Uv-curable immersion coating matte varnish for tapes and method for its preparation

Abstract

The present application relates to a kind of UV-cured dip coating matt varnish on tape and its preparation method, including oligomer, functional active monomer, photoinitiator, extinction powder, adhesion promoter, surface auxiliary agent, the oligomer is by polyurethane acrylate, acrylate and nano SiO2 Composition, wherein polyurethane acrylate is by terminal hydroxyl polybutadiene, isocyanate, hydroxyethyl methacrylate, long alkyl structure acrylate, catalyst, polymerization inhibitor composition;Wherein acrylate is by hydroxypropyl acrylate, styrene, isodecyl acrylate, cyclohexyl methacrylate, isophorone diisocyanate, hydroxyethyl acrylamide, 1,4-dioxane, catalyst, polymerization inhibitor preparation.The present application is finally under the condition of thickness 15um, sand resistance reaches 50L, gloss is less than 20 °, completely odor after curing, and suitable for cold pressing process, good bending scratch resistance, and good tough performance.

Description

Technical Field

[0001] This invention belongs to the field of UV-curable coating preparation, and specifically relates to a UV-curable matte varnish for use on measuring tapes. Background Technology

[0002] Measuring tapes are common tools in daily life. As basic consumables in industries such as processing, manufacturing, building materials, and decoration, they have a huge and continuous consumer demand. Currently, the varnish used in printing and coating measuring tapes is water-based, which has been replaced by solvent-based varnishes in recent years due to environmental pressures. Although water-based varnishes are more environmentally friendly than solvent-based varnishes, solving the problem of large VOC emissions from solvent-based varnishes, they still require baking at high temperatures of over 200 degrees Celsius and still require exhaust gas treatment. This results in high energy consumption, cumbersome exhaust gas treatment, and no economic advantage.

[0003] Ultraviolet (UV) curing is the most widely used type of radiation curing technology. UV-curable varnishes can instantly react and form a film under UV light irradiation. They have the advantages of fast curing, low energy consumption, no exhaust gas treatment, and excellent economic value, making them significantly superior to water-based varnishes. However, there are currently no reports or patented technologies related to the application of UV-curable varnishes in measuring tapes.

[0004] UV curing technology primarily achieves matte finish by adding a large amount of matting powder. However, excessive addition of matting powder can lead to problems such as high viscosity, thickening, high thixotropy, poor coating performance, and unstable gloss. Patent CN202210823831.3 uses a photo-thermal dual curing method to create layering and displacement in the coating, forming an uneven surface to achieve matte finish. CN201710172765.7 synthesizes a matte resin with high viscosity. CN202110206727.5 utilizes the different shrinkage rates of monomers to achieve matte finish. Compared to existing technologies, this invention utilizes the principle of micro-immiscibility to synthesize a photocurable self-matte oligomer, which is very suitable for low-viscosity matte systems, and the synthesized oligomer has excellent adhesion. This invention specifically proposes a UV-curable dip-coating matte varnish, which can be applied to a measuring tape via dip-coating to achieve a coating effect with excellent performance in all aspects. Summary of the Invention

[0005] To address the issues of high energy consumption and low economic value in the coating process of measuring tapes, this invention specifically synthesizes a self-matting oligomer and discloses a photocurable matte varnish for use on measuring tapes and its preparation method.

[0006] The technical solution of this invention is: a UV-curable matte varnish for use on measuring tapes, comprising, by weight:

[0007]

[0008] The oligomer is 20-30 parts of polyurethane acrylate, 13-20 parts of acrylate, 0.1-0.3 parts of super dispersant and 0.5-1 part of nano-SiO2 by mass fraction;

[0009] The polyurethane acrylate is composed of isocyanate 11-18 parts, hydroxyl-terminated polybutadiene 75-99 parts, polymerization inhibitor 0.1-0.15 parts, catalyst 0.05-0.20 parts, hydroxyethyl methacrylate 7-15 parts, and long-alkyl-structure acrylate 23-35 parts by mass fraction.

[0010] The acrylate is composed of hydroxypropyl acrylate 15-25 parts, styrene 9-16 parts, isodecyl acrylate 13-22 parts, cyclohexyl methacrylate 20-30 parts, isophorone diisocyanate 25-43 parts, hydroxyethyl acrylamide 13-23 parts, 1,4-dioxane 30-40 parts, azobisisobutyronitrile and organic bismuth 0.5-1.5 parts, and p-hydroxyanisole 0.2-1.0 parts by mass fraction.

[0011] The polyurethane acrylate is prepared by slowly adding hydroxyl-terminated polybutadiene to long-alkyl-structure acrylate, isocyanate and polymerization inhibitor, controlling the temperature at 60-65℃ for 3h, then adding hydroxyethyl methacrylate and catalyst, and controlling the temperature at 75-78℃ for 3h.

[0012] The isocyanate is one or more of toluene diisocyanate, diphenylmethane isocyanate and isophorone diisocyanate; the hydroxyl-terminated polybutadiene has a number average molecular weight of 1500-3000g / mol; the long-alkyl-structure acrylate is one or more of isononyl acrylate, isodecyl acrylate, isooctyl acrylate and lauryl (meth) acrylate; the polymerization inhibitor is p-hydroxyanisole; and the catalyst is one or more of bisdimethylaminoethyl ether, dibutyltin dilaurate, organic bismuth and pentamethyldiethylenetriamine.

[0013] The acrylate is synthesized by slowly adding azobisisobutyronitrile to hydroxypropyl acrylate, styrene, isodecyl acrylate, cyclohexyl methacrylate and 1,4-dioxane under nitrogen protection, controlling the reaction temperature at 80℃ for 3h, then slowly adding isophorone diisocyanate and organic bismuth, polymerization inhibitor p-hydroxyanisole, and controlling the temperature at 60-65℃ for 3.5h, then adding hydroxyethyl acrylamide, increasing the temperature to 70-75℃ for 3h, and then increasing the temperature to 80℃ for 2h, and finally separating to obtain the required photo-curable acrylate.

[0014] The oligomer is prepared by mixing polyurethane acrylate, acrylate, nanosilica and hyperdispersant uniformly, and then reacting at 50 DEG C for 4 hours to obtain a photocuring oligomer with self-extinction effect.

[0015] The functional active monomer is one or more of ethoxylated trimethylolpropane triacrylate, 4-tert-butylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclotrimethylolpropane formal acrylate, 2-phenoxyethyl acrylate and 1,6-hexanediol diacrylate.

[0016] The photoinitiator is one or more of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide and methyl o-benzoylbenzoate.

[0017] The adhesion promoter is alkyl acrylate phosphate ester.

[0018] The surface aid is leveling agent and defoaming agent.

[0019] The preparation method of the ultraviolet curing dip-matt varnish for the tape measure comprises the following steps: preparing an oligomer, and then mixing and stirring the components uniformly.

[0020] Beneficial effects:

[0021] The ultraviolet curing dip-matt varnish prepared by the method can be creatively applied to the tape measure, can meet the construction process of the steel tape measure dip-matt, has a viscosity of 30-70 mpa.s at 25 DEG C, a sand resistance of greater than 50L, a gloss of less than 20 DEG, complete odor after curing, good cold-pressing scratch resistance, bending performance, good toughness, hardness, construction performance and other performances, and meets the requirements of the tape measure coating, and the tape measure has other excellent performances, compared with the traditional solvent type and water-based varnish, has the characteristics of low energy consumption, fast production speed, high economic value and the like. DETAILED DESCRIPTION

[0022] The preparation used in the application is only qualified industrial product, and is not limited to manufacturers, and is a conventional product on the market.

[0023] In the entire patent application, the following terms have the specified meanings:

[0024]

[0025]

[0026] A composition for light-cured dip-coating matt varnish on a tape measure, comprising an oligomer, a functional active monomer, a photoinitiator, a flatting powder, an adhesion promoter, a surface aid.

[0027] The oligomer is a product with self-extinction effect obtained by reacting polyurethane acrylate, acrylate, nano-silica and hyperdispersant at 50℃ for 4 hours, and the mass fraction of the components is: polyurethane acrylate 20-30; acrylate 13-20; nano-silica 0.5-1; and hyperdispersant 0.1-0.3, and the hyperdispersant is preferably CH10 of Shanghai Sanyezhi High Polymer Material.

[0028] The polyurethane acrylate is obtained by slowly adding hydroxyl-terminated polybutadiene to long-alkyl-structure acrylate, isocyanate and polymerization inhibitor, controlling the temperature at 60-65℃ for 3 hours, then adding hydroxyethyl methacrylate and catalyst, controlling the temperature at 75-78℃ for 3 hours, and the mass fraction of the components is: isocyanate 11-18; hydroxyl-terminated polybutadiene 75-99; polymerization inhibitor 0.1-0.15; catalyst 0.05-0.20; hydroxyethyl methacrylate 7-15; and long-alkyl-structure acrylate 23-35, the isocyanate is one or more of toluene diisocyanate, diphenylmethane isocyanate and isophorone diisocyanate, the hydroxyl-terminated polybutadiene has a number-average molecular weight of 1500-3000 g / mol, the long-alkyl-structure acrylate is one or more of isononyl acrylate, isodecyl acrylate, isooctyl acrylate and lauryl (methyl) acrylate, the polymerization inhibitor is p-hydroxytoluene, and the catalyst is one or more of bisdimethylaminoethyl ether, dibutyltin dilaurate, organic bismuth and pentamethyldiethylenetriamine.

[0029] The acrylate is synthesized by slowly adding catalyst azobisisobutyronitrile to hydroxypropyl acrylate, styrene, isodecyl acrylate, cyclohexyl methacrylate and 1,4-dioxane under nitrogen protection, controlling the reaction temperature at 80℃ for 3 hours, then slowly adding isophorone diisocyanate and catalyst organic bismuth under the condition of controlling the temperature at 60-65℃ for 3.5 hours, then adding hydroxyethyl acrylamide, increasing the temperature to 70-75℃ for 3 hours and then to 80℃ for 2 hours, and finally separating the light-cured acrylate, and the mass fraction of the components is: hydroxypropyl acrylate 15-25; styrene 9-16; isodecyl acrylate 13-22; cyclohexyl methacrylate 20-30; isophorone diisocyanate 25-43; hydroxyethyl acrylamide 13-23; 1,4-dioxane 30-40; catalyst 0.5-1.5; and polymerization inhibitor 0.2-1.0.

[0030] The functional active monomer is one or more of ethoxylated trimethylolpropane triacrylate, 4-tert-butylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclotrimethylolpropane formal acrylate, 2-phenoxyethyl acrylate, 1,6-hexanediol diacrylate.

[0031] The photoinitiator is one or more of 2-hydroxy-2-methylpropiophenone, 1- hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide, methyl o-benzoylbenzoate.

[0032] The adhesion promoter is alkyl acrylate phosphate, preferably PM1590 from Rhoplex.

[0033] The matting powder is one or more of Rhodia OK500, OK520, Grace Rad2105.

[0034] The surface agent is one or more of BYK333, Tego920, Tego432, BYK3510, BYK358N.

[0035] Example 1 Preparation of polyurethane acrylate

[0036] The polyurethane acrylate was synthesized according to the formulation in Table 1 below.

[0037]

[0038] The isocyanate, MEHQ, EM2192 were first added into the reactor, HTPB was added slowly, and the temperature was controlled in the range of 60-65°C, the reaction was carried out for 3h, then hydroxyethyl methacrylate and catalyst were added, the temperature was controlled at 75-78°C, the reaction was carried out for 3h, and the NCO was tested to be less than 1%, finally the polyurethane acrylate with a number average molecular weight of 2000-3500g / mol was obtained.

[0039] Example 2 Preparation of acrylate

[0040] The acrylate was synthesized according to the formulation in Table 2 below.

[0041]

[0042] The hydroxypropyl acrylate, styrene, isodecyl acrylate, cyclohexyl methacrylate, 1,4-dioxane is protected by nitrogen, the reaction temperature is controlled at 80°C, the catalyst azobisisobutyronitrile is slowly added dropwise for 3h, then the temperature is controlled at 60-65°C, isophorone diisocyanate and the catalyst organobismuth polymerization inhibitor p-hydroxyanisole are slowly added dropwise, and reacted for 3.5h, then hydroxyethyl acrylamide is added, the temperature is increased to 70-75°C, reacted for 3h, then the temperature is increased to 80°C, reacted for 2h, the isocyanate is less than 1%, and finally the light-cured acrylate is obtained by rotary separation.

[0043] Example 3: Preparation of light-cured self-extinction oligomer

[0044] The light-cured self-extinction oligomer is synthesized according to the following Table 3.

[0045] ZXG-1 ZXG-2 ZXG-3 ZXG-4 1 PUA-1 25.0 - 25.0 - 2 PUA-2 - 25.0 - 25.0 3 PA-1 15.0 15.0 - - 4 PA-2 - - 15.0 15.0 5 CH10 0.1 0.1 0.1 0.1 6 nano-SiO2 0.5 0.5 0.5 0.5

[0046] The polyurethane acrylate, acrylate, and hyperdispersant are first heated to 50°C, the nano-SiO2 is slowly added dropwise while controlling the temperature, dispersed and reacted for 4h to obtain the product. The obtained product is a micro-fog liquid, the viscosity at 25°C is 500-800mpa.s, when 3% of the light initiator is added and the paint film is scraped, the measured gloss is 5-9°.

[0047] Example 4: Preparation of UV-cured dip-coating matte varnish on tape

[0048] The UV-cured dip-coating matte varnish is configured according to the following Table 4.

[0049] 4-A 4-B 4-C 4-D 4-E 1 63608 50.0 - - - - 2 ZXG-1 - 50.0 - - - 3 ZXG-2 - - 50.0 - - 4 ZXG-3 - - - 50.0 - 5 ZXG-4 - - - - 50.0 6 TMP3EOTA 8.0 8.0 8.0 8.0 8.0 7 Rad2105 1.0 1.0 1.0 1.0 1.0 8 PM1590 5.0 5.0 5.0 5.0 5.0 9 PHEA 4.0 4.0 4.0 4.0 4.0 10 CTFA 14.0 14.0 14.0 14.0 14.0 11 TBCHA 13.0 13.0 13.0 13.0 13.0 12 819 1.5 1.5 1.5 1.5 1.5 13 MBF 3.0 3.0 3.0 3.0 3.0 14 Tego920 0.2 0.2 0.2 0.2 0.2 15 BYK333 0.1 0.1 0.1 0.1 0.1 16 BYK358N 0.2 0.2 0.2 0.2 0.2

[0050] Example 5: Test method and results

[0051] The dip-coating matte varnish on the tape is UV-cured, the curing energy of UVA is 500mj / cm 2 , and the test film thickness is 15um.

[0052]

[0053]

[0054] From the above data, it can be seen that the self-synthesized light-cured self-extinction oligomer has lower gloss and better adhesion than the commercially available self-extinction resin. Finally, the light-cured varnish adjusted by the self-synthesized light-cured extinction oligomer meets the coating requirements of the tape, which has good adhesion, low gloss, good toughness, and the wear and sand resistance performance reaches more than 50L, and the bending performance is good.

[0055] Example 6: Comparison of UV-cured varnish and water-based varnish

[0056] water-based gloss oil 4-B / C / D / E adhesion (crosshatch) OK OK coating effect OK OK sand abrasion resistance (L) 40 >50 gloss ° 20 13 pencil hardness 2H 4H 180° bend OK OK cold press OK OK

[0057] From the above data, it can be seen that the light-cured gloss oil has better sand washing and wear resistance and higher hardness than the water-based gloss oil, and the ultraviolet light curing has faster curing speed. The gloss oil developed by us has a curing time of less than 1s under the energy of 500mj / cm 2 , while the water-based gloss oil needs 220℃ for 2min and also needs related tail gas treatment. The ultraviolet light-cured gloss oil has very obvious advantages in curing efficiency, energy saving, coating performance, etc.

Claims

1. An ultraviolet light-cured dip-coated matte varnish for use on a tape measure, characterized in that, Composition by mass fraction: The oligomer is 20-30 parts of polyurethane acrylate, 13-20 parts of acrylate, 0.1-0.3 parts of super dispersant and 0.5-1 part of nano-SiO2 by mass fraction; the oligomer is prepared by mixing polyurethane acrylate, acrylate, nano-silica and super dispersant uniformly, and then reacting at 50℃ for 4 hours to obtain a light-cured oligomer with self-extinction effect; The polyurethane acrylate is prepared by slowly adding the hydroxyl-terminated polybutadiene to the long-alkyl-structure acrylate, isocyanate and polymerization inhibitor, controlling the temperature at 60-65℃ and reacting for 3h, then adding hydroxyethyl methacrylate and catalyst, controlling the temperature at 75-78℃ and reacting for 3h. The acrylate is prepared by slowly adding the hydroxyethyl methacrylate, catalyst, and polymerization inhibitor to the long-alkyl-structure acrylate, isocyanate, and polymerization inhibitor, controlling the temperature at 60-65℃ and reacting for 3h, then adding hydroxyethyl methacrylate and catalyst, controlling the temperature at 75-78℃ and reacting for 3h.

2. The ultraviolet light cured immersion varnish matte finish for tapes according to claim 1, wherein, The acrylate is prepared by slowly adding the hydroxyethyl methacrylate, catalyst, and polymerization inhibitor to the long-alkyl-structure acrylate, isocyanate, and polymerization inhibitor, controlling the temperature at 60-65℃ and reacting for 3h, then adding hydroxyethyl methacrylate and catalyst, controlling the temperature at 75-78℃ and reacting for 3h.

3. The ultraviolet light cured immersion varnish matte finish for tapes according to claim 1, wherein, The isocyanate is one or more of toluene diisocyanate, diphenylmethane isocyanate, and isophorone diisocyanate; the number average molecular weight of the hydroxyl-terminated polybutadiene is 1500-3000g / mol; the long-alkyl-structure acrylate is one or more of isononyl acrylate, isodecyl acrylate, isooctyl acrylate, and lauryl (meth) acrylate; the polymerization inhibitor is p-hydroxyanisole; and the catalyst is one or more of bisdimethylaminoethyl ether, dibutyltin dilaurate, organic bismuth, and pentamethyldiethylene triamine. The functional active monomer is one or more of ethoxylated trimethylolpropane triacrylate, 4-tert-butylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclotrimethylolpropane formal acrylate, 2-phenoxyethyl acrylate, and 1,6-hexanediol diacrylate.

4. The ultraviolet light cured immersion varnish matte finish for tapes according to claim 1, wherein, The photoinitiator is one or more of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, methyl o-benzoylbenzoate.

5. The ultraviolet light cured immersion varnish matte finish for tapes according to claim 1, wherein, The adhesion promoter is alkyl acrylate phosphate ester.

6. The ultraviolet light cured immersion varnish matte finish for tapes according to claim 1, wherein, The surface aid is leveling agent, defoaming agent.

7. The process for the preparation of an ultraviolet light-cured dip-coated matt varnish for tapes according to any one of claims 1 to 6, characterized in that, First, the oligomer is prepared, and then the components are mixed and stirred uniformly.

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