JPH09132872A - Water repellent and antistatic fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fabric, having durability in washing, water repellency and antistatic properties by joining a specific reactional product onto a polymerized coating film of a specific monomer formed on the surface of fibers. SOLUTION: This water repellent and antistatic fabric is obtained by coating the surfaces of fibers with a coating film prepared by polymerizing a monomer having plural acrylic and/or methacrylic groups in at least one terminal of the main chain consisting essentially of a polyalkylene oxide segment or as a side chain (polyethylene glycol diacrylate, etc.). A reactional product of (A) an acrylic copolymer containing a polyfluoroalkyl group (a fluorine-based water repellent) and (B) an aminoplast resin and/or a urethane resin containing a polyfunctional blocked isocyanate is joined onto the coating film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cloth which has both water repellency with washing durability and antistatic property.

[0002]

2. Description of the Related Art Conventionally, it has been difficult to obtain both water repellency and antistatic properties at the same time. Water repellency is a property obtained by making fibers hydrophobic, and antistatic properties makes fibers hydrophilic. By doing so, the electrical resistance of the fiber surface can be reduced and the obtained performance can be obtained. It was extremely difficult to achieve both of these performances that are completely contradictory.

In general, a method of using a cationic electrolyte, an antistatic agent of a polyelectrolyte such as a polycationic derivative at the time of water repellent treatment is used, but the antistatic property is temporary and is washed. It was poor in durability. Also, at the same time that this antistatic agent comes off by washing,
Since the water repellent is also removed, both the water repellency and the antistatic property are significantly reduced after the washing.

Japanese Patent Application Laid-Open No. 56-144274 proposes a woven fabric which is water-repellent and antistatic, which is obtained by applying a water repellent to one side of a woven fabric which has been previously treated with an antistatic agent. Has been done. However, it was poor in washing durability, and water entering between the yarns of the woven or knitted fabric soaked into one water-absorbing surface, and when worn as clothes, the feeling of wearing was significantly reduced.

Further, Japanese Patent Application Laid-Open No. 57-106776 proposes a fiber structure having a coating film of a copolymer of a fluorine compound and polyalkylene oxide as having both water repellency and antistatic properties. ing. However, the water-repellent performance is difficult to develop, and the washing durability is not satisfactory.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide a fabric having both washing durability and water repellency and antistatic properties.

[0007]

The present invention has the following constitution in order to satisfy the above-mentioned problems.

That is, a film formed by polymerizing a monomer having at least two acryl and / or methacryl groups as both ends or one end of a main chain mainly composed of a polyalkylene oxide segment or side chains of the main chain. A fabric composed of monofilaments whose surface is covered with, the coating having a polyfluoroalkyl group-containing acrylic copolymer, and at least one of a reaction product of an aminoplast resin and a polyfunctional blocked isocyanate-containing urethane resin. It is a water-repellent antistatic cloth characterized by having.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

Examples of the compound of the present invention containing two or more acrylic or methacrylic groups include polyethylene glycol diacrylate, polyethylene glycol polypropylene glycol dimethacrylate, polyethylene glycol w- (α, α-dimethacryloxymethyl). ) Acetate w'acrylate, and those containing a vinyl group in the side chain of the main chain such as the following general formulas [I] and [II] can be used.

[0011]

Embedded image

Embedded image (However, R ₁ and R ₂ are hydrogen or a methyl group, and 1 = 5 to 5
00. ) As a method for forming a polymerized film of the compound on the surface of a single fiber, an aqueous solution containing the compound and a polymerization initiator is applied to a cloth, and then steam heat treatment is performed at 80 to 140 ° C. to perform a polymerization reaction of the compound. It is preferable to wash the unreacted material with hot water and dry it after the completion of the polymerization.

The means for applying the treatment liquid to the fabric is not particularly limited and may be any method such as a dipping method, a pad method, a spray method and a textile printing method. In the present invention, the pad method is the most preferable. .

As the above-mentioned polymerization initiator, general vinyl polymerization initiators such as ammonium persulfate, potassium persulfate, azobisisobutyronitrile and the like can be used, and by selecting the kind of the polymerization initiator, A coating can be formed on the fiber surface under desired processing conditions.

The coating film thus formed has a thickness of 0.01 to 10 μm on the surface of the single fiber from the viewpoint of antistatic property and feeling.
Is preferably present, and more preferably 0.1 to 5 μm. This coating is preferably formed continuously or discontinuously with a polymer of the above compound.

According to the present invention, a water repellent having a polyfluoroalkyl group-containing acrylic copolymer as a main component (hereinafter referred to as a fluorine-based water repellent), an aminoplast resin or a polyfunctional blocked isocyanate is further provided on the coating. It is a fabric in which the reaction product of the contained urethane resin is joined.

Alternatively, it is a cloth in which a reaction product of a fluorine-based water repellent, an aminoplast resin, and a urethane resin containing a polyfunctional blocked isocyanate is bonded.

The fluorinated water repellent used in the present invention is not particularly limited, but is, for example, a homopolymerization of only a C _{3 to} C ₂₀ polyfluoroalkyl group or a monomer having a polyfluoroalkyl group. Those produced or those produced by copolymerization of the vinyl monomer with a polyfluoroalkyl group and another vinyl monomer having no polyfluoroalkyl group can be used. As the polyfluoroalkyl group or the vinyl monomer having a polyfluoroalkyl group, for example, those shown below can be used.

CH ₂ ═CHCOOCH ₂ C ₇ F ₁₅ CH ₂ ═C (CH ₃ ) COOCH ₂ C ₆ F ₁₂ CF ₃ (C
_{F 3) CH 2 = CHCOO (} CH 2) 2 N (C 3 H 7) SO 2
C ₈ F ₁₇ C ₆ F ₁₃ CH ₂ CH ₂ OH C ₈ F ₁₇ SO ₂ (C ₃ H ₇ ) CH ₂ CH ₂ OH C ₈ F ₁₇ SO ₂ (C ₃ H ₇ ) CH ₂ OOCNH (C
H ₂ ) ₆ NH (CH ₂ CH ₂ O) ₁₁ CH ₃ polyfluoroalkyl groups and other vinyl monomers having no polyfluoroalkyl group include, for example, ethylene, vinyl chloride, vinylidene chloride, acrylamide, styrene, Fluorine-based water repellents containing a copolymer containing benzyl acrylate, vinyl alkyl ketone, maleic anhydride, isoprene, siloxane, vinyl monomer of blocked isocyanate and the like as a main component are preferable.

As the aminoplast resin, known ones can be used, and specifically, melamine resins such as trimethylolmelamine and hexamethylolmelamine, dimethylolpropyleneurea, dimethylolethyleneurea, dimethylolhydroxyurea. It is possible to use urea-based resins such as, and uron resins such as dimethyloluron.

A curing catalyst may be used together with the aminoplast resin. For example, inorganic acids such as phosphoric acid, sulfuric acid and nitric acid such as ammonium, aluminum and zinc salts such as formic acid, acetic acid, acrylic acid and succinic acid may be used. It is possible to use salts of organic acids such as

The other functional blocked isocyanate urethane resin is not particularly limited as long as it is an organic compound containing two or more blocked isocyanate functional groups in the molecule. Specific examples include tolylene diisocyanate, hexamethylene diisocyanate, diphenyl methane diisocyanate, hydrogenated diphenyl methane diisocyanate, triphenyl triisocyanate, xylidine isocyanate, dicyclohexyl methane diisocyanate, trimethylolpropane tolylene diisocyanate adduct, glyceryl tolylene diisocyanate. A polyfunctional blocked isocyanate urethane obtained by reacting phenol, diethyl malonate, methyl ethyl ketoxime, sodium bisulfite ε-caprolactam, etc. as a blocking compound capable of regenerating an active isocyanate group by dissociating with an adduct upon heating at 70 to 200 ° C. A resin can be used. The polyfunctional blocked isocyanate urethane resin is preferably used as a water-dispersed liquid in which a small amount of a surfactant is mixed and forcibly emulsified.
Among the above, the methylphenylketoxime of diphenylmethane diisocyanate and the aqueous dispersion of methylethylketoxime of trimethylolpropane tolylene diisocyanate adduct are preferable.

Further, a dissociation catalyst may be used in order to improve the heat separation rate of the blocked isocyanate and to lower the thermal dissociation temperature. For example, dibutyltin citrate, dibutyltin stearate, stearyl zinc and organic amine compounds are preferable. .

The method for joining the reaction product of the fluorine-based water repellent, aminoplast resin, and polyfunctional blocked isocyanate-containing urethane resin onto the coating is not particularly limited, and the fluorine-based water repellent and the amino are used. A treatment liquid containing a plast resin or a urethane resin containing a polyfunctional blocked isocyanate in one bath or a fluorine-based water repellent,
It is preferable that a treatment liquid containing an aminoplast resin and a urethane resin containing a polyfunctional blocked isocyanate in one bath is applied to the fabric on which the coating has been formed and heat treatment is performed.

In order to obtain water repellency with washing durability on the cloth covered with the film, 100 parts by weight of the cloth is used.
The fluorine-based water repellent is preferably 0.01 to 10 parts by weight in solid content, more preferably 0.03 to 5 parts by weight, and the aminoplast resin is also 0.01 to 10 parts by weight in solid content. 2 parts by weight is preferable, and 0.02 to 1 part by weight is more preferable.

Similarly, with respect to the urethane resin containing a polyfunctional blocked isocyanate, the solid content is preferably 0.01 to 4 parts by weight, more preferably 0.03 to 1 part by weight.

A treatment liquid containing these in a bath is uniformly applied to the film-formed cloth by a method such as a pad method, a coating method or a spray method, and dried at about 100 ° C., preferably 120 to 200. ° C, more preferably 1
The reaction product can be bonded onto the coating by heat treatment at 40 to 180 ° C. for 15 seconds to 5 minutes.

The term "joined" as used in the present invention means that it is bonded or chemically bonded. Whether the bonding is adhesive bonding or chemical bonding does not directly affect whether or not the effect of the present invention is exerted.

In order to impart other properties to the cloth according to the present invention, generally used treating agents such as amino or hydrogen polysiloxane silicone softener, polyester or fluorine antifouling agent, ultraviolet absorber, Heat stabilizer, ceramic, antibacterial agent, deodorant, pigment, etc. are mixed with a treatment liquid containing a fluorine-based water repellent and at least one of aminoplast resin and polyfunctional blocked isocyanate-containing urethane resin. It can also be processed.

The cloth referred to in the present invention means a natural fiber, a synthetic fiber, a mixed spinning of these, a mixed twist, a mixed knit, and a mixed woven fabric. In particular, a cloth made of polyester fiber, polyamide fiber, polyurethane fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, polyvinyl chloride fiber, or the like is preferable.

By forming the coating and the reactants bonded to the coating on the fibers as described above,
Water repellency after 20 washes (JIS L-103 method) was 70 points or more (JIS L-1096 spray method) and friction electrification voltage was 2000 V or less (JIS L-1094 (20 ° C x 30 % R
It is possible to obtain a fabric which has both H)) water repellency and antistatic properties.

[0031]

The present invention will be described in more detail with reference to examples.

The water repellency shown in the examples and comparative examples was expressed by the water repellency score according to JIS L-1092 spray method. For friction electrification voltage, see JI
It measured by SL-1094 (20 degreeC x 30% RH) method.

[Examples 1 to 3 and Comparative Examples 1 to 3] Textile yarns made of 100% polyester are subjected to relax scouring, drying, dyeing, reduction washing, and drying by a usual method, and then the formula [II
The treatment liquid prepared by adding 0.3% by weight of the polymerization initiator APS was padded to an aqueous solution of 3% by weight of polyethylene glycol dimethacrylate of [1] to adjust the amount of adhesion to 88% by weight.

[0034]

Embedded image Then, steaming heat treatment was performed at 105 ° C. for 5 minutes. Subsequently, the unreacted product was treated with Sandet G-29 1g / l (Sanyo Kasei Co., Ltd. surfactant) at a bath ratio of 1: 100, 60.
After soaping at ℃ × 20 minutes, washed with water and dried. This process is called [A].

Further, the treatment liquid prepared according to the formulation shown in Table 1 was padded to an adhesion amount of 60% by weight, dried at 120 ° C. for 2 minutes, and then dried at 160 ° C. for 45 seconds.

The processing order was 1 and 2.

[0037]

[Table 1] (In the table, Maxguard EC-243 (fluorine-based water repellent): Kyokin Kasei Co., Ltd., Sumitex Resin MK
(Hexamethylolmelamine): Sumitomo Chemical Co., Ltd., Catalyst RC-W (organic amine catalyst): Kyokin Chemical Co., Ltd., Super Fresh JB-7200
(Polyfunctional Block Isocyanate Urethane Resin): Kyoshin Kasei Co., Ltd., Catalyst WL-2 (Organotin Catalyst): Kyoshin Kasei Co., Ltd., Nice Pole FE-26
(Cationic Antistatic Agent: Nika Kagaku Co., Ltd.) As is clear from Table 1, the processed cloth according to the method of the present invention showed water repellency of 70 points and friction electrification voltage of 2000 V or less even after 20 times of washing, and was excellent. It had durable water repellency and durable antistatic properties.

The film thickness of [A] was 0.8 μm as a result of microscopic examination with an electron microscope.

[0039]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a cloth having both excellent water repellency and excellent antistatic property, which has been difficult to achieve in the past, and which is most suitable for casual clothes such as coats and blouson. be able to.

Claims (3)

[Claims] 1. A coating polymerized with a monomer having at least two acryl and / or methacryl groups as both ends or one end of a main chain mainly composed of a polyalkylene oxide segment or side chains of the main chain. A fabric composed of monofilaments whose surface is covered with, the coating having a polyfluoroalkyl group-containing acrylic copolymer, and at least one of a reaction product of an aminoplast resin and a polyfunctional blocked isocyanate-containing urethane resin. A water-repellent antistatic cloth characterized by having 2. The water repellency after washing 20 times (JIS-L-130) is 70 points or more (JIS L-1096 spray method), and the friction electrification voltage is 2.
The water repellent antistatic cloth according to claim 1, which is 000 V or less (JIS L-1094 (20 ° C. × 30% RH)). 3. The water repellent antistatic fabric according to claim 1 or 2, wherein the coating is a continuous or discontinuous coating formed of a polymer having a thickness of 0.01 to 10 μm. .