JP3206941B2 - Water / oil repellent, polishing agent, solidifying agent or lubricant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water / oil repellent, a polishing agent, a solidifying agent or a lubricant, and relates to water / oil repellency, durability, weather resistance, smoothness, non-adhesion, mold release and The present invention relates to car wax, floor and furniture wax, leather cleaner, plastic additives, etc., which have excellent antifouling properties.

[0002]

2. Description of the Related Art As a surface treatment of leather, painted surface, etc., a painted surface is polished with a natural resin or a synthetic resin paint to give a luster, improve aesthetic appearance, and impart water and oil repellency and stain resistance. It has been practiced for a long time, and various water-repellent, oil-repellent, and polish compositions based on waxes (natural wax or synthetic wax), silicone oil, and oily substances are commercially available.

[0003] Examples of natural waxes and synthetic waxes include carnauba wax, candelilla wax, sugar wax, rice wax, wood wax, bayberry wax, occury wax, esparto wax, and other plant-based natural waxes, beeswax, insect wax, and the like. Animal waxes such as whale wax, shellac wax, lanolin wax, petroleum natural waxes such as paraffin wax and microcrystalline wax, mineral natural waxes such as montan wax, ozokerite wax, and ceresin, and Hoechst wax, polyethylene wax, and carbowax Waxes, castor waxes, Fischer-Tropsch waxes, kesol waxes, etc. and higher fatty acids and higher aliphatic alcohols of the above animal and plant waxes, alone and in combination Synthetic esters are known.

[0004] However, conventionally known natural waxes are natural products, and therefore have variations in quality and also have a problem in terms of stable supply. Although synthetic and natural waxes have moderate gloss, they are not sufficient in terms of having excellent water and oil repellency, durability and antifouling properties.

[0005]

The object of the present invention is to provide excellent water and oil repellency, durability, weather resistance, smoothness, non-adhesion,
An object of the present invention is to provide a water-repellent / oil-repellent agent, a polishing agent, a solidifying agent, or a lubricant having both release properties and antifouling properties.

[0006]

SUMMARY OF THE INVENTION The present invention provides a compound represented by general formula 1,
A water-repellent / oil-repellent agent, a polishing agent, a solidifying agent or a lubricant prepared by blending an esterification product containing a polyfluoroalkyl group or a partial fluoroalkyl group represented by the following chemical formula 2, 3, 4 or 5. is there.

The polyfluoro saturated carboxylic acid used in the general formula 1 includes, for example, polyfluorovaleric acid,
Polyfluorocaproic acid, polyfluoroenanthic acid, polyfluorocaprylic acid, polyfluoropelargonic acid, polyfluorocapric acid, polyfluoroundecanoic acid, polyfluorolauric acid, polyfluorotridecyl acid, polyfluoromyristic acid, polyfluoropentadecyl Acid, polyfluoropalmitic acid, polyfluoromalgaric acid, polyfluorostearic acid, polyfluorononadecyl acid, polyfluoroarachidic acid, polyfluorohenicosanoic acid, etc., among which industrially useful poly Examples of the fluorosaturated carboxylic acid include polyfluorocaprylic acid, polyfluorodecanoic acid, polyfluorolauric acid, and polyfluoromyristic acid. Further, as the partially fluoro-saturated carboxylic acid, for example, 2,2-H-polyfluorocaproic 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-polyfluoropentadecylic acid, 2,2-H-polyfluoromargaric acid,
2,2,3,3,4,4-H-polyfluoroarachidic acid, 2,2-H-polyfluorobehenic acid, 2,2,3
3,4,4,5,5-H-polyfluoropentacosanoic acid and the like can be mentioned.

The partially fluorosaturated carboxylic acids used in the general formula 2 include, for example, 5-H-polyfluorovaleric acid, 14-H-polyfluoromyristic acid, 21-
H-polyfluorohenicosanoic acid, 2,2,12-H-
Polyfluorolauric acid, 2,2,3,3,4,4,1
8-H-polyfluorostearic acid, 2,2,3,3
4,4,5,5,9-H-polyfluoropelargonic acid,
2,2,3,3,4,4,5,5,25-H-polyfluoropentacosanoic acid and the like.

The polyfluoro saturated dicarboxylic acid used in the general formula 3 includes, for example, polyfluoroadipic acid,
Polyfluoropimelic acid, polyfluorosuberic acid, polyfluoroazeleic acid, polyfluorosebacic acid and the like can be used. Among them, polyfluoroadipic acid can be mentioned as an industrially useful polyfluorosaturated dicarboxylic acid. . Further, examples of the partially fluoro-saturated dicarboxylic acid include 2,2-H-polyfluoropimelic acid and 2,2,3,3,8,8,9,9-H-polyfluorosebacic acid. .

The fluorinated aromatic monocarboxylic acid used in the general formula 4 includes 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, 3,4,5,6-tetrafluorobenzoic acid, pentafluoro Benzoic acid and the like can be mentioned.

The fluorine-containing aromatic dicarboxylic acid used in the general formula 5 includes 2,3,4-trifluorophthalic acid, 2,3,5-trifluorophthalic acid, 3,4,5-
Trifluorophthalic acid, tetrafluorophthalic acid and the like can be mentioned.

In general formulas (1) and (2), a is an integer of 4 or more and 20 or less and b is an integer of 0 or 4 or less. In general formula 3, c is an integer of 4 or more and 8 or less and d + e is 0 or more. 4
The following integers, and in general formulas 4 and 5, at least three of Y are fluorine and the rest are hydrogen are those wherein a and c are less than 4 in general formulas 1, 2 and 3; b, d + e is 4
In general formulas 4 and 5, fluorine in Y is 3
If it is less than this, sufficient water / oil repellency cannot be obtained.

Further, the present invention provides a compound represented by the following general formulas:
In the fluorinated esterification product of Chemical formula 4 or Chemical formula 5,
It is characterized in that a saturated alcohol having 30 to 70 carbon atoms is used.

As the saturated alcohol having 30 or more carbon atoms, for example, Unilin Alcobol manufactured by PETROLITE, USA
Unilin 425 (hydroxyl value 110), Unilin 550 (hydroxyl value 85) and Unilin 700 (hydroxyl value 66) can be used. Unilin 425, 55
The average molecular weight of each of 0,700 is 510,6, respectively.
60,850, and the average carbon number calculated therefrom is 35, 46, 60, respectively. It should be noted that other saturated alcohols having 30 or more carbon atoms can be used.

When a saturated alcohol having less than 30 carbon atoms is used, the melting point of the fluorinated esterified product is lowered, and sufficient water / oil repellency and solidification cannot be obtained.

On the other hand, when the number of carbon atoms is 70 or more, it is difficult to obtain industrially, the compatibility with other oils / solvents is deteriorated due to the high molecular weight, and the fluorine content in one molecule is low. , And it is difficult to obtain the desired physical properties of the present invention.

Further, by increasing the fluorine content in the fluorinated esterified product, water and oil repellency can be further improved. However, commercially available fluorine-containing carboxylic acids are limited, and if the fluorine content is too high, the compatibility with other oils and solvents will be poor, and the desired physical properties of the present invention will be obtained. Absent.

From the above, the object of the present invention can be attained by the esterification product of the aliphatic saturated alcohol and the fluorinated carboxylic acid as set forth in the claims.

The ester of the present invention can be synthesized by a usual esterification method without a catalyst or in the presence of a catalyst, and is not particularly limited. The esterification product can be used alone, or may be used in combination with a conventional natural wax or synthetic wax depending on the purpose.

[0020]

【Example】

Synthesis Example In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas, blowing tube, and water separator, 41 g of polyfluorocaprylic acid, Un
85 g of ilin700 (trade name, saturated alcohol, manufactured by PETROLITE, carbon number 60) and 0.2 g of tin chloride as a catalyst were further charged, and 5% of the charged amount was further added as xylene as a refluxing solvent. 1
The temperature was raised to 240 ° C. at 60 ° C., and the reaction was carried out until a calculated amount of water was distilled off. The required time was 10 hours.
After completion of the reaction, xylene was distilled off under reduced pressure, followed by decolorization filtration using activated clay to obtain a slightly yellow solid. The yield was 112 g, the acid value was 3.3, the saponification value was 45, the melting point was 102 to 104 ° C., and the penetration was 3 (25 ° C., 50 g, load 5 sec). Less than,
In the same manner, the esters shown in Table 1, Table 2, Table 3, Table 4, and Table 5 were produced.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

Example 1 Car wax A solid car wax was prepared according to the following formulation. Formulation Example Micro wax (mp 155 ° F.) 5 parts (weight; the same applies hereinafter) Synthetic ester of the present invention 15 parts Dimethyl silicone (350 cs) 10 parts Mineral spirit 50 parts Using the obtained car wax, wiping the painted surface of an automobile with a gloss. ,
Table 6 shows the results of evaluation of elongation during wiping with gloss, wiping properties, and water repellency, and gloss and water repellency after washing 10 times with water.

[0027]

[Table 6] Evaluation method: Three-level evaluation ○: good △: normal ×: not possible (same as below)

Example 2 Paste Solvent Type Floor and Furniture Wax A floor and furniture wax was prepared according to the following formulation. Synthetic ester of the present invention 15 parts Ceresin 5 parts Paraffin wax (mp 145 ° F.) 10 parts Mineral spirit 70 parts Using the obtained wax, luster is applied to wood plywood coated with urethane paint, and elongation, gloss, The water repellency, and the gloss and water repellency after washing the detergent 10 times were evaluated. Table 7 shows the results.

[0029]

[Table 7] Commercial product C: Carnauba wax 5%, paraffin wax 20%

Example 3 Shoe Cream A shoe cream was prepared according to the following formulation. Synthetic ester 17 parts Beeswax 15 parts Mineral spirit 27 parts Triethanolamine 3 parts Stearic acid 5 parts Water 33 parts Using the obtained shoe cream, elongation at the time of wiping gloss, gloss, water repellency and three times during rainfall on cowhide shoes Later, the gloss and the water repellency were evaluated. Table 8 shows the results.

[0031]

[Table 8]

[0032]

According to the present invention, the esterification product has excellent water repellency, oil repellency, durability, weather resistance, smoothness, non-adhesion, release property and antifouling property. Since it is a high melting point monoester wax containing a group, it has unprecedented solidification and lubricity. Therefore, it exhibits excellent performance as various water repellents, oil repellents, polishing agents, solidifying agents or lubricants, for example, car wax, floor and furniture wax, leather cleaner and plastic additive.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09K 3/00 112 C09K 3/00 112E 3/18 102 3/18 102 C10M 105/54 C10M 105/54 169/04 169/04 // C10M 109: 00 131: 12 C10N 30:00 30:06 30:20 40:36

Claims (7)

(57) [Claims] 1. A water / oil repellent comprising an esterified product containing a polyfluoroalkyl group or a partial fluoroalkyl group represented by the following general formula 3, 3, or 5. ## STR1 ## F (CF2) a (CH2) bCOOR (where a: an integer of 4 or more and 20 or less, b: an integer of 0 or 4 or less) H (CF2) a (CH2) bCOOR (however, , A: an integer of 4 or more and 20 or less, b: an integer of 0 or 4 or less ROOC (CH2) d (CF2) c (CH2)
eCOOR (c is an integer of 4 or more and 8 or less, d and e are the same or similar, and d + e is an integer of 0 or 4 or less) Embedded image In the above chemical formulas 1 and 2, R: carbon number 41
An alkyl group having not less than 70 and not more than 70,
, R: an alkyl group having 30 or more and 70 or less carbon atoms. 2. An esterification product containing a polyfluoroalkyl group or a partial fluoroalkyl group, which is represented by the general formula 1, 2, 3, 4 or 5, according to claim 1. Polishing agent. 3. Formulation of an esterification product containing a polyfluoroalkyl group or a partial fluoroalkyl group represented by the general formula 1, 2, 3, 4 or 5 according to claim 1. Become a solidifying agent. 4. A lubricant comprising a polyfluoroalkyl group or a partially fluoroalkyl group-containing esterification product represented by the general formula (3), (4) or (5). 5. A car wax or a floor wax containing an esterification product containing a polyfluoroalkyl group or a partial fluoroalkyl group, which is represented by the general formula (3), (4) or (5). Furniture wax. 6. An esterification product containing a polyfluoroalkyl group or a partial fluoroalkyl group, which is represented by the general formula 1, 2, 3, 4 or 5, according to claim 1. Leather cleaner. 7. An esterification product containing a polyfluoroalkyl group or a partial fluoroalkyl group, which is represented by the general formula 1, 2, 3, 4 or 5, according to claim 1. Become a plastic additive.