Magenta dye, method for preparing the same, and roll material

Abstract

The present application relates to the technical field of dyes, and in particular to a magenta dye, a preparation method thereof and a roll material. The magenta dye comprises a polyether segment formed by a methoxy-containing aniline polyoxyethylene ether raw material and a keto acid segment formed by a keto acid raw material, and the polyether segment and the keto acid segment are fused into a ring. The magenta dye is a liquid, and can be uniformly mixed with a resin and can react with the resin, so that the roll material formed has good resistance to migration in a solvent.

Description

Technical Field

[0001] This invention relates to the field of dye technology, and more specifically, to a rose-red dye, its preparation method, and roll material. Background Technology

[0002] Currently, the main dyes used in the coating of rose-red PET rolls on the market are powder dyes such as Basic Violet 10, Acid Red 52, and Solvent Red 48. These dyes are added to resin, mixed evenly, and then applied to PET film, followed by high-temperature curing to form the corresponding PET roll. However, the above-mentioned rolls have very poor migration resistance in solvents such as hot water, acetone, and ethanol; uneven dissolution and mixing of powder can lead to defects such as pinholes and particle protrusions; in addition, the dust generated during the powder addition process is very harmful to human health and causes significant environmental damage.

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

[0004] The purpose of this invention is to provide a rose-red dye, its preparation method, and a roll material. An embodiment of this invention provides a rose-red dye that is liquid and can be uniformly mixed with resin and react with resin, resulting in a roll material with good migration resistance in solvents.

[0005] This invention is implemented as follows:

[0006] In a first aspect, the present invention provides a rose-red dye comprising a polyether fragment formed from a methoxylated aniline polyoxyethylene ether raw material and a keto acid fragment formed from a keto acid raw material, wherein the polyether fragment and the keto acid fragment are fused together to form a ring.

[0007] In an optional embodiment, the methoxy-containing aniline polyoxyethylene ether raw material is selected from m-methoxyaniline polyoxyethylene ether and p-methoxyaniline polyoxyethylene ether.

[0008] Preferably, the keto acid raw material is selected from any one of the compounds shown in the following structural formulas: R1 represents any one of C1-C10 alkyl, halogen, hydroxyl, and C1-C10 alkyl-substituted amino groups.

[0009] In an optional embodiment, the rose-red dye is selected from at least one of the compounds shown in the following structures:

[0010]

[0011] Where m and n represent any integers between 1 and 20, and R1 represents any one of C1-C10 alkyl, halogen, hydroxyl, and C1-C10 alkyl-substituted amino groups.

[0012] Secondly, the present invention provides a method for preparing the rose-red dye described in the foregoing embodiments, comprising: mixing a methoxylated aniline polyoxyethylene ether raw material and a keto acid raw material and carrying out a dehydration and ring-closing reaction.

[0013] In an optional embodiment, the reaction includes: mixing the methoxylated aniline polyoxyethylene ether raw material, the keto acid raw material, and a dehydrating agent;

[0014] Preferably, the dehydrating agent is selected from strong acids, and more preferably concentrated sulfuric acid.

[0015] In an optional embodiment, the molar ratio of the methoxylated aniline polyoxyethylene ether raw material to the keto acid raw material is 1.02-1.2:1;

[0016] Preferably, the amount of the dehydrating agent is 5-8% of the total mass of the reaction system;

[0017] Preferably, the reaction temperature is 155-160℃.

[0018] In an optional implementation, after the reaction is complete, the reaction system is cooled down, and then the pH is adjusted to 6.0-6.5, followed by extraction.

[0019] In an optional embodiment, the preparation steps of the keto acid raw material include: mixing phthalic anhydride and phenol derivative for reaction, followed by hydrolysis reaction;

[0020] Preferably, the method includes: mixing the phthalic anhydride and the phenol derivative in a molar ratio of 1.05-1.1:1 and reacting them at 90-110°C; cooling the mixture after the reaction is complete; and then adding a strong alkali to carry out a hydrolysis reaction.

[0021] Thirdly, the present invention provides a roll material comprising the rose-red dye described in the foregoing embodiments.

[0022] In an optional embodiment, it also includes a water-based amino baking paint coating;

[0023] Preferably, the raw materials for forming the water-based amino baking paint coating, based on 100 parts by weight, include: 20-30 parts water-soluble resin, 1-5 parts water-based adhesion promoter, 15-20 parts water-based alcohol ether solvent, 5-15 parts amino resin, 0.1-0.5 parts water-based wetting agent, 0.1-0.5 parts water-based defoamer, 0.1-0.5 parts water-based leveling agent, 1-3 parts pH adjuster, and the balance being water.

[0024] The present invention has the following beneficial effects: The rose-red dye provided in the embodiments of the present invention is a liquid dye. Simultaneously, this dye can react with the resin forming the roll material, thereby bonding the dye to the resin and improving the dye's migration resistance in various solvents. Attached Figure Description

[0025] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 The ultraviolet spectrum of the rose-red dye provided in Example 1 of this invention;

[0027] Figure 2 The nuclear magnetic resonance spectrum of the rose-red dye provided in Example 1 of this invention;

[0028] Figure 3 The following are illustrations of rolls containing different amounts of magenta dye, provided as an application example of the present invention.

[0029] Figure 4 The diagram shows the flexibility and adhesion of rolls with different amounts of magenta dye added, as an application example of the present invention.

[0030] Figure 5 The coating effect of rolls with different amounts of magenta dye provided as an application example of the present invention;

[0031] Figure 6 Figures illustrating the boiling water resistance of rolls with different amounts of magenta dye added, as an application example of the present invention.

[0032] Figure 7 The precipitation of acetone in rolls of rose red dye with different added amounts provided as an application example of the present invention. Detailed Implementation

[0033] 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. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0034] This invention provides a rose-red dye comprising a polyether fragment formed from a methoxylated aniline polyoxyethylene ether raw material and a keto acid fragment formed from a keto acid raw material, wherein the polyether fragment and the keto acid fragment are fused together to form a ring.

[0035] By fused keto acid fragments and polyether fragments, a colored product is formed, which can be used in dyes and subsequent roll materials. Furthermore, the methoxy group in the aniline polyoxyethylene ether raw material enables the polyether to react with the keto acid, thus forming the desired raw material. If the polyether raw material does not contain methoxy groups, it may not be able to form colored dyes or bond with subsequent resins.

[0036] Specifically, the methoxylated aniline polyoxyethylene ether raw material is selected from m-methoxyaniline polyoxyethylene ether and p-methoxyaniline polyoxyethylene ether; the keto acid raw material is selected from any one of the compounds shown in the following structural formulas:

[0037] R1 represents any one of C1-C10 alkyl, halogen, hydroxyl, and C1-C10 alkyl-substituted amino groups.

[0038] Furthermore, the rose-red dye is selected from at least one of the compounds shown in the following structures:

[0039]

[0040] Where m and n represent any integers between 1 and 20, and R1 represents any one of C1-C10 alkyl, halogen, hydroxyl, and C1-C10 alkyl-substituted amino groups.

[0041] For example, m and n are independently selected from any value between 1 and 20, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, or any range between any two values, such as 3-5, 3-4 or 1-5.

[0042] C1-C10 alkyl groups can be selected from any one of the C1-C10 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, and n-pentyl.

[0043] Halogens are selected from chlorine and bromine.

[0044] As can be seen, the embodiments of the present invention add hydroxyl active groups to the end of the dye, which can react with the resin to make it adhere more firmly to the roll material; increase the molecular weight of the dye to make the dye liquefied, and adjust the hydrophilicity and hydrophobicity of the dye end to adapt to the resin according to the resin used in different roll materials to improve the compatibility with the resin; in addition, the liquefied dye is safer and more environmentally friendly in terms of feeding.

[0045] Secondly, the present invention provides a method for preparing the rose-red dye described in the foregoing embodiments, comprising:

[0046] S1, forming keto acid raw materials;

[0047] Phthalic anhydride and phenol derivatives in a molar ratio of 1.05-1.1:1 were reacted in an aromatic solvent at 90-110°C, and the reaction was monitored by TLC. The aromatic solvent may include, but is not limited to, xylene and toluene. The weight ratio of the aromatic solvent to the phenol derivative was 4-8:1.

[0048] After the reaction is complete, the temperature is lowered to below 80°C, and then a strong base is added to carry out a hydrolysis reaction. The strong base may include, but is not limited to, potassium hydroxide, sodium hydroxide, and sodium ethoxide. In the embodiments of the present invention, the strong base is a 50% sodium hydroxide solution, and the weight ratio of the 50% sodium hydroxide solution to the phenol derivative is 4-8:1.

[0049] Specifically, after adding 50% sodium hydroxide solution, the temperature is raised to 90-100℃ for reaction. After the reaction is cooled to room temperature, the mixture is filtered. The filter cake is slurried with water until completely dissolved, and the pH is adjusted to 1.0-3.0 for acid precipitation. The mixture is then filtered, and the filter cake is washed with xylene and water respectively. The filter cake is collected, dried, and pulverized to obtain keto acid raw material.

[0050] S2, aggregation;

[0051] A methoxylated aniline polyoxyethylene ether raw material and a keto acid raw material with a molar ratio of 1.02-1.2:1 are reacted in a dehydrating agent (e.g., concentrated sulfuric acid or other strong acid) at a total mass of 5-8% by weight, heated to 155-160°C. After the reaction, the mixture is cooled to room temperature, diluted with water, and the pH is adjusted to 6.0-6.5. Extraction is then performed. The pH adjustment agent can be, for example, a 30% sodium hydroxide solution, and the extraction agent is a chlorinated C1-C3 alkane such as dichloroethane. The amount of dichloroethane used is 2-2.5 times the mass of the methoxylated aniline polyoxyethylene ether raw material. The lower layer is separated, and the dichloroethane is distilled off. A rose-red polymer liquid dye is finally obtained.

[0052] Thirdly, the present invention provides a roll material comprising the rose-red dye described in the foregoing embodiments. Specifically, the rose-red dye is diluted by mixing it with a solvent, and the viscosity of the diluted dye is 100-500 Pa·s. Alternatively, the rose-red dye and the solvent are mixed at a volume ratio of (50-60):(50-40).

[0053] The diluted rose-red dye is then mixed with water-based amino baking paint. The water-based amino baking paint can be purchased directly or prepared in-house. The amount of diluted dye added is 5-25%, with the remainder being the water-based amino baking paint.

[0054] Specifically, based on 100 parts by weight of raw materials forming water-based amino baking paint, the raw materials include 20-30 parts water-soluble resin, 1-5 parts water-based adhesion promoter, 15-20 parts water-based alcohol ether solvent, 5-15 parts amino resin, 0.1-0.5 parts water-based wetting agent, 0.1-0.5 parts water-based defoamer, 0.1-0.5 parts water-based leveling agent, 1-3 parts pH adjuster, and the balance being water.

[0055] The water-soluble resin is any one or at least two combinations of water-based acrylic resin, water-based polyester resin, or water-based alkyd resin; the water-based adhesion promoter is any one or at least two combinations of silane-modified coupling agent, epoxy phosphate ester, or titanate coupling agent; the water-based 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 diethylated amino resin; the water-based wetting agent is preferably any one or at least two combinations of polyether-modified polysiloxane wetting agent, organosilicon wetting agent, or acetylenic diol wetting agent; the water-based defoamer is preferably any one or at least two combinations of organosilicon defoamer and non-silicone defoamer; the water-based leveling agent is preferably any one or at least two combinations of organosilicon leveling agent and acrylic leveling agent; and the pH adjuster is preferably one or two of DMEA or AMP-95.

[0056] After adding the acid catalyst and stirring thoroughly, the mixture is ready for coating. The coating is then transferred double-sided onto a PET aluminized film using a 10μm screen printing plate, dried in a 180℃ oven for 15 seconds, cooled, and rolled up to obtain a colored PET aluminized coating. The acid catalyst is preferably any one or a combination of at least two of dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, dodecylbenzene sulfonic acid, and p-toluene sulfonic acid. The amount of acid catalyst used is 1%-3%.

[0057] The performance indicators of water-based amino baking paint coating include: bright coating color, no color spots, no pinholes, no edge shrinkage, no color bleeding, no abnormality after boiling in water for 1 hour, no fading after 30 days of acetone immersion, heat resistance and tackiness, scratch resistance, adhesion ≤1 grade, good flexibility, and good protection for vacuum-plated aluminum surfaces.

[0058] The mechanism by which the aforementioned magenta dye forms on rolls is roughly as follows:

[0059]

[0060]

[0061]

[0062] in, Representing amino resins, this mechanism only provides a portion of the reactive amino groups. M also contains four reactive groups, meaning the amino resin has six reactive groups, but due to steric hindrance, the effective functional group number is three. Specifically, the methylated amino resin can react with the hydroxyl, carboxyl, and amino groups in water-soluble alkyd resins, water-soluble acrylic resins, water-soluble polyester resins, and the polymer dyes obtained in this invention under the action of a strong acid catalyst to form a cross-linked structure. The hydroxyl and carboxyl groups contained in the polymer dyes obtained in this invention can be effectively grafted onto the amino resin matrix, thereby obtaining a color anchoring structure with excellent chemical resistance.

[0063] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0064] Example 1

[0065] This invention provides a method for preparing a rose-red dye, comprising:

[0066] Add 31.4 g (0.21 mol) of phthalic anhydride, 33.6 g (0.2 mol) of 3-diethylaminophenol, and 134.4 g of xylene to a dry 250 ml flask. Slowly raise the temperature to an internal temperature of 105-108 °C and react for 8 hours. Then cool the flask to 80 °C and add 134.4 g of 50% sodium hydroxide solution. After the addition is complete, raise the temperature to 95 °C and react for 4 hours. Cool to room temperature and filter. Collect the filter cake in a 500 ml flask, add 300 g of water, and stir until completely dissolved. Slowly add 30% dilute sulfuric acid to adjust the pH to 2.0 and precipitate. Filter the solution. Wash the filter cake first with 100 ml of xylene, then with 1000 ml of water. Dry the filter cake in a 105 °C oven, pulverize it, and obtain 56.3 g of pale yellow keto acid powder (HPLC = 99.2%).

[0067] Add 59.2 g (0.102 mol) of m-methoxyaniline polyoxyethylene ether-10EO to a dry 250 ml flask, start stirring and slowly add 31.5 g (0.1 mol) of the above-mentioned keto acid powder, then slowly add 10 g of sulfuric acid. Heat the mixture in an oil bath to 155-160 °C and maintain the temperature for 2 hours. Cool to room temperature and transfer to a 500 ml beaker, add 180 g of water, stir well, add 30% sodium hydroxide solution to adjust the pH to 6.0-6.5, and after the pH stabilizes, add 180 g of dichloroethane, stir well, and allow to stand to separate the layers. Separate the lower organic phase and distill off the dichloroethane. 85 g of a rose-red polymer liquid dye is obtained, with a yield of 94%.

[0068] The structural formula of the dye is shown below:

[0069] Its UV spectrum and NMR spectrum are shown below. Figure 1 and Figure 2 .

[0070] Example 2

[0071] This invention provides a method for preparing a rose-red dye, comprising:

[0072] The keto acid powder selected was the keto acid powder synthesized in Example 1.

[0073] Add 65g (0.102mol) of m-methoxyaniline polyoxyethylene ether-6EO-4PO to a dry 250ml flask, start stirring, and slowly add 31.5g (0.1mol) of KETO acid powder, followed by 10g of sulfuric acid. Heat the mixture in an oil bath to 155-160℃ and maintain the temperature for 2 hours. Cool to room temperature and transfer to a 500ml beaker. Add 250g of water and stir well. Adjust the pH to 6.0-6.5 with 30% sodium hydroxide solution. After the pH stabilizes, add 200g of dichloroethane, stir well, and allow to stand for separation. Separate the lower organic phase and distill off the dichloroethane. 91.7g of a rose-red polymer liquid dye is obtained, with a yield of 95%.

[0074] The dye structure obtained in Example 2 above is as follows:

[0075]

[0076] Example 3

[0077] Add 31.4 g (0.21 mol) of phthalic anhydride, 26.2 g (0.2 mol) of 3-chlorophenol, and 105 g of xylene to a dry 250 ml flask. Slowly raise the temperature to an internal temperature of 108-110 °C and react for 8 hours. Then cool the flask to 80 °C and add 105 g of 50% sodium hydroxide solution. After the addition is complete, raise the temperature to 95 °C and react for 4 hours. Cool to room temperature and filter. Collect the filter cake in a 500 ml flask, add 300 g of water, and stir until completely dissolved. Slowly add 30% dilute sulfuric acid to adjust the pH to 2.0 and precipitate. Filter the solution. Wash the filter cake first with 100 ml of xylene, then with 1000 ml of water. Dry the filter cake in a 105 °C oven, pulverize it, and obtain 49.6 g of pale yellow keto acid powder (HPLC = 98.9%).

[0078] Add 59.2 g (0.102 mol) of m-methoxyaniline polyoxyethylene ether-10EO to a dry 250 ml flask, start stirring and slowly add 28 g (0.1 mol) of keto acid powder, followed by 10 g of sulfuric acid. Heat the mixture in an oil bath to 155-160 °C and maintain the temperature for 2 hours. Cool to room temperature and transfer to a 500 ml beaker. Add 180 g of water and stir well. Add 30% sodium hydroxide solution to adjust the pH to 6.0-6.5. After the pH stabilizes, add 180 g of dichloroethane, stir well, and allow to stand to separate the layers. Separate the lower organic phase and distill off the dichloroethane. Obtain 82 g of a rose-red polymer liquid dye, with a yield of 95%.

[0079] The dye structure obtained in Example 3 above is as follows:

[0080]

[0081] Example AF

[0082] Example AF provides a water-based amino baking paint coating with the following composition:

[0083]

[0084]

[0085] Specifically, the preparation method of water-based amino baking paint is to add water-soluble resin 30, water-based adhesion promoter 3, water-based alcohol ether solvent 17, amino resin 10, water-based wetting agent 0.3, water-based defoamer 0.3, water-based leveling agent 0.3, pH adjuster 2, and the balance being water into a dispersion vessel in the following mass ratio: disperse at 600-800 rpm for 10-15 minutes, then filter and package.

[0086] Application Example 1

[0087] This application example provides a method for preparing a roll material, including:

[0088] The rose red dye of Example 1 was mixed with EtOH at a volume ratio of 60:40 to form a diluted dye. The diluted dye was then mixed with the water-based amino baking paint of Example A. The amount of diluted dye added was 5%. The mixture was transferred to a PET aluminized film on both sides using a 10μm screen printing plate. After passing through a 180°C oven for 15 seconds, the film was cooled and rolled up to obtain a PET colored aluminized coating.

[0089] Application Examples 2-7 and Comparative Application Example 1

[0090] The roll material was prepared using the same method as in Application Example 1, except that the selection of some dyes or water-based amino baking paints was different. All other conditions were the same as in Application Example 1, as follows:

[0091] Application Example 2: The amount of dye added is 10% for dilution.

[0092] Application Example 3: The amount of dye added is 15% for dilution.

[0093] Application Example 4: The rose-red dye is the rose-red dye from Example 3.

[0094] Application Example 5: The water-based amino baking paint is the water-based amino baking paint of Example B.

[0095] Application Example 6: The water-based amino baking paint is the same as that in Example C.

[0096] Application Example 7: The water-based amino baking paint is the water-based amino baking paint of Example D.

[0097] Comparative application example: The magenta dye was replaced with a commercially available powder (purchased from Ron Reagents).

[0098] See the effect diagram of the roll material formed by application example 1-3. Figure 3 .

[0099] Tests were performed on use cases 1-7 and the comparative application examples. The test items, methods, and standards are shown in Table 1, and the test results are shown in Table 2. Figure 4-7 .

[0100] Table 1. Testing Items, Methods, and Standards

[0101]

[0102] Table 2 Detection Results

[0103]

[0104]

[0105] According to Table 2 and Figure 4-7 It can be seen that it has excellent resistance to boiling water and solvents.

[0106] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A rose dye, characterized by, The preparation method of the magenta dye comprises: mixing an m-methoxy-containing aniline polyoxyethylene ether raw material and a ketonic acid raw material to perform a dehydration ring closure reaction. The m-methoxy-containing aniline polyoxyethylene ether raw material is selected from the compounds shown in the following structural formula: ; m and n each represent any integer between 1 and 5; The ketonic acid raw material is selected from any one of the compounds shown in the following structural formula: R1represents any one of C1-C10 alkyl, halogen, hydroxyl and C1-C10 alkyl substituted amino.

2. A process for the preparation of the rose dye according to claim 1, characterized in that, The preparation method of the magenta dye comprises: Mixing the m-methoxy-containing aniline polyoxyethylene ether raw material, the ketonic acid raw material and a dehydrating agent to perform a reaction.

3. The preparation method according to claim 2, characterized in that, The dehydrating agent is selected from strong acids.

4. The production method according to claim 2, characterized by, The dehydrating agent is concentrated sulfuric acid.

5. The preparation method according to claim 2, characterized in that, The molar ratio of the m-methoxy-containing aniline polyoxyethylene ether raw material to the ketonic acid raw material is 1.02-1.2:

1. The amount of the dehydrating agent accounts for 5-8% of the total mass of the reaction system. The reaction temperature is 155-160°C.

6. The preparation method according to claim 2, characterized in that, After the reaction is completed, the reaction system is cooled, and then the pH is adjusted to 6.0-6.5, followed by extraction.

7. The preparation method according to claim 2, characterized in that, The preparation steps of the ketonic acid raw material comprise: mixing phthalic anhydride and a phenol derivative to perform a reaction, and then performing a hydrolysis reaction.

8. The production method according to claim 7, characterized by, The preparation method of the magenta dye comprises: After the phthalic anhydride and the phenol derivative are mixed in a molar ratio of 1.05-1.1:1, a reaction is performed at 90-110°C, and after the reaction is completed, the system is cooled, and then a strong base is added to perform a hydrolysis reaction.

9. A roll good characterized by, The preparation method of the magenta dye comprises:

10. The web of claim 9, wherein, The aqueous amino baking paint further comprises an aqueous amino baking paint.

11. The web of claim 10, wherein, The raw materials for forming the aqueous amino baking paint, in an amount of 100 parts by weight, comprise: 20-30 parts by weight of a water-soluble resin, 1-5 parts by weight of an aqueous adhesion promoter, 15-20 parts by weight of an aqueous alcohol ether solvent, 5-15 parts by weight of an amino resin, 0.1-0.5 parts by weight of an aqueous wetting agent, 0.1-0.5 parts by weight of an aqueous defoaming agent, 0.1-0.5 parts by weight of an aqueous leveling agent, 1-3 parts by weight of a pH adjuster, and the balance being water.

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