of butyl acetates, in component A Solvent in preparation method in second step is 3 parts of S-100# solvent naphthas.

It can be seen that compared with comparative example by 1 data of table, with the increasing of Polycaprolactone modified polysiloxanes usage amount Add, the resistance to dry friction data of paint film are gradually increased, and illustrate Polycaprolactone modified polysiloxanes being added in clear coat composition, energy Enough improve the rub resistance of paint film.

Table 2

Embodiment 14：In component A in preparation method the first step 17 parts of butyl acetates of solvent, in preparation side in component A Solvent in method in second step is 8.6 parts of S-100# solvent naphthas.

Embodiment 15：In component A in preparation method the first step 1 part of butyl acetate of solvent, in preparation method in component A Solvent in middle second step is 1 part of S-100# solvent naphtha.

Embodiment 16：In component A in preparation method the first step 10 parts of butyl acetates of solvent, in preparation side in component A Solvent in method in second step is 10 parts of S-100# solvent naphthas.

Embodiment 17：In component A in preparation method the first step 12.5 parts of butyl acetates of solvent, preparing in component A Solvent in method in second step is 14 parts of S-100# solvent naphthas.

Embodiment 18：In component A in preparation method the first step 20 parts of butyl acetates of solvent, in preparation side in component A Solvent in method in second step is 20 parts of S-100# solvent naphthas.

In embodiment 14~18, BYK 315, BYK 358N, Tinuvin 292, Tinuvin 384-2 ratio be 1:1: 1:1。

The purposes of the solvent-type double-component of the present invention, the clear coat composition of high slipping can do finishing varnish for vapour Vehicle is covered with paint, lacquer, colour wash, etc..

The purposes of the solvent-type double-component of the present invention, the clear coat composition of high slipping, specially described solvent type Bi-component, high slipping clear coat composition for forming solidify coating on ground；Include the following steps：

On priming paint or floating coating application and construction to ground and it will first be cured, by colored paint application and construction to priming paint or middle painting On the ground that coating has been cured, then by the solvent-type double-component, high slipping clear coat composition application and construction to not Cured colored paint surface, finally cures two parts coating simultaneously, and to obtain the multicoat Finish, the multicoat applies Decorations system can be used for three to apply two baking systems；

Alternatively,

First by priming paint or it is middle painting application and construction to ground on, then by colored paint application and construction to uncured priming paint or middle painting Coating surface, then by the solvent-type double-component, high slipping clear coat composition application and construction to uncured colored paint coating Surface finally cures three parts coating simultaneously, and to obtain the multicoat Finish, the multicoat Finish can be used One, which is applied, in three dries system or integrated form spraying process (IPP) system；

Alternatively,

Two layers of colored paint is constructed onto no priming paint and the ground of middle painting, then molten described in second layer colored paint surface spraying The clear coat composition of dosage form bi-component, high slipping, and three parts coating is cured simultaneously, to obtain the multicoat coating decoration material System, the multicoat Finish can be used for deflation formula spraying process (CCT) system；

Alternatively,

On priming paint or floating coating application and construction to ground and it will first be cured, then by solid-shade paint application and construction to priming paint Or on the ground that has been cured of middle coating layer, then metallic coatings are constructed to uncured solid-shade paint coating surface, then by institute State solvent-type double-component, high slipping clear coat composition application and construction to uncured metallic coatings surface, finally by three Coating is divided to cure simultaneously, to obtain the multicoat Finish, the multicoat Finish can be used for four to apply two baking systems；

Alternatively,

First by priming paint or it is middle painting application and construction to ground on, then by solid-shade paint application and construction to uncured priming paint or in Coating layer surface, then metallic coatings are constructed to uncured solid-shade paint coating surface, then by the solvent-type double-component, height The clear coat composition application and construction of slipping finally cures four partial coatings simultaneously to uncured metallic coatings surface, with The multicoat Finish is obtained, the multicoat Finish can be used for four to apply a baking system.

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；The cured temperature is 100~180 DEG C；The cured time is 10~40min.

Three paintings, two baking, integrated form spraying process, tightens formula spraying process, four paintings, two baking, four paintings, one baking at three one bakings of painting Priming paint and colored paint used in system are water paint, the construction solid content of the priming paint between 35%~55%, Gu Film thickness after change is between 10~50 μm, and between 20%~40%, the film thickness after curing is situated between the construction solid content of the colored paint Between 6~20 μm.

The outermost coating of multicoat Finish is by the solvent-type double-component, the clear coat composition of high slipping It is prepared；The thickness of dry film of the multicoat Finish be 10 μm~80 μm, preferably 20 μm~70 μm, further preferred 30 μm~60 μm；The cured temperature is 100~180 DEG C, preferably 120~160 DEG C；The cured time is 10~40min.

The solvent-type double-component of the present invention, the clear coat composition of high slipping have used gathering in oneself with special construction Ester modified polysiloxanes when it is added in solvent based coating, particularly in solvent-based varnishes, can improve the superficiality of film Can, increase slipping, improve rub resistance.

The clear coat composition of solvent-type double-component provided by the invention, high slipping can effectively improve varnish combination The slipping of object film coated surface, so as to increase the rub resistance of film.

Solvent-type double-component provided by the invention, high slipping clear coat composition in, Polycaprolactone modified polysiloxanes Middle polycaprolactone is simultaneously modified polysiloxanes by block and grafting, can have the block modified poly- silica of polycaprolactone concurrently The advantages of alkyl copolymer and polycaprolactone graft modification graft polysiloxane copolymer.

Solvent-type double-component provided by the invention, high slipping clear coat composition in, Polycaprolactone modified polysiloxanes Can be used as solvent based coating auxiliary agent, when being added in solvent based coating, particularly in solvent-based varnishes when, film can be improved Surface property, increase slipping, improve rub resistance.

Solvent-type double-component provided by the invention, high slipping clear coat composition in, Polycaprolactone modified polysiloxanes It is made of special polysiloxanes segment and polycaprolactone segment, there is excellent compatibility between solvent based coating, it can As coating additive, can especially be used as surface slip agent；It is slided Polycaprolactone modified polysiloxanes as surface After refreshing agent is added in solvent based coating, coating surface tension can be reduced, so as to provide good wetability and good anti- Shrinkage cavity；It is particularly added in solvent-based varnishes, will not generate varnish muddy, moreover it is possible to further enhance varnish paint Surface slip and scratch resistance.

Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention for those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is every to belong to this hair The obvious changes or variations that bright technical solution is extended out are still in the row of protection scope of the present invention.

Claims (34)

1. a kind of clear coat composition of solvent-type double-component, high slipping, it is characterised in that：Including：

Component A, including：

At least one Hydroxylated acrylic resin or hydroxy resin；

At least one hydroxy polyester resin；

At least one amino resins；

At least one rheology control agent；

At least one Polycaprolactone modified polysiloxanes；

At least one auxiliary agent；And

At least one first solvent；

Component B, including：

At least one polyfunctionality aliphatic isocyanates；

And/or at least one polyfunctionality alicyclic isocyanate；

And/or at least one part isocyanate groups be closed but still have free isocyanate groups roll into a ball existing for it is multifunctional Spend aliphatic and or alicyclic isocyanate；Wherein, the sealer for blocked isocyanate group participates in baking process Curing reaction or sealer for blocked isocyanate group are sloughed in baking process releases isocyanate group again Group；And

At least one second solvent.

2. the clear coat composition of solvent-type double-component according to claim 1, high slipping, it is characterised in that：Including with The component of lower parts by weight：

Component A, including：

20~50 parts of at least one Hydroxylated acrylic resin or hydroxy resin；

At least one 10~30 parts of hydroxy polyester resin；

At least one 10~20 parts of amino resins；

At least one 5~30 parts of rheology control agent；

At least one Polycaprolactone modified 0.1~5 part of polysiloxanes；

At least one 0.1~7 part of auxiliary agent；And

At least one 1~40 part of first solvent；

Component B, including：

At least one 10~50 parts of polyfunctionality aliphatic isocyanates；

And/or at least one 0~20 part of polyfunctionality alicyclic isocyanate；

And/or at least one part isocyanate groups be closed but still have free isocyanate groups roll into a ball existing for it is multifunctional Spend aliphatic and or 0~10 part of alicyclic isocyanate；Wherein, it was being toasted for the sealer of blocked isocyanate group Curing reaction is participated in journey or the sealer for blocked isocyanate group is sloughed in baking process and releases isocyanide again Acid esters group；And

At least one 5~50 parts of second solvent.

3. the clear coat composition of solvent-type double-component according to claim 1 or 2, high slipping, it is characterised in that：It is described The component A and component B is using the ratio that parts by weight are counted as (1~18)：3；

The solvent-type double-component, high slipping clear coat composition in, the solid content of component A between 40%~70%, The solid content of component B is between 50%~90%；In construction, the amount of the substance of hydroxyl and isocyanic acid in component B in component A The ratio of the amount of the substance of ester group is 1：(0.2~5).

4. the clear coat composition of solvent-type double-component according to claim 1 or 2, high slipping, it is characterised in that：It is described Between 2000~20000g/mol, hydroxyl value is situated between the number-average molecular weight of Hydroxylated acrylic resin or hydroxy resin Between 60~250mg KOH/g, glass transition temperature between -40 DEG C~+60 DEG C, solid content between 50%~90% it Between；

The hydroxy functionality of the hydroxy polyester resin between 2~5, number-average molecular weight between 500~8000g/mol it Between, hydroxyl value is between 60~250mg KOH/g, and solid content is between 70%~90%；

The amino resins for butyl ether type, containing imido grpup, with melamine resin existing for polymer form and/ It is or complex etherified type, containing imido grpup, melamine resin existing in the form of oligomer and/or complex etherified type, complete Portion is etherification modified, with melamine resin existing for monomeric form and/or the amino tree with carbamate-functional Fat；

The rheology control agent is the compound containing urea bond, polymer and its derivative；And/or the macromolecule with cross-linked structure Fine particle；And/or the treated fine silica particle in surface.

5. the clear coat composition of solvent-type double-component according to claim 1 or 2, high slipping, it is characterised in that：It is described Polycaprolactone modified polysiloxanes has the structure as shown in formula (I) or (II)：

In formula (I), R₁With at least one of structure as shown in formula (III)：

In formula (II), R₅With at least one of structure as shown in formula (IV)：

R₂、R₃And R₄It is respectively provided at least one of structure as shown in formula (V)：

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

6. the clear coat composition of solvent-type double-component according to claim 1 or 2, high slipping, it is characterised in that：It is described Auxiliary agent is at least one of levelling controlling agent, ultra-violet absorber, hindered amine light stabilizer；

First solvent is aliphatic ester, in ketone, dihydric alcohol ethers, dihydric alcohol esters, aromatic series carbon hydrocarbon solvent It is at least one.

7. the clear coat composition of solvent-type double-component according to claim 6, high slipping, it is characterised in that：It is described to help Agent further includes antioxidant and/or antisettling agent；

First solvent includes following compound：Toluene, dimethylbenzene, S-100# solvent naphthas, trimethylbenzene solvent naphtha, S-150# are molten Agent oil, durol solvent naphtha, acetone, butanone, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol fourth At least one of ether acetic acid ester, pentyl acetate, ethylene glycol ethyl ether propionic ester, propylene glycol methyl ether acetate.

8. the clear coat composition of solvent-type double-component according to claim 1 or 2, high slipping, it is characterised in that：It is described The degree of functionality of isocyanate groups is at least 2 in polyfunctionality aliphatic isocyanates, is Isosorbide-5-Nitrae-diisocyanate bases butane, 1,6- Diisocyanate base hexane, 2- methyl-1s, 5- diisocyanate bases pentane, 1,5- diisocyanate base -2,2- dimethyl-pentane, 2,2, 4- trimethyl -1,6- diisocyanate bases hexane, 2,4,4- trimethyl -1,6- diisocyanate bases hexane, the 1,10- diisocyanate base last of the ten Heavenly stems Alkane and/or tripolymer, pentamer and the polymer formed by above-mentioned aliphatic diisocyanate monomer；

The degree of functionality of isocyanate groups is at least 2 in the polyfunctionality alicyclic isocyanate, is 1,3- diisocyanate bases Hexamethylene, 1,4- diisocyanates butylcyclohexane, 2,6- diisocyanate base -1- hexahydrotoluenes, 2,4- diisocyanate base -1- methyl Hexamethylene, 1,3- be bis--and (isocyanatometyl) hexamethylene, 1,4- be bis--(isocyanatometyl) hexamethylene, two isocyanide of isophorone Acid esters, 2,4 '-diisocyanate base dicyclohexyl methyl hydride, 4,4 '-diisocyanate base dicyclohexyl methyl hydride, 1- isocyanate group -1- first Base -4 (3) isocyanato methylcyclohexane, bis- (isocyanatometyl)-norbornanes and/or by above-mentioned alicyclic diisocyanate Tripolymer, pentamer and the polymer that ester monomer is formed.

9. the clear coat composition of solvent-type double-component according to claim 1 or 2, high slipping, it is characterised in that：It is described It is that part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for polyfunctionality aliphatic and or alicyclic ring The degree of functionality of race's isocyanates middle reaches free isocyanate groups is at least 1；

Second solvent is aliphatic ester, in ketone, dihydric alcohol ethers, dihydric alcohol esters, aromatic series carbon hydrocarbon solvent It is at least one.

10. the clear coat composition of solvent-type double-component according to claim 9, high slipping, it is characterised in that：Described Two solvents include compound：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, acetic acid At least one of pentyl ester, ethylene glycol ethyl ether propionic ester, propylene glycol methyl ether acetate.

11. the preparation side of the clear coat composition of a kind of any solvent-type double-component of claims 1 to 10, high slipping Method, it is characterised in that：Include the following steps：

The first step, by the first solvent of first part, Hydroxylated acrylic resin or hydroxy resin and hydroxyl polyester tree Fat is uniformly mixed；

Second step, be kept stirring rate it is constant in the case of, sequentially add amino resins, rheology control agent, polycaprolactone and change Property the first solvent of polysiloxanes, auxiliary agent and second part, be uniformly mixed and obtain the component A；

Third walk, be kept stirring rate it is constant in the case of, by polyfunctionality aliphatic isocyanates, and/or polyfunctionality It is that alicyclic isocyanate, and/or part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for more officials Energy degree aliphatic and or alicyclic isocyanate；Wherein, the sealer for blocked isocyanate group is joined in baking process It is sloughed in baking process with curing reaction or for the sealer of blocked isocyanate group and releases isocyanate group again Group；And second solvent mixing, obtain the component B；

Component B is added in component A by the 4th step, obtained after stirring evenly the solvent-type double-component, high slipping varnish Composition.

12. the preparation method of the clear coat composition of solvent-type double-component according to claim 11, high slipping, feature It is：The rate for referring to stirring that is uniformly mixed for 400~1000 revs/min (r/min), mixing time for 10~ 60min；

Amino resins, rheology control agent, Polycaprolactone modified polysiloxanes, auxiliary agent and second are sequentially added in the second step The time interval for dividing the first solvent is 5~10min.

13. the preparation method of the clear coat composition of solvent-type double-component according to claim 11, high slipping, feature It is：The preparation method of the Polycaprolactone modified polysiloxanes includes the following steps：

Unsaturated monohydric alcohol and hexamethyldisilazane are mixed temperature reaction by the first step, and trimethyl silicane is obtained after the reaction was complete Oxygroup unsaturated compound；

Second step adds in catalyst under nitrogen protection, in the trimethylsiloxy group unsaturated compound that the first step is obtained and mixes, Trimethyl cyclotrisiloxane is added dropwise in temperature reactionThe alkyl-modified cyclotrisiloxane of trimethylsiloxy group is obtained after reaction

Third walks, under the conditions of anhydrous and oxygen-free, by monofunctional alkyl lithium or difunctional alkyl's lithium, the trimethyl silicane of second step acquisition The alkyl-modified cyclotrisiloxane of oxygroupHexamethyl cyclotrisiloxane D₃It is mixed with solvent, temperature reaction, adds in dimethyl hydrogen Chlorosilane terminates reaction, and it is poly- with silicon hydrogen group with hydroxy-protective group, single-ended or both-end to obtain side chain by post processing Siloxanes；

The side chain that third step obtains under nitrogen protection, is carried silicon hydrogen-based by the 4th step with hydroxy-protective group, single-ended or both-end The polysiloxanes of group is mixed with catalyst, temperature reaction, and it is anti-that the trimethylsiloxy group unsaturated compound that the first step obtains is added dropwise Should, obtain side chain, single-ended or the both-end polysiloxanes with hydroxy-protective group by post processing；

5th step, the side chain that the 4th step is obtained, single-ended or both-end carry polysiloxanes, the alcohols solvent of hydroxy-protective group It is mixed with weak acid catalyst, temperature reaction, obtains the polysiloxanes that side chain, single-ended or both-end carry hydroxyl alkyl；

6th step, the side chain that the 5th step is obtained, single-ended or both-end carry polysiloxanes, caprolactone and the organotin of hydroxyl alkyl Catalyst mixes, and heating is reacted, and the Polycaprolactone modified polysiloxanes is obtained by post processing.

14. the preparation method of the clear coat composition of solvent-type double-component according to claim 13, high slipping, feature It is：The temperature of temperature reaction is 90~120 DEG C in the first step, and the time is 4~8 hours (h)；

The molar ratio of unsaturated monohydric alcohol and hexamethyldisilazane is 2 in the first step:(1~2)；

Unsaturated monohydric alcohol is at least one of lower structure in the first step：

A₁)CH₂=CHCH₂OHA₂)CH₂=CHCH₂CH₂OHA₃)CH₂=CHCH₂CH₂CH₂OH

A₄)CH₂=CHCH₂CH₂CH₂CH₂OHA₅)CH₂=CHCH₂NHC(O)OCH₂CH₂OH。

15. the preparation method of the clear coat composition of solvent-type double-component according to claim 13, high slipping, feature It is：The temperature of temperature reaction is 80~110 DEG C in the second step, and the time is 4~12h；

The quality of catalyst accounts for trimethyl cyclotrisiloxane in the second stepThe 0.05%~1% of quality；

Trimethylsiloxy group unsaturated compound and trimethyl cyclotrisiloxane in the second stepMolar ratio be (3~6): 1；

Catalyst is chloroplatinic acid in the second step.

16. the preparation method of the clear coat composition of solvent-type double-component according to claim 13, high slipping, feature It is：The temperature of temperature reaction is -70 DEG C~50 DEG C in the third step, time 4-12h；

Monofunctional alkyl lithium or the molar ratio of difunctional alkyl's lithium and dimethyl silicane hydroxide are 1 in the third step:(1~ 2.2)；

Solvent includes non-polar organic solvent and polar organic solvent, the non-polar organic solvent and polarity in the third step Mass ratio between organic solvent is 1:(1~5)；

Solvent and the alkyl-modified cyclotrisiloxane of trimethylsiloxy group in the third stepHexamethyl cyclotrisiloxane D₃, it is single The total mass ratio of function lithium alkylide or difunctional alkyl's lithium is (0.25~4):1.

17. the preparation method of the clear coat composition of solvent-type double-component according to claim 13, high slipping, feature It is：The side chain with hydroxy-protective group,

The side chain with hydroxy-protective group,

Monofunctional alkyl lithium or difunctional alkyl's lithium are at least one of lower structure in the third step：

Dimethyl silicane hydroxide is dimethylchlorosilane in the third step；

Number of the side chain with the polysiloxanes of hydroxy-protective group, single-ended or both-end with silicon hydrogen group is divided equally in the third step Son amount is between 200~10000；Degree of polymerization index is between 1~1.2.

18. the preparation method of the clear coat composition of solvent-type double-component according to claim 16, high slipping, feature It is：In the third step non-polar organic solvent selected from aliphatic, it is alicyclic, in aromatic series carbon hydrocarbon solvent at least one Kind；

Polar organic solvent is selected from aliphatic ketone, alicyclic ketones, aromatic ketones, amides, sulfoxide in the third step At least one of class, nitrile, heterocyclic solvent.

19. the preparation method of the clear coat composition of solvent-type double-component according to claim 18, high slipping, feature It is：Non-polar organic solvent includes following compound in the third step：Isopentane, pentane, petroleum ether, n-hexane, ring At least one of hexane, isooctane, pentamethylene, trimethylpentane, pentamethylene, heptane, toluene, benzene, dimethylbenzene；

Polar organic solvent includes following compound in the third step：Tetrahydrofuran, formamide, acetonitrile, N, N- dimethyl methyls At least one of amide, hexamethyl phosphoramide, butanone, dimethyl sulfoxide, acetone, 1,4- dioxane, pyridine.

20. the preparation method of the clear coat composition of solvent-type double-component according to claim 13, high slipping, feature It is：The temperature reacted in 4th step is 80~110 DEG C, and the time is 4~12h；

Catalyst is chloroplatinic acid in 4th step；

Catalyst quality accounts for the poly- silicon that side chain carries silicon hydrogen group with hydroxy-protective group, single-ended or both-end in 4th step The 0.05%~1% of oxygen alkane quality；

Trimethylsiloxy group unsaturated compound is carried with side chain with hydroxy-protective group, single-ended or both-end in 4th step Molar ratio between silicon hydrogen group contained by the polysiloxanes of silicon hydrogen group is (1~2):1.

21. the preparation method of the clear coat composition of solvent-type double-component according to claim 13, high slipping, feature It is：The temperature of temperature reaction is 65 DEG C~100 DEG C in 5th step, and the reaction time is 4~12h；

Alcohols solvent is at least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol in 5th step；

Weak acid catalyst is formic acid, in acetic acid, propionic acid, lactic acid, dihydromethyl propionic acid, dimethylolpropionic acid in 5th step It is at least one；

The matter of side chain, single-ended or both-end between polysiloxanes and alcohols solvent with hydroxy-protective group in 5th step Amount is than being 1:(1~4)；

The quality of weak acid catalyst accounts for the polysiloxanes that side chain, single-ended or both-end carry hydroxy-protective group in 5th step The 0.5%~5% of quality.

22. the preparation method of the clear coat composition of solvent-type double-component according to claim 13, high slipping, feature It is：The temperature reacted that heats up in 6th step is 80 DEG C~140 DEG C, and the time is 5~20h；

In 6th step in Polycaprolactone modified polysiloxanes polycaprolactone segment number-average molecular weight between 200~5000 it Between；

Organotin catalysts are stannous iso caprylate, dibutyl tin laurate, dioctyl tin oxide, dibutyl in 6th step At least one of tin oxide, tributyl tin, dibutyltin diacetate；

Organotin catalysts quality accounts for the 0.01%~5% of caprolactone quality in 6th step.

23. the preparation method of the clear coat composition of solvent-type double-component according to claim 11, high slipping, feature It is：It is that the part isocyanate groups are closed but still have free isocyanate groups roll into a ball existing for polyfunctionality aliphatic With or the preparation method of alicyclic isocyanate include the following steps：

Polyfunctionality aliphatic isocyanates and/or polyfunctionality alicyclic isocyanate are mixed with catalyst, it then will be anti- System is answered to be warming up to 60~80 DEG C, after constant temperature, the mixed solution of sealer and solvent is slowly added dropwise, is controlled during being added dropwise Reaction temperature keeps temperature to be no more than 80 DEG C, the 4~5h that is added dropwise in this temperature that the reaction was continued, controls remaining isocyanate group Content stops reacting and discharges, obtain that the part isocyanate groups are closed but still have free isocyanate groups group to deposit Polyfunctionality aliphatic and or alicyclic isocyanate.

24. the preparation method of the clear coat composition of solvent-type double-component according to claim 23, high slipping, feature It is：The catalyst is organo-tin compound or organo-alkali compound；

The sealer has one of structure as shown in formula (VI), (VII) or (VIII)：

Wherein, R₆And R₇It is respectively selected from the aliphatic alkane base containing 1~8 carbon atom；

R₈(CH₂)_aSi(OR₉)(OR₁₀)(OR₁₁)

(VII)

HN[(CH₂)_aSi(OR₉)(OR₁₀)(OR₁₁)]

(VIII)

Wherein, R₈For at least one of primary amino group, hydroxyl, sulfydryl, a is the integer more than or equal to 1, R₉、R₁₀And R₁₁It selects respectively From the aliphatic alkane base containing 1~8 carbon atom and/or the aliphatic acyl radical of 1~8 carbon atom；

Or, sealer is the compound containing reactive hydrogen, is unary alcohol, monosubstituted alcohol ethers, ketoxime class, unitary amine, pyrrole At least one of azole, alicyclic ring amides.

25. the preparation method of the clear coat composition of solvent-type double-component according to claim 24, high slipping, feature It is：The organo-tin compound is stannous iso caprylate, the oxidation of dibutyltin dilaurate, dioctyl tin oxide, dibutyl At least one of tin, tributyl tin, dibutyltin diacetate；

The organo-alkali compound is at least one of sodium methoxide, sodium ethoxide；

The sealer includes following compound：It is methanol, ethyl alcohol, propyl alcohol, n-butanol, isobutanol, n-hexyl alcohol, n-octyl alcohol, different pungent Alcohol, benzyl alcohol, benzyl carbinol, glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexylether, propylene glycol monomethyl ether, propylene glycol list Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, methyl ethyl ketoxime, acetoxime, cyclohexanone ketoxime, At least one of diisopropylamine, N- tert-butyl benzyl amines, 3,5- dimethyl pyrazoles, caprolactam.

26. the preparation method of the clear coat composition of solvent-type double-component according to claim 23, high slipping, feature It is：The solvent is aliphatic ester, ketone, dihydric alcohol ethers, dihydric alcohol esters, in aromatic series carbon hydrocarbon solvent at least It is a kind of；

The degree of functionality of isocyanate groups is at least 2 in the polyfunctionality aliphatic isocyanates, is Isosorbide-5-Nitrae-diisocyanate base Butane, 1,6- diisocyanate bases hexane, 2- methyl-1s, 5- diisocyanate bases pentane, 1,5- diisocyanate base -2,2- dimethyl - Pentane, 2,2,4- trimethyl -1,6- diisocyanate bases hexane, 2,4,4- trimethyl -1,6- diisocyanate bases hexane, 1,10- bis- Isocyanate group decane and/or tripolymer, pentamer, the polymer formed by above-mentioned aliphatic diisocyanate monomer.

27. the preparation method of the clear coat composition of solvent-type double-component according to claim 23, high slipping, feature It is：The degree of functionality of isocyanate groups is at least 2 in the polyfunctionality alicyclic isocyanate, is 1,3- diisocyanate bases Hexamethylene, 1,4- diisocyanates butylcyclohexane, 2,6- diisocyanate base -1- hexahydrotoluenes, 2,4- diisocyanate base -1- methyl Hexamethylene, 1,3- be bis--and (isocyanatometyl) hexamethylene, 1,4- be bis--(isocyanatometyl) hexamethylene, two isocyanide of isophorone Acid esters, 2,4 '-diisocyanate base dicyclohexyl methyl hydride, 4,4 '-diisocyanate base dicyclohexyl methyl hydride, 1- isocyanate group -1- first Base -4 (3) isocyanato methylcyclohexane, bis- (isocyanatometyl)-norbornanes and/or by above-mentioned alicyclic diisocyanate Tripolymer, pentamer, the polymer of ester monomer formation.

28. the preparation method of the clear coat composition of solvent-type double-component according to claim 26, high slipping, feature It is：The solvent includes following compound：Toluene, dimethylbenzene, S-100# solvent naphthas, trimethylbenzene solvent naphtha, S-150# solvents Oil, durol solvent naphtha, acetone, butanone, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl acetate, butyl acetate, butyl glycol ether At least one of acetic acid esters, pentyl acetate, ethylene glycol ethyl ether propionic ester, propylene glycol methyl ether acetate.

29. the preparation method of the clear coat composition of solvent-type double-component according to claim 23, high slipping, feature It is：The quality of the catalyst accounts for the polyfunctionality aliphatic isocyanates and/or polyfunctionality alicyclic isocyanate Quality 0.01~1%；

The quality of the sealer accounts for the polyfunctionality aliphatic isocyanates and/or polyfunctionality alicyclic isocyanate The 20~50% of quality；

The quality of the solvent accounts for the matter of the polyfunctionality aliphatic isocyanates and/or polyfunctionality alicyclic isocyanate The 40~50% of amount.

30. the purposes of the clear coat composition of a kind of any solvent-type double-component of claims 1 to 10, high slipping, It is characterized in that：Include the following steps：

On priming paint or floating coating application and construction to ground and it will first be cured, by colored paint application and construction to priming paint or middle coating layer On the ground having been cured, then by the solvent-type double-component, high slipping clear coat composition application and construction to uncured Colored paint surface, finally two parts coating is cured simultaneously, to obtain the multicoat Finish, the multicoat coating decoration material System can be used for three to apply two baking systems；

Alternatively,

First by priming paint or it is middle painting application and construction to ground on, then by colored paint application and construction to uncured priming paint or middle coating layer Surface, then by the solvent-type double-component, high slipping clear coat composition application and construction to uncured colored paint coating surface, Finally three parts coating is cured simultaneously, to obtain the multicoat Finish, the multicoat Finish can be used for three It applies one and dries system or integrated form spraying process system；

Alternatively,

Two layers of colored paint is constructed onto no priming paint and the ground of middle painting, then in solvent type described in second layer colored paint surface spraying The clear coat composition of bi-component, high slipping, and three parts coating is cured simultaneously, to obtain the multicoat Finish, The multicoat Finish can be used for deflation formula spraying process system；

Alternatively,

On priming paint or floating coating application and construction to ground and will first be cured, then by solid-shade paint application and construction to priming paint or in It, then will be described molten on the ground that coating layer has been cured, then by metallic coatings construction to uncured solid-shade paint coating surface Dosage form bi-component, high slipping clear coat composition application and construction to uncured metallic coatings surface, finally three parts are applied Layer cures simultaneously, and to obtain the multicoat Finish, the multicoat Finish can be used for four to apply two baking systems；

Alternatively,

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 metallic coatings are constructed to uncured solid-shade paint coating surface, it is then that the solvent-type double-component, height is smooth Property clear coat composition application and construction to uncured metallic coatings surface, finally four partial coatings are cured simultaneously, to obtain The multicoat Finish, the multicoat Finish can be used for four to apply a baking system.

31. the purposes of the clear coat composition of solvent-type double-component according to claim 30, high slipping, feature exist In：The ground is the body of a motor car of standard or the component component of body of a motor car, is applied by passing through chemical pre-treatment and covering electrophoresis The cold-reduced sheet of layer is prepared；

The cured temperature is 100~180 DEG C；

The cured time is 10~40min.

32. the purposes of the clear coat composition of solvent-type double-component according to claim 30, high slipping, feature exist In：Three paintings, two baking, integrated form spraying process, tightens formula spraying process, four paintings, two baking, four paintings, one baking system at three one bakings of painting Used in priming paint and colored paint be water paint, the construction solid content of the priming paint is between 35%~55%, after curing Film thickness between 10~50 μm, the construction solid content of the colored paint between 20%~40%, film thickness after curing between 6~ Between 20 μm.

33. the purposes of the clear coat composition of solvent-type double-component according to claim 30, high slipping, feature exist In：The outermost coating of multicoat Finish is prepared by the clear coat composition of the solvent-type double-component, high slipping It forms；The thickness of dry film of the multicoat Finish is 10 μm~80 μm；The cured temperature is 100~180 DEG C；It is described The cured time is 10~40min.

34. the purposes of the clear coat composition of a kind of any solvent-type double-component of claims 1 to 10, high slipping, It is characterized in that：It is covered with paint, lacquer, colour wash, etc. as finishing varnish for automobile.