Glue-resistant ink and its preparation method and application

Abstract

The present invention relates to the field of ink technology, specifically disclosing a glue-resistant ink, its preparation method, and its application. The glue-resistant ink of the present invention comprises the following raw material components in parts by weight: 20-40 parts of an amino-functional silicone resin, 20-40 parts of an isocyanate, 40-65 parts of a pigment, and 2-10 parts of a solvent. The amino-functional silicone resin comprises an aminoalkylene group of the formula -R'-NH-R" directly bonded to a silicon atom, wherein R' is an alkylene group containing 2-5 carbon atoms, and R" is a hydrogen atom or an alkyl group containing 1-5 carbon atoms.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, in particular to a glue-resistant ink and a preparation method and application thereof. Background Art

[0002] In the electronics industry, adhesives, as key bonding materials, are widely used in product manufacturing processes, particularly in bonding mobile phone covers and midframes / bases. Currently, inks are being developed specifically for use with acrylic structural adhesives. However, with the increasing use of phenolic structural adhesives, the applicability of existing inks is insufficient to meet all product requirements. This is especially true for phenolic structural adhesives like tesa HAF® 59874, which easily penetrate the ink. This can lead to uneven coloration on the glass surface under UV irradiation, manifesting as a noticeable difference in color between the adhesive-applied and non-applied areas.

[0003] In general, some existing inks can meet conventional adhesion and other performance requirements, but their resistance to glue penetration is insufficient. This means they cannot effectively prevent glue from penetrating the coating, causing the glue to discolor under xenon lamp illumination and resulting in offset printing. Therefore, there is an urgent need for an ink that is both glue-resistant and has good adhesion. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides an application of an amino-functional silicone resin.

[0005] The present invention also provides a glue-resistant ink, wherein the raw materials for preparing the glue-resistant ink include the above-mentioned amino-functional silicone resin.

[0006] The present invention also provides a method for preparing the glue-resistant ink.

[0007] The present invention also provides the application of the glue-resistant ink.

[0008] According to one aspect of the present invention, an application of an amino-functional silicone resin in glue-resistant ink is proposed.

[0009] According to another aspect of the present invention, a glue-resistant ink is provided, comprising the following raw material components in parts by weight: 20 to 40 parts of the above-mentioned amino-functional silicone resin, 20 to 40 parts of isocyanate, 40 to 65 parts of pigment, and 2 to 10 parts of solvent.

[0010] In some embodiments of the present invention, the amino-functional silicone resin of the present invention comprises an aminoalkylene group of the formula -R'-NH-R" directly connected to a silicon atom, wherein R' is an alkylene group containing 2 to 5 carbon atoms, and R" is a hydrogen atom or an alkyl group containing 1 to 5 carbon atoms.

[0011] Those skilled in the art will appreciate that the amino-functional groups in the amino-functional silicone resin can be introduced into the reactive polysiloxane, for example, using aminosilanes. It should also be understood that the amino-functional polysiloxane can be prepared in situ. For example, amino-functional groups can be introduced by reacting a hydroxy-functional or alkoxy-functional polysiloxane with an aminosilane. For example, an aminosilane can be reacted with an α,ω-dihydroxypolydimethylsiloxane at a temperature of 20-80°C. Preferably, 0.4-1.2 alkoxy groups of the aminosilane are used per silanol group of the polysiloxane. If an excess of aminosilane is used or the reaction does not proceed to completion, a small amount of aminosilane may remain in the product. The at least one amino-functional polysiloxane is the reaction product of a polysiloxane and an aminosilane. Preferably, the amino-functional silicone resin of the present invention does not contain hydrolyzable and / or condensable groups, such as alkoxy, acyloxy, ketoimino, alkoxy, and / or alkenyloxy groups.

[0012] In some embodiments of the present invention, the amino-functional silicone resin is a silsesquioxane, generally having [RSiO 3 / 2 ]t structure, wherein R represents an organic group and t is an integer from 6 to 12, and t is preferably 6, 8, 10, or 12.

[0013] In some preferred embodiments of the present invention, the silsesquioxane of the present invention has the following structural formula , wherein at least one of the R'1 to R'8 groups is a phenyl group, at least one of the R'1 to R'8 groups is a hydroxyl group or an aminoalkylene group of the formula -R'-NH-R", and R' and R" are as defined above.

[0014] In some embodiments of the present invention, R' is an alkylene group containing 2, 3, 4, or 5 carbon atoms.

[0015] In some embodiments of the present invention, R" is an alkyl group containing 1, 2, 3, 4, or 5 carbon atoms.

[0016] In some embodiments of the present invention, the number average molecular weight of the amine-functional silicone resin is 500 g / mol to 1500 g / mol, for example, 500-1200 g / mol, 500-1000 g / mol, 500-900 g / mol, 500-800 g / mol, 600-1500 g / mol, 600-1200 g / mol, 600-1000 g / mol, about 700 g / mol, about 900 g / mol, about 1100 g / mol, about 1300 g / mol, about 1400 g / mol. The number average molecular weight of the amine-functional silicone resin can be measured by methods known to those skilled in the art, for example, by size exclusion chromatography using polystyrene-type standards.

[0017] In some embodiments of the present invention, the amine equivalent weight of the amino-functional silicone resin is 220-300. In other words, the content of the Si-R'-NH-R" units in the amino-functional silicone resin is such that the weight of the amino-functional silicone resin per mole of NH is 220-300 g, for example, 220-290 g, 220-280 g, 220-270 g, 220-260 g, 220-250 g, 220-240 g, 230-280 g, 230-270 g, 230-260 g, 230-250 g, 240-270 g, 240-260 g, or 240-250 g.

[0018] In some embodiments of the present invention, the amino functional silicone resin may be selected from Dow Chemical DOWSIL TM 3055, with an amine equivalent weight of 250-270 g / NH. The amino-functional silicone resin, through its structure containing active hydrogen amino groups, can react chemically with isocyanates to form a silicon-organic copolymer. This allows the coating and substrate to form a three-dimensional network structure, ensuring adhesion while strengthening cross-linking and improving resistance to glue penetration. An exemplary reaction formula can be shown below:

[0019] .

[0020] The active amine (amino group containing active hydrogen) in the amino-functional silicone resin reacts with the NCO group in the HDI curing agent to form a urea group. At the same time, an aminosilane coupling agent is added. One end reacts with the NCO group, while the other end dehydrates with the hydroxyl group on the material to form a hydrogen bond, forming a three-dimensional network structure.

[0021] In some embodiments of the present invention, the isocyanate is a blocked isocyanate.

[0022] In some preferred embodiments of the present invention, the effective NCO% of the blocked isocyanate is 9-11 wt%, for example, about 10 wt%.

[0023] In some preferred embodiments of the present invention, the solid content of the blocked isocyanate is 65-75 wt%, for example, about 66 wt%, about 67 wt%, about 68 wt%, about 69 wt%, about 70 wt%, about 71 wt%, about 72 wt%, about 73 wt%, about 74 wt%.

[0024] In some preferred embodiments of the present invention, the viscosity of the blocked isocyanate (measured at 25° C.) is 2500-3500 mPa·s, for example, about 2500-3300 mPa·s, about 2500-3200 mPa·s, about 2500-3000 mPa·s, about 2700-3300 mPa·s, about 2700-3000 mPa·s, about 2800-3200 mPa·s, or about 2800-3000 mPa·s.

[0025] The blocked isocyanate is selected from at least one of Asahi Kasei SBN-70D, TBN-75PS, WS20-70D, and TKA-B75S.

[0026] In some embodiments of the present invention, the pigment is selected from at least one of carbon black, graphite, iron black, aniline black, titanium dioxide, barium sulfate, zinc white, lithopone, and iron oxide red.

[0027] In some embodiments of the present invention, the pigment comprises titanium dioxide and barium sulfate. Preferably, the weight ratio of titanium dioxide to barium sulfate is 4 to 9:1, preferably about 5 to 8:1, about 6:1, or about 7:1.

[0028] In some preferred embodiments of the present invention, the titanium dioxide is selected from at least one of Chemours R-960, TS-6300, R-900, Tronox CR-828, and Huntsman TR-81.

[0029] In some embodiments of the present invention, the particle size of the pigment is 0.2-1 μm, such as 0.4-0.8 μm, 0.5-0.7 μm.

[0030] In some embodiments of the present invention, the solvent is selected from at least one of isophorone and DBE.

[0031] In some embodiments of the present invention, the raw materials for preparing the glue-resistant ink further include fillers.

[0032] In some embodiments of the present invention, the filler is selected from at least one of calcium carbonate, silicon dioxide, aluminum oxide, zinc oxide, talc, hydrotalcite, magnesium hydroxide, calcium hydroxide, wollastonite, kaolin, and montmorillonite.

[0033] In some embodiments of the present invention, the particle size of the filler is 1-5 μm, for example, 2-4 μm.

[0034] In some embodiments of the present invention, the raw materials for preparing the glue-resistant ink further include functional additives.

[0035] In some embodiments of the present invention, the functional additive is selected from at least one of an antioxidant, a defoaming agent, a surfactant, a leveling agent, a dispersant, a wetting agent, and a pH stabilizer.

[0036] In some preferred embodiments of the present invention, the dispersant is selected from at least one of BYK-161, BYK-163, Tego670, Lubrizol 20000, and BYK-110.

[0037] In some preferred embodiments of the present invention, the defoaming agent is selected from at least one of BYK-054, BYK-1790, BYK-1710, and Tego Foamex N.

[0038] In some preferred embodiments of the present invention, the wetting agent is selected from at least one of TEGO Wet 240, Euka Chemical 6345, TEGO 460N, and EFKA FL 3600.

[0039] In some embodiments of the present invention, the glue-resistant ink comprises the following raw material components in parts by weight:

[0040] 20-40 parts of amino-functional silicone resin, 20-40 parts of blocked isocyanate, 35-55 parts of titanium dioxide, 5-10 parts of barium sulfate, and 2-10 parts of solvent.

[0041] In some embodiments of the present invention, the glue-resistant ink comprises the following raw material components in parts by weight:

[0042] 20-40 parts of amino-functional silicone resin, 20-40 parts of blocked isocyanate, 35-55 parts of titanium dioxide, 5-10 parts of barium sulfate, 3-10 parts of talc, 2-5 parts of dispersant, 2-10 parts of solvent, 1-3 parts of defoaming agent, and 0-3 parts of wetting and leveling agent.

[0043] In some embodiments of the present invention, the glue-resistant ink comprises the following raw material components in parts by weight:

[0044] 20-35 parts of amino-functional silicone resin, 20-35 parts of blocked isocyanate, 35-55 parts of titanium dioxide, 5-8 parts of barium sulfate, 3-10 parts of talc, 2-5 parts of dispersant, 2-10 parts of solvent, 1-3 parts of defoaming agent, and 0.5-3 parts of wetting and leveling agent.

[0045] In some embodiments of the present invention, the weight of the amino-functional silicone resin is 20 to 40 parts, for example, about 20 parts, about 25 parts, or about 30 parts. The weight of the blocked isocyanate is 20 to 40 parts, for example, about 20 parts, about 25 parts, or about 30 parts. The weight of the dispersant is 2 to 5 parts, for example, about 2 parts, about 3 parts, or about 4 parts. The weight of the titanium dioxide is 35 to 55 parts, for example, about 38 parts, about 40 parts, about 45 parts, or about 50 parts. The weight of the barium sulfate is 5 to 8 parts, for example, about 6 parts or about 7 parts. The weight of the talc is 3 to 10 parts, for example, about 4 parts, about 5 parts, about 6 parts, about 7 parts, about 8 parts, or about 9 parts. The weight of the solvent is 2 to 10 parts, for example, about 3 parts, about 4 parts, about 5 parts, about 6 parts, about 7 parts, or about 8 parts. The weight portion of the defoaming agent is 1 to 3 parts, for example, 2 parts. The weight portion of the wetting and leveling agent is 0.5 to 3 parts, for example, about 1 part, about 1.5 parts, about 2 parts, or about 2.5 parts.

[0046] According to another aspect of the present invention, there is provided a method for preparing the above-mentioned glue-resistant ink, comprising the following steps:

[0047] According to the proportion, the amino-functional silicone resin, isocyanate, pigment and solvent are mixed. If at least one of a filler and a functional auxiliary agent is present, the at least one of the filler and the functional auxiliary agent is added in the mixing step.

[0048] In some embodiments of the present invention, the preparation method comprises the following steps:

[0049] According to the ratio, the amino functional silicone resin, isocyanate and solvent are first mixed for the first time, the dispersant is added for the second mixing, the pigment and filler are added for the third mixing, ground, and the defoamer and wetting agent are added for the fourth mixing to obtain the product.

[0050] In some embodiments of the present invention, the first mixing is carried out at a rotation speed of 500-1000 rpm for 5-15 minutes.

[0051] In some embodiments of the present invention, the second mixing is carried out at a rotation speed of 500-1000 rpm for 5-15 minutes.

[0052] In some embodiments of the present invention, the third mixing is carried out at a rotation speed of 500-1000 rpm for 5-15 minutes.

[0053] In some embodiments of the present invention, the grinding is performed to a fineness of less than 10 μm.

[0054] In some embodiments of the present invention, the grinding is performed using a three-roll mill or a high-viscosity sand mill.

[0055] In some embodiments of the present invention, the fourth mixing is performed at a rotation speed of 500-1000 rpm for 5-15 minutes.

[0056] According to another aspect of the present invention, there is provided a use of the above-mentioned glue-resistant ink in an electronic device housing.

[0057] According to some embodiments of the present invention, there are at least the following beneficial effects:

[0058] Existing technologies commonly use hydroxyl-terminated polyesters, polyurethanes, and acrylic resins to prepare glue-resistant inks. While these hydroxyl groups can dehydrate with active groups on glass to form hydrogen bonds, improving adhesion, they can also react with methacrylic acid, acrylic acid, phenolic resins, and other components in the glue, causing glue penetration and offset printing under UV irradiation. The present invention replaces the hydroxyl-containing resin with a reactive amino-functional silicone resin. This effectively reduces the reaction with the glue and, by introducing silicon groups, effectively prevents the penetration of small molecules in the glue. The active amines can simultaneously react with isocyanate curing agents and silane coupling agents to form a three-dimensional network structure, further enhancing the coating's anti-glue effect.

[0059] The present invention defines:

[0060] The term "polysiloxane" in the present invention is known in the art and is defined as a polysiloxane having a repeating silicon-oxygen backbone (Si-O) n A polymer wherein each Si atom is typically substituted by two organic groups. Typically, the organic substituents on each Si atom are selected from, for example, alkyl groups (such as methyl or ethyl) or phenyl groups.

[0061] As used herein, the term "amine-functional silicone resin" may be understood as "amine-functional polysiloxane," which refers to a polysiloxane having at least one reactive amine group attached via a carbon bond at a terminal and / or pendant position. The amine is selected from primary and secondary amines and contains a reactive hydrogen atom. In the context of this invention, there must be at least one primary amino group, at least two secondary amino groups, or at least one primary and at least one secondary amino group.

[0062] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0063] The following will clearly and completely describe the concept and technical effects of the present invention in conjunction with the embodiments to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0064] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0065] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are understood to include any and all subranges subsumed therein.

[0066] Unless otherwise specified, “about” in the present invention means that the allowable error is within ±20%, or further, within ±10%.

[0067] The terms "preferably," "more preferably," and the like, used herein refer to embodiments of the present invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the present invention.

[0068] "Parts by weight" is a basic unit of measurement used to express the weight ratio of multiple components. One part can represent any unit weight, such as 1g or 2.689g. For example, if we say that the parts by weight of component A are a parts and the parts by weight of component B are b parts, this means the ratio of the weight of component A to the weight of component B is a:b. Alternatively, we could say that the weight of component A is aK and the weight of component B is bK (where K is an arbitrary number representing a multiplication factor). It's important to note that, unlike parts by weight, the sum of the parts by weight of all components is not limited to 100 parts.

[0069] Unless otherwise specified, "room temperature" in the present invention means (25±5)°C.

[0070] Unless otherwise specified, the amino-functional silicone resins used in the embodiments of the present invention are all DOWSIL TM 3055 polysiloxane resin, CAS number: 1242619-23-3, has a number average molecular weight of about 600-800 g / mol and contains at least one phenyl group and at least one aminopropyl group directly attached to a silicon atom; the content of Si-aminopropyl units is such that the weight of each mole of NH silsesquioxane is about 260 g.

[0071] Unless otherwise specified, the solvent DBE used in the examples and comparative examples of the present invention was purchased from Omode New Materials Co., Ltd.

[0072] Example 1

[0073] This embodiment provides a glue-resistant ink.

[0074] The glue-resistant ink is composed of the following components by weight:

[0075] 20 parts of amino functional silicone resin,

[0076] Asahi Kasei SBN-70D blocked isocyanate curing agent 25 parts,

[0077] BYK-161 dispersant 2 parts,

[0078] 40 parts of Chemours R-960 titanium dioxide (particle size of about 0.5 μm),

[0079] 5 parts of barium sulfate (particle size about 0.7 μm),

[0080] 3 parts of talc powder (particle size about 3 μm),

[0081] 3 copies of DBE,

[0082] BYK-054 defoamer 1.5 parts,

[0083] 0.5 parts of TEGO Wet 240 wetting agent.

[0084] The preparation method of this glue-resistant ink is as follows:

[0085] First, disperse the amino-functional silicone resin, Asahi Kasei SBN-70D blocked isocyanate curing agent and DBE at 800 rpm for 10 minutes (temperature controlled below 60°C), then add BYK-161 dispersant and disperse at room temperature at 800 rpm for 10 minutes, then add Chemours R-960 titanium dioxide, barium sulfate and talc and continue to disperse at room temperature at 800 rpm for 30 minutes, then put it into a three-roll mill (can also be replaced by a high-viscosity sand mill) for grinding; grind 2 to 3 times until the grinding fineness is below 10μm, remove the ink, continue to add BYK-054 defoamer and TEGO Wet 240 wetting agent to the ink, and disperse at room temperature at about 700 rpm for 10 minutes to obtain glue-resistant ink.

[0086] Example 2

[0087] This embodiment provides a glue-resistant ink.

[0088] The glue-resistant ink is composed of the following components by weight:

[0089] 25 parts of amino functional silicone resin,

[0090] Asahi Kasei SBN-70D blocked isocyanate curing agent 20 parts,

[0091] BYK-161 dispersant 2 parts,

[0092] 38 parts of Chemours R-960 titanium dioxide (particle size of about 0.5 μm),

[0093] 7 parts of barium sulfate (particle size about 0.7 μm),

[0094] 3 parts of talc powder (particle size about 3 μm),

[0095] 3 copies of DBE,

[0096] BYK-054 defoamer 1.5 parts,

[0097] 0.5 parts of TEGO Wet 240 wetting agent.

[0098] The preparation method of this glue-resistant ink is as follows:

[0099] First, disperse the amino-functional silicone resin, Asahi Kasei SBN-70D blocked isocyanate curing agent and DBE at 800 rpm for 10 minutes (temperature controlled below 60°C), then add BYK-161 dispersant and disperse at room temperature at 800 rpm for 10 minutes, then add Chemours R-960 titanium dioxide, barium sulfate and talc and continue to disperse at room temperature at 800 rpm for 30 minutes, then put it into a three-roll mill (can also be replaced by a high-viscosity sand mill) for grinding; grind 2 to 3 times until the grinding fineness is below 10μm, remove the ink, continue to add BYK-054 defoamer and TEGO Wet 240 wetting agent to the ink, and disperse at room temperature at about 700 rpm for 10 minutes to obtain glue-resistant ink.

[0100] Example 3

[0101] This embodiment provides a glue-resistant ink.

[0102] The glue-resistant ink is composed of the following components by weight:

[0103] 20 parts of amino functional silicone resin,

[0104] Asahi Kasei SBN-70D blocked isocyanate curing agent 20 parts,

[0105] BYK-161 dispersant 2 parts,

[0106] 40 parts of Chemours R-960 titanium dioxide (particle size of about 0.5 μm),

[0107] 5 parts of barium sulfate (particle size about 0.7 μm),

[0108] 3 parts of talc powder (particle size about 3 μm),

[0109] 3 copies of DBE,

[0110] BYK-054 defoamer 1.5 parts,

[0111] 0.5 parts of TEGO Wet 240 wetting agent.

[0112] The preparation method of this glue-resistant ink is as follows:

[0113] First, disperse the amino-functional silicone resin, Asahi Kasei SBN-70D blocked isocyanate curing agent and DBE at 800 rpm for 10 minutes (temperature controlled below 60°C), then add BYK-161 dispersant and disperse at room temperature at 800 rpm for 10 minutes, then add Chemours R-960 titanium dioxide, barium sulfate and talc and continue to disperse at room temperature at 800 rpm for 30 minutes, then put it into a three-roll mill (can also be replaced by a high-viscosity sand mill) for grinding; grind 2 to 3 times until the grinding fineness is below 10μm, remove the ink, continue to add BYK-054 defoamer and TEGO Wet 240 wetting agent to the ink, and disperse at room temperature at about 700 rpm for 10 minutes to obtain glue-resistant ink.

[0114] Example 4

[0115] This embodiment provides a glue-resistant ink.

[0116] The glue-resistant ink is composed of the following components by weight:

[0117] 30 parts of amino functional silicone resin,

[0118] Asahi Kasei SBN-70D blocked isocyanate curing agent 20 parts,

[0119] BYK-161 dispersant 2 parts,

[0120] 40 parts of Chemours R-960 titanium dioxide (particle size of about 0.5 μm),

[0121] 5 parts of barium sulfate (particle size about 0.7 μm),

[0122] 3 parts of talc powder (particle size about 3 μm),

[0123] 3 copies of DBE,

[0124] BYK-054 defoamer 1.5 parts,

[0125] 0.5 parts of TEGO-240 wetting agent.

[0126] The preparation method of this glue-resistant ink is as follows:

[0127] First, disperse the amino-functional silicone resin, Asahi Kasei SBN-70D blocked isocyanate curing agent and DBE at 800 rpm for 10 minutes (temperature controlled below 60°C), then add BYK-161 dispersant and disperse at room temperature at 800 rpm for 10 minutes, then add Chemours R-960 titanium dioxide, barium sulfate and talc and continue to disperse at room temperature at 800 rpm for 30 minutes, and then put it into a three-roll mill (which can also be replaced by a high-viscosity sand mill) for grinding; grind 2 to 3 times until the grinding fineness is below 10μm, remove the ink, continue to add BYK-054 defoamer and TEGO-240 wetting agent to the ink, and disperse at room temperature at about 700 rpm for 10 minutes to obtain glue-resistant ink.

[0128] Comparative Example 1

[0129] This comparative example provides an ink.

[0130] The ink is composed of the following components by weight:

[0131] NP-1230D hydroxy acrylic resin from Guangzhou Xinyingyuan Chemical Co., Ltd. 20 parts,

[0132] Asahi Kasei SBN-70D blocked isocyanate curing agent 25 parts,

[0133] BYK-161 dispersant 2 parts,

[0134] 40 parts of Chemours R-960 titanium dioxide (particle size of about 0.5 μm),

[0135] 5 parts of barium sulfate (particle size about 0.7 μm),

[0136] 3 parts of talc powder (particle size about 3 μm),

[0137] 3 copies of DBE,

[0138] BYK-054 defoamer 1.5 parts,

[0139] 0.5 parts of TEGO Wet 240 wetting agent.

[0140] The preparation method of the ink is as follows:

[0141] First, disperse NP-1230D hydroxy acrylic resin, Asahi Kasei SBN-70D blocked isocyanate curing agent and DBE at 800 rpm for 10 minutes (temperature controlled below 60°C), then add BYK-161 dispersant and disperse at room temperature at 800 rpm for 10 minutes, then add Chemours R-960 titanium dioxide, barium sulfate and talc and continue to disperse at room temperature at 800 rpm for 30 minutes, then put it into a three-roll mill (can also be replaced by a high-viscosity sand mill) for grinding; grind 2 to 3 times until the grinding fineness is less than 10μm, remove the ink, continue to add BYK-054 defoamer and TEGO Wet 240 wetting agent to the ink, and disperse at room temperature at about 700 rpm for 10 minutes to obtain the ink.

[0142] Comparative Example 2

[0143] This comparative example provides an ink.

[0144] The ink is composed of the following components by weight:

[0145] Ruitai Chemical A-472 polyester resin 20 parts,

[0146] Asahi Kasei SBN-70D blocked isocyanate curing agent 25 parts,

[0147] BYK-161 dispersant 2 parts,

[0148] 40 parts of Chemours R-960 titanium dioxide (particle size of about 0.5 μm),

[0149] 5 parts of barium sulfate (particle size about 0.7 μm),

[0150] 3 parts of talc powder (particle size about 3 μm),

[0151] 3 copies of DBE,

[0152] BYK-054 defoamer 1.5 parts,

[0153] 0.5 parts of TEGO-240 wetting agent.

[0154] The preparation method of the ink is as follows:

[0155] First, disperse A-472 polyester resin, Asahi Kasei SBN-70D blocked isocyanate curing agent and DBE at 800 rpm for 10 minutes (temperature controlled below 60°C), then add BYK-161 dispersant and disperse at room temperature at 800 rpm for 10 minutes, then add Chemours R-960 titanium dioxide, barium sulfate and talc and continue to disperse at room temperature at 800 rpm for 30 minutes, and then put it into a three-roll mill (which can also be replaced by a high-viscosity sand mill) for grinding; grind 2 to 3 times until the grinding fineness is below 10μm, remove the ink, continue to add BYK-054 defoamer and TEGO Wet 240 wetting agent to the ink, and disperse at room temperature at about 700 rpm for 10 minutes to obtain the ink.

[0156] Comparative Example 3

[0157] This comparative example provides an ink.

[0158] The ink is composed of the following components by weight:

[0159] Asahi Kasei T5652 polycarbonate resin 20 parts,

[0160] Asahi Kasei SBN-70D blocked isocyanate curing agent 25 parts,

[0161] BYK-161 dispersant 2 parts,

[0162] 40 parts of Chemours R-960 titanium dioxide (particle size of about 0.5 μm),

[0163] 5 parts of barium sulfate (particle size about 0.7 μm),

[0164] 3 parts of talc powder (particle size about 3 μm),

[0165] 3 copies of DBE,

[0166] BYK-054 defoamer 1.5 parts,

[0167] 0.5 parts of TEGO Wet 240 wetting agent.

[0168] The preparation method of the ink is as follows:

[0169] First, disperse T5652 polycarbonate resin, Asahi Kasei SBN-70D blocked isocyanate curing agent and DBE at 800 rpm for 10 minutes (temperature controlled below 60°C), then add BYK-161 dispersant and disperse at room temperature at 800 rpm for 10 minutes, then add Chemours R-960 titanium dioxide, barium sulfate and talc and continue to disperse at room temperature at 800 rpm for 30 minutes, then put it into a three-roll mill (can also be replaced by a high-viscosity sand mill) for grinding; grind 2 to 3 times until the grinding fineness is below 10μm, remove the ink, continue to add BYK-054 defoamer and TEGO Wet 240 wetting agent to the ink, and disperse at room temperature at about 700 rpm for 10 minutes to obtain the ink.

[0170] Comparative Example 4

[0171] This comparative example provides an ink.

[0172] The ink is composed of the following components by weight:

[0173] 40 parts of Wacker-E15 methoxy silicone resin,

[0174] Asahi Kasei SBN-70D blocked isocyanate curing agent 5 parts,

[0175] BYK-161 dispersant 2 parts,

[0176] 40 parts of Chemours R-960 titanium dioxide (particle size of about 0.5 μm),

[0177] 5 parts of barium sulfate (particle size about 0.7 μm),

[0178] 3 parts of talc powder (particle size about 3 μm),

[0179] 3 copies of DBE,

[0180] BYK-054 defoamer 1.5 parts,

[0181] 0.5 parts of TEGO-240 wetting agent.

[0182] The preparation method of the ink of this comparative example is carried out in reference to Example 1.

[0183] Test Case

[0184] The ink components prepared in the above proportions were printed in four layers using a 250-mesh polyester screen, with a printed film thickness of 30 µm. The mixing ratio was ink: silane coupling agent (Dynasylan DAMO T, purchased from Evonik): DBE = 100:1:10. The first three layers were baked at 150°C for 5 minutes, and the last layer was baked at 150°C for 30 minutes.

[0185] The test data of the inks prepared in the test examples and comparative examples for glue resistance are as follows (Note: test standards and instruments):

[0186] Adhesion test standard: Use a tinplate (50×100×0.2-0.3 mm), a four-fold magnifying glass, and a paintbrush (25-35 mm wide). Prepare three test specimens on the tinplate (or substrate specified in the product standard). After the paint film is completely dry, test under constant temperature and humidity conditions. Before testing, inspect the needle of the adhesion tester; if it is blunt, replace it. For testing, place the specimen upright on the test bench, tighten the specimen adjustment bolts and the adjustment bolts. Move the lifting rod backward until the tip of the needle contacts the paint film. If the scratch does not expose the substrate, add a weight as appropriate. Turn the handle evenly clockwise at a speed of 80-100 rpm. The standard length of the circular line scratch is 7-8 cm. Move the lifting rod forward to raise the needle plate. Loosen the bolts securing the specimen, remove the specimen, and use a paintbrush to remove any paint chips from the scratch. Inspect the scratch with a four-fold magnifying glass and rate it.

[0187] Film thickness testing instrument: Japan Mitutoyo thin-sheet micrometer No. 293 240 30.

[0188] 8540 glue resistance test method: on the finished sample, mix 8540 glue AB glue evenly and apply glue, then cover with transparent glass material (load 4500g for 20s), then press 200g weight on it, put it in a 60℃ oven and bake for 20 minutes; take out the sample and place it with the glass side facing up at 420nm, 0.8w / cm 2 Under the conditions of irradiation for 400 hours, observe whether there is offset printing.

[0189] Test method for tesa HAF® 59874 resistance: Apply tesa adhesive to the ink layer on a pre-made sample, then cover with transparent glass. Place a 4500g weight on top and bake in a 150°C oven for 20 minutes. Remove the sample and expose it, glass-side up, at 420nm, 0.8w / cm² for 400 hours to observe for any signs of offset.

[0190] The test results are shown in Table 1.

[0191] Table 1

[0192]

[0193] As can be seen from the data in Table 1, the inks made from amino-functional silicone resins in Examples 1-4 have obvious differences when applied with different glues compared to inks made from other types of resins. In the former, no traces of glue dispensing can be seen under naked eye observation, while the control examples have obvious offset printing, which can be discovered by users during use and affect the overall aesthetics.

[0194] The above content describes the embodiments of the present invention in detail. However, the present invention is not limited to the above embodiments. Various modifications can be made within the scope of knowledge possessed by a person skilled in the art without departing from the spirit of the present invention. In addition, the embodiments of the present invention and the features thereof can be combined with each other unless there is a conflict.

Claims

1. A glue-resistant ink, characterized in that: The invention comprises the following raw material components in parts by weight: 20 to 40 parts of amino-functional silicone resin, 20 to 40 parts of isocyanate, 40 to 65 parts of pigment, and 2 to 10 parts of solvent; The amino-functional silicone resin is silsesquioxane, the number average molecular weight of the amino-functional silicone resin is 500-1500 g / mol, and the amine equivalent weight of the amino-functional silicone resin is 220-300; The isocyanate is a blocked isocyanate; the amino-functional silicone resin comprises an aminoalkylene group of the formula -R'-NH-R" directly connected to a silicon atom, wherein R' is an alkylene group containing 2 to 5 carbon atoms, and R" is a hydrogen atom or an alkyl group containing 1 to 5 carbon atoms; The amine-functional silicone resin does not contain hydrolyzable and / or condensable groups.

2. The glue-resistant ink according to claim 1, characterized in that: The effective NCO% of the blocked isocyanate is 9-11 wt %, the solid content of the blocked isocyanate is 65-75 wt %, and the viscosity of the blocked isocyanate is 2500-3500 mPa·s.

3. The glue-resistant ink according to claim 1, characterized in that: The pigment is selected from at least one of carbon black, graphite, iron black, aniline black, titanium dioxide, barium sulfate, zinc white, lithopone, and iron oxide red, and the particle size of the pigment is 0.2-1 μm.

4. The glue-resistant ink according to claim 1, characterized in that: The solvent is selected from at least one of isophorone and DBE.

5. The glue-resistant ink according to claim 1, characterized in that: The raw materials for preparing the glue-resistant ink also include at least one of a filler and a functional additive, the filler is selected from at least one of calcium carbonate, silicon dioxide, aluminum oxide, zinc oxide, talc, hydrotalcite, magnesium hydroxide, calcium hydroxide, wollastonite, kaolin, and montmorillonite, and the particle size of the filler is 1 to 5 μm; the functional additive is selected from at least one of an antioxidant, a defoaming agent, a surfactant, a leveling agent, a dispersant, a wetting agent, and a pH stabilizer.

6. A method for preparing the glue-resistant ink according to any one of claims 1 to 5, characterized in that: The following steps are involved: According to the ratio, the amino functional silicone resin, isocyanate, pigment and solvent are mixed. If at least one of a filler and a functional auxiliary agent is present, the at least one of the filler and the functional auxiliary agent is added in the mixing step.

7. Use of the glue-resistant ink according to any one of claims 1 to 5 or the glue-resistant ink prepared by the preparation method according to claim 6 in an electronic device housing.

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