JPS60235860A - Colored polyimide composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent dispersion stability and suitable for use in the production of heat-resistant ink, heat-resistant paints, etc., consisting of a polyimide, a solvent, a dye and a specified dispersant. CONSTITUTION:10-50wt% polyimide precursor (A) obtd. by reacting a tetracarboxylic acid anhydride with a diamine, 1-30wt% (based on the quantity of component A) dye (B) (e.g. BaSO4 or Benzidine Yellow G), 0.1-30wt% (based on the quantity of component B) dispersant (C) composed of a derivative obtd. by introducing a substituent such as OH, carboxyl or sulfo group into an org. dye such as azo, phthalocyanine or quinacridone dye, and a solvent (D) (e.g. dimethyl sulfoxide) are mixed with and dispersed in one another. EFFECT:A colored polyimide compsn. can be obtd. which has excellent heat resistance, developability and uniformity in color when mixed with other dyes.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyimide coloring compositions used as heat-resistant inks, heat-resistant paints, and the like.

Polyimide has excellent heat resistance, so it can be used as heat-resistant ink or heat-resistant paint. However, when making ink or paint using polyimide, it is generally necessary to disperse pigments, dyes, and other pigments, and to maintain their stability. There was a drawback that a dispersion could not be obtained.

That is, since polyimide is generally insoluble in solvents,
Polyimide precursors, which are relatively easily soluble in solvents, are dissolved in polar solvents such as dimethylformamide, dimethylacemide, and N-methyl-2-pyrrolidone and used in paints and inks. When pigments are dispersed using these polyimide solutions, they do not disperse easily, probably due to the strong polarity of the varnish, and even if they do, they aggregate over time, making it difficult to obtain a stable pigment dispersion. could not.

Also, a method that does not use polyimide precursors, that is,
Varnishes that have already been imidized and dissolved in a solvent are also known, but like polyimide precursor glue varnishes, it was difficult to obtain a stable pigment dispersion.

The present invention improves the above-mentioned drawbacks and has a good 5 dispersion.

The present invention also provides a polyimide coloring composition with good dispersion stability.

In order to achieve the above object, the present invention provides a polyimide coloring composition containing as main components a polyimide, preferably a polyimide precursor, a solvent, a pigment, and a dispersant which is a derivative of an organic pigment. The ones obtained by conventional dyeing have excellent dispersibility of one dye, have excellent two-color development property, uniformity of color when mixed, and are heat resistant.

The polyimide in the present invention is a polyimide precursor obtained by reacting a tetracarboxylic anhydride and a diamine in a solvent, or a resin obtained by imidizing a polyimide precursor, as is conventionally known. In terms of heat resistance,
Preferably a polyimide precursor is used.

The solvent used in the present invention may be any solvent as long as it can dissolve the polyimide precursor or the resin obtained by imidizing the polyimide precursor, such as dimethyl sulfoxide, dimethylformamide, dimethylacemide, N-methyl-2-pyrrolidone, hexamethylphosphor Amide or a mixed solvent thereof is used.

Dyes and pigments are used as the dyes according to the present invention, but if heat resistance is required in the application of the polyimide coloring composition, a pigment with excellent heat resistance must be used. Heat-resistant pigments include barium sulfate, zinc white,
Lead sulfate, titanium oxide, yellow lead, red iron, ultramarine, deep blue,
Chromium oxide.

Non-ta pigments such as carbon blank, Hengedine Yellow G, Benzidine Yellow GR, Lysol Fast Orange 3GL, Harkan Fast Orange GG, Pigment Scarlet 3B, Thioindigo Maroon, Phthalocyanine Blue, Phthalocyanine Green, Indanthren Blue, Green Gold, malachite green lake, etc.

The dispersant according to the present invention is a derivative of an organic pigment, and the base organic pigments include Ab-based, fuclocyanine-based, quinacridone-based, anthraquinone-based, perylene-based, perinone-based, thioindigo-based, dioxazine-based, and isoindolinone-based. , quinophthalone type, triphenylmethane type, metal complex salt type, etc. These organic dyes have substituents and 1
A derivative that is effective in dispersing the dye is used. Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfonic acid group, a carbonamide group, a sulfonamide group, or any substituent represented by the following general formula 1. A derivative having at least one substituent selected from these substituents is used.

general formula %formula% (X: oxygen or sulfur atom, Ania reel base) \ Rλ (X: alkylene group, R+, Rλ: water elementary atoms or alkyl groups, or At least nitrogen atoms in R1 and R2 (heterocycle containing) R+ \R2 (Rr: hydrogen atom, alkyl group, or Aryl group, R2: alkyl group or is an aryl group, or R and R and a complex containing at least a nitrogen atom ring) R.

(R1: hydrogen atom or alkyl group.

A: alkylene group, R2: alkyl group, alkoxyalkyl group or Chloalkyl group, R3: hydrogen atom.

(a cycloalkyl group, or a heterocycle containing at least a nitrogen atom with R2 and R3) Note that 5. The dye and the base organic dye of the 2. dispersant are usually the same ones in combination from the viewpoint of hue.

They do not necessarily have to match.

In the composition of the present invention, the composition ratio is not particularly limited, but the polyimide is usually 10 to 50% by weight based on the composition.
Although the proportion of the 9 dyes varies depending on the type of polyimide and the type of dye, it is about 1 to 30% by weight based on the polyimide, and the proportion of the 2 dispersant varies depending on the type of dye, but it is 0.9% by weight relative to the 2 dyes. It is about 1 to 30% by weight.

Furthermore, the coloring composition of the present invention can also be used as a color concentrate with a high pigment content. In addition, additives can also be blended as needed.

To make paints, inks, etc. based on the present invention.

Roll mill polyimide, solvent 1 dye 1 dispersant.

Disperse and mix using ball mills, sand mills, attritors, and other dispersing and mixing equipment. It can also be produced by predispersing polyimide 5 and dispersant 1 using a roll mill or the like, and then diluting with a solvent or a press of polyimide and a solvent. Alternatively, two dyes and a dispersant can be mixed and then mixed and dispersed using a press or the like. Note that the order of mixing and dispersion is not limited to this, and can be repeated.

The paint, ink, etc. obtained as described above is applied to the target object by painting, etc., and when a polyimide precursor is used as the polyimide, it is usually heat-treated at 200 to 350"C to create a heat-resistant skin. B odor etc. are obtained.Furthermore, when using a resin that has already been imidized as polyimide, a film etc. can be obtained by simply volatilizing the solvent used.

Since the present invention uses an organic dye derivative as a dispersant, it has excellent dispersion of a single dye and dispersion stability over time.
A good colored product can be obtained.

The paint and ink according to the present invention can be used for applications such as electronic parts that require heat resistance.The present invention will now be described in more detail with reference to Examples. "Part" indicates part by weight.

Example 1 10 parts of copper phthalocyanine was added to chlorosulfone in a four-sol flask equipped with a stirrer, a reflux condenser, and a temperature needle.
After completely dissolving in 100 parts, 21 parts of thionyl chloride was added, and the temperature was gradually raised and kept at 112-113°C for 34 hours.

After cooling, pour into ice and rinse with ice water. Transfer this paste to a four-solo flask equipped with a reflux condenser, and add 100 g of water.
21 parts of N,N-diethylaminoethylamine are added, and the mixture is stirred at room temperature for 12 hours and then heated at 60°C for 1 hour. After the reaction is completed, it is passed through one mouth, washed with water, and dried to obtain a blue powder of a copper phthalocyanine derivative. As a result of two-element analysis of this blue powder, the analysis values were close to those of a derivative into which about three substituents \CyuH1 were introduced.

The above-mentioned 0.1 part of copper phthalocyanine derivative, 16.5 parts of a mixture of α-type copper phthalocyanine pigment, and polyide precursor (
Semico Fine 5P-510) made by East Side, 100 copies, N,
The viscosity of a paint prepared by kneading 200 parts of N-dimethylformamide with a three-roll roller at 25°C during kneading was measured using a BM type viscosity needle, and the result was as follows, indicating no structural viscosity.

After leaving this product for a week, the results were measured using the same BM type viscometer.

A 1/10 cut test tube was also observed for aggregation using white paint prepared with titanium white, but no color separation or sedimentation was observed even after one month.

Example 2 In a container equipped with a stirrer, 100 parts (dry weight) of unsubstituted α-quinacridone presscake and an average of 2 N-(2-carboxy-5-nitrobenzoyl)aminomethyl having the following structure (a) were placed in a container equipped with a stirrer. 15 parts (dry weight) of the quinacridone presscake substituted with quinacridone are added, water is further added to make a slurry of about 4000 parts, and an aqueous sodium hydroxide solution is added to adjust to p) (! It, 5, 50'c The temperature was increased to
□ After adding 10.1 parts (8% by weight as 03 minutes).

Adjust the pH to 6, filter, wash with water, and dry at 100°C to form a powder.

5 parts of this pigment composition and 100 parts of a polyimide precursor (Semicofine 5P-510 manufactured by Toshi) were dispersed using a three-roll roll.
As a result of measuring the viscosity at ℃ using a BM type viscosity needle, no structural viscosity was shown. Furthermore, the paint thus obtained provided a coating film with extremely excellent surface gloss.

Example Z 10 parts of quinacridone was added to 100 parts of chlorosulfonic acid at 10-20°C, stirred for 1 hour, and then heated to 40-50°C.
The temperature was raised to , 10 parts of thionyl chloride was added thereto, and the mixture was stirred at the same temperature for 3 hours. Add the reaction solution to 1000 parts of ice water and filter 2.
A water cake of dichlorosulfonated quinacridone was quantitatively obtained by washing with water. This water cake of dichlorosulfonate was added to 300 parts of ice water to reslurry it, and 30 parts of N
, N-diethylaminoethylamine was added, and the mixture was stirred at 10°C or lower for 3 hours, then heated, stirred at 40 to 50°C for 1 hour, filtered, and washed with water.

This water cake was added to 300 parts of 0.5% sodium carbonate aqueous solution, stirred for 1 hour, filtered, washed with water, and dried to obtain 20 parts of a quinacridone derivative having the following structure.

The elemental analysis value of this compound (b) agreed with the calculated value.

In the dichlorosulfonated product obtained in the same manner, L, N
, N-dibutylaminopropylamine, N.

N-dimethylaminopropylamine and N,N-diethylaminopentylamine were reacted in the same manner to quantitatively obtain a quinacridone derivative having the following structure.

0.1 part of the above pigment derivative, 10 parts of quinacridone, and 100 parts of polyicide precursor (Semicofine 5P-910) were kneaded using three rolls, and the viscosity at 25°C at the time of kneading and after being left for one month was determined as BM type viscosity. As a result of measuring with a needle,
No viscosity change was observed. Furthermore, the paint film thus obtained had a significantly superior surface gloss.

It also has good fluidity and exhibits excellent printing effects when used in gravure inks such as packaging gravure.

patent applicant Toyo Ink Manufacturing Co., Ltd.

Claims (1)

[Scope of Claims] 1. A polyimide coloring composition characterized in that the main components are polyimide, a solvent 1 dye, and a dispersant that is a derivative of an organic dye. 2. The polyimide coloring composition according to claim 1, wherein the polyimide is a polyimide precursor obtained by reacting a tetracarboxylic anhydride and a diamine. 3. Claim 1 or 2 in which the dye is a pigment
The polyimide coloring composition described in .