EP2499202A2

EP2499202A2 - Solid preparations

Info

Publication number: EP2499202A2
Application number: EP10776085A
Authority: EP
Inventors: Sascha Oestreich; Ronald Klagge; Shailesh C. Shah; Harald Frommelius; Thomas Schliwka
Original assignee: Cognis IP Management GmbH
Current assignee: Cognis IP Management GmbH
Priority date: 2009-11-09
Filing date: 2010-11-02
Publication date: 2012-09-19
Also published as: US20120227626A1; CN102686678A; WO2011054492A2; WO2011054492A3; CN102686678B

Abstract

The invention relates to nonionic surfactants, selected from the group consisting of (a) the addition products of 1 to 40 mol alkylene oxide per mol allyl alcohol, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide, and (b) the addition products of 1 to 40 mol alkylene oxide per mol allyl alcohol, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and styrene oxide, wherein the OH group of these addition products is end-capped in the sense that it is replaced by a group OR, where R is an alkyl radical with 1 to 20 carbon atoms, which can be saturated or non-saturated, straight-chained or branched. Said surfactants are suitable as dispersants in the production of solids preparations, in which one or more solids are dispersed in a liquid medium.

Description

"Solid formulations"

Field of the invention

The invention relates to solid preparations comprising (i) a liquid carrier medium, (ii) one or more solids and (iii) a dispersant, wherein the dispersant is a specific nonionic surfactant.

State of the art

Formulations of solids in a liquid carrier medium play a major role in the various technical fields. These are used, for example, in the production and processing of paints, printing inks, paper, leather and textile dyes, pastes, pigment concentrates, ceramics and cosmetic preparations. Also in the production or processing of casting and molding compositions based on synthetic, semisynthetic or natural polymers, preparations of solids, such as pigments and / or fillers, are used. For example, solid preparations are also used in the production of casting compounds, PVC plastisols, gel coats, polymer concrete, printed circuit boards, industrial coatings, wood and furniture coatings, vehicle paints, marine paints, anti-corrosion paints, can and coil coatings, painter and builder paints. wherein customary known binders and / or solvents, pigments and, if appropriate, fillers, dispersants and other customary auxiliaries are mixed with the solids. Surfactants are frequently used as dispersants. These surfactants are usually nonionic or anionic in nature. The literature describes a large number of different surfactant dispersants. The dispersants act as surfactants wetting the particles to be dispersed and facilitate the breaking up of agglomerates. The dispersants also have a stabilizing effect on the resulting dispersions and prevent re-agglomeration or flocculation of the solid particles. Of particular importance are dispersants, for example for the dispersion of pigments and fillers in the production of printing inks, paints and coatings.

When surfactant dispersants are used, however, unwanted foaming often occurs during the dispersion process. As a rule, this foam development is attempted by the additional use of strong defoamers (for example regrind defoamers). Unfortunately, these strong defoamers in the process chain can lead to undesirable effects (cratering, pinholes, etc.).

Pigment concentrates are prepared by opening pigments with the aid of shearing machines in a liquid carrier medium and finely distributed so that the pigment is permanently present in the form of the primary particles. Suitable shearing machines are known to the person skilled in the art.

Because of the importance of dispersing for the paint, coatings and printing ink industry, both the dispersing process and the low molecular weight and higher molecular weight compounds suitable for stabilizing the primary particles are described in detail in the specialist literature. From the known state of the art, no teaching can be derived for the targeted selection of additives which effectively support the formulation of pigment concentrates, especially if these pigment concentrates are to allow the production of low-emission, or even emission-free, inks or inks, or if they are to be free of ecological or ecotoxicologically questionable substances.

A particular difficulty is the formulation of aqueous pigment concentrates, especially if this is to take place without the addition of low molecular weight cosolvents such as ethylene glycol or propylene glycol. So, as the expert knows, so-called Although pigment dispersers based on polyphosphates or polyacrylates are eminently suitable for retaining pigments and fillers in addition to the latex particles stabilized by dispersants or protective colloids in emulsion paints, they are not suitable for producing pigment concentrates having the above-described requirement profile.

Most dispersants, which are excellently suitable in organic carrier oils of different polarity, fail when water is selected as the continuous phase for the pigment concentrates. Good pigment-wetting surfactant dispersants such as alkylphenol polyglycol ethers, in turn, have recently come into ecological discussion with regard to their biodegradability, both in the detergents and cleaners industry, where they are already completely replaced as surfactants in Germany, as well as in the emulsions. Polymerization, d. H. in the production of aqueous binders for emulsion paints.

Further aggravating the choice of additives for the formulation of pigment concentrates is that the dispersing additive must be selected such that, largely independently of the carrier oil, the viscosity of the continuous phase decreases with increasing shear, i. H. structurally viscous and in no case may be dilatant.

Care must be taken in the formulation of the pigment concentrates that a specially balanced balance between water retention and hygroscopy must be set, such that the self-drying of the concentrate is greatly delayed. Dried pigment concentrates should be easily redispersible. On the other hand, water retention and hygroscopicity must not be so high that the finished paint becomes water sensitive. Other useful properties of the finished paint such as freeze / thaw Stabüität, storage stability, shear stability may not be negatively affected as well as properties of the cured film, eg. Clarity, gloss or resistance to whitening.

Another requirement that is to be met by the present invention to be developed pigment concentrates, is that compatibility must be given with a wide range of binders and basecoats, but also with both water and with the different solvents used in paints, as well as with The silicate paints used high alkaline water glasses.

For the preparation of aqueous solid preparations, e.g. Pigment pastes or pigment concentrates, surfactants are often used. These surfactants are usually nonionic or anionic in nature. The literature describes a large number of different surfactant dispersants.

A common problem associated with the use of surfactant dispersants is the appearance of foam during the dispersion process. One tries to prevent the occurrence of foam by the use of strong defoamers. Often, the use of these so-called Mahlgutentschäumer associated with other problems in the process chain. It is therefore desirable to provide surface-active dispersing aids which exhibit a low foam tendency and nevertheless permit the formulation of stable solid preparations.

Description of the invention

The present invention was based on the object, effective additives for the production of solid preparations, in which one or more solids in a Are dispersed in a liquid medium, in particular aqueous pigment concentrates, and provide the thereby accessible pigment concentrates themselves, which meet the variety of the above criteria with respect to the desirable property profile of such additives or the pigment concentrates themselves.

In particular, it has been an object of the present invention to provide surface-active dispersants exhibiting low foaming tendency and making the formulation more stable, in view of the above-described problems associated with the production of solid preparations, especially aqueous pigment concentrates Allow solid preparations. In particular, these dispersants should have a positive influence on the viscosity of the solid preparations produced. Furthermore, the pigment concentrates prepared using these dispersants should be characterized by an increased color intensity in inks of white color, be well compatible with the base color and not flocculate.

The present invention is the use of nonionic surfactants selected from the group

(A) the addition products of 1 to 40 moles of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide and

(B) the addition products of 1 to 40 moles of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group of ethylene oxide, propylene oxide, butylene oxide and styrene oxide, wherein the OH group of these addition products is end-capped in the sense that it is replaced by a group OR where R is an alkyl radical having 1 to 20 C atoms, which may be saturated or unsaturated, straight-chain or branched,

as dispersants in the preparation of solid preparations in which one or more solids are dispersed in a liquid medium. In a preferred embodiment, the present invention relates to the use of the dispersants (a) and / or (b) as additives for the preparation of aqueous pigment concentrates. The amount of the dispersants (a) and / or (b) to be used according to the invention depends, on the one hand, on the nature of the dyes to be dispersed and, on the other hand, on the amount of dyes to be dispersed. Preference is given to the compounds (a) and / or (b) in an amount of 0.1 to 20 wt .-% - based on the total pigment concentrate - a.

The dispersants to be used according to the invention are distinguished to a very particular extent by reducing foaming during the dispersion process and positively influencing the viscosity of the solid preparations produced. Furthermore, aqueous pigment concentrates produced in this way are characterized in that they lead to increased color intensity during use.

Another subject of the invention are solid compositions containing

(i) a liquid carrier medium,

(ii) one or more solids and

(iii) a dispersant,

with the proviso that the dispersant used is a nonionic surfactant which is selected from the group

(B) the addition products of 1 to 40 moles of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group of ethylene oxide, propylene oxide, butylene oxide and styrene oxide, wherein the OH group of these addition products is end-capped in the sense that it is replaced by a group OR is where R is an alkyl radical having 1 to 20 C atoms, which may be saturated or unsaturated, straight-chain or branched.

In one embodiment, the solid preparations contain

15 to 85% by weight of a liquid carrier medium (i),

10 to 80% by weight of one or more solids (ii) and

0.1 to 20% by weight of a dispersant (iii) from the group of compounds (a) and (b). In a preferred embodiment, the compounds (ii) are pigments. With regard to the selection of the pigments (ii), there are no limitations in the context of the present invention per se. As is known to those skilled in the art, pigments are particulate organic or inorganic substances which are practically insoluble in solvents or binders and which may be either coloring or matting themselves. Many inorganic pigments also function as fillers and vice versa. Examples of particularly common classes of pigments can be found in the relevant specialist literature.

Liquid carrier media (i) - such as organic carrier oils or water - are known in the art. In a preferred embodiment, the liquid carrier medium (i) is water and the solids (ii) are pigments. In this case, it is therefore an aqueous pigment concentrates.

The present invention further relates to a process for the preparation of aqueous, at 25 ° C pumpable and flowable solid preparations, in particular aqueous pigment concentrates, wherein a nonionic surfactant which is selected from the group (A) the addition products of 1 to 40 moles of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide and

(b) the addition products of from 1 to 40 mol of alkylene oxide per mole of allyl alcohol, the alkylene oxide being selected from the group of ethylene oxide, propylene oxide,

Butylene oxide and styrene oxide, wherein the OH group of these addition products is end-capped in the sense that it is replaced by a group OR, wherein R is an alkyl radical having 1 to 20 carbon atoms, which may be saturated or unsaturated, straight-chain or branched,

mixed with water, added to the resulting mixture, the solid and this dispersed.

By "pumpable and free-flowing at 25 ° C" is meant that the viscosity of the solid preparations at 25 ° C below 20,000 mPas, preferably below 5,000 mPas (cone / plate l ° cone, d = 40mm, shear rates would be: 10 s ^"1 , Malvern Instruments).

When the solid is dispersed, there are no particular limitations on the way in which the dispersion is technically accomplished. Thus, the person skilled in the art can fall back on all techniques of dispersion known to him. In particular, he will resort to methods in which shear and / or grinding forces act intensively on the system.

The desired fine adjustment of fineness and consistency of the dispersion can be influenced in the process according to the invention by various techniques, for example by the type of stirrer or mixing aggregate, further by the amount of added dispersant (a) and / or (b). A further process for the preparation of the solid preparation according to the invention comprises first dry-mixing a pigment with the dispersants (a) and (b), resulting in a pulverulent solid preparation. If necessary, this can be dispersed in water in a second step to give the aqueous solid preparation according to the invention.

Solids for the purposes of this invention may be inorganic or organic solids. Preferred solids are pigments, for example titanium dioxide, carbon black, iron oxides, organic pigments, phthalate etc.

If desired, additional further dispersing aids which are different from the compounds (a) and (b), such as, for example, polyacrylate, polyurethane or polyether derivatives, can be used to prepare the aqueous solid preparations according to the invention.

The dispersants according to the invention can be used both alone and in combination with other nonionic, anionic or cationic dispersants. Addition products of 1 to 50 mol of ethylene oxide or propylene oxide with fatty alcohols are preferred here.

The solid preparations prepared with the aid of the dispersants according to the invention can be used in a large number of applications. Examples include colors, paints, printing inks, textile dyes, paper coating, ceramics and molding and molding compounds. The applications may be aqueous and / or solvent-containing nature.

If desired, further auxiliaries, such as defoamers, condensates, can be used in the preparation of the solid-state preparations according to the invention, especially aqueous ones. Serving aids, wetting agents, deaerators or the prior art appropriate anti-setting agents, waxes or rheology additives.

To the compounds (a

The compounds (a) are addition products of 1 to 40 mol of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group of ethylene oxide, propylene oxide, butylene oxide and styrene oxide.

To the compounds (b)

The compounds (b) are addition products of from 1 to 40 mol of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group of ethylene oxide, propylene oxide, butylene oxide and styrene oxide, wherein the OH group of these addition products is end-capped in the sense in that it is replaced by a group OR, where R is an alkyl radical having 1 to 20 C atoms, which may be saturated or unsaturated, straight-chain or branched.

Alkylene oxide units

The compounds (a) and (b) to be used according to the invention comprise alkylene oxide units (AO) as structural elements, namely ethylene oxide (EO), propylene oxide (PO), butylene oxide (BuO) and styrene oxide (StO).

It should be noted that each of the AO structural elements can be composed both exclusively of EO-, and exclusively of PO-, and exclusively of BuO-, as well as exclusively of StO building blocks, as well as EO-, PO-, BuO and StO blocks in mixed form, block by block or statistically distributed, may contain. Such compounds (a) and (b) containing EO and / or PO building blocks as AO structural elements are preferred in the context of the present invention.

The compounds from group (a) and (b) to be used according to the invention can be used as sole dispersants (primary dispersants) in the preparation of solid preparations, such as e.g. aqueous pigment concentrates are used. However, it is also possible to use them together with one or more anionic, cationic or other nonionic dispersants other than compounds (a) and (b).

The dispersants of group (a) and (b) to be used according to the invention are used in an amount of from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5% by weight. the wt .-% - data are in each case based on the total amount of the solid preparations - used.

In a further embodiment, the solid preparations according to the invention - in particular pigment concentrates - in addition to the obligatory constituents a), b) and c) additionally contain 0.1 to 30 wt .-% of one or more co-additives from the group of polyethylene glycols and polyglycol ethers (obtainable by ethoxylation of 1,2- or 1,3-propanediol, 1,2- or 1,4-butanediol, hexanediol, glycerol, trimethylolpropane or pentaerythritol), these compounds having a molecular weight in the range from 200 to 1000, preferably 200 to 600 should have.

The solid preparations according to the invention-in particular pigment concentrates-may contain, in addition to the stated obligatory constituents a), b) and c), further ingredients which are customary in pigment concentrates. Examples include defoamers, preservatives, anti-drying retardants and anti-settling agents. The pigment concentrates of the invention are suitable for coloring paints, z. B. by the handyman or by the expert in paint banks, or even the producer of the paints. However, the pigment concentrates according to the invention can likewise be used for coloring other paints or coatings, such as printing inks, leather finishes, wallpaper paints, wood stains, wood protection systems and wood stains, overprint varnishes or air- or oven-drying industrial coatings, and for pigmenting colored pencil leads, felt pens, ink jet Inks, fountain pens, pen pens, shoe polishes, nonwoven webbings, paper wipes and pulp colourants, cardboard inks, spin dyes and foils.

B e i s p e e l e

Substances used

FA-IOEO: Addition product of 10 mol of ethylene oxide to a fatty alcohol (Disponil LS 30, Cognis)

Breox I: ethylene oxide adduct of allyl alcohol (Breox AA E 450 H, Cognis)

DM-V: "Hydropalat 1080" from Cognis (commercial dispersant mixture for comparison)

Dehydran 1650: commercially available defoamer (Cognis)

AMP: 2-amino-2-methyl-1-propanol (Angus); is used to adjust the pH

DM-E (dispersant mixture according to the invention): was prepared by mixing 455 g of FA-10EO and 195 g of Breox I with the addition of water (active substance content of the mixture = 80% by weight).

application testing

The data in Tables a) and b) are parts by weight. a fiction, solid preparations:

The dispersion of the components took place first in the so-called premix and then over 60 min in a Skandex mixer with 3 mm beads (1: 1). b non-inventive solid preparations:

The dispersion of the components takes place first in the so-called. Premix and then over 60min in a Skandex mixer with 3mm beads (1: 1).

Test results:

Foaming behavior:

Foaming behavior was visually evaluated after the dispersion process

(5 = very good, 1 = very bad): c) solid preparations according to the invention: d) non-inventive solid preparations: viscosities:

The viscosities were measured using a CVO 100 rotary viscometer from Bohlin at 25 ° C. (cone / plate 1 ° cone, d = 40 mm, shear rate specification: 1-1000 s ^-1 , from Malvern Instruments) after storage for 1 day Room temperature, after storage for 2 weeks at 40 ° C. and after storage for 4 weeks at 40 ° C. The viscosity data in tables e) and f) are in mPas e viscosities of the solid preparations according to the invention:

f) Viscosities of non-inventive solid preparations:

evap. = thickened

Gloss, color intensity and rub-out:

The solid preparations were dissolved with a paint of the following formulation (in parts by weight):

Paintwork, white, high gloss

1. 1, 2 propylene glycol 2.10

2. Add ethyl diglycol 3.70 with stirring:

3. AMP 0.23 (1)

4. Dehydran 1293 0.30 (x)

5. Demineralized water 8,00

6. Hydropalate 3275 1.20 (x)

7. Tioxide R-HD-2 23.00 (2), particle size: <ΙΟμηι

(Dissolver, without beads, approx. 30min)

8. DSX 1514 0.70 (x)

9. NeoCryl XK-90 56,00 (3)

10. Dehydran 1293 0.70 (x)

11. Demineralized water 4.07

It means:

(x) Cognis GmbH, Dusseldorf;

(1) Angus Chemie GmbH, Essen;

(2) Tioxide Europe GmbH, Ratingen;

(3) NeoResins, AC Waalwijk (NL) For varnishing, 95g of paintwork (white) were mixed with 5g of the solid preparations. Subsequently, the color obtained with a paint dumbbell (150 μπι, wet) was applied.

I V1 l V2 | V3 l V4 V5 | V6 l V7 | V8 | V9 l V10

The gloss was measured using a Micro-tri-gloss from Byk-Gardner Instruments.

The colorimetry was measured with an X-rite SP64 Spetralphotometer (measurement geometry d / 8 °) from the company X-rite.

To determine the so-called rub-out, the lower third of the color film was rubbed 5 minutes after application until it was almost dry or the pigment no longer separated by viscostats. After final drying, delta E (total color separation) and delta L (brightness difference) between rubbed and unexposed areas were measured.

It was found that the solid formulations according to the invention had lower foaming and lower viscosities. Gloss and color strength development were not adversely affected. The solid preparations according to the invention also showed a reduced rub-out.

Claims

claims

1. Use of nonionic surfactants selected from the group (a) of the adducts of 1 to 40 moles of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide and (b) the adducts of 1 to 40 moles of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group of ethylene oxide, propylene oxide, butylene oxide and styrene oxide, wherein the OH group of these addition products is end-capped in the sense that it is replaced by a group OR, wherein R is an alkyl radical 1 to 20 carbon atoms, which may be saturated or unsaturated, straight-chain or branched, as dispersants in the preparation of solid preparations in which one or more solids are dispersed in a liquid medium.

2. Use according to claim 1, wherein the liquid medium is water.

3. Use according to claim 2, wherein pigments are used as the solid.

4. Solid preparations containing (i) a liquid carrier medium, (ii) one or more solids and (iii) a dispersant, with the proviso that the dispersant used is a nonionic surfactant selected from the group (a) Addition products of 1 to 40 moles of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group of ethylene oxide, propylene oxide, butylene oxide and styrene oxide and (b) the addition products of 1 to 40 moles of alkylene oxide per mole of allyl alcohol, wherein the alkylene oxide is selected from the group Ethylene oxide, propylene oxide, butylene oxide and styrene oxide, wherein the OH group of these addition products is end-capped in the sense that it is replaced by a group OR, where R is an alkyl radical having 1 to 20 carbon atoms, which is saturated or unsaturated, straight-chain or branched can be.

5. Preparations according to claim 4, wherein the liquid medium is water.

6. Preparations according to claim 5, wherein pigments are used as the solid.

7. Preparations according to one of claims 4 to 6, wherein in addition to the dispersants (iii) which are selected from the group of compounds (a) and (b) according to claim 4, one or more further dispersants used by the compounds (a) and (b) are different.

8. A process for the preparation of aqueous, at 25 ° C pumpable and flowable solid preparations, especially aqueous pigment concentrates, wherein a nonionic surfactant selected from the group (a) of the addition products of 1 to 40 moles of alkylene oxide per mole of allyl alcohol in which the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide and (b) the adducts of from 1 to 40 moles of alkylene oxide per mole of allyl alcohol, the alkylene oxide being selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide, wherein the OH group of these addition products is end-capped in the sense that it is replaced by an OR group, where R is an alkyl radical having 1 to 20 C atoms, which may be saturated or unsaturated, straight-chain or branched, mixed with water, to the solid mixture is added to the resulting mixture and dispersed.

The method of claim 8, wherein the liquid medium is water.

10. The method according to claim 9, wherein the solid is used pigments.

1 1. A process according to any one of claims 8 to 10, wherein, in addition to the nonionic surfactant selected from the group of compounds (a) and (b) according to claim 8, one or more further dispersants used by the compounds ( a) and (b) are different.