A production process of optical micro-hole engraving based on color crystal CMF integration

Abstract

The invention discloses a production process for optical micropore engraving based on color crystal CMF integration, which belongs to the technical field of color crystal glass preparation, and comprises the following steps: coating a layer of metallic color coating on the air surface of tempered glass, coating a bottom cover protective layer with polyurethane coating, and then pre-baking; arranging and finalizing the micropore matrix, micropore density and dot matrix trend changes according to preset parameters; performing arc-shaped engraving and direct writing on the air surface of the tempered glass, and then performing secondary baking and rapid cooling to obtain a finished product, wherein the polyurethane coating comprises a first polyol and a second polyol, wherein the first polyol has a double bond structure conjugated with malonylurea, and the second polyol has a symmetrical imine structure, and the good wear resistance and scratch resistance of the polyurethane coating of the invention makes it possible to directly perform arc-shaped engraving and direct writing on the glass.

Description

Technical Field

[0001] The present invention relates to the technical field of colored crystal glass preparation, and in particular to a production process for optical micro-hole engraving based on the integration of colored crystal CMF. Background Art

[0002] CMF is an abbreviation of the first letters of three English words: Color, Material, and Finishing. It is a sub-field of industrial design. In product design, it focuses on the synergistic relationship between factors such as color, material, and craft, and uses this to enhance the added value and emotional experience of the product. As an important type of CMF material, colored crystal glass uses forward-looking color patterns, material textures, and molding processes as product design strategies to achieve a balance between product aesthetics, performance requirements, and low cost, making the product more competitive in the market.

[0003] With the continuous development of the glass industry today, the display window at the position of the glass coating display control panel is usually produced by the traditional process of adjusting the transmittance with acrylic ink. In the above-mentioned glass appearance processing, there are generally problems that the visible and hidden windows look like "patches" under natural light and the semi-transparent visible and hidden parts have many impurities. In addition, this method has high requirements on the cleanliness of the production workshop and the manual operation of the host, and the production efficiency is low. Summary of the invention

[0004] In view of the above problems, the present invention provides a production process for optical micro-hole engraving based on the integration of colored crystal CMF.

[0005] The purpose of the present invention is achieved by the following technical solutions:

[0006] A production process for optical micro-hole engraving based on color crystal CMF integration includes the following steps:

[0007] (1) Apply a metallic coating on the air surface of the tempered glass, then apply a polyurethane coating on the bottom protective layer, and then pre-bake;

[0008] (2) Arrange and finalize the micropore matrix, micropore density, and dot matrix trend changes according to preset parameters;

[0009] (3) performing arc-shaped engraving and direct writing on the air surface of the tempered glass according to the fixed plate described in step (2), and then performing secondary baking and rapid cooling to obtain a finished product, with a cooling rate of 5-20°C / s;

[0010] Wherein, the polyurethane coating comprises a first polyol and a second polyol;

[0011] The preparation method of the first polyol comprises the following steps:

[0012] Weigh an alkylamine and dissolve it in a solvent, slowly add diisocyanate under stirring, continue stirring and reacting for 12-20 hours after the addition is completed, separate the precipitate and wash it after the reaction is completed to obtain product A; dissolve the product A in an acetic acid solution of acetic anhydride, add malonic acid, heat it to 80-90° C., keep it warm and stir it for 10-18 hours, cool it and concentrate it under reduced pressure, add ice-cold methanol solvent to dilute the concentrated product, separate the precipitate and wash it to obtain product B; disperse the product B in methanol solvent, stir and heat it until it is dissolved, add p-hydroxybenzaldehyde and L-proline, stir and reflux it for 2-4 hours after sufficient mixing, cool it after the reaction is completed, separate the precipitate and wash it to obtain the first polyol;

[0013] The preparation method of the second polyol comprises the following steps:

[0014] Weigh p-phenylenediamine and dissolve it in methanol solvent, add p-hydroxybenzaldehyde, mix, stir and reflux for reaction for 2-4 hours, cool after the reaction is completed, separate and wash the precipitate to obtain the second polyol.

[0015] In some preferred embodiments, the polyurethane coating comprises diisocyanate, hexylene diisocyanate trimer, the first polyol, the second polyol, an auxiliary agent and a solvent.

[0016] In some preferred embodiments, the mass ratio of the diisocyanate to the hexethylene diisocyanate trimer, the first polyol, the second polyol, and the auxiliary agent is 1: (4-5): (12-18): (7-11): (0-1).

[0017] In some preferred embodiments, the diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, biphenyl diisocyanate, and paraphenylene diisocyanate.

[0018] In some preferred embodiments, the method for preparing the polyurethane coating comprises the following steps:

[0019] The first polyol and the second polyol are prepared separately for use; the first polyol, the second polyol, the diisocyanate and the hexamethylene diisocyanate trimer are added to the solvent in sequence, stirred and heated to 70-80° C. to completely dissolve, the auxiliary agent is added, and mixed again to obtain the product.

[0020] In some preferred embodiments, the microporous matrix has a dot diameter of 70-130 μm and a row spacing of 90-160 μm.

[0021] In some preferred embodiments, the micropore density is 1-15%.

[0022] In some preferred embodiments, the lattice trend change is selected to transition from the circumference to the middle.

[0023] In some preferred embodiments, the pre-baking temperature of step (1) is 100-120° C., and the baking time is 0.5-1 h; the secondary baking temperature of step (3) is 120-150° C., and the baking time is 0.5-3 h.

[0024] In some preferred embodiments, in the method for preparing the first polyol, the molar ratio of the alkylamine to the diisocyanate is 1:(0.36-0.43); the mass ratio of the product A to the malonic acid is 1:(0.98-1); the mass ratio of the product B to the p-hydroxybenzaldehyde and the L-proline is 1:(0.58-0.6):(0.05-0.06).

[0025] In some preferred embodiments, in the method for preparing the second polyol, the mass ratio of the p-phenylenediamine to the p-hydroxybenzaldehyde is 1:(1.9-2).

[0026] The beneficial effects of the present invention are:

[0027] (1) The present invention directly performs arc-shaped engraving and direct writing on the glass by arranging and finalizing the micropore matrix, spacing, and trend changes, so that the glass appearance forms a hidden effect when the light is turned off and displayed when the light is turned on. It has a neat appearance, the visible and hidden parts are not abrupt, and the visible and hidden windows are integrated and have a strong appearance effect. Since the production process of the present invention can be directly carried out on the polyurethane bottom cover, it will not damage the protective layer, which is impossible to do with the traditional screen printing process. At the same time, the production process of the present invention is reasonably designed, simple to operate, and convenient and fast to manufacture, which can improve the appearance diversity of the product. It is a major breakthrough and innovation in the glass appearance process;

[0028] (2) The present invention obtains a coating material with good wear resistance and scratch resistance by modifying the components of the polyurethane bottom coating and using two polyols with different structures as reaction components. Specifically, the present invention reacts diisocyanate with amine to generate diurea, which is then amidated with malonic acid to generate malonylurea, and then the active methylene of malonylurea reacts with aldehyde groups containing active carbonyl groups to introduce double bonds and alcohol hydroxyl groups conjugated with malonylurea to obtain a first polyol, and p-phenylenediamine is added to aldehyde groups containing active carbonyl groups to form a symmetrical imine structure to obtain a second polyol. The present invention uses two polyols with different structures to achieve secondary crosslinking of the polyurethane bottom coating to improve its wear resistance and scratch resistance, including nucleophilic addition polymerization crosslinking based on isocyanate and alcohol and double bond crosslinking under thermal conditions. The secondary crosslinking makes it possible to directly write arc-shaped engraving on glass. After the engraving is completed, secondary crosslinking is performed to shape the coating and give it good wear resistance and scratch resistance. DETAILED DESCRIPTION

[0029] The present invention is further described in conjunction with the following examples.

[0030] Example 1

[0031] A production process for optical micro-hole engraving based on color crystal CMF integration includes the following steps:

[0032] (1) A metallic coating is applied on the air surface of the tempered glass, and then a bottom protective layer is coated with a polyurethane coating, and then pre-baking is performed; this embodiment uses commercial metallic glass coating ink; the pre-baking temperature is 100° C., and the baking time is 0.5 h;

[0033] (2) Arranging and finalizing the micropore matrix, micropore density and dot matrix trend change according to preset parameters; the dot diameter of the micropore matrix is ​​100 μm, the line spacing is 100-120 μm; the micropore density is 10%; the dot matrix trend change is selected to transition from the circumference to the middle;

[0034] (3) performing arc-shaped engraving and direct writing on the air surface of the tempered glass according to the fixed plate in step (2), and then performing secondary baking and rapid cooling to obtain a finished product; the secondary baking temperature is 135°C, the baking time is 1.5h, and the cooling rate is 12°C / s;

[0035] Wherein, the preparation method of the polyurethane coating comprises the following steps:

[0036] Prepare the first polyol and the second polyol separately for use; add the first polyol, the second polyol, the diisocyanate and the hexylene diisocyanate trimer into DMF solvent in sequence, stir and heat to 70-80° C. to completely dissolve, add an auxiliary agent, and mix again to obtain a uniform mixture;

[0037] The preparation method of the first polyol comprises the following steps:

[0038] Weigh ethylamine and dissolve it in dichloromethane solvent, slowly add hexamethylene diisocyanate under stirring, continue stirring and react for 14 hours after the addition, separate the precipitate after the reaction is completed and wash to obtain product A; dissolve the product A in a mixed solution of acetic anhydride and acetic acid (m 乙酸酐 / m 乙酸=1 / 1, the dissolving concentration is 0.07g / mL), malonic acid is added, the temperature is raised to 80-90℃ and the reaction is stirred for 13h, the product is concentrated under reduced pressure after cooling, a methanol solvent cooled by ice water is added to dilute the concentrated product, the precipitate is separated and washed to obtain product B; the product B is dispersed in the methanol solvent, stirred and heated to dissolve, p-hydroxybenzaldehyde and L-proline are added, stirred and refluxed for 2.5h after sufficient mixing, cooled after the reaction, the precipitate is separated and washed to obtain the first polyol; the molar ratio of the ethylamine to the hexamethylene diisocyanate is 1:0.39; the mass ratio of the product A to the malonic acid is 1:0.99; the mass ratio of the product B to the p-hydroxybenzaldehyde and the L-proline is 1:0.59:0.054;

[0039] The preparation method of the second polyol comprises the following steps:

[0040] Weighing p-phenylenediamine and dissolving it in methanol solvent, adding p-hydroxybenzaldehyde, mixing, stirring and refluxing for 3 hours, cooling after the reaction is completed, separating and washing the precipitate, and obtaining the second polyol; the mass ratio of the p-phenylenediamine to the p-hydroxybenzaldehyde is 1:1.93;

[0041] The diisocyanate is a mixture of hexamethylene diisocyanate and isophorone diisocyanate in equal molar ratios;

[0042] The additives may include conventional coating additives, such as pigments, rheological agents, dispersants, coupling agents, antioxidants, waterproofing agents, etc. To avoid the influence of the additives on the test comparison results of the coating properties, no additives are added in the embodiments of the present invention;

[0043] The mass ratio of the diisocyanate to the hexylene diisocyanate trimer, the first polyol, and the second polyol is 1:4.3:14.8:9.2.

[0044] Comparative Example 1

[0045] A production process for optical micropore engraving based on integrated color crystal CMF is the same as Example 1, except that the first polyol is not included.

[0046] Comparative Example 2

[0047] A production process for optical micropore engraving based on integrated color crystal CMF is the same as that of Example 1, except that the second polyol is not included.

[0048] Comparative Example 3

[0049] A production process for optical micropore engraving based on integrated color crystal CMF is the same as that of Example 1, except that the first polyol and the second polyol are replaced by polyether polyols with equal hydroxyl values.

[0050] Comparative Example 4

[0051] A production process for optical micro-hole engraving based on integrated color crystal CMF is the same as that of Example 1, except that step (3) is: arc-shaped engraving is directly written on the air surface of the tempered glass according to the fixed version described in step (2) to obtain a finished product.

[0052] Example 2

[0053] A production process for optical micro-hole engraving based on color crystal CMF integration includes the following steps:

[0054] (1) A metallic coating is applied on the air surface of the tempered glass, and then a polyurethane coating is applied to the bottom protective layer, and then pre-baking is performed; this embodiment uses commercial metallic glass coating ink; the pre-baking temperature is 110° C., and the baking time is 1 hour;

[0055] (2) Arranging and finalizing the micropore matrix, micropore density and dot matrix trend change according to preset parameters; the dot diameter of the micropore matrix is ​​100 μm, the line spacing is 100-120 μm; the micropore density is 1%; the dot matrix trend change is selected to transition from the circumference to the middle;

[0056] (3) performing arc-shaped engraving and direct writing on the air surface of the tempered glass according to the fixed plate in step (2), and then performing secondary baking and rapid cooling to obtain a finished product; the secondary baking temperature is 150°C, the baking time is 0.5h, and the cooling rate is 5°C / s;

[0057] Wherein, the preparation method of the polyurethane coating comprises the following steps:

[0058] The first polyol and the second polyol are prepared separately for use; the first polyol, the second polyol, the diisocyanate and the hexylene diisocyanate trimer are added to the DMF solvent in sequence, stirred and heated to 70-80° C. to completely dissolve, an auxiliary agent is added, and mixed again to obtain a uniform mixture;

[0059] The preparation method of the first polyol comprises the following steps:

[0060] Weigh ethylamine and dissolve it in dichloromethane solvent, slowly add hexamethylene diisocyanate under stirring, continue stirring and react for 12 hours after the addition is completed, separate the precipitate after the reaction is completed and wash to obtain product A; dissolve the product A in a mixed solution of acetic anhydride and acetic acid (m acetic anhydride / m acetic acid = 1 / 1, dissolution concentration is 0.07 g / mL), add malonic acid, heat to 80-90°C and stir and react for 18 hours, cool and concentrate under reduced pressure, add methanol solvent cooled with ice water to dilute the concentrated product, separate the precipitate and washing to obtain product B; dispersing the product B in methanol solvent, stirring and heating until dissolved, adding p-hydroxybenzaldehyde and L-proline, stirring and reflux for 4 hours after fully mixing, cooling after the reaction is completed, separating the precipitate and washing to obtain the first polyol; the molar ratio of the propylamine to the hexamethylene diisocyanate is 1:0.36; the mass ratio of the product A to the malonic acid is 1:0.99; the mass ratio of the product B to the p-hydroxybenzaldehyde and the L-proline is 1:0.6:0.05;

[0061] The preparation method of the second polyol comprises the following steps:

[0062] Weighing p-phenylenediamine and dissolving it in methanol solvent, adding p-hydroxybenzaldehyde, mixing, stirring and refluxing for 2 hours, cooling after the reaction is completed, separating and washing the precipitate to obtain the second polyol; the mass ratio of the p-phenylenediamine to the p-hydroxybenzaldehyde is 1:2;

[0063] The diisocyanate is biphenyl diisocyanate;

[0064] The mass ratio of the diisocyanate to the hexethylene diisocyanate trimer, the first polyol, and the second polyol is 1:4:18:7.

[0065] Example 3

[0066] A production process for optical micro-hole engraving based on color crystal CMF integration includes the following steps:

[0067] (1) A metallic coating is applied on the air surface of the tempered glass, and then a polyurethane coating is applied to the bottom protective layer, and then pre-baking is performed; this embodiment uses commercial metallic glass coating ink; the pre-baking temperature is 120° C., and the baking time is 0.5 h;

[0068] (2) Arranging and finalizing the micropore matrix, micropore density and dot matrix trend change according to preset parameters; the dot diameter of the micropore matrix is ​​100 μm, the line spacing is 100-120 μm; the micropore density is 15%; the dot matrix trend change is selected to transition from the circumference to the middle;

[0069] (3) performing arc-shaped engraving and direct writing on the air surface of the tempered glass according to the fixed plate in step (2), and then performing secondary baking and rapid cooling to obtain a finished product; the secondary baking temperature is 120°C, the baking time is 3h, and the cooling rate is 20°C / s;

[0070] Wherein, the preparation method of the polyurethane coating comprises the following steps:

[0071] The first polyol and the second polyol are prepared separately for use; the first polyol, the second polyol, the diisocyanate and the hexylene diisocyanate trimer are added to the DMF solvent in sequence, stirred and heated to 70-80° C. to completely dissolve, an auxiliary agent is added, and mixed again to obtain a uniform mixture;

[0072] The preparation method of the first polyol comprises the following steps:

[0073] Weigh ethylamine and dissolve it in dichloromethane solvent, slowly add hexamethylene diisocyanate under stirring, continue stirring and react for 20 hours after the addition is completed, separate the precipitate and wash it after the reaction is completed to obtain product A; dissolve the product A in a mixed solution of acetic anhydride and acetic acid (m acetic anhydride / m acetic acid = 1 / 1, dissolution concentration is 0.07 g / mL), add malonic acid, heat to 80-90°C and stir and react for 10 hours, cool and concentrate under reduced pressure, add methanol solvent cooled with ice water to dilute the concentrated product, separate the precipitate, The product B is dispersed in a methanol solvent, stirred and heated to dissolve, p-hydroxybenzaldehyde and L-proline are added, the mixture is fully mixed and stirred and refluxed for 2 hours, and after the reaction is completed, the mixture is cooled, the precipitate is separated and washed to obtain the first polyol; the molar ratio of the ethylamine to the hexamethylene diisocyanate is 1:0.43; the mass ratio of the product A to the malonic acid is 1:1; the mass ratio of the product B to the p-hydroxybenzaldehyde and the L-proline is 1:0.58:0.06;

[0074] The preparation method of the second polyol comprises the following steps:

[0075] Weigh p-phenylenediamine and dissolve it in methanol solvent, add p-hydroxybenzaldehyde, mix, stir and reflux for reaction for 4 hours, cool after the reaction is completed, separate and wash the precipitate to obtain the second polyol; the mass ratio of the p-phenylenediamine to the p-hydroxybenzaldehyde is 1:1.9;

[0076] The diisocyanate is hexamethylene diisocyanate;

[0077] The mass ratio of the diisocyanate to the hexethylene diisocyanate trimer, the first polyol, and the second polyol is 1:5:12:11.

[0078] Experimental example

[0079] The wear resistance and scratch resistance of the polyurethane coatings prepared in Examples 1-3 and Comparative Examples 1-4 were measured, wherein the test of coating hardness was based on GB / T26704-2011, the test of impact resistance was based on GB / T1732-1993, the test of flexibility was based on GB / T1731-1993, the wear resistance was expressed as the wear per unit area per unit time under the conditions of a load of 750 g and a rotation speed of 500 r, and the scratch resistance was based on the method A-metal scratch finger method in the current standard SN / T4419. The test results are as follows:

[0080]

[0081] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A production process for optical micro-hole engraving based on CMF integration, characterized in that: The following steps are involved: (1) Apply a metallic coating on the air surface of the tempered glass, then apply a polyurethane coating on the bottom protective layer, and then pre-bake; (2) Arrange and finalize the micropore matrix, micropore density, and dot matrix trend changes according to preset parameters; (3) performing arc-shaped engraving and direct writing on the air surface of the tempered glass according to the fixed plate described in step (2), and then performing secondary baking and rapid cooling to obtain a finished product; Wherein, the polyurethane coating comprises a first polyol and a second polyol; The preparation method of the first polyol comprises the following steps: Weigh an alkylamine and dissolve it in a solvent, slowly add diisocyanate under stirring, continue stirring and reacting for 12-20 hours after the addition is completed, separate the precipitate and wash it after the reaction is completed to obtain product A; dissolve the product A in an acetic acid solution of acetic anhydride, add malonic acid, heat it to 80-90° C., keep it warm and stir it for 10-18 hours, cool it and concentrate it under reduced pressure, add ice-cold methanol solvent to dilute the concentrated product, separate the precipitate and wash it to obtain product B; disperse the product B in methanol solvent, stir and heat it until it is dissolved, add p-hydroxybenzaldehyde and L-proline, stir and reflux it for 2-4 hours after sufficient mixing, cool it after the reaction is completed, separate the precipitate and wash it to obtain the first polyol; The preparation method of the second polyol comprises the following steps: Weigh p-phenylenediamine and dissolve it in methanol solvent, add p-hydroxybenzaldehyde, mix, stir and reflux for reaction for 2-4 hours, cool after the reaction is completed, separate and wash the precipitate to obtain the second polyol.

2. According to claim 1, a production process for optical micro-hole engraving based on color crystal CMF integration is characterized in that: The polyurethane coating comprises diisocyanate, hexylene diisocyanate trimer, the first polyol, the second polyol, an auxiliary agent and a solvent.

3. According to claim 2, a production process for optical micro-hole engraving based on color crystal CMF integration is characterized in that: The mass ratio of the diisocyanate to the hexylene diisocyanate trimer, the first polyol, the second polyol, and the auxiliary agent is 1:(4-5):(12-18):(7-11):(0-1).

4. The production process of optical micro-hole engraving based on color crystal CMF integration according to claim 2 or 3, characterized in that: The diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, biphenyl diisocyanate and paraphenylene diisocyanate.

5. The production process of optical micro-hole engraving based on color crystal CMF integration according to claim 2 or 3, characterized in that: The preparation method of the polyurethane coating comprises the following steps: The first polyol and the second polyol are prepared separately for use; the first polyol, the second polyol, the diisocyanate and the hexamethylene diisocyanate trimer are added to the solvent in sequence, stirred and heated to 70-80° C. to completely dissolve, the auxiliary agent is added, and mixed again to obtain the product.

6. The production process of optical micro-hole engraving based on color crystal CMF integration according to claim 1 is characterized in that: The dot diameter of the microporous matrix is ​​70-130 μm, and the row spacing is 90-160 μm.

7. The production process of optical micro-hole engraving based on color crystal CMF integration according to claim 1 is characterized in that: The micropore density is 1-15%.

8. The production process of optical micro-hole engraving based on color crystal CMF integration according to claim 1 is characterized in that: The baking temperature of the pre-baking in step (1) is 100-120° C., and the baking time is 0.5-1 h; the baking temperature of the secondary baking in step (3) is 120-150° C., and the baking time is 0.5-3 h.

9. The production process of optical micro-hole engraving based on color crystal CMF integration according to claim 1 is characterized in that: In the preparation method of the first polyol, the molar ratio of the alkylamine to the diisocyanate is 1:(0.36-0.43); the mass ratio of the product A to the malonic acid is 1:(0.98-1); the mass ratio of the product B to the p-hydroxybenzaldehyde and the L-proline is 1:(0.58-0.6):(0.05-0.06).

10. The production process of optical micro-hole engraving based on color crystal CMF integration according to claim 1 is characterized in that: In the preparation method of the second polyol, the mass ratio of the p-phenylenediamine to the p-hydroxybenzaldehyde is 1:(1.9-2).

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