JP2014070304A - Polyester fiber fabric and manufacturing method thereof, and clothing using the polyester fiber fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fabric having little deterioration in bacteriostatic, antistatic and deodorant properties even after a high pressure steam sterilization treatment by an industrial cleaning and autoclaving, to provide a manufacturing method of the fabric, and to provide clothing composed of the fabric.SOLUTION: A polyester fiber fabric contains a polyester fiber of 60 mass% or more, and a polymer containing following (A) to (D) as constituents is formed on a surface of the polyester fiber. (A) Bifunctional unsaturated carboxylic ester containing polyalkylene glycol, (B) an ester compound of undecylenic acid and/or a derivative of undecylenic acid and a compound having a vinyl group, (C) vinyl carboxylic acid, and (D) a compound having an oxazoline group.

Description

  The present invention relates to a polyester fiber fabric, and more particularly to a fabric with little functional deterioration due to sterilization performed for medical use.

  Polyester fibers are used in a wide range of applications such as clothing and industrial materials because of their excellent strength, fastness to dyeing, and high versatility of processing. In recent years, since consideration for hygiene has become very important, polyester fiber fabrics having antibacterial, deodorant, and antistatic functions have been studied.

  A bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol, an esterified product of undecylenic acid and / or a derivative of undecylenic acid and a compound having a vinyl group, and an antibacterial treatment agent formed by mixing vinyl carboxylic acid are applied to the fiber surface. A polyester fiber fabric obtained by polymerization and polymerization is known (for example, see Patent Document 1). According to the fabric, for example, a washing manual (JEC326) II. It is said that it exhibits excellent antibacterial properties even after repeated industrial washing according to the high temperature accelerated washing method.

  Polyester fiber in which a treatment liquid obtained by adding a bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol and vinyl carboxylic acid to collagen or / and a compound having a radically polymerizable double bond is applied to the fiber surface and polymerized. Fabrics are known (for example, see Patent Document 2). According to the fabric, excellent antibacterial and antistatic properties can be obtained even after repeated washing using a household electric washing machine specified in JIS L-0217: 1995 103 (hereinafter abbreviated as household washing). Property and antifouling property.

  A polyester fiber fabric in which a specific bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol, a compound having a vinyl carboxylic acid and an oxazoline group is applied to the fiber surface and polymerized is known (for example, see Patent Document 3). . According to the fabric, it is said that it exhibits excellent antistatic properties even after repeated home washing, and the tear strength after autoclaving is small.

Japanese Patent Laid-Open No. 2004-210665 Japanese Patent Laid-Open No. 7-300770 JP 2003-227015 A

  Among the above-mentioned uses, it has been found that sanitation considerations are further required in clothing worn at food manufacturing sites, pharmaceutical manufacturing sites, medical sites, precision device manufacturing sites, and the like. Specifically, it has been found that a polyester fiber fabric having excellent antibacterial, deodorant and antistatic properties is required even after repeated industrial washing and high-pressure steam sterilization.

  However, although the polyester fiber fabric of Patent Document 1 has antibacterial properties and durability against industrial washing, it does not have durability against high-pressure steam sterilization. Regarding the deodorizing property of the fabric, it has home washing durability, but it does not have durability against industrial washing or high-pressure steam sterilization treatment. As for the antistatic property of the fabric, it does not have durability even at home washing, and cannot withstand industrial washing or high-pressure steam sterilization.

  The polyester fiber fabric of Patent Document 2 has home washing durability with respect to antibacterial and antistatic properties, but does not have durability against industrial washing or high-pressure steam sterilization treatment. With regard to deodorizing properties, the fabric reduces the odor by sterilizing bacteria that cause odor with an antibacterial agent, and has a function of decomposing and deodorizing odor components such as ammonia. Absent.

  The polyester fiber fabric of Patent Document 3 has little decrease in tear strength with respect to the high-pressure steam sterilization treatment. However, the fabric has antibacterial, deodorant and antistatic functions, and the antistatic property only has durability for home washing, and has no durability against industrial washing or high-pressure steam sterilization treatment. Not done.

  The present invention solves the above-described problems of the prior art, and even after repeated industrial washing and high-pressure steam sterilization, the fabric has excellent antibacterial properties, antistatic properties, and deodorizing properties, a method for producing the fabric, and the fabric. It is an object to provide a clothing item.

  The present inventor has conventionally used a compound having an oxazoline group, which has been used for improving mechanical properties such as tear strength, as a bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol, undecylenic acid and / or undecylenic acid. An esterified product of the above derivative and a compound having a vinyl group, and vinyl carboxylic acid were added to the fabric to polymerize. As a result, surprisingly, the fabric is completely different from the improvement in mechanical properties, in that it is excellent in antibacterial properties, antistatic properties and deodorizing properties even after repeated industrial washing and high-pressure steam sterilization treatment. As a result, the present invention has been completed. That is, the gist of the present invention is as follows. ~ 6. It is as follows.

1. A polyester fiber fabric comprising 60% by mass or more of polyester fiber, wherein a polymer having the following components (A) to (D) as a constituent component is formed on the surface of the polyester fiber.
(A) Bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol (B) Esterified product of undecylenic acid and / or a derivative of undecylenic acid and a compound having a vinyl group (C) Vinyl carboxylic acid (D) Having an oxazoline group Compound

2. Each adhesion rate (X _A , X _B , X _C and X _D ) (mass%) of each constituent component of the above (A) to (D) with respect to the mass of the entire polyester fiber fabric satisfies the following formula: The above 1. 2. A polyester fiber fabric as described in 1.

However, X _P represents the deposition rate of the entire polymer as a constituent component relative to the total mass of the polyester fiber fabric and (A) ~ (D).

3. 1. The fabric according to the above 1., wherein the fabric after the industrial washing and then autoclave treatment steps are repeated 5 times satisfies the following requirements (1) to (3). Or 2. 2. A polyester fiber fabric as described in 1.
(1) The ammonia depletion rate in the deodorization test method (detector tube method) specified in the deodorant processed fiber product certification standard (JED301) of the Japan Fiber Evaluation Technology Council is 70% or more.
(2) The bactericidal activity value L of Klebsiella pneumoniae, Staphylococcus aureus, and MRSA by the bacterial liquid absorption method defined in JIS L 1902: 2008 is L> 0.
(3) The frictional voltage specified in JIS L 1094: 1997 in an environment of 20 ° C. and 40% RH is 1000 V or less.

4). Polymerization in the step of applying the following (A) to (D) to a fabric containing 60% by mass or more of polyester fiber, the step of polymerizing the (A) to (D) applied to the fabric, and the step of polymerizing A process for producing a polyester fiber fabric, comprising a step of removing the unreacted (A) to (D) without performing the above process.
(A) Bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol (B) Esterified product of undecylenic acid and / or a derivative of undecylenic acid and a compound having a vinyl group (C) Vinyl carboxylic acid (D) Having an oxazoline group Compound

  5. The above-mentioned polymerizing step is a steam heat treatment step or a low-temperature plasma treatment step. The manufacturing method of the polyester fiber fabric of description.

  6). Above 1. ~ 3. A clothing product comprising the polyester fiber fabric according to any one of the above, wherein the clothing product is worn at a food manufacturing site, a pharmaceutical manufacturing site, a medical site or a precision instrument manufacturing site.

  According to the fabric of the present invention, even if industrial washing and high-pressure steam sterilization treatment are repeated, a remarkable effect of being excellent in antibacterial properties, antistatic properties and deodorizing properties can be obtained. Therefore, the fabric can be preferably used for apparel for food manufacturing sites, pharmaceutical manufacturing sites, medical institutions, and precision equipment manufacturing sites with particularly stringent hygiene management.

  Hereinafter, the present invention will be described in detail.

  The fabric in the present invention needs to contain 60% by mass or more of polyester fiber, and preferably contains 80% by mass or more.

  When the polyester fiber is not contained in an amount of 60% by mass or more, the resulting fabric cannot obtain durability against antibacterial, antistatic and deodorant industrial washing and autoclaving. When the polyester fiber is contained in an amount of 80% by mass or more, the resulting fabric is preferable since it has excellent antibacterial properties, antistatic properties, deodorizing properties, and durability against industrial washing and autoclave treatment. Although the reason for this is not clear, it is presumed that when other fibers are used, the adhesion between the polymer and the fiber surface described later is inferior to that when polyester fibers are used.

  In the present invention, the polyester is composed of a polybasic acid and a polyhydric alcohol. For example, in addition to polyethylene terephthalate (hereinafter abbreviated as PET) composed of terephthalic acid as the polybasic acid and ethylene glycol as the polyhydric alcohol, polybutylene terephthalate, polypropylene terephthalate, polylactic acid, and the like can be mentioned. It is preferable to use PET that is 95 mol% or more of all repeating units. The polyester may be a polybasic acid, a polyhydric alcohol, or a copolyester used in two or more types of both the polybasic acid and the polyhydric alcohol.

  The polyester fiber used for the fabric of the present invention can be a composite fiber made of two or more component polyesters, in addition to a fiber made of a single component polyester. When it is set as a composite fiber, it does not specifically limit as a composite form, For example, the cross-sectional shape with respect to a fiber longitudinal direction becomes a core-sheath type or a parallel type.

  The form of the polyester fiber used in the present invention may be either a long fiber or a short fiber. For example, a multifilament yarn, a monofilament yarn, a spun yarn, and a short fiber are mentioned. The polyester fiber may be processed yarn subjected to false twisting, actual twisting, or the like. The single yarn fineness and the total fineness of the polyester are not particularly limited, but it is preferable that the single yarn fineness is 0.3 to 10.0 dtex and the total fineness is 50 to 300 dtex.

  As long as the essential effects of the present invention are not impaired, the fabric of the present invention, in addition to polyester fiber, polyamide fiber such as nylon 6 and nylon 66, acrylic fiber, polyurethane fiber, cotton, animal hair fiber, silk, Natural fibers such as hemp and bamboo, viscose rayon, copper ammonia rayon, regenerated fibers such as solvent-spun cellulose fibers, and semisynthetic fibers such as acetate can be included. As a method using a plurality of fibers, methods such as knitting, blending, blending, knitting, and knitting can be used.

  In the present invention, the form of the fabric is not particularly limited, and can be, for example, a woven or knitted fabric or a nonwoven fabric.

In the polyester fiber fabric of the present invention, a polymer having the following compounds (A) to (D) as constituent components (hereinafter abbreviated as a polymer in the present invention) is formed on the surface of the polyester fiber constituting the fabric. Need to be.
(A) Bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol (hereinafter sometimes abbreviated as component (A))
(B) Esterified product of undecylenic acid and / or a derivative of undecylenic acid and a compound having a vinyl group (hereinafter sometimes abbreviated as component (B))
(C) Vinylcarboxylic acid (hereinafter sometimes abbreviated as component (C))
(D) Compound having an oxazoline group (hereinafter sometimes abbreviated as component (D))

  The compounds (A) to (D), which are liquids, are mixed in water to form a treatment liquid (hereinafter abbreviated as a treatment liquid), and the treatment liquid is applied to a polyester fiber fabric to provide the treatment liquid. The fabric is squeezed with a mangle or the like and polymerized as described later, whereby the polymer is formed on the surface of the polyester fiber constituting the fabric. At this time, the non-polymerized compounds (A) to (D) (unreacted substances) are removed by washing such as soaping performed after the polymerization process. On the other hand, the polymer in the present invention remains on the surface of the polyester fiber without being removed even when soaping or the like is performed. The fabric thus obtained has excellent durability against antibacterial, antistatic and deodorant industrial washing and autoclaving.

  (A) Bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol

  The component (A) is polymerized on the surface of the polyester fiber together with the components (B) to (D), so that the polyester fiber fabric of the present invention is particularly excellent in antistatic and deodorizing properties. It will be a great place to help.

  As the component (A), diacrylate and dimethacrylate containing polyethylene glycol or polypropylene glycol represented by the following general formula (I), or epoxy diacrylate and epoxy containing polyethylene glycol or polypropylene glycol represented by the following general formula (II) Dimethacrylate is preferred. In addition, in the following general formulas (I) and (II), the molecular weight of polyethylene glycol and polypropylene glycol is preferably 100 to 1000.

Formula (I):

General formula (II):

In the general formulas (I) and (II), n represents an integer of 1 to 23, and R represents H or CH ₃ .

The adhesion rate (X _A ) of the constituent component (A) with respect to the mass of the entire polyester fiber fabric is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and 1 to 10% by mass. % Is particularly preferred.

However, in the present invention, the adhesion rates (X: X _{A to} X _D ) of the constituent components (A) to (D) are calculated according to the following formula (A).

W ₁ : Absolute dry mass (g / 100 cm ² ) of the polyester fiber fabric after the formation of the polymer and after washing such as soaping to remove unreacted components
W ₂ : Absolute dry mass (g / 100 cm ² ) of the polyester fiber fabric before applying the treatment liquid
m: Content of components (A) to (D) in the treatment liquid (g / l)
S: Total (g / l) content of each constituent (A) to (D) in the treatment liquid

  When the adhesion amount of the constituent component (A) is less than 0.5% by mass, the resulting fabric tends to be difficult to obtain desired antistatic properties and deodorizing properties. On the other hand, if it exceeds 30% by mass, the resulting fabric tends to have a rough texture. When the content is 1 to 20% by mass, the resulting fabric is particularly preferable in terms of antistatic and deodorizing properties. Furthermore, when it is 1-10 mass%, since the fabric obtained has an antistatic property and a deodorizing property and tends to be excellent in the texture, it is particularly preferable.

  (B) Undecylenic acid and / or esterified product of undecylenic acid derivative and compound having vinyl group

  In the above components, undecylenic acid is a component that is also contained in human skin and sweat, and has the ability to control bacteriostasis and sterilization of microorganisms and viruses in the skin. In particular, it is known that the symptoms of cold sores in humans and the bactericidal effect of ringworm bacteria are about 20 times that of salicylic acid, and is excellent in hygroscopicity. Moreover, since undecylenic acid is obtained by thermally decomposing castor oil, which is a naturally derived component, it is excellent in safety to the human body.

  Examples of the undecylenic acid derivative include undecylenol obtained by reducing undecylenic acid.

  In the present invention, the undecylenic acid and / or the undecylenic acid derivative can be polymerized on the surface of the polyester fiber by reacting with a compound having a vinyl group to form an esterified product.

  Although it does not specifically limit as a compound which has the said vinyl group, For example, hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate And (meth) acrylic acid polyalkylene oxide modified products such as polyethylene glycol mono (meth) acrylate, allyl alcohol, polyalkylene oxide monoallyl ether, and vinyl alcohol. Among these, a polyethylene glycol mono (meth) acrylate modified with a (meth) acrylic acid polyalkylene oxide is preferable because the polymerization can be efficiently performed on the polyester fiber surface.

  The component (B) is excellent in the polyester fiber fabric of the present invention by being polymerized on the surface of the polyester fiber together with the components (A), (C) and (D). The place which contributes to providing antibacterial property becomes a big thing.

  The component (B) is preferably water-soluble, preferably undecylenoxypolyethylene glycol methacrylate, which is a methacrylic acid ester to which 8 to 12 moles of undecenol ethylene oxide has been added. It is particularly preferable that 12 mol of oxide ethylene oxide is added.

In the present invention, adhesion of the constituent components relative to the total mass of the polyester fiber fabric _{(B) (X} B) is preferably from 0.5 to 30 mass%, more preferably 1 to 20 mass%, 1 to 5 wt% Particularly preferred.

  If the adhesion rate is less than 0.5% by mass, the resulting fabric tends to be inferior in antibacterial properties. On the other hand, when the adhesion rate exceeds 30% by mass, the resulting fabric tends to have a hard texture. Moreover, it is preferable that it is 1-20 mass%, since the resulting fabric is particularly excellent in antibacterial properties. Furthermore, in the case of 1 to 5% by mass, the resulting fabric is particularly preferable because it has excellent antibacterial properties and at the same time has excellent texture.

  (C) Vinylcarboxylic acid

  The component (C) is polymerized on the surface of the polyester fiber together with the components (A), (B) and (D), so that the polyester fiber fabric of the present invention has antibacterial and antistatic properties. This will greatly contribute to the provision of durability against high-pressure steam sterilization by an industrial wash and an autoclave.

  As the component (C), for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, butenetricarboxylic acid, fumaric acid, crotonic acid, and vinylpropionic acid are preferably used.

Regarding the adhesion rate of the component (C), the ratio (X _C / X _P ) of the adhesion rate (X _C ) of the component (C) to the adhesion rate (X _P ) of the whole polymer in the present invention is 0.001 to 0.001. It is preferable to be in the range of 0.3.

In the present invention, the adhesion rate (X _P ) of the whole polymer in the present invention is calculated according to the following formula (B).

W ₁ : Absolute dry mass (g / 100 cm ² ) of the polyester fiber fabric after the formation of the polymer and after washing such as soaping to remove unreacted components
W ₂ : Absolute dry mass (g / 100 cm ² ) of the polyester fiber fabric before applying the treatment liquid

When the ratio (X _C / X _P ) is less than 0.001, the resulting fabric is inferior in durability to high-pressure steam sterilization treatment by industrial washing and autoclave, which is antibacterial, antistatic and deodorant. It is easy to become a thing. On the other hand, when the ratio exceeds 0.3, the resulting fabric tends to have a hard texture. The ratio is preferably 0.005 to 0.2, and more preferably 0.01 to 0.1.

  (D) Compound having oxazoline group

  Conventionally, compounds having an oxazoline group have been used to improve mechanical properties of fabrics such as tear strength. The fabric of the present invention is antibacterial and antistatic even when industrial washing and high-pressure steam sterilization are repeated by polymerizing the compound together with the components (A) to (C) on the surface of the polyester fiber. In addition, the improvement in mechanical properties, which is excellent in deodorizing properties, is completely different from the above-described improvement in mechanical properties, and can provide a remarkable effect.

  The compound having an oxazoline group of the present invention has a polyethyleneimine skeleton, and has a structure in which a substituent such as a methyl group or a phenyl group is bonded to a nitrogen atom constituting the skeleton via a carbonyl group It is. Specific examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2- Examples include isopropenyl-4-methyl-2-oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline. Among them, 2-isopropenyl-2-oxazoline is preferable because it is easily available industrially.

Regarding the adhesion rate of the component (D), the ratio (X _D / X _P ) of the adhesion rate (X _D ) of the component (D) to the adhesion rate (X _P ) of the whole polymer in the present invention is 0.001 to 0.001. It is preferable to be in the range of 0.3. When the ratio is less than 0.001, the resulting fabric tends to be inferior in durability to high-pressure steam sterilization by industrial washing and autoclave, which are antibacterial, antistatic and deodorant. On the other hand, when the ratio exceeds 0.3, the resulting fabric tends to have a hard texture. The ratio is preferably 0.005 to 0.2, and more preferably 0.01 to 0.1.

The adhesion rate (X _P ) of the entire polymer in the present invention relative to the mass of the entire polyester fiber fabric is preferably in the range of 3 to 10% by mass. Also, when the said range, adhesion of the whole polymer in the present invention _(X P) components for (mass%) (A), (B ), each deposition rate (C) and (D) _(X A, X _B , X _C , X _D ) (mass%) ratios (X _A / X _P , X _B / X _P , X _C / X _P and X _D / X _P ) are respectively represented by the following formulas (c) to (f) ) Are preferably satisfied at the same time.

  When the adhesion rate of the whole polymer and the adhesion rates of the components (A) to (D) in the present invention satisfy the above conditions, the resulting fabric is antibacterial, antistatic, and deodorant industrial laundry and autoclave. This is preferable because the durability and texture against the high-pressure steam sterilization treatment are particularly excellent.

  The polyester fiber fabric of the present invention preferably satisfies the following requirements (1) to (3) after the industrial washing and then the autoclave treatment are repeated five times. However, the industrial laundry is performed in accordance with the F-2 method (medium temperature washer method) defined in JIS L 1096: 2010. In the F-2 method, the operation time in warm water (about 60 ° C.) Instead of 30 minutes, the time is 300 minutes, and drying is performed at 80 ° C. for 30 minutes using a tumble dryer. The autoclave treatment means that a test piece (polyester fiber fabric) subjected to industrial washing is put into an autoclave and subjected to high-pressure steam treatment at 135 ° C. for 80 minutes.

(1) The ammonia depletion rate in the deodorization test method (detector tube method) specified in the deodorant processed fiber product certification standard (JED301) of the Japan Fiber Evaluation Technology Council is 70% or more.
(2) The bactericidal activity value L of Klebsiella pneumoniae, Staphylococcus aureus, and MRSA by the bacterial liquid absorption method defined in JIS L 1902: 2008 is L> 0. However, the number of viable bacteria is measured using a luminescence measurement method (ATP method).
(3) The frictional voltage specified in JIS L 1094: 1997 in an environment of 20 ° C. and 40% RH is 1000 V or less.

  In the above (1), the ammonia reduction rate is set to 70% or more because the deodorant processed fiber product certification standard (JED301) of the Japan Fiber Evaluation Technology Council is the ammonia reduction rate of 70%. It is because it is made more than%.

  In the above (2), when the bactericidal activity value L is L> 0, it indicates that the growth of various bacteria on the fiber is suppressed (has antibacterial properties), and when L <0, the bacteria grow. (Not antibacterial). Therefore, it shows that it is excellent in antimicrobial property, so that the value of L is large.

  In the above (3), if the friction band voltage of the JIS L1094: 1997 B method is 1000 V or less in an environment where the friction band voltage is 20 ° C. and 40% RH, there is no clinging of the fabric to the body when the sewn product is worn, Moreover, since there is no adhesion of dust to a sewing product, it is preferable.

  In the present invention, as one of the methods in which the polyester fiber fabric of the present invention that has been subjected to industrial washing and autoclave treatment satisfies the above (1) to (3), the amount of the polymer in the present invention, the amount of each component in the polymer It is mentioned that the mass ratio is appropriate.

  Next, an example is given and demonstrated about the manufacturing method of the polyester fiber fabric of this invention.

  First, (A) a diacrylate mainly composed of a bifunctional vinyl-based monomer containing polyalkylene glycol, (B) an esterified product obtained by an esterification reaction between an undecylenic acid and / or a derivative of undecylenic acid and a compound having a vinyl group, (C) A compound having vinyl carboxylic acid and (D) an oxazoline group is added to water to obtain a treatment liquid. The treatment liquid preferably contains a polymerization initiator in order to efficiently carry out the polymerization of the polymer in the present invention.

  Examples of the polymerization initiator include inorganic polymerization initiators such as ammonium persulfate, potassium persulfate, cerium ammonium nitrate, and hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2, Examples thereof include radical initiators such as organic radical initiators such as 2'-azobis (N, N'-dimethyleneisobutyramide) dihydrochloride and 2- (carbamoylazo) isobutyronitrile.

  In order to further increase the polymerization efficiency, a so-called redox initiator that uses a peroxide and a reducing substance in combination can also be used as a polymerization initiator. Examples of the peroxide include ammonium persulfate and potassium persulfate, and examples of the reducing substance include a reaction product of sodium sulfoxylate and formalin, hydrosulfite, and the like.

  As a usage-amount of a polymerization initiator, it is preferable to set it as 0.1-15.0 mass% with respect to the sum total of the mass of structural component (A)-(D) contained in the said processing liquid.

  Furthermore, a polymerization inhibitor may be contained in the treatment liquid. By using a polymerization inhibitor in combination, polymerization in a low temperature range can be suppressed, and it becomes easy to obtain a polymer having a desired degree of polymerization. Polymerization inhibitors include quinones such as benzoquinone, hydroquinone and methoxyphenol, polyoxy compounds such as tert-butylcatechol, organic sulfur compounds such as sodium dimethyldithiocarbamate and diethylhydroxylamine, nitro compounds, diethylhydroxylamine and isopropylhydroxyl. Examples include amino compounds such as amines.

  As a usage-amount of a polymerization inhibitor, it is preferable to set it as 0.01-2.00 mass% with respect to the sum total of the mass of structural component (A)-(D) contained in the said processing liquid.

  The components (A) to (D), the polymerization initiator, and the polymerization inhibitor are not limited to a form that is mixed as one treatment liquid and then applied to a polyester fiber fabric that has not been provided with the treatment liquid. However, when it mixes as one process liquid, it is preferable at the point which is easy to adjust so that the said structural component (A)-(D) may become a desired adhesion rate.

  After preparing the said process liquid, this process liquid is provided to the polyester fiber fabric which has not provided this process liquid. The fabric may be subjected to scouring, alkali weight loss, dyeing and the like as necessary. The method for applying the treatment liquid is not particularly limited, and a known method such as a padding method, a spray method, a kiss roll coater method, or a slit coater method can be appropriately used. The polyester fiber fabric to which the treatment liquid is applied may be subjected to preliminary drying such as air drying or heating as appropriate according to the treatment method described below for reacting the components (A) to (D).

  In the polymerization process for obtaining the polymer in the present invention by reacting the components (A) to (D), a steam heating process or a low temperature plasma process is preferable in terms of cost, polymerization efficiency, and stability.

  In the steam heat treatment, treatment with normal pressure steam or high pressure steam is performed without preliminary drying. The treatment with normal pressure steam is preferable from the viewpoints of cost and work efficiency because the polymerization treatment can be carried out continuously. The temperature of the steam heat treatment is preferably 80 to 180 ° C, more preferably 98 to 150 ° C. Further, the time for the steam heat treatment is preferably 1 to 20 minutes.

  On the other hand, in the low temperature plasma treatment, the polyester fiber fabric that has been pre-dried to remove moisture is subjected to a low temperature plasma treatment in a non-polymerizable gas. Plasma is a discharge state obtained by applying electric energy to a gas, and means a state in which negatively charged electrons, positively charged ions, and electrically neutral radicals are included. The low temperature plasma is a plasma state in a normal temperature range by glow discharge, atmospheric pressure glow discharge, corona discharge or the like performed under reduced pressure, and is a plasma state in which only the electron temperature is high. By performing the low temperature plasma treatment, the esterified product can be polymerized without using a polymerization initiator.

  In the present invention, the low temperature plasma treatment is performed as follows. That is, gas molecules are excited by applying high-frequency energy to a non-polymerizable gas in a reduced pressure state to generate a low-temperature plasma, and a polyester fiber fabric is allowed to stand in this low-temperature plasma atmosphere for a certain period of time, thereby Perform processing.

  The non-polymerizable gas is preferably at least one selected from oxygen, nitrogen, hydrogen, helium, argon, and carbon dioxide. Among these, oxygen is particularly preferable in order to efficiently polymerize the polymer in the present invention on the polyester fiber surface.

  The frequency of the high-frequency energy is not particularly limited as long as it is a frequency that can generate low-temperature plasma, and can be used in the range of 1 to 3000 MHz. Practically, it is preferable to use any of 13.56 MHz, 27.12 MHz, 40.68 MHz, 915 MHz, and 2450 MHz according to regulations such as the Radio Law.

  The power of the high frequency energy (high frequency power) is preferably 0.1 to 15.0 KW, more preferably 0.4 to 10 W, from the viewpoint of the kinetic energy of the generated low temperature plasma.

  The degree of vacuum during the plasma treatment is preferably 13 to 2670 Pa, more preferably 40 to 1330 Pa, from the viewpoint of obtaining a stable plasma state.

  The plasma treatment time is preferably in the range of 1 to 60 minutes and more preferably 1 to 10 minutes in order to efficiently polymerize the polymer in the present invention on the polyester fiber surface.

  After polymerizing the polymer in the present invention on the surface of the polyester fiber, it is preferable to perform soaping in order to remove the unreacted material composed of the unreacted components (A) to (D) from the surface of the polyester fiber fabric. When soaping is not carried out, the polyester fiber fabric is liable to cause elution of the unreacted material remaining on the surface of the polyester fiber fabric in the subsequent drying step and use thereof, thereby easily causing discoloration, and the dyeing fastness. Tends to decrease.

  As the apparatus for performing the soaping, a continuous apparatus such as a known open soaper or a batch apparatus such as a wince or a liquid dyeing machine can be used. In order to sufficiently remove the unreacted substances, the temperature at which the soaping is performed is preferably 60 to 100 ° C., and the time for the soaping is preferably 1 to 60 minutes. In the case of soaping, it is preferable to use a surfactant in combination from the viewpoint of increasing cleaning efficiency.

  And after performing soaping, the polyester fiber fabric of this invention can be obtained by drying.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the industrial laundry / autoclave treatment conditions and the evaluation methods of ammonia deodorizing property, antibacterial property, antistatic property and texture in Examples and Comparative Examples are as follows.

1. Industrial washing / autoclave treatment Industrial washing is performed according to the F-2 method (medium temperature washer method) defined in JIS L 1096: 2010. In the F-2 method, the operation time in warm water (about 60 ° C.) is 30 minutes. The drying was performed for 300 minutes, and drying was performed at 60 to 80 ° C. for 10 to 30 minutes with a tumble dryer. In the autoclave treatment, the test piece (polyester fiber fabric) subjected to the industrial washing was put into an autoclave and steamed at 135 ° C. for 80 minutes. The process of performing the industrial washing and then performing the autoclave treatment was defined as one cycle, which was repeated five times.

2. Ammonia deodorant Deodorant test method (detection) specified in the deodorant processed fiber product certification standard (JED301) of the Japan Fiber Evaluation Technology Council for fabrics that have been processed and industrially washed and autoclaved Ammonia reduction rate was determined by the tube method), and 70% or more was determined to be acceptable.

3. Antibacterial properties of the finished fabric and the fabric subjected to the industrial washing / autoclave treatment are determined for the bactericidal activity value L of Klebsiella pneumoniae, Staphylococcus aureus and MRSA by the bacterial liquid absorption method defined in JIS L 1902: 2008. A value exceeding 0 was considered acceptable. However, the luminescence measurement method (ATP method) was used for the measurement of the number of viable bacteria.

4). Antistatic property About the fabric after processing and the fabric subjected to the industrial washing and autoclave treatment, the friction withstand voltage was obtained in accordance with JIS L 1094: 1997 in an environment of 20 ° C. and 40% RH. did.

5. The sensory evaluation by the panelists of five persons was performed about the texture (softness | flexibility) of this fabric which performed texture finishing cloth and the said industrial washing and autoclave process. Each sample had a good texture (soft) with a maximum score of 10 and was evaluated in 10 grades of 1 to 10 points, and was shown as an average value of 5 people (7 points or more were accepted).

Example 1
A warp yarn obtained by subjecting a PET multifilament (167 dtex / 48f) having an ethylene terephthalate unit of 95 mol% or more in all repeating units to false twisting, and a weft yarn having an ethylene terephthalate unit of 95 mol% or more in all repeating units. A twill woven fabric having a warp density of 128 yarns / 2.54 cm and a weft density of 58 yarns / 2.54 cm was woven using a PET multifilament (334 dtex / 96f). The twill fabric was scoured by a conventional method, and preset with a tenter at 190 ° C. for 30 seconds to obtain a twill fabric with an off-white basis weight of 210 g / m ² .

  Next, after impregnating the twill fabric into the treatment liquid shown in the following prescription 1, squeezing with a mangle at a drawing rate of 80% by mass, and without drying, steaming treatment at 100 ° C. with steam at normal pressure is performed as a polymerizing treatment. It went for 10 minutes. Subsequently, using an open soaper, soaping was performed for 5 minutes with warm water at a temperature of 80 ° C. to sufficiently remove unreacted substances from the twill fabric, followed by drying for 2 minutes to obtain a polyester fiber fabric of the present invention.

<Prescription 1>

: 50 g / l
(Manufactured by Shin-Nakamura Chemical Co., Ltd., n = 23 polyethylene glycol dimethacrylate in the formula)

: 20 g / l
(Shin Nakamura Chemical Co., Ltd., undecylenoxypolyethylene glycol methacrylate)
Methacrylic acid: 3 g / l
Epocros WS-500: 5g / l
(Nippon Shokubai, oxazoline group-containing polymer, solid content 40%)
Ammonium persulfate: 3 g / l

(Example 2)
A polyester fiber fabric of the present invention was obtained in the same manner as in Example 1 except that the treatment liquid shown in the following prescription 2 was used instead of the treatment liquid shown in the prescription 1.
<Prescription 2>

: 40 g / l
(New Nakamura Chemical Co., Ltd., n = 14 polyethylene glycol dimethacrylate in the formula)

: 30 g / l
(Shin Nakamura Chemical Co., Ltd., undecylenoxypolyethylene glycol methacrylate, n = 8 in the formula)
Methacrylic acid: 3 g / l
Epocros WS-700: 8g / l
(Nippon Shokubai Co., Ltd., oxazoline group-containing polymer, solid content 25%)
Ammonium persulfate: 3 g / l

(Example 3)
A warp yarn obtained by subjecting a PET multifilament (167 dtex / 48f) having an ethylene terephthalate unit of 95 mol% or more in all repeating units to false twisting, and a weft yarn having an ethylene terephthalate unit of 95 mol% or more in all repeating units. A twill fabric having a warp density of 100 yarns / 2.54 cm and a weft density of 46 yarns / 2.54 cm was woven using a polyester / cotton blend spun yarn # 34 with a blending ratio of 50% by mass of PET. The twill fabric was scoured by a normal method, pre-set at 190 ° C. for 30 seconds with a tenter to obtain a twill fabric with an off-white basis weight of 300 g / m ² , under the same conditions as in Example 1. A polyester fiber fabric was obtained.

Example 4
Jacquard structure jacquard with a 28 gauge, 30 inch round knitting machine using a false twisted PET multifilament (84 dtex / 72f) whose ethylene terephthalate unit is 95 mol% or more of all repeating units Knitted pattern knitted fabric. The knitted fabric was scoured by a normal method and pre-set at 190 ° C. for 30 seconds with a tenter to obtain a jacquard patterned knitted fabric with an off-white basis weight of 150 g / m ² . An inventive polyester fiber fabric was obtained.

(Example 5)
Except for performing the plasma treatment under the following condition 1 instead of the steam heating treatment with atmospheric pressure steam as the polymerizing treatment until the place where it is squeezed at 80% by mass with the mangle and dried as in Example 1. A polyester fiber fabric of the present invention was obtained under exactly the same conditions as in Example 1.
<Condition 1>
Gas type: Oxygen vacuum degree: 133 Pa
Frequency: 13.56MHz
High frequency power: 1.0 W / cm ²
Processing time: 60 seconds

(Comparative Example 1)
A fabric was obtained under exactly the same conditions as in Example 1 except that the formulation 1 of Example 1 was changed to the following formulation 3.

<Prescription 3>

: 70 g / l
(Manufactured by Shin-Nakamura Chemical Co., Ltd., n = 23 polyethylene glycol dimethacrylate in the formula)
Methacrylic acid: 3 g / l
Epocros WS-500: 5g / l
(Nippon Shokubai Co., Ltd., oxazoline group-containing polymer, solid content 40%)
Ammonium persulfate: 3 g / l

(Comparative Example 2)
A fabric was obtained under exactly the same conditions as in Example 1, except that Formula 1 in Example 1 was changed to Formula 4 below.

<Prescription 4>

: 70 g / l
(Shin Nakamura Chemical Co., Ltd., undecylenoxypolyethylene glycol methacrylate)
Methacrylic acid: 3 g / l
Epocros WS-500: 5g / l
(Nippon Shokubai Co., Ltd., oxazoline group-containing polymer, solid content 40%)
Ammonium persulfate: 3 g / l

(Comparative Example 3)
A fabric was obtained under exactly the same conditions as in Example 1 except that the formulation 1 of Example 1 was changed to the following formulation 5.

<Prescription 5>

: 50 g / l
(Manufactured by Shin-Nakamura Chemical Co., Ltd., n = 23 polyethylene glycol dimethacrylate in the formula)

: 20 g / l
(Shin Nakamura Chemical Co., Ltd., undecylenoxypolyethylene glycol methacrylate)
Ammonium persulfate: 3 g / l

(Comparative Example 4)
A fabric was obtained under exactly the same conditions as in Example 1 except that the formulation 1 of Example 1 was changed to the following formulation 6.

<Prescription 6>

: 50 g / l
(Manufactured by Shin-Nakamura Chemical Co., Ltd., n = 23 polyethylene glycol dimethacrylate in the formula)

: 20 g / l
(Shin Nakamura Chemical Co., Ltd., undecylenoxypolyethylene glycol methacrylate)
Methacrylic acid: 3 g / l
Ammonium persulfate: 3 g / l

(Comparative Example 5)
A fabric was obtained under exactly the same conditions as in Example 1 except that the formulation 1 of Example 1 was changed to the following formulation 7.

<Prescription 7>

: 50 g / l
(Manufactured by Shin-Nakamura Chemical Co., Ltd., n = 23 polyethylene glycol dimethacrylate in the formula)

: 20 g / l
(Shin Nakamura Chemical Co., Ltd., undecylenoxypolyethylene glycol methacrylate)
Epocros WS-500: 5g / l
(Nippon Shokubai Co., Ltd., oxazoline group-containing polymer, solid content 40%)
Ammonium persulfate: 3 g / l

(Comparative Example 6)
As the warp, a polyester / cotton blend spun yarn with 30 blends of 50% by mass of PET having an ethylene terephthalate unit of 95 mol% or more in all repeating units is used, and the ethylene terephthalate unit is 95 in all repeating units. Weaving a twill fabric with a warp density of 90 yarns / 2.54 cm and a weft density of 58 yarns / 2.54 cm using a polyester / cotton blend spun yarn with a blending ratio of 50% by mass or more and 30% yarn. did. The twill fabric was scoured by a normal method and pre-set at 190 ° C. for 30 seconds using a tenter to obtain a fabric under the same conditions as in Example 1 except that the twill fabric had an off-white basis weight of 280 g / m ^2. It was.

(Comparative Example 7)
A warp knitted fabric having a warp density of 112 yarns / 2.54 cm and a weft density of 36 yarns / 2.54 cm was obtained using a 20% yarn of 100% cotton spun as warp and a 10th yarn of 100% cotton spun as weft. Weaved. The twill fabric was scoured by a normal method and pre-set at 190 ° C. for 30 seconds using a tenter to obtain a fabric under the same conditions as in Example 1 except that the twill fabric had an off-white basis weight of 280 g / m ^2. It was.

  The fabric obtained in Examples 1 to 5 and Comparative Examples 1 to 7 after processing and the industrial washing / autoclave treatment was evaluated for deodorizing property, antibacterial property, antistatic property and texture. The evaluation results are shown in Table 1.

As is clear from Table 1, the polyester fiber fabrics of Examples 1 to 5 were all excellent in deodorizing property, antibacterial property, antistatic property and texture even after repeated industrial washing and autoclave treatment. . In particular, since (X _D / X _P ) was in the range of 0.001 to 0.3, the texture was particularly excellent. That is, the polyester fiber fabric of the present invention was an optimal material for clothing worn in food manufacturing sites, pharmaceutical manufacturing sites, medical institutions, precision device manufacturing sites, etc., where hygiene management is strict.

  On the other hand, in the polyester fiber fabrics of Comparative Examples 1 to 5, the compound having an oxazoline group is a bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol, undecylenic acid and / or a derivative of undecylenic acid, and a compound having a vinyl group. It was not added to the fabric together with the esterified product and vinyl carboxylic acid. Therefore, even if the industrial washing and the autoclave treatment are repeated, it has been impossible to obtain a fabric having good deodorizing properties, antibacterial properties, antistatic properties and texture.

  Specifically, the polyester fiber fabric of Comparative Example 1 was inferior in bactericidal properties after processing and after industrial washing and autoclave treatment because the polymer in the present invention did not contain the component (B).

  In the polyester fiber fabric of Comparative Example 2, since the polymer in the present invention did not contain the constituent component (A), the deodorizing property was somewhat inferior after processing, and the deodorizing property was further improved after industrial washing / autoclave treatment. It was inferior.

  The polyester fiber fabric of Comparative Example 3 is inferior in deodorizing property, antibacterial property, and antistatic property after industrial washing and autoclave treatment because the polymer in the present invention does not contain the components (C) and (D). It was a thing.

  The polyester fiber fabric of Comparative Example 4 was inferior in deodorizing property, antibacterial property and antistatic property after industrial washing and autoclave treatment because the polymer in the present invention did not contain the constituent component (D). .

  The polyester fiber fabric of Comparative Example 5 was inferior in deodorizing property, antibacterial property and antistatic property after industrial washing / autoclave treatment because the polymer in the present invention did not contain the constituent component (C). .

  The fabric of Comparative Example 6 was inferior in texture after processing and after industrial washing / autoclave treatment because the blending ratio of polyester fibers was less than 60%. And it was a little inferior in deodorizing property after industrial washing and an autoclave process.

  Since the fabric of Comparative Example 7 did not contain polyester fiber, it was inferior in texture after processing and after industrial washing and autoclave treatment. And it was a little inferior in deodorizing property after industrial washing and an autoclave process.

  The polyester fiber fabric of the present invention has little deterioration in antibacterial properties, antistatic properties, and deodorizing properties even when subjected to high-pressure steam sterilization by industrial washing and autoclave. In addition, the texture is excellent, and problems such as discoloration and a decrease in dyeing fastness do not occur. From these, the polyester fiber fabric of the present invention can be preferably used for uniform garments in food manufacturing sites, pharmaceutical manufacturing sites, medical institutions, precision equipment manufacturing sites, and the like.

Claims (6)

A fabric containing 60% by mass or more of polyester fiber,
A polyester fiber fabric characterized in that a polymer comprising the following components (A) to (D) as a constituent component is formed on the surface of the polyester fiber.
(A) Bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol (B) Esterified product of undecylenic acid and / or a derivative of undecylenic acid and a compound having a vinyl group (C) Vinyl carboxylic acid (D) Having an oxazoline group Compound Each adhesion rate (X _A , X _B , X _C and X _D ) (mass%) of each of the constituent components (A) to (D) with respect to the mass of the entire polyester fiber fabric is represented by the following formulas (a) to (d). The polyester fiber fabric according to claim 1, wherein:




However, X _P represents the deposition rate of the entire polymer as a constituent component relative to the total mass of the polyester fiber fabric and (A) ~ (D). The polyester fiber fabric according to claim 1 or 2, wherein the fabric after the industrial washing and then the autoclave treatment are repeated five times satisfies the following requirements (1) to (3): .
(1) The ammonia depletion rate in the deodorization test method (detector tube method) specified in the deodorant processed fiber product certification standard (JED301) of the Japan Fiber Evaluation Technology Council is 70% or more.
(2) The bactericidal activity value L of Klebsiella pneumoniae, Staphylococcus aureus, and MRSA by the bacterial liquid absorption method defined in JIS L 1902: 2008 is L> 0.
(3) The frictional voltage specified in JIS L 1094: 1997 in an environment of 20 ° C. and 40% RH is 1000 V or less. The step of applying the following (A) to (D) to a fabric containing 60% by mass or more of a polyester fiber;
A step of polymerizing the following (A) to (D) applied to the fabric:
And a step of removing the unreacted (A) to (D) which are not polymerized in the polymerizing step.
(A) Bifunctional unsaturated carboxylic acid ester containing polyalkylene glycol (B) Esterified product of undecylenic acid and / or a derivative of undecylenic acid and a compound having a vinyl group (C) Vinyl carboxylic acid (D) Having an oxazoline group Compound   The method for producing a polyester fiber fabric according to claim 4, wherein the polymerizing step is a steam heat treatment step or a low temperature plasma treatment step.   A garment comprising the polyester fiber fabric according to any one of claims 1 to 3, wherein the garment is worn at a food manufacturing site, a pharmaceutical manufacturing site, a medical site, or a precision device manufacturing site. .