阅读说明：本技术 一种可降解的水性塑料油墨连接料树脂及其制备方法 (Degradable water-based plastic ink binder resin and preparation method thereof ) 是由 赵志辉 刘涛 黄浩 左宗朝 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种可降解的水性塑料油墨连接料树脂及其制备方法,选择天然油料亚麻油作为可生物降解原料,通过先将亚麻油进行改性,然后与含有多羧基的树脂聚合后,经过胺化成为水溶性连接料。由于亚麻油的引入,使其对各类塑料薄膜基材具有良好的耐性、附着力及印刷适应性。本发明的连接料树脂制备方法简单,原材料天然易获得,配制的油墨印刷适应性好,可用于各类塑料基材,具有良好的耐性,并且以水作为溶剂,无刺激性气体,绿色环保。(The invention discloses degradable water-based plastic ink binder resin and a preparation method thereof. Due to the introduction of the linseed oil, the linseed oil has good resistance, adhesive force and printing adaptability to various plastic film base materials. The binder resin disclosed by the invention is simple in preparation method, natural and easily available in raw materials, good in printing adaptability of the prepared ink, capable of being used for various plastic base materials, good in tolerance, free of irritant gas and green and environment-friendly by taking water as a solvent.)

1. The degradable water-based plastic ink vehicle resin is characterized by comprising the following raw materials in parts by weight: 21-32 parts of modified linseed oil resin, 12-20 parts of polycarboxyl resin, 6-12 parts of ammonia water and 36-61 parts of water.

2. The degradable aqueous plastic ink vehicle resin of claim 1, wherein the modified linseed oil resin has a specific acid value in the range of 20 to 70 mgKOH/g.

3. The degradable aqueous plastic ink vehicle resin of claim 1, wherein the modified linseed oil resin is comprised of the following raw materials: linseed oil, polyols and polyamines.

4. The degradable aqueous plastic ink vehicle resin of claim 3, wherein the modified linseed oil resin is composed of the following raw materials in parts by weight: 22 parts of linseed oil, 3-4 parts of polyhydric alcohol and 4-5 parts of polyamine.

5. A degradable aqueous plastic ink vehicle resin according to claim 3 or 4, wherein said polyol is one or more of pentaerythritol, 1, 4-butanediol, glycerol, xylitol, sorbitol.

6. A degradable aqueous plastic ink vehicle resin according to claim 3 or 4, wherein said polyamine is one or more of diethanolamine, hexamethylenetetramine, triethanolamine, methyldiethanolamine.

7. The degradable aqueous plastic ink vehicle resin of claim 1, wherein the polycarboxy resin is one or more of homopolymers or copolymers of maleic acid, maleic anhydride, fumaric acid, itaconic acid.

8. A degradable aqueous plastic ink vehicle resin according to any one of claims 1 to 7, prepared by a process comprising the steps of:

s001, adding the modified linseed oil resin into a reaction kettle provided with a reflux condenser, heating to 230 ℃, adding the carboxyl-containing resin, and reacting at the constant temperature of 230 ℃ for 1-1.5 hours;

s002, cooling to below 100 ℃, slowly adding ammonia water for amination reaction, and then adding the required water amount.

9. The modified linseed oil resin according to any one of claims 1 to 4, which is prepared by a process comprising the steps of:

s001, adding linseed oil into a reaction kettle provided with a reflux condenser, introducing nitrogen for protection, heating to 140 ℃, and adding polyol;

s002, slowly heating to 180 ℃ and maintaining for 40-60 minutes;

and S003, cooling to 110 ℃, adding polyamine, and reacting for 50-70 minutes.

Technical Field

The invention relates to the technical field of ink binder and preparation thereof, in particular to degradable water-based plastic ink binder resin and a preparation method thereof.

Background

In recent years, with the continuous improvement of the living standard of people, the packaging industry develops rapidly, so that the plastic ink technology and the market develop continuously. For example, in the fields of food, medicine, agricultural and sideline products, daily necessities and the like, the application range of the plastic film substrate package almost includes all the packaging fields. However, the amount of disposable commodity packaging is very large, which is a major source of "white contamination", and therefore biodegradable, environmentally friendly materials are favored.

The ink printing coating is still the traditional solvent system in the plastic packaging industry as the main part, and the water-based coating has the coating tolerance which can not meet the requirement generally and can only be suitable for the packaging printing with low requirement. At present, although strict requirements are made on oily and alcohol-soluble plastic printing ink in the aspects of solvent residue and the like, the requirements of real environmental protection cannot be met, a coating of the ink cannot be completely degraded, and the residual VOC can cause serious pollution to air, water sources, food and the like.

Related ink enterprises and research institutions are constantly engaged in research and development of "green and environment-friendly" inks in an effort to replace conventional oily or alcohol-soluble inks with clean, non-polluting/biodegradable water-soluble inks to reduce environmental pollution. Therefore, in order to promote the development of pollution-free/biodegradable water-soluble ink, improve the adhesion and the resistance of the ink on various plastic film substrates, and meet the application requirements under different conditions, biodegradable environment-friendly water-based ink is a recent research hotspot. Some related patent publications have been disclosed so far, such as patent publication No. CN 104387552A, which discloses a degradable ultraviolet curing resin and a preparation method and application thereof; patent application No. CN 201210334816.9 discloses a novel environment-friendly paper surface glazing finishing emulsion and a preparation method thereof; patent application No. CN 201310179621 discloses a preparation method of water-based environment-friendly plastic ink resin; compared with the traditional oil-based or alcohol-soluble ink, the resin binder and the prepared plastic ink have certain environmental protection advantages, but do not completely meet the requirement of the resistance required by the plastic ink.

It is seen that improvements and enhancements to the prior art are needed.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a degradable aqueous plastic ink vehicle resin and a preparation method thereof, and aims to solve the problem of insufficient resistance of water-soluble ink in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a degradable water-based plastic ink vehicle resin comprises the following raw materials in parts by weight: 21-32 parts of modified linseed oil resin, 12-20 parts of polycarboxyl resin, 6-12 parts of ammonia water and 36-61 parts of water.

In the degradable aqueous plastic ink vehicle resin, the specific acid value range of the modified linseed oil resin is 20-70 mgKOH/g.

In the degradable aqueous plastic ink binder resin, the modified linseed oil resin is composed of the following raw materials: linseed oil, polyols and polyamines.

In the degradable water-based plastic ink binder resin, the modified linseed oil resin is prepared from the following raw materials in parts by weight: 22 parts of linseed oil, 3-4 parts of polyhydric alcohol and 4-5 parts of polyamine.

In the degradable water-based plastic ink vehicle resin, the polyalcohol is one or more of pentaerythritol, 1, 4-butanediol, glycerol, xylitol and sorbitol.

In the degradable water-based plastic ink binder resin, the polyamine is one or more of diethanolamine, hexamethylenetetramine, triethanolamine and methyldiethanolamine.

In the degradable aqueous plastic ink vehicle resin, the polycarboxy resin is one or more of homopolymers or copolymers of maleic acid, maleic anhydride, fumaric acid and itaconic acid.

The preparation method of the degradable water-based plastic ink vehicle resin comprises the following steps:

s001, adding the modified linseed oil resin into a reaction kettle provided with a reflux condenser, heating to 230 ℃, adding the carboxyl-containing resin, and reacting at the constant temperature of 230 ℃ for 1-1.5 hours;

s002, cooling to below 100 ℃, slowly adding ammonia water for amination reaction, and then adding the required water amount.

The preparation method of the modified linseed oil resin comprises the following steps:

s001, adding linseed oil into a reaction kettle provided with a reflux condenser, introducing nitrogen for protection, heating to 140 ℃, and adding polyol;

s002, slowly heating to 180 ℃ and maintaining for 40-60 minutes;

and S003, cooling to 110 ℃, adding polyamine, and reacting for 50-70 minutes.

Has the advantages that:

the resin used for the connecting material is water-soluble, so that the pollution to the external environment and the working environment of workers is reduced to a great extent, and the environment-friendly effect is realized; the connecting material resin is made of biodegradable natural raw materials, can be biodegraded under aerobic or anaerobic conditions, and can meet the environmental protection requirements of cleanness, no pollution and biodegradability. The ink using the binder resin also has good adhesive force and tolerance, can ensure that the surface of a printed product is smooth and has bright color and good printing effect.

Detailed Description

The invention provides a degradable aqueous plastic ink binder resin and a preparation method thereof, and in order to make the purpose, technical scheme and effect of the invention clearer and clearer, the invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

A degradable water-based plastic ink vehicle resin comprises the following raw materials in parts by weight: 21-32 parts of modified linseed oil resin, 12-20 parts of polycarboxyl resin, 6-12 parts of ammonia water and 36-61 parts of water. The ink binder resin prepared from the raw materials in parts by weight is non-toxic and biodegradable, and the water-based plastic ink prepared on the basis has good gloss, water resistance, alcohol resistance and other properties, and has good resistance, adhesive force and printing adaptability to various plastic film base materials. .

Further, the modified linseed oil consists of the following raw materials: linseed oil, polyols and polyamines. The natural oil linseed oil is a biodegradable raw material, the linseed oil contains a large amount of unsaturated fatty acids, about 74%, in addition, the linseed oil contains about 9% of saturated fatty acids and about 17% of oleic acid, wherein the unsaturated fatty acids mainly comprise linolenic acid and linoleic acid, the unsaturated degree in the vegetable oil determines the activity of molecules, the conjunctiva drying performance of the vegetable oil molecules is reflected, the higher the unsaturated degree is, the better the drying performance is, the unsaturated fatty acids in the sesame oil can reach 74%, and the prepared ink binder resin is used for preparing water-based plastic ink and can quickly dry the ink. The carboxyl in the linseed oil can be subjected to esterification reaction with the hydroxyl in the polyalcohol, the linseed oil is modified by the polyalcohol, and then polyamine is used for amination, so that the biodegradable modified linseed oil resin can be obtained. The water resistance and the alcohol resistance of the linseed oil are better, and the acid value of the prepared modified linseed oil resin is lower.

Further, the modified linseed oil resin has a specific acid value in the range of 20 to 70 mgKOH/g. The unsaturated linseed oil resin with a specific acid value range can be obtained by modifying linseed oil with polyhydric alcohol and aminolysis with polyamine. The acid value refers to the amount of free fatty acid contained in the binder or the amount of unreacted carboxyl groups in the resin. The acid value is too high, the performance of the printing ink is unstable, the water resistance is reduced, the printing ink is easy to react with alkaline materials, even to be gelatinized and agglomerated, the printing ink is deteriorated, and the vehicle with high acid value is used in offset printing ink and is easy to generate emulsification; the binder has too low acid value, poor wettability to the pigment, is not beneficial to the mixing of the pigment and the binder, and has poor fluidity and small brightness after being prepared into the ink. Therefore, as a main influence component of the acid value in the binder, the acid value of the modified linseed oil resin should be kept within an appropriate range of values.

Further, the modified linseed oil resin is prepared from the following raw materials in parts by weight: 22 parts of linseed oil, 3-4 parts of polyhydric alcohol and 4-5 parts of polyamine. The modified linseed oil resin prepared from linseed oil, polyol and polyamine in a certain proportion is easy to crosslink and has good gloss.

Further, the polyalcohol is one or more of pentaerythritol, 1, 4-butanediol, glycerol, xylitol and sorbitol. The hydroxyl of the polyalcohol and the carboxyl of the linseed oil are subjected to esterification reaction to modify the linseed oil, so that the gloss, the water resistance, the heat resistance and the like of the ink can be improved.

Further, the polyamine is one or more of diethanolamine, hexamethylenetetramine, triethanolamine and methyldiethanolamine. The polyamine further modifies the modified linseed oil resin, can improve the solubility and the film forming property of the resin, and can improve the wear resistance and the flatness, accelerate the drying speed and the like when being used as an ink binder. The diethanol amine can be heated together with higher fatty acid to generate amide and ester, and in addition, the diethanol can enable a triglyceride structure in the linseed oil to be connected with hydroxyl through aminolysis, so that the water resistance is enhanced. The hexamethylenetetramine can be used as a curing agent to improve the curing degree of the resin, improve the crosslinking density and improve the thermal stability. The colloid phase formed by triethanolamine and higher fatty acid or higher fatty alcohol has good stability and stable product quality. And the methyldiethanolamine is a hydrophilic chain extender, so that the drying speed can be accelerated.

Further, the polycarboxyl resin is one or more of homopolymers or copolymers of maleic acid, maleic anhydride, fumaric acid and itaconic acid. The ink binder prepared from the polycarboxy resin can improve the heat resistance, the adhesive force, the wettability and the like of the ink. Maleic acid, also known as maleic acid, is used to produce unsaturated polyester resins, and the maleic acid segment can improve the water-based, weather-resistant and adhesive properties of the resin. The maleic anhydride segment in the maleic anhydride copolymer has good hydrophilicity, so the maleic anhydride segment can be used for dispersing red lake pigment after ammonium salinization, wherein, the styrene-maleic anhydride copolymer (SMA) is an amphiphilic polymer with excellent performance and low price, and has excellent dyeing property, heat resistance, processing performance and strong chemical reaction activity. Fumaric acid, also known as fumaric acid and fumaric acid, can be used for producing unsaturated polyester resins, which are characterized by good chemical resistance and good heat resistance. Itaconic acid is an unsaturated dibasic organic acid, is relatively active in chemical property and easy to polymerize, and can be copolymerized with other monomers, such as acrylonitrile, succinic acid and styrene.

The preparation method of the degradable water-based plastic ink vehicle resin comprises the following steps:

s001, adding modified linseed oil into a reaction kettle provided with a reflux condenser, heating to 230 ℃, adding carboxyl-containing resin, and reacting at the constant temperature of 230 ℃ for 1-1.5 hours;

s002, cooling to below 100 ℃, slowly adding ammonia water for amination reaction, and then adding the required water amount.

Ammonia is easily decomposed into ammonia and water, and therefore, when the temperature is too high, the reaction is carried out by adding ammonia, which causes large loss. The temperature is reduced to be below 100 ℃ through a reflux condenser in the reaction kettle, so that the loss caused by rapid decomposition of ammonia water in the presence of heat can be reduced, and the reaction can be fully carried out by keeping a certain temperature.

The preparation method of the modified linseed oil resin comprises the following steps:

s001, adding linseed oil into a reaction kettle provided with a reflux condenser, introducing nitrogen for protection, heating to 140 ℃, and adding polyol;

s002, slowly heating to 180 ℃ and maintaining for 40-60 minutes;

and S003, cooling to 110 ℃, adding polyamine, and reacting for 50-70 minutes.

Oxygen and moisture in the air can influence the polymerization reaction, the nitrogen with good stability can be introduced to protect the reaction from being interfered by external factors, and in addition, the nitrogen can be used as a carrier to take away the moisture generated in the polymerization reaction, thereby being beneficial to the smooth operation of the reaction. Polyamine is easily decomposed at high temperature, so that the temperature is reduced to below 110 ℃ before amination is carried out, which is beneficial to reducing the loss of polyamine caused by high-temperature decomposition.

Example 1

A degradable water-based plastic ink binder resin is composed of the following raw materials in parts by weight:

30 parts of modified linseed oil resin, 12 parts of polycarboxyl resin, 8 parts of ammonia water and 50 parts of water.

The modified linseed oil resin consists of the following raw materials in parts by weight:

22 parts of linseed oil, 3 parts of pentaerythritol and 5 parts of diethanolamine.

The preparation method of the degradable water-based plastic ink vehicle resin comprises the following steps:

s001, introducing nitrogen to a reaction kettle provided with a reflux condenser for protection and heating to 140 ℃, adding pentaerythritol, and starting to react;

s002, slowly heating to 180 ℃ and maintaining for 40-60 minutes;

s003, cooling to 110 ℃, adding diethanolamine for aminolysis, and reacting for 50-70 minutes to prepare modified linseed oil resin;

s004, heating the reaction kettle provided with the reflux condenser to 230 ℃, adding carboxyl-containing resin, and reacting at the constant temperature of 230 ℃ for 1-1.5 hours;

s005, cooling to below 100 ℃, slowly adding ammonia water for amination reaction, and then adding the required water amount.

The performance parameters of the degradable aqueous plastic ink vehicle resin prepared by the method are as follows:

fineness (micrometer)	Adhesion force	Steaming-resistant cooking utensil	Alcohol resistance
				<10	By passing	No abnormality	No abnormality

Example 2

A degradable water-based plastic ink binder resin is composed of the following raw materials in parts by weight:

26 parts of modified linseed oil resin, 12 parts of polycarboxyl resin, 6 parts of ammonia water and 56 parts of water.

The modified linseed oil resin consists of the following raw materials in parts by weight:

22 parts of linseed oil, 4 parts of glycerol and 4 parts of diethanolamine.

The preparation method of the degradable water-based plastic ink vehicle resin comprises the following steps:

s001, introducing nitrogen to a reaction kettle provided with a reflux condenser for protection and heating to 140 ℃, adding glycerol, and starting to react;

s002, slowly heating to 180 ℃ and maintaining for 40-60 minutes;

s003, cooling to 110 ℃, adding diethanolamine for aminolysis, and reacting for 50-70 minutes to prepare modified linseed oil resin;

s004, heating the reaction kettle provided with the reflux condenser to 230 ℃, adding carboxyl-containing resin, and reacting at the constant temperature of 230 ℃ for 1-1.5 hours;

s005, cooling to below 100 ℃, slowly adding ammonia water for amination reaction, and then adding the required water amount.

The performance parameters of the degradable aqueous plastic ink vehicle resin prepared by the method are as follows:

fineness (micrometer)	Adhesion force	Steaming-resistant cooking utensil	Alcohol resistance
				<15	By passing	No abnormality	No abnormality

Example 3

A degradable water-based plastic ink binder resin is composed of the following raw materials in parts by weight:

32 parts of modified linseed oil resin, 16 parts of polycarboxyl resin, 12 parts of ammonia water and 40 parts of water.

The modified linseed oil resin consists of the following raw materials in parts by weight:

22 parts of linseed oil, 4 parts of glycerol and 4 parts of diethanolamine.

The preparation method of the degradable water-based plastic ink vehicle resin comprises the following steps:

s001, introducing nitrogen to a reaction kettle provided with a reflux condenser for protection and heating to 140 ℃, adding glycerol, and starting to react;

s002, slowly heating to 180 ℃ and maintaining for 40-60 minutes;

s003, cooling to 110 ℃, adding diethanolamine for aminolysis, and reacting for 50-70 minutes to prepare modified linseed oil resin;

s004, heating the reaction kettle provided with the reflux condenser to 230 ℃, adding carboxyl-containing resin, and reacting at the constant temperature of 230 ℃ for 1-1.5 hours;

s005, cooling to below 100 ℃, slowly adding ammonia water for amination reaction, and then adding the required water amount.

The performance parameters of the degradable aqueous plastic ink vehicle resin prepared by the method are as follows:

fineness (micrometer)	Adhesion force	Steaming-resistant cooking utensil	Alcohol resistance
				<15	By passing	No abnormality	No abnormality

Example 4

A degradable water-based plastic ink binder resin is composed of the following raw materials in parts by weight:

22 parts of modified linseed oil resin, 20 parts of polycarboxyl resin, 10 parts of ammonia water and 48 parts of water.

The modified linseed oil resin consists of the following raw materials in parts by weight:

22 parts of linseed oil, 3 parts of pentaerythritol and 5 parts of hexamethylenetetramine.

The preparation method of the degradable water-based plastic ink vehicle resin comprises the following steps:

s001, introducing nitrogen to a reaction kettle provided with a reflux condenser for protection and heating to 140 ℃, adding pentaerythritol, and starting to react;

s002, slowly heating to 180 ℃ and maintaining for 40-60 minutes;

s003, cooling to 110 ℃, adding hexamethylenetetramine for aminolysis, and reacting for 50-70 minutes to prepare modified linseed oil resin;

s004, heating the reaction kettle provided with the reflux condenser to 230 ℃, adding carboxyl-containing resin, and reacting at the constant temperature of 230 ℃ for 1-1.5 hours;

s005, cooling to below 100 ℃, slowly adding ammonia water for amination reaction, and then adding the required water amount.

The performance parameters of the degradable aqueous plastic ink vehicle resin prepared by the method are as follows:

fineness (micrometer)	Adhesion force	Steaming-resistant cooking utensil	Alcohol resistance
				<15	By passing	No abnormality	No abnormality

Example 5

Adding 35kg of deionized water, 50kg of modified binder resin for water-based ink, 15kg of pigment Taijin red, 0.1kg of organic silicon defoamer and 0.1kg of surfactant into a batching apparatus, and stirring for 20 minutes by using a high-speed dispersion machine to uniformly mix the materials; taking out the uniformly mixed materials, sending the materials into a sand mill for sand milling, and filtering after the fineness is lower than 15 micrometers; and after the water-based plastic ink is qualified through inspection, packaging to obtain the water-based plastic ink.

Example 6

Adding 30kg of deionized water, 55kg of connecting material water-based resin for water-based plastic surface printing ink, 15kg of pigment phthalocyanine blue, 0.1kg of organic silicon defoamer and 0.1kg of surfactant into a mixer, and stirring for 20 minutes by using a high-speed dispersion machine to uniformly mix the materials; taking out the uniformly mixed materials, sending the materials into a sand mill for sand milling, and filtering after the fineness is lower than 15 micrometers; and after the water-based plastic ink is qualified through inspection, packaging to obtain the water-based plastic ink.

It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.