JP3407757B2 - 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. It relates to excellent binder wax for thermal transfer ink, car wax, floor / furniture wax, leather cleaner, and the like.

[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-based natural wax such as whale wax, shellac wax and lanolin wax, petroleum-based natural wax such as paraffin wax and microcrystalline wax, mineral-based natural wax such as montan wax, ozokerite wax, ceresin, Hoechst wax, polyethylene wax, carbo wax Synthetic waxes such as wax, castor wax, Fischer-Tropsch wax, and kesol wax, and higher fatty acids and higher aliphatic alcohols of the above-mentioned animal / vegetable waxes, alone And those of 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]

The present invention is obtained by heating and condensing a linear saturated aliphatic dibasic acid having 10 to 24 carbon atoms and a linear saturated diol having 6 to 10 carbon atoms. The complex partial esterification product has 12 carbon atoms.
A complex esterification product having an average molecular weight of 1,000 to 7,000 and a melting point of 45 ° C. or higher obtained by reacting a linear saturated aliphatic monobasic acid having a carbon number of 50 or less or a linear saturated aliphatic monoalcohol having a carbon number of 12 or more and 50 or less It is a water / oil repellent agent, a polish agent, a solidifying agent, or a lubricant (hereinafter, referred to as “water repellent agent or the like”) obtained by blending a substance.

As the linear saturated aliphatic dibasic acid having 10 to 24 carbon atoms, sebacic acid, 1,9-nonamethylenedicarboxylic acid, 1,10-decamethylenedicarboxylic acid, 1,11-
Undecamethylenedicarboxylic acid, 1,12-dodecamethylenedicarboxylic acid, 1,13-tridecamethylenedicarboxylic acid,
1,14-tetradecamethylenedicarboxylic acid, 1,15-pentadecamethylenedicarboxylic acid, 1,16-hexadecamethylenedicarboxylic acid, 1,17-heptadecamethylenedicarboxylic acid, 1,18-octadecamethylenedicarboxylic acid, 1,19-nonadecamethylenedicarboxylic acid, 1,20-icosamethylenedicarboxylic acid, 1,20-henicosamethylenedicarboxylic acid,
1,22-docosamethylene dicarboxylic acid and the like can be mentioned. As the linear saturated diol having 6 to 10 carbon atoms, 1,6-hexanediol, 1,7-heptanediol,
Mention may be made of 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol. If such a linear saturated aliphatic dibasic acid or a linear saturated diol having a carbon number outside the above range is used, it becomes impossible to impart desired properties to the water repellent agent of the present invention. .

As the monobasic acid, various monocarboxylic acids can be used, but especially fatty acids derived from fats and oils and / or synthetic fatty acids obtained by the paraffin oxidation method, the oxo method, the Koch method, the Guerbet method, and the alkali melting method. Is good. As these fatty acids, linear saturated fatty acids having 12 to 50 carbon atoms 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 Fatty acids, fish hard fatty acids (hydrogenated fish oil fatty acids), US PETR
OLITE Unicid 425 (acid value 94, average molecular weight 59
6), Unicid 550 (acid value 72, average molecular weight 77
8), Unicid700 (acid value 63, average molecular weight 888)
Etc. can be given. The linear saturated aliphatic monobasic acid having 12 or more and 50 or less carbon atoms is limited to the use of linear saturated fatty acid having less than 12 carbon atoms, side chain saturated fatty acid, unsaturated fatty acid, etc., resulting in complex esterification. This is because the melting point of the product is lowered and sufficient water / oil repellency and solidification cannot be obtained. When the carbon number exceeds 50, it is difficult to obtain industrially.

On the other hand, the monoalcohol has 12 carbon atoms.
A linear saturated aliphatic monoalcohol having 50 to 50 can be used. For example, 1-decanol, 1-tridecanol, 1-
Tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-
Nonadecanol, 1-Icosanol, 1-Docosanol, 1-
Tetracosanol, 1-hexacosanol, 1-octacosanol, 1-triacontanol, U made by PETROLITE, USA
nilin Alcohol 425 (hydroxyl value 110, average molecular weight 5
10), Unilin Alcohol 550 (hydroxyl value 85, average molecular weight 660), Unilin Alcohol 700 (hydroxyl value 6)
6, average molecular weight 850) and the like. The linear saturated aliphatic monoalcohol having 12 to 50 carbon atoms is limited to the linear saturated aliphatic monoalcohol having 12 or less carbon atoms, the side chain saturated aliphatic monoalcohol, and the unsaturated aliphatic monoalcohol. This is because the melting point of the complex esterification product is lowered when such a compound is used, and sufficient water / oil repellency and solidification cannot be obtained. When the carbon number exceeds 50, it is difficult to obtain industrially.

The complex partial esterification product obtained in the present invention has a molar ratio of the linear saturated aliphatic dibasic acid to the linear saturated diol of 1: 1.1.
~ 2 or 1.1 to 2: 1, preferably 1: 1.1 to
It is obtained by an esterification reaction at a raw material ratio of 1.5 or 1.1 to 1.5: 1, and has an unreacted carboxyl group or hydroxyl group in the partially esterified product. When the raw material ratio is out of the above range, it is polymerized or becomes a low molecular weight ester, and these do not give desired properties to the water repellent and the like of the present invention. The proportion of carboxyl groups remaining in the partially esterified product according to the present invention can be evaluated by the acid value, and the residual hydroxyl groups can be evaluated by the hydroxyl value. Such partially esterified product is
Then, an esterification reaction can be carried out with the above-mentioned linear saturated aliphatic monobasic acid or linear saturated aliphatic monoalcohol to obtain a complex esterified product. The average molecular weight is determined by the molecular weight and the molar ratio of each of the components used as a raw material, but in the present invention, an average molecular weight of 1,000 to 7,000 and a melting point of 45 ° C. or higher are desirable. If the average molecular weight exceeds 7,000, other oil agents,
The compatibility with waxes and solvents gradually decreases, and conversely, when the average molecular weight is less than 1000, it has a mere solvent-like action, making it difficult to obtain the physical properties intended by the present invention. on the other hand,
If the melting point is less than 45 ° C., the melting point of the product is too low, and sufficient water / oil repellency and solidification cannot be obtained.

The ester of the present invention can be synthesized by a conventional esterification method using the above raw materials without catalyst or in the presence of a catalyst, and the method is not particularly limited. The water repellent and the like can be produced by a conventional method, and the esterification product may be used alone or 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.

[0012]

【Example】

Synthesis example (Sample symbol in Table 1: A) 4 equipped with stirrer, thermometer, nitrogen gas blowing pipe, water separator
In a two-necked flask, 1,10-decamethylene dicarboxylic acid 46
0 g (2 molar equivalents), 1,9-nonanediol 480 g (3
(Molar equivalent) was charged, 1.9 g of tin chloride was charged as a catalyst, and the reaction was carried out at 160 to 240 ° C. until a calculated amount of water was distilled. The required time was 3 hours and the acid value was 0.2. After completion of the reaction, the mixture was cooled and charged with 568 g (2 molar equivalents) of stearic acid, and the reaction was carried out at 160 to 240 ° C. until a calculated amount of water was distilled. The time required was 5 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 12
60 g, acid value 2.1, saponification value 240, average molecular weight 14
00, melting point (° C.) 63-64. Hereinafter, the complex esterification products (Sample Codes B to J) of the present invention shown in Table 1 were produced by the same method.

[0013]

[Table 1]

Example 1 Binder wax for heat-sensitive transfer ink Using the complex esterification product (sample code: A) shown in Table 1, a composition comprising the following components was thoroughly mixed by a ball mill to prepare an ink liquid. It was The parts in the composition are parts by weight (the same applies hereinafter). [Composition of ink] Complex esterification product (Table 1, sample symbol: A) 40 parts Carnauba wax (penetration 1) 45 parts Polyester resin 5 parts (softening point 127 ° C, glass transition point 10 ° C, breaking Elongation: 750%) Nigrosine 10 parts (Nigrosine base EX, manufactured by Orient Chemical Industry Co., Ltd.) Toluene 500 parts This ink was applied to a PET film having a thickness of 4 μm and dried to prepare a thermal transfer sheet having an ink layer thickness of 3 μm. Use this ink sheet as a thermal printer (heating element density:
Thin film type line thermal head with print quality of 8 dots / mm)
Attached to, the applied power 0.2w / dot, application time 8ms
When printed on plain paper with a pulse width of ec, a clear printed image with no background stains, blurred print, or bleeding was obtained. Further, when the printed image was rubbed with a finger, no rubbing stain was generated. Further, when the ink sheet was subjected to a hand rubbing test, sufficient peeling resistance was obtained.

Example 2 Binder wax for thermal transfer ink An ink liquid was prepared in the same manner as in Example 1 with the following composition. [Ink composition] Complex esterification product (Table 1, sample code: G) 60 parts Ethylene / vinyl acetate copolymer 25 parts (Mitsui DuPont Polychemical Co., Ltd., EV-310) Carbon black (Mitsubishi Kasei) MA-100 manufactured by Co., Ltd. 15 parts This ink was applied to a PET film having a thickness of 7 μm by a hot melt wire bar method to prepare an ink sheet for thermal transfer having an ink layer thickness of 4 μm. When this ink sheet was subjected to a printing test in the same manner as in Example 1, a clear printed image free of background stains, print blurring, bleeding, and rubbing stains was obtained. Further, the peeling resistance of the ink layer by the same hand rubbing test as in Example 1 was good.

Example 3 Carwax Using the sample symbols C, F, G or H in Table 1 below, a solid carwax was prepared by a conventional method in the following formulation example. [Prescription example] Microcrystalline wax (mp 68.3 ° C) 5 parts Complex esterification product (sample code: C) 15 parts Dimethyl silicone (350cs) 10 parts Mineral spirit 70 parts Automotive surface coated with the obtained car wax Gently wipe
Elongation during wiping, wiping off, water repellency and water washing 1
The gloss and water repellency after 0 times 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 4 Pasty Solvent-Type Floor and Furniture Wax Using the sample symbols B, D or J in Table 1, floor and furniture waxes were prepared according to the following formulation examples. [Formulation example] Complex esterification product (Sample code: J) 15 parts Ceresin 5 parts Paraffin wax (mp 62.8 ° C) 10 parts Mineral spirit 70 parts Using the wax obtained, luster is applied to wood plywood coated with urethane paint. The elongation, gloss and water repellency at the time of wiping and gloss wiping and the gloss and water repellency after 10 times of washing with a 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 5 Shoe Cream A shoe cream was prepared according to the following formulation using the sample code E or I shown in Table 1. Complex esterification product (Sample code: E) 17 parts Beeswax 15 parts Mineral spirits 27 parts Triethanolamine 3 parts Stearic acid 5 parts Water 33 parts Using the shoe cream obtained, the elongation and gloss of the leather shoes when wiped with gloss , Water repellency and gloss after 3 uses in rain,
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]

INDUSTRIAL APPLICABILITY According to the present invention, a water / oil repellent having excellent water / oil repellency, durability, weather resistance, smoothness, releasability, antifouling property, solidifying property, lubricity, etc. An agent, a solidifying agent or a lubricant is obtained, and these can be suitably used as binder wax for heat-sensitive transfer ink, car wax, wax for floor / furniture, cleaner for leather and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09K 3/18 101 C09D 5/00 C09D 167/02-167/03 C09G 1/06-1/18 C09K 3 / 00

Claims (8)

(57) [Claims] 1. A complex partial esterification product obtained by heat-condensing a linear saturated fatty acid dibasic acid having 10 to 24 carbon atoms and a linear saturated diol having 6 to 10 carbon atoms, Complex ester having an average molecular weight of 1000 to 7,000 and a melting point of 45 ° C. or higher obtained by reacting a linear saturated aliphatic monobasic acid having a number of 12 or more and 50 or less or a linear saturated aliphatic monoalcohol having a carbon number of 12 or more and 50 or less A water and oil repellent compounded with chemical products. 2. The complex partial esterification product has a molar ratio of the linear saturated aliphatic dibasic acid to the linear saturated diol of 1: 1.1 to 2 or 1.1 to 2: The water / oil repellent according to claim 1, which is obtained by an esterification reaction at a raw material ratio of 1. 3. The water / oil repellent according to claim 1, which is a wax. 4. The water / oil repellent according to claim 1, which is a leather cleaner. 5. A complex partially esterified product obtained by heating and condensing a linear saturated fatty acid dibasic acid having 10 to 24 carbon atoms and a linear saturated diol having 6 to 10 carbon atoms, Complex ester having an average molecular weight of 1000 to 7,000 and a melting point of 45 ° C. or higher obtained by reacting a linear saturated aliphatic monobasic acid having a number of 12 or more and 50 or less or a linear saturated aliphatic monoalcohol having a carbon number of 12 or more and 50 or less A polish which is a mixture of chemical products. 6. The complex partial esterification product has a molar ratio of the linear saturated aliphatic dibasic acid to the linear saturated diol of 1: 1.1 to 2 or 1.1 to 2: The polishing agent according to claim 5, which is obtained by an esterification reaction at a raw material ratio of 1. 7. The polish according to claim 5, which is a wax. 8. The polish according to claim 5, which is a leather cleaner.