JPS62181306A - Petroleum resin for gravure ink - Google Patents

Abstract

PURPOSE:The titled resin having high drying rate in the case when it is used as gravure ink, having improved color concentration, luster, etc., of print, obtained by adding an unsaturated carboxylic acid to a resin having a high softening point obtained by a specific method from a specific cracked oil fraction of petroleum. CONSTITUTION:Firstly, 100pts.wt. fraction having 140-220 deg.C boiling point among cracked oil fractions obtained by thermal cracking of petroleum is polymerized with 0.1-3pts.wt. fatty acid amide (e.g., lauric acid amide, etc.) by the use of Friedel-Crafts catalyst (preferably boron trifluoride, etc.) preferably at -30-60 deg.C for 10min-15hr to give a resin having >=150 deg.C softening point. 0.01-0.2mol unsaturated carboxylic acid is subjected to addition reaction with 100g of the resin having high softening point to give the aimed resin.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a high softening point petroleum resin for gravure ink that, when used in gravure ink, has a fast drying speed, a color density of 1 for printed matter, and excellent gloss. .

[Prior Art J As a binder for paper gravure in 4-, lime rosin, which is a rosin derivative, and a modified petroleum resin obtained by adding maleic anhydride to petroleum resin and esterifying it with alcohol are used.

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

(1) It has a high softening point and a fast drying speed, (2) It has a relatively low molecular weight and shows an appropriate solution viscosity when dissolved in toluene, etc., (3) [1 ingredient @bamboo is good] ,
(4) good viscosity stability when made into ink; (5)
) Good gloss and density of the printed surface, etc.

The above-mentioned modified petroleum resin almost satisfies the basic requirements (1) to (5) and is used as a binder for gravure ink.
Improvements in the density of the printed surface, etc. are required.

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

In other words, the present invention involves adding 0.1 to 0.1 to 10,000 parts of fatty acid amide to 100,000 parts of the fraction having a boiling point within the range of 140 to 220°C out of the cracked oil fraction used in the thermal decomposition of petroleum.
Resin 1007 with a softening point of 150°C or higher obtained by polymerizing with a Friedel-Crafts type catalyst in addition to a 3.0 type opening
It consists of a petroleum resin for gravure ink, characterized in that 0.01 to 0.2 mol of an unsaturated carboxylic acid or anhydride thereof is added thereto.

The raw material oil used in the present invention is a cracked oil fraction obtained by thermal decomposition of petroleum, and has a boiling point within the range of 140 to 220°C, and the unsaturated compounds contained therein are substantially composed of subolene and The fraction is an alkyl derivative, indene and its alkyl derivative.

In order to obtain a petroleum resin with a softening point of 150°C or higher, which is one of the structural characteristics of the present invention, it is usually possible to polymerize using the above raw material oil, but in particular, the sum of indene and its alkyl derivatives in the above raw material oil is If a feedstock oil with a content of 20 wt % or more and an indene content defined by the following formula (1) is adjusted to 30% or more is used, it will be much better.

Indene content i' (%) - Each component of the raw oil is analyzed by gas chromatography, for example in the following article f1.

A. Styrene, allylbenzene, 1,3,5-trimethylbenzene, and 〇-edyl 1-1-1-20% by weight
7 Viaison and grease (^piczon l.

greacc, As5ociated [1ectr
Celite (Cclite, a product of Johns-Hanvi)
A product of I Ie Corp) was packed into a 3 TrL column and heated with a helium flow of 60 cc/mi at 100°C.
Analyze under conditions of n.

Each component other than those shown in A and A was made of Celite containing 20 wt% polyethylene glycol 4000.
Packed into a column of m and heated with a helium flow ffi at 125 °C.
Analyze under the condition of 60cc/min.

Styrene and its alkyl derivatives, indene and its furkyl yt conductor, and cyclopentadiene and methylcyclopentadiene, each containing a, analyzed by the above method, are used as polymerizable components.

The adjustment of such raw material oil is such that the above boiling point range is 140 to 2.
The cracked oil fraction at 20° C. can be subjected to precise distillation, extractive distillation, or the like.

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

In the present invention, the cracked oil fraction 1 with a boiling point of 140 to 220°C
The above fatty acid amide is added to ooim part by λ of 0.1 to 3.0, and monopolymerized using a Friedel-Kura 71 type catalyst. Examples of the Friedel-Crafts type catalyst include boron trifluoride, aluminum chloride, and boron trifluoride complex compounds, preferably boron trifluoride, boron trifluoride etherate, Add 0.01 to 5 wt% of boronic trifluoride felt to the raw material oil and heat the mixture to -30°C to +
Polymerize and immerse at a temperature within the range of 60°C for a time within the range of 10 minutes to 15 hours, decompose and remove the catalyst with an alkali such as caustic soda or soda carbonate, wash with water as necessary, and further evaporate or By separating unreacted oil and low-molecular polymers by distillation, it is possible to obtain an aromatic hydrocarbon resin having a high softening point of 150° C. or higher and a bromine number of 40 or lower, for example.

The appropriate amount of fatty acid amide to be 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. If the amount of fatty acid amide added is less than 0.1 part by weight, gravure ink using the resulting resin will not have the effect of improving the gloss of the printed surface, color density, etc.
, if it exceeds 0 weight parts, the yield of resin based on the raw material oil will decrease. In addition, although good gloss and color density of the printed surface can be obtained, repellency phenomenon called pinholes occurs on the printed surface, which is undesirable.

Next, the present invention is directed to E
1III Unsaturated carboxylic acid 3 or its anhydride is added to FA resin, but in this case, the above petroleum resin 1001. l
0.01 to 0.2 mol based on the temperature of 140 to 250'C for 30 minutes to 1 mol in the absence of a catalyst or in the presence of a radical initiator such as an organic peroxide.
51F, reacts within the range between '1.

Examples of unsaturated carboxylic acids or anhydrides thereof used in the present invention include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, detrahydronotal M and its anhydride, fumaric acid, citraconic acid, itaconic acid, etc. .

If the amount of unsaturated carboxylic acid or its anhydride added to 100 U of resin is less than 0.01 mol,
Due to its low fi, when used in gravure ink, pigment dispersibility is poor and it cannot be used in ink. Moreover, if the amount exceeds 0.2 mol, not only will the addition reaction be difficult, but when the resin is dissolved in toluene to prepare a gravure ink varnish, the solution viscosity will be abnormally high and it will not be possible to obtain a re-ink. On the other hand, in order to appropriately adjust the viscosity of the solution as a gravure ink varnish, the resin temperature must be lowered by (degrees).
(This results in a disadvantage that the gloss of the finished in-U is reduced and uniform printed matter cannot be obtained.

If an unsaturated carboxylic acid or its anhydride within the above range is subjected to an addition reaction under the above conditions to the 6-oil resin with a softening point of 150°C or higher used in the present invention (hereinafter, this resin will be referred to as acid-modified petroleum resin). ) has an addition Qlj with a reaction rate close to 100%.
Since addition reaction (flame) is possible, it is not necessary to specifically remove unreacted substances, but if necessary, trace amounts of unreacted substances may be removed by blowing heated inert gas or the like.

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.

If the softening point is low, for example at 140° C., the drying rate will be extremely slow when used as a gravure ink, and blocking will occur.Therefore, the resin cannot withstand use 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 used independently as a new gravure ink resin for each color ink, and is superior to the conventionally used rosin-based gravure ink resin. , printing suitability J3 and viscosity stability.

(a) Since gravure ink can be manufactured using the same formulation and manufacturing method as conventional rosin-based resins, there is no need to install new equipment to produce ink.

The resin of the present invention was added to an aromatic hydrocarbon solvent such as toluene at a concentration of 35 to 55 wt%! A gravure ink is obtained by blending an organic pigment into a varnish prepared at a temperature of about 40 centipoise at 40° C. and kneading it with a sand mill or the like.

(1) If necessary, it is also possible to use 01 with conventional rosin resins.

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

(e) It can be manufactured through a relatively easy process and the cost required for manufacturing may be low.

[Examples] Examples are shown below to specifically clarify the content of the present invention, but these are merely examples, and the present invention is not limited to these Examples unless it goes against the spirit thereof. do not have.

In addition, the ink test used for evaluation of the present invention will be explained.

[Ink test]

5 parts of Chikaramin 6B, 10 parts of calcium carbonate, and 30 parts of a 50 wt % toluene solution of resin were kneaded in 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 to 15 seconds using a Zahnkatsub Co., Ltd. 3.

Using a test gravure printing tester, printing was performed on coated paper at a speed of about 50 m 2 /min, and the gloss and color density of the printed surface were measured.

Example 1 140-22 produced by steam cracking of naphtha
The cracked oil fraction with a boiling point range of 0°C was separated into a fraction with a temperature of 118 to 220°C using a 30-stage rectification column. The polymerizable component of this fraction was 70 wt%, the total S content of indene and mediyl indene was 35 W%, and the indene content was 50%.

After adding 0.5 g of oleic acid amide to 100 tJ of this fraction and stirring, 0.6 wt% of a trifluoride phenol complex compound based on the raw material oil was added and heated at 40°C for 3 hours. After polymerization, the catalyst was removed with a caustic soda aqueous solution, and after washing with water, unreacted oil and low polymer were removed by distillation to form the resin (I).
I got it. The yield of resin (1) based on the raw material oil was 67 wt%, and the softening point was 161°C.

Put this resin (I) into a reaction pot equipped with a stirrer and
Melt maleic anhydride (I) while stirring while heating to °C.
It was added at a rate of 6 g (0,061 mol) per 100 g and reacted for 5rI! An M-modified resin (IA) was obtained. (
The softening point of I-A> was 172°C and the acid value was 32. (
I-A) is dissolved in toluene and the temperature of 11116 degrees is 50w.
A t% toluene solution was prepared. Viscosity of this solution: 25℃
It was 54 centipoise.

The above-mentioned ink test was carried out using this solution.

The results are shown in Table '1.

Example 2 Resin (I[) was obtained in the same manner as in Example 1 except that the amount of oleic acid amide added was changed to 27. (
The yield of II) based on the feedstock oil was 63 wt%, and the softening point was 1.
The temperature was 59°C. Anhydrous maleic Pli49 was added per 100 g of this resin (II), and acid-modified resin (II-A) was obtained by the same procedure as in Example 1. The softening point of (IA) was 166°C, the acid value was 24, and Ic0 (If-A)
The viscosity of a solution of sowt% resin dissolved in toluene was 48 centipoise. The results of the ink test are not shown in Table 1.

4. Proceed as in Example 4, except that 0.05 g of stearic acid amide was added to 100 g of the fraction used in Example 1.
Il fat (III) was obtained. The yield of (11) based on the feedstock oil was 68 wt%, and the softening point was 163°C. Acid-modified resin (
III-A> was obtained. The softening point of (1-A) is 111°C,
The acid value was 25. The viscosity of a solution of (II-A) dissolved in toluene at a resin concentration of 50 wt% was 52 centivoices. The results of the ink test are shown in Table 1.

L squeezing -1 5 g of lyrinic acid amide to 100 g of the fraction used in Example 1
After addition and stirring, o, awt% of boron trifluoride ether complex compound was added to the raw material oil and polymerized at 50°C for 3 hours, followed by the same procedure as in Example 1 to obtain resin (IV). Ta.

The yield of (IV) was 43w%, and the softening point was 156°C.
Met. An acid-modified resin (IV-A) was obtained by adding 8 g of maleic anhydride per 10,047 g of this resin (■) and performing the same procedure as in Example 1. (IV-A')
The other point (F) was 167℃, @t41. (IV-
The viscosity of a solution obtained by dissolving A) in toluene at a resin concentration of 50 wt% was 48 Il 17 ind. The results of the ink test are shown in Table 1.

Table 1 Ink test results 8 parts of maleic anhydride was added to 100 parts of commercially available petroleum resin at 125° C. and reacted under the same conditions as in Example 1.
A resin having a softening point of 138°C and an acid value of 42 was obtained. When this resin was subjected to the ink test described in F, the gloss of the printed surface,
The color density was insufficient, and the drying speed during printing was extremely slow, giving it unsatisfactory properties as a resin for gravure ink.

[Effects of the Invention] As detailed above, the resin for gravure ink of the present invention has excellent drying properties, gloss of the printed surface, color density, etc. when made into ink, and can be printed in a relatively 1 m Therefore, the industrial value of 1 is 1.

Claims (1)

[Claims] 140 of the cracked oil fraction obtained by thermal decomposition of petroleum
Add 0.1 to 3.0 parts by weight of a fatty acid amide to 100 parts by weight of a fraction having a boiling point within the range of ~220°C, and polymerize with a Friedel-Crafts type catalyst. A petroleum resin for gravure ink, characterized in that 0.01 to 0.2 mol of an unsaturated carboxylic acid or its anhydride is added per 100 g of resin.