WO2021000897A1 - 清漆涂料组合物及其应用 - Google Patents

清漆涂料组合物及其应用 Download PDF

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Publication number
WO2021000897A1
WO2021000897A1 PCT/CN2020/099814 CN2020099814W WO2021000897A1 WO 2021000897 A1 WO2021000897 A1 WO 2021000897A1 CN 2020099814 W CN2020099814 W CN 2020099814W WO 2021000897 A1 WO2021000897 A1 WO 2021000897A1
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Prior art keywords
coating composition
varnish coating
hyperbranched
parts
acid
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PCT/CN2020/099814
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English (en)
French (fr)
Inventor
李海荣
王爽
王娴娴
王迁
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立邦涂料（中国）有限公司
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Publication of WO2021000897A1 publication Critical patent/WO2021000897A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the invention relates to the field of coatings. More specifically, it relates to a varnish coating composition and its application.
  • Hyperbranched polymers are highly branched macromolecules with a three-dimensional branched structure.
  • the molecular structure is relatively regular and has a very narrow relative molecular mass distribution. It has a similar structure to dendrimers, but the synthesis method is simple, and generally one step can be used. Synthesis by polymerization.
  • hyperbranched polymers Compared with linear macromolecules, hyperbranched polymers have a compact structure similar to a spherical shape, a small hydrodynamic radius of gyration, a high degree of branching, and less molecular chain entanglement, so they have a lower viscosity than the former at the same molecular weight. And the change is small with the increase of relative molecular mass.
  • hyperbranched polymers began to be more and more used in the field of coatings.
  • Sweden's Perstorp company has produced a series of hyperbranched polymer products.
  • the second-generation hyperbranched polymer Boltorn H20 the third-generation hyperbranched polymer Boltorn H30 and the fourth-generation hyperbranched polymer Boltorn H40.
  • These hyperbranched polymers have high hydroxyl functionality, strong polarity, strong hydrogen bonds between molecules, easy to agglomerate, and cannot be effectively dispersed in coatings.
  • the compatibility of protic solvents also lacks compatibility with general hydroxyl resins.
  • Hyperbranched resins have the advantage of high functionality, which is disadvantageous for the preparation of high hardness and high chemical resistance coatings.
  • compatibility resins (functionally similar to grinding resins in color pastes) are mixed to improve the compatibility of resin derivatives with hyperbranched structures and coating compositions.
  • the first object of the present invention is to provide a varnish coating composition, which solves the need to add a third-party resin to improve the relationship between the hyperbranched polymer and the existing coating composition containing hyperbranched polymer.
  • the compatibility of other components in the coating composition and the compatibility is still not high, and the varnish coating composition has an improved and better paint film appearance.
  • the second object of the present invention is to provide an application of the varnish coating composition.
  • the present invention adopts the following technical solutions:
  • a varnish coating composition comprising:
  • Hyperbranched polyester said hyperbranched polyester is a hyperbranched hydroxyl polymer in which part of the terminal hydroxyl groups is esterified with C5-C12 linear saturated fatty acids;
  • the relationship between the solubility parameter A of the hyperbranched polyester and the solubility parameter B of the film-forming resin is:
  • the relationship between the solubility parameter A of the hyperbranched polyester and the solubility parameter B of the film-forming resin is:
  • the C5-C12 linear saturated fatty acids are selected from one or more of valeric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, and lauric acid.
  • the hyperbranched hydroxyl polymer is prepared by vacuum melt polycondensation using Bm type polyhydroxy compound as the core molecule and ABn type polyhydroxy acid as the diverging molecule, wherein A represents carboxylic acid, B represents hydroxyl, and its functionality m ⁇ 2, functionality n ⁇ 2.
  • the hyperbranched hydroxyl polymer is selected from one of Boltorn H20, Boltorn H30, and Boltorn H40.
  • the varnish coating composition contains: 1-30 parts of hyperbranched polyester.
  • the varnish coating composition contains: 1-25 parts of hyperbranched polyester.
  • the varnish coating composition contains: 5-15 parts of hyperbranched polyester.
  • the varnish coating composition further includes a curing agent, a curing reaction catalyst, an additive and an organic solvent.
  • the additives include one or more of surface modifiers, defoamers, rheology control agents, ultraviolet absorbers and hindered amine light stabilizers.
  • the varnish coating composition comprises: 20-80 parts of solid content or non-volatile matter content, and 20-80 parts of organic solvent.
  • the varnish coating composition is a one-component amino baking paint or a two-component polyurethane baking paint.
  • the present invention provides the application of the above-mentioned varnish coating composition.
  • the varnish coating composition is used as a top coat for automobiles, woodware, steel coils, parts, anticorrosion, and general industries.
  • the varnish coating composition provided by the present invention is a solvent-based coating composition.
  • a specific hyperbranched polyester is added and the relationship between the solubility parameter and the film-forming resin is limited so that the coating composition is The compatibility between the components has been fundamentally improved, and the coating composition has lower viscosity and good mechanical properties and appearance of the paint film. It can be used as a top coat.
  • the coating composition The unique properties of the hyperbranched polyester in the composition can also be fully utilized. At the same time, the composition overcomes the problem that existing varnish coating compositions containing hyperbranched polymers need to rely on third-party resins or tailor products to improve the compatibility of products.
  • the varnish coating composition of the present invention When used as a top coat in automobiles, woodware, steel coils, parts, anti-corrosion, and general industries, it not only gives the top coat low viscosity, good bonding strength with the primer, but also gives it good Exterior.
  • One embodiment of the present invention provides a varnish coating composition, which comprises:
  • Hyperbranched polyester said hyperbranched polyester is a hyperbranched hydroxyl polymer in which part of the terminal hydroxyl groups is esterified with C5-C12 linear saturated fatty acids;
  • the relationship between the solubility parameter A of the hyperbranched polyester and the solubility parameter B of the film-forming resin is:
  • a hyperbranched hydroxy polymer in which part of the terminal hydroxyl groups are esterified with C5-C12 linear saturated fatty acids is used as the hyperbranched polyester, and the absolute difference between the solubility parameter and the film-forming resin is defined.
  • a value within 0.5 is good as a general-purpose solvent-based varnish coating composition.
  • the solubility parameter of the obtained hyperbranched polyester can be controlled to be in accordance with the solubility parameter of the film-forming resin The absolute value of the difference is controlled within 0.5.
  • the relationship of improving the compatibility between the hyperbranched polyester and the film-forming resin in the coating composition is achieved.
  • the resulting varnish coating composition has low viscosity, good surface fluidity and leveling properties, and good mechanical properties of the obtained paint film.
  • the hyperbranched polyester obtained by the method helps to improve the paint film appearance of the varnish coating composition (especially reducing the long-wave value and short-wave value), so that the varnish coating composition can be used as a top coat (that is, The cured film of the varnish coating composition is located in the outermost layer of the coating film).
  • This method overcomes the existing hyperbranched polymer-containing coatings, usually by adding third-party compatible resins (such as polyisocyanate, etc.) to improve the compatibility of the hyperbranched polymer with other components in the coating.
  • third-party compatible resins such as polyisocyanate, etc.
  • the relationship between the solubility parameter A of the hyperbranched polyester and the solubility parameter B of the film-forming resin is preferably
  • the hyperbranched polyester has a structure shown in the following formula I:
  • the above-mentioned hyperbranched hydroxyl polymer is preferably prepared by using Bm-type polyhydroxy compound as the core molecule and ABn-type polyhydroxy acid as the diverging molecule, and is prepared by vacuum melt polycondensation, wherein A represents carboxylic acid, B represents hydroxyl, and the functionality m ⁇ 2 , The functionality n ⁇ 2.
  • A represents carboxylic acid
  • B represents hydroxyl
  • the functionality m ⁇ 2 The functionality n ⁇ 2.
  • one of trihydroxypropane, pentaerythritol, and dipentaerythritol can be used as a nuclear molecule, and 2,2-dimethylolpropionic acid can be prepared through a one-step reaction.
  • hyperbranched hydroxyl polymers include, but are not limited to Perstorp's Boltorn H20, H30, H40, and the like. It can be understood that the hyperbranched hydroxyl polymer herein refers to the structure before the esterification reaction with the C5-C12 linear saturated fatty acid acid.
  • Exemplary C5-C12 linear saturated fatty acids include, but are not limited to: valeric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, and lauric acid.
  • part of the terminal hydroxyl groups are esterified by C5-C12 linear saturated fatty acids
  • part of the terminal hydroxyl groups is esterified by C5-C12 linear saturated fatty acids, that is, the In hyperbranched polyester, the terminal hydroxyl group and the structure formed by esterification coexist.
  • the above-mentioned hyperbranched polyester is prepared by esterification reaction between hyperbranched hydroxyl polymer and C5-C12 linear saturated fatty acid.
  • Those skilled in the art can control the progress of the specific reaction and the degree of esterification according to the conditions of the esterification reaction, which will not be repeated here.
  • the film-forming resin there is no specific requirement for the selection of the film-forming resin, as long as the film-forming resin can be used for the varnish.
  • Exemplary film-forming resins include, but are not limited to, one or more of acrylic resin, alkyd resin, polyester resin, epoxy resin and the like.
  • the varnish coating composition contains: 1-30 parts of hyperbranched polyester.
  • the hyperbranched polyester has a certain viscosity reduction effect in the varnish coating composition, and the aforementioned added amount of the hyperbranched polyester can have the best viscosity reduction effect for the composition.
  • the added amount of hyperbranched polyester includes, but is not limited to, 1-25 parts, 5-15 parts, 5-10 parts, and the like.
  • the varnish coating composition further includes a curing agent, a curing reaction catalyst, an additive, and an organic solvent.
  • the additives include, but are not limited to, one or more selected from surface modifiers, defoamers, rheology control agents, ultraviolet absorbers and hindered amine light stabilizers. Those skilled in the art can specify the components and dosage of each additive according to actual needs.
  • the organic solvent may be a polar solvent, for example, an ester or alcohol solvent.
  • the varnish coating composition contains: 20-80 parts of solid content or non-volatile matter content, and 20-80 parts of organic solvent.
  • the above-mentioned varnish coating composition is a one-component amino baking paint or a two-component polyurethane baking paint.
  • the use of the varnished coating composition as a top coat in automobiles, woodware, steel coils, parts, anti-corrosion and general industries is provided.
  • the paint coating composition can be used as original paint or repair paint.
  • Boltorn H20 provided by Perstorp.
  • the second-generation hyperbranched polyester polyol theoretically has 16 terminal hydroxyl functional groups, and the hydroxyl value is 490-530mg KOH/g based on solid content.
  • Boltorn H30 provided by Perstorp.
  • the third-generation hyperbranched polyester polyol theoretically has 32 terminal hydroxyl functional groups, and the hydroxyl value is 480-510mg KOH/g based on solid content.
  • Caprylic acid (>96%) and capric acid (>96%) were purchased from IOI Acidchem Sdn Bhd, Malaysia.
  • Pencil hardness ASTM D3363;
  • Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 product H2040-8 H2050-8 H2060-8 H3040-8 H3050-8 H4040-8 H4050-8 H4060-8 H20 50 40 30 - - - - H30 - - - 50 40 30 - - - H40 - - - - - 50 40 30 bitter 30 40 50 30 40 50 30 40 50 30 40 50 p-TSA 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Xylene 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Butyl acetate 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 Total / copy 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • the SP values of Examples 1-18 were measured and are listed in Table 2. It can be seen that: 1) As the modification amount of fatty acid increases, the SP value decreases, that is, the polarity decreases; 2) Decanoic acid has a longer alkyl chain than caprylic acid, and under the same modification amount (quality) condition , The SP value is lower; 3) Under the same modified amount of the same fatty acid, the SP value decreases as the generation number of hyperbranched polyester increases.
  • Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 product H2040-8 H2050-8 H2060-8 H3040-8 H3050-8 H3060-8 H4040-8 H4050-8 H4060-8 SP 11.25 10.71 10.28 11.08 10.56 10.12 10.87 10.41 9.86
  • Example Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 product H2040-10 H2050-10 H2060-10 H3040-10 H3050-10 H3050-10 H4040-10 H4050-10 H4060-10 SP 10.99 10.45 10.01 10.84 10.35 9.87 10.63 10.21 9.62
  • the compatibility of Examples 1-18 with acrylic resin was measured.
  • the specific method is to add the products of Examples 1-18 to a designated acrylic resin at a ratio of 5% and 10% respectively.
  • SP value 10.48: Setalux 1760 VB-64.
  • a score of 5 indicates the best compatibility and a score of 1 is the worst.
  • the results are shown in Table 3. It can be seen from the results that the compatibility follows the principle of similar compatibility. The closer the SP value of the examples and the SP value of the host resin, the better the compatibility. When the difference in SP value is greater than 0.3, the compatibility is considerably reduced, and when the difference in SP value is greater than 0.5, the compatibility is poor.
  • Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 product H2040-8 H2050-8 H2060-8 H3040-8 H3050-8 H3060-8 H4040-8 H4050-8 H4060-8 SP 11.25 10.71 10.28 11.08 10.56 10.12 10.87 10.41 9.86 compatibility 1 4 4 1 5 2.5 3.5 5 2 VRE - 20.75% 20.67% - 23.13% 16.75% 18.90% 22.92% -
  • Example Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 product H2040-10 H2050-10 H2060-10 H3040-10 H3050-10 H3050-10 H4040-10 H4050-10 H4060-10 SP 10.99 10.45 10.01 10.84 10.35 9.87 10.63 10.21 9.62 compatibility 3 5 2 3.5 5 2 5 4 1 VRE 18.46 22.81% 16.28% 18.73% 22.50% - 22.34% 19.58% -
  • the clear coating used as the top coating of the automobile of the present invention is stirred with the aid of a laboratory disperser.
  • the preparation method of the coating material is added and mixed in the order from top to bottom as indicated in Table 4, and after all is added, the mixture is stirred for 30-60 minutes.
  • the intermediate coating OP 308-105 (gray) electrodeposition coating panel prepared according to the standard process on the automatic OEM production line) of Nippon Paint (China) Co. Ltd.
  • the dry film with a thickness of ⁇ 3 ⁇ m is then thermally cured, and then coated with Nippon Paint's black base paint SPM-155, and then the diluted transparent paint samples of Examples 21-28 and Comparative Example 1 of the present invention are wet-on-wet Technology is applied to it. After that, it was cured at 140°C for 30 minutes.
  • a cured paint layer film (dry film thickness of 40 ⁇ 4 ⁇ m) obtained from the base paint (dry film thickness of 15 ⁇ 1 ⁇ m) and the clear paint is formed.
  • the clear coating used as the top coating of the automobile of the present invention is stirred with the aid of a laboratory disperser.
  • the preparation method of the paint follows the same sequence of steps to ensure product consistency and quality.
  • the viscosity of the viscosity cup was measured after the configuration was completed, and the results are listed in Table 6.
  • the viscosity of the formulation decreases as the amount of modified hyperbranched polyester added increases, but there is a minimum viscosity value, that is, the optimal addition amount. Beyond this amount, the viscosity increases instead.
  • Different systems correspond to different optimal dosages.
  • Example 29 Example 30
  • Example 31 Example 32 raw material Number of copies Number of copies Number of copies Number of copies Number of copies Number of copies Setalux 1760 VB-64 34.8 29.8 24.8 19.8 14.8 Setalux 91796 SS-69 13.7 13.7 13.7 13.7 13.7 Setamine US-138 23.6 23.6 23.6 23.6 23.6 AAC 2500 1 1 1 1 1 1 1 1 TINUVIN 292 0.5 0.5 0.5 0.5 0.5 TINUVIN 384-2 0.75 0.75 0.75 0.75 0.75 0.75 BYK-358N 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Propylene glycol butyl ether acetate 3 3 3 3 3 3 3 3 Solvesso 100 solvent oil 5 5 5 5 5 5 5 N-butanol 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Butyl acetate 13.75 13.75 13.75 13.75 Example 8 - 5 - - - Example 8 - 10 - - Example 8 -
  • the resin composition of component 1 in Table 8 (based on the content of parts by mass), as well as additives and solvents were stirred with the aid of a laboratory disperser to prepare the transparent coating of the present invention as a top coating for automobiles.
  • the intermediate coating OP 308-105 (gray) electrodeposition coating panel (prepared according to the standard process on the automatic OEM production line) of Nippon Paint (China) Co. Ltd.
  • the dry film with a thickness of ⁇ 3 ⁇ m is then thermally cured, and then coated with Nippon Paint's black base paint SPM-155.
  • Example 34 Example 35
  • Example 36 Example 37
  • hyperbranched polyester the raw materials and preparation method are the same as in Example 1, except that caprylic acid is changed to isooctanoic acid, and the hyperbranched polyester is prepared by esterification.
  • the esterification reaction cannot be fully reacted due to steric hindrance, and a considerable part of free fatty acid remains, and subsequent tests cannot be carried out. Therefore, the use of branched fatty acids in the above examples has no practical value.
  • the present invention clearly clarifies that the hyperbranched polymer is specifically modified to achieve the best compatibility with the main resin and varnish system; at the same time, by evaluating the effect of the addition amount on the viscosity and appearance, The coating formulation is optimized.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

本发明公开了一种清漆涂料组合物，它包含：超支化聚酯，所述超支化聚酯为部分端羟基被C5-C12的线性饱和脂肪酸的酸酯化的超支化羟基聚合物；成膜树脂；其中，所述超支化聚酯的溶解度参数A与所述成膜树脂的溶解度参数B的关系为：|A-B|≤0.5。该清漆涂料组合物解决了现有的含有超支化聚合物的涂料组合物中，需要通过添加第三方树脂来提高超支化聚合物与该涂料组合物中其他组分相容性且相容性依旧不高的问题。本发明还公开了该清漆涂料组合物的应用。

Description

清漆涂料组合物及其应用 技术领域
本发明涉及涂料领域。更具体地，涉及一种清漆涂料组合物及其应用。
背景技术
超支化聚合物是具有三维支化结构的高度支化大分子，分子结构比较规整，具有很窄的相对分子质量分布，与树枝型聚合物有类似的结构，但合成方法简单，一般可采用一步聚合法合成。与线性大分子相比，由于超支化聚合物具有类似球形的紧凑结构，流体力学回转半径小，支化度很高，分子链缠结少，因此在同等分子量时比前者具有更低的粘度，而且随相对分子质量的增加变化较小。从而，超支化聚合物开始越来越多的应用于涂料领域中来。
在应用方面，瑞典的Perstorp公司已生产了一系列超支化聚合物产品。例如第二代超支化聚合物Boltorn H20，第三代超支化聚合物Boltorn H30和第四代超支化聚合物Boltorn H40。这些超支化聚合物由于羟基官能度高，极性强，分子间容易形成强的氢键，容易团聚，不能有效的分散在涂料中，其溶解度参数SP>12，从而缺乏与非极性，非质子溶剂的相容性，也缺乏和一般羟基树脂的相容性，为了降低超支化树脂的溶解度参数，增加其相容性，中国专利CN101679589B提到应用单羧酸和超支化羟基树脂进行酯化，封掉大部分羟基，降低超支化羟基聚合物的极性，从而达到和非极性，非质子溶剂以及一般羟基树脂的相容性。然而这种方法如果封端太少，则不足以降低超支化羟基聚合物的极性，提高其相容性；如果封端太多，这会大大降低了超支化树脂的官能度，消弱了超支化树脂高官能度的优势，这对于制备高硬度的，高耐化学性的涂料是不利的。在一些涂料中，有通过混拼相容性树脂(功能类似于色浆中的研磨树脂)来提高超支化结构的树脂衍生物与涂料组合物的相容性。可以确认的是：这些树脂在溶剂型清漆体系中可以降低体系的粘度和提升外观，但同时也存在一系列的问题：1)依赖于量身定制产品，价格高昂，交货周期长且品控问题不断；2)依赖于第三方树脂作为增容树脂，提升不必要的成本；3)合成步骤较长；4)相容性依旧不高，没有充分发挥其独特结构所带来的特性；5)品控稳定性较差，有严格的添加顺序，且由于添加量受到限制而无法充分发挥其特性。
发明内容
基于以上事实，本发明的第一个目的在于提供一种清漆涂料组合物，解决了现有的含有超支化聚合物的涂料组合物中，需要通过添加第三方树脂来提高超支化聚合物与该涂料组合物中其他组分相容性且相容性依旧不高的问题，同时该清漆涂料组合物具有改善的更好的漆膜外观。
本发明的第二个目的在于提供一种清漆涂料组合物的应用。
为达到上述第一个目的，本发明采用下述技术方案：
一种清漆涂料组合物，它包含：
超支化聚酯，所述超支化聚酯为部分端羟基被C5-C12的线性饱和脂肪酸的酸酯化的超支化羟基聚合物；
成膜树脂；
其中，所述超支化聚酯的溶解度参数A与所述成膜树脂的溶解度参数B的关系为：|A-B|≤0.5。
可选地，所述超支化聚酯的溶解度参数A与所述成膜树脂的溶解度参数B的关系为：|A-B|≤0.3
可选地，所述C5-C12的线性饱和脂肪酸选自戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸中的一种或几种。
可选地，所述超支化羟基聚合物是以Bm型多羟基化合物为核分子，以ABn型多羟基酸为发散分子，真空熔融缩聚制备得到，其中A代表羧酸，B代表羟基，官能度m≥2，官能度n≥2。
可选地，所述超支化羟基聚合物选自Boltorn H20、Boltorn H30、Boltorn H40中的一种。
可选地，以所述清漆涂料组合物总质量份为100份计，它包含：1-30份超支化聚酯。
可选地，以所述清漆涂料组合物总质量份为100份计，它包含：1-25份超支化聚酯。
可选地，以所述清漆涂料组合物总质量份为100份计，它包含：5-15份超支化聚酯。
可选地，所述清漆涂料组合物中还包含固化剂、固化反应催化剂、添加剂和有机溶剂。
可选地，所述添加剂包括表面改性剂、消泡剂、流变控制剂、紫外线吸收剂和受阻胺类光稳定剂中的一种或几种。
可选地，以所述清漆涂料组合物总质量份为100份计，它包含：20-80份的固含量或非挥发性物质含量，以及20-80份有机溶剂。
可选地，所述清漆涂料组合物为单组份氨基烤漆或双组份聚氨酯烤漆。
为达到上述第二个目的，本发明提供如上所述的清漆涂料组合物的应用。
可选地，所述清漆涂料组合物作为面漆用于汽车、木器、卷钢、零部件、防腐和一般工业。
本发明的有益效果如下：
本发明提供的清漆涂料组合物为溶剂型涂料组合物，该涂料组合物中，通过添加特定的超支化聚酯及限定其与成膜树脂间的溶解度参数间的关系从而使得该涂料组合物各组分间相容性得到根本提升，且该涂料组合物具有较低的粘度以及好的漆膜机械性能及外观，可作为面漆使用，另外，由于各组分间相容性好，该涂料组合物中超支化聚酯本身所特有的性能也能得到更充分的发挥。同时，该组合物克服了现有的含有超支化聚合物的清漆涂料组合物中需要通过依赖第三方树脂或是需量身定制产品来提高产品的相容性的问题。将本发明的清漆涂料组合物作为面漆用于汽车、木器、卷钢、零部件、防腐和一般工业时，不仅赋予该面漆低粘度、与底漆好的结合强度、还赋予其良好的外观。
具体实施方式
为了更清楚地说明本发明，下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。
本发明的一个实施方式提供了一种清漆涂料组合物，它包含：
超支化聚酯，所述超支化聚酯为部分端羟基被C5-C12的线性饱和脂肪酸的酸酯化的超支化羟基聚合物；
成膜树脂；
其中，所述超支化聚酯的溶解度参数A与所述成膜树脂的溶解度参数B的关系为：|A-B|≤0.5。
上述清漆涂料组合物中，通过将部分端羟基被C5-C12的线性饱和脂肪酸的酸酯化的超支化羟基聚合物作为超支化聚酯，以及限定其与成膜树脂的溶解度参数差值的绝对值在0.5以内即可很好的作为通用型的溶剂型清漆涂料组合物。本发明的技术方案中，采用C5-C12的线性饱和脂肪酸与超支化羟基聚合物的部分端羟基酯化后，得到的超支化聚酯的溶解度参数可以可控的与成膜树脂的溶解度参数的差值绝对值控制在0.5以内。进而通过控制两者的溶解度参数之间的关系，来达到提高超支化聚酯与涂料组合物中成膜树脂间的相容性的关系。使得得到的清漆涂料组合物粘度低，表面流动性和流平性好，得到的漆膜的机械性能好。同时，该方法得到的超支化聚酯有助于提升该清漆涂料组合物的漆膜外观(尤其是降低长波值和短波值)，使得该清漆涂料组合物可很好的作为面漆(也即，该清漆涂料组合物的固化膜位于涂料膜中的最外层)使用。
该方法克服了现有的包含超支化聚合物的涂料中，通常是通过增加第三方相容性树脂(如多异氰酸酯等)改善超支化聚合物与涂料中其他组分的相容性。然而，这些方法通常都是只能针对特定的成膜主树脂，且对相容性的改善效果依然有限，从而无法很好的发挥出超支化聚合物在涂料中的作用的问题。
上述超支化聚酯的溶解度参数A与所述成膜树脂的溶解度参数B的关系优选为|A-B|≤0.3，也即两者间的溶解度参数间的差值越小，相容性更好，降粘效果越好。
其中，所述超支化聚酯具有如下式I所示的结构：
Figure PCTCN2020099814-appb-000001
其中，
Figure PCTCN2020099814-appb-000002
为所述超支化羟基聚合物的骨架；1≤y＜x，且x和y均为自然数，优选地，x≥8；R选自C4-C11的线性链烷基。
上述的超支化羟基聚合物优选是以Bm型多羟基化合物为核分子，以ABn型多羟基酸为发散分子，真空熔融缩聚制备得到，其中A代表羧酸，B代表羟基，官能度m≥2，官能度n≥2。具体地，可以以三羟基丙烷、季戊四醇、双季戊四醇中的一种为核分子，以2,2-二羟甲基丙酸通过一步反应制得。示例性的超支化羟基聚合物包括但不限于Perstorp的Boltorn H20、H30、H40等。可以理解，此处的超支化羟基聚合物均是指在与C5-C12的线性饱和脂肪酸的酸发生酯化反应前的结构。
示例性的C5-C12的线性饱和脂肪酸包括但不限于：戊酸、己酸、庚酸、辛酸、壬酸、 癸酸、月桂酸。
需要说明的是，本实施方式中，“部分端羟基被C5-C12的线性饱和脂肪酸的酸酯化”是指部分的端羟基被C5-C12的线性饱和脂肪酸的酸酯化，也即，该超支化聚酯中，端羟基和端羟基被酯化形成的结构共存。
上述超支化聚酯是通过采用超支化羟基聚合物与C5-C12的线性饱和脂肪酸经过酯化反应制备得到。本领域技术人员可根据酯化反应的条件对具体反应的进度以及酯化程度进行控制，在此不赘述。
该清漆涂料组合物中，对成膜树脂的选择没有特定要求，能够用于清漆的可成膜的树脂即可。示例性的成膜树脂包括但不限于丙烯酸树脂、醇酸树脂、聚酯树脂，环氧树脂等中的一种或几种。
在一些优选示例中，以所述清漆涂料组合物总质量份为100份计，它包含：1-30份超支化聚酯。超支化聚酯在清漆涂料组合物中具有一定的降粘作用，前述添加量的超支化聚酯可以对该组合物具有最佳的降粘效果。此外，在同样的添加量的情况下，超支化聚酯与成膜树脂越相溶，降粘效果越好。在又一些优选示例中，超支化聚酯的添加量包括但不限于1-25份、5-15份、5-10份等。
本实施方式中，清漆涂料组合物中还包含固化剂、固化反应催化剂、添加剂和有机溶剂。所述添加剂包括但不限于选自表面改性剂、消泡剂、流变控制剂、紫外线吸收剂和受阻胺类光稳定剂中的一种或几种。本领域技术人员可以根据实际需要具体各添加剂的组分及用量。
所述有机溶剂可为极性溶剂，例如可为酯类或醇类溶剂。
在一个优选示例中，以所述清漆涂料组合物总质量份为100份计，它包含：20-80份的固含量或非挥发性物质含量，以及20-80份有机溶剂。
在一个优选示例中，上述清漆涂料组合物为单组份氨基烤漆或双组份聚氨酯烤漆。
在本发明的又一个具体实施方式中，提供如上清漆涂料组合物作为面漆在汽车、木器、卷钢、零部件、防腐和一般工业中的用途。
在一个优选示例中，可将该漆涂料组合物为原厂漆或修补漆使用。
以下结合一些具体实施例对本发明的技术方案进行说明：
本发明实施例中所用原料情况如下：
1.Boltorn H20，由Perstorp公司提供。第二代超支化聚酯多元醇，理论上有16个端羟基官能团，羟基值按固含计算为490-530mg KOH/g。
2.Boltorn H30，由Perstorp公司提供。第三代超支化聚酯多元醇，理论上有32个端羟基官能团，羟基值按固含计算为480-510mg KOH/g。
3.Boltorn H40，由Perstorp公司提供。第四代超支化聚酯多元醇，理论上有64个端羟基官能团，羟基值按固含计算为470-500mg KOH/g。
4.辛酸(>96％)和癸酸(>96％)从马来西亚IOI Acidchem Sdn Bhd购得。
5.配方用到的其他的树脂、溶剂和助剂都是通过市售购买获得。
本发明实施例中所用树脂，漆料和漆膜的表征方法：
1.铅笔硬度(划伤/划破)：ASTM D3363；
2.摆杆硬度计
Figure PCTCN2020099814-appb-000003
ASTM D4366；
3.溶解度参数测定：ASTM D3132；
4.杯凸试验：ASTM E643；
5.耐冲击试验：ADTM D5420；
6.粘度测定：涂-4杯，23℃，GB1723-79；
7.外观测定：桔皮仪(Wave-scan dual)，从毕克化学购得。
实施例1-18
超支化聚酯的制备实施例：
表1.原料组成
实施例 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7 实施例8 实施例9
产品 H2040-8 H2050-8 H2060-8 H3040-8 H3050-8 H3050-8 H4040-8 H4050-8 H4060-8
H20 50 40 30 - - - - - -
H30 - - - 50 40 30 - - -
H40 - - - - - - 50 40 30
辛酸 30 40 50 30 40 50 30 40 50
p-TSA 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
二甲苯 5 5 5 5 5 5 5 5 5
醋酸丁酯 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5
总计/份 100 100 100 100 100 100 100 100 100
实施例 实施例10 实施例11 实施例12 实施例13 实施例14 实施例15 实施例16 实施例17 实施例18
产品 H2040-10 H2050-10 H2060-10 H3040-10 H3050-10 H3050-10 H4040-10 H4050-10 H4060-10
H20 50 40 30 - - - - - -
H30 - - - 50 40 30 - - -
H40 - - - - - - 50 40 30
癸酸 30 40 50 30 40 50 30 40 50
p-TSA 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
二甲苯 5 5 5 5 5 5 5 5 5
醋酸丁酯 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5
总计/份 100 100 100 100 100 100 100 100 100
在带有机械搅拌，温度控制，氮气保护和Dean-Stark回流管的四口烧瓶中，加入表1所列原料组成，除了醋酸丁酯。以每小时15-20℃的温度加热至230℃。三小时后每隔半小时测定酸值，直至酸值不再变化为反应终点，冷却至80℃加入醋酸丁酯。继续冷却至50℃，出料，过滤，包装制得脂肪酸改性的超支化聚酯目标产物。
表征实施例
实施例19
测定实施例1-18的SP值，列于表2。可以看出：1)随着脂肪酸改性量的提升，SP值下降，即极性下降；2)癸酸相对于辛酸由于具有更长的烷基链，在相同改性量(质量)条件下，SP值更低；3)在相同改性量的同一脂肪酸条件下，SP值随着超支化聚酯的代数增加而下降。
表2.实施例1-18的SP值
实施例 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7 实施例8 实施例9
产品 H2040-8 H2050-8 H2060-8 H3040-8 H3050-8 H3060-8 H4040-8 H4050-8 H4060-8
SP 11.25 10.71 10.28 11.08 10.56 10.12 10.87 10.41 9.86
实施例 实施例10 实施例11 实施例12 实施例13 实施例14 实施例15 实施例16 实施例17 实施例18
产品 H2040-10 H2050-10 H2060-10 H3040-10 H3050-10 H3050-10 H4040-10 H4050-10 H4060-10
SP 10.99 10.45 10.01 10.84 10.35 9.87 10.63 10.21 9.62
实施例20
测定实施例1-18在丙烯酸树脂的相容性。具体做法是，将实施例1-18的产品以5％和10％的比例分别加入一款指定的丙烯酸树脂，在本实施例中，我们选用一款SP值为10.48的羟基丙烯酸树脂：Setalux 1760 VB-64。混合后在60℃充分搅拌，冷却后观察树脂通透性，并在玻璃板上刮膜，烘干观察漆膜的通透性。给每个样品打分：1到5，5分表示相容性最好，1分最差。结果列于表3。从结果可知，相容性遵循相似相溶原理，实施例的SP值与主体树脂的SP值越接近，相容性越好。当SP值的差距大于0.3时，相容性有可观下降，当SP值的差距大于0.5时，相容性较差。
同时，我们也测定了实施例1-18在此树脂中的降粘效果。具体做法是，将实施例1-18的产品以5wt％的比例分别加入Setalux 1760 VB-64。用Brookfield粘度计测定粘度(#3号转子，23℃，30rpm，1min)，计算降粘效率(Viscosity reduction efficacy,VRE/％)，计算公式如下：
Figure PCTCN2020099814-appb-000004
结果列于表3。从测量结果可以得出的结论是：相溶性越高，即SP值越接近，降粘效果越好。考虑到实验误差和理论计算的误差，我们认为，只要SP值的差距小于±0.5，都会得到不错的相溶性和降粘效果；当SP值差距小于±0.3，两者的相容性以及降粘效果更优。此外，表3中，“-”表示未测试，原因在于，此时，因为SP值差距较大，此时，该超支化聚酯在丙烯酸树脂体系中析出较多，整个漆不通透，漆膜光泽度差，实用性差。
表3.实施例1-18的SP值和相容性评估
实施例 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7 实施例8 实施例9
产品 H2040-8 H2050-8 H2060-8 H3040-8 H3050-8 H3060-8 H4040-8 H4050-8 H4060-8
SP 11.25 10.71 10.28 11.08 10.56 10.12 10.87 10.41 9.86
相容性 1 4 4 1 5 2.5 3.5 5 2
VRE - 20.75％ 20.67％ - 23.13％ 16.75％ 18.90％ 22.92％ -
实施例 实施例10 实施例11 实施例12 实施例13 实施例14 实施例15 实施例16 实施例17 实施例18
产品 H2040-10 H2050-10 H2060-10 H3040-10 H3050-10 H3050-10 H4040-10 H4050-10 H4060-10
SP 10.99 10.45 10.01 10.84 10.35 9.87 10.63 10.21 9.62
相容性 3 5 2 3.5 5 2 5 4 1
VRE 18.46 22.81％ 16.28％ 18.73％ 22.50％ - 22.34％ 19.58％ -
配方实施例
实施例21-28，对比例1
通过混合表4中规定的树脂成分(基于质量份数含量)，以及催化剂，添加剂和溶剂借助实验室分散器搅拌制备本发明作为汽车顶层涂料的透明涂料。所述涂料的制备方法按照表4中标出的原料从上到下的顺序添加混合，全部加入后，搅拌30-60min即可。
表4.清漆配方
Figure PCTCN2020099814-appb-000005
Figure PCTCN2020099814-appb-000006
将立邦涂料(中国)有限公司(Nippon Paint(China)Co.Ltd.)的中间涂料OP 308-105(灰色)电沉积涂料面板(在自动OEM生产线上按标准工艺进行制备)上进行得到30±3μm厚度的干膜随后热固化，再涂覆立邦涂料公司的黑色基础涂料SPM-155，然后将本发明稀释后的实施例21-28透明涂料样品及对比例1涂料样品采用湿碰湿技术施加于其上。之后，在140℃固化30分钟。形成由基础涂料(干膜厚15±1μm)和透明涂料得到的固化的涂料层膜(干膜厚40±4μm)。由此得到的全涂层漆膜测试杯凸，硬度，和漆料粘度(涂-4杯，23℃，秒)的结果列于表5。从粘度数据可知，添加改性超支化聚酯能明显降低涂料粘度；在添加量不变的情况下，添加的改性超支化聚酯的VRE越高，漆料的粘度就越低。也就是说，改性超支化聚酯与涂料主树脂的相容性越好，漆料的粘度越低，但总体而言差距不大，因为配制清漆时所选的超支化树脂都是与体系相容的。此外，由于添加量不多，机械性能与参考配方(对比例1)相比差距不大。
表5.漆料粘度和漆膜机械性能表征
Figure PCTCN2020099814-appb-000007
实施例29-32，对比例2
通过混合表6中规定的树脂成分(基于质量份数含量)，以及催化剂，添加剂和溶剂借助实验室分散器搅拌制备本发明作为汽车顶层涂料的透明涂料。所述涂料的制备方法按照相同的步骤顺序以确保产品的一致性和质量。配置完成后测定黏度杯粘度，结果列于表6。显而易见地，配方粘度随着改性超支化聚酯的添加量的提高而降低，但是有一个粘度最低 值，即最佳添加量，超过这个量，粘度反而提高。不同体系对应的最佳添加量不同，我们也测定了几支其他改性超支化聚酯，得到的趋势是一致的，即有一个最低粘度极限，只是最佳添加量和最低粘度值略有不同，在此不再赘述。
表6.漆料配方和粘度
  对比例2 实施例29 实施例30 实施例31 实施例32
原料 份数 份数 份数 份数 份数
Setalux 1760 VB-64 34.8 29.8 24.8 19.8 14.8
Setalux 91796 SS-69 13.7 13.7 13.7 13.7 13.7
Setamine US-138 23.6 23.6 23.6 23.6 23.6
AAC 2500 1 1 1 1 1
TINUVIN 292 0.5 0.5 0.5 0.5 0.5
TINUVIN 384-2 0.75 0.75 0.75 0.75 0.75
BYK-358N 0.4 0.4 0.4 0.4 0.4
丙二醇丁醚醋酸酯 3 3 3 3 3
Solvesso 100溶剂油 5 5 5 5 5
正丁醇 3.5 3.5 3.5 3.5 3.5
醋酸丁酯 13.75 13.75 13.75 13.75 13.75
实施例8 - 5 - - -
实施例8 - - 10 - -
实施例8 - - - 15 -
实施例8 - - - - 20
总计/份 100 100 100 100 100
粘度(涂-4,23℃,秒) 36.9 32.1 29.5 28.3 29.1
此外，我们也测定了漆膜的外观，结果列于表7。从结果可以看出，随着改性超支化聚酯添加量的增加，不仅粘度降低，而且外观也得到提升，长波(LW)的下降率尤为明显，这是因为在固化过程中，超支化聚酯由于分子链缠结少而促进涂料表面的流动和流平，提升漆膜的外观。
表7.漆膜外观数据
Figure PCTCN2020099814-appb-000008
实施例33-37，对比例3
将表8中组分1的树脂成分(基于质量份数含量)，以及添加剂和溶剂借助实验室分散器搅拌制备本发明作为汽车顶层涂料的透明涂料。将立邦涂料(中国)有限公司(Nippon Paint(China)Co.Ltd.)的中间涂料OP 308-105(灰色)电沉积涂料面板(在自动OEM生产线上按标准工艺进行制备)上进行得到30±3μm厚度的干膜随后热固化，再涂覆立邦涂料公司的黑色基础涂料SPM-155。将本发明透明涂料样品组分2加入混合好的组分1中，搅拌3min。然后采用湿碰湿技术施加于其上。之后，在140℃固化30分钟。从测定的原漆粘度数据可知，添加改性超支化聚酯能明显降低涂料粘度；在添加量不变的情况下，添 加的改性超支化聚酯的相溶性越高，漆料的粘度就越低。主树脂AC-1020的SP值测定为10.65，与之相溶性较好的实施例5(SP＝10.56)和实施例16(SP＝10.63)赋予的降粘效果也优于另外3个。
表8.漆料配方和粘度
Figure PCTCN2020099814-appb-000009
对漆膜的外观也进行了测定，结果列于表9。从结果可以看出，添加相溶性较好的超支化聚酯(即实施例34和37)，不仅粘度降低更多，而且外观提升也较明显，反之，加入不相容的超支化聚脂(即实施例33，35和36)，虽然降粘效果依然明显，漆膜不通透，外观还不如无添加的对比例3。总之，结论同前述实施例一致。
表9.漆膜外观数据
外观 对比例3 实施例33 实施例34 实施例35 实施例36 实施例37
Du 1.0 8.6 2.8 19.2 17.9 3.8
LW 6.8 4.8 2.8 4.2 3.5 2.8
SW 9.3 21.3 10.1 24.3 25.0 12.0
DOI 94.3 89.7 94.1 84.0 84.9 93.1
CF 65.7 62.0 71.6 57.0 59.5 70.2
对比例4
制备超支化聚酯，原料及制备方法同实施例1，区别在于，将辛酸改为异辛酸，酯化反应制备超支化聚酯。在实际制备过程中，酯化反应由于位阻关系无法充分反应，有相当一部分游离的脂肪酸残留，无法进行后续试验，从而采用支化脂肪酸用于上述实施例中并 无实用价值。
综上可知，本发明清晰阐明：通过对超支化聚合物进行特定的改性，使之与主体树脂和清漆体系达到最佳相容性；同时，通过评估添加量对粘度和外观的影响，使涂料配方最优化。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (10)

  1. 一种清漆涂料组合物，其特征在于，它包含：
    超支化聚酯，所述超支化聚酯为部分端羟基被C5-C12的线性饱和脂肪酸的酸酯化的超支化羟基聚合物；
    成膜树脂；
    其中，所述超支化聚酯的溶解度参数A与所述成膜树脂的溶解度参数B的关系为：|A-B|≤0.5。
  2. 根据权利要求1所述的清漆涂料组合物，其特征在于，所述C5-C12的线性饱和脂肪酸选自戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸中的一种或几种。
  3. 根据权利要求1所述的清漆涂料组合物，其特征在于，所述超支化羟基聚合物是以Bm型多羟基化合物为核分子，以ABn型多羟基酸为发散分子，真空熔融缩聚制备得到，其中A代表羧酸，B代表羟基，官能度m≥2，官能度n≥2。
  4. 根据权利要求3所述的清漆涂料组合物，其特征在于，所述超支化羟基聚合物选自Boltorn H20、Boltorn H30、Boltorn H40中的一种。
  5. 根据权利要求1所述的清漆涂料组合物，其特征在于，以所述清漆涂料组合物总质量份为100份计，它包含：1-30份超支化聚酯；优选地，所述超支化聚酯的质量份为1-25份，更优选地，所述超支化聚酯的质量份为5-15份。
  6. 根据权利要求1或5所述的清漆涂料组合物，其特征在于，所述清漆涂料组合物中还包含固化剂、固化反应催化剂、添加剂和有机溶剂；所述添加剂包括表面改性剂、消泡剂、流变控制剂、紫外线吸收剂和受阻胺类光稳定剂中的一种或几种。
  7. 根据权利要求1所述的清漆涂料组合物，其特征在于，以所述清漆涂料组合物总质量份为100份计，它包含：20-80份的固含量或非挥发性物质含量，以及20-80份有机溶剂。
  8. 根据权利要求1所述的清漆涂料组合物，其特征在于，所述清漆涂料组合物为单组份氨基烤漆或双组份聚氨酯烤漆。
  9. 如权利要求1-8任一项所述的清漆涂料组合物的应用，其特征在于，将所述清漆涂料组合物作为面漆用于汽车、木器、卷钢、零部件、防腐和一般工业。
  10. 根据权利要求9所述的应用，其特征在于，所述清漆涂料组合物为原厂漆或修补漆。
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