JP6381873B2 - Long-term dirt removing fabric - Google Patents

Description

  The present invention relates to a long-term soil-removable fabric having excellent soil-removability over a long period of time.

  Interior materials such as seats and ceilings for transportation equipment such as automobiles, trains, ships, aircraft, and strollers, interior materials for buildings such as curtains, carpets, and wall materials, or outer surfaces such as beds and sofas that cannot be removed Unlike cloth for clothing, fabrics used for fabrics such as candy cannot be washed by washing etc. even if they are used repeatedly, so that the surface is regularly wiped and soiled. In addition, the dirt is wiped off with water or a very thin cleaning solution, struck, or sucked with a vacuum cleaner.

  Such fabrics that are used for removing dirt by wiping (hereinafter collectively referred to as “stain-removable fabrics”) have hydrophilic properties that allow easy removal of dirt by water wiping, drinks, etc. It is required to have antifouling performance that prevents stains even if spilled. In view of this, several techniques have been proposed for applying a modification treatment for improving the performance of the fabric surface.

  For example, by adhering a hydrophilic polyester resin compound and a fluorine-containing antifouling resin compound to the fabric, it is possible to achieve both the removal of dark stains due to sebum and the like, and the antifouling property of aqueous stains, and only with a wipe An interior fabric has been proposed in which dirt can be easily removed (see Patent Document 1).

  Further, after fixing the hydrophilic resin composition to the surface of the fiber fabric, a composition containing a fluorine-based compound and silica fine particles is adhered to the surface of the fiber fabric, thereby removing sebum stains (dark stains), etc. Seat sheets with excellent antifouling properties that can be easily removed by rubbing with a cloth containing water, and sand and dust can be easily removed by simply hitting them with a hand or sucking them with a vacuum cleaner. An outer skin material has been proposed (see Patent Document 2).

JP 2011-12364 A JP 2011-47085 A

  However, these fabrics imparted with antifouling properties certainly have the ability to easily remove dirt by wiping with water, but for example, when used as an outer material for seats of automobiles, trains, etc. Exhibits excellent dirt removal performance, but when used over a long period of 1 year or 2 years, the surface of the fabric is worn due to repeated getting on and off of people, and hydrophilic and fluorine-containing resins that have exhibited antifouling performance There is a problem that the performance drops sharply. And if the cloth used for such an application is equipped for interiors of automobiles or the like, it is often used as it is for a long period of time without being washed or replaced. In addition, when used as interior materials such as carpets and wall materials, or cloths for straw, they are often used without washing for a long time, although they repeatedly touch the human body.

  For this reason, if it is used continuously for a long time, the repeatedly worn portion of the fabric surface remains darkened or stained, which not only impairs the beauty but also is not preferable for hygiene. Recently, since there is a tendency to prefer bright colors as interior materials for automobiles, it is strongly desired to provide particularly excellent antifouling performance and dirt removal performance in bright-colored fabrics that are easily noticeable. .

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide an excellent long-term stain-removable fabric that is excellent in stain removal performance over a long period of time and can maintain the appearance of the fabric beautifully. .

In order to achieve the above object, the present invention provides a fabric having an L ^* value of 45 or more in the CIELAB color system and used for applications in which dirt is removed by wiping, wherein at least the surface of the fabric is The hydrophilic resin (A) and the hydrophilic resin (A) are treated with a silicone-based treatment agent (B) made of a water-repellent silicone resin (excluding methyl hydrogen silicone resin) whose water repellency rating is quaternary. The weight ratio (A: B) of the adhesion amount of the silicone-based treatment agent (B) is set to 1: 1.05 to 1: 1.27, and the hydrophilic resin (A) and the silicone-based treatment agent The first gist is a long-term stain-removable fabric in which stain removal performance is maintained over a long period of time due to the adhesion of (B).

In particular, the present invention has an adhesion amount of 0.35 to 1.75 g / m ² to the fabric of the hydrophilic resin (A) and the silicone treatment agent (B) to the fabric. amount shall be the second aspect of the long-term soil removal resistant fabric that is set to 0.5 to 10 g / m ^2.

That is, the long-term soil-removable fabric of the present invention has a color having an L ^* value of 45 or more in the CIELAB color system, and the fabric surface is composed of a hydrophilic resin (A) and a specific water-repellent silicone resin. It is processed by the combination with the silicone-based treatment agent (B). And by adhering (A) and (B) to each other at a specific ratio, not only the antifouling performance and dirt removal performance are added to the fabric, but the performance is maintained over a long period of time. It has become.

This is because the silicone-based treatment agent (B) is made of a specific water-repellent silicone resin and repels liquid stains, making it difficult for stains to permeate the inside, so that stains do not easily occur. In addition, in order to improve the smoothness of the fabric surface, it is considered that the contact surface slips well even when it repeatedly comes into contact with a human body and the degree of wear of the fabric surface due to frictional resistance is greatly reduced. . If the wear on the fabric surface is small even after long-term use, the hydrophilic resin (A) and the silicone-based treatment agent (B) are not easily removed from the fabric surface, and the antifouling performance and stain removal performance of these treatment agents are maintained. Therefore, even after long-term use, the fabric surface can be kept beautiful in the same manner as at the start of use. In the present invention, “long-term” means a period of one year or longer, and “long-term stain-removable fabric” maintains its antifouling performance and stain-removing performance to some extent even when used for one year or longer. Fabric.

And among the long-term stain-removable fabrics of the present invention, in particular, the amount of the hydrophilic resin (A) attached to the fabric is 0.35 to 1.75 g / m ² , and the silicone treatment agent (B) Those having an adhesion amount to the fabric of 0.5 to 10 g / m ² are suitable because they have particularly excellent performance and excellent properties such as touch and flame retardancy.

  Next, an embodiment for carrying out the present invention will be described.

  The fabric targeted by the present invention is a fabric used for applications in which dirt cannot be washed by washing or the like and dirt is removed by wiping such as water wiping. Specifically, as already mentioned, interior materials such as seats and ceilings for transportation equipment such as automobiles, trains, ships, airplanes, and strollers, interior materials for buildings such as curtains, carpets, and wall materials, or beds, For example, the outer surface of a sofa or the like, which cannot be removed, or the fabric of straw.

  Examples of the form of the fabric include various forms such as a woven fabric, a knitted fabric, and a non-woven fabric depending on the application. However, those whose surface is less likely to fluff are preferable, and those whose surface is less uneven are more preferable.

  The type of fibers constituting the fabric is not particularly limited, but for example, those used as interior materials for vehicles, ships, aircrafts, etc. are particularly required to be durable, so synthetic fibers, especially polyester fibers are used. It is preferable to use it. Moreover, what combined several fiber material may be sufficient, and the thing which combined the polyester fiber and the other fiber in that case is also preferable.

Also, the fabric used in the present invention, it is the fabric of bright colors Ri yo is, it is possible to remarkably exhibit the effects of the present invention that no or with stain Dari dark colors by contamination, is suitable. More specifically, it is intended for a fabric having a high brightness with an L ^* value of 45 or more in the CIELAB color system, with 55 or more being preferred, and 65 or more being more preferred.

The L ^* value is obtained by using a spectrocolorimeter (for example, trade name: Color Eye5, manufactured by tagMacbeth, trade name: CM-1000, manufactured by Minolta Camera Co., Ltd., etc.), and the reflectance spectrum of the D65 light source. It can be obtained by measuring and calculating using color calculation software based on the measured value.

  In the present invention, the hydrophilic resin (A) used for the treatment of the fabric is a polymer having a hydrophilic functional group, such as a hydrophilic polyester resin, a hydrophilic polyurethane resin, a hydrophilic silicone resin, and the like. Can be given. These may be used alone or in combination of two or more. Depending on the fiber material of the fabric, an appropriate material can be selected in consideration of the adhesion to the fiber material and the like. For example, for a fabric using polyester fiber, it is preferable to use a hydrophilic polyester resin from the viewpoint of excellent adhesion to the fiber and little influence on the flammability.

Examples of the silicone treating agent (B) used together with the hydrophilic resin (A) include various water-repellent silicone resins (excluding methyl hydrogen silicone resins) . These water-repellent silicone resins are polymers having a siloxane bond as a skeleton in which silicon (Si) and oxygen (O) are alternately arranged, and the siloxane bond is three-dimensionally crosslinked. Incidentally, the silicone oil is one in which the siloxane bond extends in a chain.

  Further, the silicone-based treatment agent (B) preferably has a function of enhancing the smoothness of the fabric surface by imparting it to the fabric surface. Therefore, the static friction coefficient of the untreated fabric is It is preferably 60 to 98% of the static friction coefficient. Especially, it is especially preferable that it is 70 to 90%. The dynamic friction coefficient is more preferably 70 to 98% of the dynamic friction coefficient of the untreated fabric.

  The “static friction coefficient” and the “dynamic friction coefficient” can be measured as follows.

[Friction coefficient calculation method]
First, a dipping process is performed on the polyester fabric so that the dry adhesion amount of the silicone-based treatment agent (B) is 5 g / m ² and dried at 150 ° C. for 3 minutes to prepare a test piece. The friction coefficient is measured in accordance with the static friction coefficient / dynamic friction coefficient test method of JIS K 7125 except that the load for measurement is changed to 1700 g.

That is, the sliding piece is moved at a constant speed (100 mm / min), and the peak when the maximum tensile load is reached is the static friction force (F _s ). Further, to the start of testing dynamic friction force of the average load between 50~100mm and (F _D). Then, the normal force generated by all the mass in accordance with the test specimen (F _p) in the case of load 1700 g, is 16.66N.

Using these values, the static friction coefficient and the dynamic friction coefficient are calculated by the following formula.
Coefficient of static friction (μ _s ) = F _s / F _p
Coefficient of dynamic friction (μ _D ) = F _D / F _p

The silicone-based treatment agent (B) has water repellency in order to enhance the antifouling property of the fabric surface, and in particular to enhance the antifouling property against water-based stains . And in the following water repellency evaluation, it is necessary to have quaternary water repellency.

[Water Repellency Evaluation of Silicone Treatment Agent (B)]
First, the polyester fabric (woven fabric) was subjected to an adhesion treatment with the silicone treatment agent (B) so that the dry adhesion amount was 2 g / m ² . Then, the obtained treated fabric was placed on a horizontal table, and one drop of water was dropped from about 3 cm above. After 10 seconds, water droplets were wiped off, and the wet state of the treated fabric surface was visually observed and evaluated. The evaluation criteria are as follows.

First grade: Water drops soak into the fabric surface and cannot be wiped off. The soaked water droplets spread and moisten the back side. Second grade: Water droplets can be wiped off slightly, but the soaked water droplets spread and wet the back.
3rd level: Water droplets can be wiped off, but the surface is wet. The back side does not get wet.
Grade 4: Water droplets can be wiped off, but the surface becomes slightly wet.
Grade 5: Water droplets can be wiped off and the surface is not wet.

By the way, when the water-repellent silicone resin as the silicone-based treatment agent (B) of the present invention and other various silicone-based treatment agents were evaluated according to the above evaluation criteria, the results shown in Table 1 below were obtained . .

  The long-term soil-removable fabric of the present invention can be obtained, for example, as follows using these materials. That is, first, the hydrophilic resin (A) and the silicone-based treatment agent (B) are both mixed at a predetermined ratio with water as a dispersion medium and stirred to prepare a treatment liquid. Then, the treatment liquid is added to the fabric to treat the fabric surface, and then dried by heating. As a result, the intended long-term soil-removable fabric is obtained.

  In addition, in the said manufacturing method, when giving hydrophilic resin (A) and a silicone type processing agent (B) to a fabric, these are mixed with the water which is a dispersion medium, and are used as a process liquid, but depending on the case, Processing solutions may be prepared individually, and processing may be performed sequentially from either one.

  Moreover, various additives can be mix | blended with the said process liquid as needed in the range which does not inhibit the effect of this invention.

  And as a method of giving and processing the said processing liquid to a cloth, it is preferable to use a dipping from a viewpoint that a processing liquid can be uniformly supplied to the whole fabric. In addition, when it is desirable to apply the treatment liquid only to the fabric surface and not to apply it to the back surface due to economic reasons or requests from customers, a gravure coater, a spray coater, and the like can be given.

  In addition, in the application of the treatment liquid, the treatment conditions depend on the material and form of the fabric used, but it is generally preferable to set the treatment temperature to 130 to 190 ° C. and the treatment time to 1 to 5 minutes. If the conditions are looser than the above conditions, even if a silicone-based treatment agent (B) having water repellency is used, the water repellency may not be sufficiently exhibited. Further, if the conditions are severer than the above-described processing conditions, the fabric may become hard and uncomfortable.

  The blending amount of the hydrophilic resin (A) and the silicone-based treatment agent (B) in the treatment liquid is determined from the optimum adhesion amount of the long-term soil-removable fabric finally obtained in consideration of the pickup rate of the treatment liquid. Determined by back calculation.

The preferable adhesion amount of the hydrophilic resin (A) to the fabric is 0.35 to 1.75 g / m ² . That is, if the adhesion amount is less than 0.35 g / m ² , there is a possibility that the stain removal effect by water wiping may not be sufficiently obtained. Conversely, if it exceeds 1.75 g / m ² , the resin adhesion layer becomes thick. The friction part becomes white due to friction, so-called choke marks may be generated and the appearance may be deteriorated. Moreover, when wet with water, steam heating when installed as an interior material, etc., or when wet by rain, etc., the hydrophilic resin (A) becomes uneven as if it was spread outward by water, and when this part dries, There is a possibility that the boundary of the unevenness will remain round like a ring and become a stain, and so-called creaking may occur.

On the other hand, the preferable adhesion amount to the fabric of the said silicone type processing agent (B) is 0.5-10 g / m < ² >. That is, when the adhesion amount is less than 0.5 g / m ² , the fabric surface becomes insufficiently smooth, and the durability of stain removal may be impaired. Moreover, when it exceeds 10 g / m < ² >, the hydrophobicity of a silicone type processing agent (B) may inhibit the hydrophilic property of a hydrophilic resin (A), and there exists a possibility that the stain | pollution | contamination removability by water wiping may be impaired.

In addition, these adhesion amounts can be obtained as follows. That is, the untreated fabric weight W ₀ is measured, and the fabric weight W after treatment with the treatment liquid and drying is measured. The calculated amount of adhered After obtaining the value of (W-W _0), the solid content ratio of the component composition of the processing solution, the hydrophilic resin per fabric unit area (A), a silicone-based agent (B) can do.

Then, the hydrophilic resin (A) and the silicone-based agent (B), the weight ratio of mutual adhesion amount (A: B) is 1: 1.05 to 1: needs to be 1.27 is there. That is, if the amount of the silicone treatment agent (B) is less than the above range of the weight ratio, the soil removability may deteriorate after use over time, or the water-based stain may soak into the fabric and the water wiping removal effect may be impaired. Conversely, if the amount of the silicone treating agent (B) is too much than the range of the above weight ratio, there is a possibility that the stain removability by water wiping may be impaired. In addition, since a large amount of silicon contained in the silicone-based treatment agent (B) adheres to the fabric, it may not be possible to satisfy the flame retardancy when used in applications such as vehicle interior materials.

  Since the fabric surface obtained in this way is treated with a combination of the hydrophilic resin (A) and the silicone-based treatment agent (B), the fabric surface has antifouling performance. In addition to being applied, the smoothness of the fabric surface is enhanced, and the fabric surface is less likely to wear due to frictional resistance. Therefore, even if this soil-removable fabric is used for a long period of time, the hydrophilic resin (A) and the silicone-based treatment agent (B) are not easily removed from the fabric surface, and the antifouling performance and soil removal performance of these treatment agents are maintained. Therefore, the fabric surface can be kept beautiful after a long period of use as in the case of the start of use.

And when this long-term stain-removable fabric is a bright color (for example, a color having an L ^* value of 45 or more in the CIELAB color system), the bright color is maintained even after long-term use. An excellent effect can be obtained.

  Next, the present invention will be described based on examples and comparative examples. However, the present invention is not limited to the following examples.

[Example 1]
10 parts by weight of hydrophilic polyester resin (SR1000, manufactured by Takamatsu Yushi Co., Ltd .: solid content: 10%) as the hydrophilic resin (A), and water-repellent silicone resin (Polon MK206, manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone treatment agent (B). : Solid content 32%) 4 parts by weight, catalyst (CAT-FZ, manufactured by Shin-Etsu Chemical Co., Ltd .: solid content 18%) 2 parts by weight and water 86 parts by weight were mixed and stirred to obtain an antifouling treatment solution. In addition, the static friction coefficient of the said silicone type processing agent (B) is 0.60, and is 66% of untreated cloth ratio. Similarly, the dynamic friction coefficient is 0.51, and the untreated cloth ratio is 91%.

Then, the treatment solution was applied to the polyester tricot knitted fabric (weight per unit area 350 g / m ² ) by dipping the antifouling treatment solution at a pickup rate of 60%. And the target stain | pollution | removability fabric was obtained by heat-processing at 150 degreeC for 3 minute (s). The adhesion amount of the hydrophilic polyester resin in this fabric was 1.65 g / m ² , and the adhesion amount of the water repellent silicone resin was 2.1 g / m ² . The weight ratio of hydrophilic polyester resin (A): water-repellent silicone resin (B) is 1: 1.27.

[Examples 2 and 3, Reference Examples 1 to 8 ]
The adhesion amount of the hydrophilic polyester resin and the adhesion amount of the water-repellent silicone resin were changed as shown in Tables 2 and 3 below. Other than that was carried out similarly to Example 1, and obtained the target soil-removable fabric.

[Comparative Example 1]
A polyester tricot knitted fabric similar to that in Example 1 (weight per unit area: 350 g / m ² ), which was not treated at all, was prepared as an untreated fabric.

[Comparative Example 2]
In Example 1, the water-repellent silicone resin was changed to 4.9 parts by weight of a fluororesin (solid content 26%, SR2020, manufactured by Nikka Chemical Co., Ltd.), and no catalyst was used. Other than that was carried out similarly to Example 1, and obtained the soil-removable fabric used as a comparative example. The fluororesin has a static friction coefficient of 1.11 and an untreated cloth ratio of 122%. Similarly, the dynamic friction coefficient is 0.46, and the untreated cloth ratio is 82%. The adhesion amount of the hydrophilic polyester resin in the fabric is 1.65 g / m ^2, the adhesion amount of the fluorine resin was 2.1 g / m ^2.

About these Example goods, Reference example goods, and Comparative example goods, it measured and evaluated about each item shown below. These results are also shown in Tables 2 to 4 below.

[Stain removal, color difference measurement]
(1) Application of dirt First, 12 types of carbon black X specified in JIS Z 8901 and a composition comprising 70% by weight of oleic acid, 20% by weight of palmitic acid and 10% by weight of stearic acid are sufficiently mixed with stirring. The synthetic sebum Y thus prepared was mixed so that X: Y was 3: 200 to produce a synthetic soil powder.

  Then, a cloth P (raised tricot knitted fabric) is set on a special triple anti-stain test machine (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) using a double-sided tape, and a friction cloth (0.203 g of the synthetic soil powder applied) The fabric P is soiled by 10 reciprocations with a load of 61.3 N, a stroke of 100 mm, and a friction speed of 60 reciprocations / minute with a friction element (sliding surface dimension: 25 mm × 25 mm) attached with JIS L 3202 cotton canvas No. 9). Was attached.

And in the above-mentioned special type triple anti-stain tester, a test piece (Example product, Reference product, Comparative product) is set with a double-sided tape, and a friction element attached with the fabric P to which the dirt is attached, Dirt was adhered to the test piece by rubbing 40 reciprocations at a load of 20.6 N, a stroke of 100 mm, and a friction speed of 60 reciprocations / min. However, after reciprocating 20 times, the soiled fabric P was replaced with a new soiled fabric P, and the reciprocating operation was repeated 20 times, for a total of 40 reciprocations.

(2) Dirt removal The smeared test piece thus obtained was set on a Gakushin type friction fastness tester (RT-200, manufactured by Daiei Kagaku Seisakusho Co., Ltd.) using double-sided tape, and 150 mm A friction element (sliding surface dimension: 20 mm × 20 mm) with a 150 mm non-woven fabric (BENCOT M-1, manufactured by Asahi Kasei Fibers Corp.) folded in 1 cc and loaded with a load of 4.9 N (500 g · f) The specimen was soiled by rubbing 40 strokes at a stroke of 100 mm and a friction speed of 30 strokes / minute. However, after reciprocating 20 times, the nonwoven fabric was replaced with a new non-woven fabric and reciprocating again with 20 frictions, resulting in a total of 40 reciprocations. Thereafter, the test piece (after removing the stain) was left at room temperature and dried.

(3) Evaluation of stain removability CIELAB was measured using a spectrocolorimeter (CM-1000, manufactured by Minolta Camera Co., Ltd., D65 light source) for the portion of the above-mentioned test piece (after removing the stain) that had been soiled and wiped off. The L ^* value, a ^* value, and b ^* value in the color system were measured at three locations, and the average value of each was determined. In addition, the L ^* value, a ^* value, and b ^* value of the test piece before soiling were measured in the same manner to obtain the average value, and the color difference ΔE ^* with this as a reference was obtained. It can be evaluated that the smaller the value is, the more dirt is removed.

Moreover, sensory evaluation was performed according to the following reference | standard about the said test piece (after dirt removal). Grade 5: No dirt is observed.
4th grade: Slightly dirty, but I don't mind.
3rd level: Dirt is recognized, but I don't care much.
2nd level: Dirt is recognized and I am worried.
1st grade: Dirt is noticeably noticeable and very worrisome.

[Durability of dirt removal performance]
A surface abrasion tester (T-TYPE, Daiei Kagaku Seiki Co., Ltd.) is attached to the back of the test piece (Example product, Reference product, Comparative product) with a 70 mm wide, 300 mm long, 10 mm thick urethane foam. (Manufactured by Koki Seisakusho). Then, with a friction element attached with a cotton cloth (cotton canvas), a reciprocating friction was performed 10,000 times at a load of 9.8 N, a stroke of 140 mm, and a friction speed of 60 reciprocations / minute. However, every 1000 reciprocations of friction, a new cotton canvas was exchanged for a total of 10,000 reciprocations.

[Color of fabric (lightness)]
From the L ^* value (measured at three points) in the CIELAB color system of the test piece before the soil adhesion, measured for evaluation of the soil removal property, the average value is obtained, and an index of the color (lightness) of the fabric It was.

From these results, it can be seen that the products of Examples 1 to 3 have excellent dirt removal performance even after 10,000 reciprocating frictions. On the other hand, the comparative example 1 product which is an untreated cloth does not have the dirt removal performance from the beginning, and the comparative example 2 product using the fluororesin has a dirt removal performance at first, but 10,000. After two rounds of reciprocating friction, it can be seen that the performance is greatly reduced and there is no long-term durability.

  The present invention can be widely used as a fabric that is used for applications such as removing dirt by wiping and is required to maintain the appearance of the fabric over a long period of time.

Claims (2)

A cloth having a color with an L ^* value of 45 or more in the CIELAB color system and used for removing dirt by wiping, wherein at least the surface of the cloth has a hydrophilic resin (A) and water repellency evaluation It is treated with a silicone-based treatment agent (B) made of a quaternary water-repellent silicone resin (excluding methyl hydrogen silicone resin ), and the adhesion amount of the hydrophilic resin (A) and the silicone-based treatment agent (B) The weight ratio (A: B) is set to 1: 1.05 to 1: 1.27, and dirt removal performance over a long period due to the adhesion of the hydrophilic resin (A) and the silicone-based treatment agent (B). Is a long-term soil-removable fabric characterized in that The amount of the hydrophilic resin (A) attached to the fabric is 0.35 to 1.75 g / m ² , and the amount of the silicone-based treatment agent (B) attached to the fabric is 0.5 to 10 g / m ² . The long-term soil-removable fabric according to claim 1, which is set.