JPH0655778B2 - Petroleum resin for gravure ink - Google Patents

Description

TECHNICAL FIELD The present invention relates to a petroleum resin for gravure ink, which has a high drying speed when used in a gravure ink and has a high softening point which is excellent in color density and gloss of a printed matter.

[Prior Art] As binders for paper gravure inks, lime rosin, which is a derivative of rosin, and modified petroleum resin obtained by adding maleic anhydride to petroleum resin and then esterifying with alcohol are used.

The basic properties required for paper gravure ink are as follows.

(1) It has a high softening point and a high drying rate, (2) it has a relatively low molecular weight and exhibits an appropriate solution viscosity when dissolved in toluene, etc., (3) it has good pigment dispersibility, (4) ) The viscosity stability when used as an ink is good, (5) the gloss and density of the printed surface are good, etc.

The modified petroleum resin described above substantially satisfies the basic requirements of (1) to (5) and is used as a binder for gravure ink, but further quality improvement, especially pigment dispersibility, concentration on the printing surface, etc. Improvement is required.

[Structure of the Invention] The present invention improves the above-mentioned drawbacks of the petroleum resin for gravure ink and improves the quality of the resin, particularly the pigment dispersibility and the density of the printing surface.

That is, the present invention is a fraction 100 having a boiling point within the range of 140 to 220 ° C. among the cracked oil fractions obtained by the thermal decomposition of petroleum.
0.01 to 0.2 mol of unsaturated carboxylic acid or its anhydride per 100 g of resin having a softening point of 150 ° C. or higher obtained by polymerizing with a Friedel-Crafts type catalyst by adding 0.1 to 3.0 parts by weight of fatty acid amide to 100 parts by weight. It is made of petroleum resin for gravure ink, which is characterized by adding.

The feedstock used in the present invention has a boiling point within the range of 140 to 220 ° C among the cracked oil fractions obtained by the thermal cracking of petroleum, and the unsaturated compound contained therein is substantially styrene and its alkyl. It is a fraction which is a derivative, indene and its alkyl derivative.

In order to obtain a petroleum resin having a softening point of 150 ° C. or higher, which is one of the constitutional requirements of the present invention, it is usually obtained by polymerizing using the above-mentioned feedstock, but in particular, the total content of indene and its alkyl derivative in the above-mentioned feedstock is included. The amount should be 20wt% or more and the following (1)
It is more preferable to use a feedstock oil having an indene content defined by the formula adjusted to 30% or more.

Each component of the feedstock oil is analyzed by gas chromatography under the following conditions, for example.

A. Styrene, allylbenzene, 1,3,5-trimethylbenzene and 0-ethyltoluene are 20 wt% of Apiezon Lgreace, Associated Electri
(Celite, J, including cal Industriee Ltd)
Ohns-Manville Corp.) is packed in a column having a length of 3 m, and analysis is carried out at 100 ° C. under a helium flow rate of 60 cc / min.

I. A. For each component other than the components shown in 1 above, Celite containing 20 wt% of polyethylene glycol 4000 is packed in a column having a length of 3 m, and analyzed at 125 ° C. under a helium flow rate of 60 cc / min.

The total amount of the contents of styrene and its alkyl derivative, indene and its alkyl derivative, and cyclopentadiene and methylcyclopentadiene analyzed by the above method is used as the polymerizable component.

The above boiling point range is 140-220 ℃
The cracked oil fraction can be subjected to operations such as precision distillation and extractive distillation.

The fatty acid amide of the present invention is an amidated fatty acid contained in vegetable oil, animal oil or the like, or a mixture thereof, and specific examples of the fatty acid amide include lauric acid amide, myristic acid amide, palmitic acid amide and stearic acid amide. And saturated fatty acid amides such as oleic acid amide, linoleic acid amide, linolenic acid amide, and eleostearic acid amide.

In the present invention, 0.1 to 3.0 parts by weight of the above fatty acid amide is added to 100 parts by weight of a cracked oil fraction having a boiling point of 140 to 220 ° C., and polymerization is carried out using a Friedel-Craft type catalyst. Examples of Friedel-Crafts type catalysts include boron trifluoride, aluminum chloride, boron trifluoride complex compounds, etc., and preferred are boron trifluoride, boron trifluoride etherate, and boron trifluoride. 0.01% elemental phenolate to the feedstock
-10 ℃ at a temperature within the range of -30 ℃ to + 60 ℃ with addition of ~ 5wt%.
After polymerizing within a range of 15 minutes to 15 hours, the catalyst is decomposed and removed with an alkali such as caustic soda or sodium carbonate, washed with water if necessary, and unreacted oil and low molecular weight polymer are separated by evaporation or distillation. Softening point 150 ℃
With the above high softening point, for example, an aromatic hydrocarbon resin having a bromine number of 40 or less can be obtained.

The amount of fatty acid amide added to 100 parts by weight of the cracked oil fraction is
0.1 to 3.0 parts by weight, preferably 0.3 to 2.0 parts by weight are suitable. Gravure ink using the resin obtained when the amount of fatty acid amide added is less than 0.1 parts by weight has no effect on improving the gloss and color density of the printing surface. Yield is reduced. Further, although good gloss and color density can be obtained on the printed surface, a cissing phenomenon called pinhole occurs on the printed surface, which is not preferable.

In the present invention, an unsaturated carboxylic acid or its anhydride is added to the petroleum resin having a softening point of 150 ° C. or higher obtained in the above. In this case, it is added in an amount of 0.01 to 0.2 mol based on 100 g of the petroleum resin. The reaction is carried out at a temperature in the range of 140 to 250 ° C. for 30 minutes to 15 hours in the presence of a catalyst or a radical initiator such as an organic peroxide.

Examples of the unsaturated carboxylic acid or its anhydride used in the present invention are acrylic acid, methacrylic acid, maleic acid, maleic anhydride, tetrahydrophthalic acid and its anhydride, fumaric acid, citraconic acid, itaconic acid and the like.

When the amount of the unsaturated carboxylic acid or its anhydride added to 100 g of the resin is less than 0.01 mol, the amount of polar groups is small, and when used in gravure ink, the pigment dispersibility is poor and it cannot be used in ink. On the other hand, if the amount exceeds 0.2 mol, not only the addition reaction becomes difficult, but also when the resin is dissolved in toluene to prepare a gravure ink varnish, the solution viscosity becomes extremely high and the ink cannot be formed. On the contrary, in order to properly adjust the solution viscosity as a gravure ink varnish, the resin concentration must be extremely lowered, so that the gloss of the obtained ink is lowered and a uniform printed matter cannot be obtained. .

If an unsaturated carboxylic acid or an anhydride thereof in an amount within the above range is subjected to an addition reaction with a petroleum resin having a softening point of 150 ° C. or higher used in the present invention (hereinafter this resin is referred to as an acid-modified petroleum resin) Since it is possible to add at a reaction rate close to 100%, it is not necessary to remove unreacted substances after the addition reaction, but if necessary, a slight amount of unreacted substances can be removed by blowing a heated inert gas. You may do it.

The high softening point-modified petroleum resin obtained as described above has a high softening point of 155 ° C. or higher, and is optimal as a resin for gravure ink.

When the softening point is low, for example, when the temperature is 140 ° C., the drying speed becomes extremely slow when a gravure ink is used, and there are various defects such as blocking, and the resin cannot be used as a gravure ink resin.

The features of the present invention are listed below.

(A) The resin obtained by the method of the present invention can be independently used as a new gravure ink resin for each color ink, and has excellent printing effects and printing compared to the conventionally used rosin-based gravure ink resin. It has properness and viscosity stability.

(B) Since gravure ink can be manufactured with the same formulation and manufacturing method as the conventional rosin-based resin, it is not necessary to provide new equipment for ink conversion. That is, by blending the resin of the present invention in an aromatic hydrocarbon solvent such as toluene at a resin concentration of 35 to 55 wt% at 40 ° C. to about 40 centipoise with an organic pigment and kneading with a sand mill or the like. Gravure ink is obtained.

(C) If necessary, it can be used in combination with a conventional rosin resin.

(D) Since a light-colored resin is obtained, the reproducibility of the color tone is good and the color development is good even if any pigment is used.

(E) It can be manufactured by a relatively easy process and the cost required for manufacturing can be small.

[Examples] Examples are shown below for clarifying the content of the present invention, but these are examples and the present invention is not limited to these examples unless it goes against the gist thereof. .

The ink test used for the evaluation of the present invention will be described.

[Ink test]

Carmine 6B 5 parts, calcium carbonate 10 parts, resin 50 wt
% Toluene solution was kneaded by a ball mill so that the particle size was 10 μm or less. Toluene was added to the obtained ink, and the viscosity was adjusted with Zahn cup No. 3 for 15 seconds.

A test gravure printing tester was used to print on coated paper at a speed of about 50 m / min, and the gloss and color density of the printed surface were measured.

Example 1 A cracked oil fraction having a boiling point range of 140 to 220 ° C., which is a by-product of steam cracking of naphtha, was collected using a 30-stage rectification column to produce 178 to 2
The 20 ° C. fraction was separated. The polymerizable component of this fraction is 70 wt.
%, The total content of indene and methylindene is 35 wt.
%, The indene content was 50%.

After adding 0.5 g of oleic acid amide to 100 g of this fraction and stirring, 0.6 wt% of boron trifluoride phenol complex compound was added to the raw material oil and polymerized at 40 ° C for 3 hours, followed by catalysis with caustic soda solution. The resin (I) was obtained by removing the unreacted oil and the low polymer by distillation after washing with water. The yield of resin (I) based on the raw material oil was 67 wt%, and the softening point was 161 ° C.
Met.

This resin (I) was placed in a reaction kettle equipped with a stirrer and heated to 210 ° C.
(I) 100 g of maleic anhydride while heating, melting and stirring
6 g (0.061 mol) per 1 part was added and reacted for 5 hours to obtain an acid-modified resin (IA). The softening point of (IA) is
The acid value was 32 at 172 ° C. (IA) was dissolved in toluene to prepare a toluene solution having a resin concentration of 50 wt%. The viscosity of this solution was 54 centipoise at 25 ° C.

The above ink test was conducted using this solution.

The results are shown in Table 1.

Example 2 A resin (II) was obtained in the same manner as in Example 1 except that the amount of oleic acid amide added was changed to 2 g. (I
The yield of raw material oil (I) was 63 wt% and the softening point was 159 ° C. 4 g of maleic anhydride per 100 g of this resin (II)
Acid-modified resin (II-
The softening point of (II-A) obtained in (A) was 166 ° C. and the acid value was 24. Resin concentration of (II-A) dissolved in toluene 50 wt%
The solution viscosity was 48 centipoise. The results of the ink test are shown in Table 1.

Comparative Example 1 100 g of the distillate used in Example 1 was treated with 0.06 stearamide.
Resin (III) was prepared in the same manner as in Example except that 5 g was added.
Got The yield of the raw material oil (III) was 68 wt% and the softening point was 163 ° C. The acid-modified resin (III-A) was obtained in the same manner as in Example 1 except that 4 g of maleic anhydride was added to 100 g of the resin (III). (III-A) had a softening point of 171 ° C. and an acid value of 25. The viscosity of a solution of (III-A) dissolved in toluene at a resin concentration of 50 wt% was 52 centipoise. The results of the ink test are shown in Table 1.

Comparative Example 2 5 g of linolenic acid amide was added to 100 g of the fraction used in Example 1.
After adding and stirring, 0.8 wt% of boron trifluoride ether complex compound was added to the raw material oil and polymerized at 50 ° C. for 3 hours. Then, the same procedure as in Example 1 was carried out to obtain a resin (IV). The yield of (IV) was 43 wt% and the softening point was 156 ° C. The acid-modified resin (IV-A) was added in the same manner as in Example 1 by adding 8 g of maleic anhydride to 100 g of the resin (IV).
Got (IV-A) had a softening point of 167 ° C. and an acid value of 41. The solution viscosity of (IV-A) dissolved in toluene at a resin concentration of 50 wt% was 48 centipoise. The results of the ink test are shown in Table 1.

Comparative Example 3 Maleic anhydride 8 was added to 100 parts of a commercially available petroleum resin having a softening point of 125 ° C.
Was added to the reaction mixture under the same conditions as in Example 1 to give a softening point of 138.
A resin having an acid value of 42 at ℃ was obtained. When the above ink test was conducted on this resin, the glossiness and color density of the printing surface were insufficient, and the drying speed during printing was extremely slow, which was unsatisfactory as a resin for gravure ink.

[Advantages of the Invention] As described in detail above, the resin for gravure ink of the present invention is excellent in drying property, gloss of printed surface, color density, etc. when used as an ink, and is sufficient because it can be produced by a relatively simple method. Has industrial value.

Claims (1)

[Claims] 1. Friedel containing 0.1-3.0 parts by weight of a fatty acid amide is added to 100 parts by weight of a fraction having a boiling point within the range of 140 to 220 ° C. among the cracked oil fractions obtained by the thermal decomposition of petroleum.・ Softening point 15 obtained by polymerization with Kraft-type catalyst
A petroleum resin for gravure ink, wherein 0.01 to 0.2 mol of unsaturated carboxylic acid or its anhydride is added to 100 g of the resin at 0 ° C or higher.