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CN117903745B - Stripping primer for spraying vehicle coating and preparation method and application thereof - Google Patents

Stripping primer for spraying vehicle coating and preparation method and application thereof Download PDF

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Publication number
CN117903745B
CN117903745B CN202410078209.3A CN202410078209A CN117903745B CN 117903745 B CN117903745 B CN 117903745B CN 202410078209 A CN202410078209 A CN 202410078209A CN 117903745 B CN117903745 B CN 117903745B
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China
Prior art keywords
primer
hydroxyl
spray
oligomer
automobile
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CN202410078209.3A
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CN117903745A (en
Inventor
韩阳
张燕
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Guangzhou Boli New Material Technology Co ltd
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Guangzhou Boli New Material Technology 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4222—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic polyhydroxy compounds and polycarboxylic acids
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The application relates to the field of automobile films/automobile coats, and particularly discloses a release primer for spraying automobile coats, a preparation method and application thereof. A release primer for spray-coating vehicle clothing comprises oligomer, hydrogenated C5 petroleum resin and organic solvent; the oligomer is synthesized by the reaction of a prepolymer and hydroxyl-terminated polyester; the prepolymer is synthesized by the reaction of hydrogenated hydroxyl-terminated polybutadiene and isophorone diisocyanate; hydroxyl terminated polyesters are synthesized from the reaction of hydrogenated bisphenol A with 1, 4-cyclohexanedicarboxylic acid. The preparation method of the stripping primer for the spray-coated vehicle coating comprises the steps of uniformly mixing all the components to obtain the stripping primer for the spray-coated vehicle coating. The spray coating automobile coating provided by the application has wide application prospect in the field of automobile films/automobile jackets, can be coated on the surface of an automobile in various modes such as spraying, brushing and the like, has good weather resistance and moderate bonding strength, and effectively avoids the problem of residual adhesive layers of the automobile body when the primer is stripped in the later stage.

Description

Stripping primer for spraying vehicle coating and preparation method and application thereof
Technical Field
The invention relates to the field of automobile films/automobile coats, in particular to a release primer for spraying automobile coats, a preparation method and application thereof.
Background
With the rapid development of the automotive industry, automotive films/skins have become one of the important products for automotive cosmetology and protection. Among them, TPU automotive clothing is widely popular for its excellent performance and aesthetic appearance. The prior TPU car cover is usually stuck on the surface of the car by using a car cover primer.
Through years of development, the prior automobile coating primer commonly adopts acrylic acid type pressure-sensitive adhesive. The acrylic acid pressure-sensitive adhesive has good weather resistance, can withstand aging for many years, still has moderate bonding strength, is suitable for pasting TPU automobile coats, and can meet the requirements of moderate adhesive force and long adhesive time of the TPU automobile coats on automobile bodies. However, since the acrylic pressure-sensitive adhesive has a high molecular weight and a high construction viscosity, it is difficult to perform the construction by spraying although the solid content thereof can be reduced by dilution.
In the prior art, a roller coating mode is generally adopted to coat the acrylic pressure-sensitive adhesive on the TPU car coat formed by casting to form a precoated primer. However, this method of pre-coating the primer on the TPU coating also has some problems. First, the process of pre-coating the primer is complex, requiring additional equipment and human input. Secondly, aiming at the spraying process of directly spraying the coating on the automobile body to form the sprayed automobile cover, the mode of pre-coating the primer cannot be adopted at all, so that the development of the automobile cover primer capable of being directly sprayed on the automobile body by adopting the spraying process is necessary.
Disclosure of Invention
The application provides a removable primer for spraying a vehicle coat, a preparation method and application thereof, and aims to solve the technical problems that the conventional vehicle coat primer is high in construction viscosity and difficult to construct in a spraying mode. The application prepares the oligomer solution by mixing hydroxyl-terminated polyester and prepolymer in proportion, and then adds hydrogenated C5 petroleum resin, dimethylbenzene, butyl acetate and the like to prepare the removable primer for spraying the vehicle cover, thereby perfectly solving the problem that the conventional solvent type polyacrylate pressure-sensitive adhesive has too high viscosity and cannot be used for spraying construction, and meanwhile, the removable primer for spraying the vehicle cover has excellent weather resistance, moderate bonding strength and lower self strength, has good stripping effect, can meet the requirement of spraying the vehicle cover, and has the advantages of simple operation, controllable adhesive force, long service life and the like compared with the conventional solvent type polyacrylate pressure-sensitive adhesive.
In a first aspect, the application provides a removable release primer for a spray-coated vehicle coating, which adopts the following technical scheme:
A spray-on car cover useable release primer comprising an oligomer, a hydrogenated C5 petroleum resin, and an organic solvent;
The oligomer is prepared from a prepolymer and hydroxyl-terminated polyester according to the following formula 1: (1.6-1.8) an oligomer having an average molecular weight of 1.0X10 4～1.2×104;
the prepolymer is prepared from hydrogenated hydroxyl-terminated polybutadiene with an average molecular weight of 3000 and isophorone diisocyanate according to a weight ratio of 1: (1.9-2.1) a prepolymer having an average molecular weight of 3500 and synthesized by a molar ratio reaction;
the hydroxyl-terminated polyester is prepared from hydrogenated bisphenol A and 1, 4-cyclohexanedicarboxylic acid according to the following weight ratio of 1: (0.8-0.85) and the molecular weight of hydroxyl-terminated polyester is 2000-2500.
In the technical scheme, the hydrogenated bisphenol A and the 1, 4-cyclohexanedicarboxylic acid are adopted to prepare the hydroxyl-terminated polyester as the hard segment of the oligomer, so that good bonding strength of the available stripping primer of the sprayed automobile coating is ensured. The application further introduces hydrogenated hydroxyl-terminated polybutadiene with average molecular weight of 3000 as a soft segment of the oligomer, and the hydrogenated hydroxyl-terminated polybutadiene is a special polyester, so that the problem that the polyacrylate is too high in construction viscosity and is unfavorable for spraying in the prior art is effectively avoided, and the low construction viscosity can be maintained while good weather resistance of the available stripping primer of the sprayed vehicle is ensured. The application obtains the block copolymer with proper proportion of soft segment and hard segment and good matching by the common reaction of the prepolymer generated by hydrogenated hydroxyl-terminated polybutadiene and isophorone diisocyanate and hydroxyl-terminated polyester, and the oligomer with good weather resistance and bonding strength is obtained. The oligomer provided by the application has good bonding strength and weather resistance under the condition of low construction viscosity, so that the spraying operation requirement is met, the problems that the bonding strength of primer is overlarge or primer interacts with attachments and the like caused by aging of the oligomer in the later stage can be avoided, the stripping effect of the usable stripping primer of a sprayed vehicle coating is avoided, and the problem of residual adhesive layer of the vehicle body in the later stage of stripping the primer is avoided.
The oligomer is used as the main component of the stripping primer for spraying the vehicle coating, has excellent weather resistance and moderate bonding strength, and can be effectively attached to the surface of the vehicle without corroding the vehicle coating/vehicle film or the vehicle paint. In addition, the release primer for spray-coating the vehicle cover also comprises hydrogenated C5 petroleum resin and an organic solvent. The hydrogenated C5 petroleum resin matched oligomer can further adjust the viscosity and weather resistance of the available stripping primer of the spraying vehicle coating under the condition of ensuring that the available stripping primer of the spraying vehicle coating has good construction viscosity, so that the problem of overlarge construction viscosity when the acrylic resin is matched with the hydrogenated C5 petroleum resin in the prior art is avoided, and the viscosity and drying speed of the available stripping primer of the spraying vehicle coating can be further adjusted by an organic solvent. The application can obtain the spray-coating removable primer with excellent weather resistance and moderate bonding strength by uniformly mixing the oligomer, the hydrogenated C5 petroleum resin and the organic solvent.
Preferably, the hydroxyl-terminated polyester is prepared as follows:
hydrogenated bisphenol A and 1, 4-cyclohexanedicarboxylic acid were mixed in an amount of 1: (0.8-0.85) and carrying out high-temperature melt polycondensation for 7-8 h at 235-240 ℃ under the protection of nitrogen to obtain the hydroxyl-terminated polyester with the molecular weight of 2000-2500.
In the technical scheme, the melt polycondensation is carried out under the high-temperature condition, so that the uniform molecular weight distribution of the hydroxyl-terminated polyester can be ensured, and the heat resistance and weather resistance of the hydroxyl-terminated polyester can be improved.
Preferably, the preparation method of the prepolymer is as follows:
Hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000 and isophorone diisocyanate were mixed at a ratio of 1: (1.9-2.1) and reacting for 10-12 h at 80-85 ℃ to obtain the prepolymer with average molecular weight of 3500.
In the technical scheme, the preparation method is used for reacting for 10-12 hours at the specific temperature of 80-85 ℃, and the prepolymer with narrow molecular weight distribution and moderate viscosity can be obtained by controlling the reaction time and the reaction temperature, so that the workability and the bonding strength of the stripping primer for spraying the vehicle coating are improved.
Preferably, the preparation method of the oligomer is as follows: the prepolymer and hydroxyl-terminated polyester were prepared according to 1: (1.6-1.8) and reacting for 10-12 h at 90-95 ℃ to obtain the oligomer with the average molecular weight of 1.0X10 4～1.2×104.
In the technical scheme, the low polymer with narrow molecular weight distribution and moderate viscosity can be obtained by reacting for 10-12 hours at the specific temperature of 90-95 ℃ and controlling the reaction time and temperature, and the low polymer is used for preparing the stripping primer for spraying the automobile coating, so that the weather resistance of the stripping primer for spraying the automobile coating can be improved, and moderate bonding strength can be maintained.
Preferably, the removable primer for spraying the vehicle cover comprises the following components in percentage by mass: 45-50% of oligomer, 5-10% of hydrogenated C5 petroleum resin and 40-50% of organic solvent.
According to the technical scheme, the viscosity, the drying speed, the bonding strength and other performances of the available stripping primer of the spray coating car are adjusted to the optimal ratio by controlling the content ratio of the oligomer, the hydrogenated C5 petroleum resin and the organic solvent in the available stripping primer of the spray coating car, so that the solid content of the available stripping primer of the spray coating car is about 55%, and the requirements of different use occasions such as spraying, brushing and the like can be met.
Preferably, the organic solvent is selected from: xylene, toluene, ethylbenzene, butyl acetate, t-butyl acetate, isobutyl acetate, ethyl acetate, and the like.
Preferably, the organic solvent consists of 15-20% of dimethylbenzene and 25-30% of butyl acetate by mass percent of the strippable primer for spraying the vehicle coating.
In the technical scheme, the application uses the combination of the dimethylbenzene and the butyl acetate as the organic solvent, so that the oligomer and the hydrogenated C5 petroleum resin can be better dissolved, and the viscosity and the workability of the primer can be better regulated, so that the primer is more suitable for different use scenes.
In a second aspect, the preparation method of the removable release primer for spraying the vehicle cover provided by the application adopts the following technical scheme:
a preparation method of the stripping primer for the spray-coated vehicle coating comprises the step of uniformly mixing an oligomer, hydrogenated C5 petroleum resin and an organic solvent to obtain the stripping primer for the spray-coated vehicle coating.
According to the technical scheme, the low polymer, the hydrogenated C5 petroleum resin and the organic solvent are uniformly mixed according to a specific proportion, so that the spray-coating removable primer with excellent weather resistance and moderate bonding strength for the vehicle coating can be obtained. The preparation method of the removable release primer for the spray coating car cover is simple, convenient to operate and capable of meeting the requirement of mass production.
In a third aspect, the application of the removable release primer for spraying the vehicle cover provided by the application adopts the following technical scheme: an application of the spray-coated vehicle coating usable release primer based on the first aspect in the field of vehicle films/vehicle coatings.
According to the technical scheme, the stripping primer for the spray coating automobile cover can be coated on an automobile body in various modes such as spraying, brushing and the like, can be effectively attached to the surface of an automobile, has good weather resistance and moderate bonding strength, and avoids the problem of residual adhesive layers of the automobile body when the primer is stripped in the later stage. The spray-coated car cover provided by the application has wide application prospect in the field of car films/car jackets by stripping the primer.
In summary, the release primer for the spray coating provided by the application can be used for preparing the block copolymer by adopting the combination of the oligomer, the hydrogenated C5 petroleum resin and the organic solvent and controlling the content and the preparation method of each component, especially controlling the preparation method of the oligomer, especially specially selecting three substances, namely hydrogenated bisphenol A, 1, 4-cyclohexanedicarboxylic acid and hydrogenated hydroxyl-terminated polybutadiene, so as to obtain the oligomer with proper soft segment and hard segment proportion and good matching, thereby successfully solving the problem that the conventional solvent type polyacrylate pressure-sensitive adhesive has too high viscosity and cannot be used for spray coating construction. Compared with the existing solvent type polyacrylate pressure-sensitive adhesive, the stripping primer for spraying the vehicle cover has the advantages of low construction viscosity, simplicity and convenience in operation, controllable bonding strength, long service life and the like.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Preparation example 1
An oligomer comprising the following preparation steps:
step 1, prefabricating:
Step 1-1, synthesizing hydroxyl-terminated polyester with the molecular weight of 2000-2500:
Hydrogenated bisphenol A and 1, 4-cyclohexanedicarboxylic acid were mixed in an amount of 1: mixing the components in a molar ratio of 0.8, and carrying out high-temperature melt polycondensation for 7 hours at 235 ℃ under the protection of nitrogen to obtain the hydroxyl-terminated polyester with the molecular weight of 2000-2500.
Step 1-2, synthesis of prepolymer with average molecular weight of 3500:
hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000 and isophorone diisocyanate were mixed at a ratio of 1:1.9, and reacting at 80 ℃ for 10 hours to obtain a prepolymer with average molecular weight of 3500.
Step2, synthesis of oligomer with average molecular weight of 1.0X10 4～1.2×104:
The prepolymer and hydroxyl-terminated polyester were prepared according to 1:1.6, and reacting at 90℃for 10 hours to obtain an oligomer having an average molecular weight of 1.0X10 4～1.2×104.
Preparation example 2
An oligomer, unlike in preparation 1, comprises the following preparation steps:
step 1, prefabricating:
Step 1-1, synthesizing hydroxyl-terminated polyester with the molecular weight of 2000-2500:
Hydrogenated bisphenol A and 1, 4-cyclohexanedicarboxylic acid were mixed in an amount of 1: mixing in a molar ratio of 0.85, and carrying out high-temperature melt polycondensation for 8 hours at 240 ℃ under the protection of nitrogen to obtain the hydroxyl-terminated polyester with the molecular weight of 2000-2500.
Step 1-2, synthesis of prepolymer with average molecular weight of 3500:
Hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000 and isophorone diisocyanate were mixed at a ratio of 1:2.1, and reacting for 12 hours at 85 ℃ to obtain a prepolymer with average molecular weight of 3500.
Step2, synthesis of oligomer with average molecular weight of 1.0X10 4～1.2×104:
The prepolymer and hydroxyl-terminated polyester were prepared according to 1:1.8, and reacted at 95℃for 12 hours to give an oligomer having an average molecular weight of 1.0X10 4～1.2×104.
Preparation example 3
An oligomer, unlike in preparation 1, comprises the following preparation steps:
step 1, prefabricating:
Step 1-1, synthesizing hydroxyl-terminated polyester with the molecular weight of 2000-2500:
Hydrogenated bisphenol A and 1, 4-cyclohexanedicarboxylic acid were mixed in an amount of 1: mixing the components in a molar ratio of 0.82, and carrying out high-temperature melt polycondensation for 7.5 hours at 238 ℃ under the protection of nitrogen to obtain the hydroxyl-terminated polyester with the molecular weight of 2000-2500.
Step 1-2, synthesis of prepolymer with average molecular weight of 3500:
Hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000 and isophorone diisocyanate were mixed at a ratio of 1:2, and reacting at 82 ℃ for 11 hours to obtain a prepolymer with average molecular weight of 3500.
Step2, synthesis of oligomer with average molecular weight of 1.0X10 4～1.2×104:
The prepolymer and hydroxyl-terminated polyester were prepared according to 1:1.7, and reacted at 93℃for 11 hours to give an oligomer having an average molecular weight of 1.0X10 4～1.2×104.
Comparative preparation example 1
An oligomer is different from preparation example 1 in that in step 1-1, hydrogenated bisphenol A is replaced with hydrogenated bisphenol F in an equivalent amount.
Comparative preparation example 2
An oligomer was different from preparation example 1 in that 1, 4-cyclohexanedicarboxylic acid was replaced with 1, 3-cyclohexanedicarboxylic acid in the same amount in step 1-1.
Comparative preparation example 3
An oligomer, unlike in preparation example 1, in step 1-2, hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000 was replaced with polypropylene glycol having an average molecular weight of 3000 in an equivalent amount.
Comparative preparation example 4
An oligomer is different from preparation example 1 in that in step 1-2, hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000 is replaced with hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 2000 in an equivalent amount.
Comparative preparation example 5
An oligomer, unlike in preparation example 1, in step 1-2, hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000 was replaced with a hydroxyl-terminated acrylic resin having an average molecular weight of 5000, the hydroxyl value of the resin being 35mg KOH/g and a glass transition temperature of-25℃and being obtained by copolymerizing butyl acrylate, methyl methacrylate and hydroxyethyl acrylate.
Example 1
A spray-on car cover release primer comprises 45kg of oligomer, 10kg of hydrogenated C5 petroleum resin, 15kg of xylene and 30kg of butyl acetate.
Wherein the oligomer is from preparation 1.
The preparation method of the stripping primer for the spraying vehicle coating comprises the step of uniformly mixing the components to obtain the stripping primer for the spraying vehicle coating.
Example 2
Unlike example 1, the spray-applied vehicle cover useable release primer included 50kg of oligomer, 5kg of hydrogenated C5 petroleum resin, 20kg of xylene, and 25kg of butyl acetate.
Wherein the oligomer is from preparation 2.
Example 3
Unlike example 1, the spray-applied vehicle cover useable release primer included 48kg of oligomer, 8kg of hydrogenated C5 petroleum resin, 18kg of xylene, and 26kg of butyl acetate.
Wherein the oligomer is from preparation 3.
Comparative example 1
A primer was prepared, unlike example 1, with the oligomer from comparative preparation 1.
Comparative example 2
A primer was prepared, unlike example 1, with the oligomer from comparative preparation 2.
Comparative example 3
A primer was prepared, unlike example 1, with the oligomer from comparative preparation 3.
Comparative example 4
A primer was prepared, unlike example 1, with the oligomer from comparative preparation 4.
Comparative example 5
A primer was prepared, unlike example 1, with the oligomer from comparative preparation 5.
Performance detection
Detection 1, construction viscosity: reference is made to the method B in GB/T1723-1993 "paint viscometry": the application viscosity of the primer of each of the above examples and comparative examples was measured by a coating-4 viscometer method.
Detection 2, adhesive strength: the primer of each example and comparative example was sprayed on a vehicle panel of the paint side of the original automobile factory, the sprayed thickness was 10 μm, the organic solvent was volatilized, and then a TPU sprayed vehicle coat of 200 μm was sprayed, and the adhesive strength (MPa) of the primer of each example and comparative example was measured.
Detection 3, peeling condition: the primer of each example and the primer of the comparative example are sprayed on an automobile panel of the original paint surface of an automobile factory, after the organic solvent is volatilized, the TPU sprayed automobile coating with the thickness of 200 mu m is sprayed, the transparent TPU automobile coating is peeled off from the automobile panel, the peeling hand feeling is recorded, and the residual glue condition of the peeling surface of the automobile panel is observed.
Detection 4, bonding strength after aging: the primer of each example and the primer of the comparative example are sprayed on an automobile panel of the original paint surface of an automobile factory, the thickness of the sprayed primer is 10 mu m, the organic solvent volatilizes, then a TPU sprayed automobile coating of 200 mu m is sprayed, and after the TPU sprayed automobile coating is irradiated by a xenon lamp for 1000 hours, the bonding strength (MPa) after aging of the primer of each example and the primer of the comparative example is detected.
Detection 5, peeling condition after aging: the primer of each example and the primer of the comparative example are sprayed on an automobile panel of the original paint surface of an automobile factory, after the organic solvent is volatilized, the TPU sprayed automobile coating with the thickness of 200 mu m is sprayed, and after the irradiation of a xenon lamp for 1000 hours, the transparent TPU automobile coating is peeled off from the automobile panel, the peeling hand feeling is recorded, and the residual glue condition of the peeling surface of the automobile panel is observed.
The results of the above detection are shown in Table 1.
Table 1:
the inventors of the present application have found that examples 1 to 3 have good adhesive strength, weather resistance and peeling effect, in combination with examples 1 to 3, comparative examples 1 to 5 and table 1.
By specifically combining the analysis of the embodiment 1 and the comparative example 1-2, it is clear that the comparative example 1-2 replaces hydrogenated bisphenol A and 1, 4-cyclohexanedicarboxylic acid respectively, and the embodiment 1 has good bonding strength, weather resistance and stripping effect, so that only when the hydrogenated bisphenol A and the 1, 4-cyclohexanedicarboxylic acid are reacted together to prepare hydroxyl-terminated polyester, the oligomer can be endowed with proper bonding strength, and the oligomer is ensured to have better structural stability, so that the available stripping primer of the sprayed automobile coating has good stripping effect when stripped, and the residual of the available stripping primer of the sprayed automobile coating on the automobile body is reduced, that is, the hydroxyl-terminated polyester prepared by the co-reaction of the hydrogenated bisphenol A and the 1, 4-cyclohexanedicarboxylic acid can further promote the available stripping primer of the sprayed automobile coating to be more uniformly and stably attached on the automobile body, and the viscosity of the available stripping primer of the sprayed automobile coating is adjusted to a proper level, so that the available stripping primer of the sprayed automobile coating has better stripping effect.
In particular, by combining the analysis of example 1 and comparative examples 3-5, it is clear that, in comparative example 3, polypropylene glycol with an average molecular weight of 3000 is selected, in comparative example 4, hydrogenated hydroxyl-terminated polybutadiene with different average molecular weights is selected, in comparative example 5, hydroxyl acrylic resin with an average molecular weight of 5000 is selected, and in example 1, the adhesive strength, weather resistance and stripping effect are good, and only if hydrogenated hydroxyl-terminated polybutadiene with an average molecular weight of 3000 is selected to react with isophorone diisocyanate, it can be ensured that the finally obtained oligomer is a block copolymer with proper soft segment and hard segment proportion and good matching, so that the adhesive strength of the available stripping primer of the sprayed automobile can be further and better adjusted, and the available stripping primer of the sprayed automobile can have better structural stability when in use, so that the available stripping primer of the sprayed automobile can have proper adhesive strength, good weather resistance and better stripping effect.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (8)

1. The removable primer for the sprayed vehicle coating is characterized by comprising an oligomer, hydrogenated C5 petroleum resin and an organic solvent;
The oligomer is prepared from a prepolymer and hydroxyl-terminated polyester according to the following formula 1: (1.6-1.8) an oligomer with an average molecular weight of 1.0X10 4~1.2×104 synthesized by a molar ratio reaction;
The prepolymer is prepared from hydrogenated hydroxyl-terminated polybutadiene with an average molecular weight of 3000 and isophorone diisocyanate according to a weight ratio of 1: (1.9-2.1) a prepolymer with average molecular weight of 3500 synthesized by a molar ratio reaction;
The hydroxyl-terminated polyester is prepared from hydrogenated bisphenol A and 1, 4-cyclohexanedicarboxylic acid according to the following weight ratio of 1: (0.8-0.85) and synthesizing hydroxyl-terminated polyester with molecular weight of 2000-2500.
2. The spray-applied, peel-off primer for automotive garments of claim 1, wherein the hydroxyl-terminated polyester is prepared by the process comprising:
Hydrogenated bisphenol A and 1, 4-cyclohexanedicarboxylic acid were mixed in an amount of 1: (0.8-0.85) and carrying out high-temperature melt polycondensation for 7-8 hours at 235-240 ℃ under the protection of nitrogen to obtain the hydroxyl-terminated polyester with the molecular weight of 2000-2500.
3. The spray-applied, peel-off primer for automotive garments of claim 1, wherein the prepolymer is prepared by the following method:
hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000 and isophorone diisocyanate were mixed at a ratio of 1: (1.9-2.1) and reacting for 10-12 hours at 80-85 ℃ to obtain the prepolymer with the average molecular weight of 3500.
4. The spray-applied, peel-off primer for automotive garments of claim 1, wherein the oligomer is prepared by the following method: the prepolymer and hydroxyl-terminated polyester were prepared according to 1: (1.6-1.8) and reacting for 10-12 hours at 90-95 ℃ to obtain the oligomer with the average molecular weight of 1.0X10 4~1.2×104.
5. The spray-coated vehicular coating available release primer according to claim 1, wherein the spray-coated vehicular coating available release primer comprises the following components in percentage by mass: 45-50% of oligomer, 5-10% of hydrogenated C5 petroleum resin and 40-50% of organic solvent.
6. The spray-coated removable primer for automotive coatings according to claim 5, wherein the organic solvent comprises 15% -20% of xylene and 25% -30% of butyl acetate by mass percent of the spray-coated removable primer.
7. A method for preparing the release primer for spray-coated vehicle coatings according to any one of claims 1 to 6, wherein the release primer for spray-coated vehicle coatings is obtained by uniformly mixing an oligomer, hydrogenated C5 petroleum resin and an organic solvent.
8. An application of the release primer for spraying car coats according to any one of claims 1-6 in the field of car films/car coats.
CN202410078209.3A 2024-01-19 2024-01-19 Stripping primer for spraying vehicle coating and preparation method and application thereof Active CN117903745B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160528A (en) * 2022-07-27 2022-10-11 雅图高新材料股份有限公司 Preparation method and application of bio-based waterborne polyurethane liquid vehicle coat
CN116731280A (en) * 2023-07-03 2023-09-12 郑州中远氨纶工程技术有限公司 Polyether ester type polyurethane film car cover and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100729804B1 (en) * 2005-12-29 2007-06-20 (주)디피아이 홀딩스 Invisible paint of the uv curable and method of preparing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160528A (en) * 2022-07-27 2022-10-11 雅图高新材料股份有限公司 Preparation method and application of bio-based waterborne polyurethane liquid vehicle coat
CN116731280A (en) * 2023-07-03 2023-09-12 郑州中远氨纶工程技术有限公司 Polyether ester type polyurethane film car cover and preparation method thereof

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