JP2878392B2 - Vehicle skin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a seat cover in a vehicle interior, a door lining, a ceiling material,
The present invention relates to a vehicular skin material having a function of removing a bad smell in a vehicle cabin by being used as a floor carpet or the like.

[Conventional technology]

In recent years, as the performance of passenger cars, such as driving performance, safety, and comfort, has become more complete, interest in vehicle interior odor, which has a significant effect on passenger comfort, has increased, and odors in the vehicle interior atmosphere have been reduced. More effective measures to meet such demands have been required. The bad smell here is, for example, a smell such as a cigarette smell, a sweat smell, a musty smell, an exhaust gas smell, a solvent smell or a plasticizer smell generated from a resin interior material or an adhesive.

Conventionally, as a countermeasure to prevent these odors, there is a method of masking or sensually neutralizing the odor using an aromatic agent, and a method of spraying or volatilizing a liquid deodorant. That effect is not satisfactory. In addition, air purifiers have also been used to remove odors, but small ones have not been able to provide sufficient effects. , Power consumption is also large. Further, no effect can be expected while the air purification device is not operating, such as in a parked vehicle interior.

On the other hand, as a material having a deodorizing property, a sheet material to which a hydrous silicon magnesium clay mineral is added is known (JP-A-62-282926, JP-A-62-282927). As a deodorizing member having improved deodorizing performance, there is a member using a combination of sepiolite and activated carbon (JP-A-63-283649). Furthermore, while improving these deodorizing performance, as a skin material for vehicles having an antistatic effect,
A vehicle skin material in which a hydrated magnesium silicate clay mineral and activated carbon are added to a back coating layer for improving the bonding strength between yarns constituting a fabric is considered. This vehicle skin material can be expected to have excellent deodorizing performance due to the adsorption properties of hydrated magnesium silicate clay minerals and the combined action with activated carbon, etc., but when the skin material has a complex structure such as jacquard moquette However, there is a disadvantage that the pile yarn is insufficiently fixed due to insufficient permeation into the fabric, and the strength as a vehicle skin material cannot be sufficiently obtained. Therefore, conventionally, anionic surfactants such as sodium alkyl sulfate, higher alcohol sulfate, sodium alkyl sulfonate, sodium alkyl glycolate, sodium alkyl benzene sulfonate, dodecyl alcohol and the like to impart permeability to the back coating agent. Nonionic surfactants such as condensates of alcohol and ethylene oxide, ethylene oxide condensates of alkylphenols, and alcohols such as isopropyl alcohol have been added as penetrants to back coating agents. However, when such a penetrant is added to a back coating agent having deodorizing performance, these penetrants are not only adsorbed on the surface of the deodorant but have no effect of increasing the permeability, but also have a remarkable ability to adsorb odor components. It will be hindered. Alternatively, there has been a problem that the penetrant itself volatilizes and becomes a source of odor.
In addition, many of these substances have a high foaming property and foam during production of the back coating agent, making it difficult to prepare,
This has caused the water resistance of the coating layer to be significantly reduced.

[Object of the invention]

Accordingly, an object of the present invention is to provide a vehicular skin material which is excellent in mechanical properties such as abrasion resistance and seam fatigue resistance, can effectively remove odor in a vehicle interior, and can maintain the effect for a long period of time. Is to provide.

[Configuration of the invention]

The present inventors have conducted intensive studies in order to solve the above-mentioned conventional problems, and as a result of repeating various systematic experiments, the fabric and the particles applied to the fabric at 15 to 135 g per square meter are fused together. A polymer latex layer layered between the yarns constituting the fabric and between the yarns and on the surface of the fabric; 5 to 160 parts by weight based on 100 parts by weight of the polymer latex particles in the polymer latex layer Dispersed and fixed hydrous magnesium silicate clay mineral, In the polymer latex layer, activated carbon dispersed and fixed to be 50 to 180 parts by weight together with the clay mineral with respect to 100 parts by weight of the polymer latex particles. 1-3 parts per 100 parts by weight of the polymer latex particles
A vehicle skin material comprising 0 parts by weight of a penetrant and having a structure in which the thread and the polymer latex particles are uniformly adhered by the penetrant has been completed.

Polymer latex includes synthetic resin latex and rubber latex. The polymer latex is an emulsion composed of resin colloid particles as a dispersoid and water or the like as a dispersion medium. As it dries, the particles fuse together and effectively act as a binder.

The hydrous magnesium silicate clay mineral (hereinafter, referred to as a clay mineral) is a clay mineral having hydrous magnesium silicate as a produced component and having a highly reactive hydroxyl group on its surface. This clay mineral is composed of fibers having a diameter of about 0.005 to 0.6 μm, and has pores (channels) having a rectangular cross section of about 1 to 0.6 nm in parallel with the fibers. It has the property of adsorbing bad smell and water vapor. In addition, in the clay mineral, magnesium or silicon may be partially replaced by aluminum, iron, nickel, sodium, or the like.

As activated carbon, those in which micropores having pores with a radius of 20 angstroms or less are developed are effective. Specifically, those obtained by using a coconut shell as a raw material and activated by a gas activation method are suitable.

These clay minerals and activated carbon are used in the form of granules or powder, and constitute a back coating agent by being dispersed in a polymer latex. The particle diameter of these clay minerals and activated carbon is not more than the same size as the thickness of the fabric when attached to the fabric, specifically, it may be about 3 mm or less, but if it is too large, the texture as the fabric deteriorates. When the size is too small, the clay mineral and the activated carbon are buried in the polymer lux, and the deodorizing property is reduced. Specifically, it is desirable that the particle size is in the range of 1 to 200 μm.

As a penetrant added to enhance the permeability of the back coating agent to the fabric, a penetrant which does not adsorb to the adsorbent and lowers its adsorbing ability and has low volatility is preferred. Therefore, those having a large molecular weight are suitable. The penetrant is added to the back coating agent in an amount of 1 to 30 parts by weight based on 100 parts by weight of the solid content of the polymer latex. 50 to 180 parts by weight of the clay mineral and the activated carbon are added as other additives. If the sum of the amounts of the clay mineral and the activated carbon is less than 50 parts by weight, sufficient deodorizing performance cannot be expected, and if it exceeds 180 parts by weight, the polymer latex becomes relatively short, and the inherent properties of the back coating agent, that is, the dimensions of the fabric This is because improvement in accuracy, prevention of fraying and opening of the yarn, improvement of the strength of the fabric, retention of the flame retardant, and the like become insufficient.

The application amount of the back coating agent is in the range of 50 to 200 g in terms of solid content per square meter of the fabric, and if it is less than 50 g / m ² , the amount of activated carbon and clay minerals is small, so the deodorizing performance becomes insufficient, and 200 g / m ² If the coating is applied in excess of this, the rigidity of the fabric becomes too large and the texture is impaired.

[Function of the invention]

The polymer latex used in the present invention is a main element of the back coating agent, and by combining the fibers constituting the fabric with the fibers, improves the dimensional accuracy of the fabric, prevents the fibers from fraying, and , Which retains additives such as hydrated magnesium silicate clay minerals, activated carbon, and flame retardants, and acts as a binder for fixing to fabric.

The polymer latex itself has almost no deodorizing property, but forms a porous film without covering the clay mineral and the activated carbon when the back coating agent is applied to the fabric and dried. Therefore, it is considered that according to the configuration of the present invention, the excellent deodorizing performance of the clay mineral and the activated carbon can be sufficiently exhibited without hindering the deodorizing performance.

The clay mineral, which is one of the main components of the back coating agent of the present invention, is an aggregate of fibers having a diameter of about 0.005 to 0.6 μm, and has a narrow cross section having a rectangular shape of about 1 × 0.6 nm parallel to the fibers. There are holes. Therefore, the specific surface area of clay mineral is 15
It is 0 to 400 m ₂ / g, and there are many pores around 1 nm due to the crystal structure and many pores around 20 nm probably due to the fiber diameter.
This large specific surface area and pores make ammonia, amines,
It is considered that it functions as a site for receiving malodorous substances such as fatty acids and expresses deodorizing properties.

On the other hand, activated carbon contained as the main component of the back coating agent along with the clay mineral has a specific surface area of 500 to 1300 m ² / g
And mainly has pores in the vicinity of 10 nm. And, due to the difference between the specific surface area and the size of the pores, the clay mineral exhibits different adsorption characteristics from the above clay minerals, such as sulfide-based odors such as hydrogen sulfide, methyl mercaptan, methyl sulfide, and methyl disulfide, and toluene and styrene. It is thought that it functions as a site for accepting hydrocarbon odors such as odors and exhibits deodorization.

 The action of activated carbon will be described in more detail.

Activated carbon is amorphous carbon in crystal structure. In its structure, the basic crystallites of graphite are irregularly arranged,
There are a myriad of pores formed after the crystallites that have been activated by a gas or a chemical, and are formed after crystallites that have disappeared or partially disappeared.

The pores are classified into three types: macropores, transitional pores, and micropores. Macropores have a radius of 20 ~
It is larger than 1000 Angstroms and its volume is
0.2~0.5ml / g, the surface area is 0.5~2m ² / g. The transitional pore has a radius of 20 to 1000 angstroms, a volume of 0.02 to 1.0 ml / g, and a surface area of 1 to 800 m ² / g. Micropores intended follows radius 20 Å, volume 0.25~0.9m ² / g, the surface area is 500~1400m ² / g.

Since most of the odor gas molecules in the atmosphere can enter the micropores, the micropores contribute most to the adsorption capacity. Transient pores have a large effect on the diffusion rate of adsorbate in the pores, and capture gas by capillary condensation in regions where the relative pressure of the adsorbate is high. Macropores have little effect on gas adsorption. These pore structures vary depending on the raw materials and activation conditions.

When a high molecular weight surfactant with a molecular weight of 10,000 or more is used, the large size of the molecule does not penetrate into the pores of the clay mineral and the activated carbon, so it may occupy an adsorption site that works for odor components. There is no evaporation. Further, it is chemically stable and has little interaction with odorous substances.

Further, the penetrating agent acts so that the back coating agent penetrates well into the skin material structure, and the pile yarn and the ground yarn and the ground yarn are securely fixed to each other. As a result, mechanical properties such as wear resistance and seam fatigue resistance of the vehicle skin material are improved. By using a penetrant having a large molecular weight, it is not adsorbed by the adsorbent in the back coating agent, and the adsorbing ability of the back coating agent is not reduced. Such a penetrant has low volatility and does not volatilize and become a source of odor, and does not have too strong an action as a surfactant to enhance the foaming property too much.

〔The invention's effect〕

The skin agent of the present invention can remove complex odors composed of various malodorous components by the action of the clay mineral and the activated carbon contained in the back coating agent. Further, the skin material for vehicles of the present invention has a high mechanical strength because the back coating material penetrates well into the fabric structure by the action of the penetrating material to securely fix the pile yarn and the ground yarn and the ground yarn to each other. It has excellent abrasion resistance.

[Other inventions]

Examples of the polymer latex include polyvinyl chloride latex, polyvinylidene chloride latex, polyurethane latex, polyacrylate latex, polyvinyl acetate latex, polyacrylonitrile latex, and modified products and copolymers thereof. Specific examples of the rubber latex include natural rubber, styrene butadiene rubber, acrylonitrile rubber, acrylonitrile butadiene rubber, isoprene isobutylene rubber, polyisobutylene, polybutadiene, polyisoprene, polychloroprene, and polyethylene propylene.

Examples of the hydrous magnesium silicate clay mineral include sepiolite, sirotile, laphrinite, falcondite, and palygorskite. This is what is commonly called mountain cork, mountain leather, mountain wood, sepiolite, and attapulgite. These may be calcined in a temperature range of 400 to 800 ° C. Also, this clay mineral is powdered,
It may be used in any form of granular or plate, but it is preferable that the fine particles are ground to the extent that the pores of the clay mineral remain, and the aggregate of microcrystals with a length of 10 μm or less and an aspect ratio of 100 or less It is preferred that The pulverization at this time is performed by wet pulverization or dry pulverization using a mixer, a ball mill, a vibration mill, a hammer mill, a pin mill, a beater or the like.

As a raw material of activated carbon, any substance which is carbonized by heating is applicable, but raw materials which can be stably supplied in large quantities at low cost include sawdust, charcoal, coconut shell, lignite, peat, coal, pulp waste liquid and the like. The activation method includes a chemical activation method and a gas activation method. The chemicals used in the chemical activation method include chemicals that have a dehydrating and eroding effect on the raw materials, specifically zinc chloride,
Phosphoric acid, sulfuric acid, calcium chloride, sodium hydroxide, etc.,
An oxidizing chemical, specifically, potassium dichromate, potassium permanganate, or the like is used. In the gas activation method,
First, the raw material is carbonized, and then activated by contact with a gas at a high temperature. As the gas to be brought into contact, steam, carbon dioxide gas, air, a mixed gas thereof, or the like is used. Any of the thus obtained activated carbons can be suitably used in the present invention.

In order to stably disperse the clay mineral and activated carbon in the polymer latex, a dispersant may be added in an amount of 2 to 20 parts by weight based on 100 parts by weight of the polymer latex particles. When the amount of the dispersant is less than 2 parts by weight, the stability of the back coating agent becomes insufficient, and when it exceeds 20 parts by weight, the water resistance and weather resistance of the back coating agent deteriorate. As the dispersant, a polymer surfactant having a molecular weight of 10,000 or more is preferably used. Low-molecular surfactants penetrate the pores of clay minerals or activated carbon to reduce the deodorizing function, low-molecular surfactants themselves vaporize and become odor sources, or exist in the atmosphere It is not desirable because it may generate a bad smell due to a chemical reaction with the substance. When a high molecular weight surfactant with a molecular weight of 10,000 or more is used, since the size of the molecule is large, it does not penetrate into the pores of the clay mineral and the activated carbon, so it may occupy an adsorption site that works for odor components. There is no evaporation.
Further, it is chemically stable and has little interaction with odorous substances.
Examples of the polymer surfactant include a synthetic polymer and a cellulose derivative. Examples of the synthetic polymer include polyphosphates such as sodium tripolyphosphate, sodium tetraphosphate, and sodium hexametaphosphate, polyvinyl alcohol, and sodium polyacrylate. Polyvinylpyrrolidone, styrene-maleic acid copolymer and the like can be mentioned. Examples of the cellulose derivative include methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like.

Further, as the polyether surfactant having a molecular weight of 2,000 or more as the penetrant of the present invention, desirably, a nonionic polymer surfactant having a molecular weight of 2,000 or more in which the lipophilic group is polypropylene glycol and the hydrophilic group is polyethylene glycol It is better to use

It is not adsorbed on hydrated magnesium silicate clay minerals or activated carbon because of its high molecular weight, and because of its low volatility, it can be added to the back coating agent to increase the permeability without reducing the adsorption capacity of odor components be able to.

The fabric to which the back coating agent is applied in the present invention is a woven fabric, a knitted fabric, or a nonwoven fabric composed of natural fibers, chemical fibers or both fibers, and specifically, woven fabrics, moquettes, towel fabrics, tricots, double raschels, Circular knitting,
Needle punch and the like can be mentioned. The fibers referred to here include natural fibers such as cotton, hemp, silk, and wool, or rayon, acetate, protein fibers, chlorinated rubber, polyamide,
Examples include chemical fibers such as polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyester, polyethylene, polypropylene, polyurethane, polyvinylidene cyanide, and polyfluoroethylene. Further, a fabric composed of both of these fibers may be used.

Furthermore, in the present invention, since the activated carbon contained in the back coating agent has electrical conductivity, by combining this with a conductive cloth, it is possible to simultaneously exhibit a deodorizing function and a static electricity removing function. It is. The function of removing static electricity is considered as follows.

The static electricity generated by the friction between the clothing and the skin material for the vehicle is charged on the surface of the skin material and the clothing when the normal skin material is used, and the human body is charged by the static electricity charged on the clothing. On the other hand, in the skin material of the present invention, since the resin layer derived from the cloth and the back coating agent are both conductive, static electricity generated by friction between the clothing and the vehicle skin material is included in the skin material. The collected static electricity is collected by the conductive fiber and corona discharged into the air, or the collected static electricity is diffused throughout the skin material by the activated carbon in the back coating agent, and the generation of local high voltage is suppressed, and gradually Is discharged into the air. So in the human body,
No high-voltage static electricity is generated by electrostatic induction. In this way, static electricity is effectively removed, and an unpleasant discharge phenomenon when the vehicle gets off the vehicle is prevented.

The conductive fabric referred to here is a material in which conductive materials such as copper, aluminum, stainless steel, carbon, and a conductive polymer are mixed into organic fibers in a particulate form, or a vacuum evaporation method is applied to the surface of the organic fibers. Woven fabric, knitted fabric, non-woven fabric which is coated with or coated with the organic fiber, or contains 0.1 to 20% by weight of a conductive fiber consisting of a conductive substance itself with respect to the fabric. Include woven fabric, moquette, toweling, tricot, double raschel, circular knitting, needle punch and the like. In this case, as fibers mainly constituting the fabric, natural fibers such as cotton, hemp, silk, wool, rayon, acetate, protein fibers, chlorinated rubber, polyamide, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, Examples thereof include chemical fibers such as polyester, polyethylene, polypropylene, polyurethane, polyvinylidene cyanide, and polyfluoroethylene, and may be composed of both of these fibers. When the content of the conductive fiber is less than 0.1% by weight, static electricity is not sufficiently dissipated due to poor conductivity of the fabric, and when the content exceeds 20% by weight, the effect of the color of the conductive fiber itself on the color of the entire fabric is applied. This impairs the original appearance and texture of the fabric. In addition, the effect of suppressing static electricity does not increase while the cost is high.

As a method for adding conductive fibers to the fabric, mixing in a fiber state, mixing in a sliver state, twisting in a thread form,
Any of a mixture in the form of a filament, a twisted yarn, and an arrangement on a texture may be used.

In this case, the content of the activated carbon contained in the back coating agent is preferably set to 40 to 90% by weight of the total amount of the clay mineral and the activated carbon. Activated carbon content is 40% by weight
If less, the effect of dissipating static electricity is not sufficient,
On the other hand, when the content exceeds 90% by weight, as described above, the adsorption properties of the clay mineral are not sufficiently exhibited, so that the deodorizing performance is impaired.

Further, in the present invention, a common liquid deodorant or powdered deodorant, for example, plant extraction oil, oxidizing agent, organic acid,
It is also possible to use a metal salt or the like in combination. In this case, these deodorants are used, for example, by adding them to the fibers constituting the back coating agent or the fabric, or by directly applying them to the fabric using a spray or a brush.

Other additives such as a flame retardant may be added to the back coating agent of the present invention as long as the properties are not impaired. Common flame retardants include phosphorus compounds, chlorine compounds, bromine compounds, guanidine nitrogen compounds, antimony compounds, boron compounds, ammonium compounds, and the like. Ammonium acid phosphate, phosphoric acid triester, phosphite, phosphonium salt, phosphoric acid triamide, chlorinated paraffin, dechlorane, ammonium bromide, tetrabromobisphenol A, tetrabromoethane, guanidine hydrochloride, guanidine carbonate, phosphorus Acid guanylurea, antimony oxide, sodium tetraborate decahydrate (borax), ammonium sulfate, ammonium sulfamate and the like.

〔Example〕

Hereinafter, the present invention will be described based on examples, but the present invention is not limited by these examples unless it exceeds the gist.

35 parts by weight of sepiolite of 100 mesh or less, 35 parts by weight of coconut shell activated carbon of 325 mesh or less, 3 parts by weight of carboxymethyl cellulose with a molecular weight of 100,000, a nonionic penetrant with a molecular weight of 10,000 (hydrophilic group: polyethylene glycol, lipophilic group: polypropylene glycol) ) Was dry-blended using a Henschel mixer to obtain a mixed powder. Next, 380 parts by weight of water and the above mixed powder were mixed and stirred at 3000 rpm for 5 minutes using a propeller type stirrer to form a slurry. Next, 120 parts by weight of a polyacrylate latex having a solid content of 50% and the above slurry were mixed with a propeller type stirrer for 1 hour.
The mixture was mixed and stirred at 500 rpm for 3 minutes to obtain a back coating agent. Next, 6.53 kg (solid material 1.56 g) of the above-mentioned back coating agent was applied to the back surface of a Jacquard moquette cloth having a width of 1.3 m and a length of 10 m made of polyester fiber using a doctor blade, and dried at 150 ° C. for 5 minutes.

As a comparative example, a vehicle skin material was produced using a back coating agent containing no penetrant. The steps will be described below.

35 parts by weight of sepiolite of 100 mesh or less, 35 parts by weight of coconut shell activated carbon of 325 mesh or less, and 3 parts by weight of carboxymethyl cellulose having a molecular weight of 100,000 were dry-mixed using a Henschel mixer to obtain a mixed powder. Next, water 380
Parts by weight and the mixed powder using a propeller-type stirrer for 3000
The mixture was mixed and stirred at rpm for 5 minutes to form a slurry. Next, 120 parts by weight of a polyacrylate latex having a solid content of 50% and the above slurry were mixed and stirred at 1500 rpm for 3 minutes using a propeller type stirrer to obtain a back coating agent. Next, the back coating agent on the back of a Jacquard moquette fabric of 1.3 m width and 10 m length made of polyester fiber 6.
72 kg (solid content: 1.56 kg) was applied using a doctor blade and dried at 150 ° C. for 5 minutes.

The bonding strength of the pile yarn of the vehicle skin material thus produced was measured as follows.

A cloth tape of 5 cm in width was cut into 15 cm, and each of the skin materials was firmly attached to the front side of the skin material, and then immediately peeled off, and the pile thread was checked for detachment.

In this example, there was no dropout, but in the comparative example, 200 to 300 pile yarns adhered to the gum tape and fell off.

This indicates that the vehicle skin material of the present embodiment is greatly improved in mechanical strength as compared with the conventional one.

In addition, a seat assembly for one vehicle was manufactured using the vehicle skin material of the present example, and attached to a four-door sedan.
After installation, the window glass, door, and ventilator were closed and one cigarette was burned in the room. In order to ascertain the odor intensity remaining in the vehicle interior after being left for one day in this state, 12 panelists stepped into the car alternately and evaluated the odor in the interior of the vehicle with a six-stage odor intensity display.

For comparison, a vehicle skin material containing no adsorbent was attached to an actual vehicle in the same manner as above, and the odor intensity was evaluated.

The odor intensity of the comparative example was 3.5, while that of the present example was 1.6, and the odor was significantly reduced by the skin material of the present example.

In addition, in the evaluation by the odor intensity display of 6 levels,
0 is "odorless", 1 is "smell that can be finally sensed", 2 is "smell smell to know what smell", 3 is "smell easily sensed", 4 is "strong smell" and 5 is "smell smell" Is shown.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 23/00 D06M 11/00 Z (72) Inventor Takatoshi Sekihara 1-1-1 Toyota-cho, Kariya-shi, Aichi Pref. 72) Inventor Akihiro Matsuyama 1-1-1 Toyota-cho, Kariya-shi, Aichi Prefecture Inside Toyota Boshoku Corporation (72) Inventor Osamu Araki 1-Toyota-cho, Toyota-shi, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Yoshio Yamada Aichi 1 Toyota Town, Toyota City, Japan Toyota Motor Corporation Inspector Kenji Sano (56) References JP-A-63-283649 (JP, A) JP-A-62-282926 (JP, A) JP-A 62-282927 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06N 7/00-7/06 D06M 15/693 D06M 11/74 D06M 11/77 D06M 23/00 B32B 25/10

Claims (1)

(57) [Claims] 1. A high-polymer latex comprising a fabric, and particles coated on the fabric in an amount of 15 to 135 g per square meter, which are fused together to form a layer between the yarns constituting the fabric and on the surface of the fabric. Layer, the polymer latex layer, 5 to 160 parts by weight of hydrous magnesium silicate clay mineral dispersed and fixed to 100 parts by weight of particles of the polymer latex, and the polymer latex layer, the polymer latex Activated carbon dispersed and fixed to be 50 to 180 parts by weight in total with the clay mineral with respect to 100 parts by weight of the particles, and 2 to 20 parts by weight with respect to 100 parts by weight of the particles of the polymer latex.
1 part by weight based on 100 parts by weight of the polymer latex particles,
A skin material for a vehicle, comprising: a weight part of a penetrant, wherein the thread and the polymer latex particles are uniformly adhered by the penetrant.