CN110760260A - Dual-curing vacuum coating primer and preparation method thereof - Google Patents
Dual-curing vacuum coating primer and preparation method thereof Download PDFInfo
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- CN110760260A CN110760260A CN201911161443.8A CN201911161443A CN110760260A CN 110760260 A CN110760260 A CN 110760260A CN 201911161443 A CN201911161443 A CN 201911161443A CN 110760260 A CN110760260 A CN 110760260A
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
- B05D7/26—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials synthetic lacquers or varnishes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention belongs to the field of new materials, and particularly relates to a dual-curing vacuum coating primer and a preparation method thereof, wherein the primer comprises the following raw materials in parts by weight: 30-60 parts of dual-curing organic silicon resin matrix, 0-20 parts of light-curing resin, 10-20 parts of light-curing monomer diluent, 0-15 parts of amine curing agent, 2-10 parts of photoinitiator, 0-1 part of flatting agent and 10-30 parts of solvent. The vacuum coating primer provided by the invention overcomes the defects of poor adhesion, poor heat resistance, poor adhesion to a coating and the like of the vacuum coating primer in the prior art, has the characteristics of high wear resistance, scratch resistance, photo-thermal dual curing and the like, has a good comprehensive performance advantage, and has a wide application space.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a dual-curing vacuum coating primer and a preparation method thereof.
Background
The vacuum plastic coating technology starts in the 30 th of the 20 th century, the industrialization is realized in the 50 th of the century, and the large-scale production is started in the 80 th of the century. The vacuum coating is carried out on the plastic product, so that the plastic product can be endowed with metallic luster, the appearance aesthetic feeling is improved, and the added value is improved, therefore, the technology is widely applied to the civil fields of automobile lamp reflectors, cosmetic packaging boxes, various plastic toys and the like.
The process flow of the plastic vacuum coating is as follows: "plastic substrate pretreatment → priming → vacuum coating → top coating". The primer and the finish coat for vacuum coating play a crucial role in the quality of products.
The primer for vacuum coating should meet the requirements of both plastic substrates and vacuum coating, not only should have good adhesion, weather resistance, heat resistance, but also should have excellent gloss, leveling property, no shrinkage cavity on the surface and no particle rising, and its basic properties are that ① primer has good adhesion with the substrate and the coating, which is the most basic property as the primer for vacuum coating, ② primer has good leveling property, which is the key to determine the gloss and mirror effect of the vacuum coating, because the coating is very thin, the flatness of the coating is determined by the flatness of the primer surface, ③ primer does not contain volatile small molecules after curing, ④ primer film has better heat resistance and temperature resistance change, vacuum coating has a temperature rise process, the coating and the substrate will expand with heat and contract with cold during the temperature rise and cooling process, the coating and the substrate are adapted to the thermal expansion property of the substrate, therefore the heat resistance, thermal deformation resistance and thermal decomposition resistance of the primer should meet the process requirements of vacuum coating, ⑤ has enough heat deformation and thermal deformation for some flexible plastic substrates, ⑤ coating has no thermal deformation, even if the thermal expansion of the coating layer is less than the thermal expansion of the coating, the thermal deformation, the thermal expansion problem of the coating is less than that the thermal expansion of the coating, so that the coating can cause the thermal curing of the vacuum coating, the coating, even if the coating has the thermal deformation, the primer has the thermal deformation, the thermal deformation of the thermal cracking problem of the coating is less.
Because the ultraviolet curing technology has some inherent defects, such as the defects of being limited by the complex structure of the base material, the release of internal stress after instant curing and the like, the development of the primer capable of carrying out UV-thermal dual curing is of great significance.
Disclosure of Invention
The invention aims to provide a dual-curing vacuum coating primer and a preparation method thereof, aiming at the defects of poor adhesion, poor heat resistance, poor adhesion to a coating and the like of the vacuum coating primer in the prior art. The coating primer effectively improves the poor adhesive force and heat resistance of the existing coating primer, has the characteristics of high wear resistance, scratch resistance, photo-thermal dual curing and the like, has good comprehensive performance advantages, and has wide application space.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
the dual-curing vacuum coating primer is characterized in that: the composite material comprises the following raw materials in parts by weight:
dual cure silicone resin matrix: 30-60 parts;
light-curing resin: 0-20 parts of a solvent;
photo-curable monomer diluent: 10-20 parts;
amine curing agent: 0-15 parts;
photoinitiator (2): 2-10 parts;
leveling agent: 0-1 part;
solvent: 10-30 parts.
Preferably, the dual-curing organic silicon resin matrix is prepared by the following method, and the following reaction is carried out to compound according to the mole fraction of the functional groups:
(1) dissolving 1 part of hydrogen-containing double-end siloxane in 80 parts of tetrahydrofuran, and mixing 0.3-0.4 part of trifunctional acrylate, 1 wt% of polymerization inhibitor and 10 parts of-5Dissolving the catalyst in 10 parts of tetrahydrofuran, adding the tetrahydrofuran into a constant-pressure dropping funnel, controlling the dropping speed, stirring, reacting at 70-120 ℃ for 4-5 hours, distilling under reduced pressure to remove the solvent, adding 50 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3 hours, separating a water phase, taking an organic layer, distilling under reduced pressure to remove the solvent to obtain the trifunctional single-end hydrogenpolysiloxane, marked as A, and having the following structural formula:
wherein: n is more than or equal to 5 and less than or equal to 10, x is more than or equal to 1 and less than or equal to 5, and y is more than or equal to 1 and less than or equal to 5; r1Is C6H11O3、C12H23O6、C15H29O6Or C5H9O4；
The amount of the polymerization inhibitor is 1 wt% of the mass of the trifunctional acrylate;
(2) dissolving 1 part of A in 80 parts of tetrahydrofuran, and mixing 2-2.1 parts of epoxy alkene, 1 wt% of polymerization inhibitor and 10 parts of-5Dissolving the catalyst in 10 parts of tetrahydrofuran, adding the tetrahydrofuran into a constant-pressure dropping funnel, controlling the dropping speed, stirring, reacting at 70-120 ℃ for 4-5 hours, distilling under reduced pressure to remove the solvent, adding 50 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3 hours, separating a water phase, taking an organic layer, distilling under reduced pressure to remove the solvent to obtain the trifunctional single-end hydrogenpolysiloxane, marked as B, with the structural formula as follows:
wherein: n is more than or equal to 5 and less than or equal to 10, x is more than or equal to 1 and less than or equal to 5, and y is more than or equal to 1 and less than or equal to 5; r1Is C6H11O3、C12H23O6、C15H29O6Or C5H9O4；R2Is C3H5O2、C2H4O、C17H24O、C2H4；R3Is H, CH3Or C3H7；
The amount of the polymerization inhibitor is 1 wt% of the mass of the epoxy alkene;
(3) dissolving 1 part of B in 80 parts of tetrahydrofuran, and dissolving 1-1.2 parts of trifunctional acrylate, 1 wt% of polymerization inhibitor and 10 parts of-5Dissolving catalyst in 10 portions of tetrahydrofuran, adding into a constant pressure dropping funnel, controlling the dropping speed, stirring, reacting at 70-120 ℃ for 4-5h, distilling under reduced pressure to remove the solvent, adding 50 portions of toluene and excessive sodium bicarbonate to obtain the final productAnd 10 parts of deionized water, stirring for 3 hours at 60 ℃, separating a water phase, taking an organic layer, and distilling under reduced pressure to remove the solvent to obtain a target product, marked as C, which has the following structural formula:
wherein: n is more than or equal to 5 and less than or equal to 10, x is more than or equal to 1 and less than or equal to 5, and y is more than or equal to 1 and less than or equal to 5; r1Is C6H11O3、C12H23O6、C15H29O6Or C5H9O4；R2Is C3H5O2、C2H4O、C17H24O、C2H4；R3Is H, CH3Or C3H7。
The amount of the polymerization inhibitor is 1 wt% of the mass of the trifunctional acrylate.
Preferably, the trifunctional acrylate is trimethylolpropane triacrylate, ethoxytrimethylolpropane triacrylate, propoxytrimethylolpropane triacrylate or pentaerythritol triacrylate.
Preferably, the epoxy alkene is glycidyl methacrylate, allyl glycidyl ether, cardanol glycidyl ether or 1, 2-epoxy-5-hexene.
Preferably, the catalyst is chloroplatinic acid, carbene alkane, tetrakis (triphenylphosphine) rhodium hydride or aluminum trichloride.
Preferably, the polymerization inhibitor is 2, 6-di-tert-butyl-p-methylphenol, hydroquinone or p-hydroxyanisole.
Preferably, the light-cured resin is one or more of bisphenol A epoxy diacrylate, epoxy soybean oil acrylate, aromatic polyether urethane diacrylate, aliphatic urethane triacrylate, aromatic polyether urethane triacrylate and aromatic urethane triacrylate.
Preferably, the photocurable monomer diluent is one or more of dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, 1, 4-butanediol diacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, butyl acrylate, hydroxyethyl methacrylate, and isobornyl acrylate.
Preferably, the amine curing agent is SM208, 6216, H-113D, or 593E.
Preferably, the photoinitiator is one or more of 184, 1173, TPO, 907, 810, 250 and 160.
Preferably, the leveling agent is EFKA3777, BYK306, BYK333 or dyhi 450.
Preferably, the solvent is one or more of ethyl acetate, butyl acetate, butanone, methyl isobutyl ketone, propylene glycol methyl ether acetate and propylene glycol butyl ether.
A preparation method of a dual-curing vacuum coating primer specifically comprises the following specific steps:
the following operations were all carried out in a dark room,
(1) pretreating a plastic molded part of the automobile lamp;
(2) uniformly mixing the dual cure primer component of claim 1 for use;
(3) coating the surface of the plastic molded part of the automobile lamp pretreated in the step (1) with the dual-curing primer prepared in the step (2), pre-drying at 50-80 ℃ for 5-15min, placing under a UV lamp, and curing energy reaching 500-2000mJ/cm2And then thermally curing at 80-120 ℃ for 1-3h, controlling the final dry film thickness to be 10-30 mu m, and then carrying out vacuum coating primer.
The invention has the following beneficial effects:
(1) the invention provides a preparation method of a dual-curing vacuum coating primer, which adopts acrylic monomers and epoxy vinyl monomers to modify organic silicon resin as main bodies. The adopted modified organic silicon resin has higher heat resistance; secondly, the epoxy structure has good adhesive force with the base material and the coating; third, the presence of the acrylate structure gives the primer the possibility of UV curing. Making it play an important advantage in light (UV) -heat dual cure systems.
(2) The invention provides a preparation method of a dual-curing vacuum coating primer, which adopts photocuring resin and photocuring monomer diluent which are firstly used as crosslinking points in a primer system and can provide the functions of strengthening and toughening; secondly, according to different requirements, corresponding hard sections and soft sections are matched, and comprehensive performance is improved; thirdly, the photo-curing monomer diluent provides higher reactivity and simultaneously can adjust the viscosity of the system, thereby facilitating construction.
(3) The invention provides a preparation method of a dual-curing vacuum coating primer, wherein a photoinitiator is used as an important component of a photocuring coating to provide a reaction active center; in addition, the free radical photoinitiator and the cationic photoinitiator are matched in the selected photoinitiator, so that oxygen inhibition and efficient photocuring can be overcome in the reaction process, the acrylate structure and the epoxy group are both input into a molecular chain in a chemical bond mode, and the comprehensive performance of the primer is improved.
(4) The invention provides a preparation method of a dual-curing vacuum coating primer, under the heating condition, an amine curing agent and an epoxy group can be rapidly cured, and meanwhile, the structure of acrylic ester can also be subjected to addition reaction, so that the coating primer with excellent comprehensive performance can be finally obtained.
(5) The invention provides a preparation method of a dual-curing vacuum coating primer, which is added with a leveling agent and a solvent, and aims to achieve a good leveling effect of the primer and a good mirror surface effect after vacuum plating.
(6) The invention provides a dual-curing vacuum coating primer, which can be respectively subjected to light (UV) -heat dual curing and can also be subjected to heating deep-setting curing after UV curing. The paint has excellent adhesive force and heat resistance, is efficient and energy-saving in the construction process, and is particularly suitable for large-scale popularization and use.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Example 1
The dual-curing vacuum coating primer comprises the following raw materials in parts by weight:
dual cure silicone resin matrix: 60 parts;
light-curing resin: 0 part of (C);
photo-curable monomer diluent: 20 parts of a light-cured monomer diluent consisting of trimethylolpropane triacrylate, tripropylene glycol diacrylate and butyl acrylate according to the mass ratio of 2:3: 3;
amine curing agent: 593E 15 parts;
photoinitiator (2): 184 and 810 by mass ratio of 2: 32;
leveling agent: 1 part;
solvent: 10 parts.
Examples 2-6, otherwise identical to example 1, differ as set forth in the following table:
the dual cure silicone resins used in examples 1-6 above were prepared by the following method:
(1) 1 part of hydrogen-terminated siloxane was dissolved in 80 parts of tetrahydrofuran, and 0.3 part of trimethylolpropane triacrylate, 1 wt% of 2, 6-di-t-butyl-p-methylphenol, 10 wt% were added-5Dissolving chloroplatinic acid in 10 parts of tetrahydrofuran, adding into a constant pressure dropping funnel, controlling the dropping speed, stirring, reacting at 70 ℃ for 5 hours, distilling under reduced pressure to remove the solvent, adding 50 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3 hours, separating the water phase, taking the organic layer, distilling under reduced pressure to remove the solvent to obtain the single-end hydrogen-containing polysiloxane (IR: 1644 cm)-1、813cm-1: -C ═ C — disappearance), noted a;
the using amount of the 2, 6-di-tert-butyl-p-methylphenol is 1 wt% of the mass of the trimethylolpropane triacrylate.
(2) Dissolving 1 part of A in 80 parts of tetrahydrofuran, and mixing 2.1 parts of glycidyl methacrylate, 1 wt% of 2, 6-di-tert-butyl-p-methylphenol, and 10 parts of-5Dissolving chloroplatinic acid in 10 parts of tetrahydrofuran, adding into a constant pressure dropping funnel, controlling the dropping speed, stirring, reacting at 70 ℃ for 5 hours, distilling under reduced pressure to remove the solvent, adding 50 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3 hours, separating the water phase, taking the organic layer, distilling under reduced pressure to remove the solvent to obtain the bifunctional epoxy-terminated hydrogenpolysiloxane (IR: 1641 cm)-1、811cm-1: -C ═ C — disappearance; 911cm-1: epoxy group present), as B;
the using amount of the 2, 6-di-tert-butyl-p-methylphenol is 1 wt% of the mass of the glycidyl methacrylate.
(3) Dissolving 1 part of B in 80 parts of tetrahydrofuran, and dissolving 1.2 parts of trimethylolpropane triacrylate, 1 wt% of 2, 6-di-tert-butyl-p-methylphenol, 10 wt% of-5Dissolving chloroplatinic acid in 10 parts of tetrahydrofuran, adding into a constant pressure dropping funnel, controlling the dropping speed, stirring, reacting at 70 ℃ for 5 hours, distilling under reduced pressure to remove the solvent, adding 50 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3 hours, separating the water phase, taking the organic layer, distilling under reduced pressure to remove the solvent to obtain a target product (IR: 1635 cm)-1、811cm-1: -C ═ C-is present; 911cm-1: epoxy group present), noted C;
the using amount of the 2, 6-di-tert-butyl-p-methylphenol is 1 wt% of the mass of the trimethylolpropane triacrylate.
The primer is prepared by using the formula for vacuum coating of the dual-curing car lamp obtained in the specific example 1.
Application example 1
A preparation method of a dual-curing vacuum coating primer specifically comprises the following specific steps:
the following operations were all carried out in a dark room,
(1) pretreating a plastic molded part of the automobile lamp;
(2) uniformly mixing the dual cure primer component of claim 1 for use;
(3) coating the surface of the plastic molded part of the automobile lamp pretreated in the step (1) with the dual-curing primer prepared in the step (2), prebaking at 80 ℃ for 5min, placing under a UV lamp, and curing energy reaching 2000mJ/cm2And then thermally curing at 80 ℃ for 1h, and controlling the thickness of the final dry film to be 30 mu m, thus obtaining the vacuum coating primer.
Application examples 2 to 4 were the same as application example 1 except that the following table was used
Comparative examples 1 to 5 are all compared with example 1, with the following differences:
comparative example 1
The vacuum coating primer for the car lamp comprises the following raw materials in parts by weight:
common silicone resin matrix: 60 parts;
light-curing resin: 0 part of (C);
photo-curable monomer diluent: 20 parts of a light-cured monomer diluent consisting of trimethylolpropane triacrylate, tripropylene glycol diacrylate and butyl acrylate according to the mass ratio of 2:3: 3;
amine curing agent: 593E 15 parts;
photoinitiator (2): 184 and 810 by mass ratio of 2: 32;
leveling agent: 1 part;
solvent: 10 parts.
A preparation method of a dual-curing vacuum coating primer is used for performing dual curing according to the parameters of application example 1.
Comparative example 2
The dual-curing vacuum coating primer comprises the following raw materials in parts by weight:
dual cure silicone resin matrix: 60 parts;
light-curing resin: 0 part of (C);
photo-curable monomer diluent: 20 parts of a light-cured monomer diluent consisting of trimethylolpropane triacrylate, tripropylene glycol diacrylate and butyl acrylate according to the mass ratio of 2:3: 3;
amine curing agent: 593E 15 parts;
photoinitiator (2): 184 and 810 by mass ratio of 2: 32;
leveling agent: 1 part;
solvent: 10 parts.
A preparation method of a dual-curing vacuum coating primer specifically comprises the following specific steps:
the following operations were all carried out in a dark room,
(1) pretreating a plastic molded part of the automobile lamp;
(2) uniformly mixing the dual cure primer component of claim 1 for use;
(3) coating the surface of the plastic molded part of the automobile lamp pretreated in the step (1) with the dual-curing primer prepared in the step (2), prebaking at 80 ℃ for 5min, placing under a UV lamp, and curing energy reaching 2000mJ/cm2And ensuring the paint film to be dried completely, and controlling the thickness of the final dry film to be 30 mu m, thus being capable of carrying out vacuum coating priming paint.
Comparative example 3
The dual-curing vacuum coating primer comprises the following raw materials in parts by weight:
dual cure silicone resin matrix: 60 parts;
light-curing resin: 0 part of (C);
photo-curable monomer diluent: 20 parts of a light-cured monomer diluent consisting of trimethylolpropane triacrylate, tripropylene glycol diacrylate and butyl acrylate according to the mass ratio of 2:3: 3;
amine curing agent: 593E 15 parts;
photoinitiator (2): 184 and 810 by mass ratio of 2: 32;
leveling agent: 1 part;
solvent: 10 parts.
A preparation method of a dual-curing vacuum coating primer specifically comprises the following specific steps:
the following operations were all carried out in a dark room,
(1) pretreating a plastic molded part of the automobile lamp;
(2) uniformly mixing the dual cure primer component of claim 1 for use;
(3) and (3) coating the surface of the plastic molded part of the automobile lamp pretreated in the step (1) with the dual-curing primer prepared in the step (2), performing heat curing at 80 ℃ to ensure that a paint film is dried completely, and controlling the thickness of the final dry film to be 30 microns to perform vacuum coating of the primer.
Comparative example 4
The dual-curing vacuum coating primer comprises the following raw materials in parts by weight:
dual cure silicone resin matrix: 60 parts;
light-curing resin: 0 part of (C);
photo-curable monomer diluent: 20 parts of a light-cured monomer diluent consisting of trimethylolpropane triacrylate, tripropylene glycol diacrylate and butyl acrylate according to the mass ratio of 2:3: 3;
amine curing agent: 593E 15 parts;
photoinitiator (2): 184 and 810 by mass ratio of 2: 32;
leveling agent: 1 part;
solvent: 0 part of (A).
A preparation method of a dual-curing vacuum coating primer is used for performing dual curing according to the parameters of application example 1.
The primer coatings prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to a paint film property test after curing, and the test results are shown in Table 1.
TABLE 1
The test method comprises the following steps:
1) pencil hardness: pencil hardness was measured according to GB/T6739-2006 standard.
2) Adhesion force: the adhesion of the coating was tested by cross-hatch according to GB/T9286-1998.
3) Scratch resistance: the coating was fully cured and dried, and the scratch resistance of the coating surface was tested using a hand pencil hardness tester, a pencil with a hardness of H, a load of 250g force.
4) Wear resistance: the coating was fully cured and dried, tested using a multifunctional alcohol rubber rub tester, with a load of 1000 g.
5) Heat resistance: the panels were left to stand at 200 ℃ for 2 hours and heated, and the appearance of the paint film before and after heating was visually observed.
6) Appearance: level 5 is smooth and flat surface, high gloss, no color bleeding and no blistering; grade 1 is a severe coloration, loss of gloss or blistering.
7) Pencil hardness, adhesion, scratch resistance, abrasion resistance, heat resistance, appearance, UV curing efficiency, heat curing efficiency: 1 is worst and 5 is optimal.
As can be seen from the test results in Table 1, the photo-thermal cured primer for vacuum coating of the dual-cured automobile lamp prepared in the examples 1-6 of the present invention has the advantages of obvious heat resistance, appearance, curing efficiency, etc., and has good comprehensive properties, while the properties of the primer coating are reduced to different degrees in the comparative examples 1-4 with the changes of the formula system and the curing process.
In addition, according to the performance indexes such as appearance, wear resistance, scratch resistance, hardness and the like, the double-curing coating does not exclude the possibility of application in the vacuum coating finish paint.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The dual-curing vacuum coating primer is characterized in that: the composite material comprises the following raw materials in parts by weight:
dual cure silicone resin matrix: 30-60 parts;
light-curing resin: 0-20 parts of a solvent;
photo-curable monomer diluent: 10-20 parts;
amine curing agent: 0-15 parts;
photoinitiator (2): 2-10 parts;
leveling agent: 0-1 part;
solvent: 10-30 parts.
2. The dual cure vacuum coating primer according to claim 1, wherein: the dual-curing organic silicon resin matrix is prepared by the following method, and the following reactions are carried out to prepare the materials according to the mole parts of functional groups:
(1) dissolving 1 part of hydrogen-containing double-end siloxane in 80 parts of tetrahydrofuran, and mixing 0.3-0.4 part of trifunctional acrylate, 1 wt% of polymerization inhibitor and 10 parts of-5Dissolving the catalyst in 10 parts of tetrahydrofuran, adding the tetrahydrofuran into a constant-pressure dropping funnel, controlling the dropping speed, stirring, reacting at 70-120 ℃ for 4-5 hours, distilling under reduced pressure to remove the solvent, adding 50 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3 hours, separating a water phase, taking an organic layer, distilling under reduced pressure to remove the solvent to obtain the trifunctional single-end hydrogenpolysiloxane, and marking as A;
the amount of the polymerization inhibitor is 1 wt% of the mass of the trifunctional acrylate;
(2) dissolving 1 part of A in 80 parts of tetrahydrofuran, and mixing 2-2.1 parts of epoxy alkene, 1 wt% of polymerization inhibitor and 10 parts of-5Dissolving the catalyst in 10 parts of tetrahydrofuran, adding the tetrahydrofuran into a constant-pressure dropping funnel, controlling the dropping speed, stirring, reacting at 70-120 ℃ for 4-5 hours, distilling under reduced pressure to remove the solvent, adding 50 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3 hours, separating a water phase, taking an organic layer, distilling under reduced pressure to remove the solvent to obtain the trifunctional single-end hydrogenpolysiloxane, and marking as B;
the amount of the polymerization inhibitor is 1 wt% of the mass of the epoxy alkene;
(3) dissolving 1 part of B in 80 parts of tetrahydrofuran, and dissolving 1-1.2 parts of trifunctional acrylate, 1 wt% of polymerization inhibitor and 10 parts of-5Dissolving catalyst in 10 portions of tetrahydrofuran, adding the mixture into a constant pressure dropping funnel, controlling the dropping speed, stirring, and reacting at 70-120 DEG CAfter 4-5h, distilling under reduced pressure to remove the solvent, adding 50 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3h, separating a water phase, taking an organic layer, distilling under reduced pressure to remove the solvent to obtain a target product, and recording as C;
the amount of the polymerization inhibitor is 1 wt% of the mass of the trifunctional acrylate.
3. The dual cure vacuum coating primer according to claim 2, wherein: the trifunctional acrylate is trimethylolpropane triacrylate, ethoxytrimethylolpropane triacrylate, propoxytrimethylolpropane triacrylate or pentaerythritol triacrylate; the epoxy alkene is glycidyl methacrylate, allyl glycidyl ether, cardanol glycidyl ether or 1, 2-epoxy-5-hexene; the catalyst is chloroplatinic acid, carbene alkane, hydrogenated tetrakis (triphenylphosphine) rhodium or aluminum trichloride; the polymerization inhibitor is 2, 6-di-tert-butyl-p-methylphenol, hydroquinone or p-hydroxyanisole.
4. The dual cure vacuum coating primer according to claim 1, wherein: the light-cured resin is one or more of bisphenol A epoxy diacrylate, epoxy soybean oil acrylate, aromatic polyether urethane diacrylate, aliphatic urethane triacrylate, aromatic polyether urethane triacrylate and aromatic urethane triacrylate.
5. The dual cure vacuum coating primer according to claim 1, wherein: the light-cured monomer diluent is one or more of dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, 1, 4-butanediol diacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, butyl acrylate, hydroxyethyl methacrylate and isobornyl acrylate.
6. The dual cure vacuum coating primer according to claim 1, wherein: the amine curing agent is SM208, 6216, H-113D or 593E.
7. The dual cure vacuum coating primer according to claim 1, wherein: the photoinitiator is one or more of 184, 1173, TPO, 907, 810, 250 and 160.
8. The dual cure vacuum coating primer according to claim 1, wherein: the leveling agent is EFKA3777, BYK306, BYK333 or Digao 450.
9. The dual cure vacuum coating primer according to claim 1, wherein: the solvent is one or more of ethyl acetate, butyl acetate, butanone, methyl isobutyl ketone, propylene glycol methyl ether acetate and propylene glycol butyl ether.
10. A preparation method of a dual-curing vacuum coating primer specifically comprises the following specific steps:
the following operations were all carried out in a dark room,
(1) pretreating a plastic molded part of the automobile lamp;
(2) uniformly mixing the dual cure primer component of claim 1 for use;
(3) coating the surface of the plastic molded part of the automobile lamp pretreated in the step (1) with the dual-curing primer prepared in the step (2), pre-drying at 50-80 ℃ for 5-15min, placing under a UV lamp, and curing energy reaching 500-2000mJ/cm2And then thermally curing at 80-120 ℃ for 1-3h, controlling the final dry film thickness to be 10-30 mu m, and then carrying out vacuum coating primer.
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