JPH06145546A - Pigment composition and pigment dispersion - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in flow, stability and properties of coating film without causing a change in color tone by mixing an organic pigment with a specified dihydroquinacridone derivative. CONSTITUTION:100 pts.wt. organic pigment is mixed with 0.1-30 pts.wt. dihydroquinacridone derivative of the formula wherein R1 and R2 are each H, lower alkyl, alkoxyl or halogen; R3 to R6 are each H, Cl, Br, nitro or lower alkylalkoxyl; and m is 1-4, and the obtained mixture is surface-treated by means of coating or dispersed in a vehicle.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic pigment composition and a pigment dispersion exhibiting excellent fluidity and stability of a dispersion containing a specific dihydroquinacridone derivative.

[0002]

2. Description of the Related Art Organic pigments used in paints, inks and the like are generally fine particles, and therefore high mechanical energy by an expensive dispersing device is required to disperse them in a vehicle. Furthermore, a phenomenon in which pigment particles once uniformly dispersed in the vehicle cause re-aggregation over time, which significantly impairs fluidity in the paint or ink state, and causes problems such as color unevenness and color separation in the coating film. Often occurs.

In order to solve these problems, various surface treatment agents and dispersion aids have been studied, and for example, materials made of polymer-based dispersants or pigment derivatives have been proposed. However, although these surface treatment agents and dispersants are effective in some paint systems, the resin composition is being reviewed and the coating film crosslinking reaction is becoming more complicated in order to improve the various resistance of the coating film. For recent paint systems,
In terms of dispersibility of the pigment, it does not always exhibit a good effect.

[0004]

[Problems to be Solved by the Invention] As described above, since conventional surface treatment agents and dispersants often do not show sufficient effects on the design of paints and resins, which are becoming increasingly complex and diversified, new There is a strong demand for development of pigment surface treatment agents and dispersants. On the other hand, the conventional pigment-derivative surface treatment agents and dispersants have a drawback that the applicable system is limited due to the fact that the performance as a colorant is imparted. The reason for this is that there is concern that the color tone of the pigment may be changed and that various fastnesses such as weather resistance may be adversely affected. Therefore, development of a pigment surface treatment agent or a dispersant that does not have a performance as a colorant is also desired.

The present inventors have studied various compounds to develop a pigment surface treatment agent and a dispersant satisfying such requirements, and as a result, mixing or surface-treating a specific dihydroquinacridone derivative with an organic pigment causes variation in color tone. The fact that excellent fluidity and good coating characteristics can be imparted without any problem was confirmed. It was also found that the same effect can be obtained when this dihydroquinacridone derivative is used as a dispersion aid together with various organic pigments.

The present invention was developed on the basis of the above-mentioned findings, and its purpose is to exhibit excellent fluidity when dispersed in a vehicle, and to obtain a good coating film while maintaining the original hue and luster of the pigment. It is intended to provide a pigment composition and a pigment dispersion capable of imparting weather resistance.

[0007]

The pigment composition according to the present invention for achieving the above object contains 0.1 to 30 parts by weight of the dihydroquinacridone derivative represented by the following chemical formula 1 with respect to 100 parts by weight of the organic pigment. The composition is characterized by being mixed or surface-treated in an amount of parts by weight.

Wherein R ₁ and R ₂ are hydrogen atoms, lower alkyl groups, alkoxy groups or halogen atoms, R ₃ and R ₄ ,
R ₅ and R ₆ are hydrogen, chlorine, bromine, a nitro group, a lower alkyl group or an alkoxy group, and m is an integer of 1 to 4.

The pigment dispersion according to the present invention comprises 0.1 to 30 parts by weight of the same dihydroquinacridone derivative (Chemical Formula 2) as a dispersant, dispersed in a vehicle with respect to 100 parts by weight of an organic pigment. Is a structural feature.

The dihydroquinacridone derivatives of the chemical formulas 1 and 2 are compounds obtained by introducing a phthalimidomethyl group into dihydroquinacridone, and these derivatives are described, for example, in US Pat.
It can be produced by a known method described in the specification of 275637. During production, sulfone groups may be introduced depending on the concentration of concentrated sulfuric acid or fuming sulfuric acid used, the reaction temperature, the reaction time, and the like. Therefore, filtration of the reaction product may become difficult due to the progress of sulfonation, but since it does not become a negative factor for the performance as a surface treatment agent or a dispersant, it does not affect the effect of the present invention. do not do.

The substitution number of phthalimidomethyl group can be up to 4 in the case of unsubstituted dihydroquinacridone. In general, as the number of introduced substituents increases, adverse effects such as an increase in reaction impurities and a decrease in yield may occur. Therefore, it is preferable to adjust the number of phthalimidomethyl groups to be 1 or 2. . However, one substituent is sufficient for the purpose of the present invention, and even when the number of substituents is less than one, the desired effect can be obtained by appropriately increasing the surface treatment amount and the addition amount. .

Examples of the organic pigment which is the main component of the pigment composition and the pigment dispersion of the present invention include quinacridone, substituted quinacridone such as dimethylquinacridone and dichlorquinacridone, and diketopyrrolopyrrole compound. However, not limited to these, all organic pigments are targeted.

The pigment composition of the present invention is formed by mixing these organic pigments with the above-mentioned dihydroquinacridone derivative or surface-treating it using a coating means such as coating. Further, the pigment dispersion is formed by dispersing a dihydroquinacridone derivative as a dispersion aid together with an organic pigment in a vehicle.

At this time, the amount of the dihydroquinacridone derivative to be mixed, coated or dispersed is set in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the organic pigment. If this amount is less than 0.1 part by weight, the fluidity of the dispersion and the gloss of the coating film
The improvement effect on the clarity and color separation does not appear,
If it exceeds 30 parts by weight, the effect cannot be expected to increase, and it is not preferable in terms of pigment suitability (hiding power and coloring power). Further, even if 0.1 part by weight or more and less than 1 part by weight, the above-mentioned effects may not be exhibited for some pigments, and most pigments have an improvement effect saturated at an amount of 10 parts by weight or less. Also, regarding the various fastnesses of the coating film, it is more preferable to use the dihydroquinacridone derivative in the range of 1 to 10 parts by weight, since keeping the upper limit to 10 parts by weight shows a good effect.

[0014]

The dihydroquinacridone derivative represented by the chemical structural formulas (1) and (2), which constitutes the present invention, is non-crystalline and has good dispersibility when incorporated into a vehicle and does not cause re-aggregation over time. Exhibits extremely excellent fluidity. Moreover, there is no change in color tone. Therefore, it becomes possible to always impart stable performance to a paint or ink component having a complicated composition as a pigment composition or a pigment dispersion.

[0015]

The present invention will be described in detail below with reference to examples and comparative examples.

Synthesis of dihydroquinacridone derivative: (1) Derivative A 300 parts by weight of 6% fuming sulfuric acid and dihydroquinacridone 2
5 parts by weight was added, and the mixture was stirred at a temperature of 40 to 50 ° C for 30 minutes. This solution was cooled to 35 ° C., 13 parts by weight of phthalimide was added, and the mixture was stirred for 30 minutes. Then, 2.8 parts by weight of paraformaldehyde was added, the temperature was raised to 80 ° C., and the reaction was carried out while maintaining this temperature for 5 hours.
After the reaction was completed, it was cooled to 35 ° C. The cooled solution was poured into 3 l of water with stirring to precipitate and precipitate. The slurry was filtered, washed with water until the filtrate became neutral, and the obtained cake was dried at a temperature of 90 ° C. Thus, 40 parts by weight of a phthalimidomethyl derivative of dihydroquinacridone was obtained. The elemental analysis value of this compound almost agreed with the calculated value.

(2) Derivative B Dihydroquinacridone having two phthalimidomethyl groups was reacted in the same manner as in (1) except that the amount of phthalimide was changed to 26 parts by weight and the amount of paraformaldehyde was changed to 5.6 parts by weight. 50 parts by weight of the derivative was obtained.

(3) Derivative C (1) In place of dihydroquinacridone, 25 parts by weight of 2,
The same reaction was carried out using 9-dimethyldihydroquinacridone to obtain 38 parts by weight of a phthalimidomethyl derivative of 2,9-dimethyldihydroquinacridone.

(4) Derivative D (1) In place of the phthalimide, 25 parts by weight of tetrachlorophthalimide was used, and the same reaction was carried out at 90 ° C. for 8 hours to obtain 48 parts by weight of a tetrachlorophthalimide methyl derivative of dihydroquinacridone. Obtained.

Dispersion of paint: pigment (pigment composition) 10
Parts by weight, 40 parts by weight of synthetic fatty acid modified polyester resin varnish and thinner (xylene / butanol = 8/2)
Add 20 parts by weight and put in a container with glass beads.
Disperse using a paint shaker. To the compound after dispersion, 40 parts by weight of oil-free polyester resin varnish and 20 parts by weight of melamine resin varnish were added, and mixed with a paint shaker to be enamelized. All the resin varnishes had a solid content of 50% by weight, and the ratio of the pigment (pigment composition) to the resin solid content was 20% by weight.

The evaluation as a dispersion aid is pigment 10
The weight part used was determined with respect to 0 part by weight, and the total amount was set to within 10 parts by weight of the above-mentioned pigment.

Method of performance evaluation: (1) Fluidity evaluation method The viscosity of the pigment dispersion was measured at 6 rpm and 6 by a B-type viscometer.
It was measured under the condition of 0 rpm. (2) Coating gloss evaluation method The final diluted paint was adjusted with a thinner in Ford Cup # 4 for 23 seconds, sprayed on a tin plate with an air spray gun, and then baked. The gloss of the coated plate was measured with a gloss meter at 20 degrees. (3) Spray the paint prepared in the weather resistance evaluation method (2) onto a steel plate that has undergone intermediate coating and water polishing,
Baking was performed to prepare a weatherproof plate. This weatherproof plate was irradiated with sunshine W-O-M for up to 1000 hours, and a plurality of coated plates were irradiated with an eye super UV tester (manufactured by Iwasaki Electric Co., Ltd.) for 100 hours. The superiority or inferiority of the weather resistance was judged by the color difference.

Example 1 The surface of a γ-quinacridone pigment (specific surface area 40 m ² / g) was coated with 3 parts by weight of derivative A per 100 parts by weight of the pigment. Using the pigment composition after the surface treatment, a paint was prepared according to the above-mentioned formulation and various evaluations were performed. The results are shown in Table 1.

Example 2 The surface of γ-quinacridone pigment (specific surface area 75 m ² / g) was coated with 5 parts by weight of derivative B per 100 parts by weight of the pigment. Using the pigment composition after the surface treatment, a paint was prepared according to the above-mentioned formulation and various evaluations were performed. The results are also shown in Table 1.

Example 3 The surface of dimethylquinacridone pigment (specific surface area 50 m ² / g) was coated with 5 parts by weight of derivative C per 100 parts by weight of the pigment. Using the pigment composition after the surface treatment, a paint was prepared according to the above-mentioned formulation and various evaluations were performed. The results are also shown in Table 1.

Example 4 The surface of dichlorquinacridone pigment (specific surface area 60 m ² / g) was coated with 5 parts by weight of derivative D per 100 parts by weight of the pigment. Using the pigment composition after the surface treatment, a paint was prepared according to the above-mentioned formulation and various evaluations were performed. The results are also shown in Table 1.

Example 5 γ-type quinacridone pigment (Sinkasha Red 759-
When D) is dispersed, 5 parts are added to 100 parts by weight of the pigment.
Part by weight of derivative A was added as a dispersion aid, and a coating material (pigment dispersion) was prepared according to the above formulation. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Example 6 γ-type quinacridone pigment (Shinkasha Red 759-
When D) is dispersed, 5 parts are added to 100 parts by weight of the pigment.
Part by weight of derivative B was added as a dispersion aid, and a coating material (pigment dispersion) was prepared according to the above formulation. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Example 7 Diketopyrrolopyrrole Pigment (Irgazin DPP Red B
When the O) is dispersed, the amount is 5 per 100 parts by weight of the pigment.
Part by weight of derivative A was added as a dispersion aid, and a coating material (pigment dispersion) was prepared according to the above formulation. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Example 8 Diketopyrrolopyrrole Pigment (Irgazin DPP Red B
When the O) is dispersed, the amount is 5 per 100 parts by weight of the pigment.
Part by weight of derivative B was added as a dispersion aid, and a coating material (pigment dispersion) was prepared according to the above formulation. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Example 9 γ-type quinacridone pigment (Shinkasha Red 759-
When D) is dispersed, 5 parts are added to 100 parts by weight of the pigment.
A coating composition (pigment dispersion) is prepared by adding 10 parts by weight of the basic resinous additive (BYK-160) to 100 parts by weight of the pigment, and 10 parts by weight of the derivative A as a dispersion aid. Was prepared. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Example 10 γ-type quinacridone pigment (Shinkasha Red 759-
When D) is dispersed, 5 parts are added to 100 parts by weight of the pigment.
Part by weight of the derivative B is added as a dispersion aid, and further 10 parts by weight of a basic resinous additive (BYK-160) is added to 100 parts by weight of the pigment, and the coating composition (pigment dispersion) is prepared according to the above-mentioned formulation. Was prepared. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Example 11 Diketopyrrolopyrrole Pigment (Irgazin DPP Red B
When the O) is dispersed, the amount is 5 per 100 parts by weight of the pigment.
A coating composition (pigment dispersion) is prepared by adding 10 parts by weight of the basic resinous additive (BYK-160) to 100 parts by weight of the pigment, and 10 parts by weight of the derivative A as a dispersion aid. Was prepared. Various evaluations were performed on the obtained paints, and the results are also shown in Table 1.

Example 12 Diketopyrrolopyrrole Pigment (Irgazin DPP Red B
When the O) is dispersed, the amount is 5 per 100 parts by weight of the pigment.
Part by weight of the derivative B is added as a dispersion aid, and further 10 parts by weight of a basic resinous additive (BYK-160) is added to 100 parts by weight of the pigment, and the coating composition (pigment dispersion) is prepared according to the above-mentioned formulation. Was prepared. Various evaluations were performed on the obtained paints, and the results are also shown in Table 1.

Comparative Example 1 A coating material was prepared according to the above-mentioned formulation using only the γ-quinacridone pigment (specific surface area 40 m ² / g). Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Comparative Example 2 A paint was prepared in accordance with the above-mentioned formulation, using only the γ-type quinacridone pigment (specific surface area 75 m ² / g). Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Comparative Example 3 A coating material was prepared according to the above-mentioned formulation using only dimethylquinacridone pigment (specific surface area 50 m ² / g). Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Comparative Example 4 A paint was prepared using only the dimethylquinacridone pigment (specific surface area 60 m ² / g) and following the above formulation. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Comparative Example 5 Diketopyrrolopyrrole Pigment (Irgazin DPP Red B
A coating material was prepared according to the above-mentioned formulation using only O). Various evaluations were performed on the obtained paints, and the results are also shown in Table 1.

Comparative Example 6 γ-type quinacridone pigment (Shinkasha Red 759-
When D) is dispersed, 1 part is added to 100 parts by weight of the pigment.
0 part by weight of a basic resinous additive (BYK-160) was added, and a coating material was prepared according to the above formulation. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

Comparative Example 7 Diketopyrrolopyrrole Pigment (Irgazin DPP Red B
When dispersing O), 1 is added to 100 parts by weight of the pigment.
0 part by weight of a basic resinous additive (BYK-160) was added, and a coating material was prepared according to the above formulation. Various evaluations were performed on the obtained paint, and the results are also shown in Table 1.

[0042]

[Table 1]

From the results shown in Table 1, the paints according to the examples using the pigment composition of the present invention have significantly improved fluidity as compared with the paints of the corresponding comparative examples which do not use the pigment compositions. It turns out that the film gloss is also excellent. It was also confirmed that there is no problem in terms of weather resistance.

[0044]

INDUSTRIAL APPLICABILITY As described above, the pigment composition according to the present invention in which a specific dihydroquinacridone derivative is mixed with or surface-treated with an organic pigment and a pigment dispersion using the same as a dispersion aid have excellent fluidity and clear coating film. And weather resistance. Therefore, it always exhibits stable performance even for vehicles having a complex composition, and is extremely useful for all kinds of paints and inks.

Claims (2)

[Claims] 1. A pigment composition, which comprises mixing or surface-treating the dihydroquinacridone derivative represented by Chemical formula 1 in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of an organic pigment. [Chemical 1] However, in the formula, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group, an alkoxy group or a halogen atom, and R ₃ , R ₄ , R ₅ and R ₆ are hydrogen, chlorine, bromine, a nitro group, a lower alkyl group or an alkoxy group. , M is an integer of 1 to 4. 2. A pigment dispersion, wherein 0.1 to 30 parts by weight of the dihydroquinacridone derivative represented by Chemical formula 2 is dispersed in a vehicle as a dispersion aid with respect to 100 parts by weight of an organic pigment. [Chemical 2] However, in the formula, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group, an alkoxy group or a halogen atom, and R ₃ , R ₄ , R ₅ and R ₆ are hydrogen, chlorine, bromine, a nitro group, a lower alkyl group or an alkoxy group. , M is an integer of 1 to 4.