JP2003165919A - Pigment yellow 74 and printing ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a printing ink superior to the conventional pigment yellow 74 in transparency and density. <P>SOLUTION: The pigment yellow 74 is characterized in that it is obtained by coupling a coupling component containing 2-methoxyacetoacetoanilide and an acetoacetoanilide derivative represented by formula (1) [wherein X's may be the same or different and are each a CONR<SB>1</SB>R<SB>2</SB>, an SO<SB>2</SB>NR<SB>1</SB>R<SB>2</SB>, an NHCOR1, a CONH(CH<SB>2</SB>)kNR<SB>1</SB>R<SB>2</SB>or an SO<SB>2</SB>NH(CH<SB>2</SB>)kNR<SB>1</SB>R<SB>2</SB>(wherein R<SB>1</SB>and R<SB>2</SB>are each independently H or an alkyl, or may be combined together to form a cyclic structure; and (k) is an integer of 1 to 4); (m) is 1 or 2; Y's may be the same or different and are each R<SB>3</SB>, OR<SB>3</SB>(wherein R<SB>3</SB>is H or an alkyl), COOH or SO<SB>3</SB>H; and (n) is an integer of 0 to 2], in amount of 0.1-10 mol% based on the 2-methoxyacetoacetoanilide, with a diazo component containing 2-methoxy-4- nitroaniline. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to Pigment Yellow 74 and a printing ink using the same. More specifically, it relates to Pigment Yellow 74 having improved tinting strength and transparency, and a printing ink using the same.

[0002]

2. Description of the Related Art Conventionally, disazo yellow pigments containing 3,3'-dichlorobenzidine as a tetrazo component and an acetoacetanilide compound as a coupling component have been used as yellow pigments for printing inks. However, since the disazo yellow pigment contains a biphenyl skeleton in its structure and also contains chlorine, it is feared that a toxic substance is generated when the printed matter is disposed of.

Therefore, there is a strong demand for the development of a yellow pigment having a pigment performance comparable to that of the disazo yellow pigment, a low production cost, and excellent hygiene. 2-methoxy-4-
Pigment Yellow 74, which has nitroaniline as a diazo component and 2-methoxyacetoacetanilide as a coupling component, has the advantage of being excellent in light resistance and sharpness, but has the drawback of being extremely inferior in transparency and coloring power. It was

Pigment Yellow 74, a surface treatment technique which has been conventionally used to solve the transparency and coloring power,
That is, a rosin alkali salt solution (so-called rosin soap) is added to the coupler component or to the pigment slurry after coupling, and then a metal salt for lakes such as aluminum sulfate is added to transform the rosin into an insoluble rosin lake metal salt. A method of finely controlling the shape of the pigment particles by precipitating the pigment has been tried, but it cannot be said to be sufficient.

Therefore, Pigment Yellow 74 is actually used as a part of a coating material for building materials, etc., which requires concealing property, and has hardly been applied to printing inks requiring higher transparency and coloring power. It was

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide Pigment Yellow 74 having improved transparency and tinting strength without impairing the original light resistance and clarity of Pigment Yellow 74. To do.

[0007]

That is, according to the present invention,
-Coupling component containing 0.1 to 10 mol% of acetoacetanilide derivative represented by the following formula (1) with respect to methoxyacetoacetanilide and 2-methoxyacetoacetanilide, and dimethoxylation of 2-methoxy-4-nitroaniline Pigment Yellow 74, which is obtained by coupling a diazo component of Formula (1)

[0008]

[Chemical 3]

[In the formula, X may be the same or different.
Good, conr₁R₂, SO₂NR₁R ₂, NHCOR1,
CONH (CH₂) KNR₁R₂Or SO₂NH (CH₂)
kNR₁R₂(R₁, R₂Are each independently a hydrogen atom,
Kill group or R₁, R₂Ring structure that is integrated by combining
And k represents an integer of 1 to 4. ), M is 1 or 2
And Y may be the same or different, and R₃,
OR₃(R₃Represents a hydrogen atom or an alkyl group. ), CO
OH or SO₃Represents H, and n represents an integer of 0 to 2
You ] Further, in the present invention, the diazo component is 2-methoxy-4-nit
Roaniline and 2-methoxy-4-nitroaniline
In contrast, 0.1 to 10 mol% of the compound represented by the following formula (2)
The present invention relates to Pigment Yellow 74, which is a compound. Formula (2)

[0010]

[Chemical 4]

[In the formula, Z may be the same or different, and CONR ₁ R ₂ , SO ₂ NR ₁ R ₂ , CONH (C
H ₂ ) kNR ₁ R ₂ , SO ₂ NH (CH ₂ ) kNR ₁ R ₂ (R ₁ ,
R ₂ is independently a hydrogen atom, an alkyl group or R ₁ ,
Represents a ring structure in which R ₂ is bonded to form one unit, and k is 1 to
Represents an integer of 4. ), COOH or SO ₃ H, s
Represents an integer of 1 or 2, Q may be the same or different, and R ₃ , OR ₃ (R ₃ represents a hydrogen atom or an alkyl group) or NO ₂ , and t is 0 to 2 Represents an integer. Further, the present invention relates to a printing ink composition comprising Pigment Yellow 74 and a vehicle for printing ink.

In the present invention, R _{1 and} R ₂ in the acetoacetanilide derivative represented by the formula (1) and the aniline derivative represented by the formula (2) represent a hydrogen atom or an alkyl group, and the alkyl group has 1 carbon atom. The alkyl group having 18 to 18 carbon atoms is preferable, and the alkyl group having 1 to 4 carbon atoms is more preferable. Further, the cyclic structure in which R _{1 and} R ₂ are bonded and integrated is a 5-membered ring or a 6-membered ring, and these nitrogen-containing structures may have a further nitrogen atom or oxygen atom as a constituent component.

Examples of the amine residue represented by --NR ₁ R ₂ in the formulas (1) and (2) are methylamino group, ethylamino group, stearylamino group, dimethylamino group,
Examples thereof include, but are not limited to, a diethylamino group, a methylaminopropylamino group, a dimethylaminopropylamino group, a diethylaminopropylamino group, and an N-aminoethyl-4-pipecolinyl group.

R ₃ in the formula (1) represents a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the aniline derivative having a carboxyl group or a sulfonic acid group include 4-methoxyaniline-2-sulfonic acid, 2,5-dimethoxyaniline-4-sulfonic acid and 2-nitroaniline-4-sulfone. Examples thereof include acid and 2-chloro-4-sulfo-5-aminobenzoic acid.

The pigment yellow 74 of the present invention can be manufactured according to a conventionally known method. That is, 2-
Methoxy-4-nitroaniline was diazotized, while 2
-0.1 to 10 mol% of acetoacetanilide derivative relative to methoxyacetoacetanilide, preferably 1 to
5 mol% was added and the mixture was adjusted according to a conventional method, and both were coupled according to a conventional method.

When the aniline derivative is used as the diazo component, 0.1 to 10 mol%, preferably 1 to 5 mol% of the aniline derivative is added to 2-methoxy-4-nitroaniline, and then the diazo derivative is added. Then, it may be coupled and similarly coupled. The coupling reaction is not particularly limited, and may be either a batch method which is usually called acid precipitation method under acidic acetic acid, or a continuous method in which the diazo solution and the coupling solution are simultaneously added in equal reaction amounts.

Pigment Yellow 74 of the present invention is used to produce a printing ink by flushing with a vehicle for a printing ink in the state of a wet cake of pigment, or by kneading a dried powder pigment with a vehicle for a printing ink to obtain a printing ink. . The flushing pigment is obtained as a wet cake by filtering the slurry after coupling, washing with water, and squeezing so that the pigment content is 26 to 32% by weight. A powder pigment is obtained by drying and crushing the wet cake.

When an offset printing ink is produced using Pigment Yellow 74 of the present invention, the flushing step is performed by adding 180 to 220 parts by weight of the offset printing ink vehicle to 100 parts by weight of wet cake (dry pigment). Is performed using. The formation of an ink from a powder pigment is carried out by using a three-roll roll by adding 350 to 450 parts by weight of a vehicle for offset printing ink to 100 parts by weight of the powder pigment.

Pigment Yellow 74 of the present invention can be used as a yellow pigment of offset printing ink for process. The offset printing ink composition comprises Pigment Yellow 743 to 35% by weight of the present invention, vehicle for offset printing ink 97 to 45% by weight, other auxiliary agents (dryer, leveling improving agent, thickener) and extender pigments 0 to 0.
It consists of 20% by weight. Vehicles for offset printing inks are resins 20 to 50 such as rosin-modified phenol resin, petroleum resin, alkyd resin, or drying oil-modified resin thereof.
% By weight, vegetable oils such as linseed oil, tung oil and soybean oil 0 to 30% by weight, and solvents such as n-paraffin, isoparaffin, aromatic, naphthene and α-olefin 10 to 60% by weight. Further, various known ink additives such as a dryer and a leveling improver are blended to obtain a printing ink composition.

Pigment Yellow 74 of the present invention can be used as a yellow pigment of gravure printing ink for process. Examples of vehicles for gravure printing inks include:
Gum rosin, wood rosin, tall oil rosin, lime rosin, rosin ester, maleic acid resin, polyamide resin, vinyl resin, nitrocellulose, cellulose acetate,
Ethyl cellulose, chlorinated rubber, cyclized rubber, ethylene-vinyl acetate copolymer resin, polyurethane resin, polyester resin, alkyd resin, acrylic resin, gilsonite, dammar, shellac, etc. or mixtures thereof, or the above resins or mixtures thereof are water-solubilized. Water soluble resin,
Or 10 to 50% by weight of emulsion resin and hydrocarbon,
Alcohol, ketone, ether alcohol, ether,
Examples include those containing 30 to 80% by weight of a solvent such as ester and water.

Pigment Yellow 74 of the present invention is used as a yellow pigment for a resist ink containing a photosensitive resin as a main component for a color electrophotographic toner, an aqueous and oil-based ink jet recording liquid, and a color filter for a liquid crystal display. be able to.

[0023]

EXAMPLES The present invention will be described in detail below based on examples. In the examples, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified.

[0024]

Example 1 2-Methoxy-4-nitroaniline 168
Parts were dissolved in a solution consisting of 2000 parts of water and 260 parts of 35% hydrochloric acid, 1000 parts of ice was added thereto, and the mixture was cooled to 0 ° C.
A solution consisting of 200 parts of water and 70 parts of sodium nitrite was added, and the mixture was stirred at 3 ° C or lower for 60 minutes to obtain a diazo component. On the other hand, 200 parts of 2-methoxyacetoacetanilide and 8 parts of the compound represented by the following formula (3) were dissolved in a solution consisting of 5000 parts of water and 100 parts of sodium hydroxide. To this, 200 parts of 80% acetic acid was added little by little to form a suspension, which was used as a coupler component. 6 diazo components as coupler components
It took 0 minutes and was added. During this time, the reaction was kept at about 20 ° C. PH of the resulting pigment slurry with sodium hydroxide
After adjusting to 9.5 to 10.0, 25% rosin soap 7
0 part was added. After stirring this slurry for 10 minutes, hydrochloric acid was added to adjust the pH to 5.0 to deposit rosin on the pigment surface. Then, filter, wash with water, squeeze to obtain a pigment content of 27.5.
% Wet cake was obtained. Further, a part of this was dried and pulverized to obtain a pigment powder.

Ink formation by flushing was performed using a 1 L flasher. That is, 100 parts by dry weight of the wet cake and 190 parts of the offset ink vehicle preheated to 100 ° C. were simultaneously put into a flasher to perform flushing. Next, after removing the water coming out by flushing, decompression (1 to 8 × 10 ³ Pa) and heating were carried out for 30 minutes until the internal temperature of the kneaded product reached 100 ° C. to completely remove the water of the kneaded product. To this kneaded product, 280 parts of the offset ink vehicle and 50 parts of the solvent were gradually added and then taken out from the flasher. Thereafter, a roll temperature of 60 ° C. and a pressure of 10 Barr were used to knead the three coarse rolls to remove coarse particles to obtain a base ink. The ink vehicle 25 for offset is added to 62 parts of this base ink.
Parts, 10 parts of solvent, 3 parts of auxiliary agent, and tack 5.8 to 6.
The final ink was obtained by adjusting to 0.

In the case of pigment powder, 100 parts of the pigment is added to 400 parts of the offset ink vehicle and dispersed by using a three-roll to form a base ink, and then the offset ink vehicle, a solvent, and an auxiliary agent are added to tack 5.8. Adjusted to ~ 6.0 to obtain the final ink. Formula (3)

[0027]

[Chemical 5]

[0028]

Example 2 In Example 1, except that 168 parts of 2-methoxy-4-nitroaniline was used as a diazo component, 200 parts of 2-methoxyacetoacetanilide and 11 parts of a compound represented by the following formula (4) were used as coupler components, The same operation as in Example 1 was performed to obtain a wet cake and a pigment powder having a pigment content of 27.0%. The inking method was the same as in Example 1 to obtain the final ink. Formula (4)

[0029]

[Chemical 6]

[0030]

Example 3 In Example 1, except that 168 parts of 2-methoxy-4-nitroaniline was used as a diazo component, 200 parts of 2-methoxyacetoacetanilide and 11 parts of a compound represented by the following formula (5) were used as coupler components, The same operation as in Example 1 was performed to obtain a wet cake and a pigment powder having a pigment content of 27.5%. The inking method was the same as in Example 1 to obtain the final ink. Formula (5)

[0031]

[Chemical 7]

[0032]

Example 4 In place of 168 parts of 2-methoxy-4-nitroaniline in Example 3, 165 parts of 2-methoxy-4-nitroaniline and 4 parts of 2-nitroaniline-4-sulfonic acid were used as diazo components. In the same manner as in Example 1, a wet cake and a pigment powder having a pigment content of 27.0% were obtained. The inking method was the same as in Example 1 to obtain the final ink.

[0033]

Example 5 In place of 168 parts of 2-methoxy-4-nitroaniline in Example 3, 164 parts of 2-methoxy-4-nitroaniline and 9 parts of the compound represented by the following formula (6) were used as diazo components. In the same manner as in Example 1, a wet cake and a pigment powder having a pigment content of 27.0% were obtained. The inking method was the same as in Example 1 to obtain the final ink. Formula (6)

[0034]

[Chemical 8]

[0035]

Comparative Example 1 In Example 1, except that 168 parts of 2-methoxy-4-nitroaniline was used as the diazo component and 207 parts of 2-methoxyacetoacetanilide was used as the coupler component,
The same operation as in Example 1 was performed to obtain a wet cake and a pigment powder having a pigment content of 27.3%. The inking method was the same as in Example 1 to obtain the final ink.

The results from the wet cake and pigment powder are summarized in Table 1 above. L * indicates the transparency of the ink, and the smaller the value, the higher the transparency, and the density is the coser value (reflectance density), and the higher the value, the higher the density. Table 1 Wet cake Pigment powder Transparency Concentration Transparency Concentration Example 1 75.7 2.10 78.0 1.57 Example 2 66.3 2.11 76.5 1.69 Example 3 67.1 2. 12 76.7 1,72 Example 4 66.8 2.10 75.3 1.74 Example 5 66.3 2.11 75.0 1.76 Comparative Example 1 84.7 1.50 85.1 1 .38

[0037]

According to the present invention, Pigment Yellow 74 having improved transparency and coloring power without impairing the light resistance and sharpness originally possessed by Pigment Yellow 74 was obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Osamu Jomaru             2-3-13, Kyobashi, Chuo-ku, Tokyo Toyo             Nki Manufacturing Co., Ltd. F-term (reference) 4J039 AB02 AB07 AB08 AD10 AD15                       AD18 AE02 AE04 AE06 AE08                       BE12 CA04 EA17 GA02 GA03

Claims (3)

[Claims] 1. A 2-methoxyacetoacetanilide and
0.1 to 2-methoxyacetoacetanilide
10 mol% of acetoacetani represented by the following formula (1)
A coupler component containing a lido derivative, and 2-methoxy-4
-The diazo component formed by diazotizing nitroaniline
Pigment yellow which is characterized by being pulled
-74. Formula (1) [Chemical 1] [In the formula, X may be the same or different, and CO
NR₁R₂, SO₂NR₁R₂, NHCOR₁, CONH (C
H₂) KNR₁R₂Or SO₂NH (CH₂) KNR ₁R
₂(R₁, R₂Are each independently a hydrogen atom or an alkyl group.
Or R₁, R₂Represents a ring structure in which
k represents an integer of 1 to 4. ), M represents 1 or 2, and Y
R may be the same or different and R₃, OR₃(R₃
Represents a hydrogen atom or an alkyl group. ), COOH
Is SO₃Represents H, and n represents an integer of 0 to 2. ] 2. The diazo component is 2-methoxy-4-nit.
Roaniline and 2-methoxy-4-nitroaniline
On the other hand, 0.1 to 10 mol% of the following formula (2)
The pigment yellow according to claim 1, which contains a nirin derivative.
74. Formula (2) [Chemical 2] [In the formula, Z may be the same or different, and CO
NR₁R₂, SO₂NR₁R ₂, CONH (CH₂) KNR₁R
₂, SO₂NH (CH₂) KNR₁R₂(R₁, R₂Are each
Independently hydrogen atom, alkyl group or R₁, R₂Combined with
Represents an integrated ring structure, k is an integer of 1 to 4
You ), COOH or SO₃Represents H, s is 1 or 2
Represents the integer, and Q may be the same or different.
R₃, OR₃(R₃Represents a hydrogen atom or an alkyl group
You ) Or NO₂, T represents an integer of 0 to 2. ] 3. A printing ink composition comprising the pigment yellow 74 according to claim 1 or 2 and a vehicle for printing ink.