JP2503657B2 - Water and oil repellent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is particularly excellent in abrasion resistance of a water and oil repellent agent, and further, it is light-resistant and NO _X- resistant, and can be dried naturally after washing or dry cleaning at home. The present invention relates to a water and oil repellent agent that exhibits sufficient water repellency.

[Conventional technology]

Conventionally, for the purpose of imparting water and oil repellency to fibers, homopolymers of perfluoroalkyl group-containing (meth) acrylates, or those perfluoroalkyl group-containing (meth) acrylates and alkyl (meth) acrylates, vinyl chloride, styrene, A water- and oil-repellent agent comprising a copolymer such as N-methylol (meth) acrylamide, an aminimide group-containing monomer and aziridinyl (meth) acrylate is widely used commercially.

As a water- and oil-repellent agent having excellent durability against household laundry or dry cleaning, one obtained by polymerizing a perfluoroalkyl group-containing (meth) acrylate and a blocked polyisocyanate group-containing (meth) acrylate is known. (JP-A-54-128991 and JP-A-62-11)
6613 publication).

[Problems to be Solved by the Invention]

However, the water- and oil-repellent agents described in the above-mentioned publications have the drawback of significantly impairing the texture of the substrate to be treated, and their durability (wear resistance) has not improved as much as expected.

[Means for solving the problem]

The present inventor, as a result of extensive studies in view of the above circumstances, a blocked isocyanate group-containing ethylenically unsaturated monomer having a specific structure and a perfluoroalkyl group-containing ethylenically unsaturated monomer and having 14 or more carbon atoms. A fiber treated with a water and oil repellent consisting of a copolymer obtained by polymerizing an alkyl group-containing ethylenically unsaturated monomer has excellent water and oil repellency and abrasion resistance without impairing the texture of the body. Sufficient recovery of water repellency during natural drying after home washing or dry cleaning, light resistance and NO _X resistance
The present invention, which has been found to have excellent properties, has been completed.

That is, the present invention relates to a perfluoroalkyl group-containing ethylenically unsaturated monomer (A) and the following general formula (I) A blocked isocyanate group-containing monomer (B)
And a water- and oil-repellent agent comprising a copolymer obtained by polymerizing an ethylenically unsaturated monomer (C ₁ ) containing an alkyl group having 14 or more carbon atoms as an essential component.

The perfluoroalkyl group-containing ethylenically unsaturated monomer (A) according to the present invention may be any known and commonly used one, and is not particularly limited.

For example, the general formula (II) The ethylenically unsaturated monomer represented by

Specifically _{A-1: CF 3 (CF} 2) nCH 2 CH 2 OCOCH = CH 2 (n = 5~11, = 8) A-2: CF 3 (CF 2) 7 CH 2 CH 2 OCOC (CH _{3 = CH 2 A-3:} CF 3 (CF 2) 5 CH 2 CH 2 OCOC (CH 3 = CH 2 A-6: CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH = CH ₂ A-7: CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH _{2 OCOC (CH 3) = CH 2} A-8: CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOCH = CH 2 A-9: CF 3 (CF 2) 7 (CH 2) 4 _{OCOCH = CH 2 A-10:} CF 3 (CF 2) 6 COOCH = CH 2 A-11: CF 3 (CF 2) 7 SO 2 N (C 4 H 9) CH 2 CH 2 CH 2 CH 2 OCOCH = CH ₂ A-12: CF ₃ (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ A-13: CF ₃ (CF ₂ ) ₅ CON (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH _{3 ) = CH 2 a-14:} CF 3 (CF 2) 7 CON (C 2 H 5) CH 2 CH 2 OCOCH = CH monomers such as ₂ are exemplified.

If necessary, a molecular end such as CF ₂ Cl (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH = CH ₂ H (CF ₂ ) ₈ CH ₂ CH ₂ OCOC (CH ₃ ) = CH _2. It is also possible to use an ethylenically unsaturated monomer which also contains a fluoroalkyl group which is not substituted with a fluorine atom.

The blocked isocyanate group-containing ethylenically unsaturated monomer (B) according to the present invention is an ordinary temperature sealed with an ethylenically unsaturated double bond and a compound (blocking agent) capable of dissociating at a temperature exceeding ordinary temperature. Is an ethylenically unsaturated monomer containing an inactive isocyanate group, and its structure is a monomer represented by the general formula (I).

As the isocyanate residue of the aromatic diisocyanate, for example, Etc. Further, as the hydrogen residue of ketoxime, for example, (However, R ² and R ³ may be the same or different and are alkyl groups having 1 to 5 carbon atoms), Etc.

In particular, Etc. are illustrated.

As the monomer (B), X in the general formula (I) is
-OBO- (wherein B is an alkylene group having 2 to 10 carbon atoms which may be substituted with a halogen atom or an alkyl group) or -NH- and Z is a hydrogen residue of a ketoxime is at room temperature. Compounds that can be dissociated at a temperature above 90 ° C have low toxicity and Y is an isocyanate residue of an aromatic diisocyanate, and the dissociation temperature of a compound that can be dissociated at a temperature above room temperature is 110-130 ° C. It reaches an appropriate temperature.

The monomer (B) is, for example, an ethylenically unsaturated monomer containing an active hydrogen atom such as 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth) acrylate. After reacting one isocyanate group of aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate, the other isocyanate group has a group capable of reacting with an isocyanate group such as phenol, methylethylketone oxime, cyclohexanone oxime. And can be easily manufactured by sealing with a compound capable of dissociating at a temperature exceeding normal temperature.

The copolymer used in the present invention may contain a group other than a perfluoroalkyl group and a blocked isocyanate group, and such a group may be a group other than those copolymerizable with the monomers (A) and (B). It can be introduced into the copolymer by copolymerizing the ethylenically unsaturated monomer (C). Moreover, when an appropriate monomer is selected as the monomer (C), sufficient water repellency is exhibited only by natural drying after washing or dry cleaning (hereinafter, this property is referred to as water repellency recovery property). Not only the effect of being excellent in light resistance and NO _X resistance, but also various properties such as further improvement of water repellency recovery, improvement of feeling, and improvement of abrasion resistance can be imparted.

The other ethylenically unsaturated monomer (C) copolymerizable with the monomers (A) and (B) according to the present invention is
Ethylenically unsaturated monomer (C ₁ ) containing an alkyl group having 14 or more carbon atoms, ethylenically unsaturated monomer (C ₂ ) containing a functional group capable of reacting with an isocyanate group, and these (C ₁ ) And (C ₂ ) other than monomer (C ₃ ).

Examples of the monomer (C ₁ ) include CH ₃ (CH ₂ ) ₁₇ OCOCH = CH ₂ , CH ₃ (CH ₂ ) ₁₇ OCOC (CH ₃ ) = CH ₂ , Examples of the monomer (C ₂ ) include CH ₂ = CHCOOH, CH ₂ = CHCOOCH ₂ CH ₂ OH, CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ OH CH ₂ = CHCONH ₂ CH ₂ = CHCONHCH ₂ OH, CH ₂ = C (CH ₃ ) COOH, HOOC-CH = CH-COOH, HOOC-CH = C (COOH) 2 CH 2 = CHCONHC (CH 3) 2 CH 2 COCH 3, as the monomer (C ₃₎ such as ethylene, propylene, vinyl chloride, Vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, α-methylstyrene, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth)
Acrylate, iso-butyl (meth) acrylate, ter
t-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl vinyl ether, propyl vinyl ether, octyl vinyl ether, butadiene,
Examples thereof include isoprene and chloroprene, and these monomers (C) may be used alone or in combination of two or more kinds.

The copolymer used in the present invention is usually the monomer (A)
And (B) and (C) are copolymerized to obtain the monomer (B) in an amount of 0.5 to 20% by weight based on the total weight of the monomer.
Copolymerized by using, among them, 30 to 90% by weight of the monomer (A), 0.5 to 20% by weight of the monomer (B) and 5 to 70% by weight of the monomer (C). It is preferable that the monomer (A) is 50 to 80% by weight, the monomer (B) is 2 to 10% by weight, and the monomer (C) is 10 to 50% by weight. Are especially preferred.

In addition, when a fiber is treated with a copolymer using the monomer (C ₁ ) as the monomer (C) as a water and oil repellent, the above-mentioned water repellency recovery property, light resistance and NO _X resistance can be obtained. The water- and oil-repellent property can be imparted without impairing the texture of the unprocessed raw fabric as well as the basic effect that the copolymer (C ₁ ) and (C ₂ ) are used in combination. It is possible to impart water and oil repellency, which is further excellent in abrasion resistance, without impairing the texture of the raw fabric before processing.

As described above, the copolymerization ratio of the monomer (C ₁ ) is 10 to 50% by weight among 5 to 70% by weight of all the monomers in order to make it a water and oil repellent which does not impair the texture of the processed cloth. In order to obtain a water- and oil-repellent agent which does not impair the texture of the processed cloth and is excellent in abrasion resistance, the monomer (C ₁ ) is 10 to 5% by weight of all monomers. It is preferable to use the monomer (C ₂ ) in an amount of 0.5 to 50% by weight, and 0.5 to 3.0 in the equivalent ratio of 0.2 to 5.0 with respect to the isocyanate group of the monomer (B).

In order to obtain the copolymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected, and any of various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, radiation polymerization and photopolymerization. Can also be adopted. For example, the copolymer according to the present invention can be easily produced by emulsifying a mixture of monomers to be copolymerized in water in the presence of a surfactant and copolymerizing with stirring. As a polymerization initiation source, various polymerization initiators such as azo compounds and organic peroxides, and ionizing radiation such as ultraviolet rays or γ-rays can be used. As the surfactant, almost any of various anionic, cationic or nonionic emulsifiers can be used. Thus, the monomer to be copolymerized can be dissolved in an appropriate organic solvent and solution-polymerized by the action of the polymerization initiation source. Suitable solvents for solution polymerization are trichloroethane, trichlorotrifluoroethane, tetrachlorodifluoroethane, tetrachloroethylene and the like.
An organic solvent type, emulsion type or aerosol type water / oil repellent agent can be directly produced by solution polymerization or emulsion polymerization.

The water and oil repellent of the present invention can be applied to the object to be treated by any method depending on the type of the object to be treated and the adjustment form of the water and oil repellent. For example, the water- and oil-repellent agent of the present invention of emulsion type or organic solvent type may be diluted as necessary and applied to the surface of the object to be treated by a known coating method such as dip coating or spraying. Can be adopted.

The conditions of the heat treatment at this time are not particularly limited, but it is usually sufficient to heat the fiber at 80 to 160 ° C in a heating oven, and among them, after predrying at 80 to 120 ° C for 30 seconds to 3 minutes.
It is preferable to cure at 180 ° C for 30 seconds to 3 minutes.

The water- and oil-repellent agent of the present invention is a known conventional antistatic agent, flame retardant, anti-wrinkle agent, softening agent, soil release agent, additives such as dyes and pigments, and binders such as acrylic resin and polyester resin, if necessary. Addition of water repellent such as resin, silicone water repellent, wax water repellent, etc., water repellent such as perfluoroalkyl group-containing acrylic resin, perfluoroalkyl group-containing polyester resin, perfluoroalkyl group-containing urethane compound, etc. Can be used together.

The water and oil repellent of the present invention can treat various articles without particular limitation. For example, fiber, glass, paper, wood,
There are leather, fur, asbestos, plastic, etc. Therefore,
Examples of the fibers include natural fibers such as cotton, hemp, silk and wool, synthetic fibers such as polyamide, polyester, polyacrylonitrile and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, inorganic fibers such as asbestos fibers, or the like. The mixed and woven fabrics of Above all, the water and oil repellent of the present invention is particularly excellent in treating synthetic fibers.

Reference Example (Synthesis of Blocked Isocyanate Group-Containing Ethylenically Unsaturated Monomer) 104 g of dehydrated methyl isobutyl ketone and 174 g of 2,4-toluene diisocyanate in a flask equipped with a stirrer and a cooling tube (1
mol) and kept warm at 80 ° C. After 130 g (1 mol) of 2-hydroxyethyl methacrylate was added dropwise over 2 hours, the reaction was continued until the reaction rate of the isocyanate group reached 50%. Then 111 g of methyl isobutyl ketoxime (1 mo
After l) was added dropwise for 2 hours and reacted for 1 hour, the reaction rate of isocyanate groups became 100%.
To this monomer solution was added 500 g of n-hexane, and the mixture was cooled to 0 ° C. and passed to obtain 353 g of a white solid. Hereinafter, a blocked isocyanate group-containing ethylenically unsaturated monomer B-
1 The purity of this white solid was 96.5% as determined by gel permeation chromatography.

Blocked isocyanate group-containing ethylenically unsaturated monomers B-2 to B-7 were synthesized in the same manner as above.

Synthesis Examples 1 to 13 and Comparative Synthesis Examples 1 to 4 In a glass reaction container (internal volume: 500 ml), A-8 56
g, 2-ethylhexyl methacrylate 20 g, Block Toy
Socyanate group-containing ethylenically unsaturated monomer (B-1)
4 g, dodecyl mercaptan 0.4 g, deoxygenated pure water 276.8
g, acetone 40g, C₁₈H₃₇N (CH₃)₃Cl 1.6g and C₈H₁₇C
₆H_FourO (CH₂CH₂O)_n(= 8) Put 1.6g, azobisisop
Add 0.4 g of chillamidine dihydrochloride and stir in a nitrogen atmosphere
Then, the copolymerization reaction was carried out at 60 ° C for 10 hours. Obtained weight
The combined emulsion had a solid content concentration of 20.6%.

Copolymers (2 to 13) according to the present invention and copolymers 1 to 4 other than the present invention were synthesized in the same manner, and the copolymerization ratio thereof is shown in Table 1 together with the copolymerization ratio in Synthesis Example 1. .

All of these copolymer emulsions had excellent storage stability at 25 ° C.

In the table, EHMA is 2-ethylhexyl methacrylate,
IBMA is isobutyl methacrylate, SMA is stearyl methacrylate, SA is stearyl acrylate, ISMA is isostearyl methacrylate, HEMA is 2-hydroxyethyl methacrylate, HEA is 2-hydroxyethyl acrylate, CHPMA is 3-chloro-2-hydroxypropyl methacrylate, N -MAM is N-methylol acrylamide, N-MMAM is N-methylol methacrylate amide, and VDC is vinylidene chloride.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, "parts" means "parts by weight" unless otherwise specified.
“%” Shall mean “% by weight”.

Examples 1 to 13 A copolymer emulsion according to the present invention was diluted with water to prepare a treatment bath having a solid content concentration of 0.4%, and then a nylon taffeta dyed cloth and a polyester taffeta dyed cloth were immersed in the treatment bath for 5 seconds. Squeeze through the mangle to get a wet pickup
20%. Next, it was dried at 100 ° C. for 2 minutes, and cured at 170 ° C. for 30 seconds to be water and oil repellent treated. The water-repellent and oil-repellent performance of the thus obtained treated cloth was evaluated. The water repellency was represented by the water repellency number by the spray method of JIS L-1092, and the water repellency was represented by the oil repellency number of AATCC118 Hydrocarbon Resistance Test. In addition, the water repellency and oil repellency marked with + indicate slightly better performances.

In addition, the initial in the table shows the test results of the test cloth after processing, and after 10HL, it was washed 10 times (home washing, JIS L-0217).
・ Comply with Law 103. 4) shows the test result of the test cloth which was naturally dried overnight.

Similarly, a polyester moquette and a polyester woven fabric were dipped in the treatment bath and then squeezed to have wet pickups of 80% and 60%, respectively. Then, it was dried and cured under the same conditions as above to be treated for water and oil repellency.

The texture of the thus-obtained treated cloth was judged as follows by the feeling of touch.

<Tactile feeling><Judgment> Feel and no change of the base cloth ○ Harder than the base cloth △ Apparently harder than the base cloth × Extremely harder than the base cloth × × Also, the repellency before and after abrasion For the evaluation of the water-based property, a water drop having a diameter of about 5 mm was dropped from a height of 15 cm from the test cloth and the state of the water drop after 5 minutes was judged and indicated by the following signal. (Shown as water drop in the table.) Contact angle 120 ° or more ◎ Contact angle 90 to 120 ° ○ Contact angle 60 to 90 ° △ Contact angle 60 ° or less × Also, 1 drop of a mixture of isopropyl alcohol and water was tested. The mixing ratio of the mixture that can be left standing on the cloth for 3 minutes or more is shown by the AQ number in the table below. (In the table,
Shown as AQ. ) The wear of the cloth to be treated was measured using a Gakshin type dyeing fastness tester, cotton kanakin was used as the wear cloth, and the load was 500 g.
I went under the condition of going back and forth 00 times.

The performance results of these treated fabrics after abrasion are also shown in Table 1.

In addition, light resistance (fade meter, 63
When the resistance to NO _X (JIS L-0855) was measured, the whiteness of the hunter was high, and no coloration (yellowing) of the treated cloth was visually observed.

Comparative Examples 1 to 4 In Comparative Examples 1 to 4, cloths were treated with the water and oil repellents made of the polymers shown in Table 1 in the same manner as in Example 1 and the same tests were conducted. The results are shown in Table 1.

Incidentally, the treated fabric treated with the water- and oil-repellent agent of Comparative Examples 1 to 4 was measured for light resistance and NO _X resistance, coloration of the treated fabric was visually high Hunter whiteness was observed.

As is clear from Examples 1 to 13 and Comparative Examples 1 to 4 (Table 1), the treated fabrics treated with the water and oil repellent agent of the present invention did not lose the texture and were resistant to water and oil repellency. It can be seen that, while being excellent in both of abrasion resistance, the treated cloth treated with the conventional water and oil repellent agent is markedly inferior in any one of.

Synthetic Examples 14 to 19 and Comparative Synthetic Examples 5 to 6 (A-7) 4 in a glass reaction vessel (internal volume: 500 ml).
2g, stearyl methacrylate 15g, (B-2) 3g and
90 g of 1,1,1-trichloroethane was added, 0.6 g of azobisisobutylnitrile was added, and the mixture was stirred at 70 ° C under a nitrogen atmosphere.
The copolymerization reaction was carried out for 12 hours. In the obtained copolymer solution
250 g of 1,1,2-trichloro-1,2,2-trifluoroethane was added to a solid concentration of 15%.

In the same manner, copolymers 15 to 19 according to the present invention and copolymers other than the present invention (Comparative Synthesis Examples 5 to 6 were synthesized, and the copolymerization ratios thereof are shown in Table 2 together with the copolymerization ratios in Synthesis Example 14. Indicated.

In the table, BZMA is benzyl methacrylate and TBMA is t
-Butyl methacrylate, CHMA means cyclohexyl methacrylate (others are synonymous with the above).

Examples 14 to 19 and Comparative Examples 5 to 6 Copolymer solutions synthesized in Synthesis Examples 14 to 19 and Comparative Synthesis Examples 5 to 6 were diluted with 1,1,1-trichloroethane to obtain a solid content concentration.
A 0.45% treatment bath was prepared, treated fabrics were obtained under the same conditions as in Examples 1 to 21, and the same water and oil repellency was evaluated.

In addition, after 10DC in the table, 10 times dry cleaning (JIS L
-1018 ・ Complies with E-2 method. ) This shows the test results of the test cloth which was naturally dried overnight. Other evaluation methods were performed according to those of Examples 1 to 13.

 These performance results are also shown in Table 2.

Similarly, the polyester moquette and the polyester woven fabric were subjected to the same treatment, and the performance of the treated fabric before and after the feeling and abrasion were also shown in Table 2 (the evaluation criteria are the same as above).

The processed fabric had a high Hunter whiteness and no coloring was visually observed.

As is clear from Examples 14 to 19 and Comparative Examples 5 to 6 (Table 2), the treated fabrics treated with the water and oil repellent of the present invention did not lose the texture and were water and oil repellant and wear resistant. It can be seen that, while excellent in both properties, the treated cloth treated with the conventional water and oil repellent is markedly inferior in any one of.

〔The invention's effect〕

The fiber product treated with the water- and oil-repellent agent of the copolymer of the monomers (A), (B) and (C ₁ ) of the present invention has a water- and oil-repellent property without impairing the texture of the raw fabric before processing. It can be made into a certain textile product, and the water and oil repellent consisting of a copolymer in which the (C ₁ ) monomer and (C ₂ ) are used in combination does not impair the texture of the raw fabric before processing and is resistant to abrasion. It can be made into a textile product with excellent water and oil repellency with excellent abrasion resistance, and it has excellent NO _X resistance and light resistance, and also has excellent water repellency recovery just by natural drying after home washing or dry cleaning. can get.

Further, the water and oil repellent of the present invention has not only water and oil repellency but also a high surface modification effect such as antifouling property, surface lubricity and releasability. It can be applied to various articles.

Claims (2)

(57) [Claims] 1. A perfluoroalkyl group-containing ethylenically unsaturated monomer (A) and the following general formula (I): A blocked isocyanate group-containing monomer (B)
And a water- and oil-repellent agent comprising a copolymer obtained by polymerizing an ethylenically unsaturated monomer (C ₁ ) containing an alkyl group having 14 or more carbon atoms as an essential component. 2. The water- and oil-repellent agent according to claim 1, wherein an ethylenically unsaturated monomer (C ₂ ) having a functional group capable of reacting with an isocyanate group is further polymerized as a copolymerization component.