CN116200115A - Nail scratch-resistant coating for automotive upholstery, and preparation method and application thereof - Google Patents

Nail scratch-resistant coating for automotive upholstery, and preparation method and application thereof Download PDF

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CN116200115A
CN116200115A CN202310170314.5A CN202310170314A CN116200115A CN 116200115 A CN116200115 A CN 116200115A CN 202310170314 A CN202310170314 A CN 202310170314A CN 116200115 A CN116200115 A CN 116200115A
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parts
component
resin
auxiliary agent
solvent
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朱忠敏
罗宾
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DONGLAI COATING TECHNOLOGY (SHANGHAI) CO LTD
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DONGLAI COATING TECHNOLOGY (SHANGHAI) CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a nail scratch resistant coating for automotive upholstery and a preparation method thereof, wherein the coating comprises a component A and a component B, and the mass ratio of the component A to the component B is (75-125): 25, mixing uniformly; the weight portions are as follows: the component A comprises the following components: 2-20 parts of nano color paste, 3-30 parts of resin coated inorganic metal oxide, 10-60 parts of main resin, 2-20 parts of shaking auxiliary agent, 0.5-10 parts of auxiliary agent and 10-40 parts of solvent; the component B comprises the following components: 2-20 parts of diisocyanate, 0.2-2 parts of auxiliary agent and 2-20 parts of solvent. Compared with the prior art, the coating disclosed by the invention has the black appearance texture of a piano with high gloss, high fullness and high brightness, and simultaneously has the water resistance, wear resistance, weather resistance and high nail scratch resistance.

Description

Nail scratch-resistant coating for automotive upholstery, and preparation method and application thereof
Technical Field
The invention relates to the technical field of coatings, in particular to a nail scratch resistant coating for automotive upholstery, and a preparation method and application thereof.
Background
With the recent improvement of the living standard of people, in addition to the automobile as an important transportation means for traveling, consumers further look at the comfort, safety and decoration of the interior space of the automobile, and develop to a higher level. However, the plastic itself is not ideal in terms of resistance to environmental aging such as ultraviolet light, and various defects are often generated on the surface during the processing and molding process. It is therefore desirable to coat the surface of a plastic mold, impart a particular color or a certain gloss to the plastic, and conceal imperfections in the surface of the plastic, giving it a more attractive appearance. Meanwhile, the plastic can also play a role in protecting the plastic from being damaged by bad factors such as high temperature, chemicals, alcohol solvents, scraping of hard substances or nail scraping.
The automotive interior coating not only needs to have the basic properties of common coatings. Such as resistance to chemicals, good mechanical properties, low gloss, weatherability, normal or low temperature cure, etc. But also to meet other special properties such as high and low temperature variation resistance; the design of the paint meets the environmental protection requirement; in order to meet the needs of users, various automobile manufacturers have put forward very high practical performance requirements on the wear resistance and nail scratch resistance of the coating for the automobile interior trim parts.
The existing high-gloss piano black paint for automotive upholstery can generally produce the appearance effect with high gloss and high distinctness of image DOI value. However, the coating is required to have a certain covering power, and is limited by the inherent characteristics of the main resin of the coating, and the film forming hardness and the mechanical properties of the paint film, particularly abrasion resistance, nail scratch resistance and other performances are not good.
Disclosure of Invention
The invention aims to overcome one of the defects in the prior art and provides a nail scratch resistant coating for automotive upholstery, a preparation method and application thereof. The coating has the advantages of high gloss, high fullness, high brightness, piano black appearance texture, water resistance, wear resistance, weather resistance and high nail scratch resistance
The invention selects the resin coated inorganic metal oxide dispersoid as a matrix, effectively realizes organic-inorganic integration, can effectively strengthen the affinity between main film-forming resin, inorganic pigment and inorganic filler in the coating, enhances the physical strength of the resin material and simultaneously endows the inorganic pigment filler in the coating system with flexibility. The prepared paint has good adhesiveness with materials and good chemical resistance. Meanwhile, the inorganic metal oxide is coated by the organic-inorganic hybrid resin with excellent flexibility, so that the mechanical strength and flexibility of a coating system containing the organic-inorganic hybrid resin are effectively improved, and the special requirements on nail scratch resistance and the like of the coating for the automotive interior parts are met. Finally, the invention selects acrylic resin as main resin to coat the inorganic metal oxide split, and the organic-inorganic hybrid metal oxide dispersoid is obtained. The acrylic resin may be either an octadecyl acrylate having a long linear chain structure of a hydrophobic aliphatic alone or an AL-M (chemical formula 1) having undergone an organic-inorganic hybridization treatment in advance may be used in combination to participate in the surface coating treatment of the inorganic metal oxide.
The aim of the invention can be achieved by the following technical scheme:
the invention aims at providing a nail scratch resistant coating for automotive upholstery, which comprises a component A and a component B, wherein the component A and the component B are in mass ratio of (75-125): 25, mixing uniformly; the weight portions are as follows:
the component A comprises the following components: 2-20 parts of nano color paste, 3-30 parts of resin coated inorganic metal oxide, 10-60 parts of main resin, 2-20 parts of shaking auxiliary agent, 0.5-10 parts of auxiliary agent and 10-40 parts of solvent;
the component B comprises the following components: 2-20 parts of diisocyanate, 0.2-2 parts of auxiliary agent and 2-20 parts of solvent.
Preferably, the used nano color paste is self-made nano color paste with high hiding power, the particle size range of a dispersion D50 is 5 mu m, and the pigment content of the nano color paste is high, so that the hiding power of the prepared paint film coating is excellent, and the black texture of a high-gloss piano of a paint film can be effectively improved.
The component A comprises the following components: 5-15 parts of nano color paste, 5-20 parts of resin coated inorganic metal oxide, 30-50 parts of main resin, 3-10 parts of shaking auxiliary agent, 0.5-3 parts of auxiliary agent and 10-40 parts of solvent;
the component B comprises the following components: 8-15 parts of diisocyanate, 0.2-2 parts of auxiliary agent and 2-20 parts of solvent.
Further, the nano color paste is blue-phase black nano color paste; the blue phase black nano color paste comprises, by weight, 125-175 parts of carbon black, 75-125 parts of a dispersing agent and 500-700 parts of a solvent. Preferably, 150 parts of carbon black, 100 parts of dispersant and 600 parts of solvent; the carbon black is Birla Bola high pigment carbon black Raven5000Ultra III, the dispersing agent is a mixture of AJISPER PB821 and EFKA4310 manufactured by Weisu refining, and the proportion of AJISPER PB821 and EFKA4310 manufactured by Weisu refining is 1:1, the solvent is 3-ethoxypropionic acid ethyl ester.
Further, the preparation method of the blue phase black nano color paste comprises the following steps:
dispersing carbon black and a dispersing agent in a solvent to obtain a pre-dispersion system, and grinding until the dispersion fineness of the pre-dispersion system is below 5 mu m to obtain the nano color paste.
More specifically:
s1, selecting 5000Ultra III 150 parts of Birla bola high pigment carbon black Raven, 50 parts of AJISPER PB821, manufactured by Weisu refining, 4310 50 parts of EFKA, and uniformly stirring at a low speed to be pre-dispersed in 600 parts of 3-ethoxypropionic acid ethyl ester.
S2, selecting a nano color paste grinder to further grind and disperse the pre-dispersion obtained in the step S1 until the dispersion fineness of the system is below 5 mu m, so as to obtain the nano color paste.
Further, the main resin is a hydroxy acrylic polyol resin. Preferably, a high hydroxyl group content acrylic polyol resin A-859 of Dielsen synthetic resin (Zhongshan Co., ltd.) or the like is selected. The theoretical glass transition temperature of the high-hydroxyl acrylic polyol resin is 70 ℃, the paint film is good in fullness after the matched curing agent is thermally cured into a film, the glossiness and the distinctness of image are high, and the coating has excellent performances of water resistance, chemical resistance, high weather resistance and the like.
Further, the weight average molecular weight of the resin-coated inorganic metal oxide is mw=22000, and the molecular weight distribution is 2.0.
Further, the resin coated inorganic metal oxide is prepared from the following components in parts by weight:
s1, 10 parts of hydroxyethyl methacrylate, 30 parts of methacrylic acid, 20 parts of isooctyl acrylate, 10 parts of octadecyl acrylate and 20 parts of dispersing agent are dissolved in 150 parts of n-butyl ester, the temperature is raised to 90 ℃ under the protection of nitrogen, and 10 parts of nano aluminum oxide is added while stirring, so that an inorganic metal oxide dispersion is obtained;
s2, 3 parts of azodiisobutyronitrile is dissolved in 50 parts of methyl ethyl ketone, and a titration solution is obtained after uniform mixing;
and S3, dripping the titration solution obtained in the step S2 into the inorganic metal oxide dispersion obtained in the step S1 in a uniform titration mode, and obtaining the resin coated inorganic metal oxide after condensation reflux reaction.
Preferably, the dispersing agent is selected from refined and refined gourmet powder AL-M, and the nanometer aluminum oxide is selected from nanometer aluminum oxide DK410-2 (average particle diameter D) 50 =20 nm). The stirring speed in the step S2 is 800-1200rpm.
More specifically:
s1, adding 10 parts of hydroxyethyl methacrylate, 30 parts of methacrylic acid, 20 parts of isooctyl acrylate, 10 parts of octadecyl acrylate and 150 parts of n-butyl ester which are dissolved in AL-M/20 parts of refined sodium chloride, adopting nitrogen protection, and then heating to 90 ℃, and adding 10 parts of nano aluminum oxide DK410-2 (average particle size D50=20 nm) produced by Beijing island gold while stirring at a high speed (the rotating speed is 800-1200 rpm) to obtain a mixed inorganic metal oxide dispersion;
s2, 3 parts of azodiisobutyronitrile is dissolved in 50 parts of methyl ethyl ketone, and a titration solution is obtained after uniform mixing;
s3, dripping the titration solution obtained in the step S2 into the mixed solution obtained in the step S1 in a manner of uniform titration for 2 hours, and condensing and refluxing for 6 hours to obtain the resin coated inorganic metal oxide;
the resin coated inorganic metal oxide takes acrylic resin as a main body, and octadecyl acrylate with a hydrophobic aliphatic long straight-chain structure and AL-M (chemical formula 1) which is subjected to organic-inorganic hybridization treatment in advance are simultaneously blended into the same resin molecule to participate in the surface coating process of the inorganic metal oxide, so that the chemical binding force between the inorganic metal oxide and the organic acrylic resin main body is further improved, and an organic film is formed on the surface of the inorganic metal oxide, thereby forming a more complete surface coating effect.
The inorganic metal oxide is coated by the organic-inorganic hybrid resin with excellent flexibility, so that the mechanical strength of a coating system containing the organic-inorganic hybrid resin is effectively improved while the flexibility of the system is ensured to a certain extent, the paint film fully meets the friction resistance requirements, particularly meets the special requirements of the paint for automotive interior trim, such as nail scratch resistance, and the like, and has good performance in the initial stage of nail scratch experiments and the gloss retention rate of the paint film after standing for 24 hours after the experiments.
Figure BDA0004097742120000051
Further, the shaking auxiliary agent is DISPARON 4200-100 of Nippon Ten Kabushiki Kaisha, and can form loose aggregation structure with high hiding power nanometer color paste and other fillers, so that sedimentation of pigment can be effectively prevented to ensure uniformity and effective arrangement of pigment in a coating film;
the diisocyanate is selected from DESMODUR N3390 curing agent of Bayer company, and the diisocyanate contains NCO effective groups.
The auxiliary agent is selected from any one or more of EFKA4310, monosodium glutamate fine chemistry PB821 and Additive TI of OMG Borchers company;
the solvent is an organic solvent selected from one or more of esters, ethers, ketones, alcohols or hydrocarbons. Specifically, the hydrocarbon may be methylcyclohexane, the alcohol may be ethanol, isopropanol, etc., the ester may be ethyl acetate, butyl acetate, etc., the ketone may be methyl butanone, methyl isobutyl ketone, etc., and the ether may be ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc.
The second object of the invention is to provide a preparation method of the nail scratch resistant paint for automotive upholstery, which comprises the following steps:
s1, uniformly stirring nano color paste, main resin, resin coated inorganic metal oxide and auxiliary agent, then adding a solvent into the mixture, sequentially stirring at a low speed and at a high speed, grinding and dispersing until the fineness is less than 20 mu m, and then adding a shaking auxiliary agent to adjust the viscosity to 60-90S to prepare a component A;
s2, dissolving diisocyanate and an auxiliary agent in a solvent, and sequentially stirring at a low speed and at a high speed to obtain a component B;
s3: the component A and the component B are mixed according to the mass ratio of 100:25, and preparing the nail scratch resistant coating for the automotive upholstery.
Further, the rotating speed of the low-speed stirring is 600-800rpm, and the time is 20-30min; the rotating speed of the high-speed stirring is 800-1200rpm, and the time is 35-45min.
The invention also aims at the application of the nail scratch resistant coating for preparing the automotive interior trim part, and the coating is applied to coating the automotive interior trim part. The nail scratch resistant paint is uniformly mixed according to a specified mass ratio and then is subjected to spraying construction, so that the piano black surface paint has the advantages of good piano black surface effect, high fullness, high glossiness and high distinctness of image, and the coating has the properties of excellent material adhesiveness, chemical resistance, high weather resistance and the like, and particularly can improve the wear resistance of a paint film and the nail scratch resistance of the paint film. In particular, the paint film gloss retention was good both at the initial stage of the nail scratch test and after 24 hours of standing after the test.
Compared with the prior art, the invention has the following advantages:
(1) The high hiding power nano color paste selected by the invention is prepared by self, and has small dispersion particle size, uniform particle size distribution and good color development effect of the black pigment. The pigment content in the color paste is high, so that the prepared paint film coating has excellent hiding power, and the black texture of a high-gloss piano of a paint film can be effectively improved.
(2) The main resin selected by the invention is high hydroxyl acrylic polyol resin, and the paint film after being cured into a film has good fullness, high glossiness and high distinctness of image, and the coating has excellent water resistance, chemical resistance and high weather resistance. Meanwhile, the theoretical glass transition temperature of the high-hydroxyl acrylic polyol resin is higher, so that the wear resistance of a paint film after being cured into a film is ensured.
(3) The invention selects acrylic resin as main resin to coat the inorganic metal oxide split, and gets the organic-inorganic hybrid metal oxide dispersoid. The acrylic resin may be either an octadecyl acrylate having a long linear chain structure of a hydrophobic aliphatic alone or an AL-M (chemical formula 1) having undergone an organic-inorganic hybridization treatment in advance may be used in combination to participate in the surface coating treatment of the inorganic metal oxide.
The octadecyl acrylate with a long straight-chain structure and low glass transition temperature value is introduced into the coating resin, so that the flexibility of the inorganic metal oxide coated by the resin is greatly improved, the impact of external force on the metal oxide can be effectively buffered and decomposed when a paint film is subjected to external force such as nail scraping and the like, the effect of temporary buffering stress when a hard object collides with the hard object is achieved, and if the external force is continuously pressurized, the external force can be effectively shared by the hard inorganic metal oxide. The performance requirements for nail scratch resistance of automotive interior coatings are very effectively explained.
The invention selects acrylic resin as main resin to coat the inorganic metal oxide split, and gets the organic-inorganic hybrid metal oxide dispersoid. The acrylic host resin may be used in combination with AL-M (chemical formula 1) obtained by the prior organic-inorganic hybridization treatment to participate in the resin coating treatment of the inorganic metal oxide. The AL-M is blended into the coating resin, so that the chemical binding force between the inorganic metal oxide and the organic acrylic main resin can be further improved, the surface of the inorganic metal oxide is more favorable for forming an organic thin film, the side surface promotes the adhesion performance between the organic matter and the inorganic metal oxide and between the resin coating type inorganic metal oxide and the coating material, and meanwhile, the AL-M molecule also contains a hydrophobic aliphatic long straight-chain structure, so that the resin coating type inorganic metal oxide can be assisted to be endowed with flexibility, and the paint film has good water resistance, chemical resistance and other performances. In particular to the enhancement of the nail scratch resistance of the paint film.
(4) The paint disclosed by the invention is simple in preparation process, the important control parameters in the preparation process are easy to set, the prepared paint also has good nail scratch resistance, a paint film has high hiding power by using the high hiding power nano color paste, and meanwhile, the paint has excellent adhesion, water resistance, high wear resistance and other film forming properties on common automobile interior trim materials such as ABS, ABS/PC, PC and other engineering plastics. Therefore, the preparation method of the invention has wide construction convenience, and the prepared nail scratch resistant paint can effectively protect engineering plastics such as conventional decorative ABS, ABS/PC, PC and the like, and simultaneously can ensure that a coated product has the black appearance texture of a piano with high gloss, high fullness and high brightness.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
1. Preparing nano color paste
S1, selecting 5000Ultra III 150 parts of Birla bola high pigment carbon black Raven, 50 parts of AJISPER PB821, manufactured by Weisu refining, 4310 50 parts of EFKA, and uniformly stirring at a low speed to be pre-dispersed in 600 parts of 3-ethoxypropionic acid ethyl ester.
S2, selecting a nano color paste grinder to further grind and disperse the pre-dispersion obtained in the step S1 until the dispersion fineness of the system is below 5 mu m, so as to obtain the nano color paste.
2. Preparation of resin-coated inorganic Metal oxides
S1, dissolving 10 parts of hydroxyethyl methacrylate, 30 parts of methacrylic acid, 20 parts of isooctyl acrylate, 10 parts of octadecyl acrylate and 150 parts of n-butyl ester, protecting by adopting nitrogen, heating to 90 ℃, stirring at a high speed at a speed of 800-1200rpm, and adding 410-2 parts of nano aluminum oxide DK (dynamic pressure) produced by Beijing island gold while the average particle size D50 is 20nm to obtain a mixed inorganic metal oxide dispersion;
s2, 3 parts of azodiisobutyronitrile is dissolved in 50 parts of methyl ethyl ketone, a titration solution is obtained after uniform mixing, the obtained titration solution is dripped into a four-mouth flask in a 2-hour constant-speed titration mode, and condensation reflux reaction is carried out for 6 hours to obtain resin coated inorganic metal oxide;
the weight average molecular weight of the resin-coated inorganic metal oxide is mw=22000, and the molecular weight distribution is 2.0.
3. Nail scratch-resistant paint for preparing automotive upholstery
The nail scratch resistant paint of the embodiment is formed by combining an A-component resin paint and a B-component curing agent according to the mass ratio of 100:25,
the A-component resin paint comprises the following components in parts by weight: 8 parts of nano color paste, 40 parts of main resin, 17 parts of resin coated inorganic metal oxide, 2 parts of auxiliary agent, 5 parts of shaking auxiliary agent and 28 parts of solvent. Wherein, the main resin is A859, the auxiliary agent is EFKA4310, the shaking auxiliary agent is DISPARON 4200-100, and the solvent comprises 10 parts of ethyl acetate and 18 parts of n-butyl acetate.
The component B curing agent comprises the following components in parts by weight: 10 parts of diisocyanate, 0.5 part of auxiliary agent and 14.5 parts of solvent. N3390 is selected as diisocyanate, ADDITIVE TI is selected as auxiliary agent, and N-butyl acetate is selected as solvent.
The nail scratch resistant coating of the embodiment is prepared by the following steps:
s1, adding nano color paste, main resin, auxiliary agent and resin coated inorganic metal oxide into a dispersion tank according to parts by weight, uniformly stirring, then adding a solvent, stirring for 30min at a low speed, stirring for 30min at a high speed, then introducing into a sanding dispersion machine, grinding and dispersing until the fineness is below 20 mu m, adding a shaking auxiliary agent, controlling the viscosity within a range of 60-90S, and filtering to obtain component A resin paint;
s2, adding the diisocyanate resin containing NCO active groups and the auxiliary agent into a relevant solvent according to parts by weight, uniformly stirring, stirring for 30min at a low speed, and stirring for 30min at a high speed to prepare a component B curing agent;
s3, mixing and spraying the A-component resin paint and the B-component curing agent according to a specified mass ratio to prepare the nail scratch resistant paint for the automotive interior trim parts, which has the characteristics of high gloss, high fullness, high brightness, piano black appearance texture, water resistance, wear resistance, weather resistance and high nail scratch resistance.
Example 2
The nano color paste and the resin-coated inorganic metal oxide in example 2 are identical to the nano color paste and the resin-coated inorganic metal oxide in example 1.
The nail scratch resistant coating is formed by combining an A-component resin paint and a B-component curing agent according to the mass ratio of 100:25, wherein the A-component resin paint comprises the following components in parts by weight:
the A-component resin paint comprises the following components in parts by weight: 12 parts of nano color paste, 38 parts of main resin, 12 parts of resin coated inorganic metal oxide, 2 parts of auxiliary agent, 7 parts of shaking auxiliary agent and 29 parts of solvent. Wherein, the main resin is A859, the auxiliary agent is EFKA4310, the shaking auxiliary agent is DISPARON 4200-100, and the solvent comprises 14 parts of ethyl acetate and 15 parts of n-butyl acetate.
The component B curing agent comprises the following components in parts by weight: 9.5 parts of diisocyanate, 0.5 part of auxiliary agent and 15 parts of solvent. N3390 is selected as diisocyanate, ADDITIVE TI is selected as auxiliary agent, and N-butyl acetate is selected as solvent.
The nail scratch resistant coating of the embodiment is prepared by the following steps:
s1, adding high hiding power nano color paste, main resin, auxiliary agent and resin coated inorganic metal oxide into a dispersion tank according to parts by weight, uniformly stirring, then adding a solvent, stirring for 30min at a low speed, stirring for 30min at a high speed, then introducing into a sanding dispersion machine, grinding and dispersing until the fineness is below 20 mu m, adding a shaking auxiliary agent, controlling the viscosity within a range of 60-90S, and filtering to obtain the component A resin paint;
s2, adding diisocyanate resin containing NCO active groups and an auxiliary agent into a relevant solvent according to parts by weight, uniformly stirring, stirring for 30min at a low speed, and stirring for 30min at a high speed to prepare a component B curing agent;
s3, mixing and spraying the A-component resin paint and the B-component curing agent according to a specified mass ratio to prepare the nail scratch resistant paint for the automotive interior trim parts, which has the characteristics of high gloss, high fullness, high brightness, piano black appearance texture, water resistance, wear resistance, weather resistance and high nail scratch resistance.
Example 3
The nano color paste and the resin-coated inorganic metal oxide in example 3 are identical to the nano color paste and the resin-coated inorganic metal oxide in example 1.
The nail scratch resistant paint of the embodiment is formed by combining an A-component resin paint and a B-component curing agent according to the mass ratio of 100:25,
the A-component resin paint comprises the following components in parts by weight: 5 parts of nano color paste, 45 parts of main resin, 6 parts of resin coated inorganic metal oxide, 2 parts of auxiliary agent, 4 parts of shaking auxiliary agent and 38 parts of solvent. Wherein, the main resin is A859, the auxiliary agent is EFKA4310, the shaking auxiliary agent is DISPARON 4200-100, and the solvent comprises 18 parts of ethyl acetate and 20 parts of n-butyl acetate.
The component B curing agent comprises the following components in parts by weight: 11.25 parts of diisocyanate, 0.75 part of auxiliary agent and 13 parts of solvent. N3390 is selected as diisocyanate, ADDITIVE TI is selected as auxiliary agent, and N-butyl acetate is selected as solvent.
The nail scratch resistant coating of the embodiment is prepared by the following steps:
s1, adding high hiding power nano color paste, main resin, auxiliary agent and resin coated inorganic metal oxide into a dispersion tank according to parts by weight, uniformly stirring, then adding a solvent, stirring for 30min at a low speed, stirring for 30min at a high speed, then introducing into a sanding dispersion machine, grinding and dispersing until the fineness is below 20 mu m, adding a shaking auxiliary agent, controlling the viscosity within a range of 60-90S, and filtering to obtain the component A resin paint;
s2, adding diisocyanate resin containing NCO active groups and an auxiliary agent into a relevant solvent according to parts by weight, uniformly stirring, stirring for 30min at a low speed, and stirring for 30min at a high speed to prepare a component B curing agent;
s3, mixing and spraying the A-component resin paint and the B-component curing agent according to a specified mass ratio to prepare the nail scratch resistant paint for the automotive interior trim parts, which has the characteristics of high gloss, high fullness, high brightness, piano black appearance texture, water resistance, wear resistance, weather resistance and high nail scratch resistance.
Comparative example 1
The nano color paste in comparative example 1 was identical to the nano color paste in example 1, and no resin-coated inorganic metal oxide was added in comparative example 1.
The comparative coating is formed by combining an A-component resin paint and a B-component curing agent according to the mass ratio of 100:25,
the A-component resin paint comprises the following components in parts by weight: 8 parts of nano color paste, 45 parts of main resin, 0 part of resin coated inorganic metal oxide, 2 parts of auxiliary agent, 5 parts of shaking auxiliary agent and 40 parts of solvent. Wherein, the main resin is A859, the auxiliary agent is EFKA4310, the shaking auxiliary agent is DISPARON 4200-100, and the solvent comprises 15 parts of ethyl acetate and 25 parts of n-butyl acetate.
The component B curing agent comprises the following components in parts by weight: 11.25 parts of diisocyanate, 0.75 part of auxiliary agent and 13 parts of solvent. N3390 is selected as diisocyanate, ADDITIVE TI is selected as auxiliary agent, and N-butyl acetate is selected as solvent.
The coating of the comparative example is prepared by the following steps:
s1, adding high hiding power nano color paste, main resin and an auxiliary agent into a dispersion tank according to parts by weight, uniformly stirring, then adding a solvent, stirring for 30min at a low speed, stirring for 30min at a high speed, then introducing into a sanding dispersion machine, grinding and dispersing until the fineness is below 20 mu m, adding a shaking auxiliary agent, controlling the viscosity within a range of 60-90S, and filtering to obtain the component A resin paint;
s2, adding diisocyanate resin containing NCO active groups and an auxiliary agent into a relevant solvent according to parts by weight, uniformly stirring, stirring for 30min at a low speed, and stirring for 30min at a high speed to prepare a component B curing agent;
s3, mixing and spraying the A-component resin paint and the B-component curing agent according to a specified mass ratio to prepare the coating for the automotive interior trim part.
Comparative example 2
The nano color paste in comparative example 2 was consistent with the nano color paste in example 1, but the resin-coated inorganic metal oxide in comparative example 2 was inconsistent with the example.
1. Preparation of resin-coated inorganic Metal oxides
Into a four-necked flask, 10 parts of hydroxyethyl methacrylate, 30 parts of methacrylic acid, 20 parts of isooctyl acrylate and 10 parts of octadecyl acrylate are dissolved in 150 parts of n-butyl ester, and nitrogen is adopted for protection, then the mixture is heated to 90 ℃ and stirred at a high speed (the rotating speed is 800-1200 rpm) while nano aluminum oxide DK410-2 (average particle diameter D) produced by Beijing island gold is added 50 =20 nm) 10 parts to obtain a mixed inorganic metal oxide dispersion;
3 parts of azodiisobutyronitrile is dissolved in 50 parts of methyl ethyl ketone, a titration solution is obtained after uniform mixing, the obtained titration solution is dripped into a four-neck flask in a 2-hour constant-speed titration mode, and condensation reflux reaction is carried out for 6 hours to obtain the resin coated inorganic metal oxide;
the weight average molecular weight of the resin coated inorganic metal oxide 1 is M W =19000, molecular weight distribution is 2.1.
2. Preparation of the coating
The comparative coating is formed by combining an A-component resin paint and a B-component curing agent according to the mass ratio of 100:25,
the A-component resin paint comprises the following components in parts by weight: 8 parts of nano color paste, 40 parts of main resin, 12 parts of resin coated inorganic metal oxide, 2 parts of auxiliary agent, 7 parts of shaking auxiliary agent and 31 parts of solvent. Wherein, the main resin is A859, the auxiliary agent is EFKA4310, the shaking auxiliary agent is DISPARON 4200-100, and the solvent comprises 11 parts of ethyl acetate and 20 parts of n-butyl acetate.
The component B curing agent comprises the following components in parts by weight: 10 parts of diisocyanate, 0.5 part of auxiliary agent and 14.5 parts of solvent. N3390 is selected as diisocyanate, ADDITIVE TI is selected as auxiliary agent, and N-butyl acetate is selected as solvent.
S1, adding high hiding power nano color paste, main resin and an auxiliary agent into a dispersion tank according to parts by weight, uniformly stirring, then adding a solvent, stirring for 30min at a low speed, stirring for 30min at a high speed, then introducing into a sanding dispersion machine, grinding and dispersing until the fineness is below 20 mu m, adding a shaking auxiliary agent, controlling the viscosity within a range of 60-90S, and filtering to obtain the component A resin paint;
s2, adding diisocyanate resin containing NCO active groups and an auxiliary agent into a relevant solvent according to parts by weight, uniformly stirring, stirring for 30min at a low speed, and stirring for 30min at a high speed to prepare a component B curing agent;
s3, mixing and spraying the A-component resin paint and the B-component curing agent according to a specified mass ratio to prepare the coating for the automotive interior trim part.
Comparative example 3
The nano color paste in comparative example 3 was consistent with the nano color paste in example 1, but the resin coated inorganic metal oxide in comparative example 3 was inconsistent with the example.
1. Preparation of resin-coated inorganic Metal oxides
Adding 10 parts by weight of hydroxyethyl methacrylate, 30 parts by weight of methacrylic acid, 20 parts by weight of isooctyl acrylate and 150 parts by weight of n-butyl ester dissolved in AL-M/20 parts by weight of gourmet powder fine chemical system, adopting nitrogen protection, then heating to 90 ℃, and adding 10 parts by weight of nano aluminum oxide DK410-2 (average particle size D50=20 nm) produced by Beijing island gold while stirring at a high speed (the rotating speed is 800-1200 rpm) to obtain a mixed inorganic metal oxide dispersion;
3 parts of azodiisobutyronitrile is dissolved in 50 parts of methyl ethyl ketone, a titration solution is obtained after uniform mixing, the obtained titration solution is dripped into a four-neck flask in a 2-hour constant-speed titration mode, and condensation reflux reaction is carried out for 6 hours to obtain resin coated inorganic metal oxide;
the weight average molecular weight of the resin-coated inorganic metal oxide was mw=20000, and the molecular weight distribution was 2.1.
2. Preparation of the coating
The comparative coating is formed by combining an A-component resin paint and a B-component curing agent according to the mass ratio of 100:25,
the A-component resin paint comprises the following components in parts by weight: 8 parts of nano color paste, 40 parts of main resin, 12 parts of resin coated inorganic metal oxide, 2 parts of auxiliary agent, 7 parts of shaking auxiliary agent and 31 parts of solvent. Wherein, the main resin is A859, the auxiliary agent is EFKA4310, the shaking auxiliary agent is DISPARON 4200-100, and the solvent comprises 11 parts of ethyl acetate and 20 parts of n-butyl acetate.
The component B curing agent comprises the following components in parts by weight: 10 parts of diisocyanate, 0.5 part of auxiliary agent and 14.5 parts of solvent. N3390 is selected as diisocyanate, ADDITIVE TI is selected as auxiliary agent, and N-butyl acetate is selected as solvent.
S1, adding high hiding power nano color paste, main resin and an auxiliary agent into a dispersion tank according to parts by weight, uniformly stirring, then adding a solvent, stirring for 30min at a low speed, stirring for 30min at a high speed, then introducing into a sanding dispersion machine, grinding and dispersing until the fineness is below 20 mu m, adding a shaking auxiliary agent, controlling the viscosity within a range of 60-90S, and filtering to obtain the component A resin paint;
s2, adding diisocyanate resin containing NCO active groups and an auxiliary agent into a relevant solvent according to parts by weight, uniformly stirring, stirring for 30min at a low speed, and stirring for 30min at a high speed to prepare a component B curing agent;
s3, mixing and spraying the A-component resin paint and the B-component curing agent according to a specified mass ratio to prepare the coating for the automotive interior trim part.
Paint compositions 1 to 6 for automotive interior parts prepared in examples 1 to 3 and comparative examples 1 to 3 were simultaneously spray-coated on ABS/PC materials, and the dry film coatings were tested for material adhesion, moisture resistance, taber abrasion resistance, dry cloth abrasion resistance, chemical resistance, and nail scratch resistance, and the paint film properties were tested as shown in table 1.
Each sample in table 1 was tested according to the method described in the following standard, and specific criteria can be found in each specific standard:
adhesion force: GB9286-1998 standard test;
water resistance: TONGTIANcar interior TSH3130G standard test;
heat cycle resistance: GB/T1735 standard test;
gasoline resistance: GB/T1734 standard test;
moisture resistance: japanese production NES M0141 2015 standard test 6.3.1;
taber abrasion resistance test: the Honda technical research HES 0096Z TVA9000 standard test;
dry cloth friction resistance: mass automobile TL-226-2006 3.12.3.4 standard test;
acid resistance: daily nec m0141_20156.3.2 standard test;
alkali resistance: daily nec m0141_20156.3.3 standard test;
sun cream resistance: modern automobile MS-625-01.15 sun-proof standard test;
hand cream resistant to hand cream: mass automobile TL-226-2006PV3964 standard test;
alcohol resistance: mass automobile TL-226-2006 3.13 standard test;
nail scratch resistance: TSH1544G Standard test for Toyota automotive interior TSH 3130G.
TABLE 1 paint film Performance test results
Figure BDA0004097742120000141
As can be seen from Table 1, the coating compositions of examples 1 to 3 applied to the ABS/PC material for automotive interior parts all exhibited good material adhesion, hot water resistance, moisture resistance, acid and alkali resistance, abrasion resistance and nail scratch resistance. Wherein the heat-cured coating prepared in example 2 has the best comprehensive performance in the preparation and detection processes, the formula and the preparation conditions of example 2 can be used as the best examples of the invention. In contrast, the samples obtained in the comparative examples had some unacceptable properties, and were defective.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. The nail scratch resistant coating for the automotive upholstery is characterized by comprising a component A and a component B, wherein the weight ratio of the component A to the component B is (75-125): 25, mixing uniformly; the weight portions are as follows:
the component A comprises the following components: 2-20 parts of nano color paste, 3-30 parts of resin coated inorganic metal oxide, 10-60 parts of main resin, 2-20 parts of shaking auxiliary agent, 0.5-10 parts of auxiliary agent and 10-40 parts of solvent;
the component B comprises the following components: 2-20 parts of diisocyanate, 0.2-2 parts of auxiliary agent and 2-20 parts of solvent.
2. The nail scratch resistant coating for automotive upholstery of claim 1, wherein the nano color paste is blue-phase black nano color paste;
the blue phase black nano color paste comprises, by weight, 125-175 parts of carbon black, 75-125 parts of a dispersing agent and 500-700 parts of a solvent.
3. The nail scratch resistant paint for automotive upholstery according to claim 2, wherein the blue-phase black nano color paste preparation method comprises the following steps:
dispersing carbon black and a dispersing agent in a solvent to obtain a pre-dispersion system, and grinding until the dispersion fineness of the pre-dispersion system is below 5 mu m to obtain the nano color paste.
4. The nail scratch resistant coating for automotive upholstery of claim 1, wherein said primary resin is a hydroxy acrylic polyol resin.
5. The nail scratch resistant coating for automotive upholstery of claim 1, wherein said resin-coated inorganic metal oxide has a weight average molecular weight of mw=22000 and a molecular weight distribution of 2.0.
6. The nail scratch resistant coating for automotive upholstery of claim 5, wherein the resin coated inorganic metal oxide is prepared from the following components in parts by weight:
s1, 10 parts of hydroxyethyl methacrylate, 30 parts of methacrylic acid, 20 parts of isooctyl acrylate, 10 parts of octadecyl acrylate and 20 parts of dispersing agent are dissolved in 150 parts of n-butyl ester, the temperature is raised to 90 ℃ under the protection of nitrogen, and 10 parts of nano aluminum oxide is added while stirring, so that an inorganic metal oxide dispersion is obtained;
s2, 3 parts of azodiisobutyronitrile is dissolved in 50 parts of methyl ethyl ketone, and a titration solution is obtained after uniform mixing;
and S3, dripping the titration solution obtained in the step S2 into the inorganic metal oxide dispersion obtained in the step S1 in a uniform titration mode, and reacting to obtain the resin coated inorganic metal oxide.
7. The nail scratch resistant coating for automotive upholstery of claim 1, wherein said shaking aid is selected from the group consisting of dispollon 4200-100 from japan phoenix chemical company;
the diisocyanate is selected from DESMODUR N3390 curing agent of Bayer company;
the auxiliary agent is selected from any one or more of EFKA4310, monosodium glutamate fine chemistry PB821 and Additive TI of OMG Borchers company;
the solvent is an organic solvent selected from one or more of esters, ethers, ketones, alcohols or hydrocarbons.
8. A method for preparing the nail scratch resistant paint for automotive interior parts according to any one of claims 1 to 7, comprising the steps of:
s1, uniformly stirring nano color paste, main resin, resin coated inorganic metal oxide and auxiliary agent, then adding a solvent into the mixture, sequentially stirring at a low speed and at a high speed, grinding and dispersing until the dispersion fineness is less than 20 mu m, and then adding a shaking auxiliary agent to adjust the viscosity to 60-90S to prepare a component A;
s2, dissolving diisocyanate and an auxiliary agent in a solvent, and sequentially stirring at a low speed and at a high speed to obtain a component B;
s3: the component A and the component B are mixed according to the mass ratio of 100:25, and preparing the nail scratch resistant coating for the automotive upholstery.
9. The method for preparing the nail scratch resistant coating for automotive upholstery according to claim 8, wherein the low-speed stirring speed is 600-800rpm for 20-30min; the rotating speed of the high-speed stirring is 800-1200rpm, and the time is 35-45min.
10. Use of a nail scratch resistant coating for the preparation of automotive upholstery according to any one of claims 1 to 7, characterized in that the coating is applied for coating automotive upholstery.
CN202310170314.5A 2023-02-27 2023-02-27 Nail scratch-resistant coating for automotive upholstery, and preparation method and application thereof Pending CN116200115A (en)

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