CN103113787A - Alcohol-dissoluble polyurethane resin compound printing ink and preparation method thereof - Google Patents

Abstract

An alcohol-soluble polyurethane resin composite ink and a production method thereof, which are produced from alcohol-soluble polyurethane resin liquid, polyvinyl butyral resin, matte powder, adhesion enhancer, pigment, ethanol and ethyl acetate through processing procedures ; Wherein: the weight percentage of the alcohol-soluble polyurethane resin liquid is 25-35%; the weight percentage of polyvinyl butyral resin is 1-3%; the weight percentage of the dull powder is 1%; the weight percentage of the pigment can be 8-33%; the weight percentage of the adhesion enhancer is 0-0.5%; the weight percentage of ethanol is 15-40%; the weight percentage of ethyl acetate is 15-25%; in the alcohol-soluble polyurethane resin liquid , the weight percent of the polyurethane resin content is 30-35%; the invention has the advantages of being more environmentally friendly, safer, wide in application range and good in thermal stability.

Description

A kind of alcohol soluble polyurethane resin composite ink and preparation method thereof

technical field

The present invention relates to the field of ink printing and dyeing, in particular to an alcohol-soluble polyurethane resin composite ink and a production method thereof. the

Background technique

my country's plastic gravure printing ink has a development history of more than 30 years. Among them, the chlorinated polypropylene ink produced since the early 1980s is the most widely used inner printing composite ink, accounting for half of the food packaging and printing. However, this type of ink has insurmountable shortcomings, which deviates from people's increasing requirements for food safety and environmental protection, and will gradually reduce its market share until it exits the stage of history: 

a: Non-environmental protection of chlorinated polypropylene resin system:

1) In the production process of chlorinated polypropylene resin, the carbon tetrachloride used is a prohibited substance in the "Stockholm Convention on Persistent Organic Pollutants" (my country is one of the signatories);

2) The chlorinated polypropylene resin system uses toluene and other aromatic hydrocarbons as the main solvent, which needs to be used in large quantities in the ink production process, and this type of solvent will volatilize into the environment during the printing process, which will cause air pollution.

b: Unsafety of chlorinated polypropylene resin system: Toluene and other aromatic hydrocarbons are slow-drying solvents, which are easy to remain in the dry ink film layer, which will not only seriously pollute the food in the package, but also gradually volatilize into the air. It directly endangers the health of consumers; not to mention that a large amount of aromatic hydrocarbons will be volatilized during the production process, which seriously threatens the health of production line employees. the

c: The scope of application of chlorinated polypropylene ink is limited: it only has better printing suitability for BOPP (biaxially oriented polypropylene film), and the most commonly used printing film in the plastic composite flexible packaging industry is BOPP, as well as PET ( Polyester film) and BOPA (two-way stretched nylon film); chlorinated polypropylene resin has a low melting point and decomposition temperature, so it is not suitable for packaging of boiled and steamed foods. the

d: The thermal stability of chlorinated polypropylene ink is poor: due to the poor thermal stability of chlorinated polypropylene resin, chlorine is easily released during the production and storage of the ink to form hydrogen chloride, which makes the ink strongly acidic, thus affecting the ink's durability. Storage stability and printing use. the

The existing technology has the disadvantages of non-environmental protection, unsafety, limited application range and poor thermal stability. the

Contents of the invention

In order to overcome the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide an alcohol-soluble polyurethane resin composite ink with environmental protection, high safety performance, wide application range and good thermal stability and its preparation method. the

The technical solution adopted by the present invention to solve the technical problem is: an alcohol-soluble polyurethane resin composite ink and its production method, which are processed by alcohol-soluble polyurethane resin liquid, polyvinyl butyral resin, dumb powder and auxiliary raw materials process; wherein: the weight percentage of the alcohol-soluble polyurethane resin liquid is 25-35%; the weight percentage of polyvinyl butyral resin is 1-3%; the weight percentage of the matte powder is 1%; In the alcohol-soluble polyurethane resin liquid, the content of the polyurethane resin is 30-35% by weight. the

As an optimal choice of the present invention: the auxiliary added raw material is composed of titanium dioxide, adhesion enhancer, ethanol and ethyl acetate; the weight percentage of the titanium dioxide can be 25 to 33%; the adhesion enhancer The weight percentage is 0-0.5%; the weight percentage of ethanol is 15-20%; the weight percentage of ethyl acetate is 15-20%. the

As an optimal choice of the present invention: the auxiliary added raw materials are composed of pigments, adhesion enhancers, ethanol and ethyl acetate; the weight percentage of pigments can be 8 to 12%; the weight percent of adhesion enhancers can be 0 ～0.5%; the weight percentage of ethanol can be 35～40%; the weight percentage of ethyl acetate can be 20～25%. the

Selection as optimization of the present invention is: described processing procedure is as follows:

① Pre-dispersion process: add polyvinyl butyral resin liquid, ethanol, and ethyl acetate into the pre-mixing dispersion tank according to the proportion specified in the formula, start the high-speed disperser to dissolve it completely, and then mix it under the mixing condition Gradually add the pigment and matte powder in the formula amount, increase the speed of the disperser after the casting is completed, disperse at high speed for 40-50 minutes to fully wet the pigment, and prepare the pre-dispersed color paste to be ground;

②Sand milling process: put the above pre-dispersed color paste into a horizontal sand mill for grinding, and use the grinding media in the horizontal sand mill to generate impact and shear forces when impacting and rolling or sliding against each other. The dispersed color paste is ground and dispersed, and the maximum fineness of the ground color paste is 15 μm;

③ Adjustment process: Add the remaining alcohol-soluble polyurethane resin liquid, ethanol, and ethyl acetate into the pigment color paste according to the formula quantity. If the ink for BOPP film is prepared, 0.5% adhesion enhancer should be added at this time. Start the high-speed disperser and stir for 20-30 minutes to fully disperse and mix evenly, and then adjust the viscosity and hue of the ink to meet the predetermined quality requirements and make the finished ink;

④Packaging process: The above-mentioned finished ink is passed through the filter equipment to remove mechanical impurities and coarse particles, weighed and weighed, and packed for storage.

Compared with prior art, the beneficial effect of the present invention is:

1. More environmentally friendly: the alcohol-soluble polyurethane resin system uses ethanol and ethyl acetate as solvents, unlike the chlorinated polypropylene resin system that needs to use aromatic hydrocarbons, the present invention significantly reduces the use of aromatic hydrocarbon solvents such as toluene and xylene, and improves The on-site environment of ink manufacturing and printing construction has greatly promoted the solution of environmental pollution problems in the production and use of ink products, ensuring the health of production line employees; making food and drug packaging safe and odor-free, fully satisfying today's consumers The requirements for the safety of food and drug packaging will help to achieve the healthy and sustainable development of the ink industry; the excellent performance of alcohol-soluble polyurethane composite ink can completely replace the existing chlorinated polypropylene resin ink, and its wide The scope of application makes printing manufacturers not need to store and use various types of inks, thereby reducing production costs and contributing to the development of China's low-carbon and environmentally friendly society. The advantages of environmental protection are beyond doubt.

2. Safer: Due to the use of low-toxicity, volatile ethanol and ethyl acetate as solvents, no aromatic hydrocarbons and ketone solvents are introduced into the entire formula, and the resin used has excellent release properties to solvents, alcohol-soluble polyurethane composite ink The solvent residue is extremely low and has no peculiar smell, which fully meets people's requirements for the safety of food and drug packaging, and greatly reduces the health threat to employees in the production process. Under normal use, the ink solvent residue of the present invention will not More than 1.0 mg/㎡. the

3. Wide range of applications: Alcohol-soluble polyurethane resin has excellent adhesion to the most commonly used printing films BOPP, PET and BOPA in the plastic composite flexible packaging industry; alcohol-soluble polyurethane resin has good thermal stability and is suitable for packaging of boiled and steamed foods; It has good low temperature performance and is more suitable for the packaging of frozen foods. the

4. Low production cost: Compared with ketone-soluble and ester-soluble polyurethane resins, alcohol-soluble polyurethane resin systems are more environmentally friendly, and the price of ethanol is cheaper than methyl ethyl ketone and propyl acetate, and the volatilization speed is moderate, so it is more convenient to buy in the market and use. the

5. It has improved the manufacturing technology level of composite ink for plastic gravure printing, and effectively promoted the technological progress of my country's ink industry. the

Detailed ways

The present invention is achieved through the following technical solutions:

In one embodiment, each component that this printing ink comprises and weight percent thereof are:

  Alcohol-soluble polyurethane resin solution 30-35%,

  1-3% polyvinyl butyral resin,

  Matt powder 1%,

25-33% titanium dioxide,

  Adhesion enhancer 0.5% (only added when preparing BOPP film printing ink),

Ethanol 15-20%,

  Ethyl acetate 15-20%,

In the alcohol-soluble polyurethane resin liquid, the polyurethane resin content is 30-35% by weight percentage.

In another embodiment, each component that this printing ink comprises and percentage by weight thereof are:

  Alcohol-soluble polyurethane resin solution 25-30%,

  1-3% polyvinyl butyral resin,

  Matt powder 1%,

8-12% black or colored pigments,

  Adhesion enhancer 0.5% (only added when preparing BOPP film printing ink),

Ethanol 35-40%,

  Ethyl acetate 20-25%,

In the alcohol-soluble polyurethane resin liquid, the polyurethane resin content is 30-35% by weight percentage.

The functions of each component in the above-mentioned alcohol (ethanol) soluble polyurethane resin composite ink are as follows:

1) The alcohol-soluble polyurethane resin used in the alcohol-soluble polyurethane resin liquid is the main component of the ink film, providing the main performance of the ink, including adhesion, composite strength, solubility, printing adaptability, etc.; the alcohol-soluble polyurethane resin liquid In terms of weight percentage, the polyurethane resin has a solid content of 30-35%, can be completely dissolved in ethanol, 45-50% of ethanol, and 15-25% of ethyl acetate.

2) Polyvinyl butyral resin is a grinding resin that provides good dispersibility for pigments; it has excellent alcohol solubility, can be completely dissolved in ethanol, and is completely compatible with alcohol-soluble polyurethane resin; in addition It also has a drying effect, which shortens the drying time of the ink, thereby improving the film-forming property and anti-stickiness of the ink. the

3) Dumb powder is a kind of silica powder, which is used to make the surface of the oil film rough and prevent the ink from sticking back during the winding process after printing. the

4) Titanium dioxide is a kind of white pigment. Generally, rutile titanium dioxide is used for the preparation of ink color in the manufacture of white ink; black pigments can generally be carbon black, and color pigments can be phthalocyanine blue and azo lake red. , benzidine yellow and other pigments suitable for polyurethane systems are used for the deployment of ink colors in black or colored inks; but not limited to these types. the

5) The adhesion enhancer is a low molecular weight chlorinated polypropylene resin liquid with a solid content of 40%. The solvent is methylcyclohexane and ethyl acetate. It is only used to prepare BOPP film printing ink, because the molecular structure is different from that of BOPP The structure is similar, which can significantly improve the adhesion fastness of the whole formula on the BOPP film. the

6) Ethanol is a solvent, and its function is to dissolve polyurethane resin and polyvinyl butyral resin. the

7) Ethyl acetate is a solvent, one of its functions is to dissolve the ink with ethanol, and dilute the ink to a suitable printing viscosity; the other function is to adjust the drying speed of the ink, because its volatilization speed is faster than ethanol, so increase The amount of ethyl acetate can speed up the drying speed of the ink. the

The specific preparation method of described alcohol (ethanol) soluble polyurethane resin composite printing ink is as follows:

1. Pre-dispersion process: the pigment is mixed with part of the resin liquid in a certain equipment, and then dispersed with a high-speed disperser to obtain a pigment pre-dispersed color paste.

Pre-dispersion is the first process of ink production, its purpose is to:

1) Mix the pigment, resin liquid, additives, etc. evenly;

2) Make the resin liquid replace some of the air adsorbed on the surface of the pigment, so that the pigment is partially moistened;

3) Preliminarily break up large pigment aggregates. Therefore, this process is mainly based on mixing and partially disperses. It is a supporting process for grinding and dispersing.

The specific operation is to add the polyvinyl butyral resin solution, ethanol, and ethyl acetate into the premixing dispersion tank according to the proportion specified in the formula, start the high-speed disperser to dissolve it completely, and then gradually dissolve it under stirring. Add the pigment and matte powder in the prescribed amount, increase the speed of the disperser after the casting is completed, and disperse at high speed for 40 minutes to fully wet the pigment. At this time, the pre-dispersed color paste to be ground will be prepared. the

2. Sanding process: the above-mentioned pre-dispersed color paste is finely dispersed through various grinding equipment, the pigment particles are dispersed in the resin liquid, and the large aggregates of the pigment are opened and separated by external force to make it meet the requirements of the ink process. Fine particles, so as to obtain qualified pigment paste, to achieve the purpose of dispersion. the

The specific operation is to put the above-mentioned pre-dispersed color paste into a horizontal sand mill for grinding, and use the grinding medium glass beads or zirconium beads in the horizontal sand mill to generate impact force and shear when impacting and rolling or sliding each other Power to grind and disperse. Generally, it needs to be ground twice or three times to make the fineness of the color paste meet the requirements, and the maximum fineness of the ink color paste is required to be 15 μm. the

3. Adjustment process: add the qualified pigment paste obtained by grinding into the remaining components, and adjust the viscosity and hue if necessary to meet the quality requirements of the ink. the

The specific operation is to add the remaining alcohol-soluble polyurethane resin liquid, ethanol, and ethyl acetate into the pigment color paste according to the formula quantity. If the ink for BOPP film is prepared, 0.5% adhesion enhancer should be added at this time. Start the high-speed disperser and stir for 20-30 minutes to fully disperse and mix evenly, and then adjust the viscosity and hue of the ink to meet the predetermined quality requirements and make the finished ink. the

4. Packaging process: remove mechanical impurities and coarse particles through filtering equipment, and then pack. the

The specific operation is to filter and purify the above-mentioned finished ink products with a 150-mesh sand net, weigh them, and pack them manually for storage. the

the

Example 1

Prepare the following raw materials first: 320 grams of alcohol-soluble polyurethane resin, 10 grams of polyvinyl butyral resin, 10 grams of matte powder, 300 grams of titanium dioxide, 170 grams of ethanol, and 190 grams of ethyl acetate. In the alcohol-soluble polyurethane resin solution, by weight percentage, the polyurethane resin content is 35%, the ethanol content is 45%, and the ethyl acetate content is 20%.

Then mix ethanol, ethyl acetate and polyvinyl butyral resin, stir at high speed to dissolve completely, add titanium dioxide and matte powder to disperse, grind to make the fineness below 15 μm, and then prepare 1000 grams of white printing ink. the

 Mass production is equipped with production according to the above ratio. the

Example 2

Prepare the following raw materials: 300 grams of alcohol-soluble polyurethane resin, 25 grams of polyvinyl butyral resin, 10 grams of matte powder, 100 grams of carbon black, 360 grams of ethanol, and 205 grams of ethyl acetate. In this alcohol-soluble polyurethane resin liquid, by weight percentage, the polyurethane resin content is 33%, the ethanol content is 47%, and the ethyl acetate content is 20%.

Then mix ethanol, ethyl acetate and polyvinyl butyral resin, stir at high speed to dissolve completely, add carbon black and matte powder to disperse, grind to make the fineness below 15 μm, and then prepare 1000 grams of black printing ink. the

 Mass production is equipped with production according to the above ratio. the

Example 3

Prepare the following raw materials first: 300 grams of alcohol-soluble polyurethane resin, 20 grams of polyvinyl butyral resin, 10 grams of matte powder, 100 grams of phthalocyanine blue, 360 grams of ethanol, and 210 grams of ethyl acetate. In this alcohol-soluble polyurethane resin solution, by weight percentage, the polyurethane resin content is 33%, the ethanol content is 45%, and the ethyl acetate content is 22%.

Then mix ethanol, ethyl acetate and polyvinyl butyral resin, stir at a high speed to dissolve completely, add phthalocyanine blue pigment and matte powder to disperse, grind to make the fineness below 15 μm, and then obtain 1000 grams of blue printing ink. the

 Mass production is equipped with production according to the above ratio. the

Example 4

Prepare the following raw materials: 280 grams of alcohol-soluble polyurethane resin, 25 grams of polyvinyl butyral resin, 10 grams of matte powder, 90 grams of azo lake red, 380 grams of ethanol, and 215 grams of ethyl acetate. In the alcohol-soluble polyurethane resin liquid, by weight percentage, the polyurethane resin content is 30%, the ethanol content is 45%, and the ethyl acetate content is 25%.

Then mix ethanol, ethyl acetate and polyvinyl butyral resin, stir at high speed to dissolve completely, add azo lake red and matte powder to disperse, grind to make the fineness below 15 μm, and then obtain 1000 grams of red printing ink. the

 Mass production is equipped with production according to the above ratio. the

Example 5

Prepare the following raw materials first: 260 grams of alcohol-soluble polyurethane resin, 30 grams of polyvinyl butyral resin, 10 grams of matte powder, 80 grams of benzidine yellow, 370 grams of ethanol, and 250 grams of ethyl acetate. In the alcohol-soluble polyurethane resin liquid, by weight percentage, the polyurethane resin content is 32%, the ethanol content is 48%, and the ethyl acetate content is 20%.

Then mix ethanol, ethyl acetate and polyvinyl butyral resin, stir at high speed to dissolve completely, add benzidine yellow and matte powder to disperse, grind to make the fineness below 15 μm, and then prepare 1000 grams of yellow printing ink. the

 Mass production is equipped with production according to the above ratio. the

The above are several embodiments of the present invention, but the present invention is not limited to several inks involved in the embodiments. When making inks of a certain color, corresponding suitable pigments can be selected and carried out according to the above-mentioned technical scheme. Inks of corresponding colors are produced. the

Alcohol (ethanol) soluble polyurethane resin composite printing ink of the present invention, every performance index that can reach: project Example 1 color Approximate standard Tinting power (%) 95～105 Fineness(mm) <15 Viscosity (4 cups/sec/25°C) 25～35 Adhesion fastness (BOPP) 90～95 Adhesion fastness (PET) ≥ 100 Adhesion fastness (BOPA) ≥ 98～100 Initial drying (mm) 30～35 Boiling resistance (100℃/30min) No discoloration, no separation Solvent residue (mg/㎡) <1.0

To sum up, after reading the document of the present invention, those of ordinary skill in the art can make various other corresponding conversion schemes according to the technical solutions and technical concepts of the present invention without creative mental work, all of which fall within the protection scope of the present invention.

Claims (4)

1. An alcohol-soluble polyurethane resin composite ink and a preparation method thereof, which are made through processing procedures of alcohol-soluble polyurethane resin liquid, polyvinyl butyral resin, mat powder and auxiliary added raw materials; it is characterized in that: The weight percentage of the alcohol-soluble polyurethane resin liquid is 25-35%; the weight percentage of the polyvinyl butyral resin is 1-3%; the weight percentage of the dull powder is 1%; in the alcohol-soluble polyurethane resin liquid, The weight percentage of polyurethane resin content is 30-35%. 2. a kind of alcohol soluble polyurethane resin composite printing ink as claimed in claim 1, is characterized in that: described auxiliary addition raw material is made up of titanium dioxide, adhesion enhancer, ethanol and ethyl acetate; Described titanium dioxide The weight percentage of the adhesive force can be 25-33%; the weight percentage of the adhesion enhancer is 0-0.5%; the weight percentage of ethanol is 15-20%; the weight percentage of ethyl acetate is 15-20%. 3. A kind of alcohol soluble polyurethane resin composite printing ink as claimed in claim 1, it is characterized in that: described auxiliary additive raw material is made up of pigment, adhesion enhancer, ethanol and ethyl acetate; The weight percent of pigment can be 8-12%; the weight percentage of adhesion enhancer can be 0-0.5%; the weight percentage of ethanol can be 35-40%; the weight percentage of ethyl acetate can be 20-25%. 4. the preparation method of a kind of alcohol soluble polyurethane resin composite printing ink as claimed in claim 1, is characterized in that: described processing procedure is as follows: ① Pre-dispersion process: add polyvinyl butyral resin liquid, ethanol, and ethyl acetate into the pre-mixing dispersion tank according to the proportion specified in the formula, start the high-speed disperser to dissolve it completely, and then mix it Gradually add the pigment and matte powder according to the formula, increase the speed of the disperser after the casting is completed, and disperse at a high speed for 40-50 minutes to fully wet the pigment and prepare the pre-dispersed color paste to be ground; ②Sand milling process: Put the above pre-dispersed color paste into a horizontal sand mill for grinding, and use the grinding media in the horizontal sand mill to generate impact and shear forces when impacting and rolling or sliding with each other. The dispersed color paste is ground and dispersed, and the maximum fineness of the ground color paste is 15 μm; ③ Adjustment process: Add the remaining alcohol-soluble polyurethane resin liquid, ethanol, and ethyl acetate into the pigment color paste according to the formula quantity. If the ink for BOPP film is prepared, 0.5% adhesion enhancer should be added at this time. Start the high-speed disperser and stir for 20-30 minutes to fully disperse and mix evenly, and then adjust the viscosity and hue of the ink to meet the predetermined quality requirements and make the finished ink; ④Packaging process: The above-mentioned finished ink is passed through the filter equipment to remove mechanical impurities and coarse particles, weighed and weighed, and packed for storage.