JP4455915B2 - Manufacturing method of automobile flocking product based on olefin resin - Google Patents

Description

  The present invention relates to a method for producing a flocking product for automobiles such as weather strips.

  In recent years, in the housing industry, the problem of sick house (indoor air pollution) due to formaldehyde, toluene, xylene, etc. contained in building materials, construction materials and insect repellents has been emphasized. The provisional guideline value of (TVOC) was shown. According to the results of the VOC measurement in the new car, the National Life Center told the automobile industry that “TVOC generated from the new car increased its concentration as the temperature inside the car increased, exceeding the guideline value for indoor concentration established by the Ministry of Health, Labor and Welfare. "We want to build a car that minimizes the use of volatile chemicals as much as possible." Due to this social background, the automobile industry has begun to review pollution caused by chemical substances in the passenger compartment and make improvements in accordance with the guidelines set by the Ministry of Health, Labor and Welfare.

  On the other hand, with the goal of reducing the weight of members and reducing the environmental burden, products that have been manufactured with steel or vinyl chloride resin have been replaced with polyolefin resins. Low-activity resins such as polypropylene elastomer and polyethylene elastomer (TPO) in which rubber components such as EPDM components are added to those resins are inexpensive and relatively high in strength, so that they can be used for weather strips, bumpers, instrument panels, etc. Application to automotive parts is in progress.

  However, since the polyolefin resin generally has insufficient adhesion to the adhesive, it is necessary to perform a treatment for increasing the adhesion to the adhesive in order to implant the surface of the polyolefin resin substrate. It was. As a conventional technique, a primer treatment method in which a corona discharge treatment, a surface treatment by plasma discharge, a chlorinated polypropylene, or the like is applied to the surface of a substrate has been studied.

  In addition, a method of performing ultraviolet irradiation after contacting with an ultraviolet absorbing solvent as disclosed in JP-A-64-9243, and photoinitiators as disclosed in JP-A-5-271444 and JP-A-6-336575 are included. There has also been proposed a method for modifying a substrate surface by applying ultraviolet irradiation, such as a method of applying an ultraviolet ray after applying a solution to the substrate surface.

A solvent-type urethane adhesive has been reported as an electrostatic flocking adhesive for a substrate made of an olefin resin used in combination with an organic solvent-based chlorinated polypropylene primer.
JP-A 64-009243 JP 05-271444 A Japanese Patent Laid-Open No. 06-336575

  However, there are the following problems in applying these methods to general purposes.

  To perform corona discharge or plasma discharge, expensive special equipment is required. Furthermore, since the modified effect such as adhesiveness attenuates with time, there is a problem that the adhesive property, which is the purpose of the modification, varies with time and stable performance cannot be obtained. In addition, the above method has a small modification effect on polyolefin elastomers such as TPO, and does not exhibit sufficient adhesiveness.

  Since a chlorinated polypropylene primer dissolved in an organic solvent is applied to the surface of the base material, it is not preferable from the viewpoint of VOC regulations and the like on the global environment, the working environment, and the interior environment of the vehicle which is regarded as a problem in the present invention.

  Similarly, the organic solvent is used for the contact with the ultraviolet absorbing solvent and the application of the solution containing the photoinitiator, which causes a VOC problem.

  As for the adhesive, since the solvent-type urethane-based adhesive contains a large amount of solvent, there is a problem in terms of VOC.

The inventors of the present invention diligently studied an electrostatic flocking method for solving the above-mentioned problems and completed the present invention. That is, the present onset Ming, a substrate made of an olefin resin, an aqueous emulsion type primer composed mainly of acid-modified olefin resin is applied after drying of the primer, which is formed by aqueous emulsion type primer The coating layer is irradiated with light, and then a moisture-curable reactive hot melt adhesive having an isocyanate group-containing urethane prepolymer as a main component and having a melting point of 40 ° C. or higher and 150 ° C. or lower is heated and melted on the coating layer. And a method for producing an automotive flocking product based on an olefin-based resin, wherein a pile is electrostatically flocked on the adhesive layer formed thereby.

  Since the amount of VOC (volatile organic compound) can be drastically reduced by the method for producing an automobile flocking product obtained in the present invention, it leads to a significant improvement in the vehicle interior environment.

  Further, since the residual solvent can be greatly reduced from the manufacturing process, the working environment can be improved.

  Furthermore, this method has a higher modification effect than corona discharge and plasma irradiation, and is highly practical.

Olefin-based resin The olefin-based resin constituting the substrate of the present invention includes ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-pentene and the like. , Preferably a homopolymer of an α-olefin having 2 to 6 carbon atoms, a copolymer having two or more of these α-olefins as constituent monomers, or another copolymerizable monomer with the α-olefin. Specifically, polyethylene, polypropylene (including any of isotactic, syndiotactic, and atactic. The same shall apply hereinafter), poly-1-butene, and poly-4-methyl-1-pentene. Hard polyolefin materials such as: ethylene-propylene copolymer rubber; ethylene-propylene-diene copolymer rubber (EPDM) and the above-mentioned hard polyolefin Examples of the material include ethylene-propylene copolymer rubber and polyolefin elastomer (TPO) in which EPDM is blended.

  If desired, the base material of the olefin resin in the present invention may contain other resin components, additives, and fillers. Examples of the other resin components include styrene resins, styrene elastomers, and ethylene methacrylic acid resins. And ethylene vinyl acetate resin.

  A preferred ratio of the olefin resin component contained in the olefin resin substrate in the present invention is 50 wt% or more, and more preferably 60 wt% or more.

Acid-modified olefin resin The acid-modified olefin resin laminated on the olefin resin in the present invention is an olefin resin modified with an unsaturated carboxylic acid and / or an acid anhydride.

  Examples of the olefin component used in the acid-modified olefin resin of the present invention include ethylene, propylene, butylene, heptene, octene, and the like, and examples of the unsaturated carboxylic acid or acid anhydride used for modification include maleic acid, fumaric acid, and the like. Examples thereof include, but are not limited to, acid, itaconic acid, citraconic acid, allyl succinic acid, mesaconic acid, aconitic acid, and acid anhydrides thereof.

  The acid-modified olefin resin of the present invention also includes an acid-modified chlorinated polyolefin in which a part of hydrogen atoms in the olefin component of the acid-modified olefin resin is replaced with chlorine.

○ Application method of emulsion-type primer mainly composed of acid-modified olefin resin The application method of emulsion-type primer mainly composed of acid-modified olefin resin is a method of applying impregnation to brush, nonwoven fabric, etc. Examples include, but are not limited to, spray coating and dip.

  The drying method of the emulsion-type primer mainly composed of the acid-modified olefin resin coated on the olefin resin can be applied to either natural drying or forced heating drying with hot air, etc., but the substrate when the outside air temperature is low In addition, the wettability of the emulsion type primer may be reduced due to a decrease in temperature of the emulsion type primer, the wettability to the base material may be reduced due to the type of solvent, or the wettability may be decreased due to a reduction in the pressing force of coating.

  If wetting in the solution state is not sufficiently achieved in this way, solid acid-modified olefin resin that has failed to wet will be present on the olefin substrate, but the acid-modified olefin resin is heated above the softening point. Thus, the wettability between the acid-modified olefin resin and the substrate can be enhanced. Therefore, heat drying is more preferable than natural drying for obtaining stable quality.

Light irradiation The light irradiation in the present invention is performed on the coating layer formed on the base material made of the olefin resin by the emulsion type primer mainly composed of the acid-modified olefin resin after the drying. It has the effect of further improving the adhesiveness of the base material made of a resin. This is because the radicals are generated by elimination of hydrogen or chlorine from the acid-modified olefin resin as a primer by light irradiation, and oxygen atoms in the air are bonded to the radical atoms to generate oxygen-containing groups. The surface energy is increased, and the adhesion between the primer layer and the adhesive layer is improved. In addition, radical generation and formation of oxygen-containing groups by hydrogen abstraction proceed from a substrate made of an olefin resin by light irradiation, and surface energy is improved.

Examples of the light source used in the present invention include a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, and a metal halide lamp. Moreover, preferable electromagnetic waves for the surface treatment are 180 to 500 nm of ultraviolet rays and visible light. Amount of light irradiation to the surface modifying resin laminated to the olefin resin is usually 100 mJ / cm ² or more, particularly preferably in the 200~10000mJ / cm ^2.

O Moisture curable reactive hot melt adhesive 1) Composition of adhesive The adhesive in the present invention is a moisture curable reactive hot melt adhesive mainly composed of an isocyanate group-containing urethane prepolymer.

  The isocyanate group-containing urethane prepolymer is obtained by reacting one or more polyols having two or more hydroxyl groups in the molecule with one or more polyisocyanates having two or more isocyanate groups in the molecule. It is a urethane prepolymer. The preferred weight average molecular weight of the urethane prepolymer is 1000 to 50000. 1 type (s) or 2 or more types can be used as the said urethane prepolymer.

1-2) Polyol The polyol which is a raw material of the urethane prepolymer has 2 or more, preferably 5 or less hydroxyl groups in the molecule, and conventionally known polyols can be used. Preferred specific examples are shown below.

(I) Polyester polyol The polyester polyol is obtained by random copolycondensation polymerization of one or more polycarboxylic acids and one or more polyols.

  Preferred polycarboxylic acids are those having 2 or more carboxyl groups in the molecule and 4 to 24 carbon atoms. Preferred specific examples include succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, ε-caprolactone, terephthalic acid, isophthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic Acids, trimellitic acid, paraoxybenzoic acid and the like.

  A preferred polyol has two or more hydroxyl groups in the molecule and a weight average molecular weight of 60 to 10,000. Preferred specific examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1, Examples include 4-cyclohexanedimethanol, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol.

(Ii) Polyether polyol The polyether polyol has one or more ether bonds in the molecule, and preferred polyether polyols have a weight average molecular weight of 200 to 10,000. Preferred examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

(Iii) Polyolefin polyol The polyolefin polyol has a polyolefin skeleton in the molecule, and a preferred polyolefin polyol has a weight average molecular weight of 200 to 10,000. Preferable specific examples include hydrogenated polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol, and α-olefin copolymers.

(Iv) Other polyols There are polyalkylene polyols such as polybutadiene polyol and polyisoprene polyol, and polycarbonate polyol.

1-3) Polyisocyanate The polyisocyanate which is a raw material of the urethane prepolymer has two or more isocyanate groups in the molecule, and conventionally known ones can be used. Specifically, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 4,4′-diphenylene diisocyanate, 1,5-octylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexa Methylene diisocyanate, pentamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, diphenylmethane Diisocyanate, 1,4-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) Hexane, and the like isophorone diisocyanate and carbodiimide-modified 4,4'-diphenylmethane diisocyanate.

  The preferred ratio of the amount of polyisocyanate charged to the polyol when producing the urethane prepolymer in the present invention is 1 to 5 in an equivalent ratio of isocyanate group / hydroxyl group, more preferably 1.2 to 3.

  In addition, in order to increase the moisture reactivity of the adhesive of the present invention, a tertiary amine-based or tin-based catalyst, in addition, a tackifier, a silane coupling agent, a filler, a plasticizer, a wax, a stabilizer, an oxidation An inhibitor or the like can be added as necessary.

2) Adhesive melting point Since the adhesive in the present invention is composed of a urethane prepolymer having a melting point, it becomes a crystalline solid at a temperature below the melting point, so when changing from a molten state to a solid, the viscosity of the resin with the melting point as a boundary. Has a characteristic of rapidly increasing. Therefore, electrostatic flocking work is performed when the adhesive layer applied to the substrate is in a molten state, and then the adhesive is crystallized by cooling and solidifying the adhesive, so that the olefin resin and the other adherend are bonded. A certain pile is firmly fixed to the adhesive layer, and the initial adhesive strength can be easily obtained.

  Specifically, by setting the melting point of the adhesive to 40 ° C. or higher, it is solid in a normal state, and the initial adhesive strength can be obtained by the cohesive force at the time of crystallization. When the melting point is less than 40 ° C., the initial adhesive strength in the normal state cannot be obtained. On the other hand, when the melting point of the adhesive is higher than 150 ° C., harmful substances may be generated when the adhesive is heated and melted, which is not desirable.

  The melting point of the adhesive can be measured by observing the presence or absence of melting with a microscope while heating from room temperature at 1 ° C./min.

3) Melt Viscosity of Adhesive The preferable melt viscosity of the adhesive in the present invention is 200 to 100,000 mPa · s in a 120 ° C. molten state, more preferable melt viscosity is 1000 to 50000 mPa · s, and still more preferable melt viscosity is 1000 to The most preferred viscosity is 1000 to 10,000 mPa · s. The melt viscosity can be easily measured with a BM viscometer.

4) Glass transition temperature of adhesive The preferable glass transition temperature of the adhesive in this invention is -50-60 degreeC, More preferably, it is -40-30 degreeC. By adjusting the glass transition temperature to the above preferred range, an adhesive having excellent adhesion to the substrate can be obtained.

  When electrostatic flocking is performed using a hot melt adhesive, a gaseous or liquid refrigerant may be used for the purpose of quenching and solidifying the unsolidified adhesive layer on which the pile has been flocked in a short time. Examples of the refrigerant include water, a mixture of water and ethylene glycol, and other organic solvents, with VOC and safe water being particularly preferable. Although there is no restriction | limiting in particular in the temperature of a refrigerant | coolant, it needs to be lower than melting | fusing point of the adhesive agent used for flocking of a pile, and 25 degrees C or less is preferable normally. Moreover, although there is no restriction | limiting in particular in the cooling time with a refrigerant | coolant, Since the length of a manufacturing line can be shortened, so that it is short time, it is preferable normally within 1 minute.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the part irradiated with light in Example 9 shown below is an example included in the scope of the present invention, and the other examples are reference examples related to the present invention. In addition, the performance evaluation in each Example and the comparative example followed the following method.

○ Manufacture of weather strips Emulsion-type primer whose main component is the acid-modified olefin resin of the present invention at a predetermined portion of a weather strip prepared by extrusion molding of an olefinic thermoplastic elastomer (trade name: Miralastomer manufactured by Mitsui Chemicals, Inc.) After drying with hot air, with respect to the case where light irradiation is performed and the case where light irradiation is not performed, a moisture-curable reactive hot melt adhesive is applied to the treated surface, electrostatic flocking is performed, and then, 7 at room temperature. Cured for days and manufactured.

  The adhesive used for the evaluation is Aron Melt R RHT-310 (trade name, manufactured by Toagosei Co., Ltd.) with a melting point of 53 ° C. and a melt viscosity of 3,000 mPa · s in a 120 ° C. molten state.

Light irradiation The light irradiation device used was a high-pressure mercury lamp manufactured by Ushio Electric Co., Ltd. with an output of 3.2 kW, and the irradiation energy was 2000 mJ / cm ² as measured by an integrating photometer with a wavelength of 365 nm.

○ Abrasion test Abrasion test includes weather strip immediately after adhesion curing, heat aging test (80 ° C, 240 hours), weather resistance test (exposure to sunshine weather meter for 200 hours), water resistance test (immersion in water for 24 hours), And a weather strip subjected to a window washer resistance test (immersed in a window washer solution diluted to 1/3 for 24 hours) with a load of 8.33 N / 100 mm applied to the electrostatic flocking site. Ten thousand wear tests were conducted, the flocked state was confirmed, and the case where there was no peeling was regarded as acceptable, and the case where it was separated was regarded as unacceptable.

○ VOC test As a VOC test for weather strips at the extrusion molding stage and weather strips subjected to electrostatic flocking, the contents of toluene, xylene and ethylbenzene were measured using GC / MS (ATD = QP2010) manufactured by Shimadzu Corporation. .

[Example 1]
Hardlen (Toyo Kasei Kogyo Co., Ltd.) as an emulsion-type primer containing maleic anhydride-modified olefin resin as the main component on the surface of the weatherstrip produced by extruding an olefinic thermoplastic elastomer (trade name: Miralastomer manufactured by Mitsui Chemicals) A product name made by the company. Chlorine content of about 15 wt% is applied, dried with hot air, and an acid-modified olefin resin is laminated on the flocked surface, and then a moisture curing type reactive hot melt adhesive Aron Melt melted at 120 ° C After applying R RHT-310 (trade name, manufactured by Toagosei Co., Ltd.), electrostatic flocking was applied, followed by adhesion curing at room temperature for one week.

  The abrasion test includes a weather strip immediately after adhesion curing, a heat aging test (80 ° C., 240 hours), a weather resistance test (exposure to a sunshine weather meter for 200 hours), a water resistance test (immersion in water for 24 hours), and a wind resistance test. The weather strip after the washer test (immersed in window washer solution diluted to 1/3 for 24 hours) was repeated 10,000 times with a load of 8.33 N / 100 mm applied to the electrostatic flocking site. A wear test was performed.

[Example 2]
A wear test was performed under the same conditions as in Example 1 except that hard-lens (trade name, manufactured by Toyo Kasei Kogyo Co., Ltd., chlorine content: about 16 wt%) was applied as an emulsion-type primer mainly composed of maleic anhydride-modified olefin resin. .

[Example 3]
The abrasion test was performed under the same conditions as in Example 1 except that Super Clone (trade name, manufactured by Nippon Paper Chemical Co., Ltd., chlorine content: about 15 wt%) was applied as an emulsion-type primer mainly composed of maleic anhydride-modified olefin resin. It was.

[Example 4]
The abrasion test was performed under the same conditions as in Example 1 except that Super Clone (trade name, manufactured by Nippon Paper Chemicals Co., Ltd., chlorine content: about 17 wt%) was applied as an emulsion type primer mainly composed of maleic anhydride-modified olefin resin. It was.

[Example 5]
The abrasion test was performed under the same conditions as in Example 1 except that Super Clone (trade name, manufactured by Nippon Paper Chemicals Co., Ltd., chlorine content: about 20 wt%) was applied as an emulsion-type primer mainly composed of maleic anhydride-modified olefin resin. It was.

[Example 6]
The abrasion test was performed under the same conditions as in Example 1 except that aurolene (trade name, manufactured by Nippon Paper Chemical Co., Ltd., chlorine content: 0 wt%) was applied as an emulsion-type primer mainly composed of maleic anhydride-modified olefin resin. .

[Example 7]
The VOC of the weather strip prepared in Example 1 was measured.

[Example 8]
The VOC of the weather strip prepared in Example 6 was measured.

[Example 9]
Assuming a flocking in the outline, after molding a weatherstrip base material made by extruding an olefinic thermoplastic elastomer (trade name: Miralastomer, manufactured by Mitsui Chemicals), maleic anhydride is formed on the flocking surface one day later. Hardened (trade name, manufactured by Toyo Kasei Kogyo Co., Ltd., chlorine content: about 15 wt%) as an emulsion-type primer containing a modified olefin resin as the main component, dried with hot air, and then irradiated with light or not. Regarding the case, after the acid-modified olefin resin was laminated on the flocked surface, a moisture-curing reactive hot melt adhesive Aronmelt R RHT-310 (manufactured by Toagosei Co., Ltd.) in a molten state at 120 ° C. manufactured by Toagosei Co., Ltd. (Trade name) was applied, electrostatic flocking was applied, and curing was performed for 16 hours in a heated and humidified state of 40 ° C. and 85% RH.

  The degree of peeling of the adhesive layer after the above cured product was immersed in gasoline, kerosene, and toluene in a 25 ° C. environment for 6 hours was compared.

[Comparative Example 1]
A wear test was performed under the same conditions as in Example 1 except that Davybond (trade name, manufactured by Diabond Industry Co., Ltd., chlorine content: about 2.5 to 10 wt%) was applied as a solvent-type primer containing chlorinated PP as a main component. went.

[Comparative Example 2]
A wear test was performed under the same conditions as in Example 1 without applying the primer.

[Comparative Example 3]
The vegetation surface of the weatherstrip made by extruding an olefinic thermoplastic elastomer (trade name: Miralastomer, manufactured by Mitsui Chemicals, Inc.) is not treated with a primer. A wear test was performed under the same conditions as in Example 1 except that the surface treatment was performed by plasma irradiation under conditions of 3 seconds. ST-7000 manufactured by Keyence Corporation was used as the plasma irradiation apparatus.

[Comparative Example 4]
The vegetation surface of the weather strip made by extruding an olefin-based thermoplastic elastomer (trade name: Miralastomer manufactured by Mitsui Chemicals, Inc.) is not treated with a primer, but instead is irradiated with a corona discharge device at an irradiation distance of 5 mm and irradiation time. A wear test was performed under the same conditions as in Example 1 except that the surface treatment was performed by corona discharge under the condition of 15 seconds. As the corona discharge device, Polydyne manufactured by Navista Co., Ltd. was used.

[Comparative Example 5]
The VOC of the weather strip prepared under the same conditions as in Comparative Example 1 was measured except that olestar (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.) was used as the adhesive. In addition, a chemical resistance test was performed under the same conditions as in Example 9.

[Comparative Example 6]
The VOC of the weather strip produced in Comparative Example 1 was measured.

  Table 1 and Table 2 summarize the evaluation regarding the flocking adhesiveness, and Table 3 summarizes the VOC (volatile organic compound generation amount). Table 4 shows the chemical resistance evaluation results of the adhesive layer.

  As shown in Tables 1 and 2, the results of various abrasion tests for evaluating the flocking adhesion showed no substantial peeling in each example, whereas in the comparative example, there was much peeling except for Comparative Example 1. The flocking adhesion was unacceptable. In Comparative Example 1, a solvent-based adhesive is used, and the working environment is not good.

  From the results of Table 3 regarding VOC (volatile organic compound generation amount), toluene, xylene and ethylbenzene were not detected significantly in Examples 7 and 8 and the reference (without adhesive and primer), but compared. In Examples 5 and 6, volatile solvents such as toluene were detected significantly.

  From the results of Table 4 regarding the chemical resistance of the adhesive layer, in Example 9 of the present invention, the adhesive layer of the adhesive layer is hardly peeled off. In particular, when the light irradiation is performed, the adhesive layer is substantially peeled off. In contrast, in the comparative example, peeling of the adhesive layer was significant, which was an undesirable result.

極微：有意の検出が不可のレベル

Minimal: Level at which significant detection is not possible

○：接着剤層の剥がれ無し
△：接着剤層の剥がれが一部見られる
×：接着剤層が完全に剥がれる

○: No peeling of the adhesive layer Δ: Partial peeling of the adhesive layer is observed x: The adhesive layer is completely peeled off

  The present invention provides a method for producing an automotive flocking product in which a pile is firmly bonded to a base material made of an olefin resin with a solvent-free, moisture-curable reactive hot melt adhesive.

  According to the present invention, it is possible to easily replace an automobile flocking product, which has conventionally used a base material made of a vinyl chloride resin, with an olefin resin, and to reduce the environmental burden.

  Specifically, weatherstrips can be produced at low cost using polypropylene, polyethylene, and low activity resins such as polyolefin elastomer (TPO) in which rubber components such as EPDM components are added to those resins.

Claims (1)

After applying a water-based emulsion type primer mainly composed of an acid-modified olefin resin to a base material composed of an olefin-based resin and drying the primer, the coating layer formed by the water-based emulsion type primer is irradiated with light, Next, a moisture-curable reactive hot melt adhesive having an isocyanate group-containing urethane prepolymer as a main component and having a melting point of 40 ° C. or higher and 150 ° C. or lower is heated and melted on the coating layer, and formed. A method for producing an automobile flocking product based on an olefin-based resin, wherein a pile is electrostatically flocked on an adhesive layer.