Color composition that does not contain alkylphenol ethoxylates

Abstract

The color composition comprises water, a pigment containing a phenyl moiety, and a dispersant having structure (I), where R1 and R2 are each independently selected from the group consisting of H, CH3, and CH2-CH3, m is a value between 30 and 100, and n is a value between 20 and 40.

Description

[Technical Field]

[0001] (Field of invention) This disclosure generally relates to compositions that do not contain alkylphenol ethoxylates, and more specifically to color compositions that do not contain alkylphenol ethoxylates. [Background technology]

[0002] (Introduction) Aqueous color compositions typically contain pigments dispersed in water. These color compositions are used in a variety of applications, including coatings, printing inks, textile dyes, and other uses. For many color compositions, the pigments used typically contain multiple polycyclic aromatic rings (e.g., phenyl moieties) with one or more polar groups located on their outer surfaces. Examples of such pigments include carbon black and isoindolinone yellow. The molecular structure of pigments tends to make them highly hydrophobic, increasing the difficulties associated with preparing aqueous compositions using such pigments. Furthermore, pigments tend to aggregate and settle during less-than-ideal storage.

[0003] Several properties are important when determining the effectiveness of a color composition. The first property of a color composition is its viscosity stability over time. Ideally, the viscosity of the color composition should increase by less than 20% when held at 54°C for 336 hours ("viscosity aging"). An increase in viscosity of more than 20% suggests poor dispersion of pigment particles and sedimentation, which adversely affects the application of the pigment. Another important property when evaluating a color composition is the color difference of the colored coating produced using the color composition, as will be described in more detail below. Ideally, the colored coating produced from the color composition should show an initial color difference of less than 0.5 in a non-thermal aging state and a color difference of less than 0.5 after thermal aging at 54°C for 336 hours ("color difference test").

[0004] Alkylphenol ethoxylates ("APEs") are used as dispersants in color compositions. The alkylphenol portion of APEs is thought to bind to the aromatic ring portions of carbon black and other pigments, thereby increasing pigment dispersion. Improved pigment dispersibility minimizes viscosity increases and minimizes color differences in color compositions. Recently, APEs have faced increasing regulatory pressure due to their alkylphenol portion, and their use in color compositions may be prohibited. Such a prohibition would adversely affect viscosity increases and the color differences of advancing color compositions.

[0005] From the above perspective, discovering a dispersant for use in color compositions that does not contain an alkylphenol portion, but also makes it possible to produce colored coatings in which the color composition shows a viscosity increase of less than 20% after viscosity aging and a color difference of 0.5 or less after color difference testing, is remarkable and advantageous. [Overview of the Initiative]

[0006] The inventors of this application have, surprisingly, discovered a dispersant for use in color compositions that does not contain an alkylphenol moiety, yet makes it possible to produce colored coatings in which the color composition exhibits a viscosity increase of less than 20% after viscosity aging and a color difference of 0.5 or less after color difference testing.

[0007] This disclosure is the result of the discovery that a dispersant corresponding to structure (I) provided below can achieve the above properties in a color composition. Although not bound by theory, it is believed that the dispersant of structure (I) can achieve the desired properties because, even though there is no alkylphenol moiety, the amine moiety of the dispersant can bond with polar groups outside the pigment. Furthermore, the alkoxylated moiety of the dispersant increases the dispersion of the pigment by creating steric hindrance between the pigment particles.

[0008] According to the first feature of this disclosure, the color composition comprises water, a pigment containing a phenyl moiety, and a dispersant having structure (I), wherein R1 and R2 are each independently selected from the group consisting of H, CH3, and CH2-CH3, m is a value of 30-100, and n is a value of 20-40.

[0009] According to the second feature of this disclosure, the weight-average molecular weight of structure (I) is 2000 g / mol to 10000 g / mol, as measured according to hydroxyl value assay.

[0010] According to the third feature of this disclosure, the weight-average molecular weight of structure (I) is 3000 g / mol to 7000 g / mol, as measured according to hydroxyl value assay.

[0011] According to the fourth feature of this disclosure, the structure (I) of the dispersant is such that R1 is H, R2 is CH3, m is a value of 95, and n is a value of 26.

[0012] According to the fifth feature of this disclosure, the structure (I) of the dispersant is such that R1 is H, R2 is CH3, m is a value of 33, and n is a value of 33.

[0013] According to the sixth feature of this disclosure, the color composition comprises 20% to 50% by weight of pigment based on the total weight of pigment in the color composition, and 20% to 40% by weight of dispersant based on the total weight of pigment in the color composition.

[0014] According to the seventh feature of this disclosure, the color composition contains 25% to 30% by weight of a dispersant based on the total weight of the pigments in the color composition.

[0015] According to the eighth feature of the present invention, the color composition further comprises 0.1% to 3.0% by weight of a stabilizer based on the total weight of the color composition, wherein the stabilizer has structure (II), where R is a linear or branched primary C6 to C6. 18 Alkyl group or secondary C6-C 18It is an alkyl group, where each R' is independently selected from the group consisting of H, CH3, and CH2~CH3, and X is 13 When measured according to 14C nuclear magnetic resonance, it has an average value of 20-60.

[0016] According to the ninth feature of this disclosure, R in structure (II) is branch C8~C 16 It is an alkyl group.

[0017] According to the tenth feature of this disclosure, X in structure (II) is 13 When measured according to 14C nuclear magnetic resonance, it has an average value of 30-40. [Modes for carrying out the invention]

[0018] As used herein, the term "and / or" means, when used in an enumeration of two or more items, that any one of the enumerated items may be used on its own, or any combination of two or more of the enumerated items may be used. For example, if a composition is described as containing components A, B, and / or C, the composition may contain A alone, B alone, C alone, A and B in combination, A and C in combination, B and C in combination, or A, B, and C in combination.

[0019] Unless otherwise stated, all ranges include the endpoints.

[0020] The test method refers to the latest test method at the priority date of this document, unless the date is shown as a two-digit number with hyphens together with the test method number. References to test methods include both references to the test society and the test method number. The test method agency is referred to by one of the following abbreviations. That is, ASTM refers to ASTM International (formerly known as American Society for Testing and Materials), EN refers to European Norm, DIN refers to Deutsches Institut fuer Normung, and ISO refers to International Organization for Standards.

[0021] As used herein, the term "weight percent" ("wt%") indicates that the component is a weight percent of the total weight of the indicated composition.

[0022] As used herein, "CAS number" is the Chemical Services Registration Number assigned by Chemical Abstracts Service.

[0023] Color composition The present invention relates to a color composition. The color composition includes water, a pigment, and a dispersant. The color composition may contain 1% or more of water based on the total weight of the color composition. For example, the color composition may contain 5% or more, or 10% or more, or 15% or more, or 20% or more, or 25% or more, or 30% or more, or 35% or more, or 40% or more, or 45% or more, or 50% or more, or 55% or more, or 60% or more, or 65% or more, or 70% or more, or 75% or more, or 80% or more, or 85% or more, or 90% or more, or 95% or more of water, while simultaneously containing 99% or less, or 95% or less, or 90% or less, or 85% or less, or 80% or less, or 75% or less, or 70% or less, or 65% or less, or 60% or less, or 55% or less, or 50% or less, or 45% or less, or 40% or less, or 35% or less, or 30% or less, or 25% or less, or 20% or less, or 15% or less, or 10% or less of water.

[0024] Pigment The color composition includes a pigment. The pigment may include one or more phenyl moieties. Examples of pigments useful in the color composition include carbon black, isoindolinone yellow, phthalocyanine blue, phthalocyanine purple, rhodamine, anthraquinone, naphthoquinone, β-carotene, indigo, thiosan purple, alizarin, azobenzene, allura red, chrysoidine resorcinol, janus green, azo violet, aniline yellow, and / or combinations thereof.

[0025] The color composition may contain 20% to 50% by weight of pigment, based on the total weight of the color composition. For example, a color composition may contain 20% by weight or more, or 22% by weight or more, or 24% by weight or more, or 26% by weight or more, or 28% by weight or more, or 30% by weight or more, or 32% by weight or more, or 34% by weight or more, or 36% by weight or more, or 38% by weight or more, or 40% by weight or more, or 42% by weight or more, or 44% by weight or more, or 46% by weight or more, or 48% by weight or more, while simultaneously containing 50% by weight or less, or 48% by weight or less, or 46% by weight or less, or 44% by weight or less, or 42% by weight or less, or 40% by weight or less, or 38% by weight or less, or 36% by weight or less, or 34% by weight or less, or 32% by weight or less, or 30% by weight or less, or 30% by weight or less, or 28% by weight or less, or 26% by weight or less, or 24% by weight or less, or 22% by weight or less of pigment.

[0026] Dispersant The color composition has structure (I):

[0027] [ka] It has, In the formula, R1 and R2 are each independently selected from the group consisting of H, CH3, and CH2~CH3, m is the average value between 30 and 100, and n is the average value between 20 and 40. R1 and R2 may be the same or different. The m and n values ​​for structure (I) are: 13 The measurement is performed according to the ¹¹C nuclear magnetic resonance. It will be understood that the values ​​of m and n are independently selected and therefore can be different from each other. In a particular example of structure (I), R1 is H, R2 is CH3, m is a value of 95, and n is a value of 26. In another particular example of structure (I), R1 is H, R2 is CH3, m is a value of 33, and n is a value of 33.

[0028] The color composition may contain 10% to 50% by weight of a dispersant, based on the total weight of the pigments in the composition. For example, the color composition may contain 10% or more by weight of a dispersant, or 15% or more by weight of a dispersant, or 20% or more by weight of a dispersant, or 25% or more by weight of a dispersant, or 30% or more by weight of a dispersant, or 35% or more by weight of a dispersant, or 40% or more by weight of a dispersant, based on the total weight of the pigments in the color composition, while simultaneously containing 50% or less by weight of a dispersant, or 45% or less by weight of a dispersant, or 40% or less by weight of a dispersant, or 35% or less by weight of a dispersant, or 30% or less by weight of a dispersant, or 25% or less by weight of a dispersant, or 20% or less by weight of a dispersant, or 15% or less by weight.

[0029] The dispersant may have a weight-average molecular weight of 2000 g / mol to 10000 g / mol when measured according to hydroxyl value assay. For example, structure (I) may have a weight-average molecular weight of 2000 g / mol or more, or 3000 g / mol, or 4000 g / mol, or 5000 g / mol, or 6000 g / mol, or 7000 g / mol, or 8000 g / mol, or 9000 g / mol, while simultaneously having a weight-average molecular weight of 10000 g / mol or less, or 9000 g / mol or less, or 8000 g / mol or less, or 7000 g / mol or less, or 6000 g / mol or less, or 5000 g / mol or less, or 4000 g / mol or less, or 3000 g / mol or less, when measured according to hydroxyl value assay.

[0030] The dispersant may exhibit a cloud point above 10°C when measured according to ASTM D2024-09. For example, the cloud point of the stabilizer may be 11°C or higher, or 15°C or higher, or 20°C or higher, or 25°C or higher, or 30°C or higher, or 35°C or higher, or 40°C or higher, or 45°C or higher, or 50°C or higher, or 55°C or higher, or 60°C or higher, or 65°C or higher, or 70°C or higher, or 75°C or higher, or 80°C or higher, or 85°C or higher, or 90°C or higher, or 95°C or higher, while simultaneously, when measured according to ASTM D2024-09, it may be 100°C or lower, or 95°C or lower, or 90°C or lower, or 85°C or lower, or 80°C or lower, or 75°C or lower, or 70°C or lower, or 65°C or lower, or 60°C or lower, or 55°C or lower, or 50°C or lower, or 45°C or lower, or 40°C or lower, or 35°C or lower, or 30°C or lower, or 25°C or lower, or 20°C or lower.

[0031] Stabilizer The color composition may contain a stabilizer. The stabilizer has the structure (II)

[0032]

Chemical formula

[0034] The stabilizer may exhibit a cloud point above 80°C when measured according to ASTM D2024-09. For example, the cloud point of the stabilizer may be 81°C or higher, or 85°C or higher, or 90°C or higher, or 95°C or higher, when measured according to ASTM D2024-09, while simultaneously being 100°C or lower, or 90°C or lower. [Examples]

[0035] material The following materials were used to form the comparative example ("CE") and the embodiment of the present invention ("IE").

[0036] CB is a carbon black pigment that is commercially available as Pigment Black A from Shanghai Hanying (Shanghai, China).

[0037] STAB1 is an alcohol ethoxylate codispersant available as EMULSOGEN® LCN 407 with 70% wt% activity, manufactured by Clariant AG Muttenz, Switzerland.

[0038] DISP1 is an alkoxylated novolac dispersant available as DISPERSOGEN® 2774 from Clariant AG Muttenz in Switzerland.

[0039] STAB2 is a branched C2 with a secondary alcohol ethoxylate (40 EO) whose cloud point in a 1 wt% aqueous solution is >100°C. 12 ~C 14 It is available from The Dow Chemical Company (Midland, Michigan, USA).

[0040] DISP2 has structure (I) where R1 is H, R2 is CH3, m is 95, and n is 26. When measured according to hydroxyl value assay, Mw is approximately 6800, the cloud point of a 1 wt% aqueous solution is 22°C, and it is commercially available from The Dow Chemical Company (Midland, Michigan, USA).

[0041] STAB3 is a branched C8 alkyl alkoxylated primary alcohol having 5 moles of propylene oxide and 40 moles of ethylene oxide, having a cloud point of >100°C in a 1 wt% aqueous solution, and is available from The Dow Chemical Company (Midland, Michigan, USA).

[0042] DISP3 has structure (I) where R1 is H, R2 is CH3, m is a value of 33, and n is a value of 33. When measured according to hydroxyl value assay, Mw is approximately 3500, the cloud point of a 1 wt% aqueous solution is 63°C, and it is available from The Dow Chemical Company (Midland, Michigan, USA).

[0043] AF is an antifoaming agent marketed as NOPCO(trademark)NXZ by Sanyo Chemical Industries, Ltd. (Kyoto, Japan).

[0044] Shanghai is a propylene glycol manufactured by Sinopharm Chemical Reagent Company (AFREZ, China).

[0045] PH is a pH neutralizer marketed as AMP-95 (trademark) by Angus Chemical Company (Buffalo Grove, Illinois, USA).

[0046] PY110 is isoindolinone yellow and is commercially available from Kremer Pigments Inc., New York, New York.

[0047] Test method Viscosity in Krebs units ("KU") was measured at 25°C ± 0.2°C using a Brookfield viscometer (KU-2 digital stormer viscometer) according to ASTM D562.

[0048] Viscosity aging: Samples were stored in sealed plastic bottles and then aged in a MENMERT UF 110 oven at 54°C for 336 hours (i.e., 2 weeks) to produce aged samples.

[0049] The color difference test was performed using the rub-up method. First, the color composition was added to the coating (pure acrylic coating for the inner wall, 51% pigment volume concentration, 15% TiO2, the remainder being binder, water, surfactant, dispersant, filler, and thickener) at a rate of 1% by weight based on the total weight of the combined coating and color composition. The mixture was then shaken for 6 minutes using a Shanghai Modern Environment HT-30 automatic rotary mixer to obtain the colored coating. After the colored coating was formed, a coating layer with a thickness of approximately 150 μm was prepared on a paper plate using a special applicator with 150 μm grooves to ensure a uniform layer thickness. After drying for 1 minute, the coating was partially wiped by gently rotating the technician's right middle finger over the coating. The diameter of the circles was approximately 3 cm to 4 cm, and a total of 45 circles were made. Smooth and uniform wiping was required to prevent abrasion through the coating film. The coating film was held at 23°C for 24 hours. Subsequently, the color difference between the wiped and unwiped areas was measured using a BYK Spectro guide sphere gloss-S spectrophotometer. Next, the sample was placed in a MEMMERT UF 110 oven at 54°C for 336 hours (i.e., 2 weeks) to produce an aged sample. After the predetermined time, the coating was removed, and the color difference between the wiped and unwiped areas was measured using a BYK Spectro guide sphere gloss-S spectrophotometer.

[0050] Hydroxyl values ​​were measured according to ASTM D4274.

[0051] Cloud point was measured according to ASTM D2024-09.

[0052] Sample preparation The color composition samples were prepared according to the following guidelines. First, water, stabilizer, and dispersant were placed in a 100 ml ("mL") beaker and then mixed in an IKA RW 20 digital overhead stirrer to form a mixture. The mixture was stirred at 500 revolutions per minute ("RPM") for 15 minutes until the stabilizer and dispersant were completely dissolved in the water. While continuing to stir, the defoamer (AF), antifreeze (AFREZ), and pH neutralizer (PH) were added to the mixture and mixed at 500 RPM for 5 minutes. Next, the mixing was stopped and the indicated pigment was added to the solution. The pigment and mixture were mixed with a stainless steel rod for 5 minutes to form a uniform color composition. The color composition was poured together with ground beads into a 200 mL sand mirror stainless steel jar made by Shenyan Ge Rui Si. The weight of the beads was 1.5 times the weight of the color composition. Next, the color composition was ground at 4000 RPM for 1 hour. After grinding, the color composition was filtered through a 100-mesh sieve to remove the beads, and the final color composition was obtained.

[0053] result Table 1 shows the compositions of CE1, CE2, and IE1 to IE5.

[0054] [Table 1]

[0055] Table 2 shows the viscosity test results for IE and CE color compositions.

[0056] [Table 2]

[0057] As can be seen from Table 2, the viscosity increase of IE1 to IE5 is the same as, or less than, the viscosity increase achieved by CE1 to CE3. Specifically, the initial viscosity of the color composition containing IE1, IE2, and IE3 was lower than the initial viscosity obtained using CE1. These results indicate that the dispersion efficiency of IE was higher than that of CE1. Furthermore, data from thermally aged samples show that IE exhibits the same or better thermal stability as CE.

[0058] Table 3 shows the results of the color difference test data for IE and CE color compositions.

[0059] [Table 3]

[0060] Referring to Table 3, color difference data for the color compositions are provided. As can be seen from the figure, the color difference of the IE coating was equivalent to the color development of the coatings using CE1 and CE3. For CE2, the initial color difference was too high, so no thermal aging sample was produced. IE1 to IE5 showed color difference values ​​well below the target value of 0.5, and are therefore successful.

[0061] As shown in the data in Tables 2 and 3, a color composition comprising water, a pigment, and a dispersant having structure (I) can achieve the target viscosity stability and target color difference even without the presence of alkylphenol ethoxylates.

Claims

1. A color composition, Water and, Pigments containing a phenyl portion, Structure (I) 【Chemistry 1】 A dispersant having the following: In the formula, R １ and R ２ These are H and CH, respectively, independently. ３ , and CH ２ ~CH ３ A color composition selected from the group consisting of the following, where m is a value between 30 and 100, and n is a value between 20 and 40.

2. The color composition according to claim 1, wherein, when measured according to hydroxyl value measurement, the weight-average molecular weight of structure (I) is 2,000 g / mol to 10,000 g / mol.

3. The color composition according to claim 2, wherein, when measured according to hydroxyl value measurement, the weight-average molecular weight of structure (I) is 3000 g / mol to 7000 g / mol.

4. Regarding the structure (I) of the dispersant, R １ H is R ２ ga CH ３ The color composition according to any one of claims 1 to 3, wherein m is a value of 95 and n is a value of 26.

5. Regarding the structure (I) of the dispersant, R １ is H, and R ２ is CH ３ is, m is a value of 33, and n is a value of 33. The color composition according to any one of claims 1 to 3.

6. The aforementioned color composition is Based on the total weight of the color composition, 20% to 50% by weight of the pigment, The color composition according to any one of claims 1 to 5, comprising 20% ​​to 40% by weight of the dispersant based on the total weight of the pigments in the color composition.

7. The color composition according to claim 6, wherein the color composition comprises 25% to 30% by weight of a dispersant based on the total weight of the pigments in the color composition.

8. The aforementioned color composition is The color composition further comprises 0.1% to 3.0% by weight of a stabilizer based on the total weight of the color composition, wherein the stabilizer has structure (II) 【Chemistry 2】 It has, In the formula, R is a first-class carbon atom of a linear or branched chain. ６ ~C １８ Alkyl group or secondary C ６ ~C １８ It is an alkyl group, and each R' independently consists of H, CH ３ ,CH ２ ~CH ３ Selected from the group consisting of, X is １３ The color composition according to any one of claims 1 to 7, having an average value of 20 to 60 when measured according to 14C nuclear magnetic resonance.

9. In structure (II), R is branch C. ８ ~C １６ The color composition according to claim 8, wherein the alkyl group is an alkyl group.

10. In structure (II), X is, １３ The color composition according to any one of claims 8 and 9, having an average value of 30 to 40 when measured according to 14C nuclear magnetic resonance.

Images