WO2008048983A2

WO2008048983A2 - Reactive carrier for air drying coatings

Info

Publication number: WO2008048983A2
Application number: PCT/US2007/081581
Authority: WO
Inventors: Dean Thetford; John D. Schofield; Andrew J. Shooter; Patrick J. Sunderland
Original assignee: Lubrizol Advanced Materials, Inc.
Priority date: 2006-10-17
Filing date: 2007-10-17
Publication date: 2008-04-24
Also published as: WO2008048983A3

Abstract

Reactive carriers are described that can be used with dispersants and pigments in inks and coatings. The reactive carriers have at least two sets of carbon to carbon double bond that are generally reactive in alkyd type drying reactions. The substitution of reactive carriers for solvents in an ink or coating can reduce the volatile organic content of a formulated ink or coating.

Description

REACTIVE CARRIER FOR AIR DRYING COATINGS

Field of Invention

[0001] A low viscosity additive (reactive carrier) is described that can reduce the need for solvents having a VOC in a variety of applications such as coatings, inks, composites, etc. The low viscosity additive has two or more conjugated double bonds so that it can react in oxidative crosslinking reactions of alkyd type resins and become part of the binder phase in an ink, coating, etc. In one embodiment, the low viscosity additive is added to the dispersant and/or pigment so that it is present in the mill-base and carried therefrom into further downstream products. The carrier may also be used in preparing the resin(s).

Background of the Invention

[0002] Alkyd resins are well known and include various types of unsaturated polyesters and related molecules that can be converted from liquids to solids through oxidative crosslinking reactions after film formation. Some of the early alkyds were naturally occurring molecules like tung oil. Some alkyd resins use metal driers to facilitate the crosslinking reaction under milder reaction conditions. [0003] U.S. Patent 2,029,851 discloses the preparation of pentaerytliritol esters of fatty acids containing more than one double bond and their use in coating compositions to replace resins, solvent and drier. Mention is made of dehydrated ricinoleic acid. Specific claims are made to the pentaerytliritol esters of fatty acids consisting of unsaturated monobasic aliphatic carboxylic acids having at least 16 carbon atoms and having an iodine value of at least 120. U.S. Patent 2,390,202 discloses the preparation of polypentaerytlnϊtol esters of fatty acids containing more than one double bond and their use in coating compositions.

[0004] U.S. Patent 5,178,672 discloses the preparation of Ci_-I0 alcohol or glycol esters of fatty acids containing double bonds, propylene glycol was a preferred glycol. These compounds were used as a vehicle earner (solvent) for printing inks. Summary of the Invention

[0005] Specific low molecular weight polyols are reacted with unsaturated carboxylic acids (e.g., fatty acids) to create a reactive diluent that can co-react with other unsaturated molecules in a coating or ink. The reactive carrier is regarded as a nonvolatile organic compound by the standard tests used to measure volatile organic content in coatings and inks, and becomes chemically bound to the final coating. In one preferred embodiment, the polyols are those with CH(Y)-OH groups where Y is H, methyl, or ethyl group. In a particularly desirable embodiment, the unsaturated carboxylic acids are C]_8-22 conjugated fatty acids such as dehydrated ricinoleic acid. Generally, about 1.5 to about 3 or more conjugated fatty acid residues per molecule give a reactive carrier that neither hardens nor softens the final coating composition beyond its normal modulus characteristics (without reactive diluent). The use of a reactive diluent/carrier is particularly effective if added as part of the dispersant or resin or in the milling process where it can reduce or replace the amount of volatile organic solvent typically added in forming a mill-base. The reactive diluent is desirably low in color (low yellowness) as mill-bases of uniform/reproducible color are desired.

Detailed Description of the Invention

[0006] An objective was to create a product line of special (reactive) carriers for dispersions and resins such as air drying carriers for inks and decorative paints and a carrier for colours and/or dispersants into acrylic, vinyl ester or unsaturated polyester resins. Compositions include carrier with dispersant; carrier with resin; carrier, particulate solid (e.g., pigment) and dispersant (mill-base); and carrier, dispersant, pigment, and resin or polymer (mill-base, ink, or coating). Many decorative paint manufacturers are under increasing pressure to reduce volatile organic content (VOC) in their paints due to environmental legislation. In order to remove VOC, solvents and highly volatile organic chemicals must be reduced or removed. This can impact on the viscosity of the system and ultimately affect final performance of the paint and other coating properties. In the past, manufacturers have reduced solvent levels and improved viscosity of the system by reformulating with low molecular weight (MW) resins and other additives to reduce viscosity. The manufacturers have reached a point where it is very difficult to further reduce solvent levels without causing defects in their paints. The solvents in paints and inks often help in lowering viscosity for application ease, facilitating coalescence of the binder into a coherent mass, and making compatible polymeric and lower molecular weight materials that may not inherently have good interactions/attractions.

[0007] In one embodiment, we have prepared the tri-ester of trimethylolpropane and dehydrated castor oil fatty acid (Nour acid DE 656 from Akzo) and tested it as a suitable reactive carrier in an alkyd air drying paint. The earner has been used to either partially or totally replace resin and VOC solvent in the coloured mill-base thus allowing reduction or elimination of VOC from the mill-base. The carrier can also be used as a diluent carrier for any solid/liquid additive that is added to the mill-base such as a dispersant or resin. It may also be used as a reaction medium in the preparation of resins such as alkyd resins and be used as a non-VOC carrier for the alkyd resins. The carrier can partially or totally replace VOC solvent in the base or final paint. The carrier is of low viscosity and so does not detrimentally affect the viscosity of the system. It crosslinks into the final paint film because it has conjugated double bonds present in the fatty acid components that can react with other components (such as alkyd resins) containing reactive double bonds.

[0008] A generic formula below for the reactive diluent includes the di or polyfunctional branch point (labeled R) of the polyol; along with the -(H₂)C-O- portion optionally 1 ,2-alkoxy (-CH2-CH(Y)-0- where Y is H, methyl or ethyl) chain extended version of the polyol linked to the residue of an unsaturated fatty acid Ri (together forming A), and an optional B group that can be the -(H₂)C-O- portion (optionally 1 ,2- alkoxy chain extended version) of the polyol functionalized with H or a Cl -35 hydrocarbyl or hydrocarbonyl group (R₂). These are illustrated by the formulas below

(A)_x — R — (B)₂ (Formula 1 ) Where A is represented by

and B is represented by

wherein

V is H or Me

In the cases below of a), b), c), d), f), g), and h), V is H, in the case of e) V can be H or Me.

wherein

Ri ⁼ C]₈_22 conjugated fatty acid residue containing 2 or more conjugated double bonds, such as 9, 11 -Octadecadiene- 1 -carboxylic acid, 9,11,13-Octadecatriene- 1 - carboxylic acid, or 4-Keto-9,l 1,13-octadecatriene-l -carboxylic acid;

Y = H, Me or Et;

R 2 is H, or C 1.₃₅ hydrocarbyl or hydrocarbonyl group or in one embodiment a fatty acid residue including non-conjugated (poly) unsaturated fatty acids; p = 0-5; x = 2-6; and z is 0-4; and preferably in one embodiment R₂ does not include the Ci₈.₂₂ conjugated fatty acids residue defined as Ri.

R can be a) CH₃CH₂C or b) CH₃C in which case when x = 2 then z=l or when x-3 then z=0 (this would imply that the starting polyol was trimethylolpropane or trimethylolethane);

R can be c) C in which case when x = 2 then z=2, when x=3 then z=l, or when x=4 then z=0 (this would imply that the starting polyol was pentaerytliritol); R can be d) C-C(H₂)-O-C(H₂)-C in which case when x=2 then z=4, x=3 then z=3, x=4 then z=2, x=5 then z=l or x=6 then z=0 (this would imply that the starting polyol was dipentaerythritol); R can be represented by e)

wherein r = 2-12 such that (Λ) is C₂H₄ through Cj₂H₂₄;

R can be represented by T)

wherein R₃ = Me or Et;

M = C2-6 alk(en)ylene, 1 ,2-phenylene, 1,2-cycloalkyl Y and p are as defined before, and when x = 4 then z = 0, when x = 3 then z = 1 , or when x = 2 then z = 2 (implying that the starting polyol was trimethylolpropane or trimethylolethane); R can be represented by g)

wherein

M, Y and p are as defined before; and in which case when x = 2 then z = 4, or x 3 then z = 3, or x = 4 then z = 2, or x=5 then z=l, or x=6 then z=0;

(implying that the polyol used was pentaerythritol).

or R can be represented by h)

wherein

R_3, M, Y and p are as defined before; and in which case when x = 2 then z = 3, or x = 3 then z = 2, or x = 4 then z = 1 , or x=5 then z=0 (implying that the polyols used were a mixture of trimethylolpropane and pentaerythritol); or R can be blends of any of the previously set forth choices of one or more of a), b), c), d), e), f), g), and h); e.g., a blend of c) and d) implying the starting polyol was a teclmical grade pentaerythritol.

It is to be noted that formulas f), g), and h) can be generated by starting with a polyol such as pentaerythritol or triinethylol alkane wherein the branch point carbon of the polyol becomes a terminal carbon of formula f), g), or h). The A or B units of the reactive diluent are attached to that terminal carbon (two A and/or B units could attach per each trimethylol propane branch point while three A and/or B units could attach to a pentaerythritol branch point). The entire structure of the reactive diluent can be theoretically made by a variety of processes-reaction sequences. The polyol could be partially reacted with the selected R] and R₂ forming a reaction product with one non- reacted hydroxyl group, thereafter it could optionally be chain extended from that hydroxyl group with an ethylene oxide or propylene oxide, and thereafter two such molecules could be coupled with an anhydride of a dicarboxylic acid or a dicarboxylic acid where M is the central portion of the diacid or anhydride. The polyol could optionally be chain extended first and then reacted with carboxylic acids to form Ri and

R₂

[0009] It has been found that certain esters of conjugated fatty acids such as dehydrated castor oil fatty acids show excellent ability to crosslink into air drying coatings to leave hard paint films, have low viscosity making them suitable as a carrier solvent for these systems thus enabling reduction of solvent or resin and ultimately VOC in the coating system. Thus, according to the present invention in one embodiment, there is provided a composition comprising a particulate solid, a dispersant, optionally an organic medium and a compound of Formula (2) or (3) thereof:

R₄- C- (CH₂ORs)_n -(CH₂OH)_3-11 Formula (2) wherein

R₄= Me, Et; n in formula 2 is from 1-3 and is preferably 3;

(R₅-OCH₂)_n- C-(CH₂OH)_4-11 Formula (3)

n in formula 3 is from 1-4 and is preferably 3 or 4,

R₅ in both formula 2 and 3 is Ci₈-C₂₂ fatty acid containing 2 or more conjugated double bonds. R₅ can be represented by:-

9,1 1-Octadecadiene-l -carboxylic acid (i.e., dehydrated castor oil fatty acid or dehydrated ricinoleic acid),

9,11,13 -Octadecatriene-1 -carboxylic acid (i.e., Eleostearic acid from Tung oil) or 4-Keto-9,l 1,13 -octadecatriene-1 -carboxylic acid (i.e., Licanic acid from Oiticica oil). [0010] The particulate solid present in the composition may be any inorganic or organic solid material which is substantially insoluble in an organic medium or the compound. In one embodiment, the particulate solid is a pigment. [0011] Examples of suitable solids are pigments for solvent inks; pigments, extenders and fillers for paints and plasties materials; solids for oil-based and inverse- emulsion drilling muds; particulate ceramic materials; magnetic materials and magnetic recording media; fillers and fibres for composite materials, and biocides which are applied as dispersions in organic media.

[0012] In one embodiment, the particulate solid is a pigment which may be from any of the recognised classes of pigments described, for example, in the Third Edition of the Colour Index (1971) and subsequent revisions of, and supplements thereto, under the chapter headed "Pigments". Examples of inorganic pigments are titanium dioxide, zinc oxide, Prussian blue, cadmium sulphide, iron oxides, vermilion, ultramarine and the chrome pigments, including chromates, molybdates and mixed chromates and sulphates of lead, zinc, barium, calcium and mixtures and modifications thereof which are commercially available as greenish-yellow to red pigments under the names primrose, lemon, middle, orange, scarlet and red chromes. Examples of organic pigments are those from the azo, disazo, condensed azo, thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone, isodibeuzanthrone, triphendioxazine, quinaciϊdone, perylene, diketopyrrolopyrrole and phthalocyanine series, especially copper phthalocyanine and its nuclear halogenated derivatives, and also lakes of acid, basic and mordant dyes. Carbon blacks, although strictly inorganic, behave more like organic pigments in their dispersing properties. Preferred organic pigments are phthalocyanines, especially copper phthalocyanines, monoazos, disazos, indanthrones, anthranthrones, quinacridones and carbon blacks.

[0013] The particulate solid may be any inorganic solid material which is used as filler. The solids may be in the form of a granular material or in the form of a powder, especially a blown powder. Examples include calcium carbonate, calcium sulphate, calcium oxide, barium sulphate, barium carbonate, magnesium oxide, magnesium hydroxide, titanium dioxide, iron oxide, calcium and magnesium silicates, alumino silicates, kaolin, mica, talc, chalk, metal fibres and powders, zinc, aluminium, aluminium trihydroxide, glass fibres, refractory fibres, carbon black including reinforcing and non- reinforcing carbon black, alumina, quartz, wood flour, powdered paper/fibre, asbestos, crysatille, anthophylite, crocidolite, wollastonite, attapulgite and the like, particulate ceramic materials such as alumina, silica, zirconia, titania, silicon nitride, boron nitride, silicon carbide, boron carbide, mixed silicon-aluminium nitrides and metal titanates; particulate magnetic materials such as the magnetic oxides of transition metals, especially iron and chromium, e.g., gamma-Fe₂θ₃, Fe₃θ₄, and cobalt-doped iron oxides, ferrites, especially barium ferrites; and metal particles, especially metallic iron, nickel, cobalt, copper and alloys thereof.

[0014] Examples of suitable resins, as the medium for the dispersion form of the present invention, are film-forming resins such as are suitable for the preparation of paints and chips for use in various applications such as paints. Examples of such resins include polyamides, such as Versamid™ and Wolfamid™, and cellulose ethers, such as ethyl cellulose and ethyl hydroxyethyl cellulose. Examples of paint resins include short oil alkyd/melamine-formaldehyde, polyester/melamine-formaldehyde, thermosetting acrylic/melamine-formaldehyde, medium oil alkyd, long oil alkyd, long oil urethane, long oil acrylics, long oil polyamides, nitrocellulose and multi-media resins such as acrylic and urea/aldehyde. Preferably, long oil and medium oil alkyds are suitable resins for use in such applications.

[0015] Examples of suitable resins, as the medium for the dispersion form of the present invention, are resins preferably capable of undergoing a crosslinking action with a cross-linker or catalyst such as an acrylic or acrylate copolymer containing ethylenically unsaturated groups, vinyl esters and unsaturated polyesters. [0016] In one embodiment, the carrier can be used as the medium for dispersants or other additives which are used for the dispersion of particulate solids in gelcoats and thermoset composites. The thermosetting resins useful in this invention include resins which undergo a chemical reaction when heated, catalysed, or subject to UV radiation and become relatively infusible.

[0017] If desired, the dispersions may contain other ingredients, for example, resins (where these do not already constitute the organic medium), binders, fluidising agents (such as those described in GB-A-1508576 and GB-A-2108143), anti-sedimentation agents (such as those described in WO 96/14344), plasticisers, co-solvents, leveling agents, preservatives, thickeners and dispersants (such as those described specifically in U.S. Patent Nos. 2,973,382; 3,075,849; 3,332,793; 3,778,287; 3,996,059; 5,700,395; 7,008,988; and WO 00/24503).

[0018] In one embodiment, the dispersants are polyester type dispersants derived from polymerizing lactones or condensation reactions of alkylene or alkenylene hydroxycarboxylic acids. These dispersants can have a carboxylic acid, amine, quaternised amine, polyamine, polyimine, or phosphoric acid anchor groups or mixtures thereof. A subset of this group is described in WO 00/24503 from a C₈.₂o-linear alkylene and/or alkenylene hydroxycarboxylic acid reacted with a polyamine or polyimine wherein the ratio of polyester to polyamine or polyimine is from 5:1 to 20: 1. [0019] Preferably, the organic medium is at least 50% non-polar organic liquid and especially an aliphatic or aromatic hydrocarbon, or mixture thereof. Preferably, the carrier is used as a partial or total replacement of the organic medium. [0020] The dispersion may be obtained by any of the conventional methods known for preparing dispersions. Thus, the pigment, the organic medium and/or the carrier and the dispersant may be mixed in any order, the mixture then being subjected to a mechanical treatment to reduce the particles of the pigment to an appropriate size, for example, by ball milling, bead milling, gravel milling or plastic milling until the dispersion is formed. Alternatively, the pigment may be treated to reduce its particle size independently or in admixture with the organic medium and/or the carrier and the dispersant, the other ingredient or ingredients then being added and the mixture being agitated to provide the dispersion.

[0021] In addition or in lieu of adding the reactive carrier to the particulate solid and/or dispersant, the reactive carrier may be added to the resins, e.g., alkyd resin as a component to the manufacture of the resin or as a diluent to make the resin easier to handle or process. The reactive carrier can be used to reduce the amount of volatile organic solvent used in manufacture of the resin. The reactive carrier can be added after the manufacturing step and/or the reactive carrier can replace/displace residual solvent used in the manufacture. [0022] The dispersions typically contain from 5 to 95% by weight of the pigment, the precise quantity depending on the nature of the pigment and the quantity depending on the relative densities of the pigment, the carrier and the organic medium. Preferably, the dispersion contains from 15 to 60% by weight of the pigment. [0023] The paint or mill-base contains at least 0.2%, in one embodiment at least 0.5% and in another embodiment at least 1.0% dispersant based on weight of the pigment. In one embodiment, the paint or mill-base contains not greater than 100%, in another embodiment not greater than 50%, in still another embodiment not greater than 20%, and in a last embodiment not greater than 10% dispersant by weight based on the weight of pigment. The amount of dispersant in the mill-base is dependent on the amount of pigment but in one embodiment is from 0.5 to 10% by weight of the mill- base.

[0024] Typically, the mill-base contains from 10 to 70% by weight pigment based on the total weight of the mill-base. Where the pigment is an organic pigment, the mill-base preferably contains from 20 to 50% by weight. Where the pigment is an inorganic pigment, the mill-base preferably contains from 40 to 70% by weight except where the pigment is a transparent iron oxide. For transparent iron oxides the mill-base preferably contains from 20 to 50% by weight. Where the pigment is a carbon black, the mill-base preferably contains from 10 to 60% by weight. The pigment loading depends on surface area, with high surface area giving low pigment loadings and vice versa. [0025] The amount of resin in the mill-base can vary over wide limits but is preferably not less than 10%, and especially not less than 20% by weight of the continuous/liquid phase of the mill-base. Preferably, the amount of resin is not greater than 50% and especially not greater than 40% by weight of the continuous/liquid phase of the mill-base.

[0026] The amount of carrier in the mill-base can vary over wide limits but is preferably not less than 1%, and especially not less than 5% by weight of the continuous/liquid phase of the mill-base. Preferably, the carrier represents all of the continuous/liquid phase of the mill-base. [0027] The amount of carrier in the final paint can vary over wide limits hut is preferably not less than 1%, and especially not less than 5% by weight of the continuous/liquid phase of the final paint.

[0028] In one embodiment, dispersions, mill bases and base paints containing the carrier are particularly suitable for use in paints, especially long oil and medium oil air drying alkyd paints.

[0029] The invention is further illustrated by the following example wherein all references are to parts by weight unless expressed to the contrary.

[0030] Example 1 , Preparation of Reactive Carrier from 3 : 1 Dehydrated Castor Oil

Fatty Acid:Trimethylopropane

Dehydrated castor oil fatty acid (Now acid DE 656 ex Akzo) (91.18 parts 330 mmols), trimethylopropane (14.75 parts 100 mmols ex Aldrich) and zirconium butylate (0.3 parts) were stirred at 18O⁰C under a nitrogen atmosphere for 43 hours with a Dean and Stark to collect condensed water. Upon cooling, a brown liquid was obtained (95.5 g) with an acid value of 10.7 mgKOH/g.

[0031] Example 2, Preparation of Reactive Carrier from 2:1 Dehydrated Castor Oil

Fatty Acid:Trimethylopropane

Dehydrated castor oil fatty acid (Nour acid DE 656 ex Akzo) (169.82 parts 615 mmols), trimethylopropane (41.25 parts 307 mmols ex Aldrich) and ø-phosphoric acid (0.25 parts) were stirred at 18O⁰C under a nitrogen atmosphere for 21 hours with a Dean and

Stark to collect condensed water. Upon cooling, a yellow liquid was obtained (176.9 parts) with an acid value of 5.7 mgKOH/g.

[0032] Example 3, Preparation of Reactive Carrier from 3:1 Dehydrated Castor Oil

Fatty Acid:Trimethylopropane Ethoxylate MW450

Dehydrated castor oil fatty acid (Nour acid DE 656 ex Akzo) (67.66 parts 245 mmols), trimethylopropane ethoxylate MW450 (36.74 parts 81.7 mmols ex Aldrich) and o- phosphoric acid (0.125 parts) were stirred at 18O⁰C under a nitrogen atmosphere for 24 hours with a Dean and Stark to collect condensed water. Upon cooling, a yellow liquid was obtained (92.36 parts) with an acid value of 3.6 mgKOH/g. [0033] Example 4, Preparation of Reactive Carrier from 3:1 Dehydrated Castor Oil

Fatty Acid:Trimethylopropane Propoxylate MW308

Dehydrated castor oil fatty acid (Nour acid DE 656 ex Akzo) (76.54 parts 277 mniols), trimethylopropane propoxylate MW308 (28.45 parts 92.4 mmols ex Aldrich) and o- phosphoiϊc acid (0.125 parts) were stirred at 18O⁰C under a nitrogen atmosphere for 24 hours with a Dean and Stark to collect condensed water. Upon cooling, a yellow liquid was obtained (94 parts) with an acid value of 4.2 mgKOH/g.

[0034] Example 5, Preparation of Reactive Carrier from 2:1 :1 Dehydrated Castor Oil

Fatty Acid:Trimethylopropane:Acetic Anhydride

The product from Example 2 (50 parts 77 mmols) and acetic anhydride (7.85 parts 77 mmols) were stirred at 12O⁰C under a nitrogen atmosphere for 17 hours with a Dean and

Stark to collect acetic acid. Upon cooling, a yellow liquid was obtained (51 parts).

[0035] Example 6, Preparation of Reactive Carrier from 4:1 Dehydrated Castor Oil

Fatty Acid:Pentaerythritol

Dehydrated castor oil fatty acid (Nour acid DE 656 ex Akzo) (94.51 parts 342 mmols), pentaerythritol (11.64 parts 86 mmols ex Aldrich) and ø-phosphoric acid (0.25 parts) were stirred at 18O⁰C under a nitrogen atmosphere for 24 hours with a Dean and Stark to collect condensed water. Upon cooling, a yellow liquid was obtained (94.4 parts) with an acid value of 3.1 mgKOH/g.

[0036] Example 7, Preparation of Reactive Carrier from 4: 1 Dehydrated Castor Oil

Fatty Acid:Pentaervthritol Ethoxylate MW270

Dehydrated castor oil fatty acid (Nour acid DE 656 ex Akzo) (84.8 parts 307 mmols), pentaerythritol ethoxylate MW 270 (20.72 parts 77 mmols ex Aldrich) and o-phosphoric acid (0.15 parts) were stirred at 18O⁰C under a nitrogen atmosphere for 24 hours with a

Dean and Stark to collect condensed water. Upon cooling, an amber liquid was obtained

(95.5 parts) with an acid value of 5.7 mgKOH/g.

[0037] Comparative Example A, Preparation of 1 : 1 Dehydrated Castor Oil Fatty

Acid:Hexyl Alcohol

Dehydrated castor oil fatty acid (Nour acid DE 656 ex Akzo) (30 parts 109 mmols), hexyl alcohol (70 parts 109 mmols ex Aldrich) and ø-phosphoric acid (0.1 parts) were stirred at 18O⁰C under a nitrogen atmosphere for 22 hours with a Dean and Stark to collect condensed water. Upon cooling, a yellow liquid was obtained (37.4 parts) with an acid value of 3.2 mgKOH/g.

[0038] Comparative Example B, Preparation of 4:1 Dehydrated Castor Oil Fatty

Acid:Pentaerythritol Ethoxylate MW797

Dehydrated castor oil fatty acid (Nour acid DE 656 ex Akzo) (60.4 parts 219 mmols), pentaerythritol ethoxylate MW797 (43.53 parts 54.7 mmols ex Aldrich) and o- phosphoric acid (0.13 parts) were stirred at 18O⁰C under a nitrogen atmosphere for 20 hours with a Dean and Stark to collect condensed water. Upon cooling, a yellow liquid was obtained (98.5 parts) with an acid value of 3.2 mgKOH/g.

[0039] Preparation of a typical Polyester/Polyamine Dispersaut

PoIy(12-hydroxystearic acid) (MW1600, 55 parts, Polyester A, Agent A, U.S. 4,224,212) was heated to 12O⁰C with stilling under a nitrogen atmosphere. Polyethyleneimine

SP200 (MW10,000, 1 1 parts, Nippon Shokubai) was added and the reactants stirred under nitrogen at 12O⁰C for 6 hours. On cooling, the product was obtained as a brown viscous liquid (60 parts). This is Dispersant 1.

[0040] Example 8, Preparation of a Coating with the Reactive Carriers of Example 1-

White Paint Manufacture

The following white final paint was prepared using the formulation and ingredients listed below in Table 1.

TABLE 1

The Synolac 6095 WP85 and Super Gelkyd E20159 resins were added along with propylene glycol, methyl ethyl ketoxime and BAS 60 into an 8oz glass jar. 20Og of 3mm glass beads were then added followed by the Tiona 595 pigment. The jar was sealed and the mixture was milled on a Skandex lau for 40mins. The high solids driers were then added to the white paint which was sieved through a 400 micron mesh to remove the glass beads. The final paint was coated on Leneta black and white drawdown card and the coating patterns were dried at room temperature over 24 hours with a final inspection at 48 hours. The reactive carriers of Example 1-7 were formulated, into the Super Gelkyd white coating by substituting a portion of the BAS 60 solvent at a 25% level. Therefore, 3g of BAS 60 was replaced by 3g of reactive carrier. Drawdown Testing

Gloss and haze measurements were measured using a Byk-Cheinie Gloss and Haze meter after the 24 hours drying period. Sand Test

After 24 hours of drying time, two grams of sand was poured onto the coating pattern and a lOOg weight was applied to the sand spot for 10 seconds. The weight was removed and the excess sand was brushed off the coating using a soft brush.

Key for ranking the Sand Test;

1 = best (hardest film / least amount of sand remaining after brushing/shaking pattern).

5 = poorest (softest film / most amount of sand remaining after brushing/shaking pattern).

Berger Whiteness

Berger whiteness measurements were done using a Macbeth Coloreye

Spectrophotometer after the 24 hour drying period.

Results enclosed in Table 2 below show improved gloss in a coating containing the reactive carrier. The low haze value indicated there were no surface tension problems. We have also seen that the drying of the paint film was not substantially affected by the reactive carrier. The Sand test was run to determine if the coating surface became tackier due to the substitution of reactive carriers of Examples 1-5 for a portion of the solvent in the formulation. The Berger whiteness test was run to illustrate that the reactive carrier does not contribute excessive yellowness to the final coating.

TABLE 2

Drying stage:

24 hours - touch dry/all very close to be full dry except Comparative Examples A and B. 48 hours - all through dry except Comparative Example B where not totally through dry.

[0041] Example 9 Preparation of Coloured Mill-Base Replacing VOC Solvent with Reactive Carrier, Example 1 and a Final Paint Containing the Mill-Base

TABLE 3

The Synolac 6095WP85 resin was added along with BAS 40 (or reactive carrier Example 1) and the dispersant, Dispersant 1, into a 4oz glass jar. 125g of 3mm glass beads were then added followed by the fluidising agent, Solsperse 5000. Finally, the blue phthalocyanine pigment (Heliogen blue L7080) was added. The jar was sealed and the mixture was milled on a Skandex lau for 2 hours. The blue mill-base was then added to the Brillonip white base paint (25-30% TiO₂ content) in the amounts listed in Table 3, in each case the blue pigment loading of the final paint is the same in order that an equivalent colour strength result will be obtained for each paint. The final paint was coated on Leneta black and white drawdown card, flocculation was determined by a finger rub spot test on the wet coating and the coating patterns were dried at room temperature over 24 hours with a final inspection at 48 hours. Colour strength and flocculation measurements were done using a Macbeth Coloreye Spectrophotometer. Results enclosed in Table 4 below show improved gloss and haze in a coating containing the reactive carrier. The low haze value indicated there were no surface tension problems. We have also seen that the drying of the paint film was not substantially affected by the reactive carrier. Colour strength was not substantially affected by the reactive carrier and the flocculation resistance was significantly improved.

TABLE 4

Reduced Shade (Colour Stainer: White Air Drying AIkγd/l:9)

The reactive carrier has been used to replace some resin and all solvent in the coloured mill-base thus allowing reduction of VOC for the mill-base. The carrier is of low viscosity and so does not affect the viscosity of the system. It crosslinks into the final paint film because it has conjugated double bonds present in the fatty acid components.

[0042] Example 10 Preparation of a Final White Base Paint Using Reactive Carrier, Example 1 as a Replacement for the VOC Solvents

TABLE 5

The Wresinol AF9300 was added along with BAS 40 (or reactive earner Example 1), propylene glycol, Modaflow III, methyl ethyl ketoxime and the dispersant, Solplus K 500, into a 4oz glass jar. Finally, the white titanium dioxide pigment (Tiona 595) was added. 125g of 3mm glass beads were then added. The jar was sealed and the mixture was milled on a Skandex lau for 1 hour. The white mill-base was then added to the letdown in the amounts listed in Table 5, in each case the pigment loading of the final paint is the same in order that an equivalent colour strength result will be obtained for each paint. The final paint was coated on Leneta black and white drawdown card and the coating patterns were dried at room temperature over 24 hours with a final inspection at 48 hours. Gloss and haze measurements were measured using a Byk-Chemie Gloss and Haze meter after the 24 hours drying period.

Results in Table 6 show that gloss and haze of the coated paint were not affected by the presence of the reactive carrier. The paint film containing the reactive carrier was also touch dry after 24 hours.

TABLE 6

The reactive carrier and formulations using the reactive carrier have utility to reduce volatile organic content while maintaining other properties of formulated inks and coatings.

[0043] Although only a few embodiments of this invention have been described above, it should be appreciated that many modifications can be made without departing from the spirit and scope of the invention. All such modifications can be included within the scope of the invention, which is to be limited only by the following claims. Patents cited for their teachings and enablements are hereby incorporated by reference.

Claims

What is claimed is:

1. A compound comprising;

(A)_x - R - (B)₂ Formula 1 wherein A is represented by

and B is represented by

wherein

V is H or Me

In the cases below of a), b), c), d), f), g), and h), V is H, in the case of e) V can be H or

Me; wherein

Ri ⁼ C18-22 conjugated fatty acid residue containing 2 or more conjugated double bonds;

Y = H, Me or Et;

R₂ is H, C 1.₃₅ hydrocarbyl or hydrocarbonyl group or a fatty acid residue including non conjugated (poly) unsaturated fatty acids; p = 0-5; x = 2-6 with the upper limit also controlled by the available valences on the carbon(s) of

R; and z = 0-4 with the upper limit also controlled by the available valences on the carbon(s) of R;

R can be a) CH₃CH₂C; or b) CH₃C, in which case when x = 2 then z=l or when x=3 then z=0, or

R can be c) C in which case when x = 2 then z=2, when x=3 then z=l , or when x=4 then z=0,

R can be d) C-C(H₂)-O-C(H₂)-C in which case when x=2 then z=4, when x=3 then z=3, when x=4 then z=2, when x=5 then z=l or when x=6 then z=0;

R can be e)

wherein r = 2-12; or

R can be f)

wherein R₃ = Me or Et;

M = C2-6 alk(en)ylene, 1 ,2-phenylene, 1 ,2-cycloalkyl Y and p are as defined before, and when x = 4 then z = 0, when x = 3 then z = 1 , or when x = 2 then z = 2 (implying that the starting polyol was trimethylolpropane or trimethylolethane); R can be g)

wherein

M, Y and p are as defined before; and in which case when x = 2 then z = 4, when x = 3 then z = 3, when x = 4 then z = 2, when x=5 then z=l, or when x=6 then z=0;

(implying that the polyol used was pentaerythritol);

or R can be h)

wherein

R_3; M, Y and p are as defined before; and in which case when x = 2 then z = 3, when x = 3 then z = 2, when x = 4 then z = 1 , or when x=5 then z=0;

or R can be blends of one or more of a), b), c), d), e), f), g), and h).

2. A compound according to claim 1, wherein R comprises a) CH₃-CH₂-C or b) CH₃-C and when x = 2 then z=l or when x=3 then z=0.

3. A compound according to claim 1, wherein R comprises c) C and when x = 2 then z=2, when x=3 then z=l, or when x=4 then z=0 or d) C-C(H₂)-O-C(H₂)-C in which case when x=2 then z=4, when x=3 then z=3, when x=4 then z=2, when x=5 then z=l or when x=6 then z=0.

4. A compound according to claim 1, wherein R comprises e)

wherein

r = 2-12.

5. A compound according to claim 1 , wherein R comprises f)

wherein R₃ = Me or Et;

M = C2-6 alk(en)ylene, 1 ,2-phenylene, 1,2-cycloalkyl; Y= H, Me or Et and p= 0-5; and when x = 4 then z = 0, when x = 3 then z = 1, or when x = 2 then z = 2 (implying that the starting polyol was trimethylolpropane or trimethylolethane);

ϊ)

wherein

M, Y and p are as defined before; and in which case when x = 2 then z = 4, when x = 3 then z = 3, when x = 4 then z = 2, when x=5 then z=l , or when x=6 then z=0, (implying that the polyol used was pentaerythritol); or h)

wherein

R^₁ M, Y and p are as defined before; and in which case when x = 2 then z = 3, when x = 3 then z = 2, when x - 4 then z = 1, or when x=5 then z=0;

or R can be blends of one or more of e), f), g), and h).

6. A compound according to claim 1, further including dispersants. (e.g., comprising one of more solubilizing segments selected from: polyester solubilizing segments and polyether solubilizing segments, and one or more anchoring segments selected from: polyamine or polyimine anchoring groups, amine and carboxylic anchoring groups, quat amine anchoring groups, phosphate anchoring groups, phosphonate anchoring groups, sulfate anchoring groups, and sulfonate anchoring groups)

7. A compound according to claim 6, further including organic or inorganic pigments in the form of a mill-base.

8. A compound according to claim 7, further including at least one resin or polymer.

9. A compound according to claim 8, in the form of an ink or coating.

10. A compound according to claim 1, formulated with at least one air drying resin.

11. A condensation reaction product of a Ci₈-C₂₂ fatty acid containing 2 or more conjugated double bonds with a low molecular weight polyol with three or more hydroxyl groups of the following formulas: i. trimethylolethane optionally with ethoxy and/or C 1 -2 alkyl substituted ethoxy extended by up to 5 ethoxy repeat units per alkoxylation point, ii. trinietholopropane optionally with ethoxy and/or C 1-2 alkyl substituted ethoxy extended by up to 5 ethoxy repeat units per alkoxylation point, iii. pentaerythritol optionally with ethoxy and/or C 1-2 alkyl substituted ethoxy extended by up to 5 ethoxy repeat units per alkoxylation point, iv. dipentaerythritol optionally with ethoxy and/or C 1-2 alkyl substituted ethoxy extended by up to 5 ethoxy repeat units per alkoxylation point, v. H₂N-(CH₂X-NH₂ where r is 2-12, optionally extended with ethoxy, 1,2 propoxy, or 1 ,2 butoxy by up to 5 repeat units per alkoxylation point; and/or vi. C(O)-M-C(O) esterified at both ends with a) trimethylol ethane or propane or with pentaerytliritol optionally with up to 5 intermediate ethoxy, 1,2-propoxy, or 1,2 butoxy repeating units between the carbonyl group of C(O)-M-C(O) and the O of the trimethylol ethane or propane or with pentaerythritol where M is C2-6 alk(en)ylene, 1,2 phenylene, 1,2- cycloalkyl, wherein the ratio of C18-C22 fatty acid to polyol is at least 2 moles: 1 mole and residual nonreacted hydroxyl group(s) can exist on the polyol or residual hydroxyl group(s) can be reacted with C1-C35 hydrocarbyl or hydrocarbonyl groups or a fatty acid residue including non conjugated (poly) unsaturated fatty acids.