JP6925705B2 - Functional fibers, manufacturing methods for functional fibers, and functional agents - Google Patents

Description

The present invention relates to a fiber containing polyester fiber, a method for producing the fiber, and an agent adhering to the fiber containing polyester fiber.

Conventionally, textile products are known (Patent Document 1).
This textile product contains an allergen adsorbent composed of clay minerals, a water-soluble hydrazine derivative, a deodorant composition containing a porous inorganic substance and a metal oxide, and a silver-based and zinc-based antibacterial agent. The contained antibacterial composition is attached to at least a part of the binder resin.

Japanese Unexamined Patent Publication No. 2011-231432

However, although the textile products described in Patent Document 1 can exert an antibacterial function by an antibacterial agent to be attached, in addition to this antibacterial agent, an allergen adsorbent, a water-soluble hydrazine derivative, a porous inorganic substance, and a metal oxide are also used. Since it is necessary to attach it, a flammable binder resin is indispensable, and this binder resin lowers the original flameproof performance of the textile product.
Further, although polyester fiber is exemplified as a fiber of a textile product in paragraph 0034 of Patent Document 1, since the polyester fiber lacks a reactive group such as a hydroxyl group or a carboxyl group, an antibacterial agent or the like is used. There is a risk that sufficient adhesion to textile products will not be obtained.

Therefore, the present invention is a fiber material capable of achieving both "suppression of deterioration of flameproof performance" and "improvement of adhesive force" by adhering an alkoxysilane-based quaternary ammonium salt as a polymer to the fiber material. An object of the present invention is to provide a method for producing a fibrous material and an agent.

Fibers維物1 is a fiber comprising a polyester fiber, in the fiber material, polymer produced from alkoxysilane quaternary ammonium salt may be attached.

In addition, the fiber 1 is a fiber containing polyester fibers, to which a compound containing an alkoxysilane-based quaternary ammonium salt is attached, and the fiber is JIS-L-1091: 1999. The combustion area according to the A-1 method is 30 cm ² or less, the residual flame time according to the A-1 method is 3 seconds or less, and the number of flame contact according to the D method is 3 times or more, or JIS. -L-1091: In 1999, the combustion area according to the A-2 method is 40 cm ² or less, the residual flame time according to the A-2 method is 5 seconds or less, and the number of flame contact according to the D method is 3 times or more. may it der.

Other, fiber products 1, those of the fiber was, in front of the Institute fiber Evaluation Technology Council conform to the standard washing method of washing method of SEK mark textile products to enact washing and / or after, JIS-L- 1902: antibacterial activity value analogous to the bacterial liquid absorption method of 2015 may be I der 2.2 or higher.

Other fiber product 1, those the fiber comprises a yarn comprising the polyester fiber, a fabric comprising the polyester fibers, of the fiber product using the yarn and / or fabric, Tsu der either You may .

Due to these characteristics, by adhering the alkoxysilane-based quaternary ammonium salt as a polymer to the fiber 1 containing the polyester fiber 2, no easily combustible binder resin is used (without), or A polymer of an alkoxysilane-based quaternary ammonium salt can be attached to the fiber 1 without using a large amount of binder resin, and the deterioration of the flameproof performance of the fiber 1 itself can be suppressed.
At the same time, in the fiber 1, even if the polyester fiber 2 has almost no reactive groups such as a hydroxyl group and a carboxyl group, the alkoxysilane-based quaternary ammonium salt becomes a polymer and is entangled with the fiber. The adhesive force to the object 1 is improved.
That is, it is possible to achieve both "suppression of deterioration of flameproof performance" and "improvement of adhesive force".
Here, the fiber 1 is a "functional fiber" that suppresses a decrease in the inherent flameproof performance and has various functions such as "antibacterial performance" due to the polymer of the attached alkoxysilane-based quaternary ammonium salt. It can also be said that.

Further, a compound containing an alkoxysilane-based quaternary ammonium salt is attached to the fiber 1 containing the polyester fiber 2, and the combustion area according to the A-1 method of JIS-L-1091: 1999 is set to 30 cm ² or less, and the balance remains. Set the flame time to 3 seconds or less and set the number of flame contact according to the D method to 3 times or more, or set the combustion area according to the A-2 method of JIS-L-1091: 1999 to 40 cm ² or less and set the residual flame time. Is 5 seconds or less, and the number of flame contacting according to the D method is 3 times or more, so that the compound of the alkoxysilane-based quaternary ammonium salt can be attached to the fiber 1 and a predetermined adhesive force can be secured.

Further, the fiber 1 has an antibacterial activity value of 2.2 or more according to the bacterial solution absorption method of JIS-L-1902: 2015 before and / or after washing according to the standard washing method for SEK mark textile products. As a result, the washing durability of the fiber 1 to which the compound of the alkoxysilane-based quaternary ammonium salt is attached is improved.

The fiber 1 may be any one of a thread 1a containing the polyester fiber 2, a cloth 1b containing the polyester fiber 2, and a textile product 1c using the thread 1a and / or the cloth 1b. ..

The method for producing a fiber 1 according to the present invention is a method for producing a fiber containing polyester fiber, wherein the fiber is an aqueous treatment agent containing an alkoxysilane-based quaternary ammonium salt and a hydroxyethyl methacrylate. The first feature is to process by.

The second feature of the method for producing fiber 1 according to the present invention is that, in addition to the above first feature, the alkoxysilane-based quaternary ammonium salt is octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride. And / or octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride.

The third feature of the method for producing the fiber 1 according to the present invention is that, in addition to the above -mentioned first or second feature, the hydroxyethyl methacrylate is 2-hydroxyethyl methacrylate.

The fourth feature of the method for producing a fibrous material 1 according to the present invention is that the aqueous treatment agent also contains a peroxide compound in addition to any of the above-mentioned features 1 to 3.

The fifth feature of the method for producing fiber 1 according to the present invention is that, in addition to the fourth feature, the peroxide compound is hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, di The point is that it contains at least one of -tert-butyl peroxide.

Due to these characteristics, the fiber 1 is processed with an aqueous treatment agent 3 containing an alkoxysilane-based quaternary ammonium salt and a monofunctional water-soluble vinyl monomer having a hydroxyl group, whereby a monofunctional water-soluble product having a hydroxyl group is used. A bonding reaction between the hydroxyl group of the sex vinyl monomer and the alkoxysilane-based quaternary ammonium salt is expressed on the fiber product 1, and the alkoxysilane-based quaternary ammonium salt is entangled with the fiber product 1 as a polymer and adheres to the fiber product 1. Therefore, rather than treating the alkoxysilane-based quaternary ammonium salt alone, the deterioration of the flameproof performance of the fiber 1 itself can be suppressed by using the monofunctional water-soluble vinyl monomer in combination.
At the same time, in the fiber 1, even if the polyester fiber 2 has almost no reactive group, the alkoxysilane-based quaternary ammonium salt becomes a polymer and is entangled with each other, so that the adhesive force to the fiber 1 is increased. improves.
That is, it is possible to achieve both "suppression of deterioration of flameproof performance" and "improvement of adhesive force".
Here, since the fiber 1 can be said to be a "functional fiber" as described above, it can be said that the method for producing the fiber 1 is a "method for producing a functional fiber".

The alkoxysilane-based quaternary ammonium salt may be octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride and / or octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride.
The monofunctional water-soluble vinyl monomer having a hydroxyl group may be 2-hydroxyethyl methacrylate.

Further, by including the peroxide compound in the aqueous treatment agent 3 in the method for producing the fibrous material 1, the peroxide compound becomes an initiator in the polymerization reaction between the monofunctional water-soluble vinyl monomers, and as a result, the monofunctional water-soluble vinyl monomer becomes monofunctional water-soluble. The bond reaction between the hydroxyl group of the vinyl chloride monomer and the alkoxysilane-based quaternary ammonium salt is more expressed, and further "suppression of deterioration of flameproof performance" and "improvement of adhesive force" can be realized at the same time.

The peroxide compound may contain at least one of hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, and di-tert-butyl peroxide.

Agent 10 is a material which adheres to the fibers comprising polyester fibers, said agent, when attached to the fibers thereof, also include polymers produced from alkoxysilane quaternary ammonium salt Good .

Due to this feature, when the agent 10 contains a polymer produced from an alkoxysilane-based quaternary ammonium salt when attached to the fiber 1 containing the polyester fiber 2, the fiber 1 contains a hydroxyl group or a hydroxyl group. Even in the polyester fiber 2 having almost no reactive group such as a carboxyl group, the adhesive force to the fiber 1 is improved by the entanglement of the polymer of the alkoxysilane-based quaternary ammonium salt.
Here, the agent 10 provides the fiber 1 with various functions such as "antibacterial performance" due to the polymer of the alkoxysilane-based quaternary ammonium salt to be attached while suppressing the deterioration of the flameproof performance of the fiber 1. It can be said that it is a "functional agent" because it has it.

According to the fibrous material according to the present invention, the method for producing the fibrous material, and the agent, by adhering an alkoxysilane-based quaternary ammonium salt as a polymer to the fibrous material, "suppression of deterioration of flameproof performance" and "adhesive strength" It is possible to achieve both "improvement" and so on.

It is a drawing substitute photograph which exemplifies the fiber thing which concerns on this invention, and shows the cloth (sample) of Example 1 in Test 1. It is a drawing substitute photograph which exemplifies the fiber thing which concerns on this invention, and shows the cloth (sample) of Example 2 in Test 1. It is a drawing substitute photograph which shows the cloth (sample) of the comparative example 1 in test 1. FIG. It is a drawing substitute photograph which shows the cloth (sample) of the comparative example 2 in test 1. FIG. It is a drawing substitute photograph which shows the cloth (sample) of the comparative example 3 in test 1. FIG. It is a drawing substitute photograph which shows the cloth (sample) of the comparative example 4 in test 1. FIG.

<Fiber 1>
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIGS. 1 and 2 illustrate the fiber 1 according to the present invention.
A polymer produced from an alkoxysilane-based quaternary ammonium salt and a compound containing an alkoxysilane-based quaternary ammonium salt are attached to the fiber 1.

Here, as described above, "a polymer produced from an alkoxysilane-based quaternary ammonium salt adheres to the fiber 1" in the present invention means a polymer of an alkoxysilane-based quaternary ammonium salt. In addition to being entangled with the fiber 1 and adhering to the fiber 1, "adhering to the fiber 1" in the present invention means that the polyester fiber (polymer) 2 in the fiber 1 and the alkoxysilane-based quaternary ammonium salt are attached. The alkoxysilyl group in the polymer, etc., which adheres due to the intermolecular force between the polymer and the like, or is generated from the alkoxysilane-based quaternary ammonium salt, is a hydroxyl group, a carboxyl group, etc. contained in the fiber 1. It also includes binding to and adhering to reactive groups.
It can be said that the fiber before the polymer produced from the alkoxysilane-based quaternary ammonium salt adheres is the pre-adhesion fiber 1'.
Further, in the present invention, the polymer produced from the alkoxysilane-based quaternary ammonium salt may be at least adhered to the polyester fiber 2 contained in the fiber 1, and at the same time, the polyester fiber may be attached. It may be attached to fibers other than 2.

The timing at which the polymer of the alkoxysilane-based quaternary ammonium salt is attached to the fiber 1 is also not particularly limited. For example, when the fiber 1 is the cloth 1b or the fiber product 1c described later, <Pre-processing> After adhering a polymer of alkoxysilane-based quaternary ammonium salt in the state of thread 1a, it is made into cloth 1b or textile product 1c, or <post-processing> thread 1a is first applied to cloth 1b or textile product. After setting 1c, a polymer of an alkoxysilane-based quaternary ammonium salt or the like may be attached.
Such a "fiber 1" of the present invention may have any structure as long as it contains the polyester fiber 2, but includes, for example, a thread 1a containing the polyester fiber 2 and a polyester fiber 2. It may be either a cloth and a textile product 1c using the threads 1a and / or the cloth 1b.

<Thread 1a, polyester fiber 2>
As shown in FIGS. 1 and 2, the thread 1a may have any structure such as a thread, a rope, and a string as long as it contains at least the polyester fiber 2. As a specific example of the polyester fiber 2, polyethylene terephthalate may be used. (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), or the like may be used. Further, as a matter of course, all the threads 1a may be composed of the polyester fiber 2.
The thread 1a may contain fibers other than the polyester fiber 2, and for example, a polyolefin fiber such as nylon (polyamide) fiber, polyethylene (PE), polypropylene (PP), rayon fiber, cupra fiber, acetate fiber, etc. Acrylic fiber mainly composed of polyacrylonitrile (PAN), synthetic fiber such as polyvinyl alcohol (PVA) fiber (viniron fiber), polyurethane (PU) fiber, silk (silk) fiber, cotton fiber, linen fiber, wool It is a fiber, a glass fiber, or the like, and may contain a fiber that is used alone or in combination.

The number of fibers (filaments) constituting the yarn 1a is not particularly limited (that is, the yarn 1a may be a monofilament or a multifilament), and the fineness of the yarn 1a may be any value, for example. The total fineness is 20 dtex or more and 3000 dtex or less.
Further, the yarn 1a may be a flameproof treatment (flame-retardant treatment). For example, the polyester fiber 2 may be a yarn obtained by copolymerizing a flame-retardant substance or melted. It may be a yarn in which a flame-retardant substance is kneaded at the time of spinning, or a fiber to which a flame-retardant substance is added by post-treatment. Further, the flame-retardant substance may be a phosphorus-based compound, a halogen-based compound, or both compounds.

<Cloth 1b>
As shown in FIGS. 1 and 2, the cloth 1b may also contain at least the polyester fiber 2, and the cloth 1b may be entirely composed of the polyester fiber 2 or may contain fibers other than the polyester fiber 2. I do not care.
The cloth 1b is a knitted fabric, a woven fabric, a non-woven fabric, or a combination thereof.

When cloth 1b is knitted, Denby (tricot), Raschel, Double Raschel, Bandaik (Atlas), Cord, etc., flat knit (Tianzhu), Rubber (rib) It does not matter which organization is used, such as wefts such as pearls and pearls.
When the cloth 1b is a woven fabric, any woven structure may be used, but for example, a plain weave, a twill weave, a satin weave, a double weave, or a double weave or more may be used.

When the cloth 1b is a non-woven fabric, for example, it may be a needle-punched non-woven fabric in which fibers are hooked on reciprocating needles and entangled with each other. In addition, the fabric 1b contains heat-sealing fibers and is formed by heating. A thermal-bonded non-woven fabric, a spun-bonded non-woven fabric in which long fibers (filaments) spun from a nozzle are laminated and bonded on a moving screen, a stitch-bonded non-woven fabric, or the like may be bonded by a needle punch method or the like.

<Textile products 1c>
The textile product 1c may be any of the above-mentioned threads 1a and cloth 1b, but for example, a curtain, a cloth (fabric) blind, a blackout curtain, a carpet, a hairline or other floor. It may be a rug (carpet, etc.).
Here, to explain in detail, carpets and the like include carpets such as woven carpets, woolen carpets such as felt carpets, tufted carpets, nitted carpets, hook drags, adhesive carpets, needle punch carpets, rugs, artificial turf, and synthetic rugs. Includes resin floor sheets and the like.

In addition, textile products 1c can be used for chair upholstery, wall upholstery, ceiling upholstery, interior products such as sofas, vehicle interiors such as car seats, general clothing such as jackets, skirts, pants, and underwear, as well as sports. It may be clothing or clothing material.
In addition, textile products 1c are used for daily life such as cosmetics, cosmetic masks, wiping cloths, and health products, for environmental and industrial materials such as polishing cloths, filters, harmful substance removal products, and battery separators, as well as sutures and scaffolds. , Artificial blood vessels, blood filters, etc. may be used for medical purposes.

A polymer produced from an alkoxysilane-based quaternary ammonium salt is attached to the yarn 1a, the fabric 1b, and the fiber 1 of the textile product 1c described so far, but in addition to this, halogenation is performed. A flame retardant such as a phosphoric acid ester or another antibacterial agent may be attached (imparted).
In addition, extender pigments such as titanium oxide and calcium carbonate and fillers (fillers) can be arbitrarily added to the fiber 1, and deodorants, fungicides, water repellents, antifouling agents, colorants, and fragrances can be added. , A foaming agent or the like may be added.
In addition, the color of the fiber 1 may be any color tone such as red, orange, yellow, green, blue, purple, black, and white, and the saturation and lightness may be any value. I do not care.

<Water-based treatment agent 3>
The aqueous treatment agent 3 is a treatment agent containing at least an alkoxysilane-based quaternary ammonium salt and a monofunctional water-soluble vinyl monomer having a hydroxyl group, and may also contain a peroxide compound.
By processing (treating) the above-mentioned fibrous material 1 with the aqueous treatment agent 3, the fibrous material does not use (has no) easily combustible binder resin, or does not use a large amount of binder resin. A polymer produced from an alkoxysilane-based quaternary ammonium salt can be reliably attached to 1.

Further, it can be said that the compound containing the alkoxysilane-based quaternary ammonium salt can be reliably adhered to the fiber product 1 by processing the fiber product 1 described above with the water-based treatment agent 3.
In the aqueous treatment agent 3, the alkoxysilane-based quaternary ammonium salt, the monofunctional water-soluble vinyl monomer, and the peroxide compound are not only in the form of powder (solid), but also any one of them. Alternatively, all of them may be in the form of a liquid dispersed or dissolved in water, an aqueous solvent, or an organic solvent. When the aqueous treatment agent 3 is in a liquid state, it can be said that it is a treatment liquid.

<Alkoxysilane-based quaternary ammonium salt>
The alkoxysilane-based quaternary ammonium salt contained in the above-mentioned aqueous treatment agent 3 is either octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride or octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride. It may be 1 type or 2 types.
These alkoxysilane-based quaternary ammonium salts are usually prepared by using an organic solvent such as methanol or ethanol as a solvent and having a predetermined component concentration (for example, 50.0% by weight or more and 60.0% by weight or less). When processing (treating) the product 1, it is appropriately diluted with water before use.

In addition, alkoxysilane-based quaternary ammonium salts include octadecyldiethyl (3-triethoxysilylpropyl) ammonium chloride, octadecyldiethyl (3-trimethoxysilylpropyl) ammonium chloride, and octadecyldi-n-propyl (3-triethoxy). Cyrilpropyl) ammonium chloride, octadecyldi-n-propyl (3-trimethoxysilylpropyl) ammonium chloride and the like may be used.
At least one of the alkoxysilane-based quaternary ammonium salts described above can be appropriately selected and used.

Here, the "polymer produced from an alkoxysilane-based quaternary ammonium salt" in the present invention means that each of the alkoxysilane-based quaternary ammonium salts having one silicon atom (Si) has a silicon atom of each other. It is polymerized (condensation polymerization) with an oxygen atom (O) sandwiched between (Si).
Therefore, the "polymer produced from the alkoxysilane-based quaternary ammonium salt" always has a siloxane bond (Si—O—Si bond). When 1 to 4 (or 1 to 3) of these siloxane bonds are present (bonded) to one silicon atom, the polymer produced from the alkoxysilane-based quaternary ammonium salt is linear. It forms a strip structure or a three-dimensional structure and adheres to the fiber 1 by being entangled with the fiber 1.

In other words, the polymer produced from the alkoxysilane quaternary ammonium salt is a 1 to 4 functional (or 1 to 3 functional) monomer unit (general formula [R _n SiO _{(4-n) / 2} ]]. _m (Note, R represents an alkyl group such as a methyl group, an alkyl group containing quaternary ammonium salts _{(e.g., [(C 3 H 6)} N + (CH 3) 2 (CH 2) 17 CH 3] Cl - Etc.), a substituent such as a phenyl group or a vinyl group, n is an integer of 0 to 3 (or 0 to 2), and m is an integer of 2 or more).
That is, the polymer produced from the alkoxysilane-based quaternary ammonium salt is at least one of _{the above-mentioned monomer units (general formula [R n} SiO _{(4-n) / 2} ] _{m) constituting this polymer.} One monomer unit may contain an alkyl group containing at least one quaternary ammonium salt as its R.
Further, in the polymer produced from the alkoxysilane-based quaternary ammonium salt, all the monomer units may contain an alkyl group containing at least one quaternary ammonium salt as its R.
Here, the "monomer unit" in the present invention refers to "the largest structural unit formed of a polymer (polymer (polymer) or oligomer molecule) that can be a structural unit of the basic structure of a polymer". Means (“Glossary of Basic Terms in Polymer Science (IUPAC Recommendations 1996)” by the International Union of Pure and Applied Chemistry (IUPAC) Polymer Nomenclature Committee, Pure Appl. Chem., 68,2287-2311 (1996)], see definitions 1.1, 1.2, 1.3, 1.8, 1.14).

On the other hand, the "compound containing an alkoxysilane-based quaternary ammonium salt" in the present invention includes not only the alkoxysilane-based quaternary ammonium salt itself but also a polymer produced from the above-mentioned alkoxysilane-based quaternary ammonium salt. ..
In addition, substances other than these two (for example, a monofunctional water-soluble vinyl monomer having a hydroxyl group described later and a polymer produced from this monofunctional water-soluble vinyl monomer) are "alkoxysilane-based quaternary ammonium salts. It may be contained in "a compound containing".

<Monofunctional water-soluble vinyl monomer having a hydroxyl group>
Specifically, the monofunctional water-soluble vinyl monomer having a hydroxyl group (hydroxyl group) contained in the above-mentioned aqueous treatment agent 3 may be 2-hydroxyethyl methacrylate (2-HEMA). ..
The monofunctional water-soluble vinyl monomer is 1-hydroxyethyl methacrylate, or other hydroxyethyl acrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate (hydroxypropyl acrylate). It may be any one of hydroxypropylcrylate, hydroxybutyl acrylate, hydroxybutylacrylate and the like, or two or more including the above-mentioned 2-HEMA.

<Compound peroxide>
The peroxide compound when contained in the above-mentioned aqueous treatment agent 3 is an organic peroxide compound such as hydrogen peroxide, benzoyl peroxide (benzoyl peroxide), dicumyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, and di-tert-butyl peroxide. Any one or more of the above may be used.
When the solubility in water such as benzoyl peroxide is small, it may be used after being once dissolved in a solvent such as ethyl alcohol at a predetermined concentration (for example, 2.0% by weight or the like).

<Agent 10>
The agent 10 is an agent that adheres to the fiber 1 containing the polyester fiber 2.
The agent 10 contains a polymer produced from an alkoxysilane-based quaternary ammonium salt when attached to the fiber 1.

If the agent 10 contains a polymer of an alkoxysilane-based quaternary ammonium salt when attached to the fiber 1, the agent 10 contains an alkoxysilane-based quaternary ammonium salt before adhering to the fiber 1. (Furthermore, those that do not contain a polymer of an alkoxysilane-based quaternary ammonium salt) may be used.
That is, the "agent 10" in the present invention actually adheres to the polyester fiber 2 and is an alkoxysilane as long as it contains a polymer of an alkoxysilane-based quaternary ammonium salt even when it is attached to the fiber 1. In addition to those containing a polymer of a quaternary ammonium salt based on the system, those containing a polymer of an alkoxysilane-based quaternary ammonium salt that once adhered to the polyester fiber 2 but then fell off from the polyester fiber 2 and polyester fibers. It also means a polymer that can contain a polymer of an alkoxysilane-based quaternary ammonium salt if it adheres to the fiber 1 before it adheres to 2.

In particular, when the polymer of the alkoxysilane-based quaternary ammonium salt can be contained before adhering to the polyester fiber 2 and adhering to the fiber 1, the agent 10 is not in the form of powder (solid) but in water or water. It may be in the form of a liquid dispersed or dissolved in a solvent or an organic solvent.
When the agent 10 is in a liquid state, it can be said that it is a liquid.

<Manufacturing method of fiber 1>
The method for producing the fibrous material 1 is to process the fibrous material 1 with the above-mentioned aqueous treatment agent 3.
Here, "processed with an aqueous treatment agent 3" in the present invention means a solution of an alkoxysilane-based quaternary ammonium salt (a solution dissolved in a solvent such as ethanol) and a monofunctional water-soluble vinyl having a hydroxyl group. It means immersing the above-mentioned fiber 1 in a treatment solution (aqueous treatment agent 3) in which the monomer is diluted with water to a predetermined concentration (for example, 1.0% by weight, respectively).

In this processing, a solution of an alkoxysilane-based quaternary ammonium salt and the monofunctional water-soluble vinyl monomer are mixed with a solution of a peroxide compound (a solution dissolved in a solvent such as ethanol) at a predetermined concentration with water. A solution diluted to (for example, 1.0% by weight, 0.5% by weight, etc.) may be used as the aqueous treatment agent 3.
Further, in this processing, the fiber 1 immersed in the treatment liquid is squeezed with a mangle at a predetermined pickup drawing ratio (for example, 70%), and after this drawing, the fiber 1 is squeezed at a predetermined temperature. -It may be dried (leaved) under the condition of time (for example, 3 minutes at a temperature of 150 ° C.).

Here, the method for producing the fibrous material 1 will be described in detail. First, the alkoxysilane-based quaternary ammonium salt is hydrolyzed in a treatment solution diluted with water to a predetermined concentration to produce an alkoxy group (R'-). O- (R'is an alkyl group such as a methyl group, a substituent such as a phenyl group or a vinyl group) becomes a silanol group (Si-OH), and the silanol groups are condensed and polymerized to form a siloxane bond. A polymer of an alkoxysilane-based quaternary ammonium salt (siloxane oligomer or siloxane polymer) is produced.
The polymer of the alkoxysilane-based quaternary ammonium salt thus produced adheres to the polyester fiber (polymer) in the fiber 1 by being entangled with the polymer (because the adhered polyester fiber is also a polymer). , It can be said that the polymers of the alkoxysilane-based quaternary ammonium salt and the polyester fiber are compatible with each other).

On the other hand, monofunctional water-soluble vinyl monomer having a hydroxyl group, in the processing solution, the hydroxyl group is hydroxide ion (OH ^-) to generate the (ionized in), pH of the treatment liquid (hydrogen ion concentration) As a result, hydrolysis and condensation polymerization of the above-mentioned alkoxysilane-based quaternary ammonium salt are promoted. At the same time, the monofunctional water-soluble vinyl monomer itself is also addition-polymerized (the double bond of C = C in the monofunctional water-soluble vinyl monomer becomes -CC-), and the polymer of the monofunctional water-soluble vinyl monomer is obtained. (For example, if the monofunctional water-soluble vinyl monomer is 2-HEMA described above, [-CH _2- C (CH ₃ ) (COO (C ₂ H ₄ ))-] _m' (m') Is an integer greater than or equal to 2)).
The polymer of the monofunctional water-soluble vinyl monomer may also be entangled (compatible) with the polyester fiber 2 together with the polymer of the alkoxysilane-based quaternary ammonium salt.

<Tests 1 and 2>
From here, first, Examples 1 to 3 and Comparative Examples 1 to 4 of the fiber 1 according to the present invention will be referred to.
Tests 1 and 2 described later are performed using Examples 1 to 3 and Comparative Examples 1 to 4.

<Example 1>
Semidal polyester fiber 2 (84dtex36 filament with warp density 380 / 10cm) that has been flameproofed is used as the warp, and semidal polyester fiber 2 (84dtex30 filament with weft density 460 / 10cm) that has also been flameproofed is used as the warp. A woven fabric using 100% polyester fiber 2 was woven as a weft with a grain size of 80 g / m ^2.
This woven fabric is used as an ethanol solution of octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride as an alkoxysilane quaternary ammonium salt (hereinafter referred to as "agent A") and a monofunctional water-soluble vinyl monomer having a hydroxyl group. Hydroxyethyl methacrylate (hereinafter referred to as "B agent") is immersed in a treatment solution (aqueous treatment agent 3) diluted with water to a concentration of 1.0% by weight, and squeezed with a mangle at a squeeze rate of 70% pickup. After that, it was left to stand (dry) for 3 minutes at a temperature of 150 ° C. to obtain the fiber 1 (fabric 1b) of Example 1.

<Example 2>
In the treatment liquid of Example 1 (aqueous treatment agent 3), a 2.0 wt% ethanol solution of benzoyl peroxide as a peroxide compound (hereinafter referred to as “C agent”) was further added, and 1.0 wt% of each was added with water. By diluting to a concentration of%, the fiber 1 (fabric 1b) of Example 2 was obtained.

<Example 3>
Semi-dull polyester fiber 2 (300 dtex 96 filaments with a warp density of 240 threads / 10 cm) that has been flameproofed is used as the warp, and another flameproofed semi-dal polyester fiber 2 (Teijin Frontier Co., Ltd. "Super Exter (" A woven fabric using 100% polyester fiber 2 was woven with a weft density of 340 threads / 10 cm) and 300 dtex 30 filaments and a grain size of 143 g / m ^2.
After immersing this woven fabric in a treatment liquid (water-based treatment agent 3) diluted with water to a concentration of 0.5% by weight, and squeezing the woven fabric with a mangle at a squeezing rate of 70% pickup. , The fiber 1 (fabric 1b) of Example 3 was obtained by allowing it to stand (dry) for 3 minutes at a temperature of 150 ° C.

<Comparative example 1>
The woven fabric used in Example 1 is immersed in water instead of the treatment liquid (that is, without using any agents A to C), squeezed with a mangle at a squeezing ratio of 70% pickup, and then at a temperature of 150 ° C. The cloth was left (dried) for 3 minutes to obtain the cloth of Comparative Example 1.

<Comparative example 2>
In the treatment liquid of Example 1, only the agent A was diluted with water to a concentration of 1.0% by weight to obtain the fabric of Comparative Example 2.

<Comparative example 3>
In the treatment liquid of Example 1, Agent A and Agent C were each diluted with water to a concentration of 1.0% by weight to obtain a fabric of Comparative Example 3.

<Comparative example 4>
In the treatment liquid of Example 1, the agent A and the nonionic urethane emulsion resin as the binder resin (hereinafter referred to as “agent D”) were diluted with water to a concentration of 1.0% by weight, respectively, for comparison. The fabric of Example 4 was obtained.

The agents and their concentrations contained in the treatment solutions of Examples 1 to 3 and Comparative Examples 1 to 4 described so far are summarized in Table 1 below.

<Test 1>
In Test 1, the amount of agent A (alkoxysilane-based quaternary ammonium salt) adhered to the fabrics of Examples 1 and 2 and Comparative Examples 1 to 4 among the above-mentioned Examples 1 to 3 and flameproofing. The suppression of performance deterioration was evaluated, and the results are shown in Table 2.

For the evaluation of the amount of Adhesive A, a cationic color reaction between bromophenol blue and an ammonium salt (a reaction that becomes darker as the amount of Agent A increases) was used, and washing was carried out as a pretreatment for the fiber (fabric). ..
In this washing, the JAFET standard detergent established by the Japan Textile Evaluation Technology Council (hereinafter referred to as "JTETC") as a detergent for the fabrics of Examples 1 and 2 and Comparative Examples 1 to 4. (Combined with polyoxyethylene alkyl ether and sodium alphaolefin sulfonate) Using 1.3 ml / L, wash at 40 ° C. for 5 minutes to dehydrate, then rinse with water at 40 ° C. for 2 minutes to dehydrate. By performing these washing, dehydration, rinsing, and dehydration three times as one cycle, and then drying at room temperature after performing a total of three cycles, two samples of each example and each comparative example are used for checking the coloration state. I got them one by one.
These samples were immersed in a 0.004 wt% ethanol solution of bromphenol blue for 30 seconds, washed with water, dried at room temperature, and then the coloration state (adhesion amount of agent A) was confirmed.
To confirm the coloration state, fraying occurs at the edges of the fabrics of Examples 1 and 2 and Comparative Examples 1 to 4 due to the above-mentioned washing, but since the difference in the coloration state appears particularly in the frayed portion, the fraying occurs. Judgment was made based on the coloration state (color difference) in the portion.
The evaluation criteria for the coloration state (adhesion amount of the agent A) is based on Comparative Example 2 using only the agent A as the criteria for the coloration state, and this Comparative Example 2, Examples 1 and 2, and Comparative Examples 1 and 3. Compared with 4 and 4, "◎: darker color (more adhesion)", "○: slightly darker color (slightly more adhesion)", "△: similar color (more adhesion)" than Comparative Example 2. Is about the same) ”and“ ×: No color reaction (not attached) ”.
Further, FIGS. 1 to 6 show samples (fabrics) of Examples 1 and 2 and Comparative Examples 1 to 4 actually evaluated in this test 1.

To evaluate the suppression of deterioration of flameproof performance, the residual flame time of the sample 3 seconds after ignition was measured according to the A-1 method in JIS-L-1091: 1999.
For this residual flame time, in most of the examples and comparative examples, two samples (n1 and n2) were prepared, and the residual flame time of each of n1 and n2 and the average value of n1 and n2 were obtained. In Comparative Example 3, only one (n1) was prepared as a sample, the residual flame time of n1 was determined, and the determined residual flame time is shown in Table 2 as an average value.
The "residual flame time" means the length of time that the test piece (sample) continues to generate a flame from the end of heating.
The evaluation criteria for this residual flame time (suppression of deterioration of flameproof performance) is also based on the residual flame time of Comparative Example 2 as in the evaluation of the color development state, and this Comparative Example 2 and Examples 1 and 2 are compared. Comparing Examples 1, 3 and 4, "○: Residual flame time is shorter (deterioration of flameproof performance is suppressed)" and "△: Residual flame time is about the same (Flameproof performance is better) than Comparative Example 2. (Same degree) ”,“ ×: Long residual flame time (flameproof performance is further reduced) ”.

<Evaluation of Test 1 (Amount of A agent attached / suppression of deterioration of flameproof performance)>
As shown in Table 2 and FIGS. 1 to 6, Example 1 (using agents A and B) and Example 2 (using agents A to C) are more than the standard Comparative Example 2 (using only agent A). It can be seen that the color due to the color reaction is dark and more agent A is attached to the fabric.
Therefore, it can be seen that Examples 1 and 2 using not only Agent A but also Agent B, Agent B and Agent C exhibit antibacterial performance more than Comparative Example 2 containing only Agent A.
Further, in Comparative Example 3, the agent C is used together with the agent A, but the agent C alone as a concomitant agent has only the same color intensity as that of the agent A only in Comparative Example 2, and the agent A (alkoxysilane) is used. It is not possible to improve the adhesive force of the system quaternary ammonium salt).
In Comparative Example 1, since the agent A itself is not used, there is naturally no color reaction, and since the agent A (alkoxysilane quaternary ammonium salt) is not attached, there is no antibacterial performance.

On the other hand, in Comparative Example 4 (using agents A and D), although the color due to the color-developing reaction is darker than that in Comparative Example 2 of the standard, the agent D (binder resin), which is easy to burn, is used. The average value is "22 seconds", which is 6 seconds longer than the standard "16 seconds" of Comparative Example 2, and the flameproof performance is further lowered as compared with Comparative Example 2 (the original flameproof treatment is exhibited. Compared to "0 seconds" in Comparative Example 1 (no agent used), the flameproof performance is significantly reduced).
However, in Examples 1 and 2, since Agent A is attached to the fabric without using Agent D (binder resin), the average value of their residual flame times is "16 seconds" in Comparative Example 2 of the standard. It is "9 seconds", which is 7 seconds shorter than that, which clearly suppresses the deterioration of the flameproof performance as compared with Comparative Example 2 in which only the agent A is used.
That is, it is possible to achieve both "suppression of deterioration of flameproof performance" and "improvement of adhesive force".
Comparing Example 1 (using agents A and B) and Example 2 (using agents A to C), it is better to use not only agents A and B but also agent C at the same time to suppress deterioration of flameproof performance. At the same time, since the color due to the color reaction becomes darker (that is, more agent A is attached to the fabric), further antibacterial performance can be exhibited.
Further, even if the concentrations, ratios, etc. of the agents A to C in the treatment liquids of Examples 1 and 2 change, the deterioration of the flameproof performance is suppressed and the adhesive force tends to be improved as compared with Comparative Examples 1 to 4. Can be said to be similar.

Further, comparing the flameproof performances of Examples 1 and 2 and Comparative Examples 2 and 3, Examples 1 and 2 in which the agent B was used together with the agent A used the agent A but used the agent B. It can be said that the residual flame time is shorter than that of Comparative Examples 2 and 3, and the deterioration of the flameproof performance is further suppressed.
This is because, in <1> Examples 1 and 2, the polymer of the monofunctional water-soluble vinyl monomer having a hydroxyl group is also polyester as well as the polymer of the alkoxysilane-based quaternary ammonium salt by using the agents A and B. Since it is attached to the fiber 2, CO bonds and CC bonds are present in the polymer of the monofunctional water-soluble vinyl monomer, but in Comparative Examples 2 and 3, the B agent is used. The point that only the Si—O bond of the polymer of the alkoxysilane-based quaternary ammonium salt exists.
<2> The bond energy of the CO bond (86 kcal / mol, etc.) and the bond energy of the CC bond (85 kcal / mol, etc.) in the polymer of the monofunctional water-soluble vinyl monomer are alkoxysilane-based quaternary ammonium. Considering two points that are smaller than the bond energy (108 kcal / mol, etc.) of the Si—O bond in the polymer of the salt, when the sample is burned, the CO bond and the CC bond in Examples 1 and 2 are formed. It can be said that this portion is easier to break than the Si—O bond in Comparative Examples 2 and 3, and the melt dropping (drop-off of the fire type) of the polymer fiber 2 which is the fire type is promoted, and as a result, the afterflame time is shortened. (It can be said that the polymer of the alkoxysilane-based quaternary ammonium salt and the polymer of the monofunctional water-soluble vinyl monomer having a hydroxyl group are attached so that the polyester fiber 2 can be melted and dropped).

<Test 2>
In Test 2, among the above-mentioned Examples and Comparative Examples, the flameproof performance and the antibacterial property test standard of the SEK mark textile product established by JTETC were applied to the fiber 1 (fabric 1b) of Example 3 (the criteria for the antibacterial test of the SEK mark textile product established by JTETC. Below, it is evaluated whether or not it meets (passes) the "antibacterial performance standard"), and the results are shown in Table 3.

Regarding the evaluation of flameproof performance, the combustion area and residual flame time of the sample 3 seconds after ignition according to the A-1 method of JIS-L-1091: 1999 and the contact according to the D method of JIS-L-1091: 1999. The number of flames was measured.
For the above-mentioned combustion area and residual flame time, three samples of Example 3 (n1 to n3) were prepared, and for the number of flame contact, five samples of Example 3 (n1 to n3) were prepared. n5) Prepared.
Further, the "combustion area" means the total area of the portion destroyed by heat or thermal decomposition, the "residual flame time" has the same meaning as described above, and the "flame contact count" means heating. It means the number of times (the number of flame contact) until it melts and burns completely.
The evaluation criteria for the combustion area, residual flame time, and number of flame contact (flameproof performance) are "30 cm ² or less", which corresponds to category 3 in the A-1 method of JIS-L-1091: 1999. If there is, it is passed, and if the residual flame time is "3 seconds or less" corresponding to Category 3 in the A-1 method of JIS-L-1091: 1999, it is passed, and the number of flame contact is JIS-L-1091: In the 1999 D method, if it corresponds to Category 2 "3 times or more", it is passed.

The antibacterial performance standard is evaluated according to the bacterial solution absorption method of JIS-L-1902: 2015 (hereinafter referred to as "bacterial solution absorption method"), and the standard washing method for washing SEK mark textile products established by JTETC is adopted. Before and after the corresponding washing (hereinafter referred to as "JTETC washing"), if the antibacterial activity value (hereinafter referred to as "antibacterial activity value") according to the bacterial solution absorption method is "2.2 or more", it is passed.
The test target bacterial species used in the bacterial solution absorption method was "Staphylococcus aureus NBRC 12732", and JTETC washing was performed 5 times to indicate "after washing".

<Evaluation of Test 2 (flameproof performance / antibacterial performance)>
As shown in Table 3, in Example 3 in which at least agent A (alkoxysilane quaternary ammonium salt) and agent B (monofunctional water-soluble vinyl monomer having a hydroxyl group) were used, the combustion area, residual flame time, and The number of flame contact passes the above-mentioned evaluation criteria (corresponding to the strictest category 3 in the A-1 method of JIS-L-1091: 1999 and the strictest category 2 in the D method), and the antibacterial established by JTETC. It is a fiber 1 (fabric 1b) that also passes the performance standard.
Therefore, according to the present invention, a yarn obtained by subjecting a polymer or the like produced from an alkoxysilane-based quaternary ammonium salt to a predetermined flameproof treatment while suppressing a decrease in flameproof performance due to the absence of a binder resin. By adhering to strips, fabrics, and textile products and improving the adhesive force, the flameproof performance equivalent to Category 3 of the A-1 method and Category 2 of the D method in JIS-L-1091: 1999 and the above-mentioned It is possible to realize a fiber 1 having both antibacterial performance of a SEK mark fiber product established by the Textile Evaluation Technology Council, which is evaluated by the bacterial solution absorption method of JIS-L-1902: 2015.
Further, according to the present invention, Article 8-3 of the Fire Service Act (Act No. 186 of July 24, 1948, Act No. 66 of September 11, 2015) (Detailedly, the Fire Service Act Enforcement Ordinance (Cabinet Order of Fire Service Act) March 25, 1958 Cabinet Order No. 37, December 16, 2016 Cabinet Order No. 379) Article 4-3, Fire Service Act Enforcement Regulations (April 1, 1958 Ministry of Autonomy Ordinance No. 6, 2016 May 27, 2014 Ministry of Internal Affairs and Communications Ordinance No. 60) Article 4-3, and the Fire Service Act, Fire Service Act Enforcement Ordinance, Fire Service Act Enforcement Regulations) stipulated in the Fire Service Act, and the Japan Fire Retardant Foundation It can be said that it is possible to realize a fiber 1 having antibacterial performance of SEK mark textile products established by the Japan Fire Retardant Technology Council while having flameproof performance that passes the flameproof performance test standards of the association's flameproof articles. ..
In Example 3, since the antibacterial activity value was 2.2 or more even after the JTETC washing was performed "5 times", the JTETC washing was performed "1 to 4 times" less than 5 times. Even after doing so, the antibacterial activity value is naturally 2.2 or more.
Therefore, the textile 1 of the present invention is "JIS- before and / or after washing (JTETC washing) according to the standard washing method of the SEK mark textile product washing method established by the Textile Evaluation Technology Council. It can be said that the antibacterial activity value according to the bacterial solution absorption method of L-1902: 2015 is 2.2 or more. ”In this case,“ after washing ”means, in addition to performing JTETC washing 5 times, 1 Including the case of going up to 4 times.

<Others>
The present invention is not limited to the above-described embodiment. The structure, shape, dimensions, etc. of each structure or the whole of the fiber 1 and the fiber 1 and the composition of the agent 10 and the like can be appropriately changed according to the gist of the present invention.
It can be said that at least a polymer produced from an alkoxysilane-based quaternary ammonium salt may be attached to the fiber 1.

When the fiber 1 is a thread 1a, its flameproof performance may be evaluated by a method according to the E-1 method in JIS-L-1091: 1999.
A small amount of binder resin may be used for the fiber 1 as long as the flameproof performance is not affected.
At least a polymer produced from an alkoxysilane-based quaternary ammonium salt may be attached to the polyester fiber 2 of the fiber 1, and the polymer produced from a monofunctional water-soluble vinyl monomer having a hydroxyl group may be attached. It does not have to adhere to the polyester fiber 2.

The fibers, the method for producing the textiles, and the agent of the present invention include not only threads and fabrics, but also curtains, chair upholstery, wall upholstery, ceiling upholstery, etc. using these threads and fabrics. It can be used for various textile products.

1 Textiles 1a Threads 1b Fabrics 1c Textiles 2 Polyester fibers 3 Water-based treatment agents 10 agents

Claims (5)

A method for manufacturing textiles containing polyester fibers.
A method for producing a fiber, which comprises processing the fiber with an aqueous treatment agent containing an alkoxysilane-based quaternary ammonium salt and a hydroxyethyl methacrylate. The alkoxysilane-based quaternary ammonium salt, octadecyl dimethyl (3-triethoxysilylpropyl) ammonium chloride, and / or, claim 1, characterized in that octadecyl dimethyl (3-trimethoxysilyl propyl) ammonium chloride is chloride The method for producing a fibrous material according to. The method for producing a fiber according to claim 1 or 2 , wherein the hydroxyethyl methacrylate is 2-hydroxyethyl methacrylate. The method for producing a fiber according to any one of claims 1 to 3 , wherein the aqueous treatment agent also contains a peroxide compound. The fourth aspect of claim 4, wherein the peroxide compound contains at least one of hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, and di-tert-butyl peroxide. Method for manufacturing textiles.

Images