Epoxy polyether intermediate, dye, preparation methods of epoxy polyether intermediate and dye, and coiled material

Abstract

The invention discloses an epoxy polyether intermediate, a dye, preparation methods of the epoxy polyether intermediate and the dye, and a coiled material, and relates to the technical field of dyes. The structural formula of the epoxy polyether intermediate is as follows: # imgabs0. According to the epoxy polyether intermediate provided by the invention, an H bond on aniline polyoxyethylene ether reacts with Cl on epoxy chloropropane, so that epoxy propane is grafted at the tail end of the aniline polyoxyethylene ether, and the epoxy polyether intermediate with an epoxy structure at the end part is formed; the epoxy polyether intermediate can be conveniently subsequently combined with a diazo group, so that the epoxy polyether intermediate can react with a pigment compound, an epoxy active group is added to the tail end of a dye, and the epoxy active group can react with resin to enable the dye to be more firmly attached to the coiled material; the molecular weight of the dye is improved to enable the dye to be liquified, the hydrophilic-hydrophobic property of the tail end of the dye can be adjusted according to resin used by different coiled materials to adapt to the resin, and the intermiscibility with the resin is improved; in addition, the liquid dye is safer and more environment-friendly in feeding.

Description

Technical Field

[0001] The invention relates to the technical field of dyes, and in particular to an epoxy polyether intermediate, a dye, and a preparation method and a coiled material thereof. Background Art

[0002] Nowadays, the main dyes used for PET coil coatings on the market are powder dyes such as acid red 52, solvent red 207, solvent blue 70, 104, and acid yellow 59. These dyes are added to the resin and mixed evenly, then applied to the PET film, and then cured at high temperature to form the corresponding PET coil. However, the above coils have poor migration resistance in solvents such as hot water, acetone, and ethanol; uneven dissolution and mixing of powders will lead to defective products such as shrinkage holes and particle protrusions; in addition, the dust generated during the addition of powders is very harmful to the human body and the environment. Previously, there was also a patent study on the use of aniline polyoxyethylene ether to synthesize rose red for use in coils. It relies on the reaction of hydroxyl or carboxyl groups with amino resins to make it have better resistance. In order to make the adhesive density larger, it is necessary to construct multiple hydroxyl or carboxyl groups, which limits the structure of the dye intermediate and cannot be widely promoted to various colors.

[0003] In view of this, the present invention is proposed. Summary of the invention

[0004] The object of the present invention is to provide an epoxy polyether intermediate, a dye, and a preparation method and a coiled material thereof.

[0005] The present invention is achieved in that:

[0006] In a first aspect, the present invention provides an epoxy polyether intermediate, the structural formula of which is as follows:

[0007]

[0008] Wherein R represents any one of H, CH3, OCH3, NHCOCH3 or halogen, m and n represent any integer between 0 and 20 respectively, and m+n≥5.

[0009] In a second aspect, the present invention provides a method for preparing an epoxy polyether intermediate as described in the aforementioned embodiment, wherein the epoxy polyether intermediate is prepared by a mixed reaction of aniline polyoxyethylene ether and epichlorohydrin.

[0010] In an optional embodiment, the preparation method of the epoxy polyether intermediate includes at least one of features (1) to (3):

[0011] Feature (1): The molar ratio of the aniline polyoxyethylene ether to the epichlorohydrin is 1:2.1-3.0;

[0012] Feature (2): The aniline polyoxyethylene ether and epichlorohydrin react in the presence of a first pH regulator, and the first pH regulator is selected from one or more of liquid alkali, baking soda, calcium hydroxide, potassium hydroxide, soda ash, and triethylamine;

[0013] Feature (3): When preparing the epoxy polyether intermediate, the system temperature is controlled at 40 - 80 °C and the reaction time is 5 - 10 h.

[0014] In the third aspect, the present invention provides an epoxy polyether dye, and the structural formula of the epoxy polyether dye is:

[0015] wherein Y is a pigment compound, the pigment compound includes a red compound, a yellow compound or a blue compound, the red compound is o-chloro-p-nitroaniline, the yellow compound is aniline, and the blue compound is 3-amino-5-nitro-benzisothiazole.

[0016] In the fourth aspect, the present invention provides a preparation method of an epoxy polyether dye, which includes carrying out a coupling reaction on the epoxy polyether intermediate and the diazonium salt of the pigment compound as described in the above embodiment.

[0017] In an alternative embodiment, the coupling reaction includes at least one of the following features (4) - feature (6):

[0018] Feature (4): The molar ratio of the epoxy polyether intermediate to the diazonium salt of the pigment compound is 1.01 - 1.15:1;

[0019] Feature (5): The epoxy polyether intermediate and the diazonium salt of the pigment compound react in the presence of a second pH regulator; during the coupling reaction, the second pH regulator controls the system pH to 7 - 8, and the second pH regulator is selected from one or more of liquid alkali, baking soda, calcium hydroxide, potassium hydroxide, soda ash, and triethylamine;

[0020] Feature (6): During the coupling reaction, the system temperature is controlled at 5 - 15 °C, the system pH value is adjusted to 7 - 7.5, and the reaction proceeds to the end point.

[0021] In an alternative embodiment, the diazonium salt of the pigment compound includes the diazonium salt of a red compound, the diazonium salt of a yellow compound or the diazonium salt of a blue compound;

[0022] Among them, the preparation method of the diazonium salt of the red compound or the diazonium salt of the yellow compound includes: using o-chloro-p-nitroaniline or aniline as a raw material, mixing it with hydrochloric acid, sodium nitrite and water, and performing a diazo reaction at 3-8 °C for more than 2 h; the molar ratio of o-chloro-p-nitroaniline or aniline to sodium nitrite is 1:1.01-1.1;

[0023] And / or, the preparation method of the diazonium salt of the blue compound includes: mixing nitrosyl sulfuric acid and sulfuric acid, then adding 3-amino-5-nitro-benzisothiazole, and performing a diazo reaction at 0-10 °C for 2-5 h; the molar ratio of nitrosyl sulfuric acid to the raw material of 3-amino-5-nitro-benzisothiazole is 1.2-1.7:1.

[0024] In a fifth aspect, the present invention provides a coil material, which includes an epoxy polyether dye as described in the foregoing embodiments.

[0025] In an optional embodiment, the coil material further includes a PET aluminized film and a color coating. The color coating is double-sided transferred to the PET aluminized film by a screen printing plate, dried, cooled and wound up. The color coating is formed by mixing a mixture obtained by diluting the epoxy polyether dye with a solvent and a waterborne amino baking paint, and then mixing with an acid catalyst.

[0026] In an optional embodiment, when preparing the color coating, it includes at least one of the following features (7)-(11):

[0027] Feature (7): The viscosity of the diluted epoxy polyether dye is 100-500 Pa·s;

[0028] Feature (8): The mass percentage of the diluted epoxy polyether dye to the waterborne amino baking paint is 5%-25%: 75%-95%;

[0029] Feature (9): Based on 100 parts by weight, the raw materials for forming the waterborne amino baking paint include: 20-30 parts of a water-soluble resin, 1-5 parts of a waterborne adhesion promoter, 15-20 parts of a waterborne alcohol ether solvent, 5-15 parts of an amino resin, 0.1-0.5 parts of a waterborne wetting agent, 0.1-0.5 parts of a waterborne defoaming agent, 0.1-0.5 parts of a waterborne leveling agent, 1-3 parts of a pH regulator, and the balance is water;

[0030] Feature (10): The addition amount of the acid catalyst is 1%-3% of the mixture;

[0031] Feature (11): The acid catalyst is any one or at least two combinations of dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, dodecylbenzenesulfonic acid and p-toluenesulfonic acid.

[0032] The present invention has the following beneficial effects:

[0033] The epoxy polyether intermediate provided by the present invention utilizes the H bond on aniline polyoxyethylene ether to react with the Cl on epichlorohydrin, thereby grafting propylene oxide at the end of aniline polyoxyethylene ether, so as to form an epoxy polyether intermediate with an epoxy structure at the end. This epoxy polyether intermediate can facilitate subsequent combination with diazo groups, and thus can react with pigment compounds using this epoxy polyether intermediate to add epoxy active groups at the end of the dye. It can react with the resin to make it adhere more firmly in the coil; increase the molecular weight of the dye to make the dye liquefy, and can adjust the hydrophilicity and hydrophobicity at the end of the dye according to the resin used in different coils to adapt to the resin and improve the compatibility with the resin; in addition, the liquefied dye is safer and more environmentally friendly in feeding. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for use in the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as a limitation of the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0035] Figure 1 It is the coating effect diagram of the coil of yellow, red, and blue epoxy polyether dyes provided by the application example of the present invention;

[0036] Figure 2 It is the effect diagram of the coil of yellow, red, and blue epoxy polyether dyes provided by the application example of the present invention for resistance to boiling water;

[0037] Figure 3 It is the effect diagram of the coil of yellow, red, and blue dyes provided by the application comparative example of the present invention for resistance to boiling water;

[0038] Figure 4 It is the effect diagram of the coil of yellow, red, and blue epoxy polyether dyes provided by the application example of the present invention for resistance to acetone;

[0039] Figure 5 It is the effect diagram of the coil of yellow, red, and blue dyes provided by the application comparative example of the present invention for resistance to acetone. DETAILED DESCRIPTION OF THE INVENTION

[0040] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not specified by the manufacturer can all be obtained as conventional products through commercial purchase.

[0041] The present invention provides an epoxy polyether intermediate, and its structural formula is as follows:

[0042] Wherein R represents any one of H, CH3, OCH3, NHCOCH3 or halogen, m and n respectively represent any integer between 0 and 20, and m + n ≥ 5.

[0043] For example, m and n are respectively independently selected from any values between 0 and 20 such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, or range values between any two values, such as 3 - 5 or 3 - 4 or 1 - 5, etc., but it is necessary to satisfy m + n ≥ 5.

[0044] The preparation method of the epoxy polyether intermediate in the present invention includes mixing and reacting aniline polyoxyethylene ether and epichlorohydrin.

[0045] The reaction equation is as follows:

[0046]

[0047] Wherein, the molar ratio of aniline polyoxyethylene ether and epichlorohydrin is 1:2.1 - 3.0; aniline polyoxyethylene ether and epichlorohydrin react in the presence of a first pH regulator, controlling the system temperature at 40 - 80 °C, and the reaction time is 5 - 10 h.

[0048] Wherein, the first pH regulator includes but is not limited to one or several of liquid alkali, baking soda, calcium hydroxide, potassium hydroxide, soda ash, triethylamine. Preferably, the first pH regulator is liquid alkali.

[0049] In the present invention, aniline polyoxyethylene ether reacts with Cl on epichlorohydrin by using its H bond, thereby grafting propylene oxide at the end of aniline polyoxyethylene ether, thus forming an epoxy polyether intermediate with an epoxy structure at the end. This epoxy polyether intermediate can facilitate subsequent combination with a diazo group, and thus the epoxy polyether intermediate can react with a pigment compound to add an epoxy active group at the end of the dye.

[0050] Specifically, the present invention provides an epoxy polyether dye, and the structural formula of the epoxy polyether dye is

[0051] Wherein, Y is a pigment compound.

[0052] It should be understood that the pigment compound can be any of the currently known pigment compounds, including but not limited to conventional colors such as red, yellow, blue, pink, orange, purple, green, etc. In the present invention, it is defined that the pigment compound includes a red compound, a yellow compound or a blue compound. Since the three primary colors of red, yellow and blue are used, by successfully preparing the dyes of the three primary colors, various required colors can be formulated by using the three primary colors and color matching raw materials.

[0053] Specifically, the red compound can be, for example, o-chloro-p-nitroaniline, the yellow compound can be, for example, aniline, and the blue compound can be, for example, 3-amino-5-nitro-benzothiazole.

[0054] Among them, when the pigment compound is a red compound, the structural formula of the epoxy polyether dye is:

[0055]

[0056] When the pigment compound is a yellow compound, the structural formula of the epoxy polyether dye is:

[0057]

[0058] When the pigment compound is a blue compound, the structural formula of the epoxy polyether dye is:

[0059]

[0060] Wherein R represents any one of H, CH3, OCH3, NHCOCH3, and halogen, m and n respectively represent any integer between 0 and 20, and m + n ≥ 5.

[0061] It can be seen that in the embodiment of the present invention, by adding an epoxy active group at the end of the dye, it can react with the resin to make it adhere more firmly to the coil; increasing the molecular weight of the dye to make the dye liquefy, and the hydrophilicity and hydrophobicity at the end of the dye can be adjusted according to the resin used in different coils to adapt to the resin and improve the compatibility with the resin; in addition, the liquefied dye is safer and more environmentally friendly in feeding.

[0062] Furthermore, the present invention also provides a preparation method of the above epoxy polyether dye, which includes carrying out a coupling reaction between an epoxy polyether intermediate and a diazonium salt of a pigment compound.

[0063] That is to say, in the present invention, the pigment compound is first subjected to a diazotization reaction to form a structure with a diazo group on the pigment compound, and then the diazo group is reacted with the H bond on the benzene ring, and then the pigment compound is grafted onto the epoxy polyether intermediate.

[0064] Specifically, the coupling reaction between the epoxy polyether intermediate and the diazonium salt of the pigment compound includes mixing the epoxy polyether intermediate and the diazonium salt of the pigment compound in a molar ratio of 1.01 - 1.15:1, and reacting in the presence of a second pH regulator. During the coupling reaction, the system temperature is controlled at 5 - 15°C, the pH value of the system is adjusted to 7 - 7.5, and the reaction is carried out until the end point. In the present invention, the molar ratio of the amount of the epoxy polyether intermediate is slightly more than that of the diazonium salt of the pigment compound, which can ensure the full reaction of the pigment compound.

[0065] Among them, the second pH regulator is used to control the system pH to 7 - 8, and the second pH regulator includes but is not limited to one or several of liquid alkali, baking soda, calcium hydroxide, potassium hydroxide, soda ash, and triethylamine.

[0066] The diazonium salt of the pigment compound includes the diazonium salt of a red compound, the diazonium salt of a yellow compound, or the diazonium salt of a blue compound. It should be understood that the selection of the diazonium salt of the pigment compound can also be other colors. In the present invention, the three primary colors (red, yellow, and blue) are mainly listed. Based on these three colors, dyes of other colors can be formulated. However, it does not exclude directly selecting compounds of specific colors and directly synthesizing dyes of non - primary colors according to the method of the present invention. Therefore, red, yellow, and blue in the present invention are only typical and non - restrictive examples.

[0067] Among them, the preparation method of the diazonium salt of the red compound or the diazonium salt of the yellow compound includes: using o - chloro - p - nitroaniline or aniline as a raw material, mixing it with hydrochloric acid, sodium nitrite, and water, and carrying out a diazotization reaction at 3 - 8°C for more than 2 h; the molar ratio of o - chloro - p - nitroaniline or aniline to sodium nitrite is 1:1.01 - 1.1;

[0069] and / or, the preparation method of the diazonium salt of the blue compound includes: mixing nitrosylsulfuric acid and sulfuric acid, then adding 3 - amino - 5 - nitro - benzisothiazole, and carrying out a diazotization reaction at 0 - 10°C for 2 - 5 h; the molar ratio of nitrosylsulfuric acid to the raw material of 3 - amino - 5 - nitro - benzisothiazole is 1.2 - 1.7:1.

[0070] In addition, the present invention also provides a coil, which includes the above - mentioned epoxy polyether dye.

[0071] In an alternative embodiment, the coil further includes a PET aluminized film and a color coating. The color coating is double - sided transferred to the PET aluminized film by a screen printing plate, dried, cooled, and wound. The color coating is formed by mixing a mixture obtained by diluting the epoxy polyether dye with a solvent and a water - based amino baking paint, and then mixing with an acid catalyst.

[0072] The viscosity of the diluted epoxy polyether dye is 100 - 500 Pa·s; the mass percentage of the diluted epoxy polyether dye to the waterborne amino baking paint is 5% - 25%: 75% - 95%. The addition amount of the acid catalyst is 1% - 3% of the mixture; the acid catalyst includes, but is not limited to, any one or at least two combinations of dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, dodecylbenzenesulfonic acid, and p-toluenesulfonic acid. Drying, cooling, and coiling means drying at 160 - 200 °C for 10 - 20 s and then cooling and coiling.

[0073] Among them, the waterborne amino baking paint can be directly purchased or prepared by oneself. When choosing to prepare by oneself, based on 100 parts by weight, the raw materials for forming the waterborne amino baking paint include: 20 - 30 parts of water-soluble resin, 1 - 5 parts of waterborne adhesion promoter, 15 - 20 parts of waterborne alcohol ether solvent, 5 - 15 parts of amino resin, 0.1 - 0.5 parts of waterborne wetting agent, 0.1 - 0.5 parts of waterborne defoaming agent, 0.1 - 0.5 parts of waterborne leveling agent, 1 - 3 parts of pH regulator, and the balance is water.

[0074] Among them, the water-soluble resin is any one or at least two combinations of waterborne acrylic resin, waterborne polyester resin, or waterborne alkyd resin; the waterborne adhesion promoter is any one or at least two combinations of silane-modified coupling agent, epoxy phosphate ester, or titanate coupling agent; the waterborne alcohol ether solvent is any one or at least two combinations of EtOH, n-butanol, BCS, and PM; the amino resin is any one or at least two combinations of fully methylated amino resin, partially methylated amino resin, and partially ethylated amino resin; the waterborne wetting agent is preferably any one or at least two combinations of polyether-modified polysiloxane wetting agent, silicone wetting agent, or acetylenic diol wetting agent; the waterborne defoaming agent is preferably any one or at least two combinations of silicone defoaming agent and non-silicone defoaming agent; the waterborne leveling agent is preferably any one or at least two combinations of silicone leveling agent and acrylic leveling agent; the pH regulator is preferably one or two of DMEA or AMP-95.

[0075] The mechanism of forming the coil by the above-mentioned epoxy polyether dye is roughly as follows:

[0076]

[0077] Among them, It represents an amino resin. R2 can be a group such as methyl, ethyl, phenyl, etc. A is one or several of acids such as acetic acid, p-toluenesulfonic acid, hydrochloric acid, etc. M also contains 4 reactive groups, that is, the amino resin has 6 reactive groups. Compared with the combination of traditional hydroxyl and amino resin, the hydroxyl can only react with one of the reactive groups of the amino resin, while for the dye with epoxy structure, under the action of acid catalysis, while combining with one reactive group of the amino resin, another hydroxyl group will be generated, and then it will combine with the reactive group again. Just like the last step of the mechanism, two adhesive structures will be formed, thereby making the molecular adhesive density greater and the performance of the resin better. Specifically, the methylated amino resin can react with the epoxy structure in water-soluble alkyd resin, water-soluble acrylic resin, water-soluble polyester resin and the polymer dye obtained in the present invention under the action of a strong acid catalyst to form a cross-linked structure. The epoxy structure contained in the polymer dye obtained in the present invention can be effectively grafted onto the amino resin matrix, thereby obtaining a color anchoring structure with excellent chemical resistance.

[0078] The features and properties of the present invention will be further described in detail below in conjunction with examples.

[0079] Example 1-1

[0080] The embodiment of the present invention provides a production method of an epoxy polyether intermediate, including:

[0081] Add 159 g of aniline polyoxyethylene ether (10EO) and 66 g of epichlorohydrin to a dry 500 ml flask, slowly heat up to an internal temperature of 45-50 °C, and then dropwise add 40.5 g of liquid alkali (30%) over about 2 hours. After dropping and reacting for 6 hours, an epoxy polyether intermediate is obtained.

[0082] The structural formula of the epoxy polyether intermediate is:

[0083] The hydrogen spectrum characterization of this structural formula is: 1 HNMR(500MHz,CDCl3)δ7.20(t,J=7.5Hz,2H),7.01-6.94(m,3H),3.83-3.20(m,46H),3.02(ddd,J=16.5,12.5,3.1Hz 2H),2.93-2.87(dd,J=12.4H Z ,2H).

[0084] Example 1-2

[0085] The embodiment of the present invention provides a production method of an epoxy polyether intermediate, including:

[0086] Add 71.9 g of m-toluidine polyoxyethylene (propylene) ether (6EO6PO) and 22 g of epichlorohydrin to a dry 250 ml flask. Slowly raise the temperature to an internal temperature of 45 - 50 °C, and then add 13.5 g of liquid alkali (30%) dropwise over about 2 hours. After the addition, react for 6 hours to obtain an epoxy polyether intermediate.

[0087] The structural formula of the epoxy polyether intermediate is:

[0088] Examples 1 - 3

[0089] The examples of the present invention provide a method for producing an epoxy polyether intermediate, including:

[0090] Add 70.3 g of m-methoxyaniline polyoxypropylene ether (10PO) and 22 g of epichlorohydrin to a dry 250 ml flask. Slowly raise the temperature to an internal temperature of 45 - 50 °C, and then add 13.5 g of liquid alkali (30%) dropwise over about 2 hours. After the addition, react for 6 hours to obtain an epoxy polyether intermediate.

[0091] The structural formula of the epoxy polyether intermediate is:

[0092] Example 2 - 1

[0093] The examples of the present invention provide a method for producing a yellow epoxy polyether dye, including:

[0094] Add 9.2 g of aniline, 186 g of ice water, and 30.4 g of hydrochloric acid to a dry 250 ml flask. Pulverize in the reaction flask for 30 min, turn on the stirrer and cool down to an internal temperature of 3 - 8 °C. Prepare a sodium nitrite solution with 7.4 g of sodium nitrite and 20 g of water, and slowly drop the sodium nitrite solution. After the dropping is completed, keep the temperature for reaction for 2 hours to obtain the diazonium salt of the yellow compound.

[0095] Add 88.5 g of the aniline epoxy polyether intermediate obtained in Example 1 - 1 and 200 g of ice water to a dry 500 ml flask. Turn on the stirrer and cool down to an internal temperature of 5 - 15 °C, and drop the diazonium salt of the yellow compound. Adjust the pH value to 7 - 7.5 with baking soda during the addition process. React until the end point, then add 100 g of dichloroethane, stir evenly and let it stand for stratification, separate the lower organic phase, and distill off dichloroethane. Obtain 65 g of yellow polymer liquid dye.

[0096] The structural formula of the dye is as follows:

[0097]

[0098] The 1H NMR characterization of this structural formula is: 1HNMR(500MHz,CDCl3)δ7.94 - 7.64(m,4H),7.60 - 7.35(m,3H),6.80(d,J=7.3H Z ,2H),3.88 - 3.36(m,46H),3.02(dd,J=12.0,3.0Hz,2H),2.92(d,J=3.0H Z ,1H),2.89(d,J=3.0H Z ,1H).

[0099] Example 2 - 2

[0100] The embodiment of the present invention provides a production method of a red epoxy polyether dye, including:

[0101] Add 17.2 g of o - chloro - p - nitroaniline, 186 g of ice water, and 30.4 g of hydrochloric acid into a dry 250 ml flask, slurry in the reaction flask for 30 min, start stirring and cool down to an internal temperature of 3 - 8 °C. Prepare a sodium nitrite solution with 7.4 g of sodium nitrite and 20 g of water, and slowly drop the sodium nitrite solution. After the dropping is completed, keep the reaction at a constant temperature for 2 hours to obtain a diazonium salt formed by a red compound.

[0102] Add 88.5 g of the aniline epoxy polyether intermediate obtained in Example 1 - 1 and 300 g of ice water into a dry 1000 ml flask, start stirring and cool down to an internal temperature of 5 - 15 °C, drop the diazonium salt of the red compound, adjust the pH value to 7 - 7.5 with baking soda during the addition process, react to the end point, then add 100 g of dichloroethane, stir evenly and let it stand for stratification, separate out the lower organic phase, and distill out dichloroethane. Obtain 72.3 g of a red polymer liquid dye.

[0103] The structural formula of the dye is as follows:

[0104]

[0105] Example 2 - 3

[0106] The embodiment of the present invention provides a production method of a blue epoxy polyether dye, including:

[0107] Add 40.6 g of concentrated sulfuric acid into a dry 100 ml flask, start stirring and cool down to an internal temperature below 20 °C, add 33 g of nitrosyl sulfuric acid (40%), cool down to an internal temperature of 0 - 10 °C, add 19.5 g of 3 - amino - 5 - nitro - benzisothiazole in batches, and keep it at this temperature for 2 - 3 hours to obtain a diazonium salt of a blue compound.

[0108] Add 92 g of the aniline epoxy polyether intermediate obtained in Example 1-1 and 400 g of ice water to a dry 1000 ml flask. Start stirring and cool down to an internal temperature of 0-10 °C. Dropwise add the diazonium salt of the blue compound. During the addition process, adjust the pH value to 7-7.5 with sodium bicarbonate. React until the end point, then add 100 g of dichloroethane. After stirring evenly, let it stand for layering. Separate the lower organic phase and distill off the dichloroethane. Obtain 73 g of blue polymeric liquid dye.

[0109] The structural formula of this dye is as follows:

[0110]

[0111] Example 2-4

[0112] The embodiments of the present invention provide a production method of a yellow epoxy polyether dye, including:

[0113] Add 9.2 g of aniline, 186 g of ice water, and 30.4 g of hydrochloric acid to a dry 250 ml flask. Pulverize in the reaction flask for 30 min. Start stirring and cool down to an internal temperature of 3-8 °C. Prepare a sodium nitrite solution with 7.4 g of sodium nitrite and 20 g of water, and slowly dropwise add the above sodium nitrite solution. After the addition is complete, keep the reaction at a certain temperature for 2 hours to obtain the diazonium salt of the yellow compound.

[0114] Add 117 g of the m-toluidine epoxy polyether intermediate obtained in Example 1-2 and 200 g of ice water to a dry 500 ml flask. Start stirring and cool down to an internal temperature of 5-15 °C. Dropwise add the diazonium salt of the yellow compound. During the addition process, adjust the pH value to 7-7.5 with sodium bicarbonate. React until the end point, then add 100 g of dichloroethane. After stirring evenly, let it stand for layering. Separate the lower organic phase and distill off the dichloroethane. Obtain 80.5 g of yellow polymeric liquid dye.

[0115] The structural formula of this dye is as follows:

[0116]

[0117] Example 2-5

[0118] Take 16 g of the yellow polymeric dye from Example 2-1, 32 g of the red polymeric dye from Example 2-2, 50 g of the blue polymeric dye from Example 2-3, and add 20 g of water. Disperse quickly in a disperser to obtain a black polymeric dye.

[0119] Examples A-D

[0120] Examples A-D respectively provide a waterborne amino baking paint coating, and the weight parts of its components are as follows:

[0121]

[0122]

[0123] Specifically, the production method of the water-based amino baking paint coating is to sequentially add 30 parts of water-soluble resin, 3 parts of water-based adhesion promoter, 17 parts of water-based alcohol ether solvent, 10 parts of amino resin, 0.3 part of water-based wetting agent, 0.3 part of water-based defoaming agent, 0.3 part of water-based leveling agent, 2 parts of pH regulator, and the balance being water into a dispersion kettle. After dispersing at a rotation speed of 600 - 800 rpm for 10 - 15 minutes, it is filtered and packaged.

[0124] Comparative Example 1

[0125] The comparative example of the present invention provides a production method of a yellow epoxy polyether dye, including:

[0126] Add 9.2 g of aniline, 186 g of ice water, and 30.4 g of hydrochloric acid into a dry 250 ml flask. Pulverize in the reaction flask for 30 min, start stirring and cool down to an internal temperature of 3 - 8°C. Prepare a sodium nitrite solution with 7.4 g of sodium nitrite and 20 g of water, and slowly drip the above sodium nitrite solution. After the dropping is completed, keep the temperature for reaction for 2 hours to obtain the diazonium salt of the yellow compound.

[0127] Add 54 g of aniline epoxy polyether (10 EO) and 300 g of ice water into a dry 500 ml flask. Start stirring and cool down to an internal temperature of 5 - 15°C, drip the diazonium salt of the yellow compound, adjust the pH value to 7 - 7.5 with baking soda during the addition process, react until the end point, then add 100 g of dichloroethane, stir evenly and let it stand for stratification, separate the lower organic phase, and distill off dichloroethane. Obtain 56 g of yellow polymer liquid dye.

[0128] The structural formula of the dye is as follows:

[0129]

[0130] Comparative Example 2

[0131] The comparative example 2 of the present invention provides a production method of a yellow epoxy polyether dye, including:

[0132] Add 80.3 g of aniline polyoxyethylene ether (4 EO) and 66 g of epichlorohydrin into a dry 500 ml flask, slowly raise the temperature to an internal temperature of 45 - 50°C, and then drip 40.5 g of liquid caustic soda (30%) in about 2 hours. After the dropping and adding are completed, react for 6 hours to obtain an epoxy polyether intermediate.

[0133] The structural formula of the epoxy polyether intermediate is:

[0134] Add 9.2 g of aniline, 186 g of ice water, and 30.4 g of hydrochloric acid to a dry 250 ml flask. Pulverize in the reaction flask for 30 min, start stirring and cool down to an internal temperature of 3 - 8°C. Prepare a sodium nitrite solution with 7.4 g of sodium nitrite and 20 g of water, and slowly drip the sodium nitrite solution into the above. After the dripping is completed, keep the reaction warm for 2 hours to obtain the diazonium salt of the yellow compound.

[0135] Add 65 g of the aniline epoxy polyether intermediate obtained in Example 1 - 1 and 200 g of ice water, and 10 g of dilute sulfuric acid (content 50%) to a dry 500 ml flask. Start stirring and cool down to an internal temperature of 5 - 15°C, drip the diazonium salt of the yellow compound, and adjust the pH value to 7 - 7.5 with baking soda during the addition process. React until the end point, and the material precipitates as a solid. Filter, wash with water, and dry to obtain 30.5 g of yellow epoxy polyether solid dye. When hydrolyzing this solid dye with water, it was found that the solubility was poor, and the dissolution effect was also not good when using pseudo-aqueous solvents (such as BCS, PM, PMA, etc.), so it was not used for testing.

[0136] The structural formula of this dye is as follows:

[0137]

[0138] Application Example 1

[0139] This application example provides a production method for coils, including:

[0140] Mix the yellow dye in Example 2 - 1 with EtOH in a volume ratio of 60:40 to form a diluted dye, and then mix the diluted dye with the water-based amino baking paint in Example A. The addition amount of the diluted dye is 15%. Double-sided transfer it to a PET aluminized film through a 10 μm screen printing plate, pass through a 180°C drying oven for 15 seconds, and then cool and wind up to obtain a yellow PET aluminized coating.

[0141] Application Example 2

[0142] This application example is basically the same as Application Example 1, except that in this application example, the yellow dye in Example 2 - 1 in Application Example 1 is replaced with the red dye in Example 2 - 2 to obtain a red PET aluminized coating.

[0143] Application Example 3

[0144] This application example is basically the same as Application Example 1, except that in this application example, the yellow dye in Example 2 - 1 in Application Example 1 is replaced with the blue dye in Example 2 - 3 to obtain a blue PET aluminized coating.

[0145] Application Example 4

[0146] This application example is basically the same as Application Example 1, except that in this application example, the yellow dye in Example 2-1 of Application Example 1 is replaced with the yellow dye in Example 2-4 to obtain a yellow PET aluminized coating.

[0147] Application Example 5

[0148] This application example is basically the same as Application Example 1, except that the waterborne amino baking paint coating in this application example is the yellow waterborne amino baking paint coating of Example B.

[0149] Application Example 6

[0150] This application example is basically the same as Application Example 1, except that the waterborne amino baking paint coating in this application example is the yellow waterborne amino baking paint coating of Example C.

[0151] Application Example 7

[0152] This application example is basically the same as Application Example 1, except that the waterborne amino baking paint coating in this application example is the yellow waterborne amino baking paint coating of Example D.

[0153] Comparative Application Examples 1-3

[0154] This comparative application example is basically the same as Application Example 1, except that the yellow, red, and blue epoxy polyether dyes are changed to the yellow, red, and blue powder materials purchased (the purchasing manufacturer is Zhejiang Shangyu Runtu Co., Ltd.).

[0155] Comparative Application Example 4

[0156] This comparative application example is basically the same as Application Example 1, except that the dye used in this comparative application example is the dye provided by Comparative Example 1.

[0157] For the effect diagrams of the coils formed in Application Examples 1-3, see Figure 1 .

[0158] Application Examples 1-7 and Comparative Application Examples 1-4 were tested. The test items, test methods, and test standards are shown in Table 1, and the test results are shown in Table 2 and Figure 2 .

[0159] Table 1 Test Items, Methods, and Standards

[0160] Test items Test methods Test standards Coating effect Visual inspection - Transparency Visual inspection GB / T 1721-79 Water resistance Boiling GB / T 1733-1993 Solvent resistance Immersion GB 23648.2-2015 Anti-blocking Baking GB 1762-1980 Adhesion and flexibility Pull-off method GB / T 5210-2006

[0161] Table 2 Test Results

[0162]

[0163] According to Table 2, Figure 2 , Figure 3 , Figure 4 and Figure 5, it can be seen that the epoxy polyether dyes provided by the present invention are prepared by coupling an epoxy polyether intermediate with a diazonium salt of a pigment compound. The obtained epoxy polyether dyes have excellent boiling water resistance and excellent solvent resistance. In the comparative application examples, conventional toner and hydroxy polyether were selected for preparation, and their boiling water resistance and solvent resistance are significantly worse than those of the application examples. At the same time, in comparative application example 4, the dye provided in comparative example 1 was used. Since the dye in comparative example 1 does not contain an epichlorohydrin group, its solvent resistance is significantly worse than that of the application examples.

[0164] In summary, the epoxy polyether intermediate provided by the present invention utilizes the H bond on aniline polyoxyethylene ether to react with the Cl on epichlorohydrin, thereby grafting propylene oxide at the end of aniline polyoxyethylene ether to form an epoxy polyether intermediate with an epoxy structure at the end. This epoxy polyether intermediate can facilitate subsequent binding with diazo groups, and thus can react with a pigment compound to add an epoxy active group at the end of the dye. It can react with the resin to make it adhere more firmly to the coil; increase the molecular weight of the dye to liquefy the dye, and the hydrophilicity and hydrophobicity at the end of the dye can be adjusted according to the resin used in different coils to adapt to the resin and improve the compatibility with the resin; in addition, the liquefied dye is safer and more environmentally friendly in feeding.

[0165] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, various modifications and changes can be made to the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An epoxy polyether intermediate, characterized in that, Its structural formula is as follows: Wherein R represents any one of H, CH3, OCH3, NHCOCH3 or halogen, m and n respectively represent any integers between 0 and 20, and m + n ≥ 5.

2. A method for preparing the epoxy polyether intermediate as described in claim 1, characterized in that, The epoxy polyether intermediate is formed by the mixed reaction of aniline polyoxyethylene ether and epichlorohydrin.

3. The preparation method of the epoxy polyether intermediate according to claim 2, characterized in that, The preparation method of the epoxy polyether intermediate includes at least one of features (1) - (3): Feature (1): The molar ratio of the aniline polyoxyethylene ether to the epichlorohydrin is 1:2.1 - 3.0; Feature (2): The aniline polyoxyethylene ether and the epichlorohydrin react in the presence of a first pH regulator, and the first pH regulator is selected from one or more of liquid alkali, baking soda, calcium hydroxide, potassium hydroxide, soda ash, and triethylamine; Feature (3): When preparing the epoxy polyether intermediate, the system temperature is controlled at 40 - 80 °C, and the reaction time is 5 - 10 h.

4. An epoxy polyether dye, characterized in that, The structure of the epoxy polyether dye is: Wherein, Y is a pigment compound, and the pigment compound includes a red compound, a yellow compound or a blue compound. The red compound is o-chloro-p-nitroaniline, the yellow compound is aniline, and the blue compound is 3-amino-5-nitro-benzisothiazole.

5. A method for preparing an epoxy polyether dye, characterized in that, It is prepared by coupling the epoxy polyether intermediate as described in claim 1 with the diazonium salt of the pigment compound.

6. The preparation method of the epoxy polyether dye according to claim 5, wherein, The coupling reaction includes at least one of the following features (4) - (6): Feature (4): The molar ratio of the epoxy polyether intermediate to the diazonium salt of the pigment compound is 1.01 - 1.15:1; Feature (5): The epoxy polyether intermediate and the diazonium salt of the pigment compound react in the presence of a second pH regulator; during the coupling reaction, the second pH regulator controls the system pH to be 7 - 8, and the second pH regulator is selected from one or more of liquid alkali, baking soda, calcium hydroxide, potassium hydroxide, soda ash, and triethylamine; Feature (6): During the coupling reaction, the system temperature is controlled at 5 - 15 °C, the system pH value is adjusted to 7 - 7.5, and the reaction is carried out to the end point.

7. The preparation method of the epoxy polyether dye according to claim 4, characterized in that The diazonium salt of the pigment compound includes the diazonium salt of a red compound, the diazonium salt of a yellow compound or the diazonium salt of a blue compound; Wherein, the preparation method of the diazonium salt of the red compound or the diazonium salt of the yellow compound includes: using o-chloro-p-nitroaniline or aniline as a raw material, mixing it with hydrochloric acid, sodium nitrite and water, and carrying out a diazotization reaction at 3 - 8 °C for more than 2 h; the molar ratio of the o-chloro-p-nitroaniline or the aniline to the sodium nitrite is 1:1.01 - 1.1; And / or, the preparation method of the diazonium salt of the blue compound includes: mixing nitrosyl sulfuric acid and sulfuric acid, then adding 3-amino-5-nitro-benzisothiazole, and carrying out a diazotization reaction at 0 - 10 °C for 2 - 5 h; the molar ratio of the nitrosyl sulfuric acid to the raw material of 3-amino-5-nitro-benzisothiazole is 1.2 - 1.7:

1.

8. A coiled material, characterized in that, It includes the epoxy polyether dye as described in claim 4.

9. The coil according to claim 8, characterized in that, The coil material further includes a PET aluminized film and a color coating. The color coating is double-sided transferred onto the PET aluminized film by a screen printing plate, dried, cooled, and then wound up. The color coating is formed by mixing the epoxy polyether dye diluted with a solvent with a waterborne amino baking paint coating to form a mixture, and then mixing with an acid catalyst.

10. The coiled material according to claim 9, characterized in that, When preparing the color coating, it includes at least one of the following features (7) - feature (11): Feature (7): The viscosity of the diluted epoxy polyether dye is 100 - 500 Pa·s; Feature (8): The mass percentage of the diluted epoxy polyether dye to the waterborne amino baking paint coating is 5% - 25%: 75% - 95%; Feature (9): Based on 100 parts by weight, the raw materials for forming the waterborne amino baking paint coating include: 20 - 30 parts of a water-soluble resin, 1 - 5 parts of a waterborne adhesion promoter, 15 - 20 parts of a waterborne alcohol ether solvent, 5 - 15 parts of an amino resin, 0.1 - 0.5 parts of a waterborne wetting agent, 0.1 - 0.5 parts of a waterborne defoaming agent, 0.1 - 0.5 parts of a waterborne leveling agent, 1 - 3 parts of a pH regulator, and the balance is water; Feature (10): The addition amount of the acid catalyst is 1% - 3% of the mixture; Feature (11): The acid catalyst is any one or at least two combinations of dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, dodecylbenzenesulfonic acid, and p-toluenesulfonic acid.

Images