JPH0823007B2 - Water repellent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention resides in an emulsion type water repellent composition having improved workability without impairing the water repellency of waxes. More specifically, the emulsion-type water-repellent composition has excellent storage stability, dryness, mechanical stability, and high water repellency.

[Conventional technology]

Conventionally, as the water repellency-imparting agent, paraffin wax, petroleum resin, asphalt, silicone resin, fluorine resin and the like are generally used. Among them, Paraffin wax is often used as a water repellent agent for building materials and the like from the viewpoint of water repellency and price, but it was necessary to use a considerably large amount of a surfactant when emulsifying it. When such a water repellent is used for various building materials, paper, organic and inorganic fibers,
The surfactant remains in the system, which adversely affects the water-repellent effect, and the expected effect cannot be obtained. Therefore, there has been proposed a method of compensating for this drawback by using a surfactant which can be easily decomposed by heat treatment as a surfactant used in combination with the above water repellent, but in general, a surfactant having such a property is proposed. Since HLB becomes high, there is a problem in that even if a slight amount remains on the treated paper, fibers, etc., the water repellency effect is reduced, and a satisfactory treatment effect is not achieved.

As a water-repellent composition which solves the above-mentioned problems, those using paraffin oxide in combination (Japanese Patent Publication No. 53-35811), those using monoester of styrene-maleic anhydride copolymer (Japanese Patent Publication No. 58-58304), styrene -A combination of an alkali salt of a partial ester of maleic anhydride copolymer (JP-A-54-106609) or a combination of a saturated fatty acid adduct of olefin (JP-A-60-14932) has been proposed. There is.

[Problems to be solved by the invention]

However, if these water-repellent compositions are not used in a large amount, water repellency may not be sufficiently exhibited, storage stability,
There are problems that properties such as mechanical stability and dryness are insufficient, the cost of the raw material itself is high, and water repellency does not appear depending on the type of substrate.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems.

That is, the gist of the first invention of the present invention is (A) melting point 40.
A water-repellent composition comprising an emulsion obtained by emulsifying waxes at ~ 90 ° C and (B) an olefin-maleic anhydride derivative in water in the presence of (C) a water-soluble alkaline compound. Exist.

The gist of the second invention of the present invention is (A) melting point 40-90.
C. Waxes, (B) olefin-maleic anhydride derivative, and (D) hydrocarbon resin are emulsified in water in the presence of (C) a water-soluble alkaline compound. It exists in a water repellent composition. Hereinafter, the present invention will be described in detail.

The waxes having a melting point of 40 to 90 ° C., which is one component of the water-repellent composition of the present invention, means paraffin-based or olefin-based hydrocarbons. Specific examples include paraffin wax, montan wax, and low melting point polyolefin wax.

If the melting point of waxes is lower than 40 ° C, the quality of the product deteriorates in summer, and if it is higher than 90 ° C, a product having good water repellency cannot be obtained.

The other component, an olefin-maleic anhydride derivative, is obtained by low polymerization of α-olefin having 4 to 6 carbon atoms or α-olefin having 2 to 5 carbon atoms such as ethylene, propylene, isobutylene and isoamylene. An adduct of maleic anhydride with an olefin having a double bond at the α-position having 4 to 60 carbon atoms, a copolymer obtained by copolymerizing these α-olefin and maleic anhydride with a radical initiator, and these Partial esters of organic monohydroxy compounds are used. The partial ester may be synthesized after the reaction between olephine and maleic anhydride, or by the reaction between the partial ester of maleic anhydride and olein. The molar ratio of olefin and maleic anhydride or its partial ester is preferably in the range of 3: 1 to 1: 2. When the molar ratio is outside this range, the stability of emulsion or the water repellency may be impaired depending on the substrate to which it is applied, which is not preferable.

Examples of the organic monohydroxy compound used for producing the partial ester include alcohols such as methanol, ethanol, isopropanol, butanol and 2-ethylhexanol, and cellosolves such as butyl cellosolve and ethyl cellosolve. The organic monohydroxy compound is used in the range of 1 mol or less relative to 1 mol of maleic anhydride. The reaction between the organic monohydroxy compound and maleic anhydride or olephine-maleic anhydride derivative is carried out under normal pressure or under pressure in an autoclave as necessary,
It is carried out at a temperature of 90 to 130 ° C. for about 1 to 10 hours.

The water repellent composition of the present invention can be improved in water repellency by further using a hydrocarbon resin in combination with the waxes and the olefin-maleic anhydride derivative. As the hydrocarbon resin, a molecular weight of 500 to 500 obtained by polymerizing an aromatic hydrocarbon having 9 carbon atoms or an aliphatic hydrocarbon fraction having 5 carbon atoms obtained in the process of petroleum refining or petrochemical industry with a Friedel-Crafts catalyst is used. A molecular weight of 500 to 3 obtained by polymerizing 3000 petroleum resins and tar naphtha as raw materials in the same manner.
000 coumarone-indene resin, a terpene resin with a molecular weight of 500 to 3000 obtained from turpentine oil, rosin, a molecular weight of 500
Examples include ethylene, propylene, butene, isobutylene, styrene oligomers, asphalt, etc. When using a hydrocarbon resin together,
Usually the wax: hydrocarbon resin weight ratio is 100: 3 to 30:
Used in the 70 range. If an extremely large amount of hydrocarbon resin is used, the water repellency of waxes may be impaired, and the cost of raw materials may be increased.

Specific examples of the water-soluble alkaline compound used in the emulsification include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, ammonia and hydroxide. Examples include amines such as ammonium, dimethylamine, trimethylamine and triethylamine, and ethanolamines such as triethanolamine, diethanolamine, dimethylethanolamine and methyldiethanolamine. The amount of these alkaline compounds added is 0.3 to 2 times the amount required to neutralize the olefin-maleic anhydride derivative. If the amount added is outside this range, the stability of the emulsion may become poor, which is not preferable.

The above waxes, or the composition ratio of the mixture of waxes and a hydrocarbon resin and olefin-maleic anhydride derivative is 1: 0.01 to 1: 0.7 by weight ratio, preferably 1: 0.02 to 1: 0.4.
Is appropriately selected from the range.

Further, in order to improve the storage stability of emulsion, a water-soluble polymer such as polyacrylamide, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose or the like can be coexistent if necessary.

The water-repellent composition of the present invention is produced by emulsifying the above waxes, the olefin-maleic anhydride derivative, and optionally a hydrocarbon resin in water in the presence of a water-soluble alkaline compound. Examples of the emulsification method include a mechanical emulsification method and a phase inversion emulsification method. These methods can be used alone or in combination. The mechanical emulsification method includes a homomixer, a valve homogenizer, a colloid mill, an ultrasonic method and the like, but any method can be used as long as it can produce a uniform emulsion.

The water-repellent composition of the present invention is not only useful as a water-repellency-imparting agent for gypsum, cement, paper, fibers, etc., but also as an anti-caking agent for fertilizers, a pesticide carrier spreading agent, a soil improving agent, etc. Effectively used for a wide range of purposes. Furthermore, by using various polymer emulsions in combination, it is possible to further optimize them depending on the application. In addition,
There is no restriction on the combined use of various additives during the above-mentioned processing.

Next, the present invention will be described more specifically by way of Examples, Comparative Examples and Production Examples. In the following example, "part"
And "%" mean "parts by weight" and "% by weight", respectively.

Production Example 1 1200 g of α-olefin having a carbon number of 30 to 60 (number average carbon number 48; product of Mitsubishi Kasei Kogyo Co., Ltd., trade name Dialene 30) was charged in a flask and the system was sufficiently replaced with nitrogen gas.
The mixture was heated to 185 ° C., and 180 g of maleic anhydride and 45.5 g of di-t-butyl peroxide were simultaneously fed to the mixture under stirring for 2 hours for polymerization. After further aging for 1 hour, the mixture was cooled to obtain an olefin-maleic anhydride copolymer (copolymer A) having a maleic anhydride content of 0.725 mmol / g.

Production Example 2 560 g of olefin (diisobutylene) having 8 carbon atoms and 196 g of maleic anhydride were charged into a flask, the system was sufficiently replaced with nitrogen gas, and the mixture was heated to 80 to 100 ° C. and t-butyl peroctoate was stirred. 73.3 g was fed and polymerized over 2 hours. After further aging for 1 hour, the mixture was cooled, and the polymer obtained was dried to obtain a maleic anhydride content of 2.6.
An olefin / maleic anhydride copolymer (copolymer B) of mmol / g was obtained.

Production Example 3 420 g of α-olefin having 6 carbon atoms (Mitsubishi Kasei Kogyo Co., Ltd., trade name Dialene 6) and 196 g of maleic anhydride were charged into an autoclave, and olefin-maleic anhydride co-weigher was prepared as in Production Example 2. Got Methanol
96 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an olefin-maleic anhydride partial ester (copolymer C) having a maleic anhydride content of 2.25 mmol / g.

Production Example 4 C 12 olefin (main component 2,4,6-trimethyl-
1-Nonene) (484 g) and maleic anhydride (311 g) were charged into an autoclave, the system was sufficiently replaced with nitrogen gas, and the mixture was heated to 200 ° C. with stirring and reacted at the same temperature for 8 hours. Then, unreacted olein and maleic anhydride were distilled off while gradually increasing the degree of reduced pressure, and an olefin-maleic anhydride adduct (adduct D) having a maleic anhydride content of 1.34 mmol / g.
I got

Example 1 95 parts of paraffin wax having a melting point of 68.3 ° C., 5 parts of copolymer A and 122.2 parts of warm water were heated and melted at 85 ° C. to obtain potassium hydroxide.
0.4 part was added and emulsified with a homomixer. Further, it was applied to a piston type high pressure homogenizer and homogenized at a pressure of 250 kg / cm ³ and then cooled to obtain a paraffin emulsion A having a solid content of 45%.

Example 2 Paraffin emulsion B was obtained in the same manner as in Example 1 except that the copolymer B and 1.5 parts of potassium hydroxide were used.

Example 3 Paraffin emulsion C was obtained in the same manner as in Example 1 except that the copolymer C was used and 0.6 part of potassium hydroxide was used.

Example 4 Paraffin emulsion D was obtained in the same manner as in Example 1 except that the adduct D was used and 0.75 part of potassium hydroxide was used.

Example 5 76 parts of paraffin having a melting point of 68.3 ° C., melting point of 97 ° C., bromine number of 31.2
5 parts of petroleum resin and 5 parts of copolymer B were melted at 120 ° C., then the temperature of the system was lowered to 98 ° C., 122.2 parts of hot water of the same temperature and 1.5 parts of potassium hydroxide were added, and the same procedure as in Example 1 was conducted. I got Paraffin Emulationon E.

Comparative Example 1 According to Example 1 of JP-A-60-14932, an emulsion F was obtained by the following formulation in the same manner as in the above example.

Butyric adducts of α- olefins having a melting point of 130 ° F of paraffin 45.5 parts C ₂₀ ~ ₂₈ (Mitsubishi Kasei Corporation product name Daiyaren 208) (mp.47 ℃, acid value 61) 0.5 parts potassium hydroxide 0.03 parts ( Neutralization Equivalent) 50 parts of warm water Comparative Example 2 According to Example 4 of JP-B-58-58304, emulsion G was obtained according to the following formulation in the same manner as in this Example.

Petroleum resin having a softening point of 120 ° C and a bromine number of 30 71 parts Paraffin having a melting point of 145 ° F 259 parts Aluminum stearate 40 parts 6% aqueous solution of potassium salt of styrene-maleic acid copolymer monomethyl ester 678 parts Test Example Examples 1 to 1 5, 123 g of basis weight in a bath containing 1% of solid content of paraffin emulsions A to G obtained in Comparative Examples 1 and 2
A non-sized paper of / m ² was dipped for 1 minute, the roller brush was measured for pick-up amount and then pressed at 120 ° C. for 2-3 minutes, and thereafter the water resistance (sticky second) was measured according to JIS P8122. Table 1 shows the results.

[Effects of the Invention] The water-repellent composition of the present invention is inexpensive and exhibits excellent water repellency even in a small amount.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 23/08 LDB 33/00 LHS 35/00 LHS 91/00 LSJ 91/06 LSJ // D06M 13 / 02 15/263 D21H 17/60 (72) Inventor, Yasuji Ozawa, 1000, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd. (56) Reference JP-A-60-14932 (JP , A) JP-A-55-73764 (JP, A)

Claims (7)

[Claims] 1. An emulsion obtained by emulsifying wax (A) having a melting point of 40 to 90 ° C. and (B) an olefin-maleic anhydride derivative in water in the presence of (C) a water-soluble alkaline compound. A water repellent composition characterized by the above. 2. The weight ratio of (A) to (B) is 1: 0.01 to 1: 0.
The water repellent composition according to claim 1, wherein the water repellent composition is 7. 3. An olefin-maleic anhydride derivative (B) which is an adduct or copolymer of an α-olefin having 4 to 60 carbon atoms and maleic anhydride, and a partial ester thereof. The water-repellent composition according to claim 1 or 2. 4. (A) Waxes having a melting point of 40 to 90 ° C., (B)
An olefin-maleic anhydride derivative, and (D) a hydrocarbon resin in the presence of (C) a water-soluble alkaline compound,
A water-repellent composition comprising an emulsion obtained by emulsification in water. 5. The water-repellent composition according to claim 4, wherein the weight ratio of the total amount of (A) and (D) to (B) is 1: 0.01 to 1: 0.7. Stuff. 6. An olefin-maleic anhydride derivative (B) which is an adduct or copolymer of an α-olefin having 4 to 60 carbon atoms and maleic anhydride, and a partial ester thereof. 6. The water-repellent composition according to claim 4 or 5. 7. The hydrocarbon resin (D) is a petroleum resin, coumarone-indene resin, terbene resin, rosin, low molecular weight polyolefins, and asphalt, and claims 4 and 5 above. Alternatively, the water repellent composition according to any one of item 6 above.