JPH02214792A - Water and oil repellent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention imparts a soft texture to textile products, etc.
This invention relates to a novel water and oil repellent that has excellent durability in water and oil repellency after washing and dry cleaning.

(Prior art and its problems) Homopolymers of (meth)acrylates (this term includes both acrylates and methacrylates in the present invention) containing perfluoroalkyl groups or these and alkyl (meth)acrylates have conventionally been used. Water and oil repellents comprising copolymers with other polymerizable compounds, such as vinyl chloride, butadiene, maleic anhydride, styrene, methyl vinyl ketone, etc., are 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 relates to a copolymer containing as essential units a vinyl monomer (I) having a polyorganosiloxane 3n and a vinyl monomer (n) having an isocyanate group or a blocked German cyanate group, and a perfluoroalkyl This is a water- and oil-repellent agent characterized by being mixed with a water- and oil-repellent compound having a group.

(Function) Vinyl monomer CI having a polyorganosiloxane chain)
A mixture of a copolymer containing a vinyl monomer (n) having an isocyanate group or a blocked German cyanate group as an essential unit and a water- and oil-repellent compound having a perfluoroalkyl group is used as an essential water- and oil-repellent agent. By using this as a component, 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 was difficult to do in the past.

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

As the water- and oil-repellent compound having a perfluoroalkyl group used in the present invention, conventionally known water- and oil-repellent compounds can be used, and those having active hydrogen are particularly preferred. , O is a polymer or copolymer of vinyl monomers having a perfluoroalkyl group of 2, for example, CaFryc2H40cOcH-c
tlzCaFtsC2H40(:QC(CH3)-C)
ItCaF+tCi)140COC(CHa)-C11
2C1°F21c2H40(:0CH-CH2CaF
l? 5O2N ((:2)1s) C2H40COC
H-CH2CaF, ,5o2N (C2H,)C
, H40COC(C)13) -ct+2, a polymer of a vinyl monomer typified by (meth)acrylate having a C4 to 02G perfluoroalkyl group, or a copolymer with a vinyl monomer that does not contain fluorine. One example is merging.

Examples of fluorine-free vinyl monomers include ethylene, propylene, styrene, vinyl chloride, butadiene,
Vinyl acetate, acrylonitrile, chlorobrene, maleic anhydride, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid and its alkyl esters, dimethylaminoethyl (meth)acrylate, (meth) Examples include acrylamine mint, N-methylol (meth)acrylamide, and the like.

Other examples of water- and oil-repellent compounds having perfluoroalkyl groups include urethane compounds having perfluoroalkyl groups, polyester compounds having perfluoroalkyl groups, and epoxy rust conductor compounds having perfluoroalkyl groups.

In addition, as for the vinyl monomer having a polyorganosiloxane chain constituting the copolymer of the present invention to be mixed with the water- and oil-repellent compound, as a specific example, Me (- and pH are a methyl group and a phenyl group, respectively). , n
, m and l are respectively! (expressing a numerical value from 400 to 400),
Molecular weight of polyorganosiloxane chain 100 to 100,
000 (meth)acrylate is preferred.

In addition, as a vinyl monomer having an isocyanate group,
A specific example is H,C-C(CH3)(:0-NGO(methacrylisocyanate)H2C-C(CH3)CO-0-CH,C
In addition to 112NGO (2-isocyanate ethyl methacrylisocyanate) -Q methylbenzyl isocyanate), 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 Examples include compounds in which an active hydrogen-containing (meth)acrylate such as glycol mono(meth)acrylate, t-butylaminoethyl (meth)acrylate, polyethylene glycol polypropylene glycol mono(meth)acrylate and an organic isocyanate are reacted to form a terminal isocyanate. It will be done.

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 (manufactured by Nippon Polyurethane Co., Ltd.), Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.), Coronate EH (manufactured by Nippon Polyurethane Co., Ltd.), Duranate 24A-100 (manufactured by Asahi Kasei Kogyo Co., 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.

In the present invention, other copolymerizable vinyl monomers can also be used in addition to the vinyl monomers having polyorganosiloxane chains and vinyl monomers having isocyanate groups or blocked German cyanate groups.

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, chloroprene, maleic anhydride, itaconic acid, glycidyl (meth)acrylate, dimethylaminoethyl (
Examples include meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and the like.

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. Preferably in the presence of a polymerization initiator,
It is carried out by solution polymerization or emulsion polymerization. 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 is composed of 5 to 500 parts by weight of a vinyl monomer having an isocyanate group or a blocked German cyanate group per 100 parts by weight of the above vinyl monomer having a polyorganosiloxane chain. part, preferably in the range of 20 to 200 parts by weight. 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 is obtained by mixing 1 to 300 parts, preferably 10 to 150 parts, of the above copolymer per 100 parts by weight of the above water and oil repellent compound having a perfluoroalkyl group. . However, if the water- and oil-repellent compound having a perfluoroalkyl group is solvent-based, the copolymer mixed therewith will also be solvent-based, and if the water- and oil-repellent compound having a perfluoroalkyl group is aqueous type. In this case, the copolymer mixed therewith is also made into an aqueous type to obtain a solvent type and an aqueous type water and oil repellent, respectively.

The water and oil repellent of the present invention may be used in combination with other antistatic agents, antioxidants, ultraviolet absorbers, flame retardants, anti-wrinkle 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 copolymerized with a vinyl monomer having a blocked German cyanate group, after preliminary drying, curing is performed for 30 seconds to 3 minutes at a temperature 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, linen, wool, and silk; synthetic fibers such as polyester, nylon, vinylon, acrylic, and polyvinyl chloride; and semi-synthetic fibers such as rayon and acetate; and mixtures thereof. It is also used for textile materials.

In addition, due to its excellent flexibility and durability against washing and dry cleaning, it is suitable for use in clothing such as coats, work clothes, sportswear, casual wear, mountain parkas, and jackets.
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 for softening, it will have a negative effect on water and oil repellency.

In contrast, the water and oil repellent of the present invention comprises a vinyl monomer having a polyorganosiloxane chain and a vinyl monomer having an isocyanate group or a blocked German cyanate group mixed in a water and oil repellent compound having a perfluoroalkyl group. After the copolymer made of monomers undergoes a crosslinking reaction after dry heat treatment, the polyorganosiloxane monomer part that forms a crosslinked structure has the silky-like feel of silicone and the good elasticity and flexibility of urethane. The perfluoroalkyl segments that are cross-linked or interpenetratingly cross-linked, immobilized and oriented by isocyanates provide durable water and oil repellency against washing and dry cleaning.

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

Therefore, both the flexibility of the texture and the durability of the 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, water repellency is expressed as water repellency N01 (Table 1 below) by the spray method of JIS L-1092, and oil repellency is expressed as AATCC-1 shown in Table 2 below.
18-1966 test solution on two places on the sample cloth (about 4 mm in diameter). ! After 30 seconds, the highest number that did not penetrate or absorb the oil into the fabric was considered as the degree of oil repellency.

1.No adhesive moisture on the surface.Slight adhesive moisture on the surface.Partial moisture on the surface.Moisture on the surface.Moisture on the entire surface.Completely wet on both the front and back. 1 ζJ rope 8 n-Hebutane 20.07 n
-Octane 21.06 n-decane
23.55 n-dodecane
25.04 n-tetradecane 26.
73 n-hexadecane 27.31
Nujol 31.2
0. Also, regarding laundry, JIS-L-0217-103 air dry finishing, laundry and dry cleaning,
It was carried out according to JIS-L-10113/ε-2 air dry finishing.

Example I CaF+tCJ40-COCH-CH*
80 parts 2-ethylhexyl methacrylate 18 parts 2-hydroxyethyl acrylate 2 parts 1.1.
400 parts of 1-trichloroethane and 1 part 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 water- and oil-repellent compound (A) with a solid content of 20%.

On the other hand, 100 parts of 2-isocyanate ethyl methacrylate (1.1.1-)800 parts of dichloroethane and 2 parts of azobisisobutyronitrile were charged, and a copolymerization reaction was carried out at 70°C for 10 hours in a nitrogen gas stream to reduce the solid content to 2.
0% copolymer (I) was obtained.

After mixing 60 parts of the compound (A) and 40 parts of the copolymer (I), 1.1. - 1% solids in trichloroethane
It was diluted so that Soak nylon taffeta in this,
After squeezing with a mangle, dry at 80℃ for 2 minutes, and then dry for 16 minutes.
Heat treatment was performed at 0t for 2 minutes.

Table 3 shows the texture of this cloth, and the water and oil repellency after washing and dry cleaning about 10 times each.

Example 2 &I# It is shown in Table 3.

For comparison, Compound (A) of Example 1 was used as Comparative Example 1.
was diluted with 1.1-trichloroethane to a solid content of 1%, and then tested in the same manner as in Example 1. The results are also listed in Table 3.

kshi≦Lj-e 2-isocyanate ethyl methacrylate/methyl ethyl ketoxime adduct (mole ratio of 171 each) 150 parts 1,
1,000 parts of 1-trichloroethane and 2.5 parts of azobisisobutyronitrile were charged, and a copolymerization reaction was carried out in the same manner as in Example 1 to obtain a copolymer (n
) was obtained.

Copolymer (I) in Example 1 was replaced with copolymer (II), and the results were tested in the same manner as in Example 1. Judgment was made.

DC=C Nidry Cleaning 1 season 5-Something softer than the texture of LIX cloth.

4. - Almost the same texture 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 3 CaF+tCzHaO-COC(CL)-GHz
8 0 parts 2-ethylhexyl methacrylate 15 parts N-methylolacrylamide 5 parts acetone
100 parts dimethyloctadecylamine acetate 4 parts azobisisobutyramidine dihydrochloride 0.5 parts ionized water 316 parts,
A copolymerization reaction was carried out at 65° C. for 15 hours under a nitrogen gas stream to obtain a water- and oil-repellent compound (B) with a solid content of 20%.

On the other hand, 2- and droxyethyl acrylate/tolylene diisocyanate/acetoxime adduct (1/1/1 molar ratio each)
100 parts acetone
10,000 parts nonionic emulsifier
8 parts azobisisobutyramidine dihydrochloride 1 part deionized water 732 parts were charged.
A copolymerization reaction was carried out in the same manner as above to obtain a copolymer (m) with a solid content of 20%.

60 parts of the compound (B) and 40 parts of the copolymer ([[I)
After mixing the two parts, the mixture was diluted with water to give a solid content of 1%. After soaking a cotton broadcloth in this and squeezing it with a mangle,
It was dried at 160°C for 2 minutes and then heat-treated at 160°C for 2 minutes.

Table 4 shows the texture of this cloth and its water and oil repellency after washing and dry cleaning about 10 times each.

Example 4 Example 5 I5 Methacryloyl isocyanate/acetoxime adduct (
each 171 molar ratio) 60 parts acetone
50 parts nonionic emulsifier
6 parts Azobisisobutyramidine 2
Hydrochloride 1 part deionized water 61
4 parts were charged and a copolymerization reaction was carried out in the same manner as in Example 3 to obtain a copolymer (IV) with a solid content of 20%.

Copolymer (m) in Example 3 was replaced with copolymer (IV),
Table 4 shows the results of the same tests as in Example 3.

2-hydroxypropyl acrylate 74゜4'-dicyclohexylmethane diisocyanate/methyl ethyl ketone adduct (each !/1 hamol ratio) 80 parts acetone 50 parts nonionic emulsifier 4 parts azobisisobutyramidine dihydrochloride 1 part deionized water 686 parts Preparation,
A copolymerization reaction was carried out in the same manner as in Example 3 to obtain a copolymer (V) with a solid content of 20%.

Table 4 shows the results of testing in the same manner as in Example 3, except that the copolymer (m) in Example 3 was replaced with copolymer (V).

For comparison, the compound (B) of Example 3 was used as Comparative Example 2.
was diluted with water to a solid content of 1%, and then tested in the same manner as in Example 3. The results are shown in Table 4.

ka [oka] doctor memorial hall grade plate wood repellent 0G O0 first nta sex

Claims (1)

[Claims] (1) A copolymer containing as essential units a vinyl monomer (I) having a polyorganosiloxane chain and a vinyl monomer (II) having an isocyanate group or a blocked German cyanate group, and a perfluoroalkyl group. A water and oil repellent characterized by being mixed with a water and oil repellent compound.