DE2239592A1 - ARTIFICIAL FIBER STRUCTURE WITH ANTISTATIC, DIRT-REPELLENT AND WATER-ABSORBING PROPERTIES - Google Patents

Description

2239532

Dr Hans-Heinrich Willrath d- <b Wiesbaden 7th August, 1972

Dr Dieter Weber ■ 'Postf _at hi327 i / e _P

a telegimm

PATENT LAWYERS

TP 29 204

Toray Industries, Inc.

2, Nihonbashi-Muromachi 2-chome, Chuo-ku, Tokyo / Japan

Synthetic fiber structure with antistatic, dirt-repellent and water-absorbent properties

Priority; of August 12, 1971 in Japan Note No .: 60 640/71

The invention relates to a synthetic fiber structure with permanent antistatic, dirt-repellent and water-absorbing properties and a process for their production.

About synthetic fibers and fabrics woven or knitted from them Granting antistatic properties has hitherto been a combination of electrical conductivity with a polymer its formation into fibers has been mixed. For example, polyalkylene glycol and various surfactants are used for this purpose Means known. However, there is a risk of

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that adversely affects the inherent properties of the fiber because a different type of connection has been added to the fibers. To give good antistatic properties it is also necessary to add a large amount of antistatic agent and when the obtained fiber is melt-spun and is stretched, yarn breakage and roughening often occur, which greatly deteriorates the quality of the yarn. Therefore, when such yarn is textured, the fiber breaks up into a fibril state or results in a gray pattern, when wearing fabrics made from such yarn.

It has also been proposed to use a surface active agent having antistatic properties or a post treatment agent add that by adhering to the fiber surface of a synthetic fiber thread, yarn, or woven or knitted Becomes an anti-static processing agent. Such adhesives include amines, amides, and quaternaries Ammonium salts, as well as compounds containing polyglycols, aliphatic and aromatic polyglycol ethers and their derivatives. They also include the aftertreatment agents, such as arylalkylsulfuric acid esters, Phosphoric acid esters, sulfonic acid series, phosphoric acid series, polyhydric alcohols and their derivatives, all of which must be adherent to the surface of the synthetic fiber. A fiber whose antistatic property is due to such Method has been improved, has a poor shelf life, and if a product as such fiber was washed in the house three times it completely loses its antistatic properties. Furthermore, fabrics are made from a fiber whose antistatic property is due to a cationic

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antistatic processing agent has been improved. is stained when washed. »*

These fibers have no reaction groups that interact with the attached compound. Mix as a result these compounds simply dissolve and bleed easily in the presence of water or a solvent «Indeed Many procedures using post-treatment methods have been proposed »None of the products of such procedures however, it is excellent in washfastness and weatherability. Also, many such products are regarding their grip noticeably deteriorated.

A method of graft polymerizing acrylic acid, styrene and glycidyl methacrylate into one was also envisaged Synthetic fiber and its conversion into an alkali salt, especially the sodium and potassium salt. With this method, however, have only sodium and potassium have antistatic properties, while calcium and magnesium salts have no antistatic properties can develop. In practical use, however, calcium, magnesium and iron are present in ordinary washing water, and since calcium and magnesium are easily ion exchanged with sodium and potassium salts, the antistatic disappears Effect, if a product made from such fibers has two or washed three times.

Furthermore, since a graft polymer fiber generally has the defect a noticeable decrease in colorability and youth

• ■ ■■■■ - ^: - ■■ - 4 _

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If such a fiber is to have excellent antistatic properties, the module must have physical properties Properties are sacrificed, and such fibers "have no practical value.

The invention has set itself the task of eliminating these usual deficiencies and a synthetic fiber structure with antistatic, to create dirt-repellent and water-absorbent properties that also provide practical durability owns.

For this purpose, according to the invention, a type of processing means is selected from the following species (A), (B) and (C), adhered to a synthetic fiber structure and heat-treating the affected fiber structure in the presence of moisture.

(A) is a monomer free of quaternary nitrogen compounds and having at least two acrylic groups and / or methacrylic groups at both ends, one end or a side chain of the main chain consisting mainly of a polyalkylene oxide segment consists.

(B) a polymer is one of those in the general formula reproduced compound with a polymerizable Monomer and / or a Diviny! Compound

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H ₂

R O

I Il

C-C-

(here R has the meaning of H or CH ₃ , R ¹ of Cl or Br, I, OCH ₃ , OC ₂ H ₅ , SCH ₃ or SC ₂ He and 0 <m 1 10 and 10

(C) is a mixture of a compound with a polymerizable one Vinyl group at one end or as a side chain of a polyalkylene glycol, its polyalkylene oxide segment has a molecular weight of 400 to 10,000, and a vinyl monomer having at least two vinyl groups.

It is also possible to achieve the effect according to the invention by adding either (D) or (E) to the treating agents (A), (B) or (C) causes the fiber structure to adhere and the afflicted fiber structure in the presence Treated warm from moisture. The agent (D) is a cationic antistatic agent and (E) is an alkylethylene urea derivative according to the general formula

CH ₃ - (CH ₂ ) _n -NHC-

(wherein

5 <y <30).

. > ■ ",

3 0 9809/1040

In the case of a synthetic fiber structure with durable antistatic, dirt-repellent and water-absorbing properties, as produced by the above process of the invention is the surface of a synthetic fiber such as a polyamide, polyester, polyacrylonitrile or polyolefin, covered by a polymer film of the treating agent in a thickness of 0.01 to 10 µ, preferably 0.1 to 3 µ. Such have antistatic synthetic fiber structures according to the invention surprisingly durable antistatic properties and at the same time dirt-repellent and water-absorbing properties.

The treating agent (A) used in the invention is a vinyl monomer of a polyalkylene glycol having at least two Acrylic and / or methacrylic groups in a molecule, according to, for example, the following general formulas:

R ₁ 0

I ¹ II

0 R,

Ii Γ

- C -C- (OC ₂ H ₄ ) / - (OC ₃ H ₆ ^ -0-CC-CH

or

R ₁ O

OR,

Il I ²

OC-OCH ₀

Γ I H

CH- C -C- (OC ₀ -HJZ-OC-CH 2 Z 4 · ^{Λ ι}

CH ₂ -OCC-CH ₂

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m 7 "»

(herein R _{1 and R 2 can be the} same or different and are H or CH _{3 ,; 0} <■ _m <^ J _{m 5, 500} ) ^; .

ι · i

Such treatment agents (A) include, for example, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, Polyethylene glycol triacrylate, di- or trimethacrylate of block polyalkylene glycols of polyethylene oxide and polypropylene oxide and acrylate and methacrylate derivatives of Polyalkylene oxide, according to the following general formulas:

ο oho CH ₃ -; o

CH ₂ CCOC ₃ JO ₃ ; .

HC-C- (OCH ₂ CH ^ O-CCC- (OCH-CH ₂ ) _m -0-G-CH CH ₉ = C CO-CH ₀ ■■: ■ -. ', I Ii. ■ - ■ ^CH 2 ° i "f ^CH 2 ^ - ■■

gh. o; .. [· ■■. ■ ■ -. ■

OR ₂

R ₁ C 0 0 R ₀ CH _o -0-CC «CH _o

" ¹ JI Il» Γ 'I ^{2 2}

: "A - c- (oc ₀ H,) / -oc-CH -oc-ch-ch- (oc ₀ h,) ρ -oc-ch-ch"

2 2 4 * 1 H ² A ^A O. ² .

CH ₂ -OCC-CH- (OC ₂ H ₄ ) / f -0-C-CH-CH ₂ r

Il

R ₂ CH ₂ -OO

OR ₂ CH-OC-CH

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- 8 (here R., R ~ , £ and m have the above meanings.)

Treatment agent (B) is a copolymer of the type of methoxypolyethylene glycol acrylate, ethoxypolyethylene glycol acrylate, Kthoxypolyäthyleneglycolmethacrylat, chlorinated polyethylene glycol methacrylate, chlorinated polyethylene glycol acrylate, methylsulfidpolySthyleneglycolmethacrylat, Methoxypolyäthyleneglycolglyeng, Methoxypolyäthyleneglycolmethacrylat, methylsulfidpolySthyleneglycolmethacrylat, Methoxypolyäthyleneglycolglyeng, Methoxypolyäthyleneglycol methacrylate. Such compounds develop an excellent antistatic effect when ^ C in the general formula is at least 10, preferably at least 20. If ^ is less than 10, no sufficient antistatic effect develops, and when m is above 10, the synthesis of the compound is difficult, and the connection can not be produced.

The polymerizable monomer or divinyl compound is another ingredient. Examples are acrylonitrile, Acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, acrylamide, sodium allyl sulfonate and sodium styrene sulfonate as a polymerizable monomer, and examples of the divinyl compound include ethylene glycol diacrylate, iithylene glycol dimethacrylate and polyethylene glycol diacrylate.

The treatment agent (B) is a binary or ternary polymer, that you can use known methods of aqueous redox polymerisation * tion by interpolymerizing the compound represented by the above general formula and either or both of the others

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Components received. At the same time is a mixed polymer compound, those with 10 to 40 wt .-% acrylonitrile as polymer

. monoviny! compound has been copolymerized, * especially excellent in terms of their antistatic properties

' Properties. When the degree of interpolymerization is below 10%, the effect obtained is insufficient “If he Exceeds 40%, the particle size of the interpolymer becomes large, and the antistatic properties and durability thereof become large get bad.

In the subject matter of the invention, the treatment agent containing such a copolymer is prepared as a disperse liquid or solution of water or an organic solvent, which is made to adhere to the synthetic fiber structure. The affected structure is then heat treated in the presence of moisture. When cotton or regenerated cellulose fiber is mixed with the synthetic fiber structure, excellent antistatic properties are obtained even if the adhesive structure is subjected to a dry heat treatment. However, if the adhesive structure consists of 100% synthetic fiber, it is necessary to dampen it
To undergo heat treatment.

The treating agent (G) used in the invention is obtained by mixing a polyalkylene glycol monovinyl compound with a vinyl series monomer which is at least
has two vinyl groups, i.e. it is a polyfunctional vinyl compound. The ones considered here © Polvalkvlen-.

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Glycolmonovlny! compound has a polyalkylene oxide segment a molecular weight of 400 to 10,000, preferably 800 to 4000. Examples of these are polyethylene glycol methacrylate, Methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, Ethoxy polyethylene glycol acrylate, ethoxy polyethylene glycol methacrylate, chlorinated polyethylene glycol methacrylate, Polypropylene glycol acrylate, polypropylene glycol EOl methacrylate, Methoxypolypropyleneglycolacrylat, Methylsulf idpolyäthylenglycolmethacrylat and compounds with a Viny! Group as a side chain according to the following formula

1!

t H) CH ₀ CH) -OC-CH-CH -OC-CH-CH-H) CH _o CH -} - OR

1 2 2 η 2 ν, "* ■« ^B ' ^A

CH _n OH

CH ₂ -OCC-CH ₂

(Here R ₁ and R 2 are hydrogen, methyl or ethyl, and m is an integer from 5 to 500). However, the polyalkylene glycol monovinyl compound is not limited by the above.

The reason for limiting the molecular weight of the Polyalky lenoxidsegmen te s is, as mentioned above, that at lower molecular weight than 400 of the other

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the desired effect cannot be sufficiently developed,

* t

and if IO 000 is exceeded, the synthesis of the conn becomes so difficult that it is impractical.

As for the polyfunctional vinyl compound, to name such compounds of the diacrylate and triacrylate series as mentioned above, however, is the invention

• ι

not limited to this.

The treating agent (C) is obtained by mixing the above monovinyl compound with the polyfunctional vinyl compound, transferring the resulting mixture into a dispersed liquid or solution of water or an organic solvent, causing the liquid or solution to adhere to the synthetic fiber structure, and then the affected structure treated with steam. As for the mixing ratio of these compounds, the effect of the invention becomes remarkable when the polyfunctional vinyl compound is obtained in an amount of 3.0 to 50.0 % by weight, preferably 5.0 to 40.0% by weight on the solid portion of the monovinyl compound is present.

As mentioned above, in the compound, either a cationic antistatic agent (D) or the alkylethylene urea and its derivative (E) can be used in addition to the treating agent (A), (B) or (C). The cationic antistatic agent as contemplated here consists, for example, of a compound with a poly- '

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ß-methacryloxyäthyldiäthylmethylammonium-inethoxysulfat as Main component and as a compound of the quaternary ammonium salt series, an aryltrimethylammonium salt, dialkyldlmethylammonium salt, Alkyltributylammonium salt and alkyldimethylbenzylanimonium salt, Alkyl pyridinium salt, alkyl morpholinium salt, Alkylimldazollniumsalz and compounds represented by the the following general formulas:

CH,

RN - (CH ₉ CH ₀ O) -H

ι * 2 Π CH,

Cl

CH,

XCH CH 0) -H

(I) ■ (2)

R ¹

R-C-NHCH CH CH-N-R "2 2 *

R "

I I I

(3)

(Here R, R ', R "and R'" can be identical or different and have the meaning of H or a lower alkyl group, X stands for a halogen, ro and η can be identical or different and 5 < η <30 and 5 < m <30).

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The above-mentioned alkylethylene urea and its Derivatives are represented by the following general formula, wherein a saturated alkylethylene urea preferably has 4 to 19 carbon atoms, oetadecylethylene urea is most effective.

; o gh

Ii / ■■ *

■ CH- (GH) -NHG-N

3 2 η \

(herein 1st GIL

According to the invention, “a compound (D) or (E) as explained above * is combined and mixed with one of the treatment agents (A) to (C), the mixture being an organic solution, dispersed aqueous liquid or is a solution, and then the solution, for example, liquid is brought to adhere to the synthetic fiber structure and this is then treated with steam 0? 0-3 to 7% by weight _r, calculated as solid and hexogenic on the dyeing weight, amount, no special device or corderHch is required for the sheathed liquid vapor according to the invention, but an apparatus previously used in a dyeing factory can be used be;. the afflicted synthetic fiber structure can be either continuous or further processed into individual feeds Apart from a special case, however, is a dry heat treatment is not preferable because there due to the

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BADORlGtNAt-

sought effect of the invention usually cannot be achieved. When observed under the microscope, one of the Product subjected to steam treatment, a uniform and smooth film while in a dry heat treatment a significant bump and local film formation can be observed did.

If one tries to form a good film through treatment To achieve this with steam, this is feasible, though the atmosphere contains about 100% steam. The conditions for steam treatment are not particularly restricted, however, 60 to 900 seconds is preferred because of cost permanent treatment at 80 to 150 C, one also achieves one almost complete effect according to the invention by treatment in heated vapor of an organic solvent without dissolving a polyalkylene glycol monoviny compound

In the aforementioned warm polymerization of the invention, can also at the same time a polymerisation initiator, such as ammonium persulphate, Potassium persulfate, benzoyl peroxide and azobisisobutyl nitrll, be used. By choosing the kind of such a polymerization initiator, overdrawing can be made as desired and carry out selected conditions «In particular for Using a redox polymerization initiator it is possible to obtain a film at a lower temperature which corresponds to the aim of the invention. To a polymer film according to the invention to form on a hydrophobic substance in the treatment liquid to be explained later «it is necessary to to use a hydrophobic polymerization initiator «With one

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- 15 <

hydrophilic polymerization initiator is not possible / _; to impart the effect of the invention to a hydrophobic fiber. . .

Furthermore, it is possible according to the invention, the usefulness to maintain the treatment liquid permanently and to continue the treatment according to the invention over a long period of time by forcing oxygen or air is introduced into a treatment liquid containing vinyl series monomers with (A) and (C). So far, you've had a long one Service life of the treatment liquid in such machining treatment considered a problem with a vinyl series resin. To extend the service life, has either a polymerization initiator is mixed with the treatment liquid or the reaction system on one kept low temperature. However, such methods have the defect that they are discolored or excessive Bring extension of the polymerization time with it.

In the method of the invention, this common deficiency is eliminated. The synthetic fiber structure is treated continuously while using oxygen at a flow ratio of at least 2.1 cm / 1 · min. into the treatment liquid which blows the vinyl series monomer and the polymerization initiator contains. On this occasion, the temperature of the treatment liquid can be raised accordingly, and from the viewpoint of decomposition of the polymerization initiator and formation of a polymer film, a temperature is in the range from 0 to 60 ° C is expedient. After experimental. investigation

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Continuous blowing in * in a ratio of at least 2.1 cm / 1 · min at 20 ^° C. will be sufficient for the amount of oxygen. If you use air in a ratio of at least 10 cm / 1 «min. is used, the treatment liquid can be kept long enough without initiating polymerization. Accordingly, such an amount of oxygen is sufficiently maintained by the air contained in the fiber structure while the structure is continuously treated. It is therefore not necessary to blow in further oxygen while the fiber structure is being treated continuously. What is necessary, however, is to prevent the treatment liquid from gelling, and is for this purpose. it is possible to maintain the service life of the treatment liquid when an amount of oxygen of at least 2.1 cm / l «min is supplied. If the treatment liquid according to the invention must necessarily be used at a high temperature, such as when used for coloring, for example, decomposition and disappearance of the polymerizing initiator are inevitable. By adding and supplementing the initiator appropriately, it is therefore possible to treat the fiber structure without hindrance.

Since it is therefore possible when using the method of the invention is to stabilize the treatment liquid permanently without it being attacked by the temperature, results no change over time. It becomes possible to perform good resin processing, and consequently becomes stabilizes the quality of the product. In addition, the

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'__ 17 - -. . ; * "" Treatment operationally very advantageous "

As for the method to adhere such a treatment to the fiber structure according to the invention, this can be achieved with any thawing method, padding method, coating method or spraying method " as long as the possibility of covering the fiber atrack is given.

A synthetic fiber structure as used in the invention contains a synthetic fiber such as polyamide, polyester, polyacrylonitrile, Polyolefin and polyurethane as well as those fibers whose properties have been modified and the structure includes knitted and woven fabrics, nonwovens, threads, garney. Tow and films made of so-called synthetic fibers or natural fibers, and fibers from the cellulose series, as well as mixed fibers and Mixed staple fibers made therefrom. The structure, however, is not due to the manufacturing methods of these fibers, their components and Form arrangement, limited.

The polyester fiber is obtained by freely combining an aliphatic dicarboxylic acid such as sebacic acid and adipic acid, and an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and diphenic acid with ethylene glycol, butylene glycol and condensing the resulting mixture, as well as a fiber made from another poly * polyester polymer containing ester »

- 18 30980 9/1040

The polyamide fiber is made by condensation polymerization of an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and diphenic acid and a dicarboxylic acid having an aliphatic ring or heterogeneous ring such as 1,2-cyclo-butane 2,6-dicarboxypyridine, an aliphatic diamine such as hexamethylene diamine, an aromatic diamine such as p-xylylene diamine and m-xylylene diamine, lactams such as OC- (CH ₂ J _n -NH (n >> 3,4,6,8,10 , ll) and aminocarboxylic acid obtained.

This polyacrylonitrile is a homopolymer or copolymer of acrylonitrile. Methyl methacrylate, vinyl chloride, vinylidene ch nitride, vinyl acetate, styrene, sodium styrene sulfonate and sodium allyl sulfonate polymer can be cited as other basic components of the mixing. These can be used alone or at least mixed and polymerized in pairs.

The polyolefin fiber is one obtained from ethylene and propylene

Fiber.

Furthermore, the following applies to the synthetic fibers whose properties have been modified. A polyester fiber »their Condition has been modified, for example an int Polyester, which has been obtained by mixing with the synthetic high polymer of the polyeater series, the compounds are in one or in one by the following general formula

- if ...

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appropriate combination

R-Ar-X (4)

R-Ar-W-X (5)

Here, R denotes an alkyl group with 2 to 18 carbon atoms, Ar an aromatic hydrocarbon radical or phenol nucleus, X an adipic acid group or its salt / W denotes - (- CH ₂ y- _n or -—- f- CH ₂ CH ₂ O,

where η ■ = 2 to 16.

R "

R - (K-CHCH 0-3 H '(6)

2 η

Here, R ¹ denotes hydrogen or an alkyl group, R ¹¹ denotes hydrogen or CH ₃ , ^ 2 ^Η 5 ', these substituents can also be present in a molecule that is copolymerized ) N = 2 to 500 _f -

or a designed structure of the polyester series can contain a block polyether amide with 15 to 85% of a polyalkylene ether segment in an amount of 0.1 to 5% by weight, calculated on this polyalkylene ether segment.

The effects obtained by using such a fiber, the nature of which has been modified, are one antistatic properties equivalent to those of cotton; the fiber is excellent in its dirt-repellent properties

and water-absorbing properties that are electrostatic

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Inhibition of a fabric formed from such fiber is eliminated as well as the lack of absorption of perspiration and the graying of the fiber product during washing; is all such defects adhere to a tissue eleophilen of such a polymer, such as polyester fiber, manufactured *

As for the polyamide fiber, the nature of which has been modified, it includes, for example, block polyether amide, that is, a block copolymer composed of a segment of polyether, the content of which is 15 to 85% by weight, bound in the form of a straight chain to a polyamide segment. A such block polyether amide is made by adding a monomer to form a polyamide, e.g., lactams, ^ - amino acid or a diamine and a dicarboxylic acid in the presence of a polyether having a terminal amino group or an organic one Salt of the same in solution or molten state polycondensed, the polyether having an amino group, a Has carboxyl group or an amino group and a carboxyl group at its end and the polyamide has a carboxyl group, has an amino group or a carboxyl group and an amino group at its terminal.

The polyamide, the nature of which has been modified, for example, according to the invention, consists of this block polyether amide or a mixture of the polyether amides and polyamide, which is practical possesses an antistatic property per se and is formed so that the final content of the polyether segment is 0.1 to 20 wt .-%, preferably 0.3 to 10%, can be.

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As mentioned above, the synthetic fiber, the nature of which has been modified according to the invention, is not obtained Graft polymerization. As a result, it is unnecessary to give activity to the polymerizing center. Furthermore, the Fiber per se antistatic properties, the invention also achieves that the treatment agent adheres to the synthetic fiber, the nature of which has been modified, and the affected fibers are heated in the presence of moisture, preferably in water vapor or organic solvent vapor.

The fiber thus obtained can develop another excellent effect according to the invention due to the synergistic effect of the antistatic property * of the fiber itself and the polymer layer, the treatment agent.

The method of the invention can be applied to a knitted or woven fabric made from the synthetic fiber with a fiber density of use less than 0.5 g / cm and the fabric obtained has excellent durability. The treatment agent (A,), (B) or (C) is adhered and polymerized thereon.

The fiber density, as it is specified in the invention, is obtained by multiplying the thickness of the fabric, measured under a load of 3 g / cm with the area size of the fabric to calculate the fabric volume and division de * Fabric weight through this volume ». - 22 -

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The density of taffeta or twill calculated on this catfish

3 ■ '

is about 0.7 to 1.1 g / cm, which is relatively high

1st. However, if the woven or knitted fabric is made of a Mixed yarn, consisting of the synthetic fiber and a relatively bulky fiber such as rayon or cotton, is made, it is possible to reduce the density to about 0.1 to 0.4 g / cm lower. When such a woven or knitted fabric with a density of less than 0.5 g / cm with the Treatment agent is treated, as will be explained in more detail below in particular in Example 6, excellent antistatic properties are obtained, which are obtained when in use other general antistatic agents cannot achieve. The knitted or woven fabric thus obtained is lower Density is remarkable in terms of wash resistance and can withstand 50 washes using one standardized electric household washing machine. Because of the low density of a knitted or woven fabric and the fact that a film was formed on each thread, the grip of the fabric in the hand did not become harder either. A very good product with excellent durability is obtained. Since the treatment agent has excellent hydrophilic properties, the product has excellent water-absorbing and dirt-repellent properties at the same time, which is very good is important for the application of the product of the invention to shirts or sportswear.

If, according to the invention, a hydrophobic fiber is produced using methods as they were dealt with above, it is difficult that of

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hydrophobic fiber to impart the effect of the invention. Any of the treating agents used in the invention is a hydrophilic monomer or polymer, and it is generally very difficult to polymerize a hydrophilic monomer on the surface of a hydrophobic fiber. this is based on the fact that it is difficult to get the treatment liquid and the processing means because of the properties of a to cause such fiber to adhere to the surface of a hydrophobic fiber. When you have a product in a flexible Active ingredient, a) sweater or women's knitted fabric, which by direct Knitting of the threads or yarn has been preserved, world-processed, so the padding process with the steam method is technically difficult. As a result, according to the invention is a Method have been developed that effectively polymerize allowed to perform on the surface of a hydrophobic fiber in a solution. Particularly when treating a hydrophobic fiber structure in a treatment liquid, which mainly consists of the treating agent (A) according to the invention, causes this liquid to appear on the surface to adhere to the structure and polymerize there, using a disperse system of a hydrophobic polymerization initiator used. At the same time, the temperature of the treatment bath is increased as necessary to initiate the polymerization.

The polymerization initiator used in the invention is particularly important. A practically water-insoluble hydrophobic polymerization initiator such as fine particles of a water-insoluble one Polymerization initiators, such as benzoyl peroxide,

3098 0 9 / 104Q. ₂₄ .

Acetyl peroxide, t-butyl hydroperoxide, peroxycarbamate, 2.2 -

■■■■■■■■ '· ■ ^: »''■■' Azobisisobutyronitrile and tetramethylthiuram disulfide, or« ' these stabilized initiators »mixed with example V wise magnesium sulphate are used. With a water soluble initiator such as ammonium persulfate, potassium persulfate and hydrogen peroxide is not sufficient in the invention · polymerization by immersion in such an aqueous one Ventilation system achieved over the invention.

According to the invention, disperse particles of a hydrophobic initiator are on the surface of a hydrophobic fiber in Water adsorbed «and the vinyl monomer dissolved in water is only polymerized on the fiber. It is also possible conduct polymerization at low temperature by introducing a redox type polymer as an initiator.

Furthermore, the method of the invention is characterized in that

that the polymerization takes place in a reaction system, wherein oxygen coexists. Accordingly, can a monomer containing a quaternary nitrogen atom does not be polymerized in such a method of the invention.

If, on the other hand, the fiber material is made of cotton, hemp, a fiber

the polyvinyl alcohol series or polyamide does not occur

Absorption of a hydrophobic polymerization initiator on the Material surface because the material is inherently hydrophilic

is; the effect of the invention does not therefore occur.

Below are methods of measuring the antistatic

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Properties, water-absorbing properties and adhering amounts explained as they are in the examples can be specified.

A sample treated according to the invention is kept for 5 hours in a controlled chamber at 20 ° C. and relative humidity left standing by 65%. The amount adhered is then measured. Furthermore, the sample is 15 hours left to stand at 20 ° C and relative humidity of 40% «The level of static electricity is measured«

1.) Degree of static electricity (V)

Measuring machine: Static bread tester (manufactured

from Koa Shokai, Japan)

End fabric of friction; Cotton fabric of yarn count 50 width.

Measurement conditions: 20-1 ° C., humidity 40 ± 1%.

The level of static electricity (V) is called the mean given by five measurements.

2.) Durability::

Washing machine: 'Electric washing machine, manufactured by Tokyo Shibaura Elektri Co., Ltd.

Detergent: "Zabu", a cleaning agent, manufactured by Kao Soap Co., Ltd.

«Concentration used: 0.2% by weight, washing conditions: 40 ° C and 10 minutes.

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3 O 9 8 O 9/1 O 4 O

After a sample has undergone such a wash , it is dried as follows: '- ■'

Dryer: household dryer manufactured by Osaka Gas' Co., Ltd.

Drying conditions: 70 and 10 minutes

The above information relates to a single wash. A sample subjected to ten such washes is referred to as an "after-wash sample". It goes without saying that the sample subjected to such a treatment is left to stand in the control chamber at the temperature and humidity mentioned and measured thereon. A sample washed with 0 time is one before the above washing treatment.

3.) Adhesive amount:

The 33 results from the percentage difference between the weight of a sample before and after the treatment, based on the weight of the sample before the treatment.

Ratio of attachment _w _ _w

(Amount in percent ■ χ 100

^W o

Herein let W: weight of the sample before treatment, V /: weight of the sample after treatment

In the following examples, the phrase "loss

ratio used. This-is according to the measurement method for the adhesion ratio was measured. The loss ratio

Is the percentage of the material that remains after washing 309 H 0 9/1040 - 27 -

falls off or is removed, based on the adherent 'Amount of the sample before washing. Or washed for Time 0.

4.) Water absorption property: /,

A drop of water (0.04 crt? / Drop is applied to a The sample was dropped from a position 5 cm high and the time was measured until the drop was completely absorbed. has been brewed. The less the time, the better it is the water-absorbing nature *

Below are various aspects of the invention, in particular with reference to examples.

Example 1 . '.

A polyethylene terephthalate yarn of 250 denier and 84 threads was twisted incorrectly, woven into a fabric and the fabric delayed wetting or cleaning according to standard methods. Then he was dried and such Subjected treatments according to the invention as indicated by ml to m5. The adherent crowd and that Static electricity levels for these substances are given in Table 1.

The composition of the treatment liquid and the treatment conditions of the polymerizable compound were as follows:

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3098U9 / 1040

Sample ml: An aqueous solution containing 3% by weight of polyethylene glycol dimethacrylate, the polyoxyethylene segment of which had a molecular weight of 500, was admixed with 0.3% by weight of ammonium persulfate as a polymerization initiator (APS).

Sample m2: An aqueous solution of polyethylene glycol dimethacrylate of 3 wt .-%, its. A polyoxyethylene segment with a molecular weight of 1000 was admixed with 0.3% by weight of APS as a polymerization initiator.

Sample m3; _# An aqueous solution of 3% by weight of polyethylene glycol dimethacrylate, the polyoxyethylene segment of which had a molecular weight of 2000, was admixed with 0.3% by weight of APS as a polymerization initiator.

Sample m4t An aqueous solution of 3% by weight of polyethylene glycol trimethacrylate, the polyoxyethylene segment of which had a molecular weight of 1000, was admixed with 0.3% by weight of APS as a polymerization initiator.

Sample m5: _An aqueous solution of 3% by weight of polyethylene glycol monomethacrylate, the polyoxyethylene segment of which had a molecular weight of 1000, was admixed with 0.3% by weight of APS as a polymerization initiator.

Any of the above five solutions that differ in the molecular weight and structure of polyethylene glycol differed, was squeezed evenly by means of a pad device, and the amount adhered was determined

309809/1040

-. 29 -

88% by weight set, then the fabric was 3 minutes at

105 G treated in the presence of heated steam and then the unreacted substance in. Water with 0.05% by weight of a cake of ordinary soap at 50 ° saponified to remove this substance; it was with Water washed and dried. .

Table 1

he Sticking amount
in % before after loss
relationship Degree of static
Electricity (V) before ■ after Sample nN. 42 2.19. 522 826 1 • 2. 33 2.11. 259 ' 310 ^r • 2 ■ · ·. «... 2. 38 2.12 ■ 248. 292 2. 65 2.28 251; 283 2. 10 · 0.41 1205 3252 5 1. 5380 5460! le 9.50 · 9.44 · ' 10.92. 6.94 " 62.75 M.

M * · measured
VT β washed.

From Table 1 it can be seen that with increasing molecular weight of the polyethylene glycol, the amount of static electricity generated decreases. Compared to monovinyl compounds were divinyl and tr! vinyl compounds in the

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309809/1 OAO

Excellent adhesive properties. It was also seen that the molecular weight of the polyoxyethylene seg-; mentes of at least 1000 gave excellent antistatic properties. The film thicknesses from ml to m4 were closed this time about 0.8 / u on the basis of observation under one Electron microscope.

Example 2

A tricot knit was obtained by knitting a polyamide yarn consisting of E-Carprolactam of 40 denier and 10 threads which had been subjected to preheating and wetting. Polymerized with this using a solution Baren unsaturated vinyl was a 5% aqueous solution of polyethylene glycol diacrylate, the polyoxyethylene segment had a molecular weight of 1000, added with 0.5 ^ potassium persulfate as a polymerization initiator, and the sample was in treated in the same way as in Example 1. In this case, the adhering amount was adjusted to 79% by weight. then part of the sample obtained was treated with heated steam at 105 ° C. for five minutes, while the other part dried at 110.degree. C. and then the dry-treated sample was treated at 160.degree. C. for 45 seconds. The coated sample thus treated was saponified, washed with water and dried as in Example 1. The test values to be measured and the The measuring methods were completely the same as in Example 1, and the results obtained can be found in the table below.

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- 31 Table 2

Amount of adherence
in % Degree of static
Electricity (V) before after Hand x.
l- \.
method x ^, before after loss
relationship 3250
238
8820 4360
326
9050 dry
Heat treatment
Hot-steam
treatment
empty 0.6 0.41
3.5 3.1 31.1
11.4

M β measured
We washed.

Table 2 shows that the polymerizable compound in the presence of air, as in the dry heat treatment, only was difficult to bring to polymerize, but could polymerize completely in the presence of steam, namely with a moist heat treatment. During the dry heat treatment however, some effects were observed. Table 2 also shows that polymerization was possible in a solvent vapor such as that used for the wet bath. In one In a system in which there was not a large amount of air, the reaction occurs in the same manner as in a so-called general vinyl polymerization.

Example 3

A single yarn with the number of yarns of 48, consisting of polyacrylonitrile, was used, a dual active ingredient was used in common

309809 / 10A0

Waste and immersed in a padding bath which had been obtained by adding 0.5% by weight of APS as a polymerization initiator to a 3% aqueous solution of polyethylene glycol ⁽ diacrylate with a molecular weight of the polyoxyethylene segment of 1000. The fabric became uniform squeezed out to adjust the adhered amount to 125% by weight, and then treated with steam for 5 minutes at 105 ° C. On the other hand, the fabric was immersed in a pad bath made by adding 0.3% by weight of APS as a polymerization initiator of a 1% aqueous solution of a polymer of the same type as mentioned above was obtained, and heated to 100 ⁰ C. Then the two materials were treated in the same manner as in example 1 and tested. the results are shown in the following table .

Tabel M ₄ »measured
W ■ »washed after 3 Degree of static
Electricity (V) 0.50
3.08 Loss before after
relationship Amount of adherence
in % 17.0 2650 2400
12.5 820 980
7350 7640 Hand- >>.
lungs Ν. before * Inlay
treatment
steam
treatment
empty 0.60
3.52

Inlay treatment: the pad bath was heated to 100 °,

and the sample was immersed therein for a predetermined time.

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As can be seen from Table 3, the sample subjected to the immersion treatment was poor in adherence Quantity and anti-static properties. If the heating progressed during the inlay treatment, homopoly- sation also proceeded continued, and when the temperature reached 100 C, gelation occurred almost immediately (within 10 minutes). As a result, the formation of a film on the fiber surface was difficult. * However, the inlaid method was not totally unsatisfactory but certain improvements have been made evoked. , '

Example 4

A crepe fabric obtained by weaving a polyolefin thread yarn of 50 denier and 24 threads was made as in Example 1 and placed in a padding bath, which is obtained by adding 0.5% by weight of benzoyl peroxide as a polymerization initiator to a 5% tetrachlorethylene solution of polyethylene glycol trimethyl acrylate with a polyoxyethylene segment having a molecular weight of 1000. The adherent The amount was adjusted to 43%, the substance was treated for 3 minutes at 120 ° C in saturated tetrachlorethylene vapor, Soaked in acetone at 50 C for 20 minutes to make homopolymer remove, and then treated warm and dry for 1 minute at 160 ° C. The fabric was then applied in the same way as in Example 1 to obtain the results shown in the following table.

3098Q9 / 1040

Table 4

Hand- ^ s.
ling N.
method \ i Clinging amount of hatred of the static
in% electricity (V) Solution
middle
treatment
empty before after loss - before after
relationship 1.97 1.76 '10.6 730 860
10000 10000

M ■ measured W »washed.

As can be seen from the table, the aim of the invention achieved in a satisfactory manner if one carries out a solvent treatment.

Example 5 The same Polyesteretoff as in Example 1 was inserted and

padded in a 3% aqueous solution of a compound

the formula

CH ₂ - CC- (OC ₂ H ₄ ) ₁₀ -0

0 CIL

IP

0 0 0

1 IP I!

-C-CH-CH-OC-CH-CH- (OC H JOC-CH CH-OCC-CH ₉ CH ₉ -OCC-CH ₂

² I! I ^ * Il

- CH.

0 CH.

CH

with 0.5% potassium persulfate, then the fabric was squeezed out so that 90% adhered, and then 5 minutes in

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30980Ü / KU0

Steam treated. Then the fabric was saponified in the same way as in Example 1 and finally on the adhered * de amount measured to get 25%. If the rubbing tension before washing and after washing 10 times at Measured in this example, the results were 550 V and 280 V at 20 ° CT and 40% relative humidity.

Example 6 .

The samples used in this example are listed in the table below. As used herein the polyester was a normal polyester fiber consisting of ethylene glycol and terephthalic acid for clothes, and the used polyamide was ordinary nylon 6, which was obtained by polymerizing caprolactam "

Table 5

No. Material denier name of the thickness density

Number of knitted (mm) ( _O / _C m ^ i

Threads or woven / cm j

^ ^ th substance

1 polyester 75 - 24 Taffeta 0.095 0.84 2 Il 50-24 twill 0.085 0.70 3 η 75 - 24 twill 0.14 1.03 4th Il 250-84 Matt worsted yarn 0.55 0.23 5 M. 75 - 24 Tropical * 0.19 0.43 6th polyester
Reyon. 65%. **
35% ^Ä poplin 0.31 0.15 7th polyamide 30-6 shirt 0.11 0.56 8th If - 50-24 Taffeta 0.080 0.73 9 Il 50-24 jersey 0.58 0.21

* using a processed yarn »A ** S-Twist 40 S / 2, S (Z) -30 S / 2 *

- 36

3098Q9 / 1040

Before the samples are subjected to the antistatic treatment The following treatments were carried out. . <

Ordinary fabrics were after heating at 180 ° C for 30 seconds for 30 minutes in an aqueous solution of 2 g / liter of soda and 1 g / liter of Sandet CL-80 (a nonionic surfactant, manufactured by Sanyo Kasei Co., Ltd.)

buckled.

A tricot knit was treated similarly.

Knitted and woven fabrics using prior behände lter · yarns were treated for 30 seconds at 30 C in water in a relaxed state, gebeucht out in a similar manner, and then heated for 30 seconds 18O ⁰ C.

Table 6 shows the measurement results of the properties these substances after the treatments.

The treating agent X used here was an aqueous solution of 25% copolymer obtained by copolymerizing a mixed monomer having a gelation point of 25 obtained by mixing methoxypolyethylene glycol methacrylate having a molecular weight of IQOOr and polyethylene glycol dimethacrylate having a molecular weight of 1,100 and acrylonitrile in a ratio of 75 % ι 25%.

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309809/1040

The treating agent Y. used here was a water-soluble one Emulsion of 50% of a mixed polymer obtained by Copolymerization of 30% dimethyl terephthalate, 20% ethylene glycol and 50% polyethylene glycol with a molecular weight of 2000.

The treatment agent Z used here was a liquid water dispersion containing 30% p-ß-methaeryloxyethyldläthylmethylammonium methoxysulfate.

The treatment method consisted of padding the treatment agent in the knitting or woven fabric in those given in Table 6 Concentrations, then 3 minutes long Drying of the fabric at 120 ° C, and finally 40 seconds hot setting of the fabric at 160 ° C.

In the case of a polyester-rayon mix, i.e. number 6 in Table 5, became the following resin treating agent as a wrinkle-proofing and hand-improving agent with respect to rayon provided in a mixture with the treatment agent of Table 6 for the pad treatment.

Resin treatment agents ;

Uramin T 101 (manufactured by Mitsui Toatsu

Chemical Industries Co », Ltd») 6%

Beccamin P426, (manufactured by Japan

Reichhold Co., Ltd.) 1%

Noran silicone plasticizer (") 1%

J ₂ 0.2%

- 38 3 0 9 ß η: j / 1CJ A 0

The treated fabrics and fabrics obtained were soaked in the usual manner and then thoroughly washed with water. The results obtained can be found in the following table:

3 U :) ti DH / 1 0 i> 0

Table "6

No. Sample number

from Table 5

Treatment agents

Concentration (g / liter)

Absorption of frictional stress (V)

1 1 2 2 3 3 4th 4th to O 5 5 co co 6th / 6 O CD 7th 7th O 8th 8th O 9 9

original
licher
material after
Ablution 4300 5200 4200 5600 5600 8100 5300 5400 5200 6300 3600 5400- 4200 4600 3900 4300 6100 6300

(Continued.

co co cn

Table 6

(Continued)

No. Sample number

from Table 5

Treatment agents

Concentration (g / liter)

Absorption of frictional stress (V)

more original
material

after washing

10 1 • 6th 11 2 3 7th CaI 13th 4th O 8th i £> 14th 5 CD 9 O 15th CO 16 17th 18th

50

26 35 25

50 25

38
41
42
94
62
85
80
41
'9O

600
360
39O
12O
260
240
380
520
420

"4200 4500 5100 1100 1600 1900 2800 3900 1800

(Continued)

Table 6
(Continued)

No. Sample number

from table

Treatment agents

Concentration (g / liter)

Absorption of frictional stress (V)

,. original substance

after washing

20 "21

23 24

1 3

4 6

50

■ ■ ' Jr

50 25

45
96
88
44
94

560 410 230 320 450 .560

45OO 4300 4800 42OO 41OO 52OO

(Continued) _:

Table 6 (continued)

No. Rehearsals

from table

Treatment agents

concentration
(g / liter)

Absorption of frictional stress (V)

origin-

licher

material

after
Ablution

OO O CD

25 26 27 28 29 30

1 3 4 6 8 9 50

25th

60
25th

37 340 58OO 42 260 5900 91 120 6300 83 230 5500 43 190 3900 88 370 6800

{Continued)

Table 6 (continued)

No. '.., sample number

Tabel

•CD OO O

Treatment agent .. concentration absorption. Frictional stress (V)

'. (g / liter) ■. "■■;. ■ .. {%) r. - -—— '

^ 5 _ν

^^^^ SSS ^ r ^^ ii K

3.5. 36

si 100 50

37 38 50

39:

f '■'

From the results in Table 6 it can be seen that when using treatment agent X {see numbers 14, 13 ,, 15 and 18) Samples with densities below 0.5 g / cm were given excellent antistatic properties. On the other hand, a common antistatic agent such as Y and Z did not achieve good durability »itself if the samples had low densities (numbers 19 to 3Q)

On the other hand, it was expected that good results would be obtained by increasing the concentration itself when the samples had high densities. Numbers 31 to 40 were carried out for this purpose. Even if you have but the treatment agent X used, good results were not obtained from the high density samples. As for Y and Z, so were also no effects whatsoever when the concentration was increased.

It is understood from the result of No. 18 that a similar result was obtained when the sample was an active ingredient. From the results of Nos. 16, 17, 18, 35 and 36, it was found that similar effects were obtained when the samples were made of polyamide.

Example 7

An aqueous solution of 2% by weight of polyethylene glycol dimethacrylate, the polyethylene glycol content of which had a molecular weight of 1000, and 0.3% ammonium persulfate was padded onto the samples in Table 5, Example 6, and the samples were kept for 2 minutes

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309809/1040

heated to 105 C with steam. The samples were then weighted on and washed as in Example 6 and added to your frictional tension Measured at 20 ° C and 40% relative humidity. The results of the following table were obtained

rehearse Tabel 7th Frictional stress (V) ·. · ■■. ' ■: - 3100 number
of table E more original after the
Wash fabric 2900. NO. recording ; 450 * 520. (%) 320 '- ",; -' ■ ^! . 630 'Λ 40. 100 I. 3250 ι
^; 2 41 200 1100 3 92 610 4th 83 ', -' ■ 360 , 5 2 , 40- ι
: 6 3 90 4 ..; : ■ - 6 ^! . ; " 8th 9

Table 7 shows that Sample Nos. 3, 4 and 6 with showed excellent antistatic properties at low densities. Compared with the values in Table 6 it was seen * lent that steam treatment had better antistatic properties shafts were obtained.

Example 8

A 75-denier, 24-thread polyester thread made from polyethylene terephthalate was incorrectly twisted? vm to produce a substance vox * Amunce tint, which can be

309809/1040

sizing and bagging, then washed with water and dried. The substance was then used in treatment agents of the batches given in Table 8 and squeezed out evenly by a pad machine. The uptake ratio was 81%. Then the Fabrics placed in a moist, warm steam atmosphere at 100 C and treated warm for 5 minutes, followed by Marseille soap (0.05 wt%) treated at 50 ° C for 1 minute, sufficiently washed with water and dried.

The obtained samples were washed for a predetermined time under the above washing conditions, and the environment the samples were adjusted to predetermined temperatures and humidity. Thereupon the degrees produced became more static Electricity measured by the method mentioned above. The results shown in Table 9 were obtained.

Table 8

m ratio of mingled

Processing means
in g / g - 100/0 A-1 ²⁾ / C-1 ³⁾ »100/2 II - 100/5 11 - 100/10 It - 100/27 Il - 100/33 It

Ratio of Bemer treatment agents, calculated as solids in g / g

20/0 20/0 _? 6th

2C / 1.5 20/3 20/8 20 / 9.9

309809/1040

- 47 -

Tabel. 8 (continued)

m ratio of

mixed ₁ processing agents "in g / g

Relationship between remedies and remedies calculated as solid in g / g

7th Al / Dl ⁴ * - 50/0 10/0 , 5 • J 8th \\ -.50 / 1.7 10/1 . · ■ '■ 9 Il - 50 / 2.2 10/2 10 Il - 50 / 4.5 10/4 .5 11 Il «= 50 / 5.5 10/5 12th B-1 ⁵⁾ / C-1 β 100/0 20/0 13th Il - 100/2 20/0 .9 14th Il * 100/5 '20/1 15th .11
ί - 100/10 20/3 ■ Ι 16 η - 100/27 20/8 17th Il - 100/33 20/9 18th B-l / D-1 - 50/0 10/0 19th Il a- 50 / 1.7 , 10 / 1.5 20th 50 / 2.2 10/2 21 Il _β 50 / 4.5 10/4 i 22 H _β 50 / 5.5 10/5

A solution of 5 g / liter ammonium percolate was added as a catalyst »

- 48 -

309809/1040

Footnotes:

1) Weight ratio of a processing agent

in 1 liter of an adjusted processing agent solution.

2) 20 percent strength by weight aqueous solution of a mixed polymer obtained by copolymerizing a mixture of 70:30% by weight methoxypolyhylene glycol methacrylate

and acrylonitrile was obtained.

3) 30% aqueous solution of poly-ß-methacryloxymethyl dläthyimethyl-aminonium-methöxy sulfate

4) 90% aqueous liquid dispersion of octadecyl äthylurea.

5) 20% aqueous solution of polyethylene glycol dimethacrylate, the polyoxyethylene segment of which had a molecular weight of 1000.

- 49 -

3 (I y & Ü9MCK0

Table 9

5 Frictional stress 30th (V) 2O ^C O \ 40% RH \\ 20 ° C, 65 5 % RH 800 400 1.0 3P m \ Ο- 0 10 230 280 2000 3450 1 0 410 190 240 1100 2 0 200 200 160 800 1250; 3 5 150 190 220 550 1000 4th 0 190 450 300 1000 780 5 0 160 1000 630 '1500 1100 6th 0 380 230 320 2β00 1690 7th 5 550 240 370 UOO 3600 f 8 10 210 ' 370 400 1050 1350 9 210 600 590 1800 1400 , 10. 330 2500 1950 I.
! ■ 11 540 2580

(Continuation)

'<· 5o

04 0

Table (continue ;,)

Friction voltage (V)

20 C, 65% RH 20 °, 40% RH

30 1.0

untreated

600 300 800 1200 140 190 400 420 ί 110 200 270 300 100 150 190 220 170 230 370 360 330 250 750 760 780 530 1500 2000 190 260 500 670 200 280 500 640 290 330 720 830 450 470 1400 1580 2500 7000 7100 6900

M «■ measured value C * - measurement conditions

W * - Watch frequency (number) . -

Ί j 3 H 0 9/1 0 '♦?>

With A-I alone or B-I alone (ml and ml2) were also achieved excellent antistatic properties. To of the invention, however, much better antistatic properties are achieved with a smaller temperature gradient » The antistatic properties after washing 30 times did not decrease too much as compared with ml and ml2, from which it can be seen that the samples also have excellent durability was granted.

Incidentally, each sample was made using an oil soluble Dyestuff, Sudan -Black B, dyed, and the influence of the antistatic agent of the polyoxyethylene series was determined. It was found that untreated samples at all were not stained, but each of the treated samples stained well. From the fact that samples dyed well after washing for 30 times, it is found that the film formed according to the invention is excellent in durability.

Example 9

An Amunce tinted polyester fabric as shown in Example 8 was used was immersed in the treating agents shown in Table 10, therein according to the method of the example 8, and the amount of static electricity generated on these treated fabrics was measured fan received the results of the following table:

- 52 3 0 9 e U 9/1 0 A 0

- 52 Table 10

m ratio of ratio of

mixed.,. Treatment agents,

Treatments "" compute t as

ig / gj solid g / g

Remarks

23 A-2 ²⁾ / Cl- 100/0 20/3; 24 A-3 ³⁾ / OI - Il ti 25th 4)
A-4 / CI - Il <> 26th A-5 ⁵⁾ / Cl - ti ti 27 B-2 ⁶⁾ / Cl «= 50/5 10 / 1.5 , 28 B-3 ⁷ Vc-l - Il 29 B-4 ⁸⁾ / Cl - η

5 g / liter of ammonium persulfate solution was used as a catalyst added

Footnote:

1) Weight ratio of treatment agents in 1 liter

an adjusted treatment agent solution.

2) 20% by weight aqueous solution of a mixed polymer obtained by copolymerizing a mixture of 70: 30% by weight of a mixed mononier with a gelation point of 25 obtained by mixing methoxypolyethylene glycol methacrylate a molecular weight of 1500 with polyethylene glycol dimethacrylate of a molecular weight from 1100 with acrylonitrile.

3} 20% aqueous solution of a copolymer obtained by copolymerizing a mixture of 60 parts by weight to I from one of Figure 2) obtained with Mischmonomer

Acrylonitrile.

4) 20% aqueous solution of a mixed polymer obtained by copolymerization. a mixture of 70: 30% by weight of a monomer mixture , obtained as above in 3) with ethylene glycol diacrylate.

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3098Ü9 / 10Λ0

5) 20% aqueous solution of a mixed polymer, obtained by prepolymerizing a mixture of 70: 30% by weight from methoxypolyethylene glycol methacrylate with a molecular weight of 6500 with acrylonitrile.

6) 20% aqueous solution of polyethylene glycol dimethacrylate, the polyoxyethylene segment of which had a molecular weight of 1000.

7) 20% aqueous solution of polyethylene glycol linethacrylate, the polyoxyethylene segment of which had a molecular weight of 5,000.

8) 20% aqueous solution of polyethylene glycol trimathacrylate, the polyoxyethylene segment of which had a molecular weight of 1,000.

Table 11

20 ⁰ C Frictional stress (V) 30th 20 «C, - CF J
ι 0 , 65% RH 220 4Ö7 _O \ 30th 0 10 210 150 ICJ '~
ι 700 '23 0 190 190 140 520 670- 24 · 0 190 210 150 490 720 25th 0 170 200 150 380 690 26th 0 200 190 230 450 890 27 0 160 210 210 750 1000 28
* 0 140 200 690 780 29 170 680

M «measured value

C * «measured conditions

W * - Wascirangfrequency (Ansahi)

54 -

30988S / 1040

V er q1e1ch s beisρi e1 1

The same polyester fabric as used in Example 8 was'. placed in 1 liter of an aqueous solution adjusted in such a way that the solids ratio of the treatment agent A-2 / C-1 = 8/20 (g / g) would be, with 1 liter of an aqueous solution containing 20 g of only C-I as a solid of the same Treatment as in Example 8 was subjected. Then the frictional stresses were measured and the results of the following Get table:

Table 12

Frictional voltage (V) 2O ⁰ C, 65X RH

■ A-2 / C-1-8 / 20. 0/201

10 15

10

1000
1100

30th

2050 1980

20 ⁰ C ₁ 407 "RH

830 790

10

6300 6450

30th

7000

7000!

measured value

C * »g an ess', m ^r s conditions .1 ng u ng s

W * = washing from ä ufitj wedge: (number)

S * «solids ratio of the treatment agent in g / g

- 55 -

3 0 'J 8 U 9/1 ü 4 0

By processing in a system where C-I in an excess amount, was present, no such excellent antistatic properties and durability were found as out Examples 8 and 9 can be seen. Also were at The antistatic properties were greatly different from those when the temperature was low and at high temperature

the temperature gradient was high.

Example 10

The same polyester fabric as in Example 8 was mixed with reagents according to the approaches of Table 13 under the same treatment conditions as in Example 8 then subjected the frictional stresses were measured, and the results in Table 14 were obtained.

Table 13

m Mixing ratio
the treatment agent
in g / g Solids ratio
the treatment agent
in g / g ; 30th k-2 / C-Tp »100/10 - 20/3 31 A-2 / C-3 ²⁾ - " . ' "8th" 32 A-2 / C-4 ³ - * «" 33 A-2 / D-2 ⁴⁾ -j 100 / 3.8 34 A-2 / D-3 ⁵ ^ «100 / 3.3 "1 IS it

- 56 -

0 9 8 0 9/1040

2239532

B erne £ jtu_ngj_

1} 30% <aqueous emulsion, mainly consisting of

the end

CH | φ3

ClL CH CIL CONHCH "CH" CH "i! I-CH.

"3 2 2

CH ₃

he

2) 30% aqueous emulsion, consisting mainly of

! _Q .N-fCH CH 0-) · Η

j 2 2 3

CH

Cl '

3) 30 % Ign Weiser ige solution, consisting mainly of

Π ut y 11 Timothy 1 a rrun ο η i u m 3 a 1 ζ.

4) 80% by weight of a paste-like emulsion of alkylethylene urea of the general formula (E) , in which η was » 4.

5) 90 % by weight paste-like emulsion of alkylethylene urea of the general formula (E), in which η «■ was 9 ·

- 57 -

3 0 9 8 Q 3/1040

Tabel 14th 40% RH. I. \ Frictional stress (V)
¹ ™ * ι if ifmmk - Io 30 ' 2O ⁰ G, 690 740; '. 720 ·· ■ '■ '790. ■ •• ^: · '. · ;. f 30th . * 160 650; ■. 710.; ' 31 140 660: ■ ' 720 32 140 740 ' aoo . 33 140 34 170

In this example, too, satisfactory antistatic ©
Properties and durability achieved. For confirmation of a file created as in Example 8, elngefäirfofe % * m% ä @ ₉ EQ , the samples turned out to be 3 times a Waseh © Ea al? ·
colored.

Example 11

A treatment liquid consisting aias I Litsr aqueous solution with a solids ratio DER nimbly long © medium A-2 / CI 'of 20/8 was ssufoeraitet and the same is polyester fabric as loaded in Example 8 and uniformly squeezed with a log unit * · The AufnahmeverhSltnis was this Seitpunkt 85% "Then the fabric under © ver · treated wurd achiedenerlei conditions warm, and the grater voltages of the samples were in the same way

309809/1040

like in example 8 eaten. The results can be found in

the following table.

Tabel

Heat treatment sin \ conditions 35 36 37 38 39 40

damp ™,

warm ■ (95 ° C / 15 min)

¹¹ '(100 ⁰ C / IQ min) "(12O ⁰ C / 5 min)" (135 ° C / 2 min)

t rock rs w et r πι

Ii

i »j- 11.> ■■

(15O ⁰ C /] rain)

B e i bu η g s s ρ a η η u ng (V) 0 10 30th 20 ° C _for 40% RH ... 240 1000 1750 220 980 1050 250 950 1060 240 1000. 1100 450 1800 2510 490 2200 2900

When the heating temperatures were low, the film formation reaction proceeded slowly, and accordingly the heating period became longer. If an estimate of the durability of the Filirie was carried out on the basis of its coloration as in Example 8, the samples subjected to the moist heat treatment were better than the samples subjected to the dry heat treatment. Further, when the films formed were observed under a microscope, the samples after the wet heat treatment were more uniform and smoother than that

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303809/1040

Samples after dry heat treatment «,

Example 1 2

A polyester tricot knit made from 75 denier yarn 24 threads, a nylon 6 tricot knit fabric made from thread yarn by 40 denier and 10 threads, a polyaeryl fiber double fabric from a Kinzel yarn with a number of yarns of 48 and a polypropylene- ^ Crepon fabric made from thread yarn with 50 denier and 24 threads (all after notching and drying) were as in Example 8 treated with the same treatment agent as m23 in Table 9. The measured results of the samples can be found in the following table «,

Table 16

Material ^^ $ ί Frictional stress (V) i ■ 0 20 ° C, 40% τΈ 2900 untreated ι
\ polyester 1000 10 30th 4800 above
10,000 - \ polyamide 750 25,000 4700
4200 ¹¹ 10,000 • 41 Polyacrylic
Polypropylene 350
1200 4100 "10000
"10000 42 4000
3500 43
I.
44
I.

It was found that according to the invention, each of the various Fibers have been given excellent antistatic properties and the invention is particularly noteworthy

- 60 -

309809 / 10-0

Effect developed in polyester fibers.

At S £ J “e 1_ _ 1..3

Ei ,, η poly es tor gnm of 7 5 denier and 24 threads, consisting of

P j I y ä thy 1 e ri tere ρ Ι \ t 11 a 1 at was twisted wrongly »around a we b -

fabric ei nc: v; Tropr.cri, l.toncis to manufacture. This stuff was gobeened according to known methods and washed well with water and dried. Separated; were those in the table below. the mentioned handling flows.

Table 17

Handling f1Qs s igkeί t *

Mixing ratio of the treatment agents (g / g)

Methoxy polyethylene glycol methacrylate / Trimethylolethane trimethacrylate

I!

Il

Il

It

20/0

20 / 0.2

20 / 0.6

20/1

20/2

20/8

20/10

20/11

Mixing ratio in 1 liter of aqueous solution Molecular weight of the polyoxyethylene component

be truer 1000.

- 61 -

3 0 S bÜ 9/1040

What the trimethylolethane trimethaerylate in Table 17

tr iff ty zo vnsrda it Naeh collection of ¹ predetermined 1 ^J I in a small Menqe toluene and treated with Ο · ΐ ~ 222 solution (nichtlonischss surfactant _s h © rg © alternate · by Nippon Oil and Fat Co ₀ '' Ltd ») Sis bisp © rgi © raiittai ^ © rsetzt, to an emulsion su silver © it en. Then it was washed and used. Jade ¹ d © rs "b © riding @ t © ES ⁵ IUs was Äsunoniumpersulfat a Kojassisfciatioß ψοει 2 ff / 1 as Polymerisierkatalysator offset ₀

Xn die so s'ibereitetsa Behändl «ngsflössigkei-isn ^ rarci © riss Tropical tissue eingsfeatach-ä υ, ηά by © iß Klotsgerät equally axisgequetseht * The Äufsi &lmeves'hilteis b @ t? I'df & n this time δ4%. Dana wuzugh ösif fabric i? P. si; .i · = ^ i '? assa2 "äsa; t- ^ri atmosphere 5 minutes bsi 110 C % *? &%' Μ b © haad © lfc ₀ Ιίβυΐίΐίΐ ^ -ivasd® the fabric kit Seifs CMasrsöilla» S © £ S "© _ff O ₃ Oa C &; J ₅ « C _p 50 ^e \ _:? 1 minute) bahaadslt issä saggfilfeif siü Wsgoq ^ ge ^ Gsushea ^ RS. dried;" The Srgetoisiss fiaäea alsh Iu 3 © ^ Sel ^ e ^ öPüsi

"""'■' ti et

Ο 3 8IH? / 's θ ^

Table 18

Re ibu ηα a voltage (V) Harzanhaftverhäitni3

3οhand ·

lunq

'Vi-,

üü

?]. 00!

CiOQ * t? ^! Hj

ί (iliil 1.2

1.2

1.2

.4

450! 1,100

LfV-

6300

't

0.04

1.0

1.4

_{ 1.9 y 1.9

, 2., 2 I 2.1

2.4 j 2.4

30th

! 1.7 2.1 2.0

J-JiTi ¹ Pi; '■ .'ι · ¹ ,', », - j!. ¹

^v :> f * ^j ρ v, t π t: * - '"' r ο e ~ " h Ü t "':, * ■ ν ι ϊ ^'> -: ϊ; t;

(C. ¹ I ¹ J "

t.> .; ■■:; .. ■ hi)

Ji -; "> Π ί · '■

5,; .. ■ ■> ί. ■: ■ 1; c 1 '* c h _t da ö ,, w ο η η
¹ :, ι ' γ 1, γ. 1: κ I e ί η era 13

* · · · - "^; . ^Il 'Lt-ft- ¹

■ Λ *: ii! ': I , J) 4th r

Harsmeng «d ^ rch

, ti ¹ ί ':] άί * ί Re *. "-

S 3 "

Exercise stress while the durability was good «If, on the other hand, this amount was less than 50% by weight? became the '■. '>' Ratio of adhering resin is large and the degree of decrease of this ratio during washing is small. However, the frictional tension became bad »

Example 14

Except for a polyester fabric from Tropicalton, like the one in the example 13 was used, a double polyacrylic fiber knit became made of a single thread of 48 thread count and a polypropylene crepon fabric made of a thread of 50 denier and 24 threads (each after buckling and drying) are used.

Tetramethylol methane tetramethacrylate was added in such a way that that 2 g / l to 29 g / l of a compound of the formula

0 0

• Il Il

^ - O-C-GH-CH ₂ -0-C-CH ₂ -CH-H) CH ₂ CB5- ^ 5-CH

CHo-OCC = CH ₀

CH ₂

and an emulsion was prepared according to the method of Example 13. A similar aqueous dispersing liquid with 2 g / l ammonium persulphate was prepared, in which the aforementioned substances were immersed and padded, whereupon they were treated with steam. Then the fabrics were measured for frictional tension. The results are given in Tables 19 and 20 ₆

- 64 -

309809/1040

- 64 Table 19

O Frictional stress (V) 30th not: bohan
delt (vot
Ablution) Sample ^ \. 520
4 UO
1050 1 1600
2100
2900 10000 <
loooo <C Polyest ertropioalnt oli
Polyacrylic double
Knitted fabric
Polypropylene crepon
were 550
600
1300

E ^e estimated value W * = washing frequency (number)

Table 20

"" - ^
^ W * 0 Frictional stress (V) 30th 680
9400 1 1700
9000 treated goods
not treated
Were 720
9000

Example 1 5

(a) Metlioxypolyethylene glycol methacrylate, the polyoxyethylene portion of which had a molecular weight of 400, and 2 g of trimethylolethane trimethacrylate were dissolved and mixed according to the procedure of Example 13. The mixture was in

309809 / 1OAO - ₆ 5-

added in such an amount that 1 liter of a treatment liquid was prepared * ·,, '

(b) A completely identical treatment liquid to (a), but the molecular weight of the polyoxyethylene component being 2000, was prepared.

In each of the above two treatment liquids was dejrseLbe Evenly dipped fabric as in example L3 squeezed out with a padding device, treated in a similar manner with warmth and checked for frictional stresses (V) and ratio of the adhering resin measured. The results can be found in following table.

Table 2L

Riding voltage (V) ratio of the
adhering resin
(%) 30th 0 1 30, j sample ^ ***** ^ ¹ ^ i 2800
1300 1.9
1.4 1.7
1.4 · 1.7
.1.2 j
^; I.
a
b 0 1520
470 1300
280

As can be seen from this table, although the molecular weight of the polyalkylene content has no great influence, but that with a treatment liquid chain whose polyoxyalkylene content has a relatively high molecular weight

- 66 -

30980ü / 1040

a preferable result.

However, as can be seen from other examples, the From the point of view of synthesis technology and effect, that the cheapest treatment liquid has a polyoxyalkylene moiety with a molecular weight of about 1,000 to 5,000.

ELn taffeta fabric, made of polyethylene terephtha lat yarn from 50 Denier and 24 FikUm, obtained by pulping 1.5% Sodium Dodecy Ujühzo Lf u lEonat as ion constituents.il and 1.5% PolyäthylenylycoL with: a molecular weight of 20,000 as an electrically conductive base with polyethylene terephthalate was Ln eLnuc aqueous solution that L q / LLter sodium carbonate and 2 g / LLter of a non-longline above elite active MLttelf! bandet OL-80, (manufactured by Sanyo Kasei Co., Ltd.) cttthLeLt; the fabric was in 2% Mica-WeLß STN (manufactured by Nippon Kayaku Co., Ltd.) 120 minutes beL 120 * C dyed and dried. When applied of this example, the following antistatic treatments were used carried out:

3Ü98Ü9 / 1040

m treatment agent

Concentration (g / liter)

Handling conditions

Polyethylene glycol (mol. Weight 600) dimethacrylate

20th

treated with a > 2 g / l stream

Ammonium persulfate solution 5 minutes at 105 ° C

2 Polyethylene glycol
(MoI. Weight 600) -
methacrylate 20th Il 3 PolyMethylene Glycol
(MoI. Weight 1000) -.
trimethacrylate 20th Il 4th none - Il

A polyester fiber that does not use anti-static agents was mixed was made into a similar taffeta fabric as mentioned above. The fabric was bagged and stained with a fluorescent dye. The dyed fabric was treated as indicated for ml to m4 and designated m5, 6, 7 and 8.

After the treatment, the samples were made in the same way before dyeing to remove a polymer that was a homopolymer and was in a state that it was fell off easily. After drying, the samples were tested for their weight gain, frictional stress and water-absorbing properties measured. The results can be found in the following table.

-6B-

309809/1040

- 68 Table 22

sample

Treatment weight. ", Medium ratio ^R eibungs · would increase <%) ^s P ^ ^un 9

water-absorbing property

WHERE W 2

WHERE * W 2 *

1 modified
polyester Diester 0.7 2 Il Monoester 0.1 3 modified
polyester Trieste 0.8 4th Il not-
treated 0.0 5 unmodified
embellished poly
ester Diester 0.7 6th Il Monoester 0.1 7th Il Trieste 0.7 8th Il not-
treated 0.0

240 490 0.8 38.0

2600 0.8 600 <

210 520 0 _# 6 35.0

3100 250 600

650 1500 0.9 510

5300 2.1 600 <

590 1400 0.8 630

6800 240

600

Washed ^ma l - WHERE = not washed 2 ** ^{= zwe} *

From the results for the samples ml and m3 it can be determined that when using diester or triester on a modified one Polyester especially has antistatic properties have been improved. The wash resistance was excellent.

- 69 ..

309809/1040

Example 1 7

A salt consisting of equimolar amounts (mixture) before | . ' Polyethylene oxide with an average molecular weight of; about 4300, 95% of the ends of which had been converted into amino groups, and adipic acid and C-caprolactam were used to obtain a block polyether amide whose polyethylene * segment had a weight ratio of 40%. This block polyether amide, 0.2% titanium dioxide and nylon-6, were mixed-spun into a yarn of 30 denier and S threads made of modified polyamide, the proportion of which was 1.5% by weight of polyethylene oxide segment. This yarn was knitted into a 28 gauge, 2 strip, 88 inch knit at 74 stitches / inch. After scouring the fabric in a relaxed state was dried and then treated with treatment liquids whose compositions were located in 4p · following table under the numbers 1, 2 _e 3 ^ 4 and 5 find »» © adhering Di amounts to dlestssi
80%.

Table 23

N * "X. P * Sales of the treatment agent ;!]. . number 1 A treatment liquid
by dissolving 3% by weight of polyethylene
glycol dimethacrylate with a molecular weight
weight of the polyoxyethylene segment of 5QO ^
in water with the addition of 0.3 GeW ₀ -S
Ammonium persulfate as a polymerization initiator
to the aqueous solution.

(Continued, - 70 -

309B09 / 1040

- 70 Table 23

(Continued)

Sales of the treatment agent

A treatment liquid obtained by dissolving 3% by weight of polyethylene glycol dimethacrylate with a molecular weight of the polyoxyethylene segment of 1000 in water and the addition of 0.3% by weight Ammonium persulfate as a polymer initiator to the aqueous solution.

Treatment liquid, obtained by " solution of 3 wt .-% polyethylene glycol dimethacrylate with molecular weight of the polyoxyethylene segment of 2000 in water and addition of 0.3% by weight ammonium persulfate as a polymer initiator for the aqueous solution,

Treatment liquid obtained by dissolution of 3% by weight of polyethylene glycol tri-

methacrylate with the molecular weight of the polyoxyethylene segment of 1000 in water and the addition of 0.3% by weight ammonium persulfate

as a polymerization initiator to the aqueous Solution,

No. 5 treatment liquid obtained by Auf

solution of 3 wt. ~% polyethylene glycol monomethacrylate with a molecular weight of the polyoxyethylene segment of 1000 in water and adding 0.3 wt% ammonium persulfate as a polymerization initiator for the aqueous solution.

Rule or approach

Treatment liquid number.

Immediately after each of the above BehandlungsfIUesigkeiten the table _r was 23 prepared as a pad bath, the fabric was immersed therein, and "squeezed gleicimäßig by a block Gerst Then, the materials obtained

3 0 9 8 η 'J / 1 CU 0

3 minutes at 150 C in the presence of heated water

steam treated. The unreacted substance was then removed using soap (Marseilles soap, 0.05% by weight, 5 minutes at 50 ° C.), and the fabrics were washed well with water and dried. The measured weight increase, the water absorption time and the frictional stress of the sample obtained can be found in the following table. ^; 1 ,

Table 24

1.5 '3 Water absorption Frictional
tension
(V) 320 650 1.6 4th washed five times washing 2 times
Zeitgewä- «·
see point O 210 520 1.4 5 .8th 360 • 680 Treatment s- "......
number ^Verh * ^ltx } ¹ y.
the weight
increase (%) 1.3 6th .0 380 ^Λ 580 0.2 600 .0 700 1900 untreated
blank "» ■ 600 .1 2200 1800 1 2 3 4th 5 6th

From table 24 it can be seen that in the case of numbers 1 to 4 the ratio of weight gain great and durability

- 72 *

309809/1040

the water absorption property and the antistatic property were excellent. In case number 5 / when processing with the monovinyl monomer there was almost no Weight gained and no effect was seen.

Example 18

A polyester thread yarn of 250 denier and 84 threads made of polyethylene terephthalate was wrongly twisted and then woven into a fabric / which has been wiped in a relaxed state to produce a sample with a unit

2
to obtain a weight of 300 g / m. Using this sample, the treatments shown in the following table were carried out to obtain the results shown in Table 26.

Table 25

No treatment agent

Concentration (g / liter)

Polymerization initiator

Methoxy Polyethylene Glycol (Molecular Weight 600) methacrylate

2 g / l ammonium persulphate

0.5 g / l of benzoyl persulfate was dissolved in acetone, then the resulting solution became dispersed in a treatment bath

P ο 1 y ä t h y 1 e η g 1 y c ο 1 ■

(Molecular weight

600) linethacrylate

2 g / l ammonium persulphate

309809/1040

(Continued)

- 73

Table 25 (continued)

Polyethylene Glyco1- (Molecular Weight 600) dimethyl acrylate

0.5 g / l of bensoyl persulfate was dissolved in acetone and then the solution obtained in a treatment bath dispersed

Polyethylene glycol (molecular weight 1000) - 10 - (<K, «kd imethylacryloxymethyl) acetate acrylate

Polyethylene Glycol (Molecular Weight 1000) diacrylate

0.5 g / l acetylperoxycl was treated in one

Comment; Treatment conditions.

ax

The sample was treated by thawing at 100 ° C 30 in a bath ratio of 1:50 and then treated for 30 minutes at 80 ° C in an aqueous solution. saponified ₀ dim 2 g / l of a non-ionic ob © r £ llofe © iaakfel ^ © n By means of ₀ borrowed Sandet CL-80 produced from SaBf © Kasei and 1 g / l sodium carbonate _s contained

30980Ö / 1040

- 74 Table 26

m the
abelle 5 relationship
the weight
increase (%) Frictional stress (V) 5800 y 1 , 0.0 before after 10 times
Like to wash 6200! 2 '0.2'
I. 6100 6500 3 '. O ₁ I; 3600 640 4th 12.1 3100 480. 5 "/, 6/11 450 5200 10.2 180 6th 170

From the results of Table 26, it can be seen that in the case of methacrylate having a vinyl group, there is an increase in weight and improvement in the antistatic property could not be achieved, whether hydrophilic or hydrophobic polymerization initiator was used (ml and m2), but for methacrylate with 2 to 3 vinyl groups (m3 to m6) there was a remarkable increase in weight when a hydrophobic polymerization initiator was used, and the antistatic properties were excellent (m 4, 5 and 6) * when using a hydrophilic polymerization initiator.

- 75 -

309809 / 104Ü

namely ammonium peroxide, used, As with m3, so it is Even if the number of vinyl groups was 2, the increase in weight was small. .

Example 19

The sample from Example 18 was treated for 30 minutes at 98 ° C. in an aqueous dispersion containing 5 g / l of polyethylene glycol diacrylate with quaternary nitrogen represented by the following formula and 0.5 g / l benzoyl peroxide. It was then dried and the weight gain ratio was measured. However, no weight gain was observed. The formula was:

CH ₂ COONa

HC-CH ₂

Example 20

A polyester tow with a 2 denier thread and the total denier of which was 400,000, was immersed in a liquid prepared by dispersing 10 g / l of polyethylene glycol dimethacrylate with a molecular weight of the polyethylene glycol content of 800 and 1 g / l benzoyl peroxide in water at a bath ratio of 1:30. The treatment lasted 60 minutes at 90 ° C. After this treatment the tow was washed well with water and dried. The weight gain ratio was then measured

- 76 -

3 09809/10 40

sen and an increase of 11.1% observed *

Example 21

300 ml of a mixture of 20 g / l aqueous solution of polyethylene glycol dimethacrylate with a molecular weight of the polyethylene glycol segment of 1000 and 0.5 g / l aqueous ammonium persulfate solution were placed in a 500 ml beaker. Two portions of the solution thus composed were prepared. One portion was left to ^{stand at 20 °} C. room temperature. In the other, air was continuously introduced through a glass tube at a rate of 120 ml / min, and the aqueous solution was allowed to stand so that it gelled within 4.4 hours. However, the mixed aqueous solution into which water was introduced did not polymerize and persisted after 50 hours. When the introduction of air was stopped thereafter, the mixed aqueous solution gelled within 2 hours.

The results of the tests regarding the shelf life of the Vinyl monomer in the aqueous solution when the Concentration of polyethylene glycol dimethacrylate and ammonium persulfate can be found in Table 27. At this point there was no discoloration of the treatment liquid. Furthermore, a liquid No. 4 of Table 27 was left to stand for 50 hours and padded onto polyester taffeta, whereupon the adhered taffeta was treated with steam at 105 ° C. for 5 minutes to increase the weight gain ratio of 1.3% obtain. - 77 -

309809/1040

Table 27

No. Monomer initiator concentration concentration (g / liter) (g / liter)

Conditional gelling

enough time

(Polymer!·
sation. (h)

miscellaneous

1 20th • 5 stand
calmly 4.4 - 2 Il Il with air
treated 50 gelled inside
half past two hours
after shutdown
the air treatment 3 40 Il stand
calmly 4.6 _ 4th Il Il treated
with air 50 gelled inside
half past two hours
after shutdown
the air treatment 5 20th 10 stand
calmly 4.5 6th η ti treated
with air 50 gelled inside
half past two hours
after shutdown
the air treatment 7th 40 Il stand
calmly 2.4 -. ■ - 8th H Il treated ^
with air * 50 gelled inside
half past two hours
• after shutdown
the air treatment 9 40 20th Stand
calmly 1.3

treated. with air *

gelled within 2 hours after the air treatment was switched off.

Comment; Liquid temperature 25 C

' m supplied air volume 120 ml / min (liquid 300 ml).

- 78 -

309809/10 40

Example 22

A padding machine was set up so that a proportion of 10 cm of a 100 cm long and 15 cm wide mat polyester worsted yarn fabric in the longitudinal direction into a mixture an aqueous solution of 20 g / l polyethylene glycol dimethacrylate with the molecular weight of the polyethylene glycol component of 100 and 5 g / l ammonium persulphate was inserted. if the fabric was rotated by a motor to put it in the aqueous solution mixture at room temperature of 20 ° C to circulate, this aqueous solution was still stable without gelation even after a period of 50 hours. On the other hand, when the same mixed aqueous solution was allowed to stand, it gelled within 4.5 hours. If the above experiment was repeated, however, the circling material through a thin polyester pen with it

2
Unit weight of 70 g / m 2 was replaced, it was found that gelation did not occur. When this mixed aqueous solution was placed in a 1 liter beaker and oxygen was introduced in an amount of 4.2 ml / min, the solution did not gel. Further, when a similar experiment was carried out by reducing the air flow rate to 2.1 ml / min, it was observed that gelation did not occur. Then, when a similar experiment was carried out by reducing the air flow rate to 1.05 ml / min while introducing oxygen into 1 liter of the mixed aqueous solution, it was found after a period of 30 hours that the viscosity increased and polymerization began *

- 79 -

3 0 9 B 0 9/1 0 4 0

Claims (15)

Patent claims 1.) Procedure for issuing antistatic, dirt-repellent ~ r and water-absorbing properties on a synthetic fiber structure, characterized in that a compound consisting of (A) a monomer that is not a quaternary nitrogen compound contains and at least two acrylic groups and / or methacrylic groups at both ends, one end or as Has side chain of the main chain and consists mainly of a PolyaIkylenoxydsegment, (B) a copolymer of one of the following general g Compound shown in the formula with a polymer convertible monomer and / or a divinyl compound £ ^{: r} S £ RO t ■ * I Il where R is hydrogen or CH-, R ^{1 is} chlorine or bromine, iodine, ο ^. OCH », 0C _o H _K , SÄCH- or Sp ₀ H ₁ . mean, IV f 0 ^ m <10iind lO ^^ f) _sindr (C) a mixture of a compound with a polymerizable one Vinyl group at one end or as a side chain of a polyalkylene glycol. its polyalkylene oxide segment has a molecular weight of 400 to 10,000, with one Brings vinyl monomer with at least two vinyl groups on the fiber to adhere and the afflicted - 80 - 30980b / 1040 Fiber structure treated warm in the presence of moisture. 2.) The method according to claim 1, characterized in that the affected fiber structure is treated with steam. 3.) The method according to claim 1, characterized in that the fiber structure is immersed in an aqueous solution of the compound and subjected to a polymerization treatment in the Is subjected to heat. 4.) The method according to claim 3, characterized in that the polymerization using a polymerization initiator, is preferably carried out in dispersed form. 5.) The method according to claim 1, characterized in that the fiber structure consists of a yarn. 6.) The method according to claim 1, characterized in that the fiber structure is a knitted or woven fabric. 7.) The method according to claim 6, characterized in that the density of the knitted or woven fabric is equal to or less than Is 0.5 g / cm. 8.) The method according to claim 1, characterized in that a - 81 - 309809/104 0 cationic antistatic agent _f an alkyl ethylene urea, according to the following formula 1 Λ -NlIC-N CH ₂ (in which. 5 30) and a derivative thereof can be used at the same time. 9.) The method according to claim 1, characterized in that the ■ compound (A) and a cationic / antistatic agent are used simultaneously » 10.) Method according to claim 1, characterized in that _? that the compound (A), an alkylethylene urea represented by the following formula and a derivative thereof are used at the same time " ^H 2 (wherein 11.) The method according to claim 1, characterized in that the Compound (B) and a canonical antistatic agent be used at the same time «, 30980 9/1040 12.) The method according to claim 1, characterized in that the compound (B) is represented by the following formula Alkylethylene urea and a derivative thereof are used at the same time, CH - (CH) -NHC-N (where I 5 <η fC 30 »· 13.) The method according to claim 1, characterized in »that when using the monomer, oxygen or air is blown into the monomer solution. 14.) The method according to claim 13, characterized in that the amount of oxygen blown is equal to or greater than Is 2.1 cm / 1 min. 15.) Synthetic fiber structure with antistatic, dirt-repellent and water-absorbing properties, obtained after Method of claim 1. 309809/1040