Non-ionic thickeners for pigment compositions, in particular for paints and applications thereof

TECHNICAL SECTOR OF THE INVENTION

[0001] The present invention relates to the technical sector of pigmentary compositions and in particular pigmentary compositions for paints and similar compositions, and still more precisely the pigmentary bases for paint intended for colouring.

TECHNICAL PROBLEM POSED

[0002] In the field of many pigmentary compositions, but more especially in that of pigmentary compositions and bases for paint, the Theological profile of the composition or of the base plays a part, the base being the white-coloured aqueous composition containing a filler, the base of the coloured or pigmented pigmentary composition.

[0003] This white-coloured aqueous composition, containing a filler and/or pigmented, is formed from a liquid phase which can be water or an organic solvent miscible with water or else a mixture of the two, one or more polymers in suspension in the liquid phase called “binders”, fillers and/or pigments, at least one dispersing agent for the fillers and/or pigments which can be a hydrosoluble polymer or hydrosoluble copolymer, additives as diverse as coalescence agents, biocides, antifoaming agents or others, and finally at least one thickening agent which is a natural or synthetic polymer or copolymer.

[0004] The rheological profile is well known to persons skilled in the art, and is represented by the curve of the viscosity η as a function of the velocity gradient D.

[0005] Without duplicating what is known to persons skilled in the art, it will be indicated quickly that:

η(Pa·s)=Stress(Pa)/Gradient D (s−1)

[0006] The stress is a measure of the pressure applied to the composition or to the base (unless specifically indicated, the term “composition” will be used in the following to designate any composition, or any base for paint or the like, which is aqueous, containing a filler and/or pigmented, as defined above).

[0007] In the field of paints, the following must be obtained simultaneously (which represents the major difficulty):

[0008] good “dynamic” performance, that is to say low viscosity at large gradient (which in practice represents the requirement of low viscosity at application of the paint on the substrate, the application naturally implying a high shear stress)

[0009] and

[0010] good “static” performance, that is to say under storage conditions, which in practice amounts to desiring high viscosity (and other desired “in the pot” properties) which provides good storage and “pot life” conditions at small or medium velocity gradient.

[0011] One important quality of white pigmentary compositions is judged when, precisely, its coloured pigmentary component is added to it. As a general rule, the intensity of the colour of the composition is increased when the pigment concentration is increased.

[0012] However, a significant problem appears in the presence of shear stress, that is to say very precisely under the conditions of application of a paint to its substrate, since a dissociation of the pigment or pigments from the remainder of the composition can occur. Persons skilled in the art call this characteristic “colour acceptance”, which here will be called “pigmentary compatibility” of the composition concerned.

[0013] In practice, if the final paint composition (and/or the base for paint referred to as “white base” since it does not yet contain the coloured pigment or pigments) has an inadequate pigmentary compatibility, application will bring about a dissociation or heterogeneity of the composition, and therefore different colour density areas, for example streaks which are less dense in terms of colour, which is obviously not the aim sought.

[0014] The invention therefore aims to propose white bases and/or pigmentary compositions for paint (together below, including in the claims, as already indicated, “compositions”) having very good compatibility with the pigmentary colourants, on both matt paints and silk finish paints.

[0015] The invention aims in particular to supply compositions which provide excellent pigmentary compatibility and have a high viscosity at small and medium shear stress gradient also referred to as velocity gradient, on both matt paints and silk finish paints, that is to say in particular in a field of velocity gradient D lying between:

[0016] 0 and 20 s−1 approximately (“small” velocity gradient)

[0017] and

[0018] 100 s−1 approximately (“medium” velocity gradient).

[0019] White bases contain, as known to persons skilled in the art, fillers such as carbonates, in particular calcium carbonates, a titanium oxide, kaolin, and well-known similar fillers, usable according to the invention.

[0020] Pigmentary colourants are also well known to persons skilled in the art, and are for example chosen from amongst carbon black, phthalocyanine blue, iron oxides (which give yellow, red. etc tones), and diazo salts.

[0021] The carrying out is also known of a simple and practical test, referred to as a “test of rubbing with the finger”, known to persons skilled in the art by the term “rub out” which will be used hereinafter. This test correctly reproduces the shear stress brought about by application with a brush or the like.

[0022] The test consists of applying a coat of paint to a substrate with no shear stress, that is to say slowly and with no stress, and then of applying shear stress by a rotary movement of a finger applied to the said coat of paint.

[0023] If the composition has a good or very good pigmentary compatibility, the colour intensity on the area rubbed by the finger will remain constant or “homogeneous” compared with the non-rubbed area; in the contrary case, the rubbed area will have a heterogeneity of colour intensity compared with the non-treated area.

[0024] This heterogeneity will be expressed by a colorimetric difference measured by means of a spectrocolorimeter called Spectro-pen™.

Prior Art

[0025] To date, compositions effective at small velocity gradient are known, but in acrylic copolymer chemistry, referred to as ionic thickeners, as opposed to the so-called non-ionic thickeners.

[0026] Their major drawback is the fact that the formulation must be made at a pH higher than 7 since the acrylic thickeners must be neutralised in order to be effective.

[0027] Another drawback lies in the fact that the introduction of the said acrylic thickeners into an aqueous paint reduces the water resistance of the said paints.

[0028] Yet another drawback is the fact that these products have a low propensity for spreading, which is obviously a serious drawback in the field of paints and similar products.

[0029] Finally, the acrylic associative polymer type products are highly sensitive to salts. Polyurethane thickeners are also known which make it possible to obtain, in an aqueous paint, high viscosities at large velocity gradient but which are not capable of developing high Brookfield™ viscosities.

[0030] Generally these products are functionalised with short hydrocarbon chain ends, that is to say ones having fewer than 14 carbon atoms. These compounds have the advantage of retaining a certain pigmentary compatibility but do not allow high Brookfield™ viscosities to be obtained at small shear stress gradient.

[0031] Moreover, polyurethanes developing high Brookfield™ viscosities at small shear stress gradient are known (Synthesis and Characterization of Model Associative Polymers, Richard D. Jenkins, David R. Bassett, Cesar A. Silebi and Mohamed S. El-Aasser, J. of Applied Polymer Science, vol. 58, p 209-230 (1995); Polymeric Mat. Sci. and Engineering, vol. 59, p 1033 (1988); Polymeric Mat. Sci. and Engineering, vol. 61, p 533 (1989); Polymeric Paint Colour Journal, vol. 176, n° 4169, p 459 (June 1986)).

[0032] It has now been demonstrated that the greater the increase in the number of carbon atoms present in the hydrocarbon chains functionalising the polyurethane chains, the greater the increase in the Brookfield™ viscosities at small shear stress gradient.

[0033] These said polyurethanes, providing high Brookfield™ viscosities at small shear stress gradient, have the major drawback of dramatically reducing pigmentary compatibility in the aqueous formulations into which they are introduced.

[0034] As it has been said, the invention aims in particular to supply compositions which provide an excellent pigmentary compatibility and have a high viscosity at small and medium shear stress gradient, on both matt paints and silk finish paints, and do not have the drawbacks connected with the use of so-called ionic acrylic copolymers, namely the obligation of making the formulation at a pH greater than 7, their low water resistance, or their low propensity for spreading, or finally their very high sensitivity to salts.

[0035] The invention therefore aims to solve a particularly difficult problem often encountered by the user.

[0036] There therefore exists an important and recognised requirement for non-ionic thickeners which would make it possible to prepare “compositions” (in the general sense given above, and especially white bases, in particular for paint) having simultaneously a high Brookfield™ viscosity at small shear stress gradient and an excellent pigmentary compatibility, on both matt paints and silk finish paints.

[0037] At present no product exists combining these two qualities simultaneously on both matt paints and silk finish paints.

[0038] As will be seen below, the invention not only provides a solution to this problem, but in addition proposes thickeners which are better thickeners than those of the prior art.

[0039] The invention relates in its general principle to molecules which are thickeners having the above properties, and which are of the type of a polymer with an alkylene oxide chain, in particular an ethylene oxide (EO) chain or an ethylene oxide and propylene oxide (PO) chain, characterised in that they are based on polyisocyanate units and in particular diisocyanate units and have, at the chain end, hydrocarbon groups themselves having at least three aromatic cycles, substituted or not.

[0040] Of course thickeners having hydrocarbon groups at the chain end are already known, these groups having fairly large chain lengths and sometimes aromatic or cyclic groups, but the invention has been able to define the above selection criteria.

[0041] These thickeners are non-ionic.

DETAILED DESCRIPTION OF THE INVENTION

[0042] The invention relates in particular to thickeners fitting the formula (I) below:

R—O—(OE)x—(OP)y—(OE)z—O—DI—(—PEG—DI—)n—O—(OE)x′—(OP)y′—(OE)z′—O—R′

[0043] in which:

[0044] DI is a diisocyanate group such as toluene diisocyanate, isophorone diisocyanate or hexaamethylene diisocyanate;

[0045] PEG is a polyethylene glycol group of molecular weight ranging from 6,000 to 20,000;

[0046] n is between 1 and 40;

[0047] x, z, x′, z′ are between 1 and 40;

[0048] y, y′ are between 0 and 40;

[0049] with x+y+z+x′+y′+z′ between 2 and 80.

[0050] According to one preferred embodiment, the molecular weight of the PEG is between 6,000 and 15,000, preferably close to 10,000.

[0051] According to yet another preferred embodiment, n is close to 1.

[0052] According to yet another preferred embodiment, x+y+z+x′+y′+z′ is between 2 and approximately 50 with y=y′=z=z′=0.

[0053] According to one altogether preferred embodiment, x=x′=1.3.

[0054] According to one altogether preferred embodiment, n=x=x′=1 and y=y′=z′=0.

[0055] R or R′ are hydrocarbon groups having at least three aromatic cycles, substituted or not, and are different or identical.

[0056] It should be noted that the associative polymers, known in the prior art, are not suitable: for example, a product functionalised with a group having 8 carbon atoms, which is a pure associative, certainly gives a suitable pigmentary compatibility, but it is not a suitable thickener, and by a long way, at small or medium shear stress gradient.

[0057] Furthermore, if an attempt is made to increase the chain length beyond 8 carbon atoms, the viscosity at small or medium gradient is indeed increased, which was foreseeable, but the pigmentary compatibility is progressively lost.

[0058] The invention therefore carries out a selection which is well defined in terms of both chemical definition and surprising properties.

[0059] According to one preferred embodiment, the R group will be a tristyrylphenyl (TSP) group with formula:

[0060] with x+x′+y+y′+z+z′ between 2 and 80.

[0061] According to another preferred embodiment, the R group will be a distyrylphenyl (DSP) group with formula:

[0062] According to yet another embodiment of the invention, the R group is substituted.

[0063] The substituents of the R group are preferably chosen from amongst the following groups: phenyls, benzyls or alkyls, linear or branched, having any number whatsoever of carbon atoms.

[0064] According to yet another preferred embodiment, the said substituent or substituents are disposed on the aromatic groups, themselves possibly substituted.

[0065] According to one altogether preferred embodiment, one of the phenyl groups of the TSP group is itself substituted by at least one phenyl group.

[0066] One advantageous case according to the invention is the one where one of the styryl groups of the TSP group is itself substituted by a styryl group, the R group then being a tetrastyrylphenyl group.

[0067] The case where the TSP is substituted on a phenyl by a cyclohexanyl group has already been mentioned above.

[0068] The invention also relates to the use of the compound according to the invention as a thickener of aqueous compositions, containing a filler and/or pigmented, white or coloured.

[0069] Finally, the invention relates to aqueous compositions, containing a filler and/or pigmented, white or coloured, containing the thickening compound according to the invention.

[0070] The thickening compound according to the invention is introduced into the said compositions at the rate of 0.1% to 2.0%, preferentially at the rate of 0.2% to 1.0%, a quantity expressed as a percentage by dry weight with respect to the total mass of the composition.

[0071] The aqueous compositions, containing a filler and/or pigmented, white or coloured, according to the invention are characterised in that they contain the thickening copolymer according to the invention, preferably at the rate of 0.1% to 2.0%, and very preferentially at the rate of 0.2% to 1.0%, a quantity expressed as a percentage by dry weight with respect to the total mass of the composition.

[0072] In the field of paints, the Brookfield™ viscosity measurements, well known to persons skilled in the art, are commonly used.

[0073] The measurements at “small” shear stress gradient correspond to velocities of the apparatus set at 10 and 100 revolutions/minute.

[0074] These various Brookfield™ viscosity measurements are performed after 24 hours of storage at rest, 1 week of storage at rest and 1 month of storage at rest.

[0075] Measurement of the Stormer viscosity (expressed in Krebs Units “KU”) is also used. These measurements are also well known to persons skilled in the art. This Stormer viscosity applies to the measurements at “medium” shear stress gradient.

[0076] Industry is interested firstly by a viscosity as high as possible at small shear stress gradient (pot life), and low at large gradient (application). The most important measurement will therefore be the Brookfield™ viscosity at 10 revolutions/min.

[0077] However, for certain special paints, it is advantageous to have a Stormer viscosity as high as possible (therefore at medium gradient).

[0078] The aqueous compositions, containing a filler and/or pigmented, white or coloured, according to the invention are characterised in that they contain the thickening copolymer according to the invention, preferably at the rate of 0.1% to 2.0%, and very preferentially at the rate of 0.2% to 1.0%, a quantity expressed as a percentage by dry weight with respect to the total mass of the composition, and in that the value of the sum of the notations (ΔEmatt+ΔEsilk+ηmatt+ηsilk) is greater than or equal to 3 and very preferentially equal to 4, with the following notations, namely:

[0079] for the matt formulations; the values:

[0080] +1, if the Brookfield™ viscosity after 24 hours (denoted ηmatt) at 10 rev/min. is greater than or equal to 3,000 mPa·s,

[0081] 0, if the Brookfield™ viscosity after 24 hours (denoted ηmatt) at 10 rev/min. is between 800 inclusive and 3,000 mPa·s exclusive,

[0082] −1, if the Brookfield™ viscosity after 24 hours (denoted ηmatt) at 10 rev/min. is less than 800 mPa·s, and

[0083] +1, if ΔEmatt<1

[0084]

0
, if ΔEmatt is between 1 and 2 inclusive

[0085] −1, if ΔEmatt>2

[0086] for the silk finish formulations, the values:

[0087] +1, if the Brookfield™ viscosity after 24 hours (denoted ηsilk) at 10 rev/min. is greater than or equal to 2,000 mPa·s,

[0088] 0, if the Brookfield™ viscosity after 24 hours (denoted ηsilk) at 10 rev/min. is between 800 inclusive and 2,000 mPa·s exclusive,

[0089] −1, if the Brookfield™ viscosity after 24 hours (denoted ηsilk) at 10 rev/min. is less than 800 mPa·s, and

[0090] +1, if ΔEsilk<1.5

[0091] 0, if ΔEsilk is between 1.5 and 3 inclusive

[0092] −1, if ΔEsilk>3

[0093] The determination of the value of Delta E (ΔE) of the matt or silk finish coloured aqueous formulation is performed by addition, to the white base, of 5% by weight black pigment, that is to say 10 g. of black pigment (COLANYL™ Black marketed by CLARIANT) in 190 g. of white paint.

[0094] This ΔE measurement test is the one already aforementioned and called “test of rubbing with the finger”, known to persons skilled in the art by the term “rub out”.

[0095] This test consists of applying with no shear stress, by means of a filmograph, 150 micrometers of the formulation of the coloured matt or silk finish paint to be tested onto a contrast card, that is to say slowly and with no stress, and of waiting 45 seconds and then applying shear stress by rubbing, with the finger, the still viscous film of paint, for thirty seconds in any place whatsoever.

[0096] After drying of the film, the colorimetric difference between the shear-stressed area (rubbed area) and the non-shear-stressed area (area of the non-rubbed film), determined by means of the spectrocolorimeter called Spectro-pen, makes it possible to evaluate (value of ΔE) whether or not the paint composition tested has a good pigmentary compatibility.

[0097] The invention will be better understood from a reading of the following description, and the non-limiting examples below.

EXAMPLE 1

[0098] The aim of this example is to reveal the Theological and pigmentary compatibility properties provided by the thickening agents according to the invention for matt formulations for paint, with solvent and at constant dosage.

[0099] These formulations for paints comprise the ingredients and additives listed in the first part of Tables 1a, 1b and 1c constituting the white base, and which persons skilled in the art will recognise.

[0100] In this first part of Tables 1a, 1b and 1c:

[0101] COATEX P 90 designates a polyacrylate type dispersant marketed by COATEX under the name COATEX P 90.

[0102] Byk 034™ designates an antifoaming agent marketed by BYK.

[0103] Monoethylene glycol is a coalescence agent.

[0104] The product Mergal K6N™ designates a biocide agent marketed by TROY.

[0105] The product TiO2 RL 68 is a titanium oxide marketed by MILLENNIUM.

[0106] The product Hydrocarb™ is a known fine filler of the natural CaCO3 type, marketed by OMYA.

[0107] The product Durcal™ is a coarser filler, also known, of the natural CaCO3 type, marketed by OMYA.

[0108] Rhodopas DS 910™ is a styrene-acrylic binder marketed by RHODIA.

[0109] The product “White spirit” is a well-known petroleum fraction which has a solvent function.

[0110] For each test, preparation was carried out of the aforementioned matt paint formulation, into which the thickening agent to be tested is added.

[0111] Then, for each of the tests, the Brookfield™ and Stormer viscosity measurements of the formulation obtained are carried out.

[0112] These Brookfield™ viscosity measurements are performed, by means of an RVT type Brookfield™ viscometer equipped with the appropriate mobile, on each of the samples representative of the different tests after 24 hours of storage at ambient temperature (denoted viscosity T=24 h), after 1 week of storage at ambient temperature (denoted viscosity T=1 week), after 1 week of storage in an oven at 50° C. (denoted viscosity T=1 week 50° C.), after 1 month of storage at ambient temperature (denoted viscosity T=1 month), and after 1 month of storage in an oven at 50° C. (denoted viscosity T=1 month 50° C.).

[0113] The Stormer viscosities expressed in Krebs Units (KU) are determined by means of a Stormer viscometer.

[0114] In the second part of Tables 1a, 1b and 1c, entitled pigmentary compatibility, the L and Delta E results appear.

[0115] L determined by the use of the Spectro-pen™ spectrocolorimeter measures the whiteness of the formulation applied on the contrast card. The closer the values get to 100, the poorer the compatibility is. This value appears only by way of illustration.

[0116] Test 1:

[0117] This test illustrates the prior art and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a well-known polyurethane based on the condensation product of an alcohol having 16 carbon atoms, toluene diisocyanate and polyethylene glycol of molecular weight equal to 10,000.

[0118] Test 2:

[0119] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0120] DI is isophorone diisocyanate;

[0121] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0122] n=1;

[0123] x=x′=1;

[0124] y=y′=z=z′=0;

[0125] R=R′=TSP.

[0126] Test 3:

[0127] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0128] DI is isophorone diisocyanate;

[0129] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0130] n=1;

[0131] x=x′=1.3;

[0132] y=y′=z=z′=0;

[0133] R=R′=TSP.

[0134] Test 4:

[0135] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0136] DI is isophorone diisocyanate;

[0137] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0138] n=1;

[0139] x=x′=5;

[0140] y=y′=z=z′=0;

[0141] R=R′=TSP.

[0142] Test 5:

[0143] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0144] DI is isophorone diisocyanate;

[0145] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0146] n=1;

[0147] x=x′=15;

[0148] y=y′=z=z′=0;

[0149] R=R′=TSP.

[0150] Test 6:

[0151] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0152] DI is isophorone diisocyanate;

[0153] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0154] n=1;

[0155] x=x′=25;

[0156] y=y′=z=z′=0;

[0157] R=R′=TSP.

[0158] Test 7:

[0159] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0160] DI is isophorone diisocyanate;

[0161] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0162] n=1;

[0163] x=x′=40;

[0164] y=y′=z=z′=0;

[0165] R=R′=TSP.

[0166] Test 8:

[0167] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0168] DI is isophorone diisocyanate;

[0169] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0170] n=1;

[0171] x=x′=15;

[0172] y=y′=z=z′=0;

[0173] R=R′=DSP.

[0174] Test 9:

[0175] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0176] DI is isophorone diisocyanate;

[0177] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0178] n=1;

[0179] x=x′=7;

[0180] y=y′=z=z′=0;

[0181] R=R′=DSP.

[0182] Test 10:

[0183] This test illustrates a field outside the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0184] DI is isophorone diisocyanate;

[0185] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0186] n=1;

[0187] x=x′=23;

[0188] y=y′=z=z′=0;

[0189] R=R′=linear alkyl chain with 12 carbon atoms.

[0190] Test 11:

[0191] This test illustrates a field outside the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0192] DI is isophorone diisocyanate;

[0193] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0194] n=1;

[0195] x=x′=25;

[0196] y=y′=z=z′=0;

[0197] R=R′=linear alkyl chain consisting of a fraction of 16 to 18 carbon atoms.

[0198] Test 12:

[0199] This test illustrates a field outside the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0200] DI is isophorone diisocyanate;

[0201] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0202] n=1;

[0203] x=x′=20;

[0204] y=y′=z=z′=0;

[0205] R=R′=linear alkyl chain with 18 carbon atoms.

[0206] Test 13:

[0207] This test illustrates a field outside the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0208] DI is isophorone diisocyanate;

[0209] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0210] n=1;

[0211] x=x′=25;

[0212] y=y′=z=z′=0;

[0213] R=R′=linear alkyl chain with 22 carbon atoms.

[0214] Test 14:

[0215] This test illustrates a field outside the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0216] DI is isophorone diisocyanate;

[0217] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0218] n=1;

[0219] x=x′=25;

[0220] y=y′=z=z′=0;

[0221] R=R′=branched alkyl chain with 32 carbon atoms.

[0222] Test 15:

[0223] This test illustrates a field outside the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0224] DI is isophorone diisocyanate;

[0225] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0226] n=1;

[0227] x=x′=30;

[0228] y=y′=z=z′=0;

[0229] R=R′=nonylphenyl group.

[0230] Test 16:

[0231] This test illustrates a field outside the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0232] DI is isophorone diisocyanate;

[0233] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0234] n=1;

[0235] x=x′=20;

[0236] y=y′=z=z′=0;

[0237] R=R′=abietate group.

[0238] Test 17:

[0239] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0240] DI is isophorone diisocyanate;

[0241] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0242] n=1;

[0243] x=z′=8.3;

[0244] x′=z=0;

[0245] y=y′=12.8;

[0246] R=R′=TSP.

[0247] Test 18:

[0248] This test illustrates a field outside the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0249] DI is isophorone diisocyanate;

[0250] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0251] n=1;

[0252] x=x′=6.4;

[0253] y=y′=z=z′=0;

[0254] R=R′=beta-naphthyl group.

[0255] Test 19:

[0256] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0257] DI is isophorone diisocyanate;

[0258] PEG is a polyethylene glycol of molecular weight equal to 6,000;

[0259] n=1;

[0260] x=x′=1.3;

[0261] y=y′=z=z′=0;

[0262] R=R′=TSP.

[0263] Test 20:

[0264] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0265] DI is isophorone diisocyanate;

[0266] PEG is a polyethylene glycol of molecular weight equal to 8,000;

[0267] n=1;

[0268] x=x′=1.3;

[0269] y=y′=z=z′=0;

[0270] R=R′=TSP.

[0271] Test 21:

[0272] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0273] DI is isophorone diisocyanate;

[0274] PEG is a polyethylene glycol of molecular weight equal to 20,000;

[0275] n=1;

[0276] x=x′=1.3;

[0277] y=y′=z=z′=0;

[0278] R=R′=TSP.

[0279] Test 22:

[0280] This test illustrates the invention and uses 0.57% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0281] DI is toluene diisocyanate;

[0282] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0283] n=1;

[0284] x=x′=1.3;

[0285] y=y′=z=z′=0;

[0286] R=R′=TSP.

[0287] All the Brookfield™ viscosity (at 10 and 100 rev/min.) and Stormer viscosity results, as well as the values of L and Delta E (ΔE), for pigmented base formulations and relating to the aforementioned tests are summed up in the following Tables 1a, 1b and 1c.

1TABLE 1aPrior artInventionInventionInventionInventionInventionInventionInventionInventionTEST N°123456789Untreated water276.9272272272272272272272272Coatex P90 (40%)333333333Liquid ammonia (28%)2.32.32.32.32.32.32.32.32.3Byk 034111111111Monoethylene glycol10.210.210.210.210.210.210.210.210.2Mergal K6N222222222TiO2 RL 68404040404040404040Hydrocarb207207207207207207207207207Durcal 2316316316316316316316316316Rhodopas DS 910120120120120120120120120120White Spirit10.210.210.210.210.210.210.210.210.2ThickenersC16TSPTSPTSPTSPTSPTSPDSPDSPOE = 0OE1OE1.3OE5OE15OE25OE40OE15OE7Quantity (g)11.416.316.316.316.316.316.316.316.3Total (g)100010001000100010001000100010001000% dry thickener/total0.570.570.570.570.570.570.570.570.57formulationpH9.19.19.19.19.19.19.19.19.1Brookfield viscosity(mPa · s)T = 24 h 10 rev/min1230017300315001250036002400130011004800100 rev/min28005900114005700270018009008003500Stormer visco. (KU)107122>141122104958281109Brookfield viscosity(mPa · s)T = 1 week 10 rev/min1240017800309001100037002700140010005300100 rev/min28005990101005400260019009008003600Stormer visco. (KU)104124>141125108998784111Brookfield viscosity(mPa · s)T = 1 week 50° C. 10 rev/min1250012400271001090032002100100011005600100 rev/min3400510090005100250015007008003700Stormer visco. (KU)111122>141124106978487118Brookfield viscosity(mPa · s)T = 1 month 10 rev/min1260018100321001290039002600130012006100100 rev/min290060001200056002800200011008003700Stormer visco. (KU)106125>1411261071018983116Brookfield viscosity(mPa · s)T = 1 month 50° C. 10 rev/min1310015600334001160038002900120014006400100 rev/min36006200112005200270021008009003900Stormer visco. (KU)115128>1411271101038891121Pigmentary compatibility(addition of 5% by weight ofblack pigmentary paste)Delta E8.20.60.50.60.40.50.70.90.6L40.328.729.429.228.728.528.628.329.2

[0288]

2

TABLE 1b

Outside
Outside
Outside
Outside
Outside
Outside
Outside

Outside

invention
invention
invention
invention
invention
invention
invention
Invention
invention

TEST N°

10
11
12
13
14
15
16
17
18

Untreated water
272
272
272
272
272
272
272
272
272

Coatex P90 (40%)
3
3
3
3
3
3
3
3
3

Liquid ammonia (28%)
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3

Byk 034
1
1
1
1
1
1
1
1
1

Monoethylene glycol
10.2
10.2
10.2
10.2
10.2
10.2
10.2
10.2
10.2

Mergal K6N
2
2
2
2
2
2
2
2
2

TiO2 RL 68
40
40
40
40
40
40
40
40
40

Hydrocarb
207
207
207
207
207
207
207
207
207

Durcal 2
316
316
316
316
316
316
316
316
316

Rhodopas DS 910
120
120
120
120
120
120
120
120
120

White Spirit
10.2
10.2
10.2
10.2
10.2
10.2
10.2
10.2
10.2

Thickeners
C12
C16C18
C18
C22
C32
NP30
Abietate
TSPOE8.3
Beta N.

OE23
OE25
OE20
OE25
OE25

OP 12.8
OE 6.4

Quantity (g)
16.3
16.3
16.3
16.3
16.3
16.3
16.3
16.3
16.3

Total (g)
1000
1000
1000
1000
1000
1000
1000
1000
1000

% dry thickener/total
0.57
0.57
0.57
0.57
0.57
0.57
0.57
0.57
0.57

formulation

pH
9.1
9.1
9.1
9.1
9.1
9.1
9.1
9.1
9.1

Brookfield viscosity

(mPa · s)

T = 24 h

10 rev/min
1000
4100
29500
9700
400
600
400
1000
300

100 rev/min
500
2800
11300
2400
200
400
300
700
200

Stormer visco. (KU)
73
102
>141
100
63
69
64
72
63

Brookfield viscosity

(mPa · s)

T = 1 week

10 rev/min
1100
4600
30400
10100
400
700
500
1100
400

100 rev/min
600
2900
11600
2600
200
400
400
700
300

Stormer visco. (KU)
77
106
>141
110
65
71
69
74
65

Brookfield viscosity

(mPa · s)

T = 1 week 50° C.

10 rev/min
1300
4900
35400
12600
400
800
500
1300
400

100 rev/min
700
3200
13100
3100
300
400
300
800
200

Stormer visco. (KU)
81
110
>141
116
69
75
69
79
67

Brookfield viscosity

(mPa · s)

T = 1 month

10 rev/min
1200
5800
31800
11000
500
900
400
1100
600

100 rev/min
700
3300
12700
2800
200
500
300
900
400

Stormer visco. (KU)
79
117
>141
115
68
75
66
73
67

Brookfield viscosity

(mPa · s)

T = 1 month 50° C.

10 rev/min
1600
5300
37800
13100
500
1000
500
1200
500

100 rev/min
900
3400
14000
3300
400
600
300
900
300

Stormer visco. (KU)
85
113
>141
121
71
77
68
81
69

Pigmentary compatibility

(addition of 5% by weight

of black pigmentary paste)

Delta E
1.2
1.5
1.1
2.4
2.1
0.7
0.5
0.8
0.6

L
27.4
29.0
30.2
33.7
30.2
26.6
28.3
27.6
28.8

[0289]

3

TABLE 1c

Invention
Invention
Invention
Invention

TEST N°
19
20
21
22

Untreated water
272
272
272
272

Coatex P90 (40%)
3
3
3
3

Liquid ammonia (28%)
2.3
2.3
2.3
2.3

Byk 034
1
1
1
1

Monoethylene glycol
10.2
10.2
10.2
10.2

Mergal K6N
2
2
2
2

TiO2 RL 68
40
40
40
40

Hydrocarb
207
207
207
207

Durcal 2
316
316
316
316

Rhodopas DS 910
120
120
120
120

White Spirit
10.2
10.2
10.2
10.2

Thickeners
TSP
TSP
TSP
TSP

OE1.3
OE1.3
OE1.3
OE1.3

Quantity (g)
16.3
16.3
16.3
16.3

Total (g)
1000
1000
1000
1000

% dry thickener/total formulation
0.57
0.57
0.57
0.57

pH
9.6
9.6
9.6
9.6

Brookfield viscosity
10 rev/min
11300
26100
3800
1400

(mPa · s)
100 rev/min
3200
8700
2000
1100

T = 24 h
Stormer visco. (KU)
113
141
92
81

Brookfield viscosity
10 rev/min
9000
22300
2300
1000

(mPa · s)
100 rev/min
2700
7100
1600
700

T = 1 week
Stormer visco. (KU)
101
133
89
78

Brookfield viscosity
10 rev/min
9700
18500
2100
500

(mPa · s)
100 rev/min
2900
6300
1500
300

T = 1 week 50° C.
Stormer visco. (KU)
105
137
91
72

Brookfield viscosity
10 rev/min
9100
22100
2400
1000

(mPa · s)
100 rev/min
2600
7200
1500
600

T = 1 month
Stormer visco. (KU)
100
131
88
76

Brookfield viscosity
10 rev/min
10500
19700
1900
300

(mPa · s)
100 rev/min
3500
6300
1300
200

T = 1 month 50° C.
Stormer visco. (KU)
107
138
92
70

Pigmentary compatibility (addition of 5% by weight of black pigmentary paste)

Delta E
0.3
0.2
0.5
0.7

L
29.3
29.0
28.0
28.2

[0290] A reading of Tables 1a, 1b and 1c makes it possible to assign the notations ΔEmatt and ηmatt to the different tests.

[0291] Thus,

[0292] for Test 1: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to −1 giving a total (ΔEmatt+ηmatt) equal to 0;

[0293] for Test 2: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 2;

[0294] for Test 3: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 2;

[0295] for Test 4: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 2;

[0296] for Test 5: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 2;

[0297] for Test 6: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 1;

[0298] for Test 7: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 1;

[0299] for Test 8: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 1;

[0300] for Test 9: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 2;

[0301] for Test 10: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to 0 giving a total (Δmatt+ηmatt) equal to 0;

[0302] for Test 11: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to 0 giving a total (ΔEmatt+ηmatt) equal to 1;

[0303] for Test 12: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to 0 giving a total (ΔEmatt+ηmatt) equal to +1;

[0304] for Test 13: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to −1 giving a total (ΔEmatt+ηmatt) equal to 0;

[0305] for Test 14: the notation ηmatt is equal to −1 and the notation ΔEmatt is equal to −1 giving a total (ΔEmatt+ηmatt) equal to −2;

[0306] for Test 15: the notation ηmatt is equal to −1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 0;

[0307] for Test 16: the notation ηmatt is equal to −1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 0;

[0308] for Test 17: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 1;

[0309] for Test 18: the notation ηmatt is equal to −1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to 0;

[0310] for Test 19: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +2;

[0311] for Test 20: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +2;

[0312] for Test 21: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +2;

[0313] for Test 22: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +1.

EXAMPLE 2

[0314] The aim of this example is to reveal the rheological and pigmentary compatibility properties provided by the thickening agents according to the invention for silk finish formulations for paint, with solvent and at constant dosage.

[0315] These formulations for paints comprise the ingredients and additives listed in the first part of Tables 2a, 2b and 2c constituting the white base, and which persons skilled in the art will recognise.

[0316] In this first part of Tables 2a, 2b and 2c:

[0317] COATEX BR3 designates a polyacrylate type dispersant marketed by COATEX under the name COATEX BR3.

[0318] Tego 1488 designates an antifoaming agent marketed by TEGO.

[0319] BDG designates butyldiglycol which is a coalescence agent.

[0320] MPG designates monopropylene glycol which is a coalescence agent.

[0321] The product Mergal K6™ designates a biocide agent marketed by TROY.

[0322] The product Hydrocarb™ is a known fine filler of the natural CaCO3 type, marketed by OMYA.

[0323] The product TiO2 RHD2 is a titanium oxide marketed by ELEMENTIS.

[0324] Acronal 290D™ is a styrene-acrylic binder marketed by BASF.

[0325] Texanol marketed by EASTMAN CHEMICAL is a well-known petroleum fraction which has a solvent function.

[0326] For each test, preparation was carried out of the aforementioned silk finish paint formulation, into which the thickening agent to be tested is added.

[0327] Then for each of the tests, the Brookfield™ and Stormer viscosity measurements of the formulation obtained are carried out according to the same conditions and the same equipment used in Example 1.

[0328] The same applies for the determination of the value of ΔE on the black pigmentary paste obtained by addition of 5% by weight of the same black pigmentary paste as in the previous example, on the white bases to be tested.

[0329] Test 23:

[0330] This test illustrates the prior art and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a well-known polyurethane based on the condensation product of an alcohol having 16 carbon atoms, toluene diisocyanate and polyethylene glycol of molecular weight equal to 10,000.

[0331] Test 24:

[0332] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0333] DI is isophorone diisocyanate;

[0334] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0335] n=1;

[0336] x=x′=1;

[0337] y=y′=z=z′=0;

[0338] R=R′=TSP.

[0339] Test 25:

[0340] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0341] DI is isophorone diisocyanate;

[0342] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0343] n=1;

[0344] x=x′=1.3;

[0345] y=y′=z=z′=0;

[0346] R=R′=TSP.

[0347] Test 26:

[0348] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0349] DI is isophorone diisocyanate;

[0350] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0351] n=1;

[0352] x=x′=5;

[0353] y=y′=z=z′=0;

[0354] R=R′=TSP.

[0355] Test 27:

[0356] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0357] DI is isophorone diisocyanate;

[0358] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0359] n=1;

[0360] x=x′=15;

[0361] y=y′=z=z′=0;

[0362] R=R′=TSP.

[0363] Test 28:

[0364] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0365] DI is isophorone diisocyanate;

[0366] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0367] n=1;

[0368] x=x′=25;

[0369] y=y′=z=z′=0;

[0370] R=R′=TSP.

[0371] Test 29:

[0372] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0373] DI is isophorone diisocyanate;

[0374] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0375] n=1;

[0376] x=x′=40;

[0377] y=y′=z=z′=0;

[0378] R=R′=TSP.

[0379] Test 30:

[0380] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0381] DI is isophorone diisocyanate;

[0382] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0383] n=1;

[0384] x=x′=15;

[0385] y=y′=z=z′=0;

[0386] R=R′=DSP.

[0387] Test 31:

[0388] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0389] DI is isophorone diisocyanate;

[0390] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0391] n=1;

[0392] x=x′=7;

[0393] y=y′=z=z′=0;

[0394] R=R′=DSP.

[0395] Test 32:

[0396] This test illustrates a field outside the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0397] DI is isophorone diisocyanate;

[0398] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0399] n=1;

[0400] x=x′=23;

[0401] y=y′=z=z′=0;

[0402] R=R′=linear alkyl chain with 12 carbon atoms.

[0403] Test 33:

[0404] This test illustrates a field outside the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0405] DI is isophorone diisocyanate;

[0406] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0407] n=1;

[0408] x=x′=25;

[0409] y=y′=z=z′=0;

[0410] R=R′=linear alkyl chain consisting of a fraction of 16 to 18 carbon atoms.

[0411] Test 34:

[0412] This test illustrates a field outside the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0413] DI is isophorone diisocyanate;

[0414] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0415] n=1;

[0416] x=x′=20;

[0417] y=y′=z=z′=0;

[0418] R=R′=linear alkyl chain with 18 carbon atoms.

[0419] Test 35:

[0420] This test illustrates a field outside the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0421] DI is isophorone diisocyanate;

[0422] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0423] n=1;

[0424] x=x′=25;

[0425] y=y′=z=z′=0;

[0426] R=R′=linear alkyl chain with 22 carbon atoms.

[0427] Test 36:

[0428] This test illustrates a field outside the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0429] DI is isophorone diisocyanate;

[0430] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0431] n=1;

[0432] x=x′=25;

[0433] y=y′=z=z′=0;

[0434] R=R′=branched alkyl chain with 32 carbon atoms.

[0435] Test 37:

[0436] This test illustrates a field outside the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (1) in which:

[0437] DI is isophorone diisocyanate;

[0438] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0439] n=1;

[0440] x=x′=30;

[0441] y=y′=z=z′=0;

[0442] R=R′=nonylphenyl group.

[0443] Test 38:

[0444] This test illustrates a field outside the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0445] DI is isophorone diisocyanate;

[0446] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0447] n=1;

[0448] x=x′=20;

[0449] y=y′=z=z′=0;

[0450] R=R′=abietate group.

[0451] Test 39:

[0452] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0453] DI is isophorone diisocyanate;

[0454] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0455] n=1;

[0456] x=z′=8.3;

[0457] x′=z=0;

[0458] y=y′=12.8;

[0459] R=R′=TSP.

[0460] Test 40:

[0461] This test illustrates a field outside the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0462] DI is isophorone diisocyanate;

[0463] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0464] n=1;

[0465] x=x′=6.4;

[0466] y=y′=z=z′=0;

[0467] R=R′=beta-naphthyl group.

[0468] Test 41:

[0469] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0470] DI is isophorone diisocyanate;

[0471] PEG is a polyethylene glycol of molecular weight equal to 6,000;

[0472] n=1;

[0473] x=x′=1.3;

[0474] y=y′=z=z′=0;

[0475] R=R′=TSP.

[0476] Test 42:

[0477] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0478] DI is isophorone diisocyanate;

[0479] PEG is a polyethylene glycol of molecular weight equal to 8,000;

[0480] n=1;

[0481] x=x′=1.3;

[0482] y=y′=z=z′=0;

[0483] R=R′=TSP.

[0484] Test 43:

[0485] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0486] DI is isophorone diisocyanate;

[0487] PEG is a polyethylene glycol of molecular weight equal to 20,000;

[0488] n=1;

[0489] x=x′=1.3;

[0490] y=y′=z=z′=0;

[0491] R=R′=TSP.

[0492] Test 44:

[0493] This test illustrates the invention and uses 0.22% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0494] DI is toluene diisocyanate;

[0495] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0496] n=1;

[0497] x=x′=1.3;

[0498] y=y′=z=z′=0;

[0499] R=R′=TSP.

[0500] All the Brookfield™ viscosity (at 10 and 100 rev/min.) and Stormer viscosity results, as well as the values of L and Delta E, for pigmented base formulations and relating to the aforementioned tests, are summed up in the following Tables 2a, 2b and 2c.

4TABLE 2aPrior artInventionInventionInventionInventionInventionInventionInventionInventionTEST N°232425262728293031Untreated water135.5133.6133.6133.6133.6133.6133.6133.6133.6Coatex BR3 (40%)555555555Tego 1488222222222B.D.G252525252525252525M.P.G151515151515151515Mergal K6N333333333TiO2 RHD2200200200200200200200200200Hydrocarb150150150150150150150150150Acronal 290D450450450450450450450450450Texanol101010101010101010ThickenersC16TSPTSPTSPTSPTSPTSPDSPDSPOE = 0OE1OE1.3OE5OE15OE25OE40OE15OE7Quantity (g)4.56.46.46.46.46.46.46.46.4Total (g)100010001000100010001000100010001000% dry thickener/total0.220.220.220.220.220.220.220.220.22formulationpH8.58.58.58.58.58.58.58.58.5Brookfield viscosity(mPa · s)T = 24 h 10 rev/min770014800216001000041003300240024005300100 rev/min350060008700490020001600110010002600Stormer visco. (KU)10612514012197928280101Brookfield viscosity(mPa · s)T = 1 week 10 rev/min74001520022100980045003600260029005900100 rev/min350060008800490022001700100011002800Stormer visco. (KU)106124139120101958280103Brookfield viscosity(mPa · s)T = 1 week 50° C. 10 rev/min860016700235001210052004100330036006400100 rev/min380067009200550025001800120013003300Stormer visco. (KU)113135>1411301061008683107Brookfield viscosity(mPa · s)T = 1 month 10 rev/min760015400228001020047004000300031006600100 rev/min350061008900500022001900120012003200Stormer visco. (KU)106125140122104988681105Brookfield viscosity(mPa · s)T = 1 month 50° C. 10 rev/min890017400250001280055004700390044007100100 rev/min410069009600550026002000150014003500Stormer visco. (KU)115140>1411311101059189111Pigmentary compatibility(addition of 5% by weightof black pigmentary paste)Delta E16.20.40.40.50.41.11.31.30.7L58.139.939.539.638.638.838.738.839.2

[0501]

5

TABLE 2b

Outside
Outside
Outside
Outside
Outside
Outside
Outside

Outside

invention
invention
invention
invention
invention
invention
invention
Invention
invention

TEST N°

32
33
34
35
36
37
38
39
40

Untreated water
133.6
133.6
133.6
133.6
133.6
133.6
133.6
133.6
133.6

Coatex BR3 (40%)
5
5
5
5
5
5
5
5
5

Tego 1488
2
2
2
2
2
2
2
2
2

B.D.G
25
25
25
25
25
25
25
25
25

M.P.G
15
15
15
15
15
15
15
15
15

Mergal K6N
3
3
3
3
3
3
3
3
3

TiO2 RHD2
200
200
200
200
200
200
200
200
200

Hydrocarb
150
150
150
150
150
150
150
150
150

Acronal 290D
450
450
450
450
450
450
450
450
450

Texanol
10
10
10
10
10
10
10
10
10

Thickeners
C12
C16C18
C18
C22
C32
NP30
Abiétate
TSPOE8.3
Béta N.

OE23
OE25
OE20
OE25
OE25

OP 12.8
OE 6.4

Quantity (g)
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4

Total (g)
1000
1000
1000
1000
1000
1000
1000
1000
1000

% dry thickener/total
0.22
0.22
0.22
0.22
0.22
0.22
0.22
0.22
0.22

formulation

pH
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5

Brookfield viscosity

(mPa · s)

T = 24 h

10 rev/min
1600
2400
6300
6600
3300
1300
1100
2700
1200

100 rev/min
600
1300
3200
2100
800
500
400
1400
400

Stormer visco. (KU)
70
83
106
91
70
65
63
84
68

Brookfield viscosity

(mPa · s)

T = 1 week

10 rev/min
1700
2800
7100
7300
3400
1700
1300
2700
1400

100 rev/min
650
1300
3400
2200
1000
800
500
1500
500

Stormer visco. (KU)
72
84
106
92
74
71
66
84
71

Brookfield viscosity

(mPa · s)

T = 1 week 50° C.

10 rev/min
2200
3500
7900
10200
5000
1700
1500
3600
2100

100 rev/min
800
1600
3600
2600
1100
600
500
1700
700

Stormer visco. (KU)
77
90
114
99
76
68
66
92
75

Brookfield viscosity

(mPa · s)

T = 1 month

10 rev/min
2100
3400
8000
8100
3700
1900
1400
3100
1500

100 rev/min
800
1700
3600
2400
1100
800
500
1500
500

Stormer visco. (KU)
74
89
110
98
76
73
67
85
74

Brookfield viscosity

(mPa · s)

T = 1 month 50° C.

10 rev/min
2600
4200
8300
12600
5800
2200
1700
4400
2700

100 rev/min
900
1900
3700
2900
1400
800
600
1900
800

Stormer visco. (KU)
81
96
119
110
83
70
69
101
81

Pigmentary compatibility

(addition of 5% by weight

of black pigmentary paste)

Delta E
1
1.7
13.4
23.2
13
1.4
1.8
1.2
1.3

L
38.5
40.5
52.9
62.4
53.4
38.3
37.8
38.9
38.6

[0502]

6

TABLE 2c

Invention
Invention
Invention
Invention

TEST N°

41
42
43
44

Untreated water
133.6
133.6
133.6
133.6

Coatex BR3 (40%)
5
5
5
5

Tego 1488
2
2
2
2

B.D.G
25
25
25
25

M.P.G
15
15
15
15

Mergal K6N
3
3
3
3

TiO2 RHD2
200
200
200
200

Hydrocarb
150
150
150
150

Acronal 290D
450
450
450
450

Texanol
10
10
10
10

Thickeners
TSP
TSP
TSP
TSP

OE1.3
OE1.3
OE1.3
OE1.3

Quantity (g)
6.4
6.4
6.4
6.4

Total (g)
1000
1000
1000
1000

% dry thickener/total formulation
0.22
0.22
0.22
0.22

pH
8.4
8.4
8.4
8.4

Brookfield viscosity
10 rev/min
20700
24800
6800
5300

(mPa · s)
100 rev/min
7600
9300
2800
2300

T = 24 h
Stormer visco. (KU)
137
>141
101
98

Brookfield viscosity
10 rev/min
20200
26300
7400
5900

(mPa · s)
100 rev/min
7400
9200
2900
2600

T = 1 week
Stormer visco. (KU)
139
>141
102
100

Brookfield viscosity
10 rev/min
21500
24700
8100
5800

(mPa · s)
100 rev/min
7400
9100
3100
2300

T = 1 week 50° C.
Stormer visco. (KU)
>141
>141
108
102

Brookfield viscosity
10 rev/min
20500
27200
7700
5800

(mPa · s)
100 rev/min
7400
9300
3100
2700

T = 1 month
Stormer visco. (KU)
138
>141
103
101

Brookfield viscosity
10 rev/min
22400
25100
8500
5800

(mPa · s)
100 rev/min
7600
9200
3200
2400

T = 1 month 50° C.
Stormer visco. (KU)
>141
>141
108
102

Pigmentary compatibility (addition of 5% by weight of black pigmentary paste)

Delta E
0.6
0.4
0.3
0.1

L
37.5
36.6
35.4
36.0

[0503] A reading of Tables 2a, 2b and 2c makes it possible to assign the notations ΔEsilk and ηsilk to the different tests.

[0504] Thus,

[0505] for Test 23: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to −1 giving a total (ΔEsilk+ηsilk) equal to 0;

[0506] for Test 24: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0507] for Test 25: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0508] for Test 26: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0509] for Test 27: the notation ηmatt is equal to +1 and the notation Δmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +2;

[0510] for Test 28: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to 2;

[0511] for Test 29: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to 2;

[0512] for Test 30: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to 2;

[0513] for Test 31: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to 2;

[0514] for Test 32: the notation ηsilk is equal to 0 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to 1;

[0515] for Test 33: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to 0 giving a total (ΔEsilk+ηsilk) equal to 1;

[0516] for Test 34: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to −1 giving a total (ΔEsilk+ηsilk) equal to 0;

[0517] for Test 35: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to −1 giving a total (ΔEsilk+ηsilk) equal to 0;

[0518] for Test 36: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to −1 giving a total (ΔEsilk+ηsilk) equal to 0;

[0519] for Test 37: the notation ηsilk is equal to 0 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to 1;

[0520] for Test 38: the notation ηsilk is equal to 0 and the notation ΔEsilk is equal to 0 giving a total (ΔEsilk+ηsilk) equal to 0;

[0521] for Test 39: the notation ηsilk is equal to +1 and the notation Δsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to 2;

[0522] for Test 40: the notation ηsilk is equal to 0 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to 1;

[0523] for Test 41: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0524] for Test 42: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0525] for Test 43: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0526] for Test 44: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2.

[0527] The sum of the totals of the notations of Example 1 relating to matt paints and of Example 2 relating to silk finish paints is summed up in the following Table 3.

7TABLE 3MATT PAINTSILK FINISH PAINTTOTALx + y + z =η mattΔE mattη silkΔE silk(η matt + ΔE matt) +R GROUPx′ + y′ + z′Test n°notationnotationTest n°notationnotation(η silk + ΔE silk)Prior artC1601+1−119+1−10InventionTSP12+1+120+1+1+4InventionTSP1.33+1+121+1+1+4InventionTSP54+1+122+1+1+4InventionTSP155+1+123+1+1+4InventionTSP2560+124+1+1+3InventionTSP4070+125+1+1+3InventionDSP1580+126+1+1+3InventionDSP79+1+127+1+1+4Outside InventionC12231000280+1+1Outside InventionC16C182511+1029+10+2Outside InventionC182012+1030+1−1+1Outside InventionC222513+1−131+1−10Outside InventionC322514−1−132+1−1−2Outside InventionNP3015−1+1330+1+1Outside InventionAbietate2016−1+134000InventionTSP21.1170+135+1+1+3Outside Inventionβ naphthyl6.418−1+1360+1+1

[0528] A reading of Table 3 makes it possible to see that only the polyurethanes functionalised with groups containing at least three aromatic cycles, that is to say only compounds fitting the formula (I) in which R and R′ are hydrocarbon groups having at least three aromatic cycles, substituted or not, make it possible to develop viscosities at important small shear stress gradient without losing pigmentary compatibility, this property being retained whether matt paint or silk finish paint is concerned.

[0529] Tests 1-23, 10-32, 11-33, 12-34, 13-35, 14-36, 15-37, 16-38 and 18-40 do not make it possible to achieve the strictly defined criteria (total of notations less than 3) whereas the tests of the invention 2-24, 3-25, 4-26, 5-27, 6-28, 7-29, 8-30, 9-31, 17-39, 19-41, 20-42, 21-43 and 22-44 meet the said criteria (total of notations greater than or equal to 3).

EXAMPLE 3

[0530] The aim of this example is to reveal the rheological and pigmentary compatibility properties provided by the thickening agents according to the invention for matt formulations for paint, with solvent at variable dosage and constant rheology.

[0531] To do this, for the formulations appearing in Table 4 which follows, the operating methods and equipment used in the various tests of this example are identical to those used in Example 1.

[0532] Test 45:

[0533] This test illustrates the invention and uses 0.60% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0534] DI is hexamethylene diisocyanate;

[0535] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0536] n=1;

[0537] x=x′=1.3;

[0538] y=y′=z=z′=0;

[0539] R=R′=TSP.

[0540] Test 46:

[0541] This test illustrates the invention and uses 0.75% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0542] DI is toluene diisocyanate;

[0543] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0544] n=1;

[0545] x=x′=1.3;

[0546] y=y′=z=z′=0;

[0547] R=R′=TSP.

[0548] Test 47:

[0549] This test illustrates the invention and uses 0.56% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0550] DI is isophorone diisocyanate;

[0551] PEG is a polyethylene glycol of molecular weight equal to 20,000;

[0552] n=1;

[0553] x=x′=1.3;

[0554] y=y′=z=z′=0;

[0555] R=R′=TSP.

[0556] Test 48:

[0557] This test illustrates the invention and uses 0.13% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0558] DI is isophorone diisocyanate;

[0559] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0560] n=1;

[0561] x=x′=1.3;

[0562] y=y′=z=z′=0;

[0563] R=R′=TSP.

[0564] All the Brookfield™ viscosity (at 10 and 100 rev/min.) and Stormer viscosity results, as well as the values of L and Delta E, for pigmented base formulations and relating to the aforementioned tests, are summed up in the following Table 4.

8TABLE 4InventionInventionInventionInventionTEST N°45464748Untreated water271.3266.8272.3284.5Coatex P90 (40%)3333NH4OH2.32.32.32.3Mergal K6N2222Byk 0341111TiO2 RL 6840404040Hydrocarb207207207207Durcal 2316316316316Rhodopas DS 910120120120120Monoethylene glycol10.210.210.210.2White Spirit10.210.210.210.2ThickenersTSP OE1.3TSP OE1.3TSP OE1.3TSP OE1.3HDITDIIPDIIPDIPEG 10000PEG 10000PEG 20000PEG 10000Quantity of thickener (g)1721.5163.8Total (g)1000100010001000% dry thickener/total formulation0.60.750.560.13pH9.69.69.69.6Brookfield viscosity 10 rev/min2700250028003700(mPa · s)100 rev/min210015001700900T = 24 hStormer visco. (KU)97898871Brookfield viscosity 10 rev/min3200330031004600(mPa · s)100 rev/min2400210017001200T = 1 weekStormer visco. (KU)100868978Brookfield viscosity 10 rev/min3500340029003900(mPa · s)100 rev/min2600250018001000T = week 50° C.Stormer visco. (KU)104919276Brookfield viscosity 10 rev/min2800240027003200(mPa · s)100 rev/min2000150015001000T = 1 monthStormer visco. (KU)96888675Brookfield viscosity 10 rev/min3100320028003100(mPa · s)100 rev/min240021001700800T = 1 month 50° C.Stormer visco. (KU)102908975Pigmentary compatibility (addition of 5% by weight of black pigmentary paste)Delta E0.30.41.40.3L31.932.030.232.8

[0565] A reading of Table 4 makes it possible to assign the notations ΔEmatt and ηmatt to the different tests.

[0566] Thus,

[0567] for Test 45: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +1;

[0568] for Test 46: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +1;

[0569] for Test 47: the notation ηmatt is equal to 0 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +1;

[0570] for Test 48: the notation ηmatt is equal to +1 and the notation ΔEmatt is equal to +1 giving a total (ΔEmatt+ηmatt) equal to +2;

EXAMPLE 4

[0571] The aim of this example is to reveal the Theological and pigmentary compatibility properties provided by the thickening agents according to the invention for silk finish formulations for paint, with solvent at variable dosage and constant rheology.

[0572] To do this, for the formulations appearing in Table 5 which follows, the operating methods and equipment used in the various tests of this example are identical to those used in Example 2.

[0573] Test 49:

[0574] This test illustrates the invention and uses 0.12% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0575] DI is hexamethylene diisocyanate;

[0576] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0577] n=1;

[0578] x=x′=1.3;

[0579] y=y′=z=z′=0;

[0580] R=R′=TSP.

[0581] Test 50:

[0582] This test illustrates the invention and uses 0.12% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0583] DI is toluene diisocyanate;

[0584] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0585] n=1;

[0586] x=x′=1.3;

[0587] y=y′=z=z′=0;

[0588] R=R′=TSP.

[0589] Test 5 1:

[0590] This test illustrates the invention and uses 0.105% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0591] DI is isophorone diisocyanate;

[0592] PEG is a polyethylene glycol of molecular weight equal to 20,000;

[0593] x=x′=1.3;

[0594] y=y′=z=z′=0;

[0595] R=R′=TSP.

[0596] Test 52:

[0597] This test illustrates the invention and uses 0.04% by dry weight, with respect to the total weight of the formulation, of a compound with formula (I) in which:

[0598] DI is isophorone diisocyanate;

[0599] PEG is a polyethylene glycol of molecular weight equal to 10,000;

[0600] n=1;

[0601] x=x′=1.3;

[0602] y=y′=z=z′=0;

[0603] R=R′=TSP.

[0604] All the Brookfield™ viscosity (at 10 and 100 rev/min.) and Stormer viscosity results, as well as the values of L and Delta E, for pigmented base formulations and relating to the aforementioned tests, are summed up in the following Table 5.

9TABLE 5InventionInventionInventionInventionTEST N°49505152Untreated water136.5136.5137135Coatex BR 3 (40%)5555Tego 14882222B.D.G.25252525M.P.G.15151515Mergal K6N3333TiO2 RHD2200200200200Hydrocarb150150150150Acronal 290D450450450450Texanol10101010ThickenersTSP OE1.3TSP OE1.3TSP OE1.3TSP OE1.3HDITDIIPDIIPDIPEG 10000PEG 10000PEG 20000PEG 10000Quantity of thickener (g)3.53.531Total (g)1000100010001000% dry thickener/total formulation0.120.120.1050.04pH8.48.48.48.4Brookfield viscosity 10 rev/min3100270030003100(mPa · s)100 rev/min1500110012001200T = 24 hStormer visco. (KU)85798081Brookfield viscosity 10 rev/min3400310033003200(mPa · s)100 rev/min1700120013001300T = 1 weekStormer visco. (KU)86808181Brookfield viscosity 10 rev/min4100340040003700(mPa · s)100 rev/min1900120014001400T = 1 week 50° C.Stormer visco. (KU)92858786Brookfield viscosity 10 rev/min3500350034003300(mPa · s)100 rev/min1800130014001300T = 1 monthStormer visco. (KU)86818281Brookfield viscosity 10 rev/min4400360042003800(mPa · s)100 rev/min2000120015001500T = 1 month 50° C.Stormer visco. (KU)91848887Pigmentary compatibility (addition of 5% by weight of black pigmentary paste)Delta E0.40.40.20.4L35.135.935.035.0

[0605] A reading of Table 5 makes it possible to assign the notations Δmatt and ηmatt matt to the different tests.

[0606] Thus,

[0607] for Test 49: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0608] for Test 50: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0609] for Test 51: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0610] for Test 52: the notation ηsilk is equal to +1 and the notation ΔEsilk is equal to +1 giving a total (ΔEsilk+ηsilk) equal to +2;

[0611] The sum of the totals of the notations of Example 3 relating to matt paints and of Example 4 relating to silk finish paints is summed up in the following Table 6.

10TABLE 6MATT PAINTSILK FINISH PAINTTOTALx + y + z =η mattΔE mattη silkΔE silk(η matt + ΔE matt) +R GROUPx′ + y′ + z′Test n°notationnotationTest n°notationnotation(η silk + ΔE silk)InventionTSP1.3450+149+1+1+3InventionTSP1.3460+150+1+1+3InventionTSP1.3470+151+1+1+3InventionTSP1.348+1+152+1+1+4

[0612] A reading of Table 6 makes it possible to see that the compounds according to the invention make it possible to achieve the strictly defined criteria for different doses and more particularly for doses varying from 0.1% to 2% by dry weight of the said thickening compound with respect to the total mass of the composition.

[0613] The invention also covers all the embodiments and all the applications which will be directly accessible to persons skilled in the art from a reading of the present application, from their own knowledge, and possibly from simple routine tests.

Non-ionic thickeners for pigment compositions, in particular for paints and applications thereof

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Publication Number

Date Filed

Date Published

Inventors

CPC

US Classifications

International Classifications

Abstract

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PCT Information