LED photocuring ink and its application

Abstract

The application relates to the field of glass inks, in particular to an LED light-cured ink oil and application thereof. The LED light-cured ink oil is prepared from the following raw materials in parts by weight: 65-90 parts of a monofunctional (methyl) acrylic fatty ester, 5-24 parts of a monofunctional (methyl) acrylic hydroxyl ester, 2-8 parts of a monofunctional (methyl) acrylic nitro ester and 2-4 parts of a photoinitiator. The ink prepared from the LED light-cured ink oil has a curing speed of only 3-5 seconds, the curing speed is fast, the production efficiency is greatly improved, VOC emission is reduced, and basically no ozone is generated; basically no organic matter is left during sintering and forming, and the ability of the glass to block ultraviolet rays is not affected.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of glass ink, in particular to an LED light-cured ink oil and application thereof. BACKGROUND

[0002] The automobile windshield glass is one of the important safety parts of the automobile, and has special performance requirements: moisture resistance, high temperature resistance, high pressure resistance, UV resistance, infrared resistance, high light transmittance and high safety. The preparation process of the automobile windshield glass is as follows: the raw sheet glass is cut to the designed size, edge grinding, cleaning, printing ink, drying the solvent, and then entering the high temperature tunnel furnace, pre-burning at 560-600℃ for 10-15min, and sintering at 650-750℃ for about 180s, cooling, slicing, laminating, and adding to dissolve and cure the glue sheet at 120-180℃. In the high temperature tunnel furnace, in order to ensure the stability of the sintering temperature, air is not pumped into the furnace. Because the air in the tunnel furnace is insufficient, the organic matter in the ink is not fully decomposed, CO and carbon residues are generated, a reducing atmosphere is formed in the sintering section, the copper oxide in the ink (glass powder and copper-chromium black) is reduced to cuprous oxide, the ink after sintering appears red, and the blackness after sintering is reduced. At the same time, the residual carbon will randomly disperse in the sintered ink during the sintering process of the ink. The residual carbon does not form a network structure with other inorganic oxides, which weakens the shielding effect of the ink to the external ultraviolet rays, affects the protection of the glue after installation, and shortens the service life of the automobile.

[0003] The prior art CN111334126B discloses a high-covering silver ink for automobile rear windshield glass and a preparation method thereof, to solve the problems of poor silver paste shielding performance, insufficient acid resistance, and poor adhesion of the silver ink for rear windshield glass. The invention provides a high-covering silver ink for automobile rear windshield glass, which is composed of the following materials: glass powder: 20-80%, pigment: 5-40%, ink oil: 10-30%, organic additive: 0-6.0%, and inorganic additive: 1.0-5.0%. The beneficial effects of the invention are: the addition of metal sulfide inorganic additive makes the ink effectively absorb silver ions during sintering, so that it cannot cause color difference on the contact surface of the ink and glass, and has very excellent shielding performance. The reasonable collocation of various oxides of the glass powder, especially the introduction of niobium oxide, yttrium oxide, manganese oxide, and iron oxide, gives the ink a dense film structure, ensures the shielding of the silver paste, and at the same time ensures good acid resistance, adhesion, and ideal expansion coefficient. However, the ink oil disclosed in the invention is a solvent-based heat-cured ink oil, which is slow and has low production efficiency. In addition, the solvent is volatile. There is also a risk of incomplete decomposition of the resin affecting the use.

[0004] CN116177901A provides a light-cured way of automobile rear windshield shielding silver line ink, including the following mass percent of raw materials: glass powder 40-80%, LED light-cured ink oil 10-25%, inorganic pigment 5-30%, inorganic additive 1-8% and organic additive 0-5%; wherein, the LED light-cured ink oil includes the following mass percent of ingredients: photosensitive prepolymer 60%-90%, active diluent 10-20%, photoinitiator 1-5% and polymerization inhibitor 0.1%-0.01%, wherein; the photosensitive prepolymer includes one or more of acrylated epoxy resin, unsaturated polyester, polyurethane and polysulfide / polyene light-cured resin. The finished ink has good silver paste shielding effect, strong anti-adhesion, great advantages in environmental protection and energy efficiency, and is worth promoting. However, the ink oil curing process of the present application produces a large amount of ozone, and the light-cured resin and multifunctional monomer containing benzene ring are used, and the decomposition temperature of the formed ink polymer is high, which is easy to remain in the sintered ink. SUMMARY

[0005] The purpose of the present application is to provide a kind of LED light-cured ink oil, to solve the problem that current ordinary UV light-cured ink oil pollutes environment, resin decomposition is not complete and is easy to remain and affect use.

[0006] In order to solve the above technical problems, the technical scheme of the present application is as follows:

[0007] A kind of LED light-cured ink oil, by weight parts, its raw materials include: 65-90 parts of monofunctional aliphatic (methyl) acrylate, 5-24 parts of monofunctional (methyl) acrylate hydroxyl ester, 2-8 parts of monofunctional (methyl) acrylate nitro ester and 2-4 parts of photoinitiator.

[0008] In one preferred embodiment, the LED light-cured ink oil, by weight parts, its raw materials include: 69-90 parts of monofunctional (methyl) acrylate aliphatic ester, 5-22 parts of monofunctional (methyl) acrylate hydroxyl ester, 2-7.5 parts of monofunctional (methyl) acrylate nitro ester and 2-4 parts of photoinitiator.

[0009] In one preferred embodiment, the LED light-cured ink oil, by weight parts, its raw materials include: 70-90 parts of monofunctional (methyl) acrylate aliphatic ester, 5-20 parts of monofunctional (methyl) acrylate hydroxyl ester, 2-7 parts of monofunctional (methyl) acrylate nitro ester and 2-4 parts of photoinitiator.

[0010] In one preferred embodiment, the monofunctional (meth)acrylate ester includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, or lauryl (meth)acrylate.

[0011] In one preferred embodiment, the monofunctional (meth)acrylate ester includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate.

[0012] The carbon chain of the ester in the monofunctional (meth)acrylate ester is too long, and the formed polymer tends to wrap the hydroxyl group, affecting the wetting of the powder by the hydroxyl group.

[0013] In one preferred embodiment, the monofunctional (meth)acrylate ester includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, or lauryl (meth)acrylate.

[0014] In one preferred embodiment, the monofunctional (meth)acrylate ester includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate.

[0015] The carbon chain of the alcohol in the monofunctional (meth)acrylate ester is too long, and the formed polymer tends to wrap the hydroxyl group, affecting the wetting of the powder by the hydroxyl group.

[0016] In one preferred embodiment, the monofunctional (meth)acrylate ester includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, or lauryl (meth)acrylate.

[0017] In one preferred embodiment, the monofunctional (meth)acrylate ester includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate.

[0018] The nitro group linked to the acrylic double bond will reduce the UV curing speed.

[0019] The light-cured ink of the present application is all selected monofunctional monomer, the synthesized polymer has relatively low thermal decomposition temperature, and can be completely decomposed into small molecule linear substances or completely escaped in the 200-650℃ preheating stage of the automobile glass hot bending process, and will not cause the organic matter to be left in the subsequent sintering forming process, avoid the carbon residue in the sintering process of 650-750℃, and affect the ability of the glass to block ultraviolet rays.

[0020] Among them, the monofunctional (methyl) acrylic fatty ester is used as the main chain of LED UV curing, which does not contain a large molecular structure of cyclic structure, and the structure of the main chain determines the properties of small molecules produced by thermal decomposition. If (methyl) acrylic alicyclic ester and (methyl) acrylic aromatic ester are used, it will form a large molecular structure of cyclohexane ring and benzene ring substituent during thermal decomposition, which has a large resistance in the escaping process, is easy to be left in the baking stage, and finally part of the residual in the sintered ink, affecting its performance.

[0021] The monofunctional (methyl) acrylic hydroxyl ester is used as a block, and is copolymerized with the main chain to improve the wettability of the polymer to the glass powder and inorganic pigment in the ink, so that the ink has suitable printability.

[0022] The monofunctional (methyl) acrylic nitro ester is used as a block, and is copolymerized with the main chain to provide oxidation during the thermal decomposition of the polymer, help the organic matter to be completely decomposed into carbon dioxide, and avoid the generation of carbon monoxide to reduce copper oxide to cuprous oxide, which causes the black color of the ink to become lighter after sintering.

[0023] At the same time, the three monomers form a whole polymer, which on the one hand provides the wettability, hydrophilicity and printability required by automobile ink, and on the other hand also needs to meet the requirement of low residual degree after decomposition, so the proportion range and type selection of the three monomers are very important.

[0024] The amount of monofunctional (meth) acrylic fatty ester is too low, and the content of monofunctional (meth) acrylic hydroxyl ester or monofunctional (meth) acrylic nitro ester is too high, wherein the content of monofunctional (meth) acrylic hydroxyl ester is too high, which will cause the prepared ink to have too large hydrophilicity, poor printing, uneven black after sintering, poor protection of glue, and large ΔΕ after QUV. If the amount of monofunctional (meth) acrylic fatty ester is too high, the content of monofunctional (meth) acrylic hydroxyl ester or monofunctional (meth) acrylic nitro ester [or nitro (meth) acrylic ester] is too low, wherein the content of monofunctional (meth) acrylic hydroxyl ester is too low, which will cause the prepared ink to have too small hydrophilicity, poor wettability of ink oil to glass powder and copper-chromium black, poor ink oiliness, poor printing, uneven black after sintering, poor protection of glue, and large ΔΕ after QUV. The amount of monofunctional (meth) acrylic nitro ester [or nitro (meth) acrylic ester] is too low, the prepared ink has very low nitro content, and cannot play a good oxidation role in the heat bending process, which will cause the ink color to be red after sintering, poor blackness, poor protection of glue, and large ΔΕ after QUV.

[0025] The polymerization reaction process is as follows:

[0026]

[0027] In formula ①, ②, ③, the photoinitiator generates free radicals after being irradiated by LED UV light, the double bond of the acryloyl group in the reactant is initiated by the free radicals to form a chain reaction, and macromolecular substances are formed to bond various powders in the ink together and adhere to the glass.

[0028] In formula ①, all are connected by non-cyclic single bonds, and straight-chain small molecules are formed during thermal decomposition, which can easily escape from the fine voids of the ink and will not affect the ink bending forming during the preheating stage of the baking and bending.

[0029] In formula ②, ③, there are cyclohexane rings and benzene rings, respectively, and during thermal decomposition, cyclohexane ring and benzene ring substitutes with large molecular structures are formed, which have large resistance during the escaping process and are easily retained in the baking and bending stage, and finally part of them are retained in the sintered ink, affecting its performance.

[0030] In one preferred embodiment, the photoinitiator comprises one or more of 2-methyl-2-(4-morpholinyl)-4'-(methylthio)phenyl propanone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-2-(4-morpholinyl)-4'-(methylthio)phenyl propanone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 4-dimethylaminobenzoate + camphorquinone, isooctyl-p-dimethylaminobenzoate, camphorquinone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0031] In one preferred embodiment, the photoinitiator comprises a combination of 2-methyl-2-(4-morpholinyl)-4'-(methylthio)phenyl propanone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide.

[0032] In one preferred embodiment, the photoinitiator comprises a combination of 2-methyl-2-(4-morpholinyl)-4'-(methylthio)phenyl propanone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide.

[0033] In one preferred embodiment, the photoinitiator comprises a combination of 2-methyl-2-(4-morpholinyl)-4'-(methylthio)phenyl propanone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide.

[0034] In one preferred embodiment, the photoinitiator comprises a combination of 2-methyl-2-(4-morpholinyl)-4'-(methylthio)phenyl propanone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide.

[0035] The photoinitiator improves the UV curing speed, ensuring that the ink can be quickly cured.

[0036] In the ratio of the ink, the amount of photoinitiator is excessive, and a large amount of free radicals will be generated instantaneously during photocuring, causing the surface curing speed to be too fast and the bottom layer to be not fully cured. If the amount is too small, it will cause the photocuring speed to be slow and the curing time to be prolonged.

[0037] An ink composition, comprising by weight parts, 20-40 parts of the above LED photocuring ink oil, 50-60 parts of low melting point glass powder and 10-20 parts of black inorganic pigment.

[0038] In one preferred embodiment, the low melting point glass powder comprises the following mass percentages of ingredients: silicon dioxide 20-45%, titanium dioxide 1-15%, zirconium dioxide 1-8%, zinc oxide 5-30%, bismuth oxide 0-60%, boron oxide 4-15%, aluminum oxide 0-6%, potassium oxide 1-3%, lithium oxide 0-10%, phosphorus pentoxide 0-8%, magnesium oxide 0-15%.

[0039] In one preferred embodiment, the black inorganic pigment is one or more of copper-chromium black, iron-chromium-manganese black and cobalt black.

[0040] The present application also provides the use of the above ink composition in the preparation of automobile rear windshield.

[0041] The present application has the beneficial effects of:

[0042] 1. The curing speed is only 3-5 seconds, the curing speed is fast, the production efficiency is greatly improved, the VOC emission is reduced, and basically no ozone is generated.

[0043] 2. There is basically no organic matter residue in the sintering forming process, which will not affect the ability of the glass to block ultraviolet rays. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 The glass picture of the printed ink from the glass side after QUV and the corresponding glue of Example 1;

[0045] Figure 2 The glass picture of the printed ink from the glass side after QUV and the corresponding glue of Example 2;

[0046] Figure 3 The glass picture of the printed ink from the glass side after QUV and the corresponding glue of Example 3;

[0047] Figure 4 The glass picture of the printed ink from the glass side after QUV and the corresponding glue of Example 4;

[0048] Figure 5 The glass picture of the printed ink from the glass side after QUV and the corresponding glue of Comparative Example 1;

[0049] Figure 6 The glass picture of the printed ink from the glass side after QUV and the corresponding glue of Comparative Example 2;

[0050] Figure 7Glass picture of printed ink from glass side after QUV for Comparative Example 3 and corresponding glass picture of glue;

[0051] Figure 8 Glass picture of printed ink from glass side after QUV for Comparative Example 4 and corresponding glass picture of glue;

[0052] Figure 9 Glass picture of printed ink from glass side after QUV for Comparative Example 5 and corresponding glass picture of glue;

[0053] Figure 10 Glass picture of printed ink from glass side after QUV for Comparative Example 6 and corresponding glass picture of glue;

[0054] Figure 11 Glass picture of printed ink from glass side after QUV for Comparative Example 7 and corresponding glass picture of glue;

[0055] Figure 12 Glass picture of printed ink from glass side after QUV for Comparative Example 8 and corresponding glass picture of glue. DETAILED DESCRIPTION

[0056] The following detailed description of the application will be made in connection with the embodiments of the application, but the application can be practiced in a variety of ways by those skilled in the art.

[0057] Example 1

[0058] The formula of the ink oil is shown in Table 1.

[0059] Table 1 Formula of ink oil

[0060]

[0061] In Table 1, ethyl acrylate, isobutyl acrylate, hydroxyethyl methacrylate are mixed uniformly, 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2-isopropyl thioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide are added in turn while stirring at a speed of 500-1000 rpm, and stirred until completely dissolved. The mixture is cooled to room temperature, 2-nitrobutyl acrylate is added and uniformly dispersed, and ready for use.

[0062] The ink is prepared according to Table 2.

[0063] Table 2 Formula of ink

[0064] Component Parts by weight Supplier Model Ink vehicle 30 Low melting glass powder 55 Foshan Tao Yi T-480 Copper chrome black 15 Jiangxi Jin Ring 2282B

[0065] The ink oil, low-melting glass powder, and copper chromium black are mixed uniformly in a proportion according to Table 2, and ground to a fineness of ≤15 μ on a three-roll mill.

[0066] The prepared ink is screen printed onto glass using a 200 mesh screen and an 80° squeegee, and is cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm2and an energy of 2500-3000 mj / cm2. Sintering is performed according to the heat bending temperature parameters of automotive glass. The glass is laminated, and the Lab values before and after QUV are tested, and ΔE is calculated.

[0067] Example 2

[0068] The formulation of the ink is shown in Table 3.

[0069] Table 3 Formulation of the ink

[0070]

[0071] In Table 3, methyl methacrylate, n-propyl acrylate, and hydroxybutyl methacrylate are mixed uniformly, and 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2,4-diethylthioxanthone, and diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide are added in sequence while stirring at a speed of 500-1000 rpm. After complete dissolution, the mixture is cooled to room temperature, 2-nitrobutyl acrylate is added, and the mixture is uniformly dispersed.

[0072] The ink is formulated according to Table 4.

[0073] Table 4 Formulation of the ink

[0074] Ink component Parts by weight Supplier Model Ink vehicle (Table 3) 30 Low melting glass powder 55 Foshan Tao Yi T-480 Copper chrome black 15 Jiangxi Jin Ring 2282B

[0075] The ink, low-melting glass powder, and copper chromium black are mixed uniformly in the proportions shown in Table 4, and are ground to a fineness of ≤15 μ on a three-roll mill.

[0076] The prepared ink is screen printed onto glass using a 200 mesh screen and an 80° squeegee, and is cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm2and an energy of 2500-3000 mj / cm2. Sintering is performed according to the heat bending temperature parameters of automotive glass. The glass is laminated, and the Lab values before and after QUV are tested, and ΔE is calculated.

[0077] Example 3

[0078] The formulation of the ink is shown in Table 5.

[0079] Table 5 Formulation of the ink

[0080]

[0081] In Table 5, n-propyl acrylate, t-butyl acrylate, hydroxyethyl acrylate were mixed uniformly, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, 2- isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide were added in turn while stirring at a rotation speed of 500-1000 rpm, and stirred until completely dissolved. After cooling to room temperature, 2,2-dinitropropyl acrylate was added and uniformly dispersed, ready for use.

[0082] The ink was prepared according to Table 6.

[0083] Table 6 Ink Formula

[0084] Ink component Parts by weight Supplier Model Ink vehicle (Table 5) 30 Low melting glass powder 55 Foshan Tao Yi T-480 Copper chrome black 15 Jiangxi Jin Ring 2282B

[0085] The ink oil, low-melting glass powder, and copper-chromium black were mixed uniformly according to the proportions in Table 6, and ground on a three-roll mill to a fineness of ≤15 μ.

[0086] The prepared ink was screen printed on glass using a 200-mesh screen and 80° rubber squeegee, and cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm2and an energy of 2500-3000 mj / cm2. Sintering was performed according to the hot bending temperature parameters of automotive glass, and the glass was laminated. The Lab values before and after lamination were tested, and ΔE was calculated.

[0087] Example 4

[0088] The formula of the ink oil is shown in Table 7.

[0089] Table 7 Formula of Ink Oil

[0090]

[0091] In Table 7, methyl methacrylate, isobutyl acrylate, and hydroxybutyl acrylate were mixed uniformly, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, 2,4- diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide were added in turn while stirring at a rotation speed of 500-1000 rpm, and stirred until completely dissolved. After cooling to room temperature, 2,2-dinitropropyl acrylate was added and uniformly dispersed, ready for use. The ink was prepared according to Table 8.

[0092] Table 8 Ink Formula

[0093] Ink component Parts by weight Supplier Ink vehicle (Table 7) 30 Low melting glass powder 55 Foshan Tao Yi T-480 Copper chrome black 15 Jiangxi Jin Ring 2282B

[0094] The ink oil, low-melting glass powder, and copper-chromium black were mixed uniformly according to the proportions in Table 8, and ground on a three-roll mill to a fineness of ≤15 μ.

[0095] The prepared ink was screen printed onto glass using a 200-mesh screen and an 80° squeegee, and was cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm2and an energy of 2500-3000 mj / cm2. The glass was sintered according to the hot bending temperature parameters for automobile glass. The glass was laminated, and the Lab values before and after QUV were measured, and ΔE was calculated.

[0096] Comparative Example 1

[0097] The ink was prepared according to the formulation shown in Table 9.

[0098] Table 9 Formulation of ink

[0099]

[0100] In Table 9, ethyl acrylate, isobutyl acrylate, and hydroxyethyl methacrylate were mixed uniformly, and 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2-isopropylthioxanthone, and diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide were added in sequence while stirring at a speed of 500-1000 rpm. After complete dissolution, the mixture was cooled to room temperature, 2-nitrobenzyl acrylate was added, and the mixture was uniformly dispersed.

[0101] The ink was prepared according to Table 10.

[0102] Table 10 Formulation of ink

[0103] Ink component Parts by weight Supplier Model Ink vehicle (Table 9) 30 Low melting glass powder 55 Foshan Tao Yi T-480 Copper chrome black 15 Jiangxi Jin Ring 2282B

[0104] The ink, low-melting glass powder, and copper-chromium black were mixed according to the proportions in Table 10, and were ground to a fineness of ≤15 μ on a three-roll mill.

[0105] The prepared ink was screen printed onto glass using a 200-mesh screen and an 80° squeegee, and was cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm2and an energy of 2500-3000 mj / cm2. The glass was sintered according to the hot bending temperature parameters for automobile glass. The glass was laminated, and the Lab values before and after QUV were measured, and ΔE was calculated.

[0106] Comparative Example 2

[0107] The ink was prepared according to the formulation shown in Table 11.

[0108] Table 11 Formulation of ink

[0109]

[0110] In Table 11, ethyl acrylate, isobutyl acrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate were mixed uniformly, 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2-ethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide were added in turn under the stirring at the speed of 500-1000 rpm, and stirred until completely dissolved, and then cooled to room temperature. 2-nitrobenzyl acrylate was added and uniformly dispersed, and ready for use.

[0111] The ink was prepared according to Table 12.

[0112] Table 12 Ink Formulation

[0113] Ink component Parts by weight Supplier Ink vehicle (Table 11) 30 Low melting glass powder 55 Foshan Tao Yi T-480 Copper chrome black 15 Jiangxi Jin Ring 2282B

[0114] The ink oil, low-melting glass powder, and copper-chromium black were mixed according to the proportions in Table 12, and ground on a three-roll mill to a fineness of ≤15 μ.

[0115] The prepared ink was screen printed on glass using a 200-mesh screen and 80° rubber squeegee, and cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm 2 and an energy of 2500-3000 mj / cm 2 . Sintering was performed according to the hot bending temperature parameters for automobile glass. The glass was laminated, and the Lab values before and after lamination were tested, and ΔE was calculated.

[0116] Comparative Example 3

[0117] The ink oil was prepared according to the formulation in Table 13.

[0118] Table 13 Formulation of Ink Oil

[0119] Monomer Parts by weight Supplier Model Isophorone 49 Dow Chemical Isophorone diisocyanate Evron 21 MADE Nitrocellulose Nanjing Zhong Nitrate 10 H type Polyvinyl butyral Sekisui Chemical 20 BL-10 Ink component

[0120] In Table 13, isophorone and nitrocellulose were stirred in a plastic tank and polytetrafluoroethylene at a speed of 500-1000 rpm until dissolved. The divalent acid ester and polybutyral were stirred at a speed of 500-1000 rpm until dissolved, and then the two were mixed uniformly and ready for use.

[0121] The ink was prepared according to Table 14.

[0122] Table 14 Ink Formulation

[0123] Parts by weight Supplier Model Ink vehicle (Table 13) Low melting glass powder 30 Foshan Tao Yi 55 Copper chrome black T-480 Jiangxi Jin Ring 15 Ink component 2282B

[0124] The ink oil, low-melting glass powder, and copper-chromium black were mixed according to the proportions in Table 14, and ground on a three-roll mill to a fineness of ≤15 μ.

[0125] The prepared ink was screen printed onto glass using a 200 mesh screen and 80° squeegee, and baked at 120-150°C for 3-5 min to solidify. The ink was sintered according to the hot bending temperature parameters for automobile glass. The Lab values were tested, and the Lab values of the laminated glass before and after QUV were tested, and ΔE was calculated.

[0126] Comparative Example 4

[0127] The ink oil formulation is shown in Table 15.

[0128] Table 15 Ink oil formulation

[0129]

[0130]

[0131] In Table 15, isophorone, divalent acid ester, and rosin glyceride were dissolved by stirring at a rotation speed of 500-1000 rpm, and then the two were mixed uniformly and reserved.

[0132] The ink oil, low-melting glass powder, and copper-chromium black were mixed according to the proportions in Table 16, and ground on a three-roll mill to a fineness of ≤15 μ.

[0133] The ink was prepared according to Table 16.

[0134] Table 16 Ink formulation

[0135] Parts by weight Supplier Model Ink vehicle (Table 15) Low melting glass powder 30 Foshan Tao Yi 55 Copper chrome black T-480 Jiangxi Jin Ring 15 Ink component 2282B

[0136] The prepared ink was screen printed onto glass using a 200 mesh screen and 80° squeegee, and baked at 120-150°C for 3-5 min to solidify. The ink was sintered according to the hot bending temperature parameters for automobile glass. The Lab values were tested, and the Lab values of the laminated glass before and after QUV were tested, and ΔE was calculated.

[0137] Comparative Example 5

[0138] The ink oil formulation is shown in Table 17.

[0139] Table 17 Ink oil formulation

[0140]

[0141] In Table 17, ethyl acrylate, isobutyl acrylate, and hydroxyethyl methacrylate were mixed uniformly, and 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2-isopropylthioxanthone, and diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide were added in sequence while stirring at a rotation speed of 500-1000 rpm, and the mixture was completely dissolved by stirring, cooled to room temperature, and then 2-nitrobenzyl acrylate was added and dispersed uniformly, and reserved.

[0142] The ink was prepared according to the proportions in Table 18.

[0143] Table 18: Ink formulation

[0144] Parts by weight Supplier Model Ink vehicle (Table 17) Low melting glass powder 30 Foshan Tao Yi 55 Copper chrome black T-480 Jiangxi Jin Ring 15 Ink component 2282B

[0145] The ink vehicle, low melting point glass powder and copper chrome black were mixed according to the proportions in Table 18 and ground to a fineness of < 15 μm on a three-roll mill.

[0146] The prepared ink was screen printed onto glass using a 200 mesh screen and 80° squeegee, and cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm2and an energy of 2500-3000 mj / cm2. The glass was sintered according to the hot bending temperature parameters for automotive glass. The glass was laminated, and the Lab values were measured before and after QUV, and the ΔE was calculated.

[0147] Comparative Example 6

[0148] The ink vehicle was prepared according to the formulation in Table 19.

[0149] Table 19: Formulation of ink vehicle

[0150]

[0151] In Table 19, ethyl acrylate, isobutyl acrylate, hydroxyethyl methacrylate were mixed, and 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide were added in turn while stirring at a speed of 500-1000 rpm until completely dissolved. The mixture was cooled to room temperature, 2-nitrobenzyl acrylate was added and dispersed uniformly, and the mixture was reserved.

[0152] The ink was prepared according to the proportions in Table 20.

[0153] Table 20: Ink formulation

[0154] Parts by weight Supplier Model Ink vehicle (Table 19) Low melting glass powder 30 Foshan Tao Yi 55 Copper chrome black T-480 Jiangxi Jin Ring 15 Ink component 2282B

[0155] The ink vehicle, low melting point glass powder and copper chrome black were mixed according to the proportions in Table 20 and ground to a fineness of < 15 μm on a three-roll mill.

[0156] The prepared ink was screen printed onto glass using a 200 mesh screen and 80° squeegee, and cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm2and an energy of 2500-3000 mj / cm2. The glass was sintered according to the hot bending temperature parameters for automotive glass. The glass was laminated, and the Lab values were measured before and after QUV, and the ΔE was calculated.

[0157] Comparative Example 7

[0158] The formula of the ink oil is shown in Table 21.

[0159] Table 21 Formula of the ink oil

[0160]

[0161] In Table 21, ethyl acrylate, isobutyl acrylate, hydroxyethyl methacrylate are mixed uniformly, and 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide are added in turn while stirring at a rotation speed of 500-1000 rpm, and stirred until completely dissolved, and then cooled to room temperature, and 2-nitrobenzyl acrylate is added and uniformly dispersed, ready for use.

[0162] The ink is prepared according to Table 2.

[0163] Table 22: Ink formula

[0164]

[0165] The ink oil, low-melting glass powder, and copper-chromium black are mixed uniformly in proportions according to Table 22, and ground on a three-roll mill to a fineness of ≤15 μ.

[0166] The prepared ink is screen printed on glass using a 200-mesh screen and 80° rubber squeegee, and cured using a 395 nm or 405 nm LED UV light with an intensity of 250-350 mw / cm2and an energy of 2500-3000 mj / cm2. Sintering is performed according to the hot bending temperature parameters of automotive glass, and the glass is laminated, and the Lab values before and after QUV lamination are tested, and ΔE is calculated.

[0167] Comparative Example 8

[0168] The formula of the ink oil is shown in Table 23.

[0169] Table 23: Formula of the ink oil

[0170]

[0171] In Table 23, ethyl acrylate, isobutyl acrylate, hydroxyethyl methacrylate are mixed uniformly, and 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2-isopropylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide are added in turn while stirring at a rotation speed of 500-1000 rpm, and stirred until completely dissolved, and then cooled to room temperature, and 2-nitrobenzyl acrylate is added and uniformly dispersed, ready for use.

[0172] The ink is prepared according to Table 24.

[0173] Table 24: Ink formula

[0174] Parts by weight Supplier Model Ink vehicle (Table 23) Low melting glass powder 30 Foshan Tao Yi 55 Copper chrome black T-480 Jiangxi Jin Ring 15 Performance 2282B

[0175] The ink oil, low-melting glass powder and copper chromium black were mixed according to the proportions in Table 24 and ground to a fineness of ≤15μ on a three-roll mill.

[0176] The prepared ink was screen printed onto glass using a 200-mesh screen and 80° rubber squeegee, and cured using a 395nm or 405nm LED UV with an intensity of 250-350mw / cm2and an energy of 2500-3000mj / cm2. The ink was sintered according to the heat bending temperature parameters for automotive glass. The glass was laminated, and the Lab values before and after lamination were tested, and ΔE was calculated.

[0177] The results of the performance tests of the adhesives prepared in Examples 1-4 and Comparative Examples 1-8 are shown in Tables 25 and 26. The QUV test standard refers to GB / T 16422.2-2014, and the adhesion test standard refers to GB / T 6739-2006.

[0178] Table 25 Performance test results of the ink prepared in Examples 1-4

[0179] Example 1 Example 2 Example 3 Example 4 L value after heat bending a value after heat bending 5.6 5.69 5.72 5.68 b value after heat bending -0.64 -0.68 -0.60 -0.58 Adhesion after QUV -0.18 -0.13 -0.15 -0.21 Glue L value before QUV ≥4B ≥4B ≥4B ≥4B Glue a value before QUV 60.98 61.00 60.96 60.98 Glue b value before QUV -0.74 -0.73 -0.74 -0.75 Glue L value after QUV 4.18 4.19 4.17 4.20 Glue a value after QUV 61.02 61.43 61.67 61.75 Glue b value after QUV -0.76 -0.70 -0.72 -0.65 ΔE 4.51 4.69 4.75 4.60 ​ 0.33 0.66 0.92 0.87

[0180] Table 26 Performance test results of the ink prepared in Comparative Examples 1-8

[0181]

[0182] As shown in Table 25, the L value of the ink after sintering in Examples 1-4 is relatively small compared to the L value of Comparative Examples 1-8, indicating that the ink is darker and provides better protection for the adhesive below. The ΔE of the adhesive after QUV in Examples 1-4 is below 1, while the ΔE of the adhesive after QUV in Comparative Examples 1-8 is above 2, especially the b value changes greatly, indicating that the protection of the ink on the adhesive below is very different, the b value changes greatly, the yellowing of the adhesive is large, and the adhesive is more prone to degradation, losing its adhesive properties. Therefore, the comprehensive performance of the ink prepared in the examples is better than that of the comparative examples, and the ink prepared in the present application has better QUV resistance.

[0183] Specifically, Comparative Example 1 uses 2-nitrobenzyl acrylate containing a benzene ring instead of 2-nitrobutyl acrylate, and the decomposition temperature of the polymer formed after LED UV curing is relatively high. The small molecule substances formed by decomposition escape slowly, and are easily partially retained in the ink after sintering, reducing the ultraviolet aging resistance and causing the ΔE of the adhesive below to be relatively large after QUV, affecting the service life.

[0184] The polymer in Example 2 forms a network structure after LED UV curing, and the decomposition temperature is relatively high, so it is relatively easy to remain. In addition, the polymer does not contain a nitro group, and the decomposition forms a reducing atmosphere, which easily reduces cupric oxide to cuprous oxide, reduces the blackness of the ink after sintering, reduces the ultraviolet aging resistance, makes the ΔΕ of the glue below after QUV be large, and affects the service life.

[0185] Example 3 belongs to a solvent type ink prepared by adjusting ink oil, and the curing speed is slow, the solvent volatilization pollutes the environment, affects the health of employees, and there is a small amount of cyclic material in nitrocellulose, which is easy to partially remain in the thermal decomposition process, reduces the ultraviolet aging resistance, makes the ΔΕ of the glue below after QUV be large, and affects the service life.

[0186] Example 4 belongs to a solvent type ink prepared by adjusting ink oil, and the curing speed is slow, the solvent volatilization pollutes the environment, affects the health of employees, and the decomposition temperature of rosin glyceride is high, which is easy to remain. The polymer does not contain a nitro group, and the decomposition forms a reducing atmosphere, which easily reduces cupric oxide to cuprous oxide, reduces the blackness of the ink after sintering, reduces the ultraviolet aging resistance, makes the ΔΕ of the glue below after QUV be large, and affects the service life.

[0187] The content of acrylic-2-nitrobutyl ester in the ink oil of Comparative Example 5 is relatively high (reference data shows that the explosion limit of nitropropane is 2.6-11% V / V, and the density is 0.992 g / cm 3 , and the mass limit is 2.58%), and the content in the ink is 2.55%, which is close to the explosion limit. There is an explosion risk when used in large quantities at high temperature, and the safety use is relatively low.

[0188] The amount of hydroxyethyl methacrylate in Comparative Example 6 is relatively large, which destroys the hydrophilic-lipophilic balance of the whole system, and the prepared ink has poor printability. The ink layer formed after the ink is cured is not dense enough, which reduces the ultraviolet aging resistance, makes the ΔΕ of the glue below after QUV be large, and affects the service life.

[0189] The content of acrylic-2-nitrobutyl ester in Comparative Example 7 is relatively low, and the oxidation atmosphere formed during the thermal decomposition of the polymer is slightly poor, part of the cupric oxide is reduced to cuprous oxide, which reduces the blackness of the ink after sintering, reduces the ultraviolet aging resistance, makes the ΔΕ of the glue below after QUV be large, and affects the service life.

[0190] The acrylic acid-2-nitrobutyl ester content of Comparative Example 8 is low, the oxidation atmosphere formed during thermal decomposition of the polymer is slightly poor, part of the copper oxide is reduced to cuprous oxide, which reduces the blackness after sintering of the ink, the amount of hydroxyethyl methacrylate is too small, which destroys the hydrophilic-lipophilic balance of the entire ink system, the ink has poor printability, the density of the cured ink is poor, and both factors reduce the ultraviolet aging resistance, resulting in a large QUV after ΔE of the glue below, affecting the service life.

[0191] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Those skilled in the art can make various modifications and changes to the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An LED photocuring ink, characterized by, The raw materials include 65-90 parts of monofunctional (meth) acrylate fatty ester, 5-24 parts of monofunctional (meth) acrylate hydroxyl ester, 2-8 parts of monofunctional (meth) acrylate nitro ester and 2-4 parts of photoinitiator by weight; The LED photocuring ink oil is cured by 395nm or 405nm LED UV; The monofunctional (meth) acrylate nitro ester includes one or more of 3-nitro methyl acrylate, 3-nitro ethyl acrylate, (meth) acrylate-2-nitro butyl, (meth) acrylate 2,2-dinitro propyl; The photoinitiator includes one or more of 2-methyl-2-(4-morpholinyl)-4'-(methylthio) benzophenone, 2-isopropyl thioxanthone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, 2,4-diethyl thioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, 4-dimethylamino benzoic acid ethyl ester, camphorquinone, isooctyl p-dimethylamino benzoate, bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide.

2. The LED photocuring ink of claim 1, wherein, The monofunctional (meth) acrylate fatty ester includes one or more of (meth) acrylate methyl ester, (meth) acrylate ethyl ester, (meth) acrylate n-propyl ester, (meth) acrylate isopropyl ester, (meth) acrylate n-butyl ester, (meth) acrylate isobutyl ester, (meth) acrylate tert-butyl ester, (meth) acrylate n-octyl ester, (meth) acrylate isooctyl ester, (meth) acrylate n-decyl ester, (meth) acrylate isodecyl ester or (meth) acrylate lauryl ester.

3. The LED photocuring ink of claim 1, wherein The monofunctional (meth) acrylate hydroxyl ester includes one or more of (meth) acrylate hydroxyethyl ester, (meth) acrylate hydroxypropyl ester, (meth) acrylate hydroxybutyl ester, polyethylene glycol 200 (meth) acrylate, polyethylene glycol 300 (meth) acrylate, polyethylene glycol 400 (meth) acrylate or polyethylene glycol 600 (meth) acrylate.

4. An ink composition characterized in that, The ink oil includes 20-40 parts of the LED photocuring ink oil according to any one of claims 1-3, 50-60 parts of low melting point glass powder and 10-20 parts of black inorganic pigment by weight.

5. The ink composition according to claim 4, characterized in that, The low melting point glass powder includes the following components by mass percentage: silicon dioxide 20-45%, titanium dioxide 1-15%, zirconium dioxide 1-8%, bismuth oxide 0-60%, boron oxide 4-25%, aluminum oxide 0-6%, potassium oxide 1-3%, lithium oxide 0-10%, phosphorus pentoxide 0-8%, magnesium oxide 0-15%, zinc oxide 5-30%.

6. The ink composition according to claim 4, characterized in that, The black inorganic pigment is one or more of copper-chromium black, iron-chromium-manganese black and cobalt black.

7. Use of the ink composition according to any one of claims 4-6 in the preparation of automobile rear windshield.

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