Novel scratch-resistant varnish as well as preparation method and application thereof

Abstract

The invention relates to the technical field of glass slurry, in particular to novel scratch-resistant varnish as well as a preparation method and application thereof. The varnish is composed of the following components in percentage by weight. A resin base material: 15-25% of modified polyvinyl butyral (MPVB) and 8-15% of water-based aldehyde ketone resin; a flexibilizer: 5-10% of rosin modified maleic acid resin; the anti-scratch filler comprises 1-3% of nano aluminum oxide and 3-8% of modified polyethylene wax micro powder; a functional auxiliary agent: 0.1-0.5% of an organosilicon polyether defoaming agent; 0.5 to 1.5 percent of a water-based polyacrylate flatting agent; 1-2% of an erucyl amide slipping agent; and a solvent system: 40-45% of diethylene glycol monobutyl ether and 10-13% of propylene glycol monomethyl ether. The invention provides a novel varnish with scratch resistance, good adhesive force and good glossiness and a preparation method and application thereof through the synergistic effect of resin, optimization of composite filler and addition of an appropriate proportion of auxiliaries.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass paste, in particular to a novel scratch-resistant ink oil and its preparation method and application. BACKGROUND

[0002] Traditional ink oil has limitations in terms of wear resistance and scratch resistance, especially in the case of rapid production stacking or small space scenarios. Currently, glass printing enterprises all use a glass pad and a plastic foam to solve the problem of scratch resistance. If the glass and glass are not isolated from each other, the ink layer is prone to scratches, affecting subsequent sintering processing and product quality, etc. In the prior art, although wax or inorganic fillers are added to improve wear resistance, there are problems such as poor formula compatibility and reduced gloss. For example, although the current patent technology improves scratch resistance by using silicone modified resin, the synergistic effect of the resin is not optimized. Although rosin modified phenolic resin can enhance adhesion, it is not environmentally friendly. Therefore, it is very promising to invent a scratch-resistant ink oil with effective scratch resistance. SUMMARY

[0003] In view of the above technical problems, the present application provides a novel scratch-resistant ink oil and its preparation method and application. The ink oil prepared by the present application has good scratch resistance, good adhesion and good gloss, and can be applied to household appliance glass paste and automobile glass paste.

[0004] The present application discloses a novel scratch-resistant ink oil, which is composed of the following components by weight percentage: Modified polyvinyl butyral (MPVB) 15-25%, water-based aldehyde ketone resin 8-15%; rosin modified malin acid resin 5-10%; nano alumina 1-3%, modified polyethylene wax powder 3-8%; silicone polyether defoaming agent 0.1-0.5%; water-based polyacrylate leveling agent 0.5-1.5%; erucic acid amide slip agent 1-2%; diethylene glycol butyl ether 40-45%, propylene glycol methyl ether 10-13%.

[0005] Preferably, the average molecular weight of the modified polyvinyl butyral (MPVB) is 40000; the viscosity is 60-100 mPa.s.

[0006] Preferably, the hydroxyl content of the modified polyvinyl butyral (MPVB) is 34 mol%; the butyral content is 65 mol%.

[0007] Preferably, the solid content of the water-based aldehyde ketone resin is 41-42%.

[0008] Preferably, the viscosity of the water-based aldehyde ketone resin is mPa.s≦250 (20℃); the particle size D50 is 0.1-1.0 μm.

[0009] This invention also discloses a method for preparing a novel scratch-resistant ink, the method comprising the following steps: S1 resin pre-dispersion: Diethylene glycol butyl ether and propylene glycol methyl ether are mixed to form a solvent. Half of the above solvent is used to mix modified polyvinyl butyral, waterborne aldehyde ketone resin and rosin-modified marinic acid resin. Then the mixture is heated and stirred until completely dissolved to obtain a resin solution. S2 Filler Dispersion: Nano-alumina, modified polyethylene wax powder and erucamide are added sequentially to the remaining half of the solvent in step S1, and then ultrasonically treated to obtain the filler dispersion. S3 Mixing and Modification: Mix the resin solution and filler dispersion, add water-based polyacrylate leveling agent and organosilicon polyether defoamer, and control the stirring speed to mix evenly; S4 Filter Packaging: The ink is filtered through a 5μm filter to remove impurities and then sealed for storage to obtain the ink blending oil.

[0010] Preferably, in the S1 resin pre-dispersion step, the heating and stirring temperature is 40°C.

[0011] Preferably, in the S2 filler dispersion step, the ultrasonic treatment time is 30 minutes.

[0012] Preferably, in the S3 mixing and modification step, the stirring speed is 30 m / min and the stirring time is 1 hour.

[0013] This invention also discloses the application of a novel scratch-resistant ink oil. The ink oil prepared by the novel scratch-resistant ink oil preparation method can be applied in the fields of household appliance glass paste and automotive glass paste.

[0014] Compared with the prior art, the beneficial effects of the present invention are: This invention provides a novel scratch-resistant ink oil, its preparation method, and its application. The ink oil prepared by this invention exhibits excellent scratch resistance, adhesion, and gloss, and can be applied to glass pastes for household appliances and automobiles. Furthermore, the preparation method provided by this invention also has the following characteristics: (1) Resin synergistic effect: By combining the flexibility of modified polyvinyl butyral with the rigid cyclic structure of aldehyde and ketone resin, an interpenetrating network is formed, which enhances the shear resistance and scratch resistance of the ink layer and provides printability and dry film adhesion.

[0015] (2) Composite filler optimization: Nano-alumina improves surface hardness, modified polyethylene wax micro powder reduces the coefficient of friction, and erucamide enhances surface smoothness. The three work synergistically to reduce scratch formation. This improves the scratch resistance of the paste. The dried ink layer was tested by the pencil hardness test (GB6739-86), and the surface hardness of the ink reached the B-HB level.

[0016] (3) Environmentally friendly solvent system: diethylene glycol butyl ether as the main solvent, combined with propylene glycol methyl ether to adjust the volatilization gradient, taking into account environmental protection and film uniformity. Suitable for water-based and solvent-based ink systems, VOC content is less than 50g / L, in line with the EU RoHS standard.

[0017] (4) The technical scheme of the present application combines the innovation application of resin modification and functional filler. Compared with traditional anti-scratch ink, the present scheme significantly improves the wear resistance while maintaining high gloss through the synergistic effect of nanomaterials and resin; compared with water-based flexographic ink, the present ink does not require additional glossing process, reducing the cost by more than 30%. DETAILED DESCRIPTION

[0018] The following examples are provided to better further understand the present application, and do not limit the content and scope of protection of the present application. Any person under the inspiration of the present application or the combination of the present application with other existing technical features falls within the scope of protection of the present application.

[0019] If the specific experimental steps or conditions are not specified in the examples, the operation or conditions can be carried out according to the conventional experimental steps described in the literature in the art. If the reagents or instruments are not specified by the manufacturer, they are conventional reagent products that can be obtained by purchase.

[0020] Example 1: A new type of anti-scratch ink, consisting of the following ingredients by weight percentage: The resin base is modified polyvinyl butylal (MPVB) 15% and water-based aldehyde ketone resin 10%; the toughening agent is rosin modified malin acid resin 10%; the anti-scratch filler is nano alumina 3% and polyethylene wax powder 8%; diethylene glycol butyl ether 40%, propylene glycol methyl ether 10%, leveling agent 1.5%, defoaming agent 0.5%, slip agent 2%. Among them, the average molecular weight of modified polyvinyl butylal (MPVB) is 40000; the viscosity is 60 mPa.s; the hydroxyl content in modified polyvinyl butylal (MPVB) is 34 mol%; the butylal content is 65 mol%; the solid content of water-based aldehyde ketone resin is 41%; the particle size D50(μm) is 0.1.

[0021] A preparation method of a new type of anti-scratch ink, comprising the following steps: S1 Resin pre-dispersion: mixing diethylene glycol butyl ether and propylene glycol methyl ether to form a solvent, taking half of the above-mentioned solvent to mix modified polyvinyl butylal, water-based aldehyde ketone resin and rosin modified malin acid resin, then heating to 40℃ and stirring until completely dissolved to obtain a resin solution.

[0022] S2 filler dispersion: nano-alumina, modified polyethylene wax powder and erucamide were sequentially added to the remaining half of the solvent in step S1, and then ultrasonic treatment was performed to obtain a filler dispersion liquid.

[0023] S3 mixing and modification: the resin solution and the filler dispersion liquid were mixed, and an aqueous polyacrylate leveling agent and a silicone polyether defoaming agent were added, and high-speed stirring was performed at a linear speed of 30 m / min for 1 hour.

[0024] S4 filtration and packaging: after removing impurities by filtering through a 5 μm filter screen, the ink oil was sealed and stored to obtain the ink oil.

[0025] The ink oil obtained by mixing the above method was mixed with glass powder and printed on the surface of the glass. After drying, the scratch hardness grade (coating film hardness pencil test) was tested; the dry film adhesion was tested; and the gloss was tested at 680°C for 150 seconds.

[0026] Example 2: A new type of anti-scratch ink oil, which is composed of the following ingredients by weight percentage: The resin base is modified polyvinyl butyral (MPVB) 25% and aqueous aldehyde ketone resin 8%; the toughening agent is rosin modified marlin acid resin 5%; the anti-scratch filler is nano-alumina 1% and polyethylene wax powder 3%; diethylene glycol butyl ether 45%, propylene glycol methyl ether 11.4%, leveling agent 0.5%, defoaming agent 0.1%, and slip agent 1%. Among them, the average molecular weight of modified polyvinyl butyral (MPVB) is 40000; the viscosity is 80 mPa.s; the hydroxyl content in modified polyvinyl butyral (MPVB) is 34 mol%; the butyral content is 65 mol%; the solid content of aqueous aldehyde ketone resin is 41.3%; and the particle size D50 (μm) is 0.13.

[0027] A preparation method of a new type of anti-scratch ink oil, comprising the following steps: S1 resin pre-dispersion: diethylene glycol butyl ether and propylene glycol methyl ether were mixed to form a solvent, one half of the above solvent was used to mix modified polyvinyl butyral, aqueous aldehyde ketone resin and rosin modified marlin acid resin, and then heated to 40°C and stirred until completely dissolved to obtain a resin solution.

[0028] S2 filler dispersion: nano-alumina, modified polyethylene wax powder and erucamide were sequentially added to the remaining half of the solvent in step S1, and then ultrasonic treatment was performed to obtain a filler dispersion liquid.

[0029] S3 mixing and modification: the resin solution and the filler dispersion liquid were mixed, and an aqueous polyacrylate leveling agent and a silicone polyether defoaming agent were added, and high-speed stirring was performed at a linear speed of 30 m / min for 1 hour.

[0030] S4 filtration and packaging: after removing impurities by filtering through a 5 μm filter screen, the ink oil was sealed and stored to obtain the ink oil.

[0031] The ink oil obtained by the above method is mixed with glass powder, printed on the surface of glass, and after drying, the scratch hardness grade (coating film hardness pencil test) is tested; the dry film adhesion is tested; the gloss is tested at 680°C for 150 seconds.

[0032] Example 3: A new type of scratch-resistant ink oil, consisting of the following weight percentage of ingredients: The resin base is modified polyvinyl butyral (MPVB) 15% and water-based aldehyde ketone resin 15%; the toughening agent is rosin modified marlin acid resin 8%; the anti-scratch material is nano alumina 1.5% and polyethylene wax powder 4.2%; diethylene glycol butyl ether 42%, propylene glycol methyl ether 12%, leveling agent 0.5%, defoaming agent 0.3%, slip agent 1.5%. Among them, the average molecular weight of modified polyvinyl butyral (MPVB) is 40000; the viscosity is 90 mPa.s; the hydroxyl content in modified polyvinyl butyral (MPVB) is 34 mol%; the butyral content is 65 mol%; the solid content of water-based aldehyde ketone resin is 41.6%; the particle size D50(μm) is 0.16.

[0033] A preparation method of a new type of scratch-resistant ink oil, comprising the following steps: S1 resin pre-dispersion: mix diethylene glycol butyl ether and propylene glycol methyl ether to form a solvent, take half of the above solvent to mix modified polyvinyl butyral, water-based aldehyde ketone resin and rosin modified marlin acid resin, then heat to 40℃ and stir until completely dissolved to obtain a resin solution.

[0034] S2 filler dispersion: nano alumina, modified polyethylene wax powder and erucic acid amide are added in turn to the remaining half of the solvent in step S1, and then ultrasonic treatment is carried out to obtain a filler dispersion liquid.

[0035] S3 mixing and modification: mix the resin solution with the filler dispersion liquid, add water-based polyacrylate leveling agent and silicone polyether defoaming agent, and stir at a linear speed of 30 m / min for 1 hour.

[0036] S4 filtration and packaging: filter through a 5μm filter screen, remove impurities, and then seal and store to obtain the ink oil.

[0037] The ink oil obtained by the above method is mixed with glass powder, printed on the surface of glass, and after drying, the scratch hardness grade (coating film hardness pencil test) is tested; the dry film adhesion is tested; the gloss is tested at 680°C for 150 seconds.

[0038] Example 4: A new type of scratch-resistant ink oil, consisting of the following weight percentage of ingredients: The resin base is modified polyvinyl butyral (MPVB) 20% and water-based aldehyde ketone resin 9%; the toughening agent is rosin modified marlin acid resin 6%; the anti-scratch material is nano alumina 1% and polyethylene wax powder 4%; diethylene glycol butyl ether 45%, propylene glycol methyl ether 13%, leveling agent 0.6%, defoaming agent 0.4%, slip agent 1%. Among them, the average molecular weight of modified polyvinyl butyral (MPVB) is 40000; the viscosity is 100 mPa.s; the hydroxyl content in modified polyvinyl butyral (MPVB) is 34 mol%; the butyral content is 65 mol%; the solid content of water-based aldehyde ketone resin is 42%; the particle size D50(μm) is 0.2.

[0039] A preparation method of a new type of anti-scratch ink oil, comprising the following steps: S1 resin pre-dispersion: mixing diethylene glycol butyl ether and propylene glycol methyl ether to form a solvent, taking half of the above-mentioned solvent to mix modified polyvinyl butyral, water-based aldehyde ketone resin and rosin modified marlin acid resin, then heating to 40℃ and stirring until completely dissolved to obtain a resin solution.

[0040] S2 filler dispersion: nano alumina, modified polyethylene wax powder and erucic acid amide are added in turn to the remaining half of the solvent in step S1, and then ultrasonic treatment is carried out to obtain a filler dispersion liquid.

[0041] S3 mixing and modification: mixing the resin solution with the filler dispersion liquid, adding water-based polyacrylate leveling agent and silicone polyether defoaming agent, and stirring at a linear speed of 30 m / min for 1 hour.

[0042] S4 filtration and packaging: filtering through a 5μm filter to remove impurities, then sealing and storing to obtain the ink oil.

[0043] Mixing the ink oil obtained by the above method with glass powder, printing on the surface of glass, drying and testing the scratch hardness grade (coating film hardness pencil test method); testing the dry film adhesion; testing the gloss at 680℃ for 150 seconds.

[0044] Comparative Example 1: a new type of anti-scratch ink oil, which is composed of the following ingredients in weight percentage: The resin base is modified polyvinyl butyral (MPVB) 20% and water-based aldehyde ketone resin 10%; the toughening agent is rosin modified marlin acid resin 8%; the anti-scratch material is nano alumina 0% and polyethylene wax powder 5%; diethylene glycol butyl ether 40%, propylene glycol methyl ether 14.2%, leveling agent 1%, defoaming agent 0.3%, slip agent 1.5%. Among them, the average molecular weight of modified polyvinyl butyral (MPVB) is 40000; the viscosity is 60 mPa.s; the hydroxyl content in modified polyvinyl butyral (MPVB) is 34 mol%; the butyral content is 65 mol%; the solid content of water-based aldehyde ketone resin is 41%; the particle size D50(μm) is 0.1.

[0045] A preparation method of a new type of anti-scratch ink oil, comprising the following steps: S1 resin pre-dispersion: mixing diethylene glycol butyl ether and propylene glycol methyl ether to form a solvent, taking half of the above-mentioned solvent to mix modified polyvinyl butyral, water-based aldehyde ketone resin and rosin modified marlin acid resin, then heating to 40℃ and stirring until completely dissolved to obtain a resin solution.

[0046] S2 filler dispersion: nano alumina, modified polyethylene wax powder and erucic acid amide are added in turn to the remaining half of the solvent in step S1, and then ultrasonic treatment is carried out to obtain a filler dispersion liquid.

[0047] S3 mixing and modification: mixing the resin solution with the filler dispersion liquid, adding water-based polyacrylate leveling agent and silicone polyether defoaming agent, and stirring at a linear speed of 30 m / min for 1 hour.

[0048] S4 filtration and packaging: filtering through a 5μm filter to remove impurities, and then sealing and storing to obtain the ink oil.

[0049] Mixing the ink oil obtained by the above-mentioned method with glass powder, printing on the surface of glass, drying and testing the scratch hardness grade (coating film hardness pencil test method); testing the dry film adhesion; testing the gloss at 680℃ for 150 seconds.

[0050] Comparative example 2: a new type of anti-scratch ink oil, which is composed of the following ingredients in weight percentage: The resin base is modified polyvinyl butyral (MPVB) 20% and water-based aldehyde ketone resin 10%; the toughening agent is rosin modified marlin acid resin 8%; the anti-scratch material is nano alumina 2% and polyethylene wax powder 0%; diethylene glycol butyl ether 40%, propylene glycol methyl ether 17.2%, leveling agent 1%, defoaming agent 0.3%, slip agent 1.5%. Among them, the average molecular weight of modified polyvinyl butyral (MPVB) is 40000; the viscosity is 60 mPa.s; the hydroxyl content in modified polyvinyl butyral (MPVB) is 34 mol%; the butyral content is 65 mol%; the solid content of water-based aldehyde ketone resin is 41%; the particle size D50(μm) is 0.1.

[0051] A preparation method of a new type of anti-scratch ink oil, comprising the following steps: S1 resin pre-dispersion: mixing diethylene glycol butyl ether and propylene glycol methyl ether to form a solvent, taking half of the above-mentioned solvent to mix modified polyvinyl butyral, water-based aldehyde ketone resin and rosin modified marlin acid resin, then heating to 40℃ and stirring until completely dissolved to obtain a resin solution.

[0052] S2 filler dispersion: nano alumina, modified polyethylene wax powder and erucic acid amide are sequentially added to the remaining half of the solvent in step S1, and then ultrasonic treatment is performed to obtain a filler dispersion liquid; S3 mixing and modification: mixing the resin solution with the filler dispersion liquid, adding water-based polyacrylate leveling agent and silicone polyether defoaming agent, and high-speed stirring at a linear speed of 30 m / min for 1 hour.

[0053] S4 filtration and packaging: filtering through a 5μm filter screen, removing impurities and then sealing and storing to obtain the ink oil.

[0054] Mixing the ink oil obtained by the above-mentioned method with glass powder, printing on the surface of glass, drying and then testing the scratch hardness grade (coating film hardness pencil test method); testing the dry film adhesion; testing the gloss at 680℃ for 150 seconds.

[0055] Comparative Example 3: a new type of anti-scratch ink oil, which is composed of the following ingredients by weight percentage: The resin base is modified polyvinyl butyral (MPVB) 20% and water-based aldehyde ketone resin 10%; the toughening agent is rosin modified marlin acid resin 8%; the anti-scratch material is nano alumina 2% and polyethylene wax powder 5%; diethylene glycol butyl ether 40%, propylene glycol methyl ether 13.2%, leveling agent 0%, defoaming agent 0.3%, slip agent 1.5%. Among them, the average molecular weight of modified polyvinyl butyral (MPVB) is 40000; the viscosity is 60 mPa.s; the hydroxyl content in modified polyvinyl butyral (MPVB) is 34 mol%; the butyral content is 65 mol%; the solid content of water-based aldehyde ketone resin is 41%; the particle size D50(μm) is 0.1.

[0056] A preparation method of a new type of scratch-resistant ink oil, comprising the following steps: S1 resin pre-dispersion: mixing diethylene glycol butyl ether and propylene glycol methyl ether to form a solvent, taking half of the above-mentioned solvent to mix modified polyvinyl butyral, water-based aldehyde ketone resin and rosin modified maleic acid resin, then heating to 40℃ and stirring until completely dissolved to obtain a resin solution.

[0057] S2 filler dispersion: sequentially adding nano-alumina, modified polyethylene wax powder and erucic acid amide into the remaining half of the solvent in step S1, and then ultrasonic treatment to obtain a filler dispersion liquid; S3 mixing and modification: mixing the resin solution with the filler dispersion liquid, adding water-based polyacrylate leveling agent and silicone polyether defoaming agent, and high-speed stirring at a linear speed of 30 m / min for 1 hour.

[0058] S4 filtration and packaging: filtering through a 5μm filter screen, removing impurities, and then sealing and storing to obtain the ink oil.

[0059] Mixing the ink oil obtained by the above-mentioned method with glass powder, printing on the surface of glass, drying and then testing the scratch hardness grade (coating film hardness pencil test method); testing the dry film adhesion; testing the gloss at 680℃ for 150 seconds.

[0060] Comparative Example 4: A new type of scratch-resistant ink oil, consisting of the following ingredients by weight percentage: The resin base is modified polyvinyl butyral (MPVB) 20% and water-based aldehyde ketone resin 0%; the toughening agent is rosin modified maleic acid resin 8%; the scratch-resistant material is nano-alumina 2% and polyethylene wax powder 5%; diethylene glycol butyl ether 40%, propylene glycol methyl ether 22.2%, leveling agent 1%, defoaming agent 0.3%, slip agent 1.5%. Among them, the average molecular weight of modified polyvinyl butyral (MPVB) is 40000; the viscosity is 60 mPa.s; the hydroxyl content in modified polyvinyl butyral (MPVB) is 34 mol%; the butyral content is 65 mol%; the solid content of water-based aldehyde ketone resin is 41%; the particle size D50(μm) is 0.1.

[0061] A preparation method of a new type of scratch-resistant ink oil, comprising the following steps: S1 resin pre-dispersion: mixing diethylene glycol butyl ether and propylene glycol methyl ether to form a solvent, taking half of the above-mentioned solvent to mix modified polyvinyl butyral, water-based aldehyde ketone resin and rosin modified maleic acid resin, then heating to 40℃ and stirring until completely dissolved to obtain a resin solution.

[0062] S2 filler dispersion: sequentially adding nano-alumina, modified polyethylene wax powder and erucic acid amide into the remaining half of the solvent in step S1, and then ultrasonic treatment to obtain a filler dispersion liquid; S3 mixing and modification: the resin solution and the filler dispersion liquid are mixed, and an aqueous polyacrylate leveling agent and a silicone polyether defoaming agent are added, and high-speed stirring is performed at a linear speed of 30 m / min for 1 hour.

[0063] S4 filtration and packaging: the ink oil is obtained by filtering through a 5 μm filter screen and then sealing and storing after removing impurities.

[0064] The ink oil obtained by mixing the above method is mixed with glass powder, printed on the surface of glass, and after drying, the scratch hardness grade (pencil hardness test) is tested; the dry film adhesion is tested; the gloss is tested at 680°C for 150 seconds.

[0065] Experimental method: according to the corresponding national test standard, the glass paste is printed on the non-tempered float glass by a 250 mesh screen, the printing wet film thickness is 20±2 μm, and the printing is dried at 180°C for 60s, and then tempered at 650°C for 130s, and the performance is compared with Example 1 as the standard. The experimental results are shown in the following table:

[0066] From the above table experimental data, it can be seen that: (1) Scratch resistance grade: depending on the synergistic effect of "nano alumina + polyethylene wax micro powder", the core influencing factor of scratch resistance grade is the composition and addition amount of the anti-scratch filler. The scratch resistance grade of Comparative Example 1 (without nano alumina, only containing polyethylene wax micro powder 5%) and Comparative Example 2 (without polyethylene wax micro powder, only containing nano alumina 2%) is 3B (worst); and Examples 1-4 all contain nano alumina (1%-3%) and polyethylene wax micro powder (3%-8%), and the grade is improved to B or HB, proving that the anti-scratch filler needs the synergistic effect of two components, and the use of any single component cannot achieve the anti-scratch effect. The total proportion of the anti-scratch filler of Example 2 is the lowest, and the scratch resistance grade is B; the proportion of the anti-scratch filler of Example 1 is the highest, and the grade is HB (best), which shows that the reduction of the content of the anti-scratch filler will affect the scratch resistance to a certain extent.

[0067] (2) The water-based aldehyde ketone resin and the scratch-resistant filler synergistically ensure firmness, and the dry film adhesion is mainly affected by the composition of the resin base and the integrity of the scratch-resistant filler. The dry film adhesion of Comparative Example 4 (the resin base only contains MPVB, without water-based aldehyde ketone resin) is poor; while Examples 1-4 all contain water-based aldehyde ketone resin, except for Example 4, which is slightly poor, proving that water-based aldehyde ketone resin is a key ingredient to improve adhesion, and its absence will lead to poor adhesion of the ink oil to the glass substrate. The adhesion of Comparative Example 1 (without nano-aluminum oxide) and Comparative Example 2 (without polyethylene wax powder) is poor, compared with the good / slightly poor adhesion of Examples 1-4 (containing complete scratch-resistant filler), which shows that the synergistic effect of the scratch-resistant filler not only improves the scratch resistance, but also helps to enhance the adhesion of the coating film to the substrate. The adhesion of Example 4 (water-based aldehyde ketone resin 9%, scratch-resistant filler 5%) is slightly poor, although it is better than Comparative Examples, but weaker than other examples, it is speculated that it is caused by the slight imbalance of the proportion of resin and scratch-resistant filler, which does not affect the core performance (still better than the comparative example without the key ingredient).

[0068] (3) The leveling agent is the core of determining "glossy / matte", and the gloss is mainly affected by the presence or absence and the amount of the leveling agent, and the secondary influencing factor is the particle size of the water-based aldehyde ketone resin. The gloss of Comparative Example 3 (without leveling agent) is matte (worst); Examples 1-4, Comparative Examples 1, 2 and 4 all contain leveling agent, and the gloss is glossy / slightly glossy, proving that the leveling agent is the key to ensuring the flatness of the coating film surface and achieving glossy effect, and its absence will lead to uneven coating film surface and matte. The amount of leveling agent in Example 3 is 0.5% (lower than 1.5% in Example 1), and the particle size of the water-based aldehyde ketone resin is D50=0.16μm (larger than 0.1μm in Example 1), and the gloss is slightly glossy; other examples containing leveling agent are glossy, which shows that insufficient amount of leveling agent or slightly larger particle size of the resin may cause slight decrease in gloss, but does not affect the core effect of "non-matte".

[0069] In summary, the scratch resistance requires the synergistic effect of nano-aluminum oxide and polyethylene wax powder, and both are indispensable, and the total amount is recommended to be ≥5%; the water-based aldehyde ketone resin is the core influencing factor of adhesion, and its absence will lead to significant decrease in adhesion; whether containing leveling agent is the key to gloss, and without leveling agent is matte, and the amount of leveling agent is recommended to be ≥0.5%. The three performances of the ink oil prepared in Example 1 are all optimal (scratch resistance HB, good adhesion, and glossy).

[0070] Obviously, the above examples are only examples for the purpose of clarity, and do not limit the embodiments. For ordinary skilled persons in the art, other different forms of changes or variations can be made on the basis of the above description. It is not necessary or possible to enumerate all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present invention.

Claims

1. A novel scratch resistant fountain solution characterized in that, consists of the following ingredients by weight percentage: Modified polyvinyl butyral 15~25%, water-based aldehyde ketone resin 8~15%, rosin modified maleic acid resin 5~10%, nano-alumina 1~3%, modified polyethylene wax powder 3~8%, silicone polyether defoaming agent 0.1~0.5%, water-based polyacrylate leveling agent 0.5~1.5%, erucic acid amide slip agent 1~2%, diethylene glycol butyl ether 40~45%, propylene glycol methyl ether 10~13%.

2. A novel scratch resistant fountain solution as claimed in claim 1 wherein, The modified polyvinyl butyral has an average molecular weight of 40000; and a viscosity of 60~100 mPa.s.

3. A novel scratch resistant fountain solution as claimed in claim 1 wherein, The modified polyvinyl butyral has a hydroxyl content of 34 mol%; and a butyral content of 65 mol%.

4. A novel scratch resistant fountain solution as claimed in claim 1 wherein, The water-based aldehyde ketone resin has a solid content of 41~42%.

5. A novel scratch resistant fountain solution as claimed in claim 1, wherein, The water-based aldehyde ketone resin has a viscosity of mPa•S≦250; and a particle size D50 of 0.1~1.0 μm.

6. A method of preparing a novel scratch resistant fountain solution, characterized in that, The method comprises the following steps: S1 resin pre-dispersion: mixing diethylene glycol butyl ether and propylene glycol methyl ether to form a solvent, taking half of the solvent to mix modified polyvinyl butyral, water-based aldehyde ketone resin and rosin modified maleic acid resin, then heating and stirring until completely dissolved to obtain a resin solution; S2 filler dispersion: adding nano-alumina, modified polyethylene wax powder and erucic acid amide into the remaining half of the solvent in step S1 in turn, then ultrasonic treatment to obtain a filler dispersion liquid; S3 mixing and modification: mixing the resin solution and the filler dispersion liquid, adding water-based polyacrylate leveling agent and silicone polyether defoaming agent, and stirring uniformly at a controlled stirring speed; S4 filtration and packaging: filtering through a 5 μm filter screen to remove impurities, then sealing and storing to obtain the ink oil.

7. The method of claim 6, wherein the new scratch resistant fountain solution is prepared by the steps of: In the S1 resin pre-dispersion step, the heating and stirring temperature is 40℃.

8. The method of claim 6, wherein the new scratch resistant fountain solution is prepared by the steps of: In the S2 filler dispersion step, the ultrasonic treatment time is 30 minutes.

9. The method of claim 6, wherein the new scratch resistant fountain solution is prepared by the steps of: In the S3 mixing and modification step, the stirring speed is 30 m / min, and the stirring time is 1 hour.

10. Use of a novel scratch resistant fountain solution, characterized in that, The application field is household appliance glass paste and automobile glass paste.

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