CN114773987A - Stretchable UV hardening liquid for automobile decoration film and preparation method of hardened PC (polycarbonate) using stretchable UV hardening liquid - Google Patents
Stretchable UV hardening liquid for automobile decoration film and preparation method of hardened PC (polycarbonate) using stretchable UV hardening liquid Download PDFInfo
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- 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
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Abstract
The application relates to the field of UV (ultraviolet) coatings, and particularly discloses a stretchable UV hardening liquid for an automobile decoration film and a preparation method of hardened PC (polycarbonate) using the stretchable UV hardening liquid. A stretchable UV hardening liquid for an automobile decoration film comprises the following substances in parts by weight: 50-80 parts of modified hydroxyl acrylic resin, 30-40 parts of curing agent, 20-30 parts of light curing monomer containing hydroxyl, 0.3-0.8 part of drier, 5-10 parts of wear-resistant material, 1-3 parts of fluorine-containing auxiliary agent, 0.5-2 parts of ultraviolet absorbent, 5-7 parts of photoinitiator, 0.5-1 part of antioxidant, 0.2-0.5 part of dispersing agent and 3-5 parts of toughening agent, wherein the wear-resistant material is a nano-scale wear-resistant material. The hardened PC can be used for automotive interiors, household appliance panels, 3C products and the like, and has the advantages of good wear resistance and difficulty in cracking.
Description
Technical Field
The application relates to the field of UV coatings, in particular to a stretchable UV hardening liquid for an automobile decoration film and a preparation method of hardened PC (polycarbonate) using the stretchable UV hardening liquid.
Background
The PC sheet has good light transmittance, low haze and good forming performance, and is widely used in the fields of automobile interiors, household appliance panels, 3C product shells and the like. But the PC has lower hardness and is easily scratched and rubbed to cause damage in the using process.
In order to improve the surface wear resistance of parts made of PC materials, a hardened coating is generally coated on the surface of a PC sheet, and after the coating is cured by means of thermal curing or light curing, a wear-resistant layer with excellent wear resistance is formed on the surface of the PC sheet, so that the possibility that the PC material is scratched in the using process is reduced.
In view of the above-mentioned related technologies, the inventors believe that the conventional hardened coating, after being cured, imparts good hardness to the surface, but the wear-resistant layer is more likely to crack during PC stretch forming due to the subsequent need of treatments such as stretch forming, i.e., the hardened film formed by the hardened coating has a defect of poor toughness.
Disclosure of Invention
In order to overcome the defects that a hardened film formed by a hardened coating has poor toughness and is easy to crack, the application provides a stretchable UV hardening liquid for an automobile decoration film and a preparation method of hardened PC (polycarbonate) using the stretchable UV hardening liquid.
In a first aspect, the application provides a stretchable UV hardening liquid for an automobile decoration film, which adopts the following technical scheme:
a stretchable UV hardening liquid for an automobile decoration film comprises the following substances in parts by weight: 50-80 parts of modified hydroxyl acrylic resin, 30-40 parts of a curing agent, 20-30 parts of a hydroxyl-containing photocuring monomer, 0.3-0.8 part of a drier, 5-10 parts of a wear-resistant material, 1-3 parts of a fluorine-containing auxiliary agent, 0.5-2 parts of an ultraviolet absorbent, 5-7 parts of a photoinitiator, 0.5-1 part of an antioxidant, 0.2-0.5 part of a dispersant and 3-5 parts of a toughening agent, wherein the wear-resistant material is a nanoscale wear-resistant material, and the curing agent comprises poly-isophorone diisocyanate.
By adopting the technical scheme, firstly, the modified hydroxy acrylic resin is adopted as the main component of the hardening liquid, the hydroxyl on the hydroxy acrylic chain segment and the poly isophorone diisocyanate are subjected to crosslinking reaction in a thermosetting mode to form a polyurethane acrylate structure, the hardness of the hardened film can be effectively improved through the crosslinking structure, and the toughness of the hardened film is improved due to the good toughness of the polyurethane, so that the hardened film obtains excellent toughness and hardness.
Secondly, a hydroxyl-containing photocuring monomer is added into the hardening liquid, the polyisophorone diisocyanate can perform a grafting reaction with hydroxyl, the photocuring monomer is grafted on a chain segment of polyurethane, and an organic monomer with better toughness is formed, so that the hardening liquid forms a dual curing system of thermocuring and photocuring, the cured film can obtain excellent surface drying performance after thermosetting, and after hot stretching and UV photocuring, the crosslinking curing can be further realized, the hardness of the cured film is improved, and the possibility of cracking of the cured film is reduced.
And finally, the nano-scale wear-resistant material and the fluorine-containing auxiliary agent are added into the hardening liquid for matching, so that the surface hardness of the hardened film is improved, and meanwhile, the nano-scale wear-resistant material can be uniformly dispersed in the hardening liquid due to small particle size, so that the hardness and the wear resistance of the hardened film can be uniformly improved.
Preferably, the modified hydroxy acrylic resin is a mixture comprising a low molecular weight hydroxy acrylic resin and an ultrahigh molecular weight hydroxy acrylic resin, and the solid hydroxyl of the modified hydroxy acrylic resin is 60 to 80.
By adopting the technical scheme, the low-molecular-weight hydroxyl acrylic resin and the ultrahigh-molecular-weight hydroxyl acrylic resin are adopted in the technical scheme, and the cross-linking density of the low-molecular-weight hydroxyl acrylic resin after cross-linking is higher, while the cross-linking density of the ultrahigh-molecular-weight hydroxyl acrylic resin is lower, and the low-molecular-weight hydroxyl acrylic resin and the ultrahigh-molecular-weight hydroxyl acrylic resin are matched with each other, so that the cross-linking density of the hardening liquid during thermal curing can be effectively adjusted, the hardness of a hardening film formed by the hardening liquid is improved, the toughness of the hardening film can be improved, and the possibility of cracking of the hardening film is reduced.
Secondly, the hardening liquid needs to be subjected to secondary curing through thermal curing and photo-curing, and after the thermal curing, a photo-curing monomer in the middle of the hardening liquid remains and does not participate in the reaction, so that the ultrahigh molecular weight hydroxy acrylic resin in the hardening liquid can form a support framework in the hardening liquid, plays a role in supporting a cured film formed through the thermal curing, and effectively improves the initial mechanical strength of the cured film.
Preferably, the hydroxyl-containing photocurable monomer comprises one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and pentaerythritol triacrylate.
By adopting the technical scheme, the acrylic acid photocuring monomer containing hydroxyl is preferably adopted in the technical scheme, the photocuring monomer is grafted on the molecular chain segment in the hardening liquid through crosslinking grafting between the hydroxyl and the polyisophorone diisocyanate, and meanwhile, the acrylic chain segment can promote the compatibility and the dispersibility of the photocuring monomer containing hydroxyl in the hardening liquid, so that the hardening liquid can be uniformly and completely cured during UV curing, and the hardness of a hardened film is improved.
Preferably, the toughening agent comprises a liquid rubber comprising one or both of methacrylate (vinyl) terminated butadiene (VTB), butadiene-acrylonitrile (VTBNX).
Through adopting above-mentioned technical scheme, preferably adopted in this application technical scheme has added liquid rubber in the sclerosant, and liquid rubber can form interpenetrating network structure with the crosslinked structure in the sclerosant, because liquid rubber has the preferred viscoelasticity, consequently interpenetrating behind the network structure of wrapping up in the sclerosant, can further improve the toughness of the sclerosant film that the sclerosant formed.
Preferably, the drier is an organic metal salt catalyst, and the drier comprises one or more of butyltin dilaurate, stannous octoate and organic bismuth.
By adopting the technical scheme, the components of the drier are optimized, the crosslinking reaction between the poly-isophorone diisocyanate and the hydroxyl in the hardening liquid can be effectively promoted, the occurrence of crosslinking copolymerization is promoted, the film forming effect of the hardened film is promoted, the surface drying property of the formed hardened film is improved, and the hardened film obtains an excellent surface drying effect.
Preferably, the wear-resistant material comprises one or more of nano-alumina, nano-alumina dispersed slurry, nano-silicon nitride, nano-diamond, nano-glass powder and cage type Polysilsesquioxane (POSS).
By adopting the technical scheme, the components of the wear-resistant material are optimized in the technical scheme, the nano aluminum oxide has excellent mechanical property, wear resistance, thermal stability and the like, the hardness and the wear resistance of the hardened film can be effectively improved by adding the nano aluminum oxide into the hardening liquid, an even fine protruding structure can be formed on the surface of the hardened film, the hydrophobic effect of the hardened film can be improved, and the possibility that the hardened film is corroded by liquid is reduced.
Preferably, the wear-resistant material further comprises one or more of silicon carbide fiber, nano silicon dioxide, chitin nanocrystal and modified nano aluminum oxide, and the modified nano aluminum oxide is prepared by a supergravity method, calcination and ball milling.
Through adopting above-mentioned technical scheme, at first, add the carborundum fibre in wear-resisting material, the fibrous structure of carborundum fibre can be to carrying out the tractive between each component in the wear-resisting material, can form continuous wear-resisting structure in the hardening membrane, effectively improves the wear-resisting effect of hardening membrane. And the silicon carbide fiber can load the rest components in the wear-resistant material, so that the agglomeration among the nano-scale wear-resistant materials is damaged, and the dispersion effect of the wear-resistant material is further improved. In addition, the fiber structure of silicon carbide can pull the hardened film and can be matched with nano alumina, so that the toughness of the hardened film can be further improved.
Secondly, the chitin nanocrystalline is added into the wear-resistant material, and the chitin nanocrystalline not only has higher hardness and can improve the hardness of a hardened film; the chitin nanocrystalline also has better stability, and can improve the dispersion stability of the wear-resistant material in hardening liquid, so that the hardening film obtains uniform wear-resistant effect;
thirdly, adding the modified nano-alumina into the wear-resistant material, and optimizing the preparation steps of the modified nano-alumina so as to oxidize the modified nano-aluminaThe aluminum is gamma-Al2O3The crystal structure is adopted, random morphology is obtained, the dispersity of the modified nano aluminum oxide is improved, the combination effect between the wear-resistant material and other components in the hardening liquid is improved, and the hardness and wear-resistant effect of the hardened film are effectively improved.
Finally, the silicon carbide fiber, the nano silicon dioxide, the chitin nanocrystalline and the modified nano aluminum oxide are added into the wear-resistant material in a matched mode, the fiber structure can carry out interpenetration loading and connection on all components in the wear-resistant material, the possibility of agglomeration in the wear-resistant material is effectively damaged, the stability and the dispersity of the wear-resistant material can be improved due to the appropriate shape and crystal structure, and the hardened film can obtain uniform hardness and wear-resistant effect.
Preferably, the wear-resistant material is a wear-resistant material modified by a modifier, and the modifier comprises one or more of acrylic acid, a silane coupling agent and polypropylene oxide glycol (PPG).
By adopting the technical scheme, firstly, the wear-resistant material is wrapped by the acrylic acid and is partially grafted on the wear-resistant material, so that the dispersion effect of the wear-resistant material in the hardening liquid is effectively improved, and the film forming property of the hardening liquid is improved, thereby improving the hardness uniformity and the toughness of the formed hardening film.
Secondly, the silane coupling agent modifies the wear-resistant material, and can graft organic functional groups on the surface of the wear-resistant material, so that the adsorption effect of the wear-resistant material is reduced, the dispersion stability of the wear-resistant material in hardening liquid is improved, and the hardened film has uniform wear resistance.
In addition, the PPG modifies the wear-resistant material, can be grafted on the wear-resistant material, and effectively improves the compatibility between the wear-resistant material and hardening liquid, so that the hardening film can obtain a uniform wear-resistant effect.
And finally, the wear-resistant material is modified by matching acrylic acid, a silane coupling agent and polyoxypropylene glycol, and the compatibility of the wear-resistant material and hardening liquid can be improved by wrapping the wear-resistant material and grafting an organic functional group on the surface of the wear-resistant material, so that the hardened film can obtain a uniform wear-resistant effect.
Preferably, the polyisophorone diisocyanate is a trimer of IPDI; the fluorine-containing auxiliary agent comprises one or two of fluorine-containing photocuring monomer and fluorocarbon polymer; the initiator comprises one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and methyl benzoylformate; the ultraviolet absorbent comprises one or two of benzotriazoles and triazines; the antioxidant comprises one or two of high molecular weight hindered phenol antioxidant and phosphite antioxidant; the dispersing agent comprises one or two of BYK163, BYK110, BYK111, EFKA4061 and TTS.
By adopting the technical scheme, the technical scheme of the application optimizes the isophorone diisocyanate as the tripolymer of IPDI, improves the yellowing resistance effect of the hardening liquid, keeps the transparent effect of the hardened film, and improves the stability and the aging resistance effect of the hardened film through the matching of the isophorone diisocyanate, the antioxidant and the ultraviolet absorbent. By adding the dispersing agent, the dispersing effect among the components in the hardening liquid can be further improved, and the hardening film can obtain uniform wear resistance and toughness.
In a second aspect, the present application provides a preparation method of a hardened PC using the stretchable UV hardening liquid for an automobile decorative film, which adopts the following technical scheme:
a preparation method of hardened PC (polycarbonate) using the stretchable UV hardening liquid for the automobile decoration film comprises the following steps:
s1, preparation of resin liquid: taking the modified hydroxyl acrylic resin and butanone, and stirring and mixing to obtain a resin liquid;
s2, preparing wear-resistant liquid: taking a wear-resistant material, butanone and a dispersing agent, stirring, mixing and grinding, and controlling the grinding particle size to be less than or equal to 100nm to obtain a wear-resistant liquid;
s3, preparing a mixed solution: adding a hydroxyl light curing monomer, a fluorine-containing auxiliary agent, an ultraviolet absorbent, a photoinitiator, an antioxidant, a drier and a flexibilizer into the resin liquid, and stirring and dispersing to obtain an intermediate liquid; stirring and mixing the mixed solution and the wear-resistant solution, and shearing and dispersing to obtain a mixed solution;
s4, preparing hardening liquid: mixing butanone and isophorone diisocyanate, diluting, adding into the mixed solution, stirring at medium speed, controlling the stirring speed at 800r/min, and stirring for 15-30min to obtain a hardening liquid; s5, preparation of hardened PC: coating the hardening liquid on a PC sheet, drying, laminating, curing, stretching and shaping, and performing UV light curing to obtain the hardened PC.
By adopting the technical scheme, the thermosetting-UV curing dual curing system is adopted in the technical scheme, after thermosetting, the surface drying effect of the curing film formed by the hardening liquid is realized, the crosslinking density of the curing film is proper, the PC sheet can be stretched until the PC sheet is formed into a proper shape, and UV curing is continuously performed, so that the crosslinking degree of the curing film is improved, the hardness and the wear resistance of the curing film are enhanced, and the curing film obtains excellent wear resistance and toughness.
In summary, the present application has the following beneficial effects:
1. because the modified hydroxyl acrylic resin is adopted as the main component of the hardening liquid, the thermoplastic resin is introduced into the hardening liquid, and after the hardening liquid is initially solidified, a hardening film with better surface drying effect is obtained; meanwhile, the polyurethane can be crosslinked with the poly isophorone diisocyanate to obtain a polyurethane chain segment, so that the toughness of a hardened film is improved; adding a hydroxyl-containing light-cured monomer into the hardening liquid, and forming an organic chain segment grafted with the light-cured monomer in the hardening liquid to promote the hardening liquid to form a dual-curing system of thermal curing and light curing; before stretching, thermal curing is carried out in advance to enable the surface of the hardening liquid to be dry but part of the photo-curing monomer to be in a free state, at this time, the crosslinking density of a curing film formed by the hardening liquid is appropriate, the curing film is not easy to crack after stretching, and photo-curing is carried out after the stretching is finished to promote the crosslinking of the organic chain segment, so that the crosslinking density in the curing film is improved, and the wear resistance of the curing film is improved, therefore, the curing film formed by the hardening liquid obtains the effects of excellent toughness and wear resistance.
2. In the application, the high molecular weight hydroxyl acrylic resin and the ultrahigh molecular weight hydroxyl acrylic resin are preferably adopted to be matched, the solid hydroxyl content in the modified hydroxyl acrylic resin is adjusted, on one hand, the content of the crosslinking groups in the hardening liquid is optimized by adjusting the solid hydroxyl content, and the crosslinking density in the hardened film is optimized, so that the hardened film formed by the hardening liquid can obtain excellent toughness; on the other hand, the addition of the ultra-high molecular weight hydroxy acrylic resin forms a supporting skeleton in the hardening liquid, enables stretching of the cured film, and improves the hardness of the cured film.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples
Preparation example of modified Hydroxyacrylic resin solution
Preparation example 1
60kg of hydroxyl acrylic resin with the mark of ACR6580 and 10kg of hydroxyl acrylic resin with the mark of BM268 are respectively stirred and mixed to obtain the modified hydroxyl acrylic resin.
Example of preparation of siccative
Preparation example 2
1kg of butyltin dilaurate, designated T12, was used as a drier.
Among them, it is worth mentioning that the siccative includes but is not limited to: butyl tin dilaurate, stannous octoate, and organic bismuth.
Preparation of hydroxyl group-containing Photocurable monomer
Preparation example 3
40kg of pentaerythritol triacrylate (PETA) was taken as the hydroxyl-containing photocurable monomer.
Among them, it is worth mentioning that the hydroxyl group-containing photocurable monomer includes, but is not limited to: any one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and pentaerythritol triacrylate.
Examples of preparation of toughening Agents
Preparation example 4
6kg of VTBNX with the trade name Hypro1300X33LC was taken as toughening agent.
Wherein, it is worth to state that the toughening agent comprises liquid rubber, and the liquid rubber comprises any one or the combination of more of VTB with the mark of Hypro, VTBNX with the mark of Hypro1300X33LC, and VTBNX with the mark of Hypro1300X43 LC.
Preparation of fluorinated auxiliary
Preparation example 5
5kg of a fluorine-containing photo-curing monomer with the trademark of DSP730F is taken as a fluorine-containing auxiliary agent.
Of these, it is worth mentioning that the fluorine-containing photocurable monomer includes, but is not limited to: any one or combination of more of fluorine-containing light-cured monomer with the mark of 3700A, fluorine-containing light-cured monomer with the mark of DAC-HP, fluorine-containing light-cured monomer with the mark of DSP730F and fluorine-containing light-cured monomer with the mark of HY-1203.
Examples of preparation of initiators
Preparation example 6
5kg of 1-hydroxycyclohexyl phenyl ketone, type IGM184, and 1kg of TPO (2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide) photoinitiator were stirred and mixed to obtain the initiator.
Of these, it is worth mentioning that the initiator includes but is not limited to: 1-hydroxycyclohexyl phenyl ketone, TPO, methyl benzoylformate or a combination thereof.
Preparation of ultraviolet absorber
Preparation example 7
5kg of a benzotriazole type ultraviolet absorber having a brand number of Basff TINUVIN 1130 was used as the ultraviolet absorber.
Among them, it is worth mentioning that the ultraviolet absorbers include, but are not limited to: one or more of benzotriazole type ultraviolet absorbent such as basf TINUVIN 1130 and triazine type ultraviolet absorbent such as basf TINUVIN 400.
Preparation example of antioxidant
Preparation example 8
5kg of a high molecular weight hindered phenol antioxidant having a grade of BASF 1010 and 5kg of a phosphite antioxidant having a grade of BASF 168 were mixed under stirring to serve as antioxidants.
Among them, it is worth mentioning that antioxidants include, but are not limited to: high molecular weight hindered phenolic antioxidants such as basf 1010, phosphite antioxidants such as basf 168.
Preparation example of dispersant
Preparation example 9
5kg of titanate coupling agent TTS is taken as a dispersing agent.
Of these, it is worth mentioning that dispersants include, but are not limited to: BYK163, BYK110, BYK111, EFKA4061, TTS.
Preparation example 10
30kg of a polyisocyanate having the trade name Bayer desmodur4470 were taken.
Examples of production of abrasion resistant Material
Preparation examples 11 to 16
Respectively taking VK-L30S type nano-alumina, silicon carbide fiber, chitin nanocrystal, modified alumina and nano-silica, wherein the specific mass is shown in Table 1, and stirring and mixing to obtain 1-6 wear-resistant materials.
The preparation method of the modified alumina comprises the following steps: mixing flowing aluminum chloride, ethanol and water to prepare an aluminum salt solution with the concentration of 0.8 mol/L; stirring ammonia water, ethanol and water for 30min to obtain 4mol/L alkali liquor; adding an aluminum salt solution and an alkali liquor into a supergravity reactor together, reacting for 5min at the rotating speed of 2000rpm to obtain a suspension, filtering, retaining a filter cake, washing for 5 times by using ethanol, drying for 10h at 80 ℃, calcining at 500 ℃, performing ball milling dispersion at a ball-to-material ratio of 15:1, and performing ball milling for 10h to obtain the modified alumina.
Among these, anti-wear agents include, but are not limited to: any one or combination of more of nano alumina, nano silicon nitride, nano diamond, nano glass powder, POSS, silicon carbide fiber, chitin nanocrystal, modified alumina and nano silicon dioxide.
TABLE 1 PREPARATION EXAMPLES 11 to 16 composition of abrasion resistant materials
Examples of preparation of modifier
Preparation examples 17 to 20
Respectively taking acrylic acid, a silane coupling agent KH560, PPG, Toluene Diisocyanate (TDI) and dibutyl tin dilaurate, wherein the specific mass is shown in Table 2.
TABLE 2 PREPARATION EXAMPLES 16 to 19 COMPOSITION OF WEAR-RESISTANT MATERIAL
Preparation example 21
And (3) stirring and mixing the modifier 1 and the wear-resistant material 1, filtering, and retaining solids to obtain the wear-resistant material 1 subjected to modification treatment.
Preparation example 22
The difference from preparation 21 is that: modified abrasion-resistant material 2 was prepared by using modifier 2 in place of modifier 1 in preparation example 21.
Preparation example 23
The difference from preparation 21 is that: stirring and mixing the wear-resistant material 1, TDI in the modifier 3 and 100kg of toluene, ultrasonically oscillating and dispersing for 30min, heating to 60 ℃, adding dibutyl tin dilaurate, heating to 65 ℃, reacting for 2h, adding PPG, heating to 75 ℃, continuing to react for 2h, centrifuging, retaining solids, washing with acetone for 3 times, vacuum drying for 2h, extracting with acetone, and drying to obtain a dried substance, namely the wear-resistant material 3 subjected to modification treatment.
Preparation example 24
The difference from preparation 23 is that: and mixing the dried substance with the rest components in the modifier 4, filtering and drying to obtain the wear-resistant material 4 subjected to modification treatment.
Preparation example 25
The difference from preparation 24 is that: a wear-resistant material 5 subjected to modification treatment was prepared by using the wear-resistant material 5 instead of the wear-resistant material 1 in preparation example 24.
Preparation example 26
The difference from preparation 23 is that: a wear-resistant material 6 was prepared by using the wear-resistant material 6 in place of the wear-resistant material 1 in preparation example 23.
Examples
Examples 1 to 6
In one aspect, the present application provides a stretchable UV hardening liquid for an automobile decoration film, including the following: the modified hydroxyl acrylic resin is characterized by comprising modified hydroxyl acrylic resin, a hydroxyl-containing photocuring monomer, a drier, a wear-resistant material, a fluorine-containing auxiliary agent, an ultraviolet absorber, a curing agent, a photoinitiator, an antioxidant, a dispersant and a toughening agent, wherein the wear-resistant material is a nano-scale wear-resistant material, the curing agent is isophorone diisocyanate, and the specific mass is shown in Table 3.
In another aspect, the present application provides a method for preparing hardened PC using a stretchable UV hardening liquid for an automotive decorative film, comprising the steps of:
preparing resin liquid: the hydroxy acrylic resin was dissolved in methyl ethyl ketone to form a resin solution with a solid content of 40%.
Preparing a wear-resistant liquid: uniformly mixing the wear-resistant material 1, butanone and a dispersing agent, and grinding by using a nano horizontal sand mill, wherein the grinding particle size is controlled to be less than or equal to 100nm to form the wear-resistant liquid.
Preparing a mixed solution: adding a hydroxyl light-cured monomer, a fluorine-containing auxiliary agent, an ultraviolet absorbent, a photoinitiator, an antioxidant, a drier and a toughening agent into the resin liquid, dispersing at a high speed of 1500r/min for 1-2h to obtain an intermediate liquid, stirring and mixing the mixed liquid and the wear-resistant liquid, and shearing and dispersing to obtain the mixed liquid.
Preparing a hardening liquid: previously adopting butanone to dilute the isophorone diisocyanate until the solid content is 40 percent to obtain a dilute solution, adding the dilute solution into the mixed solution, and performing dispersion treatment at 500r/min for 30min to obtain a hardening solution.
Preparation of hardened PC: taking a PC sheet with the thickness of 375 mu m, coating the hardening liquid on the surface of the PC sheet through a process such as an anilox roller, a comma roller, a slit and the like to set the target thickness to be 15 mu m, and drying in an oven to form a touch dry film layer on the surface of the PC. And (5) rolling the adhered protective film, and curing at 50 ℃ for 24h to obtain the stretch-hardening PC. And thermally stretching and shaping the stretch hardening PC, and irradiating by UV light to obtain the hardening PC 1-6.
Table 3 examples 1-6 hardening liquid compositions
Example 7
The difference from example 2 is that: dispersing at 650r/min for 20min to obtain hardening liquid, and preparing hardened PC 7.
Example 8
The difference from example 2 is that: dispersing at 800r/min for 15min to obtain hardening liquid, and preparing hardened PC 8.
Examples 9 to 13
The difference from example 2 is that: hardened PC9-13 was prepared using wear-resistant materials 2-6 instead of wear-resistant material 1 in example 2.
Examples 14 to 19
The difference from example 2 is that: hardened PC14-19 was prepared using the wear-resistant materials 1-6 after the modification treatment instead of the wear-resistant material 1 in example 2.
Comparative example
Comparative example 1
This comparative example is different from example 2 in that no hydroxyl group-containing photocurable monomer, photoinitiator, was added to prepare hardened PC 20.
Comparative example 2
This comparative example differs from example 3 in that no wear resistant material was added to this comparative example, and hardened PC21 was prepared.
Performance test
(1) And (3) hardness testing: curing the PC hardened film at 50 degrees for 48 hours, then irradiating and curing the cured PC hardened film by using 1000 mj/cm light excitation, and testing the hardness by using a pencil hardness meter after curing, wherein the testing conditions are as follows: 1000 g weight, Mitsubishi pencil, test speed 15 m/min. The test is carried out 3 times continuously, and the test is carried out again after any 1-time breaking, namely, reducing the pencil hardness.
(2) And (3) detecting the wear resistance: curing the PC hardened film at 50 ℃ for 48 hours, irradiating and curing the cured PC hardened film by using light excitation of 1000 mj/cm, and testing the cured PC hardened film by using a steel wire velvet friction testing machine under the test conditions: loading: 1000 g weight, grinding head: 2X 2cm, speed: 70 times/min.
(3) And (3) detecting stretchability: and curing the PC hardened film for 48 hours at 50 ℃, placing the cured film on a constant-temperature clamp for heating at 165 ℃, stretching the cured film for 200 percent after the PC film is softened, and observing whether cracks exist under a microscope after cooling.
TABLE 4 Performance test of examples 1 to 19 and comparative examples 1 to 2
Table 5 example 2 performance testing
Comparing the performance tests in table 4 and table 5, it can be found that:
(1) a comparison of examples 1-3, examples 4-6 and comparative examples 1-2 shows that: the hardness, wear resistance and tensile property of the hardened PC prepared in examples 1 to 6 are improved, which shows that the application adopts the special modified urethane acrylate prepolymer prepared by matching the poly-isophorone diisocyanate and the modified hydroxy acrylic resin, and the prepared hardened liquid not only has good hardness but also has good steel wool resistance by matching the special modified urethane acrylate prepolymer, the nano wear-resistant particles and the fluorine-containing additive, and the hardened PC film prepared by the hardened PC film has the advantages of scratch resistance, no cracking after stretching, elongation rate of more than 80% at normal temperature, elongation rate of 300% at high temperature, and good hardness and wear resistance. As can be seen from tables 4 and 5, the hardened PC obtained in example 2 is excellent in wear resistance and toughness, indicating that the respective component proportions in the hardened coating are suitable at this time.
(2) A comparison of examples 9 to 11, example 12, example 13 and example 2 shows that: the hardness, wear resistance and tensile property of the hardened PC prepared in embodiments 9 to 13 are improved, which indicates that the silicon carbide fiber, the nano-silica, the chitin nanocrystal and the modified nano-alumina are added to the wear-resistant material, so that on one hand, a fiber structure can be introduced into the hardened solution, the fiber structure can play a role of drawing in a hardened film, and the fiber structure can load other components in the wear-resistant material, so as to destroy the aggregation of the wear-resistant material, and improve the dispersion uniformity and stability of the wear-resistant material in the hardened solution; on the other hand, particles with proper appearance and proper crystal form are introduced into the hardening liquid, so that the agglomeration of the wear-resistant material is further destroyed, and the hardening film obtains uniform wear-resistant effect. As can be seen from Table 4, the hardened PC obtained in example 12 is excellent in wear resistance and toughness, indicating that the respective component proportions in the wear-resistant material are appropriate.
(3) A comparison of examples 14 to 16, example 17, example 18, example 19 and example 2 shows that: the hardness, wear resistance and tensile property of the hardened PC prepared in examples 14 to 19 are improved, which shows that the application adopts acrylic acid, silane coupling agent and PPG as modifiers, and can wrap and graft the wear-resistant material, effectively improve the compatibility of the wear-resistant material and the hardening liquid, and through the divergent crosslinking structure, effectively improve the suspension effect of the wear-resistant material in the hardening liquid pool, so that the hardened film further obtains a uniform wear-resistant effect. As can be seen from Table 4, the hardened PC obtained in example 2 is excellent in abrasion resistance and toughness, indicating that the respective component proportions in the hardened coating are appropriate at this time.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The stretchable UV hardening liquid for the automobile decoration film is characterized by comprising the following substances in parts by weight: 50-80 parts of modified hydroxyl acrylic resin, 30-40 parts of a curing agent, 20-30 parts of a light curing monomer containing hydroxyl, 0.3-0.8 part of a drier, 5-10 parts of a wear-resistant material, 1-3 parts of a fluorine-containing auxiliary agent, 0.5-2 parts of an ultraviolet absorbent, 5-7 parts of a photoinitiator, 0.5-1 part of an antioxidant, 0.2-0.5 part of a dispersing agent and 3-5 parts of a toughening agent, wherein the wear-resistant material is a nano-scale wear-resistant material, and the curing agent comprises poly isophorone diisocyanate.
2. The stretchable UV hardening liquid for automotive decorative films according to claim 1, wherein: the modified hydroxyl acrylic resin is a mixture comprising low-molecular-weight hydroxyl acrylic resin and ultrahigh-molecular-weight hydroxyl acrylic resin, and the solid hydroxyl of the modified hydroxyl acrylic resin is 60-80.
3. The stretchable UV hardening liquid for automotive decorative films according to claim 1, wherein: the light-cured monomer containing hydroxyl comprises one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and pentaerythritol triacrylate.
4. The stretchable UV hardening liquid for automotive decorative films according to claim 1, wherein: the toughening agent includes a liquid rubber that includes one or both of methacrylate (vinyl) terminated butadiene (VTB), butadiene-acrylonitrile (VTBNX).
5. The stretchable UV hardening liquid for automotive decorative films according to claim 1, wherein: the drier is an organic metal salt catalyst, and comprises one or more of butyltin dilaurate, stannous octoate and organic bismuth.
6. The stretchable UV hardening liquid for automotive decorative films according to claim 1, wherein: the wear-resistant material comprises one or more of nano-alumina, nano-alumina dispersion slurry, nano-silicon nitride, nano-diamond, nano-glass powder and cage type poly-half-time siloxane (POSS).
7. The stretchable UV hardening liquid for automotive decorative films according to claim 6, wherein: the wear-resistant material also comprises one or more of silicon carbide fiber, nano silicon dioxide, chitin nanocrystalline and modified nano alumina, and the modified nano alumina is prepared by a super-gravity method, calcination and ball milling.
8. The stretchable UV hardening liquid for automotive decorative films according to claim 6, wherein: the wear-resistant material is modified by a modifier, and the modifier comprises one or more of acrylic acid, a silane coupling agent and polypropylene oxide glycol (PPG).
9. The stretchable UV hardening liquid for automotive decorative films according to claim 1, wherein: the polyisophorone diisocyanate is trimer of IPDI;
the fluorine-containing auxiliary agent comprises one or two of fluorine-containing photocuring monomer and fluorocarbon polymer;
the initiator comprises one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and methyl benzoylformate;
the ultraviolet absorbent comprises one or two of benzotriazoles and triazines;
the antioxidant comprises one or two of high molecular weight hindered phenol antioxidant and phosphite antioxidant;
the dispersant comprises one or two of BYK163, BYK110, BYK111, EFKA4061 and TTS.
10. A method for preparing hardened PC using the stretchable UV hardening liquid for automotive decorative film according to any one of claims 1 to 9, comprising the steps of:
s1, preparation of resin liquid: taking the modified hydroxyl acrylic resin and butanone, and stirring and mixing to obtain a resin liquid;
s2, preparing wear-resistant liquid: taking a wear-resistant material, butanone and a dispersing agent, stirring, mixing and grinding, and controlling the grinding particle size to be less than or equal to 100nm to obtain a wear-resistant liquid;
s3, preparing a mixed solution: adding a hydroxyl light-cured monomer, a fluorine-containing auxiliary agent, an ultraviolet absorbent, a photoinitiator, an antioxidant, a drier and a toughening agent into the resin liquid, and stirring and dispersing to obtain an intermediate liquid; stirring and mixing the mixed solution and the wear-resistant solution, and shearing and dispersing to obtain a mixed solution;
s4, preparing hardening liquid: mixing butanone and isophorone diisocyanate, diluting, adding into the mixed solution, stirring at medium speed, controlling the stirring speed at 800r/min, and stirring for 15-30min to obtain a hardening liquid;
s5, preparation of hardened PC: coating the hardening liquid on a PC sheet, drying, laminating, curing, stretching and shaping, and carrying out UV light curing to obtain the hardened PC.
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