JP2001226882A - Method for producing flocked microfiber product and flocked product of microfiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a flocked product of micro fiber good in fastness against friction, having super fine nubuck feeling or long hairs of high quality and obtain the flocked product of micro fiber. SOLUTION: This method for producing a flocked product of micro fiber is to flock a conjugate fiber comprising at least two or more of components on the surface of a base material, subsequently bring the conjugate fiber to be ultra fine by splitting at least the top end of the conjugate fiber and add a film-forming high polymer. In this flocked product of micro fiber, a polymer film is formed at least on the ultra finely flocked surface of the flocked product of micro fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-quality ultrafine nubuck-like or long-haired ultrafine fiber flocked article having good friction fastness and an ultrafine fiber flocked article.

[0002]

2. Description of the Related Art A flocked product is typically obtained by flying a staple fiber, that is, a cut pile, using gravity, air flow, or electrostatic force, and planting it on a substrate via an adhesive. It is widely used for various purposes because of its unique surface quality.

[0003] The cut pile to be planted at this time is limited in terms of the relationship between thickness and length in order to obtain a flocked product of good density. Generally, when a thin and long pile is subjected to electrostatic flocking, the pile is cut. Because of the entanglement, flying properties are poor, and it is difficult to perform high-density flocking.

On the other hand, ultrafine fibers are soft to the touch and appearance, so that higher quality fibers can be obtained. If the fiber length is longer, a seal fur tone can be obtained. The demand for flocking is great.

Therefore, conventionally, it has been proposed that the sea-island type composite fiber or the split-split type composite fiber is planted for the flocking, and then divided and made finer. This has a large fineness until it is planted, so it has no effect on flightability and workability. After flocking, sea components are dissolved and removed, or separation and separation are performed using the difference in swelling of the two components. It is possible to obtain a flocked product having a fineness and a fiber length that cannot be directly planted with microfibers in order to make the fiber ultrafine.

For example, Japanese Patent Application Laid-Open No. Sho 59-76975 discloses that a hair is planted with a composite fiber using polystyrene as a sea component,
It has been proposed to split by dissolving with a solvent such as trichlene. Japanese Patent Application Laid-Open No. 60-155745 discloses a method in which nylon 6 is used as a sea component and eluted with formic acid. Further, JP-A-62-149963
In the gazette, a pile made of a conjugate fiber containing a copolymerized polyester is treated with an acidic aqueous solution of pH 4 or less before or after flocking to embrittle the copolymerized polyester component, and after flocking, the pile is divided by an alkali treatment or a rubbing treatment. Proposed. The present inventors have also proposed that the division is performed by spraying a fine particle powder fluid.

[0007]

However, when the composite fiber is divided after flocking as described above, there are the following problems. In other words, ultrafine fibers have a large surface area,
Even when a normal dyeing and washing step is performed, the fastness may be lower than that of a large-sized fine fabric. In addition, it is often difficult to dye and wash the pile on the base material after planting, unlike ordinary fabric washing, from the viewpoint of the strength of the adhesive and the processability of the flocking base cloth or molding material.

However, when the splittable conjugate fiber is dyed and washed in a tow or cut pile state in the same manner as conventional flocking, when the flocking and splitting are performed, the surface of the ultrafine fiber newly appearing after splitting is washed. Since it has not undergone a process, the fastness to friction is apt to decrease.

Further, when one component of the conjugate fiber is a copolyester, which is embrittled in advance and used for easy division, the copolyester portion originally exhausts a large amount of dye in the dyeing step. In addition, since it remains in an embrittled state on the surface of the ultra-thin pile after division, it is easy to fall off, and the dye is also easy to come off, which causes a decrease in fastness depending on the dye and its concentration.

[0010] However, as described above, it is necessary to increase the fastness by implanting the hair, dividing the hair into extremely fine pieces and then washing the same, as described above, the adhesiveness of the pile is reduced by a washing agent such as an alkali, or the process in the case of a molded article is difficult. There are problems such as poor permeability and insufficient cleaning, and in particular, the separation method is dewatering by aqueous treatment,
In the case of using physical force instead of elution, the washing effect in the dividing step can hardly be expected, and the amount of the copolyester remaining on the pile surface is large, which tends to cause a decrease in fastness.

From the above, it has been conventionally difficult to impart sufficient robustness to a microfiber flock obtained by splitting after flocking using a conjugate fiber, and it is difficult to obtain good performance depending on the purpose of use. It was a situation.

The present invention has been made in view of the background of the prior art.
An object of the present invention is to provide a method for producing a high-quality ultrafine nubuck-like or long-haired ultrafine fiber flocked product having excellent friction fastness without impairing process passability, and an ultrafine fiber flocked product.

[0013]

The present invention employs the following means to solve the above-mentioned problems.
That is, in the method for producing a microfiber flocking product of the present invention, a composite fiber comprising at least two components is implanted on the surface of the base material, and at least the tip of the composite fiber is divided and ultrafine, and then the film forming property is formed. It is characterized by providing a polymer.

Further, the microfiber flocking product of the present invention is characterized in that a polymer coating is formed on at least the surface of the ultrafine fiber flocking fiber of the microfiber flocking product.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The object of the present invention is to thoroughly study the above-mentioned problem, a high-quality ultrafine nubuck-like or long-haired ultrafine fiber flocked product having good frictional fastness, and after dividing and ultrafinening after flocking. When a film-forming polymer was applied to the flocking surface of a microfiber flocking product to form a polymer coating, it was surprisingly found that this problem could be solved all at once.

That is, according to the present invention, the dyeing fastness, which is a particular problem in the technique of dividing the dyed conjugate fiber into fine fibers after flocking, is the cause of the unwashed state of the split fiber, that is, the fine fibers. It is possible to prevent the dye from falling off from the surface of the fiber pile.

Originally, in fiber dyeing, it is common to take a fixing or washing step after dyeing in order to improve various fastnesses. The drug differs depending on the dye and the material,
Basically, it inhibits the elution of the dye from the fiber, or
It is selected to pre-drop the easy-to-drop dye.
Washing with hot water using an alkali or a surfactant brings out the dyes that easily fall off the fiber surface layer.In addition, the adsorption of anionic drugs inhibits the elution of anionic dyes. And a method in which a disperse dye agglomerated on the fiber surface or a disperse dye dyed on the very surface layer is reduced and eluted with a reducing agent.

[0018] Even in a normal flocking pile, after dyeing in a cut pile state or in a tow state, it is usual to carry out a fixing or washing step, whereby the fastness after flocking can be maintained.

However, the microfiber-grafted product targeted in the present invention is an ultrafine fiber having a lower robustness than a regular fiber. In addition, at the stage of cut pile or tow, even after washing as a composite fiber after washing as a conjugate fiber. Since the fiber surface which appears when the fibers are finely divided in the dividing step after flocking has not been subjected to the washing step, the fastness tends to be lower than that of ordinary flocking.

Furthermore, when a composite fiber containing a copolymerized polyester is used as a component to be divided and removed, as described above, a large amount of broken debris of the copolymerized polyester remains in the ultrafine fibers after the division. This tends to affect the robustness.

On the other hand, in the present invention, the robustness is improved by forming a film-forming polymer film on the surface of the unwashed fiber or on the surface of the adhering copolymer polyester in a very fragile state. It can be done.

The fiber used for flocking in the present invention is a composite fiber composed of at least two components.

The component of the composite fiber is not particularly limited, but is preferably a combination in which peeling or removal of one component is easy. Therefore, as the component, a combination containing a polyamide such as nylon 6 or nylon 66 and a polyester such as polyethylene terephthalate, polybutylene terephthalate, or polypropylene terephthalate, or a combination of a homopolyester or nylon with a copolymerized polyester is preferable.

As the composite form, those conventionally known, such as a sea-island type, a radial wedge type, and a parallel stripe type, can be used.

In particular, in terms of the combination of the composite form and the polymer, in the case of a polyamide and a homopolyester or a copolyester, if the composite fiber is a radial wedge-shaped fiber in which these are alternately arranged, it is extremely thin or irregular due to the separation of the peeling type. It is easy to make a cross-section fiber.

In the case of a composite form having a sea-island structure in which the copolymerized polyester is used as a sea component, the sea-island structure can be easily broken by embrittlement of the copolymerized polyester, thereby enabling ultrafine division.

As such a copolymerized polyester, at least one component has a compound having a —SO ₃ M group unit (where M is a metal atom, a hydrogen atom, or a phosphonium group) in an amount of 1 mol% based on the total acid component. Modified polyesters copolymerized in proportions are more preferred. In order for the embrittlement treatment for improving the splittability described later to exhibit a sufficient effect, the proportion of such a copolymer component is required to be 1 mol% or more with respect to all the acid components. Polymerization causes problems in the spinning properties and yarn strength. Therefore, the proportion of the copolymer component is preferably 2 mol% or more and 12 mol% or less, more preferably 3 mol% or less.
It is desirable to be at least 12 mol%.

The fineness of the finely divided ultrafine fiber portion after the division of the component is not particularly limited, but is preferably 1 dtex or less, and 0.5 dtex or less in order to have a quality characteristic after the division. Is more preferred. If the lower limit is too small, the entanglement of the pile after division is large, and the feeling of nap is also lost. Therefore, 0.001 dtex or more is desirable.

In the present invention, such a conjugate fiber is planted after dyeing and divided.

In the present invention, depending on the combination or composite form of the two components, it is preferable to make one of the components embrittled before the dividing process of the present invention, so that the division is easier and easier.

As a means suitable for such embrittlement, a conventionally known embrittlement method for a copolyester may be used. For example, an acid treatment disclosed in JP-B-62-149963 or the present inventor may be used. A method of heat treatment using an alkaline aqueous solution containing a swelling agent for the copolymerized polyester to be embrittled, which has already been proposed, can be employed.

Further, in the case of a separation-split type conjugate fiber of polyamide and polyester or copolyester, splitting becomes easier by treating the polyamide swelling agent.

The substrate on which the microfiber-flocked product of the present invention is implanted can be freely used, such as a woven fabric, a knitted fabric, a nonwoven fabric, and a resin molded product. In particular, in the case of the present invention, there is an advantage that the robustness can be improved without any hindrance even to the flocking of a three-dimensional molded product having irregularities, which is particularly difficult to wash after the flocking.

Then, for the flocking made of the composite fiber,
A splitting process is performed to make the fibers extremely fine.

The dividing method is not particularly limited, and the method used in the conventional dividing may be applied. However, physical dividing is preferred in view of the properties of the flocking having the adhesive layer. As a method of physical division, brushing with a metal brush or animal hair brush, buffing with sandpaper, rubbing with rubber having a high coefficient of friction, pressing with a roll, fir treatment, and the like can be used.

The microfiber implanted product of the present invention further comprises a film-forming polymer film after the division.

The term "film-forming polymer" as used in the present invention means a polymer capable of forming a thin film on the surface of an object in a drying step, and is not particularly limited, but is preferably an acrylic polymer or a silicone polymer. , A fluorine-based polymer, a polyurethane-based polymer, a vinyl acetate-based polymer, an ethylene / vinyl acetate-based copolymer, or a mixture of two or more of them.

When the polymer to be applied is a cationic polymer, it has a high adsorptivity particularly to the copolymerized polyester and has a high effect of preventing the copolymerized polyester from falling off from the ultrafine fibers, which is preferable.

In consideration of the ease of the application step and the effect of flocking on the adhesive layer, it is preferable to apply the film-forming polymer as an aqueous emulsion instead of a solvent-based emulsion.

There is no particular limitation on the method of application, and it is only necessary to be able to sufficiently impregnate the interior of the flocking using means such as padding, dipping, spraying and the like. In this case, the concentration of the polymer liquid to be applied is not particularly limited. However, if the concentration is too high, the touch of the fine hair transplantation is lost, and if the concentration is too low, there is no effect of improving the robustness. From 0.05% to 10%
% Or less, more preferably 0.1% or more and 5% or less, because a high quality and highly robust flocking product can be obtained.

The flocked product after application of the polymer solution is preferably heat-treated to form a polymer film.

It is necessary that the heat treatment temperature does not affect the flocking fiber material, the base material, and the adhesive. However, if the heat treatment is performed at a high temperature, the migration of the dye occurs, and the fastness tends to be further reduced. Therefore, it is preferable to perform a heat treatment at 120 ° C. or less.

When the concentration of the polymer liquid is high, the fine fibers piles are adhered to each other by the coating, and the texture may be hardened. However, by brushing after forming the coating, the texture unique to the soft ultrafine fibers is reduced. It is possible to get it back.

As described above, the microfiber flocking product of the present invention is characterized in that the polymer coating is formed on the surface of the flocking product. More specifically, by dividing the composite fiber after planting it, unlike the normal flocking, the tip of the pile is divided and ultra-thin, whereas the root part of the pile is attached to the adhesive in a bundle. The polymer layer is embedded and the ultrafine fiber portion and the root portion are both covered with the polymer film.

[0045]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to this.

Examples 1-4 and Comparative Example 1 Sea-island composite fibers containing polyethylene terephthalate obtained by copolymerizing 4% by mole of dimethyl 5-sodium sulfoisophthalate with respect to the total acid component as the sea component and polyethylene terephthalate as the island component Is cut to 1.0mm and 10g
/ L of maleic acid at 130 ° C to embrittle the copolymerized polyester component.

After the obtained pile was washed with water and washed, it was dyed under the following conditions.

[0048] After dyeing at 130 ° C. for 60 minutes, reduction washing was performed under the following conditions, followed by water washing.

Sodium hydroxide 0.5 g / l Hydrosulfite 2 g / l Gran-up US-20 0.5 g / l 80 ° C. × 20 minutes The obtained dyed pile was subjected to electrodeposition according to a conventional method.

A PP resin molded product was used as the base material.
An acrylic resin emulsion was spray-applied as an adhesive, and the above-mentioned pile was implanted with an up-planting method. After the flocking, the hair was dried at 95 ° C.

The flocked product was sprayed on the flocked product using alumina particles having an average particle diameter of 100 μm and using an air flow at a pressure of 30 kPa.

Further, air was blown to blow off alumina and surplus pile on the surface.

This microfiber-flocked product is referred to as Comparative Example 1.

The following treatments were performed on this extra-fine flocking product to obtain the extra-fine fiber flocking products of Examples 1 to 4.

The following aqueous emulsion was used as a treatment liquid, sprayed, and dried at 95 ° C.

Example 1 Quinset HC (acrylic emulsion manufactured by Kotani Chemical Industry Co., Ltd.) 0.5% Example 2 〃 2% Example 3 ％ 5% Example 4 １２ 12% A fiber implanted product was immersed in the following chemical solution, heated to 80 ° C., kept for 20 minutes, pulled up, washed by spraying with a stream of water, and dried by a dryer to obtain Comparative Example 2.

Comparative Example 2 Sodium hydroxide 0.5 g / l Hydrosulfite 2 g / l Gran Up US-20 0.5 g / l Among the obtained flocks, Example 3 was slightly harder than before treatment. I felt it, but the soft touch was restored with the finishing brush. In Example 4, although some recovery was achieved by brushing, some hardness remained. Examples 1 and 2 were good touches without brushing.

On the other hand, in Comparative Example 2, the swelling of the adhesive
Hair loss was observed in some places.

Observation with an electron microscope showed that the collapsed copolyester remained on the surface of the ultrafine fiber in both the comparative example and the example. In Examples 1 and 2, there was no significant change as compared with Comparative Example 1, but a very thin polymer film was observed, and in Example 3, a large amount of polymer deposits were observed.

In Example 4, many ultra-pile piles were glued in places.

The flocks were tested for wear dye fastness.

A Gakushin-type abrasion tester was used for the test, and color transfer to a white cotton cloth by friction 100 times was confirmed under a load of 1.96 N.

In Comparative Example 1, the color transfer was strong, and the color transfer was at the secondary level. On the other hand, Examples 1 to 4 all improved, Examples 1 and 2 were in the third to fourth grades, and Examples 3 and 4 were the It was a 4-5 grade.

In Comparative Example 2, the hue was discolored, and the fastness to friction was slightly improved as compared with Comparative Example 1, and was at the third level. However, the friction surface was peeled off in a state where the hair was easily peeled off from the adhesive.

Example 5 and Comparative Example 3 Polyethylene terephthalate obtained by copolymerizing dimethyl 5-sodium sulfoisophthalate at 4 mol% with respect to the total acid component is used as a U.S.-type component to be removed, and a polyamide is used as a wedge-shaped component to be left. Radial eight-split conjugate fiber as shown in FIG. 2 (fineness before splitting 3 dtex, sea-island ratio 20/8)
0, island fineness 0.3 decitex) was cut into 0.5 mm and immersed in the following alkaline aqueous solution at a bath ratio of 1:20,
A heat treatment was performed at 95 ° C. for 90 minutes with stirring.

Tetrosin PEC 0.15% (Phenylphenol-based carrier agent manufactured by Yamakawa Pharmaceutical Co., Ltd.) Sodium hydroxide 0.2% The obtained pile is broken by applying a slight force such as squeezing with a fingertip. As it was, it was not divided. After washing, it was dyed with an acid dye, soaped, and then subjected to electrodeposition according to a conventional method.

An acrylic resin emulsion was coated and applied as an adhesive on a vinyl chloride resin plate, and after flocking, the resultant was finely divided by brushing with a pig hair brush. This extra-fine fiber flocking product is referred to as Comparative Example 3.

This microfiber-flocked product is immersed in the following chemical solution, pulled up and left to drain, and then dried with a dryer.
Example 5 was obtained after drying at 10 ° C. and heat treatment.

Example 5 GCO-02 Conc (Vinyl Emulsion, SENKA CORPORATION) 2% The friction fastness was tested in the same manner as in Examples 1-4.
Comparative Example 3 was grade 3 and Example 5 was grade 4-5.

[0070]

According to the present invention, it is possible to easily provide a fine fiber flocked product having good quality and performance, and is particularly useful in the field of clothing, the interior of automobiles, and the field of leather materials such as shoes and bags. Materials can be provided stably.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Jiro Amano 4845 Mishima-shi, Shizuoka Toray Industries, Inc. Mishima Plant (72) Inventor Takehiko Yoshida 3385 Kitaura, Suwa-ji, Kono-cho, Mie-gun, Mie Prefecture Toyo Densei Co., Ltd. In-house F-term (reference) 4F055 AA02 AA05 BA04 DA07 EA03 EA04 EA11 EA14 EA22 EA24 EA30 FA01 FA10 GA03 GA38 HA12 4F100 AK07 AK25G AK41 AK41B AL01 AL01B AT00A BA02 CB00 DG03B DG08 B EJ18 GB33 DG18B

Claims (14)

[Claims] 1. A method according to claim 1, wherein a composite fiber comprising at least two components is implanted on the surface of the base material, and at least a tip portion of the composite fiber is divided and ultrafine, and then a film-forming polymer is provided. Method for producing microfiber flocks. 2. The method according to claim 1, wherein the means for providing the film-forming polymer comprises applying a water-based emulsion of the film-forming polymer to a flocked surface, followed by heat treatment. Product manufacturing method. 3. The method according to claim 2, wherein the heat treatment is performed at 120 ° C. or lower. 4. The composite fiber according to claim 1, wherein at least one component is -SO.
₃ Copolymerized polyester obtained by copolymerizing a compound having an M group unit (M is a metal atom, a hydrogen atom, or a phosphonium group) at a ratio of 1 mol% or more based on the total acid components, and the other components are The method for producing a microfiber flocking product according to any one of claims 1 to 3, wherein the composite fiber is a composite fiber comprising a component having a lower alkali weight loss rate than the copolymerized polyester. 5. The microfiber flocking product according to claim 1, wherein the conjugate fiber is a sea-island type conjugate fiber having a homopolyester as an island component and a copolymerized polyester as a sea component. Manufacturing method. 6. The method for producing a microfiber flocking product according to claim 4, wherein the copolyester portion is embrittled before splitting the conjugate fiber. 7. The method for producing a microfiber flocking product according to claim 1, wherein the film-forming polymer contains a cationic resin. 8. The method according to claim 1, wherein the base material of the flocking product is a three-dimensional molded product. 9. The method for producing a microfiber flocking product according to claim 1, wherein the means for dividing at least the tip portion of the conjugate fiber is a high-pressure powder fluid treatment, a brushing, a rubbing treatment or a pressing treatment. Method. 10. The method for producing a microfiber flocking product according to claim 1, wherein brushing is performed after the application of the film-forming polymer. 11. A microfiber flocking product, characterized in that a polymer coating is formed on at least the surface of the microfiber flocking fiber. 12. An ultrafine fiber flocking product, characterized in that embrittled copolyester is present on the surface layer of the flocking fiber and a polymer film is formed on the surface thereof. 13. The microfiber flocking product according to claim 11, wherein the flocking is obtained by dividing a conjugate fiber into ultrafine fibers. 14. The method according to claim 11, wherein a tip portion of the flocking is made of ultrafine fibers, and a root portion of the flocking is adhered to a base material in a state where the ultrafine fibers are bundled. Microfiber flocking.