Composition for PVD rubbing and preparation method and application thereof

Abstract

The invention discloses a composition for PVD (Physical Vapor Deposition) rubbing as well as a preparation method and application thereof. Raw materials of the composition for PVD rubbing comprise the following components in parts by weight: 10-20 parts of a solvent type acrylate oligomer; 10 to 20 parts of bifunctional polyester acrylate resin; 10 to 20 parts of trifunctional polyester acrylate resin; 1 to 5 parts of aliphatic polycarbonate type polyurethane acrylate; 1 to 5 parts of trimethylolpropane triacrylate; and 1-3 parts of a photoinitiator. When the composition for PVD rubbing is applied to a PVD rubbing primer, the composition has the effects of clear rubbing texture and stable performance.

Description

Technical Field

[0001] The invention relates to the technical field of PVD rubbing, and in particular to a PVD rubbing composition and a preparation method and application thereof. Background Art

[0002] The PVD rubbing process is a composite process that combines physical vapor deposition (PVD) technology with paint rubbing technology, and is widely used in the manufacture of surface decoration and functional compositions. PVD is an efficient composition deposition method that evaporates metal or other materials into a gaseous state and condenses them on the surface of the substrate to form a thin film. This film not only has good adhesion and wear resistance, but also can achieve metallic luster, corrosion resistance and other properties. However, PVD compositions usually need to be used in combination with other composition systems to achieve more complex surface effects, among which the rubbing process is an important auxiliary process.

[0003] The rubbing process is essentially to transfer the texture on the mold to the surface of the composition by contacting the surface of the composition with a mold engraved with a pattern or texture, forming a decorative effect with depth and layering. In the application of PVD compositions, the rubbing process is often used to achieve delicate and clear surface textures, giving the product a unique appearance. The composition for rubbing usually refers to a layer of special coating applied on the surface of the substrate to ensure the rubbing effect. The composition must not only have good adhesion, wear resistance, and glossiness, but also have sufficient fluidity and good curing characteristics during the rubbing process to ensure that the delicate texture can be clearly and stably transferred to the surface of the composition.

[0004] However, in actual production, the PVD rubbing process often faces some technical difficulties, the most prominent of which is the lack of clarity of the rubbing texture and abnormal phenomena such as fogging and whitening after being left for a period of time. Existing PVD primers, especially primers used in rubbing technology, often have blurred textures during the rubbing process. The reason is closely related to the curing process of the composition and the chemical reaction characteristics of the composition materials.

[0005] First, the PVD primer needs to be taken off-line for internal texture rubbing after baking. Specifically, after the initial baking, a semi-cured coating film is formed on the surface of the PVD composition. This coating film must have a certain fluidity and adaptability in the further rubbing process so that it can perfectly contact the texture of the mold surface and transfer it to the composition. However, in this process, the degree of curing of the composition is not complete, especially in the multiple curing process, the reactivity and cross-linking density of the composition are often insufficient, resulting in a blurred rubbing effect and an inability to clearly present the details on the mold.

[0006] Another key issue arises during the curing process of the PVD rubbing composition. The curing of PVD primers usually involves a two-stage photocuring process: the first curing is usually performed by an LED curing lamp, and the second is UV curing by a mercury lamp. However, this two-stage curing process is often affected by environmental factors. In particular, the surface of the composition is easily affected by oxygen molecules in the air due to the storage time after the composition is off the production line. Oxygen molecules can react with free radicals in the composition to generate stable peroxides, thereby consuming the free radicals generated by the photoinitiator during the curing process. This enrichment effect of oxygen molecules prevents the polymerization reaction from being fully carried out, resulting in a decrease in the cross-linking density of the composition and incomplete curing, which further affects the clarity and fineness of the rubbing texture.

[0007] In the case of incomplete curing, the surface of the composition often becomes foggy or white. This is because in the case of incomplete polymerization, a sufficiently tight cross-linked network cannot be formed on the surface of the composition, resulting in an unstable structure of the coating film, and even a reaction with moisture and oxygen molecules in the air during storage to form an opaque substance, resulting in fogging and whitening. In particular, as time goes by, the surface of the composition is exposed to the air, and its reactivity is further reduced, which exacerbates the occurrence of these undesirable phenomena.

[0008] In addition, when the PVD primer is not completely cured, the adhesion and wear resistance of the composition may be greatly reduced due to insufficient cross-linking density. In this case, even if the rubbing texture can be barely achieved, it is easy to cause problems such as shedding and fading during subsequent processing and use. In order to accelerate the curing process or increase the cross-linking density, some process formulas will use additives such as accelerators or thickeners. Although these chemical additives increase the curing rate to a certain extent, they may also cause a decrease in the adhesion of the coating layer, or even delamination, further affecting the stability and performance of the composition.

[0009] When designing the formula of the PVD rubbing composition, how to balance the relationship between the curing rate and the crosslinking density becomes a key technical challenge. Although a curing rate that is too fast can shorten the production cycle, it may cause an uneven crosslinking network to form on the surface of the composition, reducing the stability and durability of the composition. Excessively high crosslinking density may cause the composition to shrink during the curing process, generate internal stress, and further affect the adhesion of the composition and the integrity of the film layer. Therefore, how to adjust the composition formula, optimize the curing process, avoid the oxygen inhibition effect, and ensure that the composition has sufficient fluidity and reactivity during the rubbing process is the key to solving the problems of the prior art. Summary of the invention

[0010] The object of the present invention is to provide a PVD rubbing composition with clear rubbing texture and stable performance.

[0011] A first aspect of the present invention is:

[0012] Provided is a PVD rubbing composition.

[0013] The second aspect of the present invention is:

[0014] Provided is a method for preparing a PVD rubbing composition.

[0015] The third aspect of the present invention is:

[0016] Application of the PVD rubbing composition.

[0017] The invention also provides a primer for PVD rubbing.

[0018] Specifically, the technical solution adopted according to the first aspect of the present invention is:

[0019] A PVD rubbing composition, wherein the raw materials of the PVD rubbing composition include the following components in parts by weight:

[0020] Solvent-based acrylate oligomer, 10-20 parts;

[0021] Difunctional polyester acrylate resin, 10-20 parts;

[0022] Trifunctional polyester acrylate resin, 10-20 parts;

[0023] Aliphatic polycarbonate type polyurethane acrylate, 1-5 parts;

[0024] Trimethylolpropane triacrylate, 1-5 parts;

[0025] Photoinitiator, 1-3 parts.

[0026] According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0027] The PVD rubbing composition of the present invention, when used in a PVD rubbing primer, has the effects of clear rubbing texture and stable performance, and is suitable for rubbing on the primer surface of a 3C mobile phone battery cover component, on which a PVD metal fine plus multiple texture effects with clear texture and fine touch can be formed; the composition of the present invention has stable performance and strong adhesion, can be coated on an epoxy+glass fiber board, and will not fall off even if boiled in water at 100°C for 2 hours.

[0028] Among them, solvent-based acrylate oligomers have good solvent release, fast surface drying and good self-drying properties, which can improve the clarity of rubbing texture and the number of rubbings, and improve adhesion;

[0029] Difunctional polyester acrylate resin has excellent plating properties, good toughness, good interlayer adhesion, elongation at break and water resistance;

[0030] The addition of trifunctional polyester acrylate resin can reduce the aggregation of oxygen molecules in the air in the shallow surface layer of the coating film after the composition is sprayed, avoid the enrichment effect of oxygen molecules so that the polymerization reaction cannot be fully carried out, thereby further improving the effect of clear rubbing texture. In addition, adding a suitable proportion of trifunctional polyester acrylate resin can increase the reaction speed of the paint film, thereby solving the problem of fogging after the primer is sprayed;

[0031] Trimethylolpropane triacrylate is a multifunctional modified acrylate having high reactivity and high crosslinking density, and can promote the adhesion of the composition;

[0032] Aliphatic polycarbonate type polyurethane acrylate can adjust the hardness and flexibility in the composition formula, balance the boiling resistance, chemical resistance and hot and cold cycle performance of the formula, thereby improving the stability of the composition.

[0033] According to one embodiment of the present invention, the raw materials of the PVD rubbing composition include the following components in parts by weight:

[0034] Solvent-based acrylate oligomer, 10-11 parts;

[0035] Difunctional polyester acrylate resin, 12-15 parts;

[0036] Trifunctional polyester acrylate resin, 10-13 parts;

[0037] Aliphatic polycarbonate type polyurethane acrylate, 1-5 parts;

[0038] Trimethylolpropane triacrylate, 1-5 parts;

[0039] Photoinitiator, 2-2.2 parts. The present invention limits the dosage of the preferred raw material components to ensure that the paint film formed by the composition in PVD printing can ensure a certain degree of flexibility and will not affect the printing due to the slow curing speed.

[0040] According to one embodiment of the present invention, the raw materials of the PVD rubbing composition include the following components in parts by weight:

[0041] Solvent-based acrylate oligomer, 11 parts;

[0042] Difunctional polyester acrylate resin, 12-15 parts;

[0043] Trifunctional polyester acrylate resin, 10-13 parts;

[0044] Aliphatic polycarbonate type polyurethane acrylate, 5 parts;

[0045] Trimethylolpropane triacrylate, 5 parts;

[0046] Photoinitiator, 2-2.2 parts.

[0047] According to one embodiment of the present invention, the raw materials of the PVD rubbing composition include the following components in parts by weight:

[0048] Solvent-based acrylate oligomer, 11 parts;

[0049] Difunctional polyester acrylate resin, 15 parts;

[0050] Trifunctional polyester acrylate resin, 10 parts;

[0051] Aliphatic polycarbonate type polyurethane acrylate, 5 parts;

[0052] Trimethylolpropane triacrylate, 5 parts;

[0053] Photoinitiator, 2 parts.

[0054] According to one embodiment of the present invention, the raw materials of the PVD rubbing composition include the following components in parts by weight:

[0055] Solvent-based acrylate oligomer, 11 parts;

[0056] Difunctional polyester acrylate resin, 12 parts;

[0057] Trifunctional polyester acrylate resin, 13 parts;

[0058] Aliphatic polycarbonate type polyurethane acrylate, 5 parts;

[0059] Trimethylolpropane triacrylate, 5 parts;

[0060] Photoinitiator, 2 parts.

[0061] According to one embodiment of the present invention, the raw materials of the PVD rubbing composition include the following components in parts by weight:

[0062] Solvent-based acrylate oligomer, 11 parts;

[0063] Difunctional polyester acrylate resin, 12 parts;

[0064] Trifunctional polyester acrylate resin, 13 parts;

[0065] Aliphatic polycarbonate type polyurethane acrylate, 5 parts;

[0066] Trimethylolpropane triacrylate, 5 parts;

[0067] Photoinitiator, 2.2 parts.

[0068] According to one embodiment of the present invention, the solvent-based acrylic ester oligomer includes Changxing 6071, which contains thermoplastic acrylic resin, has good solvent release, fast surface drying and good self-drying properties, can improve the clarity of the rubbing texture and the number of rubbings, and has good bite force on the PU color paint layer.

[0069] According to one embodiment of the present invention, the difunctional polyester acrylate resin includes Wuxing W300, which has excellent plating properties, good toughness, good interlayer adhesion, elongation at break and water resistance.

[0070] According to one embodiment of the present invention, the trifunctional polyester acrylate resin includes Corning 6008.

[0071] According to one embodiment of the present invention, the aliphatic polycarbonate polyurethane acrylate includes Sartomer CN9001NS.

[0072] According to one embodiment of the present invention, the photoinitiator includes at least one of α-hydroxycyclohexyl benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzoin dimethyl ether.

[0073] According to one embodiment of the present invention, the raw materials of the PVD rubbing composition further include auxiliary agents, and the auxiliary agents include diluents and leveling agents.

[0074] According to one embodiment of the present invention, the auxiliary agent includes 40-60 parts of a diluent and 0.05-0.2 parts of a leveling agent.

[0075] According to one embodiment of the present invention, the diluent includes at least one of ethyl acetate, butyl acetate and ethylene glycol monobutyl ether.

[0076] Specifically, the technical solution adopted according to the second aspect of the present invention is:

[0077] A method for preparing the PVD rubbing composition comprises the following steps:

[0078] The PVD rubbing composition is obtained by mixing solvent-type acrylate oligomer, difunctional polyester acrylate resin, trifunctional polyester acrylate resin, aliphatic polycarbonate type polyurethane acrylate, trimethylolpropane triacrylate and photoinitiator.

[0079] According to one embodiment of the present invention, the method for preparing the PVD rubbing composition comprises the following steps:

[0080] S1: Mix solvent-based acrylate oligomer, difunctional polyester acrylate resin, trifunctional polyester acrylate resin, aliphatic polycarbonate polyurethane acrylate, and trimethylolpropane triacrylate in part of the solvent, and stir and mix them at a speed of 500 rpm for 10-15 minutes to make the components preliminarily evenly dispersed;

[0081] S2 increases the speed to 1200 rpm and continues stirring for 30-35 minutes to allow the resin in the raw material combination to be evenly dispersed in the solution to form a uniform base paint solution;

[0082] S3: adding a photoinitiator, an auxiliary agent and a remaining amount of solvent into the paint liquid, stirring at a speed of 600 rpm, and continuously stirring for 10-15 minutes to obtain the PVD rubbing composition.

[0083] Another aspect of the present invention further provides a PVD rubbing primer. The primer is formed by spraying and curing the PVD rubbing composition described in the first embodiment. Since the application adopts all the technical solutions of the above composition, it has at least all the beneficial effects brought by the technical solutions of the above embodiments.

[0084] According to one embodiment of the present invention, when the PVD rubbing primer is cured to obtain the primer, the required curing energy is 600-800 mJ / cm 2 ; Infrared baking time is 55-65℃*5-8min.

[0085] According to one embodiment of the present invention, the PVD primer can be applied to the housing and buttons of electronic products such as mobile phones, tablet computers, and laptop computers to achieve a metallic appearance and improve the grade and competitiveness of the products. At the same time, since the PVD film layer is non-conductive, it can avoid failures of electronic products caused by static electricity during use.

[0086] According to one embodiment of the present invention, the PVD primer can be applied to the interior and exterior parts of automobiles, and the PVD printing process can achieve various complex textures and pattern decorations, such as wood grain, leather grain, metal grain, etc., to improve the beauty and personalization of the automobile. In addition, the PVD film layer has good wear resistance and corrosion resistance, which can improve the service life of automobile parts.

[0087] According to one embodiment of the present invention, the PVD primer can be used in the field of cosmetics, such as on cosmetic packaging bottles, bottle caps and other products. The PVD printing process can achieve various exquisite patterns and logo decorations, thereby improving the brand image and market competitiveness of cosmetics. At the same time, the PVD film layer has good barrier properties and can protect cosmetics from the influence of the external environment.

[0088] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0089] The words "preferred", "more preferred" and the like in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0090] When a numerical range is disclosed herein, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0091] The various types of resins used in the specific embodiments of the present invention are all known corresponding resins. The functional groups mentioned herein are the functionality of the polymer or active monomer, wherein the functionality refers to the number of unsaturated double bonds in the acrylate group contained in the polymer or active monomer.

[0092] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of the present invention.

[0093] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0094] In the examples and comparative examples, the solvent-based acrylate oligomer was purchased from 6071 of Changxing Company in Taiwan, China.

[0095] In the examples and comparative examples, the difunctional polyurethane acrylate resin was purchased from W300 of Guangzhou Wuxing Company, China.

[0096] In the examples and comparative examples, the trifunctional polyurethane acrylate resin is Corning's 6008, purchased from 9W Chemical.

[0097] In the examples and comparative examples, aliphatic polycarbonate polyurethane acrylate was purchased from CN9001NS of Sartomer.

[0098] In the examples and comparative examples, the α-hydroxycyclohexyl benzophenone in the photoinitiator is Irgacure 184, and the 2,4,6-trimethylbenzoyl diphenylphosphine oxide is Darocur TPO, which are purchased from Jiuri Chemical; the benzoin dimethyl ether BDK initiator is also purchased from Jiuri Chemical.

[0099] In the examples and comparative examples, trimethylolpropane triacrylate, model EM231, was purchased from Changxing Company, Taiwan, China.

[0100] In the examples and comparative examples, the leveling agent is polyester-modified polydimethylsiloxane containing acrylic functional groups, model BYK 371 purchased from BYK Company of Germany.

[0101] In the examples and comparative examples, ethyl acetate, butyl acetate and ethylene glycol monobutyl ether used as diluents are commercially available and of analytical grade.

[0102] Example 1

[0103] A composition, the raw materials of the composition include the components shown in Table 1:

[0104] Table 1

[0105]

[0106]

[0107] The preparation method of the above composition comprises the following steps:

[0108] S1: Mix solvent-based acrylate oligomer, difunctional polyester acrylate resin, trifunctional polyester acrylate resin, aliphatic polycarbonate polyurethane acrylate, and trimethylolpropane triacrylate in a solvent, and stir and mix them at a speed of 500 rpm for 10 minutes to make the components preliminarily evenly dispersed;

[0109] S2 increases the speed to 1200 rpm and continues stirring for 30 minutes to allow the resin in the raw material combination to be evenly dispersed in the solution to form a uniform base paint solution;

[0110] S3: adding a photoinitiator, an auxiliary agent and a solvent to the paint liquid, stirring at a speed of 600 rpm, and continuously stirring for 10 minutes to obtain the composition.

[0111] The prepared composition is used to coat and cure the sample for PVD rubbing, and the steps are as follows:

[0112] (a) Primer was sprayed onto the epoxy + fiber substrate with a coating film thickness of 6 μm and baked at 70°C for 10 minutes.

[0113] (b) Spraying PU color paint with a coating film thickness of 15 μm, and baking at 70° C. for 10 minutes to obtain a PU primer.

[0114] (c) Spray the above composition to a coating thickness of 20 μm, and level it at 50°C for 5 minutes, and then perform 3D internal texture rubbing LED primary curing and mercury lamp 600mJ / cm 2 The primer is cured at an energy of 100 to obtain a primer for PVD rubbing.

[0115] (d) Vacuum coating on PVD primer.

[0116] (e) Spray the middle paint on the metal coating and add color paste, the coating film thickness is 5μm, and leveling is carried out at 60℃ for 5 minutes and 400mJ / cm 2 solidified under the energy of

[0117] (f) Spraying topcoat, coating film thickness 20μm, leveling at 60℃ for 5 minutes and 3D external texture rubbing off line LED one-step curing and mercury lamp 900mJ / cm 2 The PVD coating is cured under an energy of 100%.

[0118] Example 2

[0119] The difference between Example 2 and Example 1 is that in Example 2, the amount of trifunctional acrylate resin added is increased, and the total amount of difunctional polyester acrylate resin and trifunctional polyester acrylate resin added remains unchanged.

[0120] Specific:

[0121] A composition, the raw materials of the composition include the components shown in Table 2:

[0122] Table 2

[0123]

[0124] The preparation method of the above composition comprises the following steps:

[0125] S1: Mix solvent-based acrylate oligomer, difunctional polyester acrylate resin, trifunctional polyester acrylate resin, aliphatic polycarbonate polyurethane acrylate, and trimethylolpropane triacrylate in a solvent, and stir and mix them at a speed of 500 rpm for 10 minutes to make the components preliminarily evenly dispersed;

[0126] S2 increases the speed to 1200 rpm and continues stirring for 30 minutes to allow the resin in the raw material combination to be evenly dispersed in the solution to form a uniform base paint solution;

[0127] S3: adding a photoinitiator, an auxiliary agent and a solvent to the paint liquid, stirring at a speed of 600 rpm, and continuously stirring for 10 minutes to obtain the composition.

[0128] The prepared composition is used to coat and cure the sample for PVD rubbing, and the steps are as follows:

[0129] (a) Primer was sprayed onto the epoxy + fiber substrate with a coating film thickness of 6 μm and baked at 70°C for 10 minutes.

[0130] (b) Spraying PU color paint with a coating film thickness of 15 μm, and baking at 70° C. for 10 minutes to obtain a PU primer.

[0131] (c) Spray the above composition to a coating thickness of 20 μm, and level it at 50°C for 5 minutes, and then perform 3D internal texture rubbing LED primary curing and mercury lamp 600mJ / cm 2 The primer is cured at an energy of 100 to obtain a primer for PVD rubbing.

[0132] (d) Vacuum coating on PVD primer.

[0133] (e) Spray the middle paint on the metal coating and add color paste, the coating film thickness is 5μm, and leveling is carried out at 60℃ for 5 minutes and 400mJ / cm 2 solidified under the energy of

[0134] (f) Spraying topcoat, coating film thickness 20μm, leveling at 60℃ for 5 minutes and 3D external texture rubbing off line LED one-step curing and mercury lamp 900mJ / cm 2 The PVD coating is cured under an energy of 100%.

[0135] Example 3

[0136] The difference between Example 3 and Example 2 is that in Example 3, a photoinitiator TPO, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, is newly added, and the total amount of the photoinitiator added remains unchanged.

[0137] Specific:

[0138] A composition, the raw materials of the composition include the components shown in Table 3:

[0139] Table 3

[0140]

[0141] The preparation method of the above composition comprises the following steps:

[0142] S1: Mix solvent-based acrylate oligomer, difunctional polyester acrylate resin, trifunctional polyester acrylate resin, aliphatic polycarbonate polyurethane acrylate, and trimethylolpropane triacrylate in a solvent, and stir and mix them at a speed of 500 rpm for 10 minutes to make the components preliminarily evenly dispersed;

[0143] S2 increases the speed to 1200 rpm and continues stirring for 30 minutes to allow the resin in the raw material combination to be evenly dispersed in the solution to form a uniform base paint solution;

[0144] S3: adding a photoinitiator, an auxiliary agent and a solvent to the paint liquid, stirring at a speed of 600 rpm, and continuously stirring for 10 minutes to obtain the composition.

[0145] The prepared composition is used to coat and cure the sample for PVD rubbing, and the steps are as follows:

[0146] (a) Primer was sprayed onto the epoxy + fiber substrate with a coating film thickness of 6 μm and baked at 70°C for 10 minutes.

[0147] (b) Spraying PU color paint with a coating film thickness of 15 μm, and baking at 70° C. for 10 minutes to obtain a PU primer.

[0148] (c) Spray the above composition to a coating thickness of 20 μm, and level it at 50°C for 5 minutes, and then perform 3D internal texture rubbing LED primary curing and mercury lamp 600mJ / cm 2 The primer is cured at an energy of 100 to obtain a primer for PVD rubbing.

[0149] (d) Vacuum coating on PVD primer.

[0150] (e) Spray the middle paint on the metal coating and add color paste, the coating film thickness is 5μm, and leveling is carried out at 60℃ for 5 minutes and 400mJ / cm 2 solidified under the energy of

[0151] (f) Spraying topcoat, coating film thickness 20μm, leveling at 60℃ for 5 minutes and 3D external texture rubbing off line LED one-step curing and mercury lamp 900mJ / cm 2The PVD coating is cured under an energy of 100%.

[0152] Example 4

[0153] The difference between Example 4 and Example 3 is that in Example 4, a photoinitiator benzoin dimethyl ether BDK is newly added, and the total amount of the photoinitiator added remains unchanged.

[0154] Specific:

[0155] A composition, the raw materials of the composition include the components shown in Table 4:

[0156] Table 4

[0157]

[0158]

[0159] The preparation method of the above composition comprises the following steps:

[0160] S1: Mix solvent-based acrylate oligomer, difunctional polyester acrylate resin, trifunctional polyester acrylate resin, aliphatic polycarbonate polyurethane acrylate, and trimethylolpropane triacrylate in a solvent, and stir and mix them at a speed of 500 rpm for 10 minutes to make the components preliminarily evenly dispersed;

[0161] S2 increases the speed to 1200 rpm and continues stirring for 30 minutes to allow the resin in the raw material combination to be evenly dispersed in the solution to form a uniform base paint solution;

[0162] S3: adding a photoinitiator, an auxiliary agent and a solvent to the paint liquid, stirring at a speed of 600 rpm, and continuously stirring for 10 minutes to obtain the composition.

[0163] The prepared composition is used to coat and cure the sample for PVD rubbing, and the steps are as follows:

[0164] (a) Primer was sprayed onto the epoxy + fiber substrate with a coating film thickness of 6 μm and baked at 70°C for 10 minutes.

[0165] (b) Spraying PU color paint with a coating film thickness of 15 μm, and baking at 70° C. for 10 minutes to obtain a PU primer.

[0166] (c) Spray the above composition to a coating thickness of 20 μm, and level it at 50°C for 5 minutes, and then perform 3D internal texture rubbing LED primary curing and mercury lamp 600mJ / cm 2 The primer is cured at an energy of 100 to obtain a primer for PVD rubbing.

[0167] (d) Vacuum coating on PVD primer.

[0168] (e) Spray the middle paint on the metal coating and add color paste, the coating film thickness is 5μm, and leveling is carried out at 60℃ for 5 minutes and 400mJ / cm 2 solidified under the energy of

[0169] (f) Spraying topcoat, coating film thickness 20μm, leveling at 60℃ for 5 minutes and 3D external texture rubbing off line LED one-step curing and mercury lamp 900mJ / cm 2 The PVD coating is cured under an energy of 100%.

[0170] Comparative Example 1

[0171] The difference between Comparative Example 1 and Example 1 is that in Comparative Example 1, no solvent-based acrylate oligomer is added.

[0172] Comparative Example 2

[0173] The difference between Comparative Example 2 and Example 1 is that in Comparative Example 2, the solvent-based acrylic ester oligomer is replaced from 6071 of Changxing Company of Taiwan, China to W3076 of Five Elements Company of Guangzhou, China.

[0174] Comparative Example 3

[0175] The difference between Comparative Example 3 and Example 1 is that in Comparative Example 3, the amount of difunctional polyester acrylic resin is increased to 20 parts, and the amount of trifunctional polyester acrylic resin is reduced to 5 parts, and the total amount of difunctional polyester acrylic resin and trifunctional polyester acrylic resin is still maintained at 25 parts.

[0176] Comparative Example 4

[0177] The difference between Comparative Example 4 and Example 1 is that in Comparative Example 4, the amount of trifunctional polyester acrylic resin is increased to 20 parts, the amount of difunctional polyester acrylic resin is reduced to 5 parts, and the total amount of difunctional polyester acrylic resin and trifunctional polyester acrylic resin is still maintained at 25 parts.

[0178] Comparative Example 5

[0179] The difference between Comparative Example 5 and Example 4 is that in Comparative Example 5, the difunctional polyurethane acrylate resin is replaced by GW300 resin from Hunan Unico Technology Co., Ltd., China, instead of W300 from Guangzhou Wuxing Company, China.

[0180] Comparative Example 6

[0181] The difference between Comparative Example 6 and Comparative Example 5 is that in Comparative Example 6, the trifunctional polyurethane acrylate resin is replaced by FSP8296 resin of Guangzhou Runao Chemical from Corning 6008.

[0182] Comparative Example 7

[0183] The difference between Comparative Example 7 and Example 1 is that the preparation method of the composition of Comparative Example 7 does not contain a high-speed dispersion step.

[0184] Specific:

[0185] A composition, the raw materials of the composition include the components shown in Table 5:

[0186] Table 5

[0187]

[0188] The preparation method of the above composition comprises the following steps:

[0189] A mixed solvent type acrylate oligomer, a difunctional polyester acrylate resin, a trifunctional polyester acrylate resin, an aliphatic polycarbonate type polyurethane acrylate, and a trimethylolpropane triacrylate are added to a part of a solvent, a photoinitiator, an auxiliary agent, and a remaining amount of solvent are added, and the mixture is stirred at a speed of 600 rpm for 10-15 minutes to obtain the composition.

[0190] The prepared composition is used to coat and cure the sample for PVD rubbing, and the steps are as follows:

[0191] (a) Spray Primer onto the epoxy + fiber substrate with a coating film thickness of 6-10 μm and bake at 70-80°C for 10-15 minutes.

[0192] (b) spraying PU color paint with a coating film thickness of 15-20 μm, and baking at 70-80° C. for 10-15 minutes to obtain PU primer.

[0193] (c) Spray the above composition to a coating thickness of 20-25 μm, and level it at 50-60°C for 5-8 minutes, and then perform 3D internal texture rubbing LED primary curing and mercury lamp 600-800 mJ / cm 2 The primer is cured at an energy of 100 to obtain a primer for PVD rubbing.

[0194] (d) Vacuum coating on PVD primer.

[0195] (e) Spray the middle paint on the metal coating and add color paste, the coating film thickness is 5-8μm, and leveling is carried out at 60-70℃ for 5-8 minutes and 400-600mJ / cm 2 solidified under the energy of

[0196] (f) Spray topcoat, coating film thickness 20-25μm, leveling at 60-70℃ for 5-8 minutes and 3D external texture rubbing off line LED one-time curing and mercury lamp 900-1100mJ / cm2 The PVD coating is cured under an energy of 100%.

[0197] Comparative Example 8

[0198] The difference between Comparative Example 8 and Example 1 is that in the preparation method of the composition of Comparative Example 8, in step S2, 1200 rpm is adjusted to 800 rpm.

[0199] Specific:

[0200] A composition, the raw materials of the composition include the components shown in Table 6:

[0201] Table 6

[0202]

[0203] The preparation method of the above composition comprises the following steps:

[0204] S1: Mix solvent-based acrylate oligomer, difunctional polyester acrylate resin, trifunctional polyester acrylate resin, aliphatic polycarbonate polyurethane acrylate, and trimethylolpropane triacrylate in part of the solvent, and stir and mix them at a speed of 500 rpm for 10 minutes to make the components preliminarily evenly dispersed;

[0205] S2 increases the rotation speed to 800 rpm and continues stirring for 60 minutes to obtain a base paint solution;

[0206] S3: adding a photoinitiator, an auxiliary agent and a remaining amount of solvent into the paint liquid, stirring at a speed of 600 rpm for 10 minutes to obtain the composition.

[0207] The prepared composition is used to coat and cure the sample for PVD rubbing, and the steps are as follows:

[0208] (a) Primer was sprayed onto the epoxy + fiber substrate with a coating film thickness of 6 μm and baked at 70°C for 10 minutes.

[0209] (b) Spraying PU color paint with a coating film thickness of 15 μm, and baking at 70° C. for 10 minutes to obtain a PU primer.

[0210] (c) Spray the above composition to a coating thickness of 20 μm, and level it at 50°C for 5 minutes, and then perform 3D internal texture rubbing LED primary curing and mercury lamp 600mJ / cm 2 The primer is cured at an energy of 100 to obtain a primer for PVD rubbing.

[0211] (d) Vacuum coating on PVD primer.

[0212] (e) Spray the middle paint on the metal coating and add color paste, the coating film thickness is 5μm, and leveling is carried out at 60℃ for 5 minutes and 400mJ / cm 2 solidified under the energy of

[0213] (f) Spraying topcoat, coating film thickness 20μm, leveling at 60℃ for 5 minutes and 3D external texture rubbing off line LED one-step curing and mercury lamp 900mJ / cm 2 The PVD coating is cured under an energy of 100%.

[0214] Performance Test:

[0215] The performance tests were performed on the compositions prepared in Examples 1-4 and Comparative Examples 1-8. The PVD rubbing coatings prepared from the above compositions were subjected to adhesion tests and boiling tests at 100°C for 2 hours. The test results are shown in Table 7.

[0216] Specifically, the adhesion test method is as follows: a. Before the test, check the appearance for bubbles, cracks, peeling and other defects, and wipe the paint surface clean with a dust-free cloth; b. Hold the knife so that the knife surface is perpendicular to the test surface, and use a uniform cutting rate to draw 10×10 1mm×1mm small grids on the coating. Each line cuts through the coating to the substrate. If the test area is too small and there is not enough space to draw grids, you can draw a 90-degree cross on the test surface instead; c. Clean the grid area with a soft brush, stick the tape on the grid area, the tape length should be at least 20mm longer than the grid, and press the tape with your fingers or other tools to make it fully contact with the coating surface (remove the bubbles remaining under the tape); d. Let it stand for 3 minutes; e. Grasp one end of the tape and tear off the tape very quickly within 1s in the direction perpendicular to the test surface. Testing standards: The final judgment result must consider both the product and the tape: ISO grade 1 and above or reaching and exceeding 4B acceptance. Unless otherwise specified, the following definitions apply: ISO Grade 1 and ASTM 4B: Small flakes of paint are peeling off along the edges of the cross-cuts or at the intersection of the knife marks, and the actual damage in the cross-cut area is ≤5%.

[0217] 100℃ boiling water test method: a. Before the test, check the appearance of the product for discoloration, bubbles, cracks, shedding and other defects, and wipe the surface of the sample with a dust-free cloth; b. Heat the pure water to 100℃, put the product into the water bath, and ensure that the product does not overlap, collide or directly contact the heating rod. c. The water bath time is 120 minutes. After the test is completed, it is naturally cooled to room temperature under room temperature. Testing standards: a. Visual inspection under standard light source, the inspection distance is about 30cm, and there is no obvious corrosion, blistering, pitting, cracking, deformation and other defects; b. Refer to the "tape method" adhesion judgment standard: the coating should not fall off when the tape is peeled off, otherwise it will be judged as NG. e. Check the appearance of the product and use the "tape method" to test the adhesion of the test surface.

[0218] Table 7

[0219]

[0220]

[0221] As can be seen from Table 7, the primers prepared in Example 3 and Example 4 have the best overall performance after adding rubbing.

[0222] The primer of Comparative Example 1 did not use solvent-based polyurethane modified acrylate resin, so the appearance of the product showed unclear rubbing texture, and the paint film was easily left on the silicone mold, and fogging and whitening occurred.

[0223] In Example 1, a solvent-based polyurethane-modified acrylate resin is added, and the clarity of the rubbing texture is better than that of Comparative Example 1.

[0224] In Comparative Example 2, a solvent-based polyurethane modified acrylate resin from a different manufacturer was used. The rubbing texture was clear, but abnormal fogging occurred in the spray paint after coating.

[0225] In Comparative Example 3, the added amount of trifunctional acrylate resin is too small, and the spray-coated intermediate paint appears foggy and white after coating.

[0226] In Example 2, the proportion of trifunctional acrylate resin added is increased, the activity and reaction speed of the primer are improved, and no fogging abnormality occurs in the spray paint after coating. Its appearance effect is better than that of Comparative Example 3.

[0227] In Comparative Example 4, the proportion of trifunctional acrylate resin added was increased. Too high an addition amount caused the activity and reaction speed of the primer to be too good, which easily led to the phenomenon of the coating layer falling off.

[0228] In Example 3, photoinitiator TPO and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are added, and the curing wavelength of the LED lamp of the rubbing machine is 365. The addition of photoinitiator TPO helps the deep curing effect of the coating, and its performance is better than that of Example 2.

[0229] In Example 4, a photoinitiator, benzoin dimethyl ether BDK, is added, which has the advantages of stable storage in dark and good bidirectional curing effect of the surface and inner layers. Its performance test is OK and better than that of Example 3.

[0230] In Comparative Example 5, when the difunctional polyurethane acrylate resin is replaced, fogging and coating shedding abnormalities easily occur.

[0231] In Comparative Example 6, the replacement of the trifunctional polyurethane acrylate resin easily resulted in fogging and abnormal coating shedding.

[0232] In Comparative Example 7, the high-speed dispersion step was omitted, resulting in unclear rubbing texture and prone to abnormal agglomeration. The adhesion test found that the primer peeled off seriously.

[0233] In Comparative Example 8, the dispersion speed step was lowered, and there was a flowery phenomenon during spraying, the rubbing texture was unclear, the lines were blurred, and the primer fell off during the water boiling test.

[0234] The above are only embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A PVD rubbing composition, characterized in that: The raw materials of the PVD rubbing composition include the following components in parts by weight: Solvent-based acrylate oligomer, 10-20 parts; Difunctional polyester acrylate resin, 10-20 parts; Trifunctional polyester acrylate resin, 10-20 parts; Aliphatic polycarbonate type polyurethane acrylate, 1-5 parts; Trimethylolpropane triacrylate, 1-5 parts; Photoinitiator, 1-3 parts.

2. A PVD rubbing composition according to claim 1, characterized in that: The raw materials of the PVD rubbing composition include the following components in parts by weight: Solvent-based acrylate oligomer, 10-11 parts; Difunctional polyester acrylate resin, 12-15 parts; Trifunctional polyester acrylate resin, 10-13 parts; Aliphatic polycarbonate type polyurethane acrylate, 1-5 parts; Trimethylolpropane triacrylate, 1-5 parts; Photoinitiator, 2-2.2 parts.

3. A PVD rubbing composition according to claim 1, characterized in that: The solvent-based acrylate oligomer includes Changxing 6071.

4. A PVD rubbing composition according to claim 1, characterized in that: The difunctional polyester acrylate resin includes Wuxing W300.

5. A PVD rubbing composition according to claim 1, characterized in that: The trifunctional polyester acrylate resin includes Corning 6008.

6. A PVD rubbing composition according to claim 1, characterized in that: The aliphatic polycarbonate type polyurethane acrylate includes Sartomer CN9001NS.

7. A PVD rubbing composition according to claim 1, characterized in that: The photoinitiator includes at least one of α-hydroxycyclohexyl benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzoin dimethyl ether.

8. A PVD rubbing composition according to claim 1, characterized in that: The raw materials of the PVD rubbing composition also include auxiliary agents, and the auxiliary agents include diluents and leveling agents.

9. A method for preparing a PVD rubbing composition as claimed in any one of claims 1 to 8, characterized in that: The following steps are involved: The PVD rubbing composition is obtained by mixing solvent-type acrylate oligomer, difunctional polyester acrylate resin, trifunctional polyester acrylate resin, aliphatic polycarbonate type polyurethane acrylate, trimethylolpropane triacrylate and photoinitiator.

10. A primer for PVD rubbing, characterized in that: The primer is formed by spraying and curing the PVD rubbing composition according to any one of claims 1 to 8.

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