KR20060094589A - Aqueous pigment composition - Google Patents

Abstract

The present invention relates to a water-disperse pigment composition, and more particularly to a water-dispersible pigment composition compatible with water-dispersed polyurethane. The water-dispersion pigment composition of the present invention is characterized in that it contains polyethylene-polypropylene glycol in order to increase the compatibility with the water-dispersed polyurethane together with the dispersant which is easy to disperse the water. The water-disperse pigment composition according to the present invention not only has high compatibility with the water-dispersed polyurethane, but also solves the environmental pollution problem caused by evaporation of the solvent.

 Preferred pigment dispersions are: a) 5 to 70% by weight of one or more organic or inorganic pigments b) 1 to 50% by weight polyethylene-polypropylene glycol copolymer, c) 2 to 25% by weight of dispersant, d) 5 to 80% by weight of water %, And e) 0 to 20% by weight of customary additives.

Poloxalen

Description

Water Disperse Pigment Composition {AQUEOUS PIGMENT COMPOSITION}

The present invention relates to a water-disperse pigment composition, and more particularly to a water-disperse pigment composition having good compatibility with water-dispersed polyurethane containing polyethylene-polypropylene glycol. Polyurethane is a material that has been used for a long time in various fields such as leather and shoes. In using a polyurethane, a method of dispersing a polyurethane in an organic solvent and then removing the organic solvent in application has been used in artificial leather manufacturing processes and the like. Since such a use method includes a problem that may cause an environmental problem by evaporation of an organic solvent, a polyurethane dispersed in water, that is, a water-dispersed polyurethane has been developed as a solution to solve this problem.

Methods of preparing water-dispersed polyurethanes are known in the art, and general methods for preparing water-dispersed polyurethanes include dispersing low molecular weight prepolymers having low viscosity and ionic groups in water, and then using a chain extender to prepare a polymer dispersion. It is a manufacturing method and the specific method is as follows.

After adding the polyol and the catalyst, the mixture was sufficiently stirred at 80 to 100 ° C., and then the isocyanate was added to react until the NCO group of the isocyanate reached the theoretical value. For adjustment, a solvent such as acetone or methyl ethtone ketone is added. When the isocyanate used at this time is aliphatic isocyanate, it is made to disperse | distribute to water in the state which residual NCO group exists, and then, it adds a chain extender of amines, and makes it react for about 3 to 4 hours. In the case of the use of aromatic isocyanates, agglomeration occurs due to the rapid reactivity with water molecules during water dispersion, or gelation results in loss of particle stability. Therefore, the residual NCO group is consumed as a chain extender of diol or diamine before water dispersion, and thereafter, it is water dispersed. In both cases, the solvent remaining in the dispersion is finally removed with a vacuum rotary evaporator.

In the case of aliphatic isocyanate, a high molecular weight polyurethane resin can be synthesized by water-dispersing the low molecular weight polyurethane prepolymer after water dispersion. Therefore, relatively excellent physical properties can be obtained without a separate curing agent, and in the case of aromatic isocyanates, chain extension is required on the bulk before water dispersion to prevent side reactions with water.

On the other hand, development for water-disperse pigments continues, and a number of pigment dispersions containing anionic and / or nonionic adjuvants as dispersants are known for a variety of applications.

In general, these adjuvants are alkylaryl compounds, their alkoxylation products and / or their sulfonation products. However, these dispersants suitable for dispersing solids in an aqueous system are unable to finish the pigment in such a way that the final formulation meets all desired properties in the presence of water as the only liquid medium. For example, flocculation and settling may occur during and after the dispersing operation, which leads to viscous changes in the application medium, changes in shading, loss of color intensity, shielding, gloss, homogeneity and brightness, and also poor reproducibility. It results in a tendency to proceed when the shading, coloring material comprises paint. In addition, there can be a significant loss in resistance to partial and total drying-up. Thus, conventional pigment formulations include alongside dispersants, wetting agents, thickeners, preservatives, viscosity stabilizers, fillers and retention agents (the purpose of which is to prevent the product from drying completely or partially before use). It includes. Ethylene glycol or propylene glycol has generally been used for this purpose. However, for reasons of environmental protection, the use of volatile glycols such as propanediol, 1,2-monoethylene glycol or diethylene glycol has been ruled out.

As an alternative to volatile ethylene glycol or propylene glycol, polyetherpolyols are used in EP 0 735 109 and α-methyl-ω-hydroxy-polyethylene glycol ether retaining agents are used in Publication 10-2004-0018449. Doing.

Despite the development of such disperse pigment dispersion systems, there is a continuing need for disperse pigment systems which are more stable and suitable for disperse polyurethanes.

It is an object of the present invention to provide a novel water disperse pigment composition.

Another object of the present invention is to provide a novel water disperse pigment composition which is compatible with polyurethane.

Another object of the present invention is to provide a dispersed pigment composition comprising polyethylene-polypropylene glycol.

It is another object of the present invention to provide a colored, water-dispersed polyurethane using a water-disperse pigment composition.

It has been found that the water-disperse pigment composition of the present invention for achieving the above object comprises polyethylene-polypropylene glycol.

The invention further comprises a) one or more organic or inorganic pigments or combinations thereof, b) polyethylene-polypropylene glycols having an average molecular weight of 1000-15,000, c) dispersants for preparing aqueous pigment dispersions, d) if desired. Conventional additives, e) providing a pigment dispersion consisting essentially of the remaining water.

Preferred pigment dispersions are a) 5 to 70% by weight of one or more organic or inorganic pigments b) 1 to 50% by weight of poloxylene, c) 2 to 25% by weight of dispersant, d) 0 to 20% by weight of conventional additives and e ) Essentially consists of 5 to 80% by weight of water.

Pigments for the purposes of the present invention can be used conventional organic pigments or inorganic pigments that have been used in polyurethane, there is no particular limitation as long as it can be dispersed in water by the dispersant of the present invention.

 In a preferred embodiment of the invention, examples of the organic pigments include monoazo pigments, disazo pigments, laced azo pigments, triphenylmethane pigments, thioindigo pigments, thiazineindigo pigments, perylene pigments, perinone pigments. , Anthrone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, isoindolin pigments, benzimidazolone pigments, naphthol pigments and quinophthalone pigments, Further included are acid to alkaline carbon blacks from furnace black or gas black groups.

Examples of suitable inorganic pigments are titanium dioxide, zinc sulfide, iron oxide, chromium oxide, ultramarine, nickel or chromium antimony titanium dioxide, cobalt oxide and bismuth vanadate. Further mention may be made of fine ores, minerals, rarely soluble or insoluble salts, wax or polymer particles, grain protective products and dispersions comprising pesticides, optical brighteners and dyes as solids.

In the present invention, the organic or inorganic pigment may be used as one or more organic or inorganic pigments or combinations thereof, and in the pigment dispersion, 5 to 70% by weight, preferably 10 to 60% by weight may be used. Can be.

In the present invention, the dispersant is used to disperse the pigment. Although the dispersant is not theoretically limited, it usually has both a hydrophilic portion and a hydrophobic portion in one molecule, so that the hydrophilic portion is in contact with water used as a dispersion medium and the hydrophobic portion is in contact with the surface of the pigment, thereby improving the dispersion stability of the pigment. Will be maintained.

Dispersants suitable in the present invention include anionic, cationic and nonionic surface-active compounds. Dispersions with one or more medium or long chain hydrocarbon chains are particularly well established. Among the various compounds, only those selected from the above viewpoints are listed, but not limited to the application of the compounds of the present invention to these examples. Examples are alkyl sulfates, alkylsulfonates, alkyl posuccinates and alkylbenzenesulfonates, such as lauryl sulphate, stearyl sulphate, dodecylsulfonate, octadecyl sulphate, dodecylsulfonate, fatty acids and taurine or hydride. Condensation products of oxyethanesulfonic acid, alkoxylation products of alkylphenols, castor oil rosin esters, fatty alcohols, fatty amines, fatty acids, and reaction products of fatty acid amides, nonylphenols and relatively short-chain substituted alkylphenols, and additionally Polymeric derivatives such as formaldehyde condensation products, and also polymeric compounds such as polyacrylates and alkoxylates thereof.

In one preferred embodiment of the invention, the dispersants are commercially available, the preferred dispersants being compatible with pigments, and products developed for water dispersion are preferred.

It is preferable to use 2 to 25% by weight, preferably 3 to 15% by weight of the dispersant of the present invention. If the blending ratio of the dispersant is too small, the effect of the desired dispersant becomes difficult to be obtained sufficiently. On the other hand, if the blending ratio of the dispersant is too large, the effect as much as it is used cannot be obtained. On the contrary, the physical properties of the water-dispersed polyurethane using the resultant pigment composition are lowered and the color of the dispersant itself is increased. As a result, the color of the dispersed pigment is greatly changed.

 In the present invention, the polyethylene-polypropylene glycol is a kind of nonionic surfactant used for improving the dispersibility and storage stability of the pigment and improving the compatibility with the water-dispersed polyurethane, usually ethylene oxide and propylene It is a block copolymer prepared by copolymerizing an oxide and is a polypropylene glycol ethylene oxide polymer.

In the present invention, the average molecular weight of the polyethylene-polypropylene glycol is preferably about 1000-15,000, more preferably about 1200 to 10,000, and most preferably about 1500 to 5000. If the molecular weight is out of the above range, the stability of the dispersion is lowered, it is possible to cause layer separation or pigment settling during long-term storage.

In one embodiment of the invention, the polyethylene-polypropylene glycol can be prepared according to a known manner or can be purchased commercially, and the preferred polyethylene-polypropylene glycol is POLOXALENE.

In the present invention, the poloethylene-polypropylene glycol is preferably used 1 to 50% by weight, more preferably 1.5 to-30% by weight, most preferably 2 to 25% by weight. .

In the present invention, suitable conventional additives include antisettling agents, wetting agents, preservatives, viscosity stabilizers, and additives that affect the rheology.

In addition, the present invention disperses the pigment component (a) in powder, granule or aqueous presscake form in a conventional manner in the presence of water and additionally a dispersant and poloxylene, and, if appropriate, water (d) and And / or mixing in the additive component (e) and adjusting the resulting aqueous pigment dispersion to the desired concentration with water to provide a process for the preparation of the pigment dispersion of the invention.

The additive may be used in an amount of 0 to 20% by weight if necessary, and in order to exhibit the properties of the additive, it is preferable to use 0.1 to 20% by weight.

In a preferred embodiment of the invention, in order to prepare the pigment dispersion of the present invention, a preliminary mixture of the above-mentioned components for 10 to 30 minutes at a speed of 500 to 700 rpm, preferably 600 rpm using a homogenizer. It is preferred to go through a premixing step. The homogenizer used at this time is not particularly limited as long as the object of the present invention is not impaired, for example, an ultrasonic homogenizer or an ultrahigh pressure homogenizer may be used.

The premix is then dispersed using a shaker, in which zirconium beads or glass beads are added to aid in the dispersion. The primary dispersion, which has been dispersed by the shaker, is optionally dispersed once more in a ball mill or dyno mill. According to the present invention, in order to minimize the size of the dispersed particles and to ensure long-term dispersion stability, it is the dispersion sequence leading to the premix-shaker-ball mill or dyno miller, and the optimum dispersion speed and the dispersion time are the size of the dispersed particles to be obtained. Can be appropriately determined by those skilled in the art.

The water dispersible pigment composition according to the present invention may be used by selecting an appropriate dispersant according to the type of water dispersible polyurethane.

In one embodiment of the invention, when impregnating the substrate for manufacturing artificial leather into the impregnation solution, the impregnation solution is about 0.001 to 10% sodium silicate (Na 2 SiF6) or potassium silicate (K2 SiF6), and in order to impart stability to the impregnating solution, an impregnation solution containing about 3 to 70% of ethyl alcohol as a weight composition ratio to the impregnation solution is used. It is particularly preferable to use Disperbyk-190, BYK-Gardner GmbH, Germany, as the water-disperse pigment composition used for the water-dispersed polyurethane for the microporous layer artificial leather.

The water-disperse pigment and the water-dispersed polyurethane according to the present invention can be used by mixing using a conventional mixing process, there is no particular limitation.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Preparation of Water Disperse Pigment Composition

Example 1

25 weight% carbon black (FW-18: B, Degussa, USA), 12 weight% dispersant (SYNTHRO ^R PON OM WB, PROTEX-INTERNATIONAL, France), 13 weight% polyethylene-polypropylene glycol (average molecular weight 2,500), A homogenizer (D-51580 Reichshof, VMA-G ETZMANN GMBH, Germany) was added after adding 0.1% by weight of an antifoaming agent (BYK-019: BYK-024 = 3: 2 mixture) and 0.5% by weight of thickener to the remaining ultrapure water. 30 minutes of pre-mixing was carried out at a speed of 600 rpm / min to sufficiently disperse the pigment aggregates. Subsequently, zirconium beads were added to the premix and dispersed for 30 minutes under conditions of input power AC 220V, 60 Hz using a paint shaker (Daecheon Industry Co., Ltd.). The visual observation of the dispersion state of the pigment particles in the dispersion was found to be very homogeneous.

Example 2

Blue pigment powder (fastblue 15: 3, Sun Chemical, Japan) 20% by weight, dispersant (SYNTHRO ^R PON OM WB, PROTEX-INTERNATIONAL, France) 10% by weight, 20% by weight of poloxylene, defoamer (BYK-019: BYK -024 = 3: 2 mixture) 0.2% by weight, and 5% by weight of thickener to the remaining ultrapure water, followed by a rate of 600 rpm / min using a homogenizer (D-51580 Reichshof, VMA-G ETZMANN GMBH, Germany) The pigment aggregate was sufficiently predispersed by 30 minutes of pre-mixing. Subsequently, zirconium beads were added to the premix and dispersed for 30 minutes under conditions of input power AC 220V, 60 Hz using a paint shaker (Daecheon Industry Co., Ltd.). The visual observation of the dispersion state of the pigment particles in the dispersion was found to be very homogeneous.

Example 3

20% by weight of red pigment powder (CIPIGMENT RED-122, Clarient, Japan), 10% by weight of dispersant (PROX ^R A300 PROTEX-INTERNATIONAL, France), 20% by weight of poloxylene, antifoaming agent (BYK-019: BYK-024 = 3 : 2 mixture) 0.5% by weight, and 2% by weight of thickener, are added to the remaining ultrapure water, followed by preparation for 30 minutes at a rate of 600 rpm / min using a homogenizer (D-51580 Reichshof, VMA-G ETZMANN GMBH, Germany). Mixing was performed to sufficiently predisperse the pigment aggregates. Subsequently, zirconium beads were added to the premix and dispersed for 30 minutes under conditions of input power AC 220V, 60 Hz using a paint shaker (Daecheon Industry Co., Ltd.). The visual observation of the dispersion state of the pigment particles in the dispersion was found to be very homogeneous.

Example 4

Red HF2b01 (pigment) 8% by weight, PV Violet 19 (Pigment) 1% by weight Dispersant (DISPERBYK 190, Germany) 4% by weight, Poloxalene 2% by weight, Defoamer (BYK-019: BYK-024 = 3: 2 mixture) 0.1 weight%, and 6 weight% thickener were added to the remaining ultrapure water and then premixed for 30 minutes at a speed of 600 rpm / min using a homogenizer (D-51580 Reichshof, VMA-G ETZMANN GMBH, Germany). mixing was carried out to sufficiently predisperse the pigment aggregates. Subsequently, zirconium beads were added to the premix and dispersed for 30 minutes under conditions of input power AC 220V, 60 Hz using a paint shaker (Daecheon Industry Co., Ltd.). The visual observation of the dispersion state of the pigment particles in the dispersion was found to be very homogeneous.

Comparative Example 1

20% by weight blue pigment powder (fastblue 15: 3, Sun Chemical, Japan), 10% by weight dispersant (PROX ^R A300 PROTEX-INTERNATIONAL, France), defoamer (BYK-019: BYK-024 = 3: 2 mixture) 0.2 % By weight and 5% by weight of thickener are added to the remaining ultrapure water and then pre-mixed for 30 minutes using a homogenizer (D-51580 Reichshof, VMA-G ETZMANN GMBH, Germany) at a speed of 600 rpm / min. ), The pigment aggregate was sufficiently predispersed. Subsequently, zirconium beads were added to the premix and dispersed for 30 minutes under conditions of input power AC 220V, 60 Hz using a paint shaker (Daecheon Industrial Co., Ltd.). When the dispersion was allowed to stand, layer separation occurred.

Dispersion Polyurethane and Application Test

Example 6

70% by weight of the water-dispersed polyurethane and 30% by weight of the water-dispersible pigment prepared according to the above example were mixed and then applied to a release paper. The water-dispersed polyurethane coated on the release paper was placed in an oven and allowed to stand to dry the polyurethane. After the polyurethane was dried, the upper polyurethane was separated from the release paper, and then the surface of the separated polyurethane was observed. Surface properties are shown in the table below.

Dispersed Polyurethane by Color Surface stickiness surface Example 1 none Clean Example 2 none Clean Example 3 none Clean Example 4 none Clean Example 5 Slightly sticky With pinhole

According to the present invention, a novel water-disperse pigment system has been implemented which, in contrast to the organic pigment system, has improved environmental problems. The water-disperse pigment system includes poloxylene, thereby providing a pigment system having good dispersibility and shelf life and improved compatibility with polyurethane.

Claims (5)

a) organic or inorganic pigment combinations on one paper; b) polyethylene-polypropylene glycol having an average molecular weight of 1,000 to 15,000; c) dispersants useful for preparing aqueous pigment dispersions; d) water; And e) water-disperse pigment compositions, if necessary, consisting of additives. a) 5 to 70% by weight of one or more organic or inorganic pigments, b) 1 to 50% by weight polyethylene-polypropylene glycol having an average molecular weight of 1,000 to 15,000, c) 2 to 25 weight percent dispersant, d) 5 to 80% by weight of water, and e) A water dispersion pigment composition consisting of 0 to 20% by weight additive. The water dispersion pigment composition according to claim 1 or 2, wherein the polyethylene-polypropylene glycol is poloxylene. The water dispersion pigment composition of claim 1 for use in a water dispersion polyurethane. The water dispersion pigment composition according to claim 4, wherein the water dispersion polyurethane is a water dispersion polyurethane for leather.