JPH064842B2 - Water and oil repellent - Google Patents

Description

The present invention relates to a water and oil repellent agent. More specifically, it relates to a water and oil repellent having durability against washing and dry cleaning.

[Conventional technology]

JP A 54-128991, JP-polyfluoroalkyl group-containing polymerizable monomer and the general formula _{CH 2 = CRCON-NR 1 R} 2 R 3 or _{CH 2 = CRCOO (CH 2 CH} 2 O) 0~50 A water- and oil-repellent agent containing a copolymer containing a functional compound represented by CONHR'NHCO-Y as a constituent unit is described.

According to the description of this patent publication, the -NCO group is effective in improving the durability of the polyfluoroalkyl group-containing water and oil repellent agent, but a polymerizable monomer having such a functional group is generally difficult to obtain, and Since the -NCO group is highly active, a water- and oil-repellent agent containing such a group is very difficult to handle, and for example, a -NCO group-containing polymerizable monomer cannot be polymerized in an aqueous medium. , Also cannot give a water and oil repellent in the form of an aqueous dispersion,
Further, it is stated that the activity is lost due to the action of water and the durability improving effect is reduced before use.

However, the functional compound represented by the above general formula is a compound that can be converted into an -NCO group, and a copolymer obtained by copolymerizing such a functional compound with a polyfluoroalkyl group-containing polymerizable monomer. It is said that the water- and oil-repellent agent containing as an active ingredient no longer exhibits the above-mentioned drawbacks and exhibits excellent durability.

By the way, in this copolymer, various comonomers other than the above-mentioned two essential components can be copolymerized, and specifically, vinyl chloride, n-butyl methacrylate or tert-butyl methacrylate. A water and oil repellent agent using a copolymer obtained by copolymerizing the above is described. Currently,
Vinyl chloride, vinylidene chloride, and the like are used as preferable comonomers in order to improve water / oil repellency, and vinylidene chloride is particularly preferably used.

In the patent publication, although vinylidene chloride is exemplified as an example of a comonomer, in the case of a water / oil repellent obtained by copolymerizing vinylidene chloride in the copolymer disclosed herein, It was found that not only the coloring was observed but also the durability was inferior, and it could not be used as a durable water repellent.

[Problems to be solved by the invention]

As a result of various investigations, the present inventors have used vinylidene chloride, which imparts good water and oil repellency as a copolymerization component, and have further studied for a water and oil repellant having durability against washing and dry cleaning. It has been found that such a problem can be effectively solved by using the blocked isocyanate monomer represented by the general formula as the third copolymerization component.

[Means for Solving Problems] and [Action] Accordingly, the present invention relates to a water and oil repellent, which comprises (a) a polyfluoroalkyl group-containing (meth) acrylate and (b) a chloride. Vinylidene and (c) the general formula CH ₂ ═CRCOOR′NHCOX [wherein R is a hydrogen atom or a methyl group, R ′ is an alkylene group having 1 to 8 carbon atoms, and X is R ₁ or R _2; A hydrogen atom or an alkyl group having 1 to 4 carbon atoms -ON = CR
₁ R ₂ group, a phenoxy group substituted with an electron-withdrawing group, or R ₃ and R ₄ are alkyl groups having 1 to ₄ carbon atoms A group consisting of a block isocyanate monomer represented by the formula [1] is used as an active ingredient.

Perfluoroalkylalkyl (meth) acrylate is preferably used as the polyfluoroalkyl group-containing (meth) acrylate of the component (a), and examples thereof include the following. Here, R is a hydrogen atom or a methyl group.

CH ₂ = CRCOO (CH ₂ ) ₂ C ₆ F ₁₃ CH ₂ = CRCOO (CH ₂ ) ₂ C ₈ F ₁₇ CH ₂ = CRCOO (CH ₂ ) ₂ C ₁₀ F ₂₁ CH ₂ = CRCOO (CH ₂ ) ₂ C ₁₂ F ₂₅ CH ₂ ═CRCOOCH ₂ C ₇ F ₁₅ CH ₂ ═CRCOOCH ₂ C ₉ F ₁₉ Other polyfluoroalkyl group-containing (meth) acrylates include the following.

CH ₂ = CRCOO (CH ₂ ) ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ CH ₂ = CRCOO (CH ₂ ) ₂ N (CH ₃ ) SO ₂ C ₈ F ₁₇ CH ₂ = CRCOOCH ₂ (CF ₂ ) ₁₀ H CH ₂ = CRCOOCH ₂ (CF ₂ ) ₁₀ CF ₂ Cl CH ₂ = CRCOOCH ₂ CF (CF ₃ ) (OC ₃ F ₆ ) ₃ OC ₃ F ₇ The blocked isocyanate of the component (c) represented by the above general formula is Isocyanate alkyl (meth) acrylates such as isocyanatoethyl methacrylate, which is already supplied by Dow Chemical Company under the trade name XAS10743.00, are added to formaldoxime, acetoxime, methylethylketoneoxime, methylisobutylketoneoxime, diisobutylketooxime, salicylic acid. And methyl ester of p-hydroxybenzoic acid, ethyl ester of p-hydroxybenzoic acid, p-nitrophenol, diethyl, dipropyl, dibutyl ester of malonic acid and the like.

Some examples of the reaction are as follows.

This reaction is carried out by mixing isocyanate alkyl (meth) acrylate and the active hydrogen compound which reacts with it at a molar ratio of 1: 1 and stirring in an aprotic solvent such as toluene or tetrahydrofuran for about 2 to 4 days. The infrared absorption spectrum of 2200 cm ^-1
The reaction is terminated by confirming the disappearance of NCO absorption, and the solvent is distilled off at room temperature to obtain the desired product.

The above three essential components include about 40% by weight or more of component (a), about 5 to 50% by weight of component (b), preferably about 15 to 35% by weight, or about 0.540% by weight of component (c), Preferably used are those copolymerized at a ratio of about 0.5 to 10% by weight.
The component (a) is a main component exhibiting water and oil repellency, and this lack of water and oil repellency can be compensated by the lack of component (b), but the copolymerization of the component (c) improves durability. However, if the ratio is higher than this, the copolymer cannot be stabilized, while if it is lower than this, the crosslinking density becomes low.

The copolymer contains about 1 to about 1 of the comonomer other than the above components.
It can be copolymerized in a proportion of 50% by weight, preferably about 5 to 30% by weight, and examples of such a comonomer include vinyl chloride, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid or methacrylic acid. Alkyl, cycloalkyl, aryl or allyl esters of acids, styrene, α-methylstyrene, alkyl vinyl ethers, alkyl vinyl ketones, butadiene, isoprene, chloroprene, acrylates or methacrylates of polyalkylene glycols, carboxylic acid vinyl esters, p-vinylbenzene Examples thereof include sulfonic acid and phosphoric acid ester of 2-hydroxyethyl methacrylate, preferably acrylic acid or methacrylic acid ester, specifically, benzyl acrylate, lauryl acrylate, steari. Acrylate, methacrylate or vinyl chloride corresponding to cyclohexyl acrylate or thereof.

For the copolymerization reaction, add an organic solvent such as water and acetone to each polymerizable monomer, emulsifier, chain transfer agent, etc. above so that the solid content concentration is about 25% by weight, and use a colloid mill or the like. After emulsifying the mixture, transferred to a reaction vessel with a stirrer, after substituting nitrogen gas for about 10 minutes,
Add a radical initiator and add about 2-24 at a temperature of about 40-70 ℃.
It is carried out by reacting for a time.

Preparation of a water / oil repellent agent from the obtained copolymer emulsion and a water / oil repellent treatment using the same are carried out according to a conventional method, for example, a method as described in Examples below.

〔The invention's effect〕

As a durable water and oil repellent, for example, a water repellency of 90 or more, or an oil repellency of 110 or more must be retained even after washing 20 times.

In the present invention, in order to increase the crosslink density in the copolymer, which is the active ingredient of the water and oil repellent agent, particularly the crosslink density of the hydrophobic crosslink points, an active isocyanate group is formed as a hydrophobic crosslink group under curing temperature conditions. By introducing the blocked isocyanate to the copolymer, a water- and oil-repellent agent having desired water- and oil-repellency and hardly colored can be obtained as an emulsion type.

〔Example〕

 Next, the present invention will be described with reference to examples.

Reference Example (Synthesis of Block Isocyanate Monomer) Isocyanate Ethyl Methacrylate CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ NCO 31 g (0.2 mol), acetoxime 14.6 g (0.2 mol) and tethydrofuran 100 ml
Was reacted at room temperature for 4 days with stirring, and the end point of the reaction was determined by the disappearance of NCO group absorption (2250 cm ⁻¹ ) in the infrared absorption spectrum.

Evaporation of volatiles from the reaction mixture under reduced pressure gave 45.2 g of a white solid material. This blocked isocyanate monomer [I] has the following structure. CH ₂ = C (C
H ₃ ) COOC ₂ H ₄ NHCOON = C (CH ₃ ) ₂ Similarly, the blocked isocyanate monomer [II] and
[III] was synthesized.

[III]: CH ₂ = C (CH ₃ ) COOC ₂ H ₄ NHCOCH (COOC ₂ H ₅ ) ₂ Example 1 56 g (7) of perfluorooctylethyl acrylate (FAA)
Vinylidene chloride (VDC) 20g (25% by weight) Blocked isocyanate monomer [I] 4g (5% by weight) N-methylol acrylamide
_{6g [CH 2 = C (CH} 3) COOCH 2 CH 2 N (CH 3) 3] + Cl - ( Toagosei product accession helix DMC) 0.2 g n-dodecyl mercaptan 0.32g mixture of acetone 60g water 152g or more of the components After being subjected to a colloid mill, the mixture was charged into a flask and replaced with nitrogen gas for 30 minutes while stirring. The temperature was raised during nitrogen gas replacement, but was set to 40 ° C. after 30 minutes. After that, 2 g of an azo radical initiator (Wako Pure Chemical Industries V-50) was added as an aqueous solution in which 50 g of water was dissolved, and a copolymerization reaction was carried out at 70 ° C. for 4 hours,
A copolymer emulsion having a solid content concentration of 25% by weight was obtained.

To the obtained copolymer emulsion, melamine resin (Sumitex resin M-3, Sumitomo Chemical Co., Ltd.) as a cross-linking agent that imparts washing durability and its curing catalyst (Sumitex Accelerator ACX, a product of the same company) were added, Liquid diluted with water (concentration of these three components is 4
%, 0.5% and 0.1%), soak the polyester Amundsen fabric sufficiently, squeeze it, dry it with warm air at 80 ° C, and further subject it to curing at 120-170 ° C for 1-3 minutes,
A water and oil repellent test cloth was used.

Put 10 sheets of this water- and oil-repellent test cloth in a washing net at a ratio of 1 net, wash in a washing machine containing warm water (40 ° C) with a detergent concentration of 1 g / 15 minutes, and then wash in 40 ° C warm water. The operation of performing dehydration for 10 minutes was repeated twice. This series of operations was repeated 20 times, and the washed water and oil repellent test cloth was water repellent (by the spray method of JIS L-1005).
And the oil repellency (by Nujol-n-heptane method) were evaluated and compared with the values before washing. The obtained results are shown in Table 1 below, and this table also shows the results of evaluation or measurement of the color tone and reflectance of the water- and oil-repellent test cloth before washing.

(Evaluation of color tone) A: No discoloration B: Slight decrease in whiteness C: Slight yellowing visible D: Yellowing observed (Measurement of reflectance) Reflectance of water- and oil-repellent-free fabric was set to 100% The value when. When this value is 90% or less, it looks slightly yellowed with the naked eye.

Examples 2-11 In Example 1, emulsions of other copolymers were similarly prepared and used. The results obtained are shown in Table 1 below.

Comparative Examples 1 to 8 In the above examples, block isocyanate monomer
Instead of [I] to [III], an emulsion of a copolymer containing the functional compounds [IV] to [VII] described in the above-mentioned patent publication as a monomer component was similarly prepared and used. Was given. The obtained results are shown in Table 2 below.

Functional compound [IV]: Hydroxyethyl acrylate 23.2g (0.2mol), toluene diisocyanate 34.8g (0.2mol), dibutyltin dilaurate 0.1g and tetrahydrofuran 100ml, 20
The reaction is carried out in the presence of nitrogen gas with stirring for 1 day at 0 ° C. After confirming disappearance of diisocyanate by gas chromatography, 14.6 g (0.2 mol) of acetoxime dissolved in 100 ml of tetrahydrofuran is added dropwise, and further reacted at room temperature for 1 day. The volatile components were distilled off from the reaction mixture under reduced pressure to obtain 71.6 g of a pale yellow solid.

In the same manner, functional compounds [V] to [VII] were synthesized.

[VI]: CH ₂ = CHCOOC ₂ H ₄ OCONH (CH ₂ ) ₆ NHCOON = C (CH ₃ ) ₂ [VII]: CH ₂ = C (CH ₃ CONN (CH ₃ ) ₂ CH ₂ CH (OH) CH ₃

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Claims (3)

[Claims] 1. A (a) polyfluoroalkyl group-containing (meth)
40% by weight or more of a unit based on acrylate, (b) 5 to 50% by weight of a unit based on vinylidene chloride, and (c) a general formula CH ₂ = CRCOOR'NHCOX [wherein R represents a hydrogen atom or a methyl group, and R ' Is an alkylene group having 1 to 8 carbon atoms, and X is R ₁ , R ₂ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms -ON = CR
₁ R ₂ group, a phenoxy group substituted with an electron-withdrawing group, or R ₃ and R ₄ are alkyl groups having 1 to ₄ carbon atoms A water- and oil-repellent agent comprising as an active ingredient a copolymer consisting of 0.5 to 40% by weight of a unit based on a blocked isocyanate monomer. 2. The water and oil repellent according to claim 1, wherein the component (a) is a copolymer having a perfluoroalkylalkyl (meth) acrylate as an active ingredient. 3. The water and oil repellent according to claim 1, which is prepared as an emulsion type.