WO2009127127A1

WO2009127127A1 - Ink resin used for intaglio printing and its preparing method

Info

Publication number: WO2009127127A1
Application number: PCT/CN2009/070116
Authority: WO
Inventors: 付勇; 王京霞; 宋延林
Original assignee: 中国科学院化学研究所
Priority date: 2008-04-18
Filing date: 2009-01-13
Publication date: 2009-10-22
Also published as: KR101098594B1; KR20100009571A; CN101260259B; CN101260259A

Abstract

An ink resin used for intaglio printing, comprises 30-50 wt% of ethyl acetate , 18-26 wt% of acrylic ester polymer , 3-6 wt% of styrene polymer , 18-25 wt% of vinyl acetate polymer, 2-4 wt% of activity function polymer, 0.2-0.6 wt% of evocating agent and 6-10wt% of alcohol diluents; the reaction monomer of the said activity function polymer is selected from at least one of acrylic acid, acrylamide, methacrylic acid, maleic acid, hydroxyl ethyl acrylate, hydroxyl propyl-hydroxyl acrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyl methyl acrylate and/or hydroxyl propyl methacrylate. And a method of preparing the ink resin.

Description

Ink resin for gravure printing and preparation method thereof

Technical field

The present invention relates to an ink resin, and more particularly to an ink resin for use in a plastic composite ink such as a gravure ink. Background technique

In recent years, with the rapid development of the packaging industry, the market for plastic gravure inks has continued to grow. Gravure printing inks are widely used in the plastic packaging industry, such as food, medicine, feed, agricultural products, daily necessities and other plastic packaging, including almost all industry packaging, especially for food packaging. However, the existing ink resins used in the plastic composite inks for gravure printing are not environmentally friendly and have a certain degree of damage to the human body. With the advent of “green food and green products”, in order to meet the needs of social development, major printing companies are also researching and launching green projects to try to reduce environmental pollution and damage. Therefore, various aqueous or alcohol-soluble ink resins have emerged.

For example, CN1970655A discloses a gravure-alcoholic aqueous composite plastic ink made from the following weight ratio raw material components:

Multi-component acrylate copolymer resin, 15-60 parts; polyketone resin, 1-6 parts; pigment, 8-30 parts; dispersant, 1-4 parts; adhesion promotion (chlorinated polyolefin), chelating agent (acetic acid acetone Titanium), 0.5-3 parts; 30-50 parts of ethanol.

CN1542066A discloses an aqueous composite ink characterized in that the aqueous ink is composed of an anionic polyurethane dispersion, an acrylate, a pigment, an imide crosslinking agent, an antifoaming agent, water and a small amount of isopropyl alcohol, and the components thereof. The weight percentage is:

Anionic polyurethane dispersion is 15-30%

Acrylate emulsion is 25-40%,

The pigment is 10-30%, The imide crosslinker is 0.5-2%,

Defoamer is 0.5-1%,

Water is 10-30%,

Isopropyl alcohol is 1-5%.

CN1613923A discloses an alcohol-soluble gravure carton preprinted ink characterized in that it is made of a component of the following content ratio (by weight):

Nitrocellulose, 6-10%;

Thermoplastic methyl methacrylate resin, 7-13%;

Propylene glycol methyl ether acetate, 4-12%;

Dioctyl phthalate, 2-6%;

Pigment preform, 15-25%;

Ethyl acetate, 12-23%;

Anhydrous ethanol, 32-43%;

Among them, the pigment preform is composed of 35% nitrocellulose, 5% dioctyl phthalate and 60% organic pigment powder.

CN100999648 discloses an alcohol-soluble paper printing varnish which is prepared from a resin, an alcohol-soluble rosin liquid, fumed silica and a solvent, characterized in that the resin is composed of 50-90% w/w acetic acid. An alcohol-soluble resin prepared from a raw material of ethylene.

CN1415637A discloses an aqueous polyacrylate emulsion for printing, characterized in that its composition and mass fraction are:

Water, 70-100;

Emulsifier, 1.0-3.0;

Methyl methacrylate, 30-80;

(meth) acrylate, 30-70;

(meth)acrylic acid, 2.0-5.0; Initiator, 0.5-1.0.

Wherein the emulsifier is one or both of sodium dodecylsulfonate and succinic acid sulfonate; the initiator is one of potassium persulfate and ammonium persulfate.

CN1415636A discloses an aqueous styrene-acrylate emulsion for printing, characterized in that its composition and mass ratio are:

Water, 70-100;

Emulsifier, 1.0-3.0;

Styrene: 30-80;

(meth) acrylate, 30-70;

(meth)acrylic acid, 2.0-5.0;

Initiator: 0.5-1.0;

Wherein (meth) acrylate is composed of 1-2 monomers of butyl acrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate and hydroxyethyl methacrylate, and The main component is butyl acrylate; (meth)acrylic acid is one of acrylic acid and methacrylic acid; the emulsifier is one or both of sodium dodecyl sulfonate and succinic acid sulfonate; The initiator is one of potassium persulfate and ammonium persulfate.

CN1718646A discloses an aqueous ink based on a synthetic aqueous solid acrylic resin, characterized in that: the weight percentage of each component is

Aqueous solid acrylic resin 5-20%, cosolvent 5-20%, pigment 10-30%, auxiliary 0.5-5%, amine 0.5-10%, balance is water, and the aqueous solid acrylic resin is A product of copolymerization of 10-50% acrylic mixed monomer, 0.1-1.5% ammonium persulfate and the balance of water.

These inks have a good environmental advantage over traditional organic solvent-based inks, which can effectively avoid the environmental pollution of traditional inks and the health threat to operators and surrounding residents. In addition, the ink can be greatly reduced due to flammable and explosive belts. The security risks that come. However, traditional water-based inks generally have a slow drying speed, low gloss, easy shrinkage of paper, water resistance of printed patterns, easy color loss, etc. Disadvantages. The alcohol-soluble ink is expensive because the alcohol is the main solvent, and the alcohol-soluble resin generally uses vinyl acetate as the monomer, so that the finally obtained ink resin is easy to be back-adhesive and has poor scratch resistance. In order to solve these problems, the present invention provides an environmentally friendly ink resin which can solve the above problems while satisfying the performance requirements of the ink application. Summary of the invention

SUMMARY OF THE INVENTION One object of the present invention is to provide an ink resin for gravure printing which has excellent scratch resistance and anti-back tack.

Another object of the present invention is to provide a process for preparing an ink resin for gravure printing which is simple in process and easy to implement.

The present invention provides an ink resin for gravure printing, wherein the ink resin contains

30-50% by weight of ethyl acetate, 18-26% by weight of acrylate polymer, 3% to 6% by weight of styrenic polymer, 18-25% by weight of vinyl acetate polymer, 2-4% by weight Active functional polymer, 0.2-0.6% by weight of initiator and 6-10% by weight of alcohol diluent;

The reactive monomer of the active functional polymer is selected from the group consisting of acrylic acid, acrylamide, methacrylic acid, maleic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, glycidyl methacrylate, and At least one of hydroxyethyl acrylate and hydroxypropyl methacrylate.

The present invention provides a method of preparing an ink resin for gravure printing, wherein the method comprises the steps of:

First, ethyl acetate of 75-85 wt% of ethyl acetate is added to the reaction vessel, stirring is started and the temperature is raised to 65-80 ° C; half of the total weight of the initiator is dissolved in the remaining ethyl acetate. The ethyl acetate solution containing the initiator is obtained, and the ethyl acetate solution containing the initiator is uniformly added to the reaction kettle, and after stirring for 10 to 60 minutes, the vinyl acetate is uniformly added at 75-78 ° C. a mixture of an ester monomer, an acrylate monomer, a styrene monomer and an active functional monomer, and a remaining initiator, for a period of 3-5 hours; after the addition, the temperature is maintained at 75-78 ° C, And continue to stir After mixing for 2-4 hours; then, after cooling to below 40 ° C, the alcohol diluent is added and lowered to room temperature; wherein the content of the acrylate monomer is 42.6-43.9 by weight based on the total amount of each polymer monomer. %, the content of the styrene monomer is 7.32-9.84% by weight, the content of the vinyl acetate monomer is 41.0-43.9% by weight, the content of the active functional monomer is 4.88-6.56% by weight; the amount of the initiator is monomer The total amount is 0.49-0.98% by weight _; based on the total amount of the obtained ink resin, the amount of each substance is such that the content of ethyl acetate is 30-50% by weight, the content of the initiator is 0.2-0.6% by weight, and the alcohol is diluted. The content of the agent is 6-10% by weight _;

Wherein the active functional monomer is selected from the group consisting of acrylic acid, acrylamide, methacrylic acid, maleic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, glycidyl methacrylate, methacrylic acid At least one of hydroxyethyl ester and hydroxypropyl methacrylate.

The ink resin for gravure printing of the present invention is obtained by a solution polymerization of a vinyl acetate monomer, an acrylate monomer, a styrene monomer, and an active functional monomer, by a radical initiator. Due to the introduction of the styrene monomer, the prepared ink resin for gravure printing can have good scratch resistance and anti-back tack. detailed description

According to the invention, the ink resin for gravure printing contains 30-50% by weight of ethyl acetate, 18-26% by weight of acrylate polymer, 3% to 6% by weight of styrenic polymer, 18-25 % by weight of vinyl acetate polymer, 2-4% by weight of active functional polymer, 0.2-0.6% by weight of initiator and 6-10% by weight of alcohol diluent;

The reactive monomer of the active functional polymer may be selected from the group consisting of acrylic acid, acrylamide, methacrylic acid, maleic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, glycidyl methacrylate, At least one of hydroxyethyl methacrylate and hydroxypropyl methacrylate.

According to the present invention, the reactive monomer of the acrylate polymer may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate monomers. Kind.

The reactive monomer of the styrenic polymer may be selected from the group consisting of styrene and/or methyl styrene. The initiator is selected from solution-polymerized free radical initiators, typically benzoyl peroxide or azobisisobutyronitrile.

The alcohol diluent is a low volatile alcohol such as ethanol, preferably ethanol having a mass concentration of 95%.

The preparation method of the ink resin for gravure printing of the present invention is carried out by a solution polymerization method, and the preparation method of the typical solution polymerization system employed includes the following steps:

First, add 75-85% by weight of ethyl acetate to the reaction kettle, start stirring and raise the temperature to 65-80 ° C; dissolve the initiator of half the total weight of the initiator in the remaining ethyl acetate. The ethyl acetate solution containing the initiator is obtained, and the ethyl acetate solution containing the initiator is uniformly added to the reaction kettle, and after stirring for 10 to 60 minutes, the vinyl acetate is uniformly added at 75-78 ° C. a mixture of an ester monomer, an acrylate monomer, a styrene monomer and an active functional monomer, and a remaining initiator, for a period of 3-5 hours; after the addition, the temperature is maintained at 75-78 ° C, And stirring is continued for 2-4 hours; then, after cooling to below 40 ° C, preferably 25-35 ° C, the alcohol diluent is added and lowered to room temperature;

Wherein, the content of the acrylate monomer is 42.6-43.9 wt%, the content of the styrene monomer is 7.32-9.84 wt%, and the content of the vinyl acetate monomer is 41.0 based on the total amount of the polymer monomers. -43.9 wt%, the content of the active functional monomer is 4.88 - 6.56 wt%; and the initiator is used in an amount of 0.49 - 0.98 wt% of the total amount of the monomers. The amount of each substance is such that the content of ethyl acetate is 30-50% by weight, the content of the initiator is 0.2-0.6% by weight, and the content of the alcohol diluent is 6-10% by weight based on the total amount of the obtained ink resin. _;

Wherein the active functional monomer is selected from the group consisting of acrylic acid, acrylamide, methacrylic acid, maleic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, glycidyl methacrylate, methacrylic acid At least one of hydroxyethyl ester and hydroxypropyl methacrylate. It is recognized in the art that during the polymerization reaction, the amount of polymer obtained by the polymerization of the added monomers is substantially the same as the amount of the monomers added. This ensures that the content of each of the polymers in the obtained ink resin coincides with the amount of each polymer defined by the above ink resin. That is, the ethyl acetate content is 30-50% by weight, the acrylate polymer content is 18-26% by weight, and the styrene polymer content is 3-6 based on the total amount of the obtained ink resin. The weight %, vinyl acetate polymer content is 18-25% by weight, the active functional polymer content is 2-4% by weight, the initiator content is 0.2-0.6% by weight, and the alcohol diluent content is 6-10% by weight.

The acrylate monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate.

The styrenic monomer is styrene and/or methyl styrene.

The diluent is a low volatile alcohol such as ethanol, preferably 95% by mass ethanol. The initiator is selected from solution-polymerized free radical initiators, typically benzoyl peroxide or azobisisobutyronitrile.

According to the invention, the agitation speed can be from 100 to 250 rpm.

According to the invention, the total reaction time is from 6 to 10 hours, preferably from 7 to 8 hours, and the total reaction time means from the dropwise addition of a vinyl acetate monomer, an acrylate monomer, a styrene monomer and an active functional monomer. And the mixture of remaining initiators begins to calculate the time until the addition of the alcohol diluent.

The amount of functional monomers in the polymerization system of the present invention is different, and the viscosity of the obtained product is adjusted. The greatest advantage of the present invention is the introduction of a functional monomer styrene which increases the strength of the film, which can effectively increase the glass transition temperature of the resin and the hardness of the polymer segment, and reduce the proportion of the viscous monomer, thereby effectively improving the preparation. The anti-back tack and scratch resistance of the ink resin have potential application prospects in gravure printing inks.

The ink resin of the invention is mainly applied to gravure printing ink, and can be used as a binder of gravure printing ink, and the composition of the gravure printing ink can be 35 wt% of binder, 30% by weight of solvent and 35% of pigment, wherein solvent and pigment are used. Kinds are known to those skilled in the art, for example, The solvent may be one or more of ethyl acetate, ethanol and isopropyl alcohol; the pigment may be one of titanium white powder, permanent yellow, lissole red, phthalocyanine blue and carbon black. The obtained gravure ink can be fined to 8 μm or less after grinding. Example 1

This embodiment is for explaining the preparation of the ink resin for gravure printing of the present invention.

First, 166.8 g of ethyl acetate was added to the reaction vessel, stirring was started and the temperature was raised to 70 ° C, the stirring speed was 150 rpm, and the initiator solution was added at a constant rate (1.225 g of benzoyl peroxide dissolved in 41.705 g of acetic acid). Ethyl ester), stirring for ten minutes, starting to add the monomer mixture at a constant rate (150.05 g of butyl acrylate, 108.01 g of vinyl acetate, 14.02 g of hydroxyethyl acrylate, 2.96 g of acrylamide, 1.225 g of benzoyl peroxide, styrene 22.5 g), the addition time was 4 hours, and the temperature was maintained at 75-78 ° C during the dropwise addition. After the addition was completed, stirring was continued for 3.5 hours, and the temperature was controlled at 75-78 °C. Then, the cooling water is turned on to cool down, and 46 g of ethanol having a mass concentration of 95% is added to the room temperature to be discharged. The ink resin finally obtained contained 40.14% by weight of ethyl acetate, 22.15% by weight of acrylate polymer, 4.33% by weight of styrenic polymer, 20.79% by weight of vinyl acetate polymer, and 3.27% by weight of active functional polymerization. , 0.47 wt% initiator and 8.85 wt% alcohol diluent. Example 2

First, 150.2 g of ethyl acetate was added to the reaction vessel, stirring was started and the temperature was raised to 75 ° C, the stirring speed was 170 rpm, and the initiator solution was added at a constant rate (1.25 g of azobisisobutyl cyanide was dissolved in 30.595 g). Ethyl acetate), stirring for ten minutes, starting to add the monomer mixture at a constant rate (112.05 g of butyl acrylate, 110.01 g of vinyl acetate, 13.02 g of hydroxyethyl acrylate, 2.96 g of methacrylic acid, azobisisobutyronitrile, 1.25 Gram, 20.5 g of styrene) 4.5 hours of dropwise addition, during the dropwise addition process Hold the temperature at 75-78 °C. After the addition was completed, stirring was continued for 3.0 hours, and the temperature was controlled at 75-78 °C. Then, the cooling water is turned on to cool down, and 40 g of a mass concentration of 95% ethanol is added to cool down to room temperature to discharge. The ink resin finally obtained contained 37.52% by weight of ethyl acetate, 23.25% by weight of acrylate polymer, 4.25% by weight of styrenic polymer, 22.74% by weight of vinyl acetate polymer, and 3.31% by weight of active functional polymerization. , 0.52% by weight of initiator and 8.30% by weight of alcohol diluent. Example 3

First, 187 g of ethyl acetate was added to the reaction vessel, stirring was started and the temperature was raised to 65 ° C, the stirring speed was 250 rpm, and the initiator solution was added at a constant rate (1.05 g of azobisisobutyl cyanide was dissolved in 33.795 g). Ethyl acetate), stirring for 30 minutes, starting to add the monomer mixture at a constant rate (112.05 g of butyl methacrylate, 110.01 g of vinyl acetate, 13.02 g of hydroxyethyl acrylate, 2.96 g of methacrylic acid, azobisisobutyronitrile , 1.05 g, 20.5 g of methyl styrene) The addition time was 4.5 hours, and the temperature was maintained at 75-78 ° C during the dropwise addition. After the addition was completed, stirring was continued for 4.0 hours, and the temperature was controlled at 75-78 °C. Then, the cooling water is turned on to cool down, and the mass concentration is 95% ethanol, 40 g, and the temperature is lowered to room temperature to discharge. The ink resin finally obtained contained 42.34% by weight of ethyl acetate, 21.49% by weight of acrylate polymer, 3.93% by weight of styrenic polymer, 21.10% by weight of vinyl acetate polymer, and 3.07% by weight of active functional polymerization. 0.40% by weight of initiator and 7.67% by weight of alcohol diluent. Example 4

First, 200.2 g of ethyl acetate was added to the reaction vessel, stirring was started and the temperature was raised to 80 ° C, the stirring speed was 200 rpm, and the initiator solution was added at a constant rate (1.20 g of azobisisobutyl cyanide dissolved in 52.4 g). Ethyl acetate), stirring for 50 minutes, starting to add the monomer mixture at a constant rate (102.05 g of butyl acrylate, 15.24 g of methyl methacrylate, 115.01 g of vinyl acetate, 13.02 g of hydroxyethyl acrylate, 1.2 g of acrylic acid, A 1.4 g of acrylic acid, 0.8 g of acrylamide, 1.20 g of azobisisobutyronitrile, 10 g of methyl styrene, 10.5 g of styrene) The dropping time was 5.0 hours, and the temperature was maintained at 75-78 ° C during the dropwise addition. After the addition was completed, stirring was continued for 2.5 hours, and the temperature was controlled at 75 to 78 °C. Then, the cooling water is turned on to cool down, and 35 g of ethanol having a mass concentration of 95% is added to cool down to room temperature to discharge. The ink resin finally obtained contained 45.17 wt% of ethyl acetate, 21.49 wt% of acrylate polymer, 1.79 wt% of styrenic polymer, 20.57 wt% of vinyl acetate polymer, and 2.57 wt% of active functional polymerization. , 0.43 wt% initiator and 6.26 wt% alcohol diluent. Example 5

This example is intended to illustrate the preparation and performance testing of gravure inks.

35 kg of the ink resin prepared in Examples 1, 2, 3 and 4 were placed in a container, and 35 kg of pigment titanium dioxide, 3 kg of ethyl acetate and 27 kg of industrial alcohol were added to the container; 8000 rpm / min. Allow the material to mix and disperse evenly for 20 minutes, and then grind it through a sand mill. Keep the material at a temperature not higher than 40 °C during grinding and grind to a fineness of 5 μm or less. The gravure ink Al-A4 was obtained separately.

The properties of the ink were tested as follows. The results are shown in Table 1.

Storage stability: Tested according to the method of GB6753.3 paint storage stability.

Anti-back tack test method: According to GB13217.8 gravure ink anti-blocking test method.

Anti-friction (dry grinding) Test method: Refer to the abrasion resistance method of GB1768-79 coating film. Fineness test method: According to GB/T13217.3 gravure plastic ink fineness test method. Viscosity test method: According to GB/T13217.4 gravure plastic ink viscosity test method. Table 1

As can be seen from the above results, the intaglio ink prepared by using the ink resin of the present invention has excellent scratch resistance and anti-back tack.

Claims

Rights request

An ink resin for gravure printing, characterized in that the ink resin contains 30 to 50% by weight of ethyl acetate, 18 to 26% by weight of an acrylate polymer, and 3 to 6% by weight of styrene. a polymer, 18-25% by weight of a vinyl acetate polymer, 2-4% by weight of an active functional polymer, 0.2-0.6% by weight of an initiator and 6-10% by weight of an alcohol diluent;

2. The ink resin according to claim 1, wherein the reactive monomer of the acrylate polymer is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate. At least one of them.

The ink resin according to claim 1, wherein the reaction monomer of the styrene-based polymer is styrene and/or methyl styrene.

The ink resin according to claim 1, wherein the initiator is benzoyl peroxide or azobisisobutyronitrile; and the alcohol diluent is ethanol.

A method of producing an ink resin for gravure printing according to claim 1, wherein the method comprises the steps of:

First, ethyl acetate of 75-85 wt% of ethyl acetate is added to the reaction vessel, stirring is started and the temperature is raised to 65-80 ° C; half of the total weight of the initiator is dissolved in the remaining ethyl acetate. The ethyl acetate solution containing the initiator is obtained, and the ethyl acetate solution containing the initiator is uniformly added to the reaction kettle, and after stirring for 10 to 60 minutes, the vinyl acetate is uniformly added at 75-78 ° C. Ester a monomer, an acrylate monomer, a mixture of a styrenic monomer and an active functional monomer, and a remaining initiator, for a period of 3-5 hours; after the addition is completed, the temperature is maintained at 75-78 ° C, and Stirring is continued for 2-4 hours; then, after cooling to below 40 ° C, the alcohol diluent is added and lowered to room temperature;

Wherein, the amount of the acrylate monomer is 42.6-43.9 wt%, the amount of the styrene monomer is 7.32-9.84 wt%, and the amount of the vinyl acetate monomer is 41.0 based on the total amount of the polymer monomers. -43.9 wt%, the amount of the active functional monomer is 4.88-6.56 wt%; the amount of the initiator is 0.49-0.98 wt% of the total amount of the monomers _; based on the total amount of the obtained ink resin, the amount of each substance is made The content of ethyl acetate is 30-50% by weight, the content of the initiator is 0.2-0.6% by weight, and the content of the alcohol diluent is 6-10% by weight _;

6. The method according to claim 5, wherein the acrylate monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate.

7. The method according to claim 5, wherein the styrenic monomer is styrene and/or methyl styrene.

8. The method according to claim 5, wherein the initiator is benzoyl peroxide or azobisisobutyronitrile; and the alcohol diluent is ethanol.

9. The method according to claim 5, wherein the stirring speed is 100-250 rpm.

10. The method according to claim 5, wherein the total reaction time is 6-10 hours, The total reaction time refers to the time from the dropwise addition of a mixture of a vinyl acetate monomer, an acrylate monomer, a styrenic monomer, and an active functional monomer, and the remaining initiator, to the time before the addition of the alcohol diluent.

An ink resin for gravure printing, characterized in that the ink resin is obtained by the method according to any one of 5-10.