JP3436773B2 - Water / oil repellent, polishing agent, solidifying agent or lubricant - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a water / oil repellent, a polish, a solidifying agent or a lubricant, and has water / oil repellency, durability, weather resistance, smoothness, releasability and antifouling property. Excellent car wax, floor / furniture wax, leather cleaner, etc.

[0002]

2. Description of the Related Art As a surface treatment method for leather, painted surface, etc.,
It has long been practiced to polish the painted surface with a natural resin or synthetic resin paint to give it a glossy appearance, improve its aesthetic appearance, and to impart water and oil repellency and stain resistance. (Natural wax or synthetic wax),
Various water / oil repellent and polish compositions based on silicone oil, oily substances and the like are commercially available.

Examples of natural waxes and synthetic waxes include plant-based natural waxes such as carnauba wax, candelilla wax, sugar wax, rice wax, wood wax, bayberry wax, ocully wax, esparto wax, beeswax, insect wax, and the like. Animal waxes such as whale wax, shellac wax and lanolin wax, petroleum natural waxes such as paraffin wax and microcrystalline wax, mineral waxes such as montan wax, ozokerite wax, ceresin and hoax wax, polyethylene wax, carbowax , Castor wax, Fischer-Tropsch wax, synthetic wax such as kesol wax, and higher fatty acids and higher aliphatic alcohols of the above-mentioned animal / vegetable waxes, and their individual substances. Beauty their synthetic esters are known.

However, conventionally known natural waxes are natural products and therefore have variations in quality, and there is a problem in terms of stable supply. Further, although synthetic and natural waxes have moderate luster, they are not sufficient in terms of having excellent water / oil repellency, durability and antifouling property.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a water-repellent / oil-repellent agent, which has excellent water-repellent / oil-repellent property, durability, weather resistance, smoothness, releasability and antifouling property, and polish. To provide an agent, a solidifying agent or a lubricant.

[0006]

DISCLOSURE OF THE INVENTION The present invention comprises a complex esterification product prepared by combining a polyol having a valence of 2 or more and a valence of 6 or less, an aromatic dibasic acid and a monobasic acid. It is a water / oil repellent, a polish, a solidifying agent or a lubricant (hereinafter referred to as “water repellent etc.”). Although various polyols having a valence of 2 or more and a valence of 6 or less constituting the complex esterification product of the present invention can be used,
Among them, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, diglycerin, triglycerin and dipentaerythritol are preferable.

As the aromatic dibasic acid, phthalic acid, isophthalic acid, terephthalic acid and the like can be used. In addition, various monocarboxylic acids can be used as the monobasic acid. Among them, fatty acids derived from fats and oils and / or synthetic fatty acids obtained by a paraffin oxidation method, an oxo method, a Koch method, a Guerbet method, an alkali melting method and / or Polyfluoro saturated carboxylic acid and / or partially fluoro saturated carboxylic acid and / or fluorine-containing aromatic carboxylic acid are preferable.

Fatty acids derived from fat and / or oil and / or synthetic paraffins obtained by the paraffin oxidation method, the oxo method, the Koch method, the Guerbet method and the alkali melting method (hereinafter referred to as “fatty acid”) have 12 or more and 30 or less carbon atoms. Linear saturated fatty acids can be used. For example, lauric acid, tridecylic acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, nonadecyl acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, coconut oil fatty acid, beef tallow Examples thereof include fatty acids and fish hard fatty acids (hydrogenated fish oil fatty acids).
The straight-chain saturated fatty acid having 12 or more and 30 or less carbon atoms is limited to the use of a straight-chain saturated fatty acid, a side chain saturated fatty acid or an unsaturated fatty acid having less than 12 carbon atoms, which lowers the melting point of the complex esterification product. However, it is not possible to obtain sufficient water / oil repellency. When the carbon number exceeds 30, it is difficult to obtain industrially.

The polyfluoro saturated carboxylic acid preferably has 5 or more and 22 or less carbon atoms and includes polyfluorovaleric acid, polyfluorocaproic acid, polyfluoroenanthic acid, polyfluorocaprylic acid, polyfluoropelargonic acid, polyfluorocapric acid, Polyfluoroundecanoic acid, polyfluorolauric acid, polyfluorotridecyl acid, polyfluoromyristic acid, polyfluoropentadecyl acid, polyfluoropalmitic acid, polyfluoromargaric acid, polyfluorostearic acid, polyfluoroarachidic acid, poly Fluorohenicosanoic acid and the like can be used, and more preferable polyfluoro saturated carboxylic acids are polyfluorocaprylic acid, polyfluorodecanoic acid, polyfluorolauric acid, and polyfluoromyristic acid. Can. Unsaturated carboxylic acids and those having less than 5 carbon atoms have too low a melting point of the product, so that sufficient water / oil repellency cannot be obtained, and those having more than 22 carbon atoms are difficult to obtain industrially.

The partially fluorosaturated carboxylic acid preferably has 5 or more and 25 or less carbon atoms, for example, 5-H-polyfluorovalerianic acid, 14-H-polyfluoromyristic acid, 21-H-polyfluorohenicosanoic acid, Two
2,12-H-polyfluorolauric acid, 2,2,3
3,4,4,5,5-H-polyfluoropelargonic acid,
2,2,3,3-H-polyfluorocapric acid, 2,
2,3,3,4,4,5,5-H-polyfluoropentadecyl acid, 2,2-H-polyfluoromargaric acid,
2,2,3,3,4,4-H-polyfluoroarachidic acid, 2,2-H-polyfluorobehenic acid, 2,2,3
Examples include 3,4,4,5,5-H-polyfluoropentacosanoic acid and the like. When the unsaturated carboxylic acid or the saturated carboxylic acid has less than 5 carbon atoms, the melting point of the product is too low to obtain sufficient water / oil repellency, and those having more than 25 carbon atoms are difficult to obtain.

The fluorine-containing aromatic carboxylic acid is 2,
3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 3,4,5-trifluorobenzoic acid,
3,4,6-trifluorobenzoic acid, 4,5,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid,
2,3,5,6-tetrafluorobenzoic acid, 3,4
Examples thereof include 5,6-tetrafluorobenzoic acid and pentafluorobenzoic acid.

Here, the complex esterification product synthesized from three components of a polyol having a valency of 2 or more and 6 or less, an aromatic dibasic acid and a monobasic acid is the number of fluorine atoms / the number of hydrogen atoms in the monobasic acid. The ratio of 0 to 1 is more desirable. If the ratio of the number of fluorine atoms / the number of hydrogen atoms in the monobasic acid exceeds 1 (the fluorine content is too high), the compatibility with other oil agents, solvents, etc. will gradually decrease, and the physical properties aimed at by the present invention. Hard to get. Further, the average molecular weight of the complex esterification product of the present invention is determined by the molar ratio of the above-mentioned three components used as raw materials, but is not particularly limited in the present invention.

The ester of the present invention can be synthesized from the above raw materials by a conventional esterification method without catalyst or in the presence of a catalyst, and the method is not particularly limited. The esterification product may be used alone, or may be used in combination with a conventional natural wax or synthetic wax depending on the purpose. The compounding amount in the water repellent or the like is 0.1 to 100% by weight, preferably 5 to 70% by weight.

[0014]

【Example】

Synthesis example (Table 1: Sample symbol A) 4 equipped with stirrer, thermometer, nitrogen gas blowing pipe, water separator
In a two-necked flask, 852 g of stearic acid (3 molar equivalents) and 402 g of trimethylolpropane (3 molar equivalents)
Was charged, and 2.5 g of tin chloride was charged as a catalyst 160
The reaction was carried out at ˜240 ° C. until the calculated amount of water distilled. The required time was 5 hours and the acid value was 1.7. After the reaction was completed, the mixture was cooled and 332 g of terephthalic acid (2 molar equivalent)
Was charged, and the reaction was carried out at 160 to 240 ° C. until a calculated amount of water was distilled off. The time required was 7 hours. After completion of the reaction, xylene was distilled off under reduced pressure, decolorized with activated clay and filtered to obtain a slightly yellow solid. Yield 1310g,
The acid value was 2.3, the saponification value was 268, and the melting point (° C) was 53 to 55. Hereinafter, the complex esterification products (Sample Codes B to J) of the present invention shown in Table 1 were produced by the same method.

[0015]

[Table 1]

Example 1 Carwax A solid carwax was prepared by the conventional method with the following formulation. Prescription example Microwax (mp 155 ° F) 5 parts (parts by weight. The same applies hereinafter) 15 parts dimethyl silicone (350 cs) 10 parts mineral spirit 70 parts Synthetic complex ester of the present invention The car wax obtained is used to polish the surface of automobiles. Wipe,
Elongation at wiping, wiping property, water repellency, and gloss and water repellency after 10 times water washing were evaluated. The results are shown in Table 2.

[0017]

[Table 2] Commercial item B: Paraffin wax 10%, microcrystalline wax 5% combination type Commercial item B: Carnauba wax 10%, paraffin wax 5% combination type Evaluation method: 3-level evaluation (○ ・ ・ ・ Good, △ ・ ・ ・ Normal ,
× ・ ・ ・ Not possible)

Example 2 Pasty Solvent-Based Floor and Furniture Wax A floor and furniture wax was prepared according to the following formulation. Synthetic complex ester of the present invention 15 parts ceresin 5 parts paraffin wax (mp 145 ° F) 10 parts mineral spirits 70 parts Using the wax obtained, a wood plywood coated with a urethane paint is wiped with a gloss, and the elongation and gloss during wiping are obtained. , Water repellency, and gloss and water repellency after washing 10 times with detergent were evaluated. The results are shown in Table 3.

[0019]

[Table 3] Commercial product C: Carnauba wax 5%, paraffin wax 2
0% formulation type evaluation method: Same as the notes in Table 2

Example 3 Shoe Cream A shoe cream was prepared with the following formulation. Synthetic complex ester of the present invention 17 parts Beeswax 15 parts Mineral spirits 27 parts Triethanolamine 3 parts Stearic acid 5 parts Water 33 parts Using the obtained shoe cream, elongation, gloss, water repellency and rainfall when wiped on cowhide shoes When used three times, the gloss,
The water repellency was evaluated. The results are shown in Table 4.

[0021]

[Table 4] Commercial products d: Candelilla wax 5%, carnauba wax 10
% Combination type evaluation method: Same as the notes in Table 2

[0022]

The various water repellents, oil repellents, polishes, solidifying agents and lubricants containing the complex esterified product of the present invention have excellent water repellency, oil repellency, durability and weather resistance, It has both smoothness, releasability and antifouling property, and has unprecedented solidification and lubricity. Therefore, for example, products exhibiting excellent performance as car wax, floor / furniture wax, and leather cleaner can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09K 3/18 101 C08L 67/02-67/03 C09G 1/16 D06M 15/507-15/513

Claims (6)

(57) [Claims] 1. From 160 to 240 ° C. from three components of a polyol having a valency of 2 or more and a valence of 6 or less, an aromatic dibasic acid and a monobasic acid.
A water / oil repellent compounded with a complex esterification product synthesized at a temperature of , wherein the complex esterification product has an acid value of 9.2 or more.
Below, the polyol is neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane,
One or more selected from the group consisting of pentaerythritol, sorbitol, diglycerin, triglycerin and dipentaerythritol, wherein the aromatic dibasic acid is selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. A water-repellent / oil-repellent agent, which is one or more of the above-mentioned monobasic acids, and wherein the monobasic acid is a linear saturated fatty acid having 12 to 30 carbon atoms. 2. The water / oil repellent according to claim 1, which is a wax. 3. The water / oil repellent according to claim 1, which is a leather cleaner . 4. 160 to 240 ° C. from three components of a polyol having a valence of 2 or more and a valence of 6 or less, an aromatic dibasic acid and a monobasic acid.
A complexing esterification product synthesized at a temperature of 10 ° C., wherein the complex esterification product has an acid value of 9.2 or more.
Below, the polyol is neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane,
One or more selected from the group consisting of pentaerythritol, sorbitol, diglycerin, triglycerin and dipentaerythritol, wherein the aromatic dibasic acid is selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. One or two or more of the above, and the above-mentioned monobasic acid is a straight-chain saturated fatty acid having 12 to 30 carbon atoms. 5. The polish according to claim 4, which is a wax. 6. The polish according to claim 4, which is a leather cleaner .