JPH02214791A - Water and oil repellent - Google Patents

Abstract

PURPOSE:To obtain a novel water and oil repellent, consisting of a copolymer containing a perfluoroalkyl group-containing vinyl monomer, etc., as essential constituent units and capable of imparting soft hand to textile products, etc., and exhibiting durable water and oil repellent performance after washing. CONSTITUTION:The objective water and oil repellent consisting of a copolymer containing (A) a vinyl monomer [preferred example; (meta)acrylate having a 4-20C perfluoroalkyl group] having the perfluoroalkyl group, (B) a vinyl monomer [preferred example; (meta)acrylate having organosiloxane chain with 100-100000 molecular weight] having the organosiloxane chain and (C) a vinyl monomer (preferred example; a compound, such as oxime, lactam or phenols, having 50-180 deg.C dissociation temperature) having (blocked) isocyanate group as constituent essential units.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a flexible texture to textile products and the like.
0, Concerning a new water and oil repellent with excellent durability of water and oil repellency after washing and dry cleaning (Prior art and its problems) The term includes both acrylates and methacrylates in this invention) or other polymerizable compounds thereof such as alkyl (meth)acrylates, vinyl chloride, butadiene, maleic anhydride, styrene, methyl vinyl ketone, etc. Water and oil repellents made of copolymers with are well known and widely used.

However, these perfluoroalkyl group-containing (
When textile products are treated with a water and oil repellent made of a polymer mainly composed of meth)acrylate, the texture becomes stiff, which can be a major drawback, especially in clothing applications.

In addition, textile products treated with water and oil repellents made of polymers mainly containing perfluoroalkyl group-containing (meth)acrylates initially exhibit excellent water and oil repellency, but they are difficult to wash and dry clean. It has the disadvantage that the subsequent water and oil repellency performance is significantly reduced.

In addition, in order to improve the durability against washing and dry cleaning, various crosslinking monomers are copolymerized, and melamine compounds, blocked German cyanate compounds, etc. are added and mixed to the treatment liquid to make it water and oil repellent. Treatment methods have been proposed, but all of the methods that have been found to be effective end up having a very hard texture, and can only be used in extremely limited applications, making them impractical.

In addition, in order to soften the texture, silicone softeners are sometimes used together with water and oil repellents made of perfluoroalkyl group-containing polymers to adjust the texture. It is generally known that when a softening effect is observed, it adversely affects the water and oil repellency properties of a water and oil repellent made of a perfluoroalkyl group-containing polymer.

Therefore, an object of the present invention is to provide a water and oil repellent that has both flexibility and good durability of water and oil repellency after washing and dry cleaning, which has been difficult in the past.

(Means for solving problems) The above objects are achieved by the present invention as described below.

That is, the present invention provides a vinyl monomer (I) having a perfluoroalkyl group, a vinyl monomer (n) having a polyorganosiloxane chain, and a vinyl monomer (III) having an isocyanate group or a blocked German cyanate group. This is a water and oil repellent characterized by being made of a copolymer containing as an essential unit.

(Function) A copolymer containing as essential constituent units a vinyl monomer having a perfluoroalkyl group, a vinyl monomer having a polyorganosiloxane chain, and a vinyl monomer having an isocyanate group or a blocked German cyanate group. By using this as an essential component of a water and oil repellent, it is possible to provide a water and oil repellent that has both flexibility and good durability of water and oil repellency after washing and dry cleaning, which has been difficult in the past.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

The vinyl monomer having a perfluoroalkyl group in the present invention may be any of the known ones conventionally used in water and oil repellents, such as CaFryc*H40c.
OcH-(:H2C,F13C2H40COC(CH3
)-(:)12CaF+tC2HnOCO(:(CHi
)-CH2C1°F2rCJnOCO(:H-Ct12
CaF l 7SO2N (C2H6) C2H40C
OC)l=cHzC,F + 7SO2N (CJs)
CJ40COC (C++J - C4 like (:)12
(meta) having a perfluoroalkyl group of from 2° to C2°
Acrylates are preferred.

In addition, regarding vinyl monomers having polyorganosiloxane chains, specific examples include lIIe (Me and pH represent methyl group and phenyl group, respectively,
n, m and l each represent a numerical value of 1 to 400), the molecular weight of the polyorganosiloxane chain is 100 to too
, ooo (meth)acrylates are preferred.

In addition, as a vinyl monomer having an isocyanate group,
Specific examples include H,C-C(C)I3)Go-Neo (methacrylic isocyanate)H,C-C(CH,)Co-0-CI2
C) 12NGO (2-isocyanate ethyl methacrylisocyanate) -dimethylbenzyl isocyanate), etc., as well as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, crystall mono(meth)acrylate, 1 .6-Hexanediol mono(meth)acrylate.

Neopentyl glycol mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate diethylene glycol mono(meth)acrylate polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, t-butyl Examples include compounds obtained by reacting an active hydrogen-containing (meth)acrylate such as aminoethyl (meth)acrylate and polyethylene glycol polypropylene glycol mono(meth)acrylate with an organic isocyanate to form a terminal isocyanate.

As the organic polyisocyanate, 4.4'-diphenylmethane diisocyanate, 4.4
'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, phenylene diisocyanate, hexamethylene isocyanate, 1,5-naphthylene diisocyanate, Coronate) IL (manufactured by Nippon Polyurethane Co., Ltd.), Coronate EH (manufactured by Nippon Polyurethane Co., Ltd.), Duranate 24A-100 (manufactured by Asahi Kasei Industries, Ltd.)
, Takenate 110N (manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.), and the like.

In addition, a vinyl monomer having a blocked German cyanate group is obtained by adding a blocking agent to a vinyl monomer having an isocyanate, and examples of the blocking agent include dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, Ethyl acetoacetate, isopropanol, t
-butanol, formaldoxime, acetaldoxime, methyl ethyl ketoxime, cyclohexane oxime, acetophenone oxime, acetoxime, benzophenone oxime, diethylglyoxime, ε-caprolactam, δ-valerolactam, γ-butyllactam, phenol, 0-methylphenol, Examples include p-nitrophenol, p-naphthol, p-ethylphenol, cresol, xylenol, N-methylacetamide, acetamide, acrylamide, phthalimide, imidazole, maleic acid imide, sodium bisulfite, potassium bisulfite, and the like. Preferred examples include compounds having a dissociation temperature of 50 to 180°C, such as oximes, lactams, and phenols.

Further, for a vinyl monomer having a blocked German cyanate group, a blocking agent and an organic polyisocyanate may be added, and then the vinyl monomer may be added to a vinyl monomer containing active hydrogen.

Other copolymerizable vinyl monomers can also be used in the present invention.

For example, in addition to the above active hydrogen-containing (meth)acrylate, ethylene, vinyl acetate, vinyl chloride, styrene,
Vinylidene halide, acrylonitrile, α-methylstyrene, p-methylstyrene, (meth)acrylic acid and its alkyl ester, (meth)acrylamide, N-
Methylol (meth)acrylamide, vinyl alkyl ether, vinyl alkyl ketone, butadiene, isoprene, chlorobrene, maleic anhydride, itaconic acid, glycidyl (meth)acrylate, dimethylaminoethyl (
Examples include meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, etc., and known methods can be used to obtain the copolymer used in the water and oil repellent of the present invention. That is, various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be used. Solution polymerization or emulsion polymerization is preferably carried out in the presence of a polymerization initiator.

Further, in the case of emulsion polymerization, it is necessary to use it in the form of a blocked German cyanate group for stabilization.

As the solvent, any of ketones, esters, ethers, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated solvents, etc. can be used.

Examples of the polymerization initiator include various azo compounds and peroxides.

The copolymer used in the water and oil repellent of the present invention preferably contains 5 to 200 parts by weight of a vinyl monomer having a polyorganosiloxane chain, based on 100 parts by weight of the vinyl monomer having a perfluoroalkyl group. is obtained by copolymerizing 20 to 100 parts by weight and 2 to 300 parts by weight, preferably 10 to 200 parts by weight of a vinyl monomer having an isocyanate group or a blocked German cyanate group.

Further, other copolymerizable vinyl monomers may also be copolymerized within a range that does not affect performance.

The water and oil repellent of the present invention may be used in combination with other antistatic agents, antioxidants, ultraviolet absorbers, flame retardants, antiwrinkle agents, dye stabilizers, and the like. When using it, it may be diluted with an organic solvent or water as appropriate.

When treating fiber fabrics and the like with the water and oil repellent of the present invention, methods such as impregnation, spraying, and gravure coating can be used, and after application, dry heat treatment may be performed.

In the case of a water- and oil-repellent agent copolymerized with a vinyl monomer having a blocked isocyanate group, after preliminary drying, curing is performed for 30 seconds to 3 minutes at a temperature equal to or higher than the dissociation temperature of the blocked German cyanate group.

Various objects can be treated with the water and oil repellent of the present invention, including textile fabrics, paper, leather, fur, glass, metals, and various plastic films.

Examples of the above-mentioned fiber fabrics include natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyester, nylon, vinylon, acrylic, and polyvinyl chloride; and semi-synthetic fibers such as rayon and acetate. Also used for mixed fiber materials.

In addition, due to its excellent flexibility and durability against washing and dry cleaning, it is also suitable for clothing such as coats, work clothes, sportswear, casual wear, mountain barkers, yacht parkas, carpets, It is useful for interior goods such as curtains, reception sets, and automobile interior seats, and is also useful for applications mainly focused on stain resistance.

(Effects) As mentioned above, textile products treated with conventional water and oil repellents containing perfluoroalkyl groups have a harder texture and
If a softener is used in combination for softening, it will have a negative effect on water and oil repellency.

In contrast, the water and oil repellent of the present invention has a perfluoroalkyl segment, a polyorganosiloxane segment, and an isocyanate group or blocked German cyanate segment on the same molecule, so it is easy to crosslink and orient, is flexible, and washable. A film with excellent durability after dry cleaning can be obtained.

In addition, after dry heat treatment, the polyorganosiloxane segment part that formed a crosslinked structure with isocyanate groups,
It provides the silky-like feel of silicone and the good elasticity and soft feel of urethane, and the perfluoroalkyl segments crosslinked and oriented with isocyanate exhibit water and oil repellency that is durable against washing and dry cleaning.

In addition, the crosslinked polyorganosiloxane segments prevent damage to the film due to abrasion during washing and dry cleaning, resulting in ultra-durable water and oil repellency.

Therefore, both the flexibility of the texture and the durability of water and oil repellency can be achieved, and the effect of the present invention cannot be obtained even if essential components are missing.

(Examples) Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the text, all parts and percentages are based on weight unless otherwise specified.

Further, the water repellency and oil repellency shown in Examples and Comparative Examples were measured by the following method.

That is, the water repellency is expressed by the water repellency No. J (Table 2 below) determined by the spray method of JIS L-1092, and the oil repellency is expressed by the ATCC-11 shown in Table 2 below.
8-1966 test solution on two places on the sample cloth (
After 30 seconds, the oil repellency was determined by the highest number that did not penetrate or absorb into the cloth.

(Left below) kl''-j (No adhesive moisture on the surface Items that show slight adhesive moisture on the surface Items that show partial moisture on the surface Items that show moisture on the surface Items that show moisture on the entire surface Items that show moisture on the entire surface Both sides shows complete wetness [Riku1 Nujol]
31.20 For items that do not meet 1, and for laundry, JIS-L-0217-10:
The air dry finishing, washing and dry cleaning of i were carried out in accordance with the air dry finishing of JIS-L-1018/ε-2.

Example I C8F, SO,N (C2)1. ) C2)14
0-COCH-C11° 100 parts n-hebutane n-octane n-decane n-dodecane n-tetradecane n-hexadecane 20° 21° 23° 25° 26° 27° 2-isocyanate ethyl methacrylate 40 parts Methyl ethyl ketone 360 parts 1 .1.
360 parts of t-trichloroethane and 1.8 parts of azobisisobutyronitrile were charged, and a copolymerization reaction was carried out at 70°C for 10 hours under a nitrogen gas stream to obtain a pale yellow transparent liquid with a solid content of 20%.

Next, this copolymer solution was diluted with 1.1.1-trichloroethane to a solid content of 0.5%. A cotton broadcloth was dipped in this, squeezed with a mangle, dried at 80°C for 2 minutes, and further heat-treated at 160°C for 2 minutes.

Table 3 shows the texture, water and oil repellency of this cloth after washing and dry cleaning about 810 times.

For comparison, Comparative Example 1 was carried out in the same manner as in Example 1 except that the methacrylate having polyorganosiloxane S in Example 1 was replaced with butyl methacrylate, and Comparative Example 2 was obtained using 2 of Example 1. -Isocyanate-
Replace ethyl methacrylate with butyl methacrylate,
The other results were conducted in the same manner as in Example 1, and the results are also shown.

(Margin below) k(≦shijku Fukukinko 51 Class Kaili Mizutate too to.

Side plate l drawing 116 wound I'' 19o-18o. -58 1 Oikidachi So 1" 15-6 3 1 From Todosha-"' 100 50 0-50 Remains of Mizutate Old J"l 5-6 3 1 1 The texture of the Okidachi is determined by touch. did.

DC=C Nidry Cleaning Gu fixed base bank 5...The texture is slightly softer than that of the original cloth.

4...The texture is almost the same as the original cloth.

3... Something a little harder than the texture of the original cloth.

2... Something that is obviously harder than the texture of the original cloth.

1.-A material that is much harder than the texture of the original cloth.

Example 2 C, F, 7C2H40-COCH-CI 2100 parts Ja e 2-isocyanate ethyl methacrylate/methyl ethyl ketoxime adduct (each l/1 nosol ratio) 50! Methyl ethyl ketone 400 parts 1.1.1-
400 parts of trichloroethane and 2 parts of azobisisobutyronitrile were charged, and the reaction was carried out in the same manner as in Example 1 to obtain a pale yellow transparent liquid with a solid content of 20%.

Next, this copolymer solution was diluted with 1,1,1-trichloroethane to a solid content of 0.5%, a nylon tack was dipped in this, squeezed with a mangle, and then dried at 80°C for 2 minutes. Then, it was further heat-treated at 160°C for 2 minutes.

Table 4 shows the texture, water and oil repellency of this cloth after washing and dry cleaning about 810 times.

For comparison, Comparative Example 3 was prepared in the same manner as in Example 2 except that the methacrylate having polyorganosiloxane chains in Example 2 was replaced with styrene.
The results of the same procedure as in Example 2 except that the 2-isocyanate ethyl methacrylate/methyl ethyl ketoxime adduct of Example 2 was replaced with styrene are also shown.

(The following is a blank space) ni 1 Lfi Kazeukyu to prayer plate selection person and 100 prayer plate selections five! +00 Example 3 CaF+tCJ40-COC(CH+)-(:1121
00 parts acetone 100 parts nonionic emulsifier 3 parts dimethyloctadecylamine acetate 3 parts azobisisobutyramidine dihydrochloride 0.8 parts deionized water 565 parts,
A copolymerization reaction was carried out at 65° C. for 15 hours under a nitrogen gas stream to obtain a latex with a solid content of 20%. Next, this latex was diluted with water to a solids content of 0.5%.

A blended fabric of polyester/cotton (65/35) was dipped in this, squeezed with a mangle, dried at 110°C for 2 minutes, and further heat-treated at 160°C for 2 minutes. Table 5 shows the texture and water and oil repellency of this cloth after washing and dry cleaning about 10 times each.

(Left below) 2- and droxyethyl acrylate/tolylene diisocyanate/acetoxime adduct (1/1/] molar ratio each)
30 parts Example 4 CaF + yCzH40-COCH-GHz 100 parts Example 5 CaF + 7C21140-(:0CH-Ctl*1
00 parts e methacryloyl isocyanate/acetoxime adduct (
each 17I molar ratio) 50 parts acetone
100 parts nonionic emulsifier
4 parts dimethyloctadecylamine acetate 4i Azobisisobutyramidine dihydrochloride 0.9 parts Deionized water 732 parts were charged.
The reaction was carried out in the same manner as in Example 3 to obtain a latex with a solid content of 20%. Next, tests were conducted in the same manner as in Example 3, and the results are shown in Table 5.

2-Hydroxypropyl acrylate/4,4' dicyclohexylmethane diisocyanate/methyl ethyl ketoxime adduct (each 1/l/l % ratio) 40 parts acetone IOO part nonionic emulsifier 3.5 parts octadecylamine acetate 3 .5 parts azobisisobutyramidine dihydrochloride 0.1 part deionized water 648 parts were charged,
A latex having a solid content of 20% was obtained by reacting in the same manner as in Example 3. The latex was then tested in the same manner as in Example 3, and the results are shown in Table 5.

Comparative Example 5 A commercially available fluorine-based polyacrylate emulsion type water and oil repellent (solid content 20%) was tested in the same manner as in Example 3, and the results are shown in Table 5.

Rapid 1JLj race Stainless Steel prayer ark water sacrifice ! 00 OO O0 Kyohadahoshasha

Claims (1)

[Claims] (1) Vinyl monomer having perfluoroalkyl group (
I) is characterized by consisting of a copolymer containing as essential constituent units a vinyl monomer (II) having a polyorganosiloxane chain and a vinyl monomer (III) having an isocyanate group or a blocked German cyanate group. Water and oil repellent.