JP2006070378A - Knitted cloth - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problems wherein a chalk mark appears and reduces the surface appearance quality when a knitted cloth easily causing the chalk mark is subjected to a resin finishing with inorganic particles having functionality. <P>SOLUTION: The usually observed chalk mark is reduced by attaching the inorganic particles and an acrylic resin having a silicone segment to the knitted fabric having ≥100 total of a warp density and a weft density. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  In the present invention, even if inorganic particles having various chemical compositions are attached to a knit fabric having a sum of the vertical density and the horizontal density of 100 or more by an acrylic resin having a silicone segment, a high-density knit fabric is resin-processed. It has the effect of reducing choke marks that are sometimes seen.

  Attempts to attach inorganic particles to the fiber have been made for a long time, and the fiber has functions such as deodorization and moisture absorption derived from the inorganic particle (see, for example, Patent Documents 1 to 5). However, since many inorganic particles tend to scatter visible light, if the inorganic particles are attached to a fiber that has a high density and a difference in gloss, the orientation of the attached inorganic particles changes due to slight friction. There was a problem that the friction part was whitened and easily became a chalk mark.

In particular, in a knit fabric where the sum of the warp density and the horizontal density is 100 or more, there is almost no unevenness on the surface of the fabric, so the difference in glossiness from the surroundings is easily noticeable, and if inorganic particles are adhered to the fabric by an adhesive resin, The occurrence was remarkable, and it was necessary to take measures to erase the chalk mark by crushing the dough after resin processing to increase the unevenness.
Japanese Patent Laid-Open No. 10-60778 JP-A-10-226962 JP 2001-279574 A JP 2002-153547 A JP 2002-180375 A

  In view of the background of such a conventional technique, the present invention has an effect of reducing chalk marks by attaching inorganic particles to the surface of a knit fabric on which chalk marks are likely to appear with an acrylic resin having silicone segments.

  The present invention employs the following means in order to solve such problems. That is, the knit fabric is characterized in that an inorganic resin and an acrylic resin having a silicone segment are attached to the surface of a knit fabric having a sum of the vertical density and the horizontal density of 100 or more.

When the inorganic particles having various chemical compositions having the functions of deodorizing and moisture absorption are attached to the knit fabric having the sum of the vertical density and the horizontal density of 100 or more by the acrylic resin having the silicone segment, the functional retention and the goodness are achieved. A knit fabric having both appearances can be obtained, and has the effect of reducing chalk marks seen when resin processing is performed on a dense knit fabric.

  The present invention has intensively studied the above problem, that is, the problem of occurrence of chalk marks when inorganic particles are attached to a knit fabric, and the surface of the knit fabric having a sum of the vertical density and the horizontal density of 100 or more has inorganic particles and The inventors have sought to solve this problem all at once by attaching an acrylic resin having a silicone segment at the same time.

    The vertical density and horizontal density in the present invention are generally called wells and courses, respectively, and the knit fabric having a sum of the vertical density and horizontal density of 100 or more has excellent fit, dimensional stability, and high strength. Often used in sports applications where these characteristics are required. The vertical density and the horizontal density as used herein refer to the number of yarn loops per 2.54 cm (pieces / 2.54 cm).

  In order to obtain a knitted fabric having a sum of warp density and horizontal density of 100 or more, it is preferable to use a yarn having a small bulk. The fineness of the yarn is preferably 80 dtex or less, more preferably 50 dtex or less, and the yarn is preferably a raw filament yarn that is not bulky. Various types of yarn cross sections, such as circles, triangles, and Y shapes, can be used.

  The knitting structure may be warp knitting or circular knitting, and knitting is preferably performed with a knitting machine of an appropriate gauge so that the sum of the warp density and the horizontal density becomes 100.

  Since the knitted fabric in the present invention requires both fit and strength, it is preferable that the knit fabric includes synthetic fibers and polyurethane fibers.

As synthetic fibers, polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate, cationic dyeable polyester fibers, polyamide fibers such as nylon 6 and nylon 66, and the like are preferably used. Among these, cationic dyeable polyester fibers and nylon 6 fibers are particularly preferred because the vivid colors required for sports applications can be easily obtained. Polyurethane fibers that are particularly preferably used are either polyester polyurethane or polyether polyurethane. Fiber is also preferably used. For knit fabrics for swimsuits, polyurethane fibers with improved chlorine resistance are also preferably used.

The knit fabric in the present invention preferably has an elongation rate of 10% or more, more preferably 20% or more, and an elongation recovery rate of 70% or more, more preferably 80% or more. The elongation rate and the elongation recovery rate are both values measured by the method described later.
If you use knit fabric that is knitted at high density and has less irregularities on the fiber surface and is easy to expand and contract, you can make clothing that is in close contact with the body, so sportswear, especially competing for time, swimming, land, skiing, It is often used for such wear. If the texture of the dough is small and the surface is smooth, the frictional resistance of water and air can be reduced, which effectively reduces the time.

  When inorganic particles having functionality are attached to a knit fabric made in accordance with such a purpose, the smoothness of the surface of the fabric becomes wrinkled and chalk marks are likely to be generated. However, the present invention solves this problem.

Inorganic particles in the present invention are at least one metal oxide selected from Li, B, Na, Mg, Al, Si, K, Ca, Ti, Mn, Fe, Zn, Ag, and W, or composite oxidation It is preferable that it is a thing. Depending on the combination and crystal structure of these elements, inorganic particles having various functions such as deodorization and moisture absorption can be obtained.
When attaching inorganic particles to the knitted fabric, it is preferable to use inorganic particles having the smallest possible diameter in consideration of texture and appearance change, and inorganic particles having an average particle diameter of 10 μm or less are preferably used.
Among inorganic particles, oxides or composite oxides containing at least Ti are preferable because many of them exhibit photocatalytic activity. Titanium oxide type photocatalyst is a material that has a wide range of applications and high attention because it exhibits various functions such as deodorizing, antibacterial, and antifouling. Among photocatalysts, composite oxides of Ti and Si are particularly preferably used because they have little embrittlement to fibers and are less harmful.

  In the present invention, an acrylic resin having a silicone segment is employed in order to prevent chalk marks generated by attaching inorganic particles to the knit fabric.

Chalk marks are a phenomenon seen in resin-treated fabrics, and it is said that if the surface of the fabric is scratched with a nail, the resin partially peels off and a difference in gloss is created between the parts that are not peeled off. . In the high-density knit fabric as in the present invention, since there is almost no unevenness on the surface of the fabric, the difference in glossiness from the surroundings is easily noticeable, and chalk marks are easily generated.
In order to prevent the occurrence of chalk marks, a method of increasing the unevenness on the surface of the fabric by loosening the knit fabric after the resin processing is sometimes used, but the number of processing steps increases, leading to an increase in cost. On the other hand, when the acrylic resin having the silicone segment of the present invention is combined with inorganic particles, there is an effect that chalk marks are hardly generated even when the resin processing is performed on the knit fabric.

  The silicone segment may be in the main chain part or side chain part of the molecular chain of the acrylic resin, but it is preferable to use the silicone segment in the side chain because it is easier to synthesize and has a higher effect of reducing chalk marks. It is done. If the acrylic resin has a strong organic part and a strong inorganic part, it has a high affinity for the knitted fabric made of organic matter and the inorganic particles, making them strongly bonded to each other and making it difficult for the resin to peel off.

  In addition, since the mixture of the acrylic resin having the silicone segment and the inorganic particles has a high chemical affinity, it becomes a uniform dispersion and adheres thinly over the entire knitted fabric, so that it is difficult to peel off even by scratching the nails.

Specific examples of the acrylic resin having a silicone segment include a polymer obtained by copolymerizing a (meth) acrylic acid monomer and a (meth) acrylic acid monomer having a silicone segment. The (meth) acrylic acid monomer having a silicone segment takes the form in which the terminal hydroxyalkyl-modified silicone is ester-bonded to (meth) acrylic acid, and the Si (CH ₃ ) ₂ O repeating unit of the silicone is 40 to 80 This is preferable because the effect of reducing chalk marks is high.
As other copolymerization components, polymerizable carboxylic acids such as acrylic acid and methacrylic acid, carboxylate salts, and carboxylic acid esters are preferably used. The ester side of the polymerizable carboxylic acid ester is preferably alkyl, hydroxyalkyl, aminoalkyl, carboxyalkyl or the like. When these monomers are copolymerized, a carboxyl group, an amino group and a hydroxyl group are introduced at the end of the side chain. The presence of these functions at the end of the side chain is desirable because the structure is densified and the strength of the resin is increased in combination with a crosslinking agent.

  It is desirable that the (meth) acrylic acid monomer having a silicone segment accounts for 5 to 50 wt% of the copolymer. When the content is less than 5%, the properties of the silicone group do not appear in the copolymer, and when the content is more than 50%, the adhesiveness to the fiber is deteriorated.

  The method for adhering the acrylic resin having inorganic particles and silicone segments to the knit fabric is not particularly limited, but in the present invention, the acrylic resin having inorganic particles and silicone segments is made into an aqueous solution and applied to the knit fabric, followed by heat treatment. Is preferred. It is preferable that the inorganic particles and the acrylic resin are preliminarily made into an aqueous dispersion because they are easily mixed and uniformly mixed. For the preparation of the aqueous dispersion, an emulsifier, a dispersant, a thickener and the like may be used. Furthermore, it is also preferable to add a crosslinking agent in order to improve the adhesiveness of the resin, or to add an organic substance such as an antibacterial agent in order to provide functionality.

  Examples of the method for applying the aqueous solution to the fiber include the following.

Pad-cure method in which fiber is impregnated with aqueous solution and subjected to dry heat treatment with mangle roll, pad-steam method in which dry heat treatment is replaced with wet heat treatment, in-bath method in which heat treatment is performed while fiber is impregnated in aqueous solution, aqueous solution in fiber There are a spray method in which a heat treatment is carried out by spraying on a coating, a coating method in which a thickener is added to the aqueous solution to increase the viscosity, and a heat treatment is carried out by applying with a knife coater, gravure coater, textile printing or the like. Of these, the pad-cure method is preferably performed because it can be easily performed.
In this way, when inorganic particles with various chemical compositions are attached to knitted fabrics together with acrylic resin having silicone segments with excellent adhesion to both organic and inorganic substances, the generation of chalk marks can be eliminated or reduced. You can do it.

  When sportswear, clothing, and the like are made using this knit fabric, clothing that retains the functionality of inorganic particles and suppresses the occurrence of chalk marks can be obtained. Examples of sportswear include swimming swimwear, land wear, ski wear, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the following method was used as various quality evaluation methods in an Example.

<Home laundry>
Using an automatic inversion swirl type electric washing machine VH-3410 (manufactured by Toshiba Corporation), commercially available detergent (Attack Compact, manufactured by Kao Corporation) 0.1%, temperature 40 ± 2 ° C., bath ratio 1:30 5 Washing by strong inversion for a minute and then rinsing for 2 minutes while draining and overflowing is repeated twice, and this is defined as one home wash (abbreviated as HL-1).

<Chalk mark generation>
Place the knitted fabric horizontally on the desk, lightly touch the nail with the palm facing up, move the hand without applying force about 20 cm, and check if the place where the nail hits remains a white line. Make a decision.

○: No nail mark left △: Nail mark left thin ×: Nail mark left white <Deodorization measurement>
The deodorization rate for ammonia gas having an unpleasant odor was measured by the following method. It shows that a deodorizing effect is so high that a deodorizing rate is large.

A 500-ml container containing 3 g of sample was charged with ammonia gas (NH ₃ ) having a concentration of 300 ppm and left for 30 minutes after sealing, and the ammonia gas concentration was measured. The ammonia deodorization rate is obtained from the initial concentration (300 ppm) and the concentration after 30 minutes (Xppm) by the following formula. A gas detector tube was used to measure the gas concentration.

Deodorization rate (%) = (1- (gas detector tube measured concentration) / (initial concentration)) × 100
<Antimicrobial measurement>
The difference in the number of Staphylococcus aureus bacteria on clothes was measured by the following method based on the JIS L1902 quantitative test method.

  Staphylococcus aureus was poured into a sterilized test cloth, the number of viable bacteria after 18 hours of culture was counted, the number of bacteria relative to the number of inoculated bacteria was determined, and the following criteria were followed.

  Under the condition of log (B / A)> 1.5, log (B / C) was defined as the difference in the number of bacteria increase / decrease, and 2.2 or more was determined as acceptable.

  However, A represents the number of bacteria dispersed and recovered immediately after inoculation of the unprocessed product, B represents the number of bacteria dispersed and recovered after 18 hours of incubation of the unprocessed product, and C represents the number of bacteria dispersed and recovered after 18 hours of incubation of the processed product.

<Hygroscopic measurement>
The ΔMR value, which is an index representing the degree of absorption of stuffiness in the clothing when exercising after wearing the clothing, was measured by the following method. In general, ΔMR of polyester is 0%, 2% of nylon, 4% of cotton, and 6% of wool. The higher this value, the less the inside of the clothes becomes dull and the comfortable wearing feeling is obtained.

The moisture absorption rate (%) when the sample is left for 24 hours in an atmosphere of 20 ° C. and 65% RH (assuming clothes in the clothes dance before wearing) from the completely dry state is MR ₁ , and 30 ° C. × 90 from the completely dry state. % RH atmosphere moisture absorption when left for 24 hours (assuming the clothes motion state) (%) as a MR _2, and ΔMR those taking the difference.

ΔMR (%) = MR ₂ −MR ₁
<Elongation rate measurement>
Measured by JIS L 1018 extension force and elongation (cut strip method).

<Measurement of elongation recovery rate>
Measured by JIS L 1018 stretch modulus A method (constant stretch method).

<Test knit fabric>
The following knitted fabrics, which had been dyed by a normal method, were used in Examples and Comparative Examples.
A. Polyester / Polyurethane knitted fabric Tricot knitted fabric (weal density 62.5 / inch) composed of cationic dyeable polyester fiber filament yarn (50 dtex, 24 filament) and urethane fiber ("Lycra" (registered trademark) T-152B) A course density of 100 / inch) was used. The knitting rate of the urethane fiber was 16%.

The stretch rate of this knitted fabric was 58%, and the stretch recovery rate was 85%.
B. Nylon / polyurethane knitted fabric Tricot knitted fabric (weil density 32 pcs / inch, course) consisting of polyamide fiber nylon 6 filament (44 dtex, 10 filament) and 44 dtex urethane fiber ("Lycra" (registered trademark) T-152B) A density of 95 / inch) was used. The knitting rate of the urethane fiber was 21%.

  The stretch rate of this knitted fabric was 93%, and the stretch recovery rate was 88%.

  Examples and comparative examples are given below.

<Example 1>
The acrylic resin having a silicone segment was prepared as follows.

  A solution obtained by mixing 35 parts by weight of 2-hydroxybutyl methacrylate, 55 parts by weight of butyl acrylate, and 10 parts by weight of an organopolysiloxane compound having methacryloxy at the end with 30 parts by weight of ion-exchanged water and 10 parts by weight of a nonionic surfactant. In addition, the mixture was emulsified with a homomixer, and 260 parts by weight of ion exchange water and 6 parts by weight of an anionic surfactant were added and stirred to obtain an emulsion. While stirring this in an inert gas atmosphere, the temperature was raised to 60 ° C., a solution in which 0.4 parts by weight of ammonium peroxodisulfate was dissolved in 30 parts by weight of ion-exchanged water was added, and the solution temperature was kept at 60 to 70 ° C. Polymerization was carried out for 4 hours to obtain a (meth) acrylic copolymer having a silicone group and a hydroxyl group in the side chain. Water and a dispersing agent were added to this copolymer aqueous solution to make an aqueous dispersion having a solid content of 20%.

As the inorganic particles, a composite oxide of Ti and Si (Ti: Si = 85: 15) having a primary particle diameter of 7 nm and a specific surface area of 150 m ² / g was used, which was made into a 21% aqueous dispersion. This composite oxide works as a photocatalyst under ultraviolet light and visible light.

  As an antibacterial agent, a 19% aqueous dispersion of 2-pyridylthiol-1-oxide zinc was used.

  The test fiber A is immersed in an aqueous solution having the following composition, drawn with a mangle roll so that the pickup becomes 80% by weight, dried at 130 ° C. for 2 minutes, heat treated at 180 ° C. for 1 minute, and a composite of Ti and Si on the fiber surface. A knit fabric with oxides was obtained.

Aqueous solution composition: 3.0 parts by weight of synthesized (meth) acrylic copolymer
1.0 weight part of aqueous dispersion of complex oxide of Ti and Si
0.5 parts by weight of an aqueous dispersion of 2-pyridylthiol-1-oxide zinc
Carbodiimide crosslinking agent (effective 40%) 0.2 parts by weight
95.3 parts by weight of water Table 1 shows the results of measuring the occurrence of chalk marks, deodorization and antibacterial properties of this knit fabric.

<Example 2>
The acrylic resin having a silicone segment was prepared as follows.

  2-aminobutyl methacrylate 5 parts by weight, acrylic acid 15 parts by weight, butyl acrylate 60 parts by weight, methacryloxy-terminated organopolysiloxane compound 20 parts by weight, ion-exchanged water 30 parts by weight and nonionic surfactant 10 parts by weight The mixture was mixed and emulsified with a homomixer, and 260 parts by weight of ion exchange water and 6 parts by weight of a nonionic surfactant were added and stirred to obtain an emulsion. The emulsion was polymerized in the same manner as in Example 1 to obtain a (meth) acrylic copolymer having a silicone group, a carboxyl group, and an amino group in the side chain. Water and a dispersing agent were added to this copolymer aqueous solution to make an aqueous dispersion having a solid content of 20%.

As the inorganic particles, TiO ₂ having an average particle diameter of 0.6 μm and a specific surface area of 320 m ² / g was used, which was made into a 35% aqueous dispersion. This TiO ₂ acts as a photocatalyst under ultraviolet light.

The test fiber B is dipped in an aqueous solution having the following composition, drawn with a mangle roll so as to be 80% by weight, dried at 120 ° C. for 2 minutes, heat treated at 170 ° C. for 1 minute, and knit having TiO ₂ on the fiber surface I got the dough.

Aqueous solution composition: 1.0 part by weight of synthesized (meth) acrylic copolymer
TiO ₂ aqueous dispersion 1.0 part by weight
98.0 parts by weight of water Table 1 shows the results of measuring the occurrence of chalk marks and the deodorizing property of this knit fabric.

<Example 3>
The acrylic resin having a silicone segment was prepared as follows.

  2-hydroxypropyl acrylate 5 parts by weight, methacryloyloxyethyl succinic acid 5 parts by weight, butyl acrylate 70 parts by weight, methyl methacrylate 10 parts by weight, methacryloxy-terminated organopolysiloxane compound 10 parts by weight, ion-exchanged water 30 parts by weight And 10 parts by weight of a nonionic surfactant were added and emulsified with a homomixer. 260 parts by weight of ion-exchanged water and 6 parts by weight of an anionic surfactant were added and stirred to obtain an emulsion. This emulsion was polymerized in the same manner as in Example 1 to obtain a (meth) acrylic copolymer having a silicone group, a carboxyl group, and a hydroxyl group in the side chain. Water and a dispersing agent were added to this copolymer aqueous solution to make an aqueous dispersion having a solid content of 20%.

As the inorganic particles, SiO ₂ having a particle size of 2.7 μm and a specific surface area of 500 m ² / g was used, which was made into a 20% aqueous dispersion.

The test fiber A is immersed in an aqueous solution having the following composition, drawn with a mangle roll so as to be 80% by weight of pickup, dried at 130 ° C. for 2 minutes, heat treated at 170 ° C. for 1 minute, and knit having SiO ₂ on the fiber surface. I got the dough.

Aqueous solution composition: 10 parts by weight of synthesized (meth) acrylic copolymer
30 parts by weight of an aqueous dispersion of SiO ₂
60 parts by weight of water Table 1 shows the results of measuring chalk mark generation and hygroscopicity of this knit fabric.

<Comparative Example 1>
Using the inorganic particle dispersion used in Example 1, an aqueous solution having the following composition was prepared, and the test fiber A was immersed in the same treatment as in Example 1, and the fiber surface was combined with Ti and Si. A knit fabric having a product was obtained.

Aqueous solution composition: aqueous dispersion of composite oxide of Ti and Si 1.0 part by weight
0.5 parts by weight of an aqueous dispersion of 2-pyridylthiol-1-oxide zinc
98.5 parts by weight of water Table 1 shows the results of measuring the chalk mark generation, deodorization and antibacterial properties of this knit fabric.

<Comparative example 2>
Create an aqueous solution having the following composition using inorganic particles dispersion used in Example 2, was immersed test fiber B to perform the same treatment as in Example 2, knit fabric having a TiO ₂ surface of the fiber Got.

Aqueous solution composition: TiO ₂ aqueous dispersion 1.0 part by weight
99.0 parts by weight of water Table 1 shows the results of measuring the occurrence of chalk marks and deodorizing properties of this knit fabric.

<Comparative Example 3>
Using the inorganic particle dispersion used in Example 3, an aqueous solution having the following composition was prepared, and the test fiber A was immersed in the same treatment as in Example 3, and the knit fabric having SiO ₂ on the fiber surface. Got.

Aqueous solution composition: 30 weight parts of aqueous dispersion of SiO ₂
70 parts by weight of water Table 1 shows the results of measuring the occurrence of chalk marks and the hygroscopicity of this knit fabric.

<Comparative example 4>
Add 35 parts by weight of methyl methacrylate, 25 parts by weight of 2-hydroxybutyl methacrylate, 20 parts by weight of butyl acrylate, and 20 parts by weight of acrylic acid to a mixture of 30 parts by weight of ion-exchanged water and 10 parts by weight of a nonionic surfactant. The mixture was emulsified with a homomixer, 260 parts by weight of ion exchange water and 6 parts by weight of an anionic surfactant were added and stirred to obtain an emulsion. This emulsion was polymerized in the same manner as in Example 1 to obtain a (meth) acrylic copolymer having a hydroxyl group and a carboxyl group in the side chain. Water and a dispersing agent were added to this copolymer aqueous solution to make an aqueous dispersion having a solid content of 20%.

The test fiber A is immersed in an aqueous solution having the following composition, drawn with a mangle roll so as to be 80% by weight of pickup, dried at 130 ° C. for 2 minutes, heat treated at 170 ° C. for 1 minute, and knit having SiO ₂ on the fiber surface. I got the dough.

Aqueous solution composition: 10 parts by weight of synthesized (meth) acrylic copolymer
SiO ₂ aqueous dispersion (same as Example 3) 30 parts by weight
60 parts by weight of water Table 1 shows the results of measuring chalk mark generation and hygroscopicity of this knit fabric.

Claims (9)

A knitted fabric characterized in that inorganic particles and an acrylic resin having a silicone segment are attached to the surface of a knitted fabric having a sum of warp density and horizontal density of 100 or more. The knitted fabric according to claim 1, wherein the knitted fabric is knitted with a yarn having a fineness of 80 dtex or less. The knitted fabric according to claim 1 or 2, wherein the knitted fabric includes a synthetic fiber and a polyurethane fiber. The knit fabric according to any one of claims 1 to 3, wherein the knit fabric has an elongation rate of 10% or more and an elongation recovery rate of 80% or more. The inorganic particles are at least one metal oxide or composite oxide selected from Li, B, Na, Mg, Al, Si, K, Ca, Ti, Mn, Fe, Zn, Ag, and W. The knit fabric according to any one of claims 1 to 4, wherein the knit fabric is provided. The knit fabric according to any one of claims 1 to 5, wherein the average particle size of the inorganic particles is 10 µm or less. The knit fabric according to claim 5, wherein the inorganic particles are an oxide or composite oxide containing at least Ti. The knit fabric according to any one of claims 1 to 7, wherein the acrylic resin has a silicone segment in a side chain. The knit fabric according to any one of claims 1 to 8, wherein the acrylic resin has at least one of a carboxyl group, an amino group, and a hydroxyl group at a side chain end.