JPS5845984B2 - Perylene -3,4,910- Tetracarboxylic diimide silicon - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a new dye based on perylene-3,4,9,10-tetracarboxylic acid diimide.

The new dye has the general formula (where Z is a group CH2 CH2 OR or H2 CH2-CH2-0R, R is an alkyl group having 1 to 8 carbon atoms, X is a chlorine or bromine atom, and n is 0 or 1 3, in which R may be the same or different), which represents an ether amine represented by the general formula (wherein 2 has the above meaning) as a primary amine or this amine. By using a mixture of
It is obtained by condensing perylene-3,4,9,10-tetracarboxylic acid or its dianhydride with a primary aliphatic amine under heat.

This dye is used for coloring varnishes, resins, printing inks and textile pastes, as well as for coloring raw materials for plastics, and is distinguished by its extremely good fastness.

Examples of the alkyl group for R include the following.

Methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, 2-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group.

As alkyl group for R, preferably a lower alkyl group having 1 to 4 carbon atoms is used.

Among the alkyl groups mentioned above, n-butyl group, isobutyl group,
2-Butyl, n-propyl, isopropyl and especially methyl or ethyl groups are preferred for color and application reasons.

Residues R may be the same or different.

Although the perylene residue may have 1 to 3 chlorine or bromine atoms.

−〇 is preferable.

The condensation of perylenetetracarboxylic acid or its dianhydride with an aliphatic ether amine is preferably carried out in an inert solvent or diluent such as an alcohol such as isobutanol, 2-ethylhexanol or a glycol.
It is carried out in a large excess of the above-mentioned -class amine serving as a solvent, or preferably in water, at elevated temperatures, for example from 80 to 200 DEG C., preferably from 130 to 1.sup.8 Q'C, optionally under pressure.

The reaction product is isolated from the reaction mixture by conventional means, such as p-filtration.

Optionally, the reaction mixture can be diluted with an inert solvent at a temperature between room temperature and 100°C.

Water or alcohols such as methanol or ethanol are preferably used as inert solvents.

To remove any traces of perylenetetracarboxylic acid that may still be present, the dyestuff can be washed with a dilute hot sodium carbonate solution or with aqueous caustic soda or potassium hydroxide solution.
can be processed.

The dye can be further purified if desired by dissolution reprecipitation or recrystallization from sulfuric acid.

As the ether amine of the formula for reaction with perylenetetracarboxylic acid, for example, the following are used.

2-pentoxyethylamine, 2-hexoxyethylamine 7.2-(2'-ethylaminexy)-ethylamine, 2-n-propoxyethylamine, 2-n-butoxyethylamine, 2-methoxyethylamine, 2-ethoxyethylamine and Mixtures of these amines, or 3-n-propoxypropylamine, 3-inpropoxypropylamine, 3-butoxypropylamine, 3-n-propoxypropylamine,
Pentoxypropylamine, 3-hexoxypropylamine, 3-β-ethylhexoxypropylamine, 3-
Ethoxypropylamine, 3-methoxypropylamine or mixtures of these amines.

Among the ether amines (n), 2-n-propoxyethylamine, 2-n-
Butoxyethylamine and especially 2-methoxyethylamine and 2-ethoxyethylamine are preferred.

For the same reason, 3-ethoxypropylamine and 3-methoxypropylamine are preferred among the ether amines (■).

The dyes are excellently suited for coloring raw materials of synthetic plastics, especially thermoplastics such as polyethylene, polycarbonate, polyvinyl chloride, especially hard polyvinyl chloride, polystyrene and copolymers thereof.

If a dye having a 3-alkoxypropyl group with three or more carbon atoms in the alkoxy group is used as Z, a very transparent and glossy yellow-orange coloring is obtained, which does not fluoresce, especially in transparent colorings. , nevertheless exhibits very good lightfastness.

Dyes in which Z is a 2-alkoxyethyl group give a strong bluish-red coloration in polyvinyl chloride or polyethylene.

On the contrary, in plastics which require high temperatures for processing, such as polystyrene or polycarbonate, a glossy orange coloration is obtained, which fluoresces as a transparent coloration and exhibits high lightfastness. .

Dyes containing an alkoxyethyl group or a 3-methoxypropyl group as 2 are outstandingly suitable for coloring varnishes, resins, printing inks or printing pastes.

This dye can be made into a pigment preparation for this purpose, which can be used as such for other colorings.

In this case, a dye having a 3-methoxyfurovir group as Z gives a glossy black coloring.

New dyes, especially those containing a 2-alkoxyethyl group or 3 as Z
- Those with methoxypropyl groups have the high solvent fastness, topcoat fastness and softener fastness required for varnish coloring and soft vinyl chloride coloring.

This applies in particular to dyes in which Z is 2-methoxyethyl, 2-ethoxyethyl, 3-methoxyfurovir or 3-ethoxypropyl.

These dyes give colorations or coatings with very good to excellent fastness properties.

The solubility of dyes (I) in plastics is determined by the alkoxy groups, dyes with alkoxypropyl groups usually being more soluble in synthetic resins than dyes with corresponding alkoxyethyl groups.

That is, the dye (I) in which R is a methyl group or an ethyl group is a pigment that dissolves in plastic only at a temperature of 280 to 290°C.

On the other hand, 2- or 3-alkoxy derivatives having three or more carbon atoms in the alkoxy group already have 180 to
Melts at 200°C.

That is, using this, a glossy orange coloring can be obtained.

As pigment dyes, crude dyes obtained during synthesis can often be used directly.

Preferably, however, the crude dye is processed by finishing means, for example by dissolving and reprecipitating from sulfuric acid or by grinding and subsequent recrystallization in water, organic solvents or mixtures thereof at higher temperatures by means known per se, to give it a special finished form. can be changed to

German Patent No. 1,130,099 describes a fluorescent dye obtained by condensation of a primary aliphatic or alicyclic amine having 4 or more carbon atoms with perylenetetracarboxylic acid, its anhydride or its derivative. ing.

In comparison, the new ether group-containing dyes are distinguished by better dispersibility in plastics.

Furthermore, the dyes obtained according to the invention exhibit advantages in synthesis.

This is especially true for dyes having lower alkoxy groups, such as .gamma.-ethoxy, propoxy and impropoxy compounds of the formula I, due to the water solubility of the ether amines used.

Due to the very easy distribution possibilities (dispersibility), dyes from 3-ethoxypropylamine are particularly preferred.

Dyes in which Z is a group -(CH2)3~OR and R is an ethyl group have the property of appearing in two different modifications that are distinguishable in the X-ray diffraction diagram.

One is Form A, which has blue-red rhombic or prismatic crystals.
The other form is Form B, which has orange spindle-shaped crystals.

Form A is preferentially formed at reaction temperatures below 160°C, while Form B is formed at higher reaction temperatures, for example 170°C.

Both forms can be changed from one to the other.

Form B is produced by heating Form A in a high boiling organic liquid such as diglycol.

Form A is obtained by heating Form B in DMF.

Both forms behave almost similarly in coloring plastics.

The parts below are parts by weight.

Absorption maximum is the value measured for the dye solution, reflection maximum is the value measured for 1:4 white dilution, and the dominant wavelength is underlined.

IR reflectance was investigated on a PVC color (made according to Example 36).

The reflectance is 70 for absolute white using a spectrophotometer Zeiss RFC16 in the range 400-700n77L.
In the range 0-1200 nm the photometer Zeiss RMQ 2
was measured against barium sulfate using

Example 1 120 parts of perylenetetracarboxylic anhydride in 360 parts of water
and 74 parts of γ-ethoxypropylamine are stirred and heated to 130-135° C. under pressure.

Stir at this temperature for about 5 hours until the sample shows that it no longer contains free perylenetetracarboxylic acid.

After cooling and releasing the pressure, dilute with water, filter, wash in neutral and dry.

Yield: bluish-red rhombic plate-like (Form A) perylenetetracarboxylic acid bis-(γ-ethoxypropylimide) 17
0 copies.

Elemental analysis' C34N3006 N2 (molecular weight 563
) as HON Calculated value (%) 72.65,417.15.0 Actual value (%) 72.05.417.25.4 parts max:
524.487.457nrrL (dissolved in polystyrene) Reflection extra thick: λ 498.569 parts m Example 2 In 400 parts of ethylene glycol, 110 parts of perylenetetracarboxylic acid anhydride and 76 parts of γ-ethoxypropylamine were mixed with stirring to Heat to 160° C. and hold at this temperature until free perylenetetracarboxylic acid is no longer detected.

This was about an hour later. It is cooled to about 80°C, diluted with 300 parts of methanol, filtered at about 40°C, and the filtered residue is washed with methyl alcohol and then with water and dried.

Yield: bluish-red rhombic plate-shaped (Form A) perylenetetracarboxylic acid bis-(γ-ethoxyglopylimide) 16
Part 1.

Elemental analysis: C34Hao Oa N2 (molecular weight 56
3) HON Calculated value (%) 72.65.417.15.0 Actual value (%) 72.25.317.35.0 parts max:
524.487.457nrfL (dissolved in ethylpenzole) Reflection extra thick: λ498.569nrrL Example 3 Proceed as in Example 2, except that during condensation 170
When heated to ~175 °C, the same dye 15 after finishing treatment
7 parts are obtained as orange-red spindle-shaped plate crystals (Form B).

Elemental analysis: C34N3006 N2 (molecular weight 563)
As HON Calculated value (%) 72.65.417.15.0 Actual value (%) 72.95.717.05.0 parts maX: 5
24.487.457 parts m (dissolved in ethylpenzole) Example 4 50 parts of the dye obtained according to Example 1 (form A) are stirred in 150 parts of ethylene glycol for about 1 hour at 195-200 DEG C.

After work-up, an orange-red spindle-shaped (form B) dye is obtained in quantitative yield.

Elemental analysis: C34N300a N2 (molecular weight 563)
As HON Calculated value (%) 72.65.417.15.0 Actual value (%) 72.35,517.25.2 parts max: 5
24.487.457 parts m (dissolved in ethylpenzole) The same results are obtained using the dye of Example 2.

Example 5 5 parts of the dye of Example 3 (Form B) were dissolved in 30 parts of dimethylformamide.
Hold at boiling temperature for 15 minutes in 0 parts.

After cooling to room temperature, uniform prismatic crystals of form A are obtained.

Elemental analysis: C34N3006 N2 (molecular weight 563)
As HON Calculated value (%) 72.65.417.15.0 Actual value (%) 72.45.517.15.5 parts maX: 5
24.487.457nrrL (dissolved in polystyrene) The same results are obtained using the dye of Example 4.

Elemental analysis: HON as C34H3006N2 (molecular weight 563) Calculated value (%) 72.65.417.15.0 Actual value (%) 72.35.516.45.5 parts maX:
524.487.457nrrL (dissolved in ethylpenzole) Example 6 Perylenetetracarboxylic anhydride 120 parts in 360 parts of water
and 84 parts of γ-isopropoxypropylamine are stirred and heated to 130-135° C. under pressure.

Stir at this temperature for about 5 hours until the sample shows that it no longer contains free perylenetetracarboxylic acid.

After cooling and releasing the pressure, dilute with water, filter, wash in neutral and dry.

Yield: Red crystalline perylenetetracarboxylic acid bis(
γ-isopropoxypropylimide) 173 parts.

Elemental analysis: C36N3406 N2 (molecular weight 591
) as HON Calculated value (%) 73.25.816.34.7 Actual value (%) 72.95.716.45.0 parts max:
524.487.457nrrL (dissolved in polystyrene) Example 7 0.05 part of the dyestuff obtained according to Example 1 was mixed with 100 g of ground polystyrene bulk polymer in a rotating drum mixer.
and dry mixture.

The mixture is melted and homogenized in a screw extruder at a cylinder temperature of 200-250°C.

The colored plastic material is granulated by hot crushing in the nozzle head or by thread withdrawal while cooling.

The granules thus obtained were subsequently placed in an injection molding machine for 20 minutes.
It is injected at 0 to 250°C to form a molded body, or compressed on a press to form any molded body.

A bright yellow-orange injection molded article is obtained which has very good lightfastness and fluoresces in a similar shade.

Instead of polystyrene bulk polymers, it is also possible to use polystyrene emulsion or suspension polymers or copolymers of butadiene and acrylonitrile or acrylic esters.

Exactly the same coloration is obtained if the dyestuff of example 2.3 or 6 is used instead of the dyestuff of example 1.

Example 8 0.1 part of the dyestuff from Example 1 is mixed as in Example 7 with 100 parts of ground polystyrene bulk polymer and 1 part of titanium dioxide.

The mixture is melted, homogenized and granulated.

The thus obtained granules are molded into a molded body by injection molding or compression molding (processing temperature: 200 to 250°C).

A glossy orange-coloured injection or compression molded article is obtained which has very good fastness properties.

If the dye of Example 1 is replaced by the same amount of the dye of Example 6, exactly the same coloration is obtained.

Example 9 0.1 part of the dye obtained according to Example 1 was mixed with 100 parts of polyvinyl chloride powder (suspension or emulsion polymerized product) and 2 parts of dibutyltin his-thioglycolic acid hexyl ester at 150 to 160 parts on a mixing roll apparatus. ' Homogenized in C (
(about 8 minutes).

The obtained rolled sheet is compressed into a plate at 140°C on a plate press at about 0.4 kg/crA.

A transparent, glossy orange compression molded product is obtained.

Exactly the same coloration is obtained if the dye of Example 6 is used instead of the dye of Example 1.

Example 10 0.1 part of the dye obtained in Example 1 was mixed with 100 parts of polyvinyl chloride powder (suspension or emulsion polymerized product), 1 part of titanium dioxide (rutile product), and 2 parts of dibutyltin bisthioglycolic acid hexyl ester. Homogenization as in Example 8 on a mixing roll apparatus followed by compaction into plates.

A transparent orange compression molded product is obtained.

Exactly the same coloration is obtained if the dye of Example 6 is used instead of the dye of Example 1.

Example 11 110 parts of perylenetetracarboxylic anhydride and γ-(2-ethylhexoxy) in 800 parts of ethylene glycol
- 138 parts of propylamine at 140-145°C with stirring
and held at this temperature until no perylenetetracarboxylic acid is detected anymore.

This was one hour later.

Cool to 80°C, dilute with 500 parts of methanol, filter at about 40°C and wash the filter residue with methanol and water.

After drying, red crystalline perylenetetracarboxylic acid bis(
190 parts of γ-ethylhexoxypropylimide are obtained.

Elemental analysis "Ca4H290oN2C1 (molecular weight 597
) as HONCI calculated value (%) 68.44,916.14.76.0
Actual value (%) 68.04.716.35.05.0
Example 12 A similar dye is obtained by operating as in Example 2, but using 119 parts of monochloroperylenetetracarboxylic anhydride instead of 110 parts of perylenetetracarboxylic anhydride.

Monochloroperylenetetracarboxylic acid or its anhydride is produced by the following method.

100 parts of perylenetetracarboxylic anhydride were mixed with 12 parts of iodine and 39 parts of sulfuryl chloride in 700 parts of nitropenzole.
Heat to 65-70° C. with part Q and stir at this temperature for 2 hours.

Heat further to 80-85°C and hold at this temperature for 7 hours.

After cooling to room temperature, it is filtered, and the filtered residue is washed with nitropenzole, methanol and water, and then dried.

A very good yield of chlorperylenetetracarboxylic acid anhydride with a chlorine content of 8.9% is obtained.

This corresponds to monochloroperylenetetracarboxylic anhydride.

Example 13 120 parts of perylenetetracarboxylic anhydride in 360 parts of water
and 55 parts of 2-methoxyethylamine are stirred and heated to 130-135°C under pressure.

Stir at this temperature for about 10 hours until the sample shows that it no longer contains free perylenetetracarboxylic acid.

After cooling and depressurization, the reaction mixture was diluted with water and 1
Wash the effluent with a warm aqueous solution of % sodium carbonate until it becomes light in color, neutral wash and dry.

153 parts of perylenetetracarboxylic acid bis(β-methoxyethylimide) in the form of a red dye powder are obtained.

Elemental analysis: C30N220a N2 (molecular weight 507
) as HON Calculated value (%) 71.14.419.05.5 Actual value (%) 71.54.519.15.6 Example 14 110 parts of perylenetetracarboxylic anhydride and 2- Methoxyethylamine 56
The mixture is heated to 170 DEG -175 DEG C. with stirring and kept at this temperature until no perylenetetracarboxylic acid can be detected any more.

This was about an hour later.

It is cooled to about 150°C, diluted with 200 parts of dimethylformamide, sweat-filtered at about 40°C, and the E filter residue is washed with 100 parts of dimethylformamide, then washed with water and dried.

125 parts of perylenetetracarboxylic acid bis-(β-methoxyethylimide) are obtained as a red powder.

Elemental analysis: Cao N2206 N2 (molecular weight 507
) as HON Calculated value (%) 71.14,419.05.5 Actual value (%) 69.74.819.95.8 Example 15 The procedure was as in Example 13, but instead of 55 parts of 2-methoxyethylamine. using 64 parts of 2-ethoxyethylamine and holding at 130-135°C for 5 hours,
After finishing treatment, perylenetetracarboxylic acid bis-(β-
161 parts of ethoxyethylimide are obtained in the form of a red dye powder.

Elemental analysis: C32N260a N2 (molecular weight 535
) as HON Calculated value (%) 71.94.918,05.2 Actual value (%) 71.45.118.25.5λmax:
520.489.457nrrL (dissolved in ethylpenzole) Example 16 110 parts of perylenetetracarboxylic anhydride and 67 parts of 2-ethoxyethylamine in 400 parts of ethylene glycol
The mixture is heated to 155 DEG -160 DEG C. with stirring and kept at this temperature until no perylenetetracarboxylic acid can be detected anymore.

This was about an hour later.

Cool to 80°C, dilute with 300 parts of methanol, filter at about 40°C, wash the filter residue with a small amount of methanol, then with water and dry.

40 parts of perylenetetracarboxylic acid bis-(β-ethoxyethylimide) 1 are obtained as a red powder.

Elemental analysis: C3□H260a N2 (molecular weight 535)
as CHN Calculated value (%) 71.94.95.2 Actual value (%) 7144.95.2 λmax: 520.489.457nrrL (dissolved in polystyrene) Example 17 Proceed as in Example 14, except that 2- 7 parts of 2-n-propoxyethylamine instead of 56 parts of methoxyethylamine
Use 2 parts.

The reaction mixture is diluted with methanol (instead of dimethylformamide).

After finishing treatment, perylenetetracarboxylic acid bis-(β
-n-propoxyethylimide) are obtained as a red powder.

Elemental analysis: C34N300a N2 (molecular weight 563)
As HON Calculated value (%) 72.65.417.15.0 Actual value (%) 72.35.417.25.3 parts max: 5
24.487.457 μm (dissolved in ethylpenzole) Example 18 Proceeding as in Example 17, but using 82 parts of 2-n-butoxyethylamine instead of 72 parts of 2-n-propoxyethylamine, perylenetetracarboxylic acid Bis-
157 parts of (β-n-butoxyethylimide) are obtained as a red powder.

Elemental analysis: C36N3406 N2 (molecular weight 591)
As HON Calculated value (%) 73.25.816.34.7 Actual value (%) 72.95.716.55.0 parts max: 5
24.487.457 μm (dissolved in ethylpenzole) Example 19 Painting for pure color baking (10%) (a) Pure color paste (30%) 3 parts of the dye of Example 13 was mixed with a varnish-like binder (Lauter Chemicals Co., Chicago). Grinding pace 100S
) with 7 parts to a 30% pure color paste on a three roll mill in 6 passes at 80 gauge atmosphere.

(b) Pure color varnish paste (10%) Pure color paste)
(a) 2 parts of alkyd resin modified with soybean oil
1 part, 2 parts of an alkyd resin modified with synthetic fatty acids and 3 parts of a solvent-free melamine resin.

(e) Carrying out the coloring with varnish paste (b) using a film applicator
is applied to a film thickness of 100 μm on cardboard and baked for 45 minutes at 120° C.

A bluish-red coloration with excellent covering power is obtained, which has excellent lightfastness and very good weather resistance.

Exactly the same coloration is obtained by substituting the dye of Example 15 for the dye of Example 13.

Example 20 Baking is painted (white dilution 1:20) (a) White paste (30%) Binder (obtained by mixing 1 part of alkyd resin modified with soybean oil and 2 parts of alkyd resin modified with synthetic fatty acids) 42 parts of titanium dioxide (rutile product)
30 parts of solvent-free melamine resin and 6 parts of colloidal silicon dioxide to a 30% white paste on a three-roll mill at 80 gauge pressure in six passes.

(b) 0.5 parts of pure color paste (30%) of Varnish Paste Example 19(a) and (
10 parts of the white paste (30%) of a) are mixed and milled on an automatic milling device.

(c) Carrying out the coloring Using a film applicator, apply varnish space h (b
) on cardboard to a film thickness of 100μ, and
Bake in dry mass at 120° C. for minutes.

A bluish-red coloration is obtained which has excellent lightfastness and very good weather resistance.

Exactly the same coloration is obtained by substituting the dye of Example 15 for the dye of Example 13.

Example 21 Baking is painting (white dilution 1:20, from dye paste) (a) Finely dispersed aqueous 29% dye paste 69 obtained by dissolving and reprecipitating the dye of Example 14 from concentrated sulfuric acid 64 parts of a solvent-free alkyd resin modified with soybean oil and 1 part of bisethylhexyl phthalate.
Processed with 6 parts by flushing on a three roll mill with 6 passes at 60 gauge pressure to give a pure colored paste.

(b) Solvent-free alkyd mJ]modified with soybean oil bis-ethylhexyl phthalate 17
, and 12.5 parts of solvent-free melamine resin were mixed together with 30 parts of titanium dioxide (rutile) and 4 parts of colloidal silicon dioxide on a 60 gauge three-roll mill. Mill to a titanium dioxide paste in 6 passes at atmospheric pressure.

(c) pure color paste produced by (a)) 0.4
Titanium dioxide paste 5 manufactured according to parts and (b)
The parts are mixed and milled on an automatic milling device.

Using this dye paste, a varnish coating is produced analogously to Example 19(c), which is baked at 120° C. for 45 minutes.

A deep bluish-red coloring with very good lightfastness is obtained.

Exactly the same coloration is obtained if the paste of the dye of Example 14 is replaced by a 28% paste of the dye of Example 16 prepared in the same way.

Example 22 Soft PVC (0.1% clear coloring) 0.05 parts of the dye obtained according to Example 13 were mixed with 65 parts of polyvinyl chloride powder, 35 parts of di-ethylhexyl phthalate and hexyl dibutyltin bis-thioglycolate. Homogenize with 50 parts of the mixture from 2 parts of ester at 150-160°C on a mixing roll apparatus (duration approximately 8 minutes).
, rolled into a sheet and smoothed on a polishing roll device.

A blue-red colored sheet is obtained which has excellent light fastness and softener fastness.

Example 23 Soft PVC (10 for white dilution) 0.25 parts of the dye obtained according to Example 13, 2.5 parts of titanium dioxide (rutile product) and 65 parts of polyvinyl chloride powder,
150-160°C on a mixing roll apparatus with 50 parts of a mixture of 36 parts of di-ethylhexyl phthalate and 2 parts of dibutyltin bis-thioglycolic acid hexyl ester.
The mixture is homogenized (during approximately 8 minutes), rolled to form a sheet, and smoothed on a polishing roll device.

A blue-red colored sheet is obtained which has excellent light fastness and softener fastness.

Example 24 Soft PVC (pure color) Proceed as in Example 23, but instead of 0.25 parts of dye 0.5 parts and 2.5 parts of titanium dioxide
．． Using 25 parts gives a deep blue-red colored sheet with excellent light and softener fastness.

Example 25 Rigid PVC (0.1% transparent coloring) 0.1 part of the dye obtained according to Example 13 was mixed with 100 parts of polyvinyl chloride powder (suspension or emulsion polymerized product) and 2 parts of dibutyltin bis-thioglycolic acid hexyl ester. With the department,
Homogenization (
It takes about 8 minutes).

The obtained rolled sheet is compressed on a plate press at 140° C. at about 0.4 kg/crA to form a plate.

A blue-red compression molded article with excellent light fastness is obtained.

A similar coloration is obtained by substituting the dye of Example 15, 17 or 18 for the dye of Example 13.

Example 26 Hard PVC (pure color) 1 part of the dye obtained in Example 13 was mixed with 100 parts of polyvinyl chloride powder (suspension or emulsion polymer product), 0.5 part of titanium dioxide (rutile product) and hexyl dibutyltin bisthioglycolate. 15 on a mixing roll apparatus with 2 parts of ester
Homogenize at 0-160°C (time approximately 8 minutes).

The obtained rolled sheet was heated to 140'C on a plate press.
・It is compressed to a plate at approximately 0.41119/crit.

A deep blue-red colored compression molded article is obtained which has outstanding lightfastness.

A similar coloration is obtained using the dyes of Example 15.17 or 18.

Example 27 Polyethylene (0.05% clear pigmentation) 0.05 part of the dyestuff obtained according to Example 13 is mixed in the dry state with 100 parts of polyethylene powder (high pressure product) in a rotating drum mixer.

The mixture is melted and homogenized in a screw extruder at a cylinder temperature of 160-2000C.

The colored plastic material is granulated by hot crushing in the nozzle head or by thread withdrawal while cooling.

The granules thus obtained were subsequently placed in an injection molding machine for 20 minutes.
A yellowish blue-red compression molded product with excellent light fastness is obtained which can be injected at 0° C. into a molded product or compressed with a press into any molded product.

Example 28 Polyethylene (white dilution 1:10) 0.1 part of the dye of Example 13 was added to polyethylene powder (high pressure method product)
100 parts and 1 part of titanium dioxide (rutile) and Example 15
The mixture is mixed and processed in the same manner as above to form a molded product.

A blue-red compression molded article is obtained which has very good lightfastness.

Example 29 Polystyrene (0.05% transparent pigment) 0.05 part of the dye obtained according to Example 16 was mixed in a rotating drum mixer.
Mix in the dry state with 100 parts of pulverized polystyrene bulk polymer.

The mixture is melted and homogenized in a screw extruder at a cylinder temperature of 200-250°C.

The colored plastic material is granulated by hot crushing in the nozzle head or by thread withdrawal while cooling.

The granules thus obtained were subsequently placed in an injection molding machine for 20 minutes.
It is injected at 0 to 250°C to form a molded body, or compressed on a press to form any molded body.

A bright orange injection molded article is obtained which has excellent lightfastness and fluoresces in a similar shade.

Instead of polystyrene bulk polymers, it is also possible to use polystyrene emulsion or suspension polymers or copolymers of butadiene and acrylonitrile or acrylic esters.

A similar coloration is obtained by substituting the dye of Example 15, 17 or 18 for the dye of Example 16.

Example 30 Polystyrene (white dilution 1:10) 0.1 part of the dyestuff of Example 16 is mixed as in Example 17 with ioo parts of ground polystyrene bulk polymer and 1 part of titanium dioxide.

The mixture is melted, homogenized and granulated.

The granules thus obtained are injected or compressed (processing temperature 200-250°C) to form a molded body.

A glossy orange-coloured injection or compression molded article is obtained which has very good lightfastness.

Similar colorations are obtained by substituting the dye of Example 15, 17 or 18 for the dye of Example 16.

Example 31* *A similar dye is obtained by operating as in Example 16, but using 119 parts of monochloroperylenetetracarboxylic anhydride instead of 110 parts of perylenetetracarboxylic anhydride.

Elemental analysis: HONCI calculated value (%) as C32N2506 N2 Cl (molecular weight 569) 67.54,416.94.96.2
Actual value (%) 67.14. ．． 517.25.05.
9 Example 32 Perylenetetracarboxylic anhydride 12 in 360 parts water
0 parts and 64 parts of γ-methoxypropylamine were stirred,
and 130-135 in a pressure-tightly closed reaction vessel.
Heat to ℃.

Stir at this temperature for about 5 hours until the sample shows that it no longer contains free perylenetetracarboxylic acid.

After cooling and depressurization, the reaction mixture is diluted with water, filtered, and the filter residue is neutrally washed and dried.

162 parts of perylenetetracarboxylic acid bis-(γmethoxypropylimide) are obtained as a black powder.

Under a microscope, brownish-black crystals can be seen.

Elemental analysis: C32N2606 N2 (molecular weight 535
) as HON Calculated value (%) 71.94.918,05.2 Actual value (%) 70.84.718.15.6 parts max: 5
23.487.457 nyrL (dissolved in polystyrene, very thick reflection: λ613.468 part m (1 in baking varnish:
4 - Measured for white dilution) IR reflectance of PVC coloring prepared according to Example 36: Example 3
3 110 parts of perylenetetracarboxylic anhydride and 6 parts of γ-methoxypropylamine in 400 parts of ethylene glycol
6 parts are heated to 170 DEG -175 DEG C. with stirring and kept at this temperature until no perylenetetracarboxylic acid can be detected anymore.

This was about an hour later.

Cool to about 150°C, dilute with 200 parts of dimethylformamide and filter at about 40°C.

The filter residue is washed with 100 parts of dimethylformamide and then with water and dried.

140 parts of perylenetetracarboxylic acid bis-(γ-methoxypropylimide) are obtained as a black powder.

Under a microscope, brownish-black crystals can be seen.

Elemental analysis: C3□H260a N2 (molecular weight 535)
As HON Calculated value (%) 71.94,918.05.2 Actual value (%) 71.45.018.25.5 parts max:
523.487.457 parts m (dissolved in ethylbe**) Reflection maximum: λ 613.468 parts m (1 in baking varnish:
4 - White dilution) IR reflectance of the PvC coloring prepared according to Example 36: Example 34 10% pure color baking is painted (a) Pure color paste (3 parts %) 3 parts of the dye of Example 32 is mixed with a varnish-like binder ( Grinding Pace 100S from Lauter Chemicals, Chicago
) with 7 parts to a 30% pure color paste on a three roll mill in 6 passes at 80 gauge atmosphere.

(b) Pure color varnish paste used for coloring (10
0%) pure color pace) (a) 2 parts to 4 parts of a binder mixture consisting of 1 part of an alkyd resin modified with soybean oil, 2 parts of an alkyd resin modified with synthetic fatty acids and 3 parts of a solvent-free melamine resin. Mix with.

(c) Carrying out the coloring using a film applicator (crocodile space) (b
) is applied to a film thickness of 100 μ on cardboard and baked at 120° C. for 45 minutes.

A black coloration with excellent light fastness and weather resistance is obtained.

Example 35 Baking is painting (white dilution 1:20) (a) White paste (30%) Binder 42 obtained by mixing 1 part of alkyd resin modified with soybean oil and 2 parts of alkyd resin modified with synthetic fatty acids 30 parts of titanium dioxide (rutile), 22 parts of solvent-free melamine resin and 6 parts of colloidal silicon dioxide on a three-roll mill at 80 gauge pressure in six passes to give a 30% white color. Make a paste.

(b) Pure color paste (30%) of varnish paste example 34 (a) 0.5 length fi
10 parts of a) white paste) (30%) are mixed and milled on an automatic milling device.

(c) Carrying out the coloring using a film applicator (crocodile space) (b
) is applied to a film thickness of 100 μ on cardboard and baked at 120° C. for 45 minutes.

A gray coloration with excellent lightfastness and weather resistance is obtained.

Example 36 0.1 part of the dye obtained according to Example 32 was homogenized with 100 parts of polyvinyl chloride powder (emulsion polymerized product) and 2 parts of dibutyltin bis-thioglycolic acid hexyl ester on a mixing roll apparatus at 150-160°C. (takes approximately 8 minutes).

The obtained rolled sheet is compressed on a plate press at 140° C. at about 0.4 kg/crA to form a plate.

Olive-coloured compression molded articles are obtained which have outstanding lightfastness.

Even if polyvinyl chloride produced by hanging candle polymerization is used,
Similar results are obtained.

Example 37 0.1 part of the dye obtained in Example 32 was mixed with 100 parts of polyvinyl chloride powder (suspension polymerized product), 1 part of titanium dioxide (rutile product), and 2 parts of dibutyltin bis-thioglycolic acid hexyl ester. Homogenize as in Example 36 on a rolling machine and then press into plates.

A reddish-gray compression molded article is obtained which has outstanding lightfastness.

Using 1 part of dye instead of 0.1 part and 5 parts of Q instead of 1 part of titanium dioxide gives black compression molded articles with remarkable lightfastness.

Even if polyvinyl chloride obtained by emulsion polymerization is used,
Similar results are obtained.

Example 38 0.05 part of the dye obtained according to Example 32 was added to 10 ml of ground polystyrene bulk polymer in a rotating drum mixer.
Mix dry with 0 parts.

The mixture is melted and homogenized in a screw extruder at a cylinder temperature of 200-250°C.

The colored plastic material is granulated by hot crushing in the nozzle head or by thread withdrawal while cooling.

The granules thus obtained were subsequently placed in an injection molding machine for 20 minutes.
It is injected at 0 to 250°C to form a molded body, or compressed on a press to form any molded body.

A glossy yellow-orange injection molded article is obtained which has excellent lightfastness and fluoresces in a similar shade.

Instead of polystyrene bulk polymers, it is also possible to use polystyrene emulsion or suspension polymers or copolymers of butadiene and acrylonitrile or acrylic esters.

Example 39 0.1 part of the dyestuff of Example 32 is mixed as in Example 38 with 100 parts of ground polystyrene bulk polymer and 1 part of titanium dioxide.

The mixture is melted, homogenized and granulated.

The granules thus obtained are injected or compressed (processing temperature 20
0 to 250°C) to form a molded body.

A glossy orange-coloured injection or compression molded article is obtained which has very good lightfastness.

Example 40 0.05 parts of the dye obtained according to Example 32 are mixed with 50 parts of a mixture of 65 parts of polyvinyl chloride powder, 35 parts of di-ethylhexyl phthalate and 2 parts of dibutyltin bis-thioglycolic acid hexyl ester. Homogenize on a roll machine at 150-160°C (time about 8 minutes), roll into a sheet and smoothen on a polish roll machine.

An olive-coloured sheet is obtained which has excellent lightfastness.

Example 41 0.25 parts of the dye obtained in Example 32 was mixed with 2.5 parts of titanium dioxide (rutile product) and 65 parts of polyvinyl chloride powder.
150-160 parts on a mixing roll apparatus with 50 parts of a mixture of 35 parts of di-ethylhexyl phthalate and 2 parts of dibutyltin bis-thioglycolic acid hexyl ester.
Homogenize (approximately 8 minutes) at <RTIgt;°C,</RTI> unrolled into a sheet, and smoothed on a polishing roll apparatus.

A gray colored sheet is obtained which has excellent lightfastness.

Using 0.5 parts instead of 0.25 parts of dye and 0.25 parts instead of 2.5 parts of titanium dioxide gives a black sheet with excellent light fastness.

Example 42 0.05 part of the dye obtained according to Example 32 is mixed dry in a rotating drum mixer with 100 parts of polyethylene powder (high pressure product).

Heat the mixture in a screw extruder at 160-200'C
melts and homogenizes at a cylinder temperature of .

The colored plastic material is granulated by hot crushing in the nozzle head or by thread withdrawal while cooling.

The granules thus obtained were subsequently placed in an injection molding machine for 20 minutes.
It is injected at 0° C. to form a molded product, or compressed on a press to form any molded product.

A black-gray compression molded article with excellent light fastness is obtained.

Example 43 0.1 part of the dye of Example 32 was added to the polyethylene powder press product) 1
00 parts and 1 part of titanium dioxide (rutile product) are mixed in the same manner as in Example 42 and processed to form a molded body.

A gray compression molded article is obtained which has very good lightfastness.

Claims (1)

[Scope of Claims] 1. A corresponding perylenetetracarboxylic acid or its corresponding perylenetetracarboxylic acid, characterized in that an ether amine represented by the general formula (wherein Z has the meaning given below) or a mixture of these amines is used as the primary amine. Dianhydride is a primary aliphatic amide (wherein Z is a group -CH2-C
H2-0R or -CH2CH2-CH2-0R, R is 1
an alkyl group having ~8 carbon atoms, X is a chlorine atom or a bromine atom, and n means O or an integer from 1 to 3;
In this case, R may be the same or different.