阅读说明：本技术 一种抗黄变金属油墨用树脂及制备方法与应用 (Resin for anti-yellowing metal ink, preparation method and application ) 是由 钟晓东 张超 于 2020-05-06 设计创作，主要内容包括：本发明公开了一种抗黄变金属油墨用树脂及其制备方法与应用,所述树脂包括以下重量份的制备原料：25～35椰子油脂肪酸、8～10苯甲酸、5～16甘油、8～15季戊四醇、5～10间苯二甲酸、15～25邻苯二甲苯酐和0.5～1.0抗氧化剂。利用苯甲酸中的苯环具有一定的干燥效果,其他油酸保证了油墨的印刷转移性能；利用树脂本身能够自干的特点可以不用加入催干剂从而有效避免高温黄变；通过选用加入HDI封闭多异氰酸酯BL 3175 SN与树脂端羟基反应固化提高油墨干燥性。(The invention discloses resin for anti-yellowing metal ink and a preparation method and application thereof, wherein the resin comprises the following preparation raw materials in parts by weight: 25-35 coconut oil fatty acid, 8-10 benzoic acid, 5-16 glycerin, 8-15 pentaerythritol, 5-10 isophthalic acid, 15-25 phthalic anhydride and 0.5-1.0 antioxidant. The benzene ring in the benzoic acid has a certain drying effect, and other oleic acid ensures the printing transfer performance of the ink; by utilizing the self-drying characteristic of the resin, a drier is not required to be added, so that high-temperature yellowing is effectively avoided; the drying property of the ink is improved by adding HDI to seal polyisocyanate BL 3175SN and reacting and curing the polyisocyanate with the resin terminal hydroxyl.)

1. The resin for the anti-yellowing metal ink is characterized by comprising the following components in parts by weight: the resin comprises the following preparation raw materials in parts by weight: 25-50 fatty acids, 8-12 benzoic acid, 5-16 glycerol, 8-18 pentaerythritol, 5-13 isophthalic acid, 13-25 phthalic anhydride and 0.5-1.0 antioxidant, wherein the number of carbon atoms in the fatty acids is 8-18; preferably, the saturated fatty acids are selected from at least one of coconut oil fatty acids, myristic acid or stearic acid.

2. The resin for anti-yellowing metallic ink according to claim 1, wherein: the antioxidant is selected from at least one of 2, 6-di-tert-butyl-p-cresol, tert-butyl hydroquinone or butyl hydroxy anisol.

3. The method for preparing resin for anti-yellowing metallic ink according to claim 1 or 2, wherein: the method comprises the following steps:

s1, taking fatty acid, benzoic acid, glycerol and pentaerythritol to carry out esterification reaction;

s2, heating and esterifying the esterified product, isophthalic acid, phthalic anhydride and water-carrying agent xylene, vacuumizing by using a water ring pump after the viscosity and the acid value reach target values to remove the water-carrying agent xylene, cooling, adding an antioxidant when the temperature is reduced to below 180 ℃, and reacting to obtain the product;

wherein the number of carbon atoms contained in the fatty acid is 8-18.

4. The method for preparing the resin for anti-yellowing metallic ink according to claim 3, wherein: the temperature of the esterification reaction in the step S1 is 200-230 ℃; preferably, the reaction temperature is 210-220 ℃.

5. The method for preparing the resin for anti-yellowing metallic ink according to claim 3, wherein: the esterification reaction in the step S1 is carried out in a protective atmosphere; preferably, the protective atmosphere is a nitrogen atmosphere.

6. The method for preparing the resin for anti-yellowing metallic ink according to claim 3, wherein: in the step S2, the esterified product has an acid value of less than 15 mgKOH/g.

7. The method for preparing the resin for anti-yellowing metallic ink according to claim 3, wherein: reducing the temperature of the reaction system to below 190 ℃ after the esterification reaction in the step S1; preferably around 180 ℃.

8. The method for preparing the resin for anti-yellowing metallic ink according to claim 3, wherein: the temperature of the reaction system in the step S2 is controlled to be 180-200 ℃ for 60-120 min, then the temperature is raised to 230-250 ℃ for reaction, and the acid value of the sample detection is less than 5 mgKOH/g.

9. A metallic ink, characterized by: the metallic ink contains the resin for an anti-yellowing metallic ink according to claim 1 or 2.

10. A milk powder jar which is characterized in that: the surface of the milk powder can is provided with a coating prepared by the metal ink as claimed in claim 9.

Technical Field

The invention relates to the technical field of printing ink, and particularly relates to resin for anti-yellowing metal printing ink, and a preparation method and application thereof.

Background

At present, metallic ink resin on the market is full of enamel, but the anti-yellowing white ink resin specially developed for the milk powder tank is rare, and the reason is that the metallic ink resin is mainly alkyd resin. The traditional alkyd resin has higher requirement on printing transferability, and needs to be subjected to esterification reaction of long-chain oleic acid and glycerol, but the long-chain oleic acid (such as soybean oil fatty acid, linseed oil fatty acid and the like) contains double bonds capable of being oxidized and dried, so that yellowing is inevitably generated during drying, the yellowing is more serious as the drying temperature is higher, and better printing transferability and drying requirement are difficult to be considered simultaneously.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the resin for the anti-yellowing metal ink provided by the invention can keep better printing transferability, can be dried at a lower temperature, and can effectively solve the problem of easy yellowing in the prior art.

The invention also provides a preparation method of the resin for the anti-yellowing metal ink.

The invention also provides an application of the resin for the anti-yellowing metal ink.

According to the resin for the anti-yellowing metal ink, the resin comprises the following preparation raw materials in parts by weight: the resin comprises the following preparation raw materials in parts by weight: 25-50 saturated fatty acids, 8-12 benzoic acid, 5-16 glycerol, 8-18 pentaerythritol, 5-13 isophthalic acid, 13-25 phthalic anhydride and 0.5-1.0 antioxidant, wherein the fatty acids contain 8-18 carbons; preferably, the saturated fatty acids are selected from at least one of coconut oil fatty acids, myristic acid or stearic acid.

According to some embodiments of the invention, the saturated fatty acid is coconut oil fatty acid, and the resin is prepared from raw materials comprising: 25-35 coconut oil fatty acid, 8-10 benzoic acid, 5-16 glycerin, 8-15 pentaerythritol, 5-10 isophthalic acid, 15-25 phthalic anhydride and 0.5-1.0 antioxidant; preferably, the resin comprises the following preparation raw materials in parts by weight: 28-32 parts of coconut oil fatty acid, 8-9 parts of benzoic acid, 7-15 parts of glycerol, 10-14 parts of pentaerythritol, 5-8 parts of isophthalic acid, 18-25 parts of phthalic anhydride and 0.5-0.8 part of antioxidant; more preferably, the resin comprises the following preparation raw materials in parts by weight: 30 coconut oil fatty acid, 9 benzoic acid, 8.5 glycerol, 14 pentaerythritol, 8 isophthalic acid, 20 phthalic anhydride and 0.8 antioxidant BHT.

According to some embodiments of the invention, the saturated fatty acid is myristic acid, and the resin is prepared from the following raw materials in parts by weight: 28-40 parts of myristic acid, 8-11 parts of benzoic acid, 6-15 parts of glycerol, 8-16 parts of pentaerythritol, 5-12 parts of isophthalic acid, 15-25 parts of phthalic anhydride and 0.5-1.0 part of antioxidant; preferably, the resin comprises the following preparation raw materials in parts by weight: 32-38 parts of myristic acid, 9-10 parts of benzoic acid, 8-12 parts of glycerol, 10-13 parts of pentaerythritol, 7-10 parts of isophthalic acid, 19-23 parts of phthalic anhydride and 0.5-0.8 part of antioxidant; more preferably, the resin comprises the following preparation raw materials in parts by weight: 34 myristic acid, 10 benzoic acid, 9 glycerol, 12 pentaerythritol, 9 isophthalic acid, 19 phthalic anhydride and 0.8 antioxidant.

According to some embodiments of the invention, the saturated fatty acid is stearic acid, and the resin is prepared from the following components in parts by weight: 35-50 stearic acid, 8-12 benzoic acid, 5-13 glycerol, 8-18 pentaerythritol, 6-13 isophthalic acid, 13-23 phthalic anhydride and 0.5-1.0 antioxidant; preferably, the resin comprises the following preparation raw materials in parts by weight: 38-45 coconut oil fatty acid, 10-12 benzoic acid, 8-12 glycerin, 12-16 pentaerythritol, 9-12 isophthalic acid, 15-20 phthalic anhydride and 0.5-0.8 antioxidant; more preferably, the resin comprises the following preparation raw materials in parts by weight: 40 stearic acid, 12 benzoic acid, 10 glycerol, 14 pentaerythritol, 12 isophthalic acid, 18 phthalic anhydride and 0.8 antioxidant.

According to some embodiments of the present invention, the antioxidant is selected from one of 2, 6-di-tert-butyl-p-cresol (BHT), tert-butyl hydroquinone (TBHQ), Butyl Hydroxy Anisol (BHA), and the like, and may be other antioxidants widely used in oils and fats, and among them, 2, 6-di-tert-butyl-p-cresol (BHT) is preferable.

The resin for the anti-yellowing metal ink provided by the embodiment of the invention has at least the following beneficial effects: according to the scheme, the oleic acid is selected to be coconut oil fatty acid, myristic acid and stearic acid, the printing applicability of the resin ink can be kept, and the coconut oil fatty acid (myristic acid and stearic acid) and benzoic acid are high-temperature baking yellowing-resistant materials, so that light-color resin can be obtained even at the temperature of more than 200 ℃ (such as 230-240 ℃) due to good thermal stability.

The preparation method of the resin for the anti-yellowing metal ink according to the second aspect of the invention comprises the following steps:

s1, taking fatty acid, benzoic acid, glycerol and pentaerythritol to carry out esterification reaction;

s2, heating and esterifying the esterified product, isophthalic acid, phthalic anhydride and water-carrying agent xylene, vacuumizing by using a water ring pump after the viscosity and the acid value reach target values to remove the water-carrying agent xylene, cooling, adding an antioxidant when the temperature is reduced to below 180 ℃, and reacting to obtain the product;

wherein the number of carbon atoms contained in the fatty acid is 8-18.

The preparation method provided by the embodiment of the invention has at least the following beneficial effects: the benzene ring in the benzoic acid has a certain drying effect, and other oleic acid ensures the printing transfer performance of the ink; by utilizing the self-drying characteristic of the resin, a drier is not required to be added, so that high-temperature yellowing is effectively avoided; the drying property of the ink is improved by adding HDI to seal polyisocyanate BL 3175SN and reacting and curing the polyisocyanate with the resin terminal hydroxyl.

According to some embodiments of the invention, the temperature of the esterification reaction in the step S1 is 200 to 230 ℃; preferably, the reaction temperature is 210-220 ℃.

According to some embodiments of the invention, the esterification reaction in step S1 is performed all the way under a protective atmosphere; preferably, the protective atmosphere is a nitrogen atmosphere. And introducing protective atmosphere to prevent high-temperature discoloration.

According to some embodiments of the invention, in step S2, the esterified product has an acid value of less than 15 mgKOH/g. After the acid value is detected to be qualified, the next reaction is carried out, so that the performance of the prepared resin is better ensured.

According to some embodiments of the present invention, the temperature of the reaction system is reduced to below 190 ℃ after the esterification reaction in the step S1; preferably around 180 ℃.

According to some embodiments of the present invention, in the step S2, the temperature of the reaction system is controlled at 180-200 ℃ for 60-120 min, and then the temperature is increased to 230-250 ℃ for reflux dehydration reaction, during which the acid value is less than 5 mgKOH/g; preferably, the target viscosity W (determined by dilution of the resin with 300 # solvent oil ═ 1:1 using the gazette viscosity method).

According to some embodiments of the invention, the method further comprises cooling the system after the reaction of step S2, and vacuumizing to recover xylene.

According to the application of the embodiment of the third aspect of the present invention, the metal ink contains the above resin.

A milk powder can is provided with a coating prepared from the metal ink on the surface.

The application of the embodiment of the invention has at least the following beneficial effects: the resin provided by the scheme of the invention has better yellowing resistance, and simultaneously still maintains the advantages of better dryness, adhesion, hardness, gloss, processability and the like, and has no pungent smell.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

FIG. 1 is a flow chart of the operation of a manufacturing process according to an embodiment of the present invention.

Detailed Description

In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.

The first embodiment of the invention is as follows: an anti-yellowing metal ink resin is prepared from the following raw materials in parts by weight: 30 coconut oil fatty acid (neutralization shengtai chemical B1210), 9 benzoic acid (Hunan Hongrun chemical 190610), 8.5 glycerol (Shandong Xuhui chemical SGBR-01), 14 pentaerythritol (Hubei Yihua chemical 0088), 8 isophthalic acid (PiA-BJ of Beijing Yanshan division), 20 phthalic anhydride (Jiangyin phthalic anhydride factory GS0429) and 0.8 antioxidant (Zhengzhou Dewang chemical T501).

The second embodiment of the invention is as follows: an anti-yellowing metal ink resin and a preparation method thereof are disclosed, wherein the preparation raw materials of the resin comprise the following components in parts by weight: 34 myristic acid (indolyloprop 983), 10 benzoic acid, 9 glycerol, 12 pentaerythritol, 9 isophthalic acid, 19 phthalic anhydride and 0.8 antioxidant.

The third embodiment of the invention is as follows: an anti-yellowing metal ink resin and a preparation method thereof are disclosed, wherein the preparation raw materials of the resin comprise the following components in parts by weight: 40 stearic acid (Indonesia Lvbao 1801), 12 benzoic acid, 10 glycerol, 14 pentaerythritol, 12 isophthalic acid, 18 phthalic anhydride and 0.8 antioxidant.

Unless otherwise specified, the stock item number information used in examples 2 to 3 was the same as in example 1.

The preparation method of the ink resin of the above embodiment is shown in fig. 1, and specifically includes the following steps:

s1, carrying out esterification reaction on coconut oil fatty acid (or asteric acid and stearic acid) with a small amount of double bonds or substances without yellowing double bonds, benzoic acid, glycerol and pentaerythritol, cooling to below 180 ℃ after the acid value is detected to be qualified, and carrying out the next reaction. Setting the temperature at 220 ℃ in the esterification reaction process, and introducing nitrogen to protect the whole process so as to prevent high-temperature discoloration; the benzoic acid is introduced, so that the benzene ring of the benzoic acid has a certain drying effect, and the printing transfer performance of the printing ink is ensured by combining with other oleic acid.

S2, after the esterification of the product after the reaction in the step S1 with glycerol and pentaerythritol is completed, adding isophthalic acid, phthalic anhydride and xylene as a water-carrying agent, controlling the temperature rise speed, and keeping the temperature at 180-200 ℃ for 1-2 hours; and then continuously heating to 240 ℃, carrying out dehydration reaction until the acid value is less than 5mgKOH/g and the viscosity is W (Gauss bubble viscosity, and the resin and 300 # solvent oil are diluted and measured at a ratio of 1: 1), cooling, vacuumizing, recovering xylene, adding antioxidant BHT (butylated hydroxytoluene) after the temperature is reduced to 180 ℃, stirring for 30min, filtering and packaging for use.

The resin prepared in example 1, the commercially available white-resistant resin and the commercially available general-purpose alkyd resin were used to prepare inks under the same conditions, wherein the preparation schemes of the commercially available white-resistant resin and the commercially available general-purpose alkyd resin are shown in table 1 below:

TABLE 1

Material	Universal alkyd resins	Anti-yellowing white ink resin
			Fatty acid of soybean oil	50	---
Coconut oil fatty acid	---	30
			Benzoic acid	---	9
Glycerol	6	8.5
			Pentaerythritol	15	14
Phthalic anhydride	25.5	20
			Phthalic acid	---	8
Antioxidant (BHT)	0.8	0.8

The anti-yellowing resin white ink is prepared under the same conditions, and the preparation scheme is shown in the following table 2:

TABLE 2

Material	Universal alkyd resin white ink	White ink made of white-resistant resin	Anti-yellowing white ink resin ink
				Universal alkyd resins	35	---	---
Commercially available white-resistant resins	---	35	---
				Anti-yellowing white ink resin	---	---	30
Titanium white powder	50	50	50
				300 # solvent oil	8	8	8
Thickener white electric oil	2	2	2
				BHT	0.4	0.4	0.4
Cobalt drier	0.3	0.3	---
				Polyethylene wax	4	4	4
Acrylic acid leveling agent	0.3	0.3	0.3
				BL 3175SN	---	---	5.3

S1, mixing and stirring the resin, the 300 # solvent oil, the antioxidant, the cerate and the auxiliary agent by using a dispersing agent, heating to 55-75 ℃, and continuously stirring;

s2, adding titanium dioxide and a thickening agent into the processed material obtained in the step S1, and continuing stirring;

s3, grinding the material processed in the step S2 by a three-roll mill until the fineness reaches 15 μm (can be further controlled to be less than 5 μm);

s4, adding the residual solvent, and stirring uniformly;

s5, adding a drier and uniformly stirring to obtain the metal printing ink;

and S6, grinding the obtained ink once by using a three-roller machine under low pressure, discharging ink gas, and packaging to obtain the product.

The inks prepared above were tested according to the QH-JMH Metal can printing ink standard and the results are shown in Table 3 below:

TABLE 3

As can be seen from Table 3, the inks prepared according to the present invention have good yellowing resistance.