JPS6351476B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to water and oil repellents. More specifically, the present invention relates to a water and oil repellent having excellent solubility in perchlorethylene and flexibility. Copolymers containing perfluoroalkyl group-containing polymerizable compounds as comonomer components have traditionally been used as water and oil repellents, but this is probably the quickest way to effectively exhibit the water and oil repellency of such copolymers. The method is
The objective is to increase the copolymerization composition ratio of the perfluoroalkyl group-containing polymerizable compound. However, in order to dissolve this copolymer well in perchlorethylene, which is a dry cleaning solvent, the above composition ratio must be 50% by weight or less. By the way, in the case of a copolymer with vinylidene chloride, which is said to be the most preferable other comonomer component from the point of view of water and oil repellency, 50% by weight:
50% by weight means about 17 mol% of perfluoroalkyl group-containing polymerizable compound; about 83% of vinylidene chloride
This results in the formation of a copolymer with a molar ratio of about 1:5, and due to the crystallization tendency based on the overwhelmingly large proportion of vinylidene chloride comonomer component, perchloroethylene of the copolymer It can be inferred that this is due to a decrease in solubility in . Therefore, as a result of various studies on comonomers below the third component that reduce the crystallinity of this copolymer, the present inventor found that when benzyl acrylate, methacrylate, or 2-chloroethyl vinyl ether is copolymerized, It has been found that the solubility in perchlorethylene can be improved without impairing the water and oil repellency and texture of the copolymer. Furthermore, since the copolymerization composition ratio of the perfluoroalkyl group-containing polymerizable compound can be increased to about 65% by weight, the water and oil repellency of the copolymer can be further improved. Therefore, the present invention relates to a water and oil repellent, which comprises (a) about 65 to 10% by weight of a polymerizable compound containing a perfluoroalkyl group, and (b) about 10 to 10% by weight of vinylidene chloride.
40% by weight and (c) about 10 to 50% by weight of benzyl acrylate or methacrylate or 2-chloroethyl vinyl ether, and the sum of (b) and (c) is about
A copolymer obtained by copolymerizing each comonomer component in a proportion of 35 to 90% by weight is used as a water- and oil-repellent component. Examples of the perfluoroalkyl group-containing polymerizable compound include compounds represented by the following general formula (where R is a hydrogen atom or a methyl group). (CF ₃ ) ₂ CF (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCR=CH ₂ C ₈ F ₁₇ SO ₂ NR′CH ₂ CH ₂ OCOCR=CH _2The following compounds can also be used in the same way. be able to. CHF ₂ (CF ₂ ) ₇ CH ₂ OCOCR=CH ₂ CClF ₂ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR=CH ₂ These perfluoroalkyl group-containing polymerizable compounds contain about 65 to 10% by weight, preferably about It is copolymerized in a proportion of 65 to 40% by weight. If the amount is about 65% by weight or more, the resulting copolymer will have poor solubility in perchlorethylene, while if it is less than about 10% by weight, it will not exhibit satisfactory water and oil repellency. Therefore,
Vinylidene chloride and benzyl acrylate or methacrylate or 2-chloroethyl vinyl ether are copolymerized in a total amount of about 35 to 90% by weight, preferably about 35 to 60% by weight. That is, if the amount is less than about 35% by weight, the obtained copolymer has poor solubility in perchlorethylene,
On the other hand, if it exceeds about 90% by weight, satisfactory water and oil repellency will not be exhibited. The copolymer may further contain acrylates or methacrylates containing epoxy groups, hydroxyl groups, amino groups, isocyanate groups, carboxyl groups, etc., such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 2-hydroxyethyl acrylate, 2-hydroxy Ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, acrylic acid, methacrylic acid and etc. can also be copolymerized within a range that does not impair the purpose of the present invention. As can be seen from the results of Examples and Comparative Examples described later, vinylidene chloride, benzyl acrylate, or
- A copolymer made by copolymerizing only one type of chloroethyl vinyl ether exhibits a certain degree of water and oil repellency when the copolymerization composition ratio of the perfluoroalkyl group-containing polymerizable compound is 50% by weight; In contrast, when the copolymer of the present invention is used, the copolymerization composition ratio of the perfluoroalkyl group-containing polymerizable compound is Even at 50% by weight, it shows good water and oil repellency, and at 60% by weight, the performance becomes even better, which is a remarkable effect. Water and oil repellent treatment uses the water and oil repellent prepared in this way to treat various fibers such as cotton, wool, silk, polyester, polyamide, and regenerated cellulose, or woven fabrics made from blends thereof, pulp products, leather, etc. This is done on the workpiece. As mentioned above, the copolymer forming the water and oil repellent in the present invention has good solubility in perchlorethylene, which is a dry cleaning solvent, so water and oil repellency treatment should be performed at the same time as dry cleaning. Can be done. Next, the effects of the present invention will be explained with reference to Examples. Reference example 1 (ternary copolymer No. 1 to 3) 900 parts by weight of 1,1,1-trichloroethane,
A total of 100 parts by weight of acrylic acid perfluorooctyl ethylene ester, vinylidene chloride and benzyl acrylate and azobisisobutyronitrile
2.5 parts by weight was added, and a three-component copolymerization reaction was carried out under reflux conditions in a nitrogen gas atmosphere for 4 hours. Reference Example 2 (Ternary Copolymer Nos. 4 to 5) In Reference Example 1, 2-chloroethyl vinyl ether was used instead of benzyl acrylate. Reference example 3 (binary copolymer Nos. 6 to 11) In reference examples 1 to 2, perfluorooctyl ethylene ester of acrylate and vinylidene chloride,
A binary copolymerization reaction with benzyl acrylate or 2-chloroethyl vinyl ether was performed. The comonomer composition (parts by weight) in each of the above reference examples is:
It is shown in Table 1 below.

[Solubility test]

Evaluation when diluted 20 times with the above perchlorethylene ◎: Remains transparent even when cooled to -20℃ 〇: Forms a transparent solution when diluted at 25℃ ×: Cloudy when diluted at 25℃ [ Water Repellency Test] A drop of water was dropped onto the treated cotton cloth, and the condition was observed after 5 minutes had elapsed.

【table】

[Table] [Oil repellency test] Drop one drop of the test liquid (mixed liquid at a specific ratio shown in the table below) onto the treated cotton cloth and observe the condition after 5 minutes have elapsed. If the dropped test solution is retained on the cloth, test with a test solution with higher n-heptane content, and conversely, if it is not retained on the cloth, test with a test solution with higher n-heptane content. do. Then, using the test liquid that can be retained on the cloth at its limit, the oil repellency is evaluated based on the oil repellency evaluation shown in the table below. In the oil repellency evaluation, the case where 100% Nudyol is retained is 50, and the case where 100% Nudyol is not retained is 0.

[Table] Not held)
[Rigidity Test] Based on the JIS L-1096B method, the stiffness is measured, and then the flexibility is calculated according to the following formula. The closer the softness value is to 1, the closer it is to untreated cloth, and the smaller the value, the harder it is. Softness=bending resistance of untreated fabric/bending resistance of treated fabric The results obtained are shown in Table 2 below.

[Table] From the above results, the following can be said. (1) Examples 1, 2, and 4 and Comparative Examples 1 and 3, all of which are copolymers using 60% by weight of perfluorooctyl ethylene acrylate;
From the comparison of No. 5, it can be seen that the binary copolymer has poor solubility in perchlorethylene and therefore has low water and oil repellency. (2) Examples 3 and 5, both using 50% by weight of perfluorooctyl ethylene acrylate
From the comparison of Comparative Examples 2, 4, and 6, it can be seen that the terpolymer has particularly excellent solubility in perchlorethylene, and is also excellent in water repellency, oil repellency, and rigidity (texture). I understand. (3) From the comparison of Examples 1, 2, 4 and Examples 3 and 5, by increasing the proportion of acrylic acid perfluorooctyl ethylene ester from 50% by weight to 60% by weight, the solubility and flexibility were slightly improved. Although it decreases, water repellency is the same or 10 points, and oil repellency is further improved by 10 to 20 points. Currently, in the evaluation of water and oil repellents, the rating is 10 to 20.
The difference in points is said to be of great practical significance, and together with the good solubility in perchlorethylene, the water and oil repellent according to the present invention is highly evaluated.

Claims (1)

[Claims] 1 (a) Perfluoroalkyl group-containing polymerizable compound
65-10% by weight, (b) vinylidene chloride approximately 10-40% by weight
and (c) benzyl acrylate or methacrylate or 2-chloroethyl vinyl ether about
A perchloroethylene soluble copolymer obtained by copolymerizing each comonomer component in a proportion of 10 to 50% by weight and a total of (b) and (c) of about 35 to 90% by weight. A water and oil repellent that acts as a water and oil repellent ingredient.