A floating color preventing dispersant applied to dry process resin of synthetic leather and preparation method and application thereof

Abstract

The present application belongs to the technical field of synthetic leather, and particularly relates to a floating color preventing dispersant for synthetic leather dry method resin, a preparation method and application thereof. The floating color preventing dispersant for synthetic leather dry method resin comprises 30-45% of partially esterified maleic anhydride modified vegetable oil acid, 5-20% of polyether modified polydimethylsiloxane, 25-35% of propylene glycol methyl ether acetate and 15-25% of butyl acetate in terms of mass percentage. The partially esterified maleic anhydride modified vegetable oil acid has better compatibility with polyurethane, so that the floating color preventing dispersant is more suitable for polyurethane resin system. In addition, the polyether modified polydimethylsiloxane can reduce the surface tension gradient among the floating color preventing dispersant, resin and color filler in the dry method resin, so that the components are better fused, and the product has the characteristics of good floating color preventing effect, high cost performance and environmental protection.

Description

Technical Field

[0001] This invention belongs to the field of synthetic leather technology, specifically relating to an anti-floating color dispersant for use in dry-process synthetic leather resins, its preparation method, and its application. Background Technology

[0002] Coloring synthetic leather is an essential step in its production, especially in dry tanning, where dry resin, color flakes, color paste, a small amount of additives, and solvents are mixed and dispersed evenly to form a paste. However, during storage, a layer of color different from the paste itself often floats on the surface; this phenomenon is called "floating color." Floating color not only affects the aesthetic appearance of the paste but, more importantly, can easily lead to color differences, even color deviation or color bleeding, during the coloring process on synthetic leather, resulting in poor product quality.

[0003] The phenomenon of floating color is mainly caused by the incompatibility between pigment pastes / flakes and the resin system, as well as the poor compatibility between white pigment pastes / flakes and colored pigment pastes / flakes. Most commercially available anti-floating dispersants are controlled flocculation dispersants. These dispersants create a network-like interaction force between organic and inorganic pigments by restricting the relative movement between pigment particles, thus achieving a certain anti-floating effect. However, the prerequisite for these dispersants to work is excellent compatibility with the system; therefore, the versatility of their anti-floating function is limited. In addition, adding silicone leveling agents can also improve the floating color phenomenon, but this adjustment function is limited. It can only improve the visual effect of some slurry surfaces and cannot create interaction between pigment particles like the controlled flocculation dispersants mentioned above. Therefore, it cannot prevent the relative movement of pigment particles in the vertical direction of the slurry, and thus cannot completely prevent the occurrence of floating color. Summary of the Invention

[0004] The purpose of this invention is to provide an anti-floating color dispersant for use in dry-process resins of synthetic leather, its preparation method and application. The anti-floating color dispersant provided by this invention has a universal and excellent anti-floating color effect.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This invention provides an anti-floating color dispersant for use in dry-process resins of synthetic leather, comprising, by weight percentage, 30-45% partially esterified maleic anhydride modified vegetable oleic acid, 5-20% polyether modified polydimethylsiloxane, 25-35% propylene glycol methyl ether acetate, and 15-25% butyl acetate.

[0007] Preferably, the degree of esterification of the partially esterified maleic anhydride-modified vegetable oleic acid is 3-10%.

[0008] Preferably, the preparation method of the partially esterified maleic anhydride modified vegetable oleic acid includes the following steps:

[0009] An alcohol, vegetable oleic acid, and maleic anhydride are mixed and partially esterified to obtain the partially esterified maleic anhydride-modified vegetable oleic acid.

[0010] Preferably, the alcohol includes one or more of n-butanol, isooctanol, dodecanol, and isothiazol.

[0011] Preferably, the plant oleic acid includes one or more of oleic acid, linoleic acid, and ricinoleic acid;

[0012] The mass ratio of the alcohol to vegetable oleic acid is 2-6:65-85.

[0013] Preferably, the mass ratio of maleic anhydride to oleic acid is 15-30:65-85.

[0014] Preferably, the partial esterification reaction is carried out at a temperature of 150–210°C for 8–16 hours.

[0015] This invention also provides a method for preparing the anti-floating color dispersant described in the above technical solution, comprising the following steps:

[0016] The anti-floating color dispersant is obtained by mixing partially esterified maleic anhydride modified vegetable oleic acid, polyether modified polydimethylsiloxane, propylene glycol methyl ether acetate and butyl acetate.

[0017] The present invention also provides the application of the anti-floating color dispersant described in the above technical solution or the anti-floating color dispersant obtained by the preparation method described in the above technical solution in the coloring of synthetic leather.

[0018] Preferably, the synthetic leather is colored using a dry resin coloring process; in the dry resin coloring process, the anti-floating dispersant has a mass percentage content of 0.1-0.5% in the synthetic leather dry resin.

[0019] This invention provides an anti-floating color dispersant for use in dry-process resins of synthetic leather, comprising, by weight percentage, 30-45% partially esterified maleic anhydride modified vegetable oleic acid, 5-20% polyether modified polydimethylsiloxane, 25-35% propylene glycol methyl ether acetate, and 15-25% butyl acetate. The anti-floating color dispersant provided by this invention contains partially esterified maleic anhydride-modified vegetable oleic acid. Compared with ordinary controlled flocculation structure maleic anhydride-modified vegetable oleic acid, the presence of the esterification structure results in better compatibility with polyurethane. Therefore, it is more suitable for polyurethane resin systems than ordinary controlled flocculation structure anti-floating color dispersants on the market. In addition, due to the compounding of polyether-modified polydimethylsiloxane, the surface tension gradient between the anti-floating color dispersant, resin, pigments and fillers in dry resin can be reduced, allowing the components to blend better and further improving the effect of the anti-floating color dispersant. It overcomes the defects of poor compatibility and poor versatility of anti-floating color additives on the market, and has the characteristics of good anti-floating color effect, high cost performance and environmental protection. Detailed Implementation

[0020] This invention provides an anti-floating color dispersant for use in dry-process resins of synthetic leather, comprising, by weight percentage, 30-45% partially esterified maleic anhydride modified vegetable oleic acid, 5-20% polyether modified polydimethylsiloxane, 25-35% propylene glycol methyl ether acetate, and 15-25% butyl acetate.

[0021] In this invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0022] The anti-floating color dispersant provided by the present invention comprises 30-45% (preferably 33-42%) of partially esterified maleic anhydride modified vegetable oleic acid, and more preferably 35-40% (by mass percentage).

[0023] In this invention, the degree of esterification of the partially esterified maleic anhydride-modified vegetable oleic acid is preferably 3-10%, more preferably 5-8%.

[0024] In this invention, the method for preparing the partially esterified maleic anhydride-modified vegetable oleic acid preferably includes the following steps:

[0025] An alcohol, vegetable oleic acid, and maleic anhydride are mixed and partially esterified to obtain the partially esterified maleic anhydride-modified vegetable oleic acid.

[0026] In this invention, the alcohol preferably includes one or more of n-butanol, isooctanol, dodecyl alcohol, and isothiazol, more preferably one or more of n-butanol, dodecyl alcohol, and isothiazol, and most preferably n-butanol and / or dodecyl alcohol; the dodecyl alcohol is preferably one or more of n-dodecyl alcohol, isothiazol, and tert-dodecyl alcohol; when the alcohol is two or more of the above specific types, this invention does not impose any special limitation on the ratio of the alcohol.

[0027] In this invention, the plant oleic acid preferably includes one or more of oleic acid, linoleic acid and ricinoleic acid, more preferably two of oleic acid, linoleic acid and ricinoleic acid, and most preferably oleic acid and ricinoleic acid; when the plant oleic acid is two or more of the above-mentioned specific types, this invention does not impose any special limitation on the ratio of the plant oleic acid.

[0028] In this invention, the mass ratio of the alcohol to vegetable oleic acid is preferably 2-6:65-85, more preferably 3-5:70-80, and most preferably 3-4:70-75.

[0029] In this invention, the mass ratio of maleic anhydride to oleic acid is preferably 15-30:65-85, more preferably 20-30:70-80, and most preferably 20-25:70-75.

[0030] The present invention does not impose any special limitations on the mixing process; any method known to those skilled in the art can be used.

[0031] In this invention, the temperature of the partial esterification reaction is preferably 150–210°C, more preferably 160–200°C, and most preferably 170–190°C; the time is preferably 8–16 h, more preferably 9–14 h, and most preferably 11–13 h.

[0032] In this invention, the reason for using partially esterified maleic anhydride-modified vegetable oleic acid is that ordinary vegetable oleic acid contains a single carboxyl group, which can only adsorb a single pigment particle; while the maleic anhydride-modified vegetable oleic acid has increased carboxyl functional groups, thereby enabling one molecule to adsorb onto multiple pigment particles, so as to form a network-like structure of interaction between pigment particles. The purpose of partial esterification is to improve the compatibility of the dispersant with polyurethane resin and organic pigments, so that the dispersant can play an effective role in the system; complete esterification means a reduction in the production of carboxyl groups and a weakening of the controlled flocculation force, which will weaken the network-like structure of interaction between pigment particles, thereby reducing the effect of the anti-floating dispersant. Therefore, the partially esterified maleic anhydride-modified vegetable oleic acid used in this invention has excellent anti-floating effect.

[0033] The anti-floating color dispersant provided by the present invention comprises 5-20% polyether-modified polydimethylsiloxane, preferably 10-20%, more preferably 10-15% by mass percentage; the polyether-modified polydimethylsiloxane is preferably one or more of Jiangxi Sangao Polymer Material SY-9733, Evcona AFCONA3030, and BYK BYK-9565, more preferably Jiangxi Sangao Polymer Material SY-9733, Evcona AFCONA3030, or BYK BYK-9565, and most preferably Jiangxi Sangao Polymer Material SY-9733 or BYK BYK-9565; when the polyether-modified polydimethylsiloxane is two or more of the above-mentioned specific types, the present invention does not impose any special limitation on the proportion of the polyether-modified polydimethylsiloxane.

[0034] The anti-floating color dispersant provided by the present invention comprises 25-35% propylene glycol methyl ether acetate, preferably 27-34%, and more preferably 29-32% by mass percentage.

[0035] The anti-floating color dispersant provided by the present invention comprises 15-25% butyl acetate, preferably 17-24%, and more preferably 19-22% by mass percentage.

[0036] The anti-floating color dispersant provided by this invention overcomes the defects of poor compatibility and poor versatility of anti-floating color additives on the market, and has the characteristics of good anti-floating color effect, high cost performance and environmental protection.

[0037] This invention also provides a method for preparing the anti-floating color dispersant described in the above technical solution, comprising the following steps:

[0038] The anti-floating color dispersant is obtained by mixing partially esterified maleic anhydride modified vegetable oleic acid, polyether modified polydimethylsiloxane, propylene glycol methyl ether acetate and butyl acetate.

[0039] The present invention does not impose any special limitations on the mixing process; the resulting anti-floating color dispersant can be made uniform and stable by means well known to those skilled in the art.

[0040] The present invention also provides the application of the anti-floating color dispersant described in the above technical solution or the anti-floating color dispersant obtained by the preparation method described in the above technical solution in the coloring of synthetic leather.

[0041] In this invention, the preferred method for coloring synthetic leather is dry resin coloring; in the dry resin coloring of synthetic leather, the mass percentage of the anti-floating dispersant in the dry resin of synthetic leather is preferably 0.1-0.5%, more preferably 0.2-0.4%.

[0042] The anti-floating color dispersant provided by this invention, when applied to the dry resin of synthetic leather, can suppress or even completely eliminate the floating color phenomenon to the greatest extent.

[0043] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, of the anti-floating color dispersant for synthetic leather dry resin, its preparation method, and its application, is provided but should not be construed as limiting the scope of protection of the present invention.

[0044] Example 1

[0045] 200 kg of castor oil acid, 150 kg of oleic acid, 23 kg of dodecanol and 120 kg of maleic anhydride were added to a reaction vessel, heated to 200 °C, and stirred for 10 h to obtain partially esterified maleic anhydride-modified vegetable oleic acid.

[0046] Add 427 kg of esterified maleic anhydride modified vegetable oleic acid, 303099 kg of polyether modified polydimethylsiloxane AFCONA, 288 kg of propylene glycol methyl ether acetate and 146 kg of butyl acetate to a mixing tank and mix and stir evenly to obtain the anti-floating color dispersant.

[0047] Example 2

[0048] 236 kg of linoleic acid, 119 kg of oleic acid, 18 kg of dodecanol, 4.3 kg of n-butanol and 117.2 kg of maleic anhydride were added to a reaction vessel, heated to 195 °C, and stirred for 14 h to obtain partially esterified maleic anhydride-modified vegetable oleic acid.

[0049] Add 373 kg of esterified maleic anhydride modified vegetable oleic acid, 129 kg of polyether modified polydimethylsiloxane BYK-9565, 313 kg of propylene glycol methyl ether acetate, and 185 kg of butyl acetate to a mixing tank and mix thoroughly to obtain the anti-floating color dispersant.

[0050] Example 3

[0051] 284 kg of castor oil acid, 97.5 kg of oleic acid, 13.5 kg of dodecanol and 102.1 kg of maleic anhydride were added to a reaction vessel, heated to 205 °C, and stirred for 15 h to obtain partially esterified maleic anhydride-modified vegetable oleic acid.

[0052] Add 316 kg of esterified maleic anhydride modified vegetable oleic acid, 189 kg of polyether modified polydimethylsiloxane SY-9733, 301 kg of propylene glycol methyl ether acetate and 199 kg of butyl acetate to a mixing tank and mix and stir evenly to obtain the anti-floating color dispersant.

[0053] Comparative Example 1

[0054] Commercially available anti-floating color dispersant BYK-104S.

[0055] Comparative Example 2

[0056] Commercially available anti-floating color dispersant EFKA-5065.

[0057] Comparative Example 3

[0058] Commercially available anti-floating color dispersant Deqian 904S.

[0059] Test case

[0060] The anti-floating dispersants corresponding to Examples 1-3 and Comparative Examples 1-3 were each prepared into 100g synthetic leather color pastes, with the following formulations: 31.7g AE-1419 polyurethane resin solution, 50g solvent N,N-dimethylformamide, 0.3g anti-floating dispersant, 15g white paste PU-2078G, 0.5g black paste PU-9100, 1.3g yellow paste PU-1067, and 1.2g red paste PU-3068.

[0061] The preparation method is as follows: First, stir AE-1419 polyurethane resin and N,N-dimethylformamide for 10 minutes until completely dissolved. Then, add the anti-floating color dispersant and continue stirring for 5 minutes to disperse it evenly in the resin solution. Next, add the four color pastes of white, black, yellow and red in sequence and stir for 20 minutes to mix the various colors evenly and adjust them into a single color.

[0062] The synthetic leather coloring pastes obtained from Examples 1-3, Comparative Examples 1-3, and the blank control group were placed for 4 hours, and the floating state of the coloring pastes was observed. The test results are shown in Table 1.

[0063] Table 1. Test results of the anti-floating color dispersant performance.

[0064]

[0065]

[0066] As shown in Table 1, during the preparation of the color paste, the blank sample (i.e., without the addition of the anti-floating dispersant) showed severe floating of color, with red, yellow, and black colors appearing. The addition of common anti-floating additives on the market, such as BYK-104S, EFKA-5065, and Deqian 904S, had very limited effect, and the floating phenomenon was still very obvious. However, with the addition of the anti-floating dispersant prepared in Examples 1 to 3 of this invention, the floating phenomenon was suppressed to the greatest extent, or even completely eliminated.

[0067] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. The application of anti-floating color dispersant in the coloring of synthetic leather, characterized in that, By weight percentage, the anti-floating color dispersant comprises 30-45% partially esterified maleic anhydride modified vegetable oleic acid, 5-20% polyether modified polydimethylsiloxane, 25-35% propylene glycol methyl ether acetate, and 15-25% butyl acetate; The degree of esterification of the partially esterified maleic anhydride-modified vegetable oleic acid is 3-10%. The method for preparing the partially esterified maleic anhydride-modified vegetable oleic acid includes the following steps: An alcohol, vegetable oleic acid, and maleic anhydride are mixed and partially esterified to obtain the partially esterified maleic anhydride-modified vegetable oleic acid. The mass ratio of the alcohol to vegetable oleic acid is 2~6:65~85; The alcohols include one or more of n-butanol, isooctanol, dodecanol, and isothiazol; The plant oleic acid includes one or more of oleic acid, linoleic acid, and ricinoleic acid; The mass ratio of maleic anhydride to oleic acid is 15~30:65~85; The partial esterification reaction is carried out at a temperature of 150~210℃ for 8~16 hours.

2. The application according to claim 1, characterized in that, The preparation method of the anti-floating color dispersant includes the following steps: The anti-floating color dispersant is obtained by mixing partially esterified maleic anhydride modified vegetable oleic acid, polyether modified polydimethylsiloxane, propylene glycol methyl ether acetate and butyl acetate.

3. The application according to claim 1, characterized in that, The synthetic leather is colored using a dry resin coloring process; in the dry resin coloring process, the anti-floating dispersant has a mass percentage content of 0.1-0.5% in the synthetic leather dry resin.

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