EP1682619A1

EP1682619A1 - Green pigment preparations

Info

Publication number: EP1682619A1
Application number: EP04791079A
Authority: EP
Inventors: Heinfred Ohleier; Joachim Weber; Olaf Schupp
Original assignee: Clariant Produkte Deutschland GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2003-11-05
Filing date: 2004-10-30
Publication date: 2006-07-26
Also published as: US7318860B2; JP2007513214A; WO2005044925A1; DE10351580A1; US20070068420A1

Abstract

The invention relates to a green pigment preparation that is characterised by a C.I. Pigment Yellow 214 and a copper phthalocyanine pigment C.I. Pigment Blue 15:3 and/or C.I. Pigment Blue 15:1 content, the ratio of C.I. Pigment Yellow 214 to copper phthalocyanine pigment being between 1 to 20 and 20 to 1. The inventive pigment preparations are especially suitable for the low-warpage colouring of semicrystalline plastics with pure green tones.

Description

description

Green pigment preparations The invention relates to pigment preparations which contain a blue copper phthalocyanine pigment and a yellow pigment, processes for their preparation and their use for pigmenting high-molecular organic materials, in particular plastics, in particular for low-distortion pigmentation of partially crystalline plastics, for example polyolefins, with pure green shades.

When coloring semi-crystalline plastics with organic pigments, there are often influences on the crystallite formation in the material, which are referred to as distortion. The pigmentation of large-volume injection molded parts, especially those made of polyethylene, often leads to deformation, shrinkage and cracking (due to internal stresses, so-called stress cracking), which, depending on the area of application, render the colored articles unusable. For example, with bottle crates, loss of stackability is to be expected due to deformation and with closures, an inaccuracy of fit.

These disadvantages relate to the majority of organic pigments, while the inorganic pigments and a minority of organic pigments are relatively neutral. It is believed that pigments can act as nucleation centers during the solidification of the polymer melt and thus lead to a polymer that tends to warp.

In addition to the described dimensional stability of the colored injection molded parts, the dyeings should have good application properties, such as heat stability, light fastness and fastness to migration. The dispersibility of the pigments used to prepare the pigment preparations must be very good in order to enable dyeing with the desired high color strength. High demands are placed on the purity of the color. There are various proposals for achieving green tones for plastic coloring by mixing blue and yellow pigments:

JP 59-147 039 discloses a mixture of copper phthalocyanines with chrome yellow pigments, with which PVC can be colored in moss green shades. The use of chromium-containing pigments is avoided nowadays because of the resulting environmental problems. The proposed mixtures are not suitable for pure shades of green. No statements are made regarding delay behavior or even an improvement in delay behavior.

DE-A-36 23 335 discloses green mixed crystal pigments of yellow quinacridonequinones with blue indigo. However, they show poor light and weather fastness, which can only be improved by using a third component. It is also pointed out that only when a mixed crystal is produced is a "strong green color" obtained, the mechanical one

Mix has a dirty brown hue. This requires an additional procedural step that causes additional costs. Large quantities of dilute sulfuric acid are produced in the present process and must be disposed of. No statements are made regarding delay behavior or even an improvement in delay behavior.

CS-A-277 656 discloses a process for the production of mixed green pigments by precipitation of soluble precursors of yellow pigments on copper phthalocyanine pigments.

JP 2000-063699 discloses special mixtures of copper phthalocyanine and azo pigments which are characterized by freedom from chlorine. No special application properties or even advantages when coloring plastics were found.

Usually, as also described in CS-A-277 656, shades are obtained by mixing a blue and a yellow pigment whose purity and saturation (chroma) is lower than that of the individual components. Even the use of the well-known PY180 in combination with a blue pigment does not meet today's requirements, since low-distortion and heat-stable stains are obtained, but the purity of the color is unsatisfactory.

The task was to make pigment preparations accessible for coloring high molecular weight materials, in particular for low-distortion coloring of semi-crystalline plastics with pure green shades. It has now been found that the object is surprisingly achieved by using pigment preparations containing a blue copper phthalocyanine pigment and C.I. Pigment Yellow 214 is dissolved.

The invention relates to a pigment preparation, characterized by a content of preferably 1 to 40% by weight of C.I. Pigment Yellow 214 and preferably 1 to 40% by weight of the copper phthalocyanine pigment C.I. Pigment Blue 15: 3 and / or C.I. Pigment Blue 15: 1, the ratio of C.I. Pigment Yellow 214 for the copper phthalocyanine pigment is 1 to 20 to 20 to 1, preferably 1 to 10 to 10 to 1, in particular 1 to 5 to 5 to 1.

Preferred pigment preparations for the purposes of the present invention contain a) 1 to 40% by weight, preferably 2.5 to 40% by weight, particularly preferably 5 to 40% by weight, Cl Pigment Yellow 214, b) 1 to 40% by weight %, preferably 2.5 to 40% by weight, particularly preferably 5 to 40% by weight, Cl Pigment Blue 15: 3 and / or 15: 1, c) 20 to 98% by weight, preferably 20 up to 95% by weight, particularly preferably 20 to 90% by weight of polyolefins, preferably polypropylenes and polyethylenes, such as commercially available LLDPE, HDPE, LDPE or polyolefin waxes, d) 0 to 40% by weight, preferably 0.1 to 25 % By weight of additives customary in masterbatch production, e) 0 to 25% by weight, preferably 1 to 20% by weight, of one or more white pigments, such as titanium dioxide, wherein the proportions of the respective components a) to e) are based on the total weight of the pigment preparation (100% by weight), and f) 0 to 40% by weight, preferably 1 to 20% by weight, based on the total the weights of components a) and b), one or more shading colorants, such as carbon black, chromium titanate, nickel titanate or bismuth vanadate.

The additives customary in masterbatch production are, for example, stabilizers, such as UV absorbers or antioxidants, optical brighteners, fillers, antistatic agents, lubricants and dispersing agents.

The pigment preparations according to the invention can be produced by the customary and known processes for producing a masterbatch. For example, pigments a) and b) are incorporated separately, optionally with components d), e) and f), as a dry mixture or as a mixture of two pigment preparations in component c). For example, the two pigments or the pigment mixture are sintered with a commercially available polyolefin and / or a polyolefin wax in a hot-cooling mixer and the mixture is then extruded; in the second case, if two pigment preparations are already assumed, a coextrusion of the two preparations is sufficient.

The pigment preparations according to the invention are outstandingly suitable for low-distortion coloring of semi-crystalline plastics with particularly pure green shades.

Another object of the present invention is therefore the use of the pigment preparations according to the invention for low-distortion pigmentation of partially crystalline plastics with particularly pure green shades.

For the purposes of the present invention, the term “low warpage” means a warp which is significantly reduced in comparison to a pigment preparation not according to the invention. Semi-crystalline plastics are understood to mean those which form small crystalline nuclei or aggregates on solidification, sometimes only in the presence of nucleating agents (for example organic pigments). Semi-crystalline plastics are generally thermoplastic, high molecular weight organic materials with a molecular weight (M _w ) of 10 ⁴ to 10 ⁸ g / mol, preferably 10 ⁵ to 10 ⁷ g / mol, and a degree of crystallinity (X _c ) of 10 to 99.9% , preferably from 40 to 99%, particularly preferably from 80 to 99%. Preferred semi-crystalline plastics are homopolymers, block or statistical copolymers and terpolymers of ethylene, propylene, butylene, styrene and / or divinylbenzene, in particular polyolefins, such as polyethylene (HDPE, MDPE, LDPE, LLDPE), polypropylene, in particular high density polyethylene (HDPE) , also POM (polyoxymethylene).

The semi-crystalline plastics can also contain additives in conventional amounts, such as e.g. Stabilizers, optical brighteners, fillers and lubricants.

When coloring the semi-crystalline plastics, the pigment preparation according to the invention is expediently used in an amount of 0.01 to 5% by weight, preferably 0.05 to 1% by weight, based on the plastic. The coloring itself can be carried out using customary methods, e.g. by extrusion or injection molding.

The warpage influence of polyolefin by the pigment preparation produced according to the invention is tested on an injection molded part in the form of a plate. After aging, the dimensions of the board (length, width) are measured and the distortion or shrinkage is determined using the following equation:

% Warpage = 100% x (% warpage vertical -% warpage horizontal) / (% warpage horizontal)

The warpage values are determined both at 220 ° C and at 280 ° C. It was surprising and unpredictable that the combination of Cl Pigment Yellow 214 with the copper phthalocyanine pigment Cl Pigment Blue 15: 3 and / or Cl Pigment Blue 15: 1 could not only be used to produce low-warpage injection molded parts, but also that the colors could be clearly seen distinguish higher purities compared to mixtures with other yellow pigments. It is not necessary to produce a mixed crystal in order to achieve the high purity. In addition, the dyeings produced with the pigment preparations according to the invention have high color strengths, good heat stability and light fastness. The fastness to migration is very good.

The pigment preparations according to the invention can of course also be used for pigmenting plastics which do not fall under the term “partially crystalline”. They can generally be used for pigmenting high molecular weight organic materials of natural or synthetic origin, for example plastics, resins, lacquers, Paints, electrophotographic toners and developers, electret materials, color filters as well as inks, printing inks and seeds.

High molecular weight organic materials that can be pigmented with the pigment preparations according to the invention are, for example, cellulose compounds, such as, for example, cellulose ethers and esters, such as ethyl cellulose, nitrocellulose, cellulose acetates or cellulose butyrates, natural binders, such as, for example, fatty acids, fatty oils, resins and their conversion products, or synthetic resins , such as polycondensates, polyadducts, polymers and copolymers, such as, for example, aminoplasts, in particular urea and melamine formaldehyde resins, alkyd resins, acrylic resins, phenoplasts and phenol resins, such as novolaks or resols, urea resins, polyvinyls, such as polyvinyl alcohols, polyvinyl acetals, polyvinyl ether polyolefins, or polyvinyl ether polyols, polyvinyl ether or polyvinyl acetates, such as polystyrene, polyvinyl chloride, polyethylene or polypropylene, poly (meth) acrylates and their copolymers, such as

Polyacrylic acid esters or polyacrylonitriles, polyamides, polyesters, polyurethanes, coumarone indene and hydrocarbon resins, epoxy resins, unsaturated synthetic resins (polyesters, acrylates) with different hardening mechanisms, Waxes, aldehyde and ketone resins, rubber, rubber and its derivatives and latices, casein, silicones and silicone resins; individually or in mixtures. It does not matter whether the high-molecular organic compounds mentioned are in the form of plastic masses, melts or in the form of spinning solutions, dispersions, lacquers, paints or printing inks. Depending on the intended use, it proves to be advantageous to use the pigment preparations according to the invention as a blend or in the form of preparations or dispersions. Based on the high-molecular organic material to be pigmented, the pigment preparations according to the invention are used in an amount of 0.01 to 30% by weight, preferably 0.1 to 15% by weight. In some cases it is also possible to use a corresponding crude with a BET surface area of greater than 2 m ² / g, preferably greater than 5 m ² / g, instead of a ground and / or finished pigment composition according to the invention. This crude can be used to produce color concentrates in liquid or solid form in concentrations of 5 to 99% by weight, alone or optionally in a mixture with other crudes or finished pigments.

The pigment preparations of the invention are also suitable as colorants in electrophotographic toners and developers, such as, for example, one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, polymerization toners and special toners. Typical toner binders are polymerization, polyaddition and polycondensation resins, such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, phenol-epoxy resins, polysulfones, polyurethanes, individually or in combination, and polyethylene and polypropylene, which also contain other ingredients, such as charge control agents, waxes or flow aids, or can be modified with these additives afterwards.

Furthermore, the pigment preparations according to the invention are suitable as colorants in powders and powder coatings, in particular in triboelectrically or electrokinetically sprayable powder coatings, which are used for surface coating of objects made of metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber, for example. Epoxy resins, carboxyl- and hydroxyl-containing polyester resins, polyurethane and acrylic resins are typically used as powder coating resins together with conventional hardeners. Combinations of resins are also used. For example, epoxy resins are often used in combination with carboxyl- and hydroxyl-containing polyester resins. Typical hardener components (depending on the resin system) are, for example, acid anhydrides, imidazoles and dicyandiamide and their derivatives, blocked isocyanates, bisacylurethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylic acids.

In addition, the pigment preparations according to the invention are suitable as colorants in ink-jet inks on an aqueous and non-aqueous basis and in inks which work according to the hot-melt process. Ink-jet inks generally contain a total of 0.5 to 15% by weight, preferably 1.5 to 8% by weight (calculated on a dry basis) of one or more of the pigment preparations according to the invention. Microemulsion inks are based on organic solvents, water and possibly an additional hydrotropic substance (interface mediator).

Microemulsion inks generally contain 0.5 to 15% by weight, preferably 1.5 to 8% by weight, of one or more of the pigment preparations according to the invention, 5 to 99% by weight of water and 0.5 to 94.5% by weight. -% organic solvent and / or hydrotropic compound. "Solvent based" ink-jet inks preferably contain 0.5 to 15% by weight of one or more of the pigment preparations according to the invention, 85 to 99.5% by weight of organic solvent and / or hydrotropic compounds. Hot-melt inks are usually based on waxes, fatty acids, fatty alcohols or sulfonamides, which are solid at room temperature and become liquid when heated, the preferred melting range being between approx. 60 ° C and approx. 140 ° C. Hot-melt ink-jet inks essentially consist, for example, of 20 to 90% by weight of wax and 1 to 10% by weight of one or more of the invention Pigment preparations. Furthermore, 0 to 20% by weight of an additional polymer (as a "dye dissolver"), 0 to 5% by weight of dispersing aid, 0 to 20% by weight of viscosity modifier, 0 to 20% by weight of plasticizer, 0 to 10% by weight % Stickiness additive, 0 to 10% by weight transparency stabilizer (prevents, for example, crystallization of the waxes) and 0 to 2% by weight antioxidant.

Furthermore, the pigment preparations according to the invention are also used as colorants for color filters, both for additive and for subtractive color production, and as colorants for electronic inks (“electronic inks” or “e-inks”) or “electronic paper” (“e- paper "). In the manufacture of color filters, both reflective and transparent color filters, pigments in the form of a paste or as pigmented photoresists in suitable binders (acrylates, acrylic esters, polyimides, polyvinyl alcohols, epoxies, polyesters, melamines, gelatins, caseins) are applied to the respective LCD components (eg TFT-LCD = Thin Film Transistor Liquid Crystal Displays or eg ((S) TN-LCD = (Super) Twisted Nematic-LCD). In addition to high thermal stability, high pigment purity is also required for stable paste or pigmented photoresist The pigmented color filters can also be applied using ink jet printing processes or other suitable printing processes.

In the following examples, percentages mean percentages by weight, unless stated otherwise. In the pigment preparations used for the production of the pigment preparations according to the invention, the pigment and its content are stated, the remaining portions consist of a mixture of commercially available polyethylene and polyethylene wax.

example 1

16.4 parts of a pigment preparation containing 38% Cl Pigment Yellow 214 are mixed with 24.5 parts of a pigment preparation containing 30% copper phthalocyanine pigment Cl Pigment Blue 15: 3, with 12.3 parts of a pigment preparation containing 70% titanium dioxide pigment Cl Pigment White 6 and coextruded with 47.6 parts LDPE. 100 parts of the pigment preparation according to the invention are obtained, which contains 17.6 parts of titanium dioxide pigment Cl Pigment White 6, 6.2 parts of Cl Pigment Yellow 214 and 7.4 parts of copper phthalocyanine pigment Cl Pigment Blue 15: 3.

Examples 2, 3 and 4 are comparative examples and were produced analogously to Example 1 by coextrusion, with C.I. Pigment Yellow 214 - an equal amount of another yellow pigment preparation was used. These four pigment preparations were used to color polyethylene.

Table 1 :

The pigment preparation from Example 3 shows a comparable warpage behavior and a comparable heat stability, but only dyeings with a significantly lower chroma, that is to say with an unacceptable purity, can be produced. In addition to the lower purity, the pigment preparation from Example 2 shows a significantly poorer warpage behavior, and the pigment preparation from Example 4 shows a significantly poorer heat stability in addition to the lower purity.

Claims

claims:

1) pigment preparation, characterized by a content of C.I. Pigment Yellow 214 and the copper phthalocyanine pigment C.I. Pigment Blue 15: 3 and / or C.I. Pigment Blue 15: 1, the ratio of C.I. Pigment Yellow 214 to copper phthalocyanine pigment is 1 in 20 to 20 in 1.

2) pigment preparation according to claim 1, characterized in that the ratio of C.I. Pigment Yellow 214 for the copper phthalocyanine pigment is 1 to 10 to 10 to 1, in particular 1 to 5 to 5 to 1.

3) pigment preparation according to claim 1 or 2, containing 1 to 40 wt .-% C.I. Pigment Yellow 214, and 1 to 40% by weight of C.I. Pigment Blue 15: 3 and / or C.I. Pigment Blue 15: 1.

4) pigment preparation according to at least one of claims 1 to 3, containing a) 1 to 40 wt .-% C.I. Pigment Yellow 214, b) 1 to 40% by weight of C.I. Pigment Blue 15: 3 and / or C.I. Pigment Blue 15: 1, c) 20 to 98% by weight of polyolefins, d) 0 to 40% by weight of additives customary in masterbatch production, e) 0 to 25% by weight of one or more white pigments, the proportions of the respective components a) to e) are based on the total weight of the pigment preparation (100% by weight), and f) 0 to 40% by weight, based on the sum of the weights of components a) and b), one or several shading colorants.

5) pigment preparation according to at least one of claims 1 to 4, containing a) 2.5 to 40 wt .-% Cl Pigment Yellow 214, b) 2.5 to 40 wt .-% Cl Pigment Blue 15: 3 and / or Cl Pigment Blue 15: 1, c) 20 to 95% by weight of polyolefins, d) 0 to 40% by weight, preferably 1 to 25% by weight, of additives customary in masterbatch production, e) 0 to 25% by weight, preferably 1 to 20% by weight, of one or more white pigments, where the proportions of the respective components a) to e) are based on the total weight of the pigment preparation (100% by weight), and f) 0 to 40% by weight, preferably 1 to 20% by weight, based on the sum of the Weights of components a) and b), one or more shading colorants.

6) Method for producing a pigment preparation according to at least one of claims 1 to 5, characterized in that the pigments a) and b) and optionally components d), e) and f) separately, as a dry mixture or as a mixture of two pigment preparations homogeneously be incorporated into component c).

7) Use of a pigment preparation according to at least one of claims 1 to 5 for pigmenting high molecular weight organic materials of natural or synthetic origin.

8) Use according to claim 7 for pigmenting plastics, resins, lacquers, paints, electrophotographic toners and developers, electret materials, color filters and inks, printing inks and seeds.

9) Use according to claim 7 or 8 for low distortion pigmentation of partially crystalline plastics.

10) Use according to one or more of claims 7 to 9 for low distortion pigmentation of polyolefins, in particular polyethylenes.