JPS6015475A - Ink composition - Google Patents

Abstract

PURPOSE:To fix a non-toxic dye in a good water-resistant state, by reacting and fixing an anionic dye with an ink vehicle using a specified copolymerization compsn. of an acrylic acid derivative. CONSTITUTION:An anionic dye is reacted and fixed by an ink vehicle using an acrylic acid derivative copolymerization compsn. of formula I or II [wherein R1 is CH3; R2 is a group of formula III (wherein n is 1,2,3...18); R3, R4 are each a group of formula III (wherein n is 1,2,3,4)], which contains 15-80% compsn. of formula I in a weight ratio of the entire copolymerization compsn. to the monomer. Water resistance can be imparted to ink by the reaction of the anionic group in the anionic dye structure with the amino group (cationic) in the compsn. of formula I . A compsn. of formula II impart flow characteristic, dryness, film strength, etc. to the ink.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a general 9971 paper.
The present invention relates to an ink composition suitable for printing and stamping on paper such as E, paper, etc., and more specifically, it relates to an ink composition suitable for printing and stamping on paper, etc. I: Dye +4? ! - This is the ink used, and it relates to an ink composition that maintains a sufficient kJ aqueous property and rT immediately after printing, so that the printed matter obtained by using this ink once has been printed.

Anionic dye and iJ elephant I'4 15oi
, -o-1-N-1-COO group.

Conventionally, a wide variety of basic dyes have been used as pigments for flexographic inks, such as meelamine (yellow), 1-no-damine (red), Victory 1-no blue (blue), and methyl violet (purple).

In recent years, it has been announced that auramine is suspected of causing pre-inking, and the printing ink industry has decided to use auramine in inks. Furthermore, from the viewpoint of food hygiene, it is desirable to avoid using basic dyes other than auramine as much as possible.

Anionic dyes can be considered as alternatives to these basic dyes in terms of hue. Anionic dyes have -SO3 groups and -COO groups during their liI formation, but dye structures with q-th 3O3 groups and -C00 groups have reduced toxicity, and these Inside is a basket of food dyes that are approved as food dyes.

Therefore, if you make an ink with anionic g (11 ingredients), from the 1jjη- side of In 4, Labor during manufacturing, and the quality of printing '+, :'+, 1jjη-. (
Be brave and effective.

However, when an ink using anionic dye 4'-1 as a coloring f1 is used with an in-vehicle of 1;L, the ink has sufficient ice cutting.11. I can't make it blue. t'j:su, the mark Ii:'I 'D' printed using an ink containing an anionic dye in the ink vehicle used in conventional [11 Yang]
When J is soaked in water, pigment is released from the knot.

Here, practical soil brother 5] l1i1 aqueous and (Jrll printing a1
:) on ice within 5 minutes after printing 3. Even if you erase it, the pigment will stick to the surface of the covered part 1i:'l ('+) and will not flow out. : , Power L゛Inserac, 1
Cosin maleic acid resin, iron fiber resin, acrylic 4', +117, etc. dissolved in an organic solvent or alkaline aqueous solution, as well as styrene resin, acrylic resin, boriamy +'4?
I. Emulsions of fats alone or in combination -C.

The present invention has been completed with the aim of fixing non-toxic dyes in a form with good water resistance by using a unique ink vehicle.

The present invention is practical for printing materials printed with inks using anionic dyes that are highly safe in terms of food hygiene.'' - As a result of various studies aimed at achieving sufficient ice resistance,
Anionic dyeing 4.1 is completely applied to the printing material using an ink vehicle using an acrylic ester copolymer composition containing a certain part by weight of the reaction a acid obtained by the reaction of acrylic ester and amines. He devised a method to obtain sufficient ice properties to adhere to the surface.

There are various fixing agents on the market for fixing anionic dyes and D7I. Requires heat treatment in bath. Regarding printing ink, there is a patent (US PaLent 4.108.812) that uses poly'/midoamine as a fixing agent, but this is for the reaction AJ1 product acid, which is a reaction between acrylic ester and amines. This is fundamentally different from the present invention.

Also, some cationic surfactants act as fixing agents for ζJ anionic dyes, but do the surfactants themselves dissolve in water? There are many things that change to L or Jo, and such cation interface l+! ll! It is not possible to obtain a sufficient LJ water-based ink by mixing LJ into an ink vehicle.

The ink composition of the present invention has long-term properties.

- In order to fix the anionic G42 material to the printing material, the above-mentioned hemolytic acid is converted into a mole in the solid content of the ink vehicle! , (Be careful in the range of 15 to 80%.

(2) In order to maintain the printing suitability of the B composition other than the acid compound J, R,, R, (, I) are removed.

(2) -C standic acid is used as a neutralizing agent for the polymerized ml according to the present invention. For example, formic acid, 01 acid, 7L acid, etc. are used, and the neutralization equivalent is 0.
8-1.2-4 nyl is suitable.

(2) Add to the ink according to the present invention an amount of ice necessary and sufficient to dissolve the anionic dye.

■1 l near the water! The 11th component is a lower alcohol used as a /8 medium when synthesizing group 1 acids. 1) Solders, etc. and lower alcohols added when adjusting the viscosity of ink.

(2) The ink composition according to the present invention dissolves in ice in the form of an ink, and is more acidic than the pH of the ink.

In the present invention, the main point is to use 64 units of hemolytic acid in the acrylic acid ester copolymer composition, but the method for obtaining the dark ice properties of this ink is to use This is due to the reactivity with amino W (cationic) held by the convex and hemi-containing acids.

In this case, if the A composition is less than 15%, the required amount of dye (approximately 1 to 12% in the ink) cannot be fixed and the ink will gel.

In addition, if the A composition exceeds 80%, problems will occur in terms of ink quality and ink cost, so the content of the hemiacetic acid should be reduced to 1.
It is limited to 5-80%.

As for the B composition other than the hemi-acid, an appropriate one is selected from the -fa j' acrylic acid esters in order to improve the ink's Aε mobility, drying properties, film strength, etc. Acrylic acid is used in a range of 0 to 20% to change the properties of the ink film, but it has no relation to the bare properties of Dye-1.

Next, examples of long cans of the present invention are not shown. All parts shown in the examples are parts by weight.

Fruit example-1□ Volume 71 equipped with a stirrer and reflux condenser! Put 180H of edylalnylene into a 4-norm flask and heat the ethanol to reflux temperature while replacing the air in the flask with carbon dioxide gas. After that, add the following composition to this? The iX mixture was added dropwise at a constant rate every 2 hours (1).

Methyl acrylic 102g Butyl acrylic 40, r Dimethylamine ethyl methacrylate 50g Acrylic i 8g Azobisisobutyronitrile 2.5g 1 hour and 2 hours after the completion of the dropwise addition, 1g of azobisisobutyconitrile was added, Thereafter, the copolymerization is completed by maintaining the reflux temperature for 6 hours. After cooling this copolymer solution,
Add and mix 15 g of formic acid, and then add 224 g of ethyl alcohol.
G in g; Jl! Copolymerization reaction composition (hereinafter referred to as resin liquid C)
).

This resin liquid C is a transparent liquid with a resin content of 50% and a viscosity of 28 voids (25°C), which can form an infinite stone shape with water. Add 40 g of a 10% aqueous solution of tartrazine (Food Yellow No. 4, manufactured by Sanei Chemical Industry 8.) and 20 g of ethyl alcohol to 40 g of this (fat liquid C) and stir for 5 minutes with a stirrer.

The thus obtained ink iJ deadness 1ofJ (#4
It is yellow in color and has good fluidity.

This Inn 4- was printed on napkin paper and tissue paper using a flexo printer. The printing condition of the ink and the quality of each printed matter were good.

Even when each printed matter was immersed in water 5 minutes after printing, no leakage of color was observed.

Example 2.

A mixture of the following composition was copolymerized according to the method of Eggplant Example 1, and then acetic acid was added to neutralize it, and ethyl alcohol 2
24g, stone-like, 4M+fat 50%, viscosity 32voices (
25°C) to obtain a polymerization reaction composition (hereinafter referred to as 4M+fat liquid).

Methyl methacrylate 90g Ethyl acrylate 20g Ethylhexyl acrylate 20 ft Dimethylaminoedyl methacrylate 70g Abhis isobutylene 1:
Add trill to 40g of this resin liquid and add J-Shin (Yoyoui-eup No. 3,
30 tr of 10% ice solution (manufactured by Sanei Ka'Y Kogyo Co., Ltd.) and 30 g of ethyl alcohol were added and stirred for 5 minutes using a stirrer. The obtained In-1- is a red ink with good permeability at l'+'i degrees for 10 seconds.

This ink was printed on napkin paper and tissue paper KjL using a flexo printing machine. The printing quality of the ink and the finish after each print were good.

Even when each printed matter was immersed in water 5 minutes after printing, no dye leakage was observed.

Example 3: A mixture with the following composition was copolymerized according to the method of Example 1. Next, a neutralizing equivalent of lactic acid was added, and ethyl alcohol was added at each station.Resin strength: 51% Viscosity: 48 voids (25°C)
Copolymerization reaction 8. A product (hereinafter referred to as resin liquid E) was obtained.

Methyl methacrylate 120g Nityl acrylate 20g Lauryl acrylate 201; Dimeg-ruaminoethyl methacrylate 401 Azobisisobutyronitrile 2.5 r3 This resin liquid E 4
30 g of a 10% aqueous solution of Brilliant Blue FCF (Food Blue No. 1, manufactured by Sanei Chemical Industry Co., Ltd.) and 30 g of ethyl alcohol are added to 0 g, and the mixture is stirred for 5 minutes using a stirrer.

The ink thus obtained has a viscosity of 11 seconds (#4y
It is a blue ink with good fluidity.

This ink was printed on Nozokin paper and tissue paper using a gravure printing machine (plate depth 30 μm, number of lines 150). The printing condition of the ink and the finish of each printed matter were good.

Even when each printed matter was immersed in water 5 minutes after printing, no dye release was observed.

Comparative Example - 1゜Commercially available acrylic resin liquid Jinkryl 61 (non-volatile content: 3
0%, made by Jiconson Wasox A) 40g of Tartrange's 10% water solution 401 and ethyl alniol 1-201K
Add and stir for 5 minutes with 1 stirring. jr
The ink was yellow ink with a viscosity of 10 seconds (4↓4) and good 'iAL movement.

This ink was printed on napkin paper and tissue paper using a flexo stamp 1ii11;l. The printing condition and finish of each printed matter were good, but when I immersed each printed matter in ice 5 minutes after printing, Color 2 completely leaked out.

Comparison II (Row - 2゜) 60 g of commercially available polyamide resin solution I/Resin DA15 (non-volatile content 15%, manufactured by Teikoku Kagaku Sangyo Co., Ltd.), 20 B of a 10% aqueous solution of erythrosine, 12 g of methyl alcohol, and the cationic dye fixing agent Arka- 1. 8 g of T-800 (manufactured by Lion Akzo) was added and stirred for 30 minutes using an L stirrer.The resulting ink was a red ink with a viscosity of 10 seconds (#4 Zahn Kasop) and good fluidity. This ink was printed on napkin paper and tissue paper using a flexo printing machine. Five minutes after printing, the printed matter was immersed in water, and 51 L of the dye was completely released.

The test results of Actual J't5 Examples 1.2.3 and Comparative Example 1.2 are shown in Table 1 as follows.

Table 1 Judgment criteria: 11 pieces ○Good,

As described above, the ink composition according to the present invention has improved ink fluidity, ink concentration, and ink drying property by employing a unique vehicle compared to conventional inks. Moreover, the water resistance of the container is also extremely excellent.

Claims (1)

[Scope of Claims] In the copolymerization reaction of acrylic acid derivatives represented by the following general formulas A and B, among the acids, all of the hemium acids (in terms of mono-2-mEt ratio in the polymer composition) An ink composition characterized in that an anionic dye is reacted and fixed by an ink vehicle using a polymerization reaction composition containing 15 to 80%. CH2=C \ ○OR2 R=H in the above formula or cri3 R2=, Cri II zn +l (however, n =
l, 2.3--------18) R3, R4= Cn Hzn +1 (However, 11-1
．． 2.3.4)