JP4862491B2 - Flocking piles and flocking products - Google Patents

Description

  The present invention relates to a pile for flocking and a flocking product. More specifically, the present invention relates to a filing pile and a flocking product using polylactic acid.

  Currently, nylon fibers are mainly used for piles used for flocking products (see, for example, Patent Document 1). In particular, for automobile applications, nylon fibers having a soft texture are often used.

  However, in recent years, there is concern about global warming caused by mass consumption of petroleum resources and the depletion of petroleum resources associated with mass consumption, and environmental awareness is increasing on a global scale. In such a background, a material made of a plant-derived material (biomass) is eagerly desired.

  Polylactic acid is a polymer made from lactic acid obtained by fermenting starch extracted from a plant, and is the best balance among mechanical properties, heat resistance, and cost among polymers using biomass. And development of various products using this is performed at a rapid pace.

The development of polylactic acid fiber is preceded by agricultural materials and civil engineering materials that take advantage of its biodegradability, but it still has a texture and color developability for use in automobiles, etc., and low environmental impact. At present, no flocking products have been proposed.
JP 2001-315235 A JP 2000-234217 A

  An object of the present invention is to provide a flocking product that has a low environmental load and can be used in practical applications such as automobiles.

  That is, the present invention is a pile for flocking comprising a polylactic acid fiber having a diameter of 0.3 to 31 μm and a pile length of 0.1 to 3 mm.

  Moreover, this invention is a flocking product characterized by including the pile for flocking of this invention.

  ADVANTAGE OF THE INVENTION According to this invention, the flocked product of the level which has a low load with respect to an environment and can be used practically in a touch, a feeling of nap, coloring property, etc. can be obtained.

In order to solve the above-mentioned problems, the present inventors have made extensive studies in order to carry out the above-mentioned problems. As a result, the diameter mainly composed of polylactic acid fibers is 0.3 to 31 μm, and the pile length is 0.1 to 3 mm. The present inventors have found that this problem can be solved at once by using a pile for flocking characterized in that polylactic acid is coated with another polymer by a sea-island structure or a polymer blend .

  Hereinafter, the best mode for carrying out the automobile interior member of the present invention will be described in detail.

  First, the pile for flocking of the present invention comprises polylactic acid fiber. Here, “polylactic acid” refers to a polymer obtained by polymerizing oligomers of lactic acid such as lactic acid and lactide. “Polylactic acid fiber” refers to a fiber comprising polylactic acid. Polylactic acid fibers are superior to other non-petroleum polymers in terms of cost, spinnability, card passing property, and the like. In addition, since it is a non-petroleum material, it can reduce the burden on the global environment without increasing carbon dioxide in the atmosphere as compared with other petroleum materials.

  Polylactic acid also exhibits excellent antibacterial properties. The reason is that polylactic acid is exposed in the fiber cross section, and the lactide and lactic acid components precipitated from the exposed polylactic acid are considered to contribute to the improvement of the bacteriostatic activity value.

  In addition, in the aspect formed by coating other polymers with polylactic acid, there are those in which polylactic acid is not exposed on the side surface of the fiber, but in that case, polylactic acid is exposed in the pile cut cross section, Appears antibacterial.

  The optical purity of L-form or D-form in polylactic acid is preferably 90% or more, and more preferably 97% or more in terms of increasing the melting point and improving heat resistance. In addition, a blend of polylactic acid having an optical purity of 90% or higher in the L form and polylactic acid having an optical purity of 90% or higher in the D form at a ratio of 70/30 to 30/70 is preferable because the melting point is further improved. is there.

  In addition, components other than lactic acid may be copolymerized within a range that does not impair the properties of polylactic acid.

  Further, it may contain additives such as particles, flame retardants, antistatic agents, matting agents, deodorants, antibacterial agents, antioxidants, and coloring pigments. Moreover, you may contain terminal blockers, such as a carbodiimide compound, for the purpose of suppression of the hydrolysis of polylactic acid by hot water treatments, such as dyeing | staining, and suppression of the physical-property fall with time.

  The molecular weight of the polylactic acid is preferably 50,000 to 500,000, more preferably 100,000 to 350,000 in terms of weight average molecular weight from the viewpoint of the balance between mechanical properties and moldability. Moreover, it is preferable that the polylactic acid is coat | covered with the other polymer in the polylactic acid fiber in the pile for hair transplantation of this invention. This is because the wear resistance and heat resistance can be improved.

  As an embodiment in which polylactic acid is coated with another polymer, sea-island type resin dispersion by a polymer blend or core-sheath type or sea-island type composite fiber can be employed.

  In the sea-island type resin dispersion by polymer blend, polylactic acid is used as an island component and other polymer as a sea component, so that polylactic acid is coated with another polymer.

  The core-sheath type composite fiber has a structure in which polylactic acid is coated with another polymer by using polylactic acid as a core component and another polymer as a sheath component.

  The sea-island type composite fiber has a structure in which polylactic acid is coated with another polymer by using polylactic acid as an island component and another polymer as a sea component.

  In addition, some island components may be exposed on the fiber surface.

  Examples of other polymers include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyamide, acrylic, and polyolefin.

  Among them, polytrimethylene terephthalate can produce trimethylene glycol, which is a component of the polytrimethylene terephthalate, from plant-derived components, and is preferable in terms of low environmental load. The polytrimethylene terephthalate has a trimethylene terephthalate unit as a main repeating unit, and the content of the unit with respect to the polytrimethylene terephthalate is preferably 20% by weight or more. Polytrimethylene terephthalate can be synthesized by combining trimethylene glycol with terephthalic acid or a functional derivative thereof such as dimethyl terephthalate.

  From the viewpoint of ease of melt composite spinning, thermoplastic polyamide, polytrimethylene terephthalate, and the like can be preferably used.

  In particular, the thermoplastic polyamide has a high affinity with polylactic acid, an excellent color developability, and a combination of a polylactic acid resin and a particularly deep silky-like gloss. This is particularly preferable from the viewpoint of excellent touch and texture as a flocking product.

  The thermoplastic polyamide is a polymer having an amide bond, and examples thereof include nylon 6, nylon 11, nylon 12, and nylon 610. From the viewpoint of increasing the affinity with polylactic acid, it is preferable that the methylene chain length of the polyamide is long, and in this respect, nylon 11, nylon 12, and nylon 610 are preferable.

  The mass fraction of polylactic acid to polylactic acid fiber in the sea-island resin dispersion by polymer blend is preferably 5% by mass or more, more preferably 7% by mass or more, and still more preferably from the viewpoint of low environmental load and color development. It is 10 mass% or more, More preferably, it is 15 mass% or more. On the other hand, in order to stably form a structure in which polylactic acid resin is an island structure and other thermoplastic resin is a sea structure, and in terms of wear resistance, 55% by mass or less is preferable, and more preferably 45% by mass. % Or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

  The mass fraction of polylactic acid in the polylactic acid fiber in a form in which polylactic acid is coated with another polymer is preferably 30% by mass or more, more preferably from the viewpoint of low environmental load, productivity, color developability, and the like. It is 50 mass% or more. On the other hand, in terms of wear resistance, 70% by mass or less is preferable.

  The pile for flocking of the present invention can be obtained by drawing an undrawn yarn tow of polylactic acid fiber, bundling the drawn yarn into a tow of several kilotex to several tens of kilotex, and cutting this with a guillotine cutter. it can.

  The diameter of the polylactic acid fiber is 0.3 to 31 μm, which is important in terms of surface quality and touch, and 10 to 20 μm is preferable from the viewpoint of cost and surface quality. By setting the diameter of the polylactic acid fiber to 31 μm or less, it is possible to obtain a flocked product having excellent quality as a material having a good touch. Moreover, abrasion resistance can be maintained by setting it as 0.3 micrometer or more.

  The fineness of the polylactic acid fiber is preferably 0.001 to 8 dtex in terms of surface quality and touch, and more preferably 0.9 to 3.3 dtex in terms of cost and surface quality. By setting it to 8 dtex or less, a flocked product having excellent quality can be obtained as a material having a good touch. Moreover, abrasion resistance can be maintained by setting it as 0.001 dtex or more.

  The pile length of the pile for flocking of this invention shall be 0.1-3 mm. When the pile length is 0.1 mm or more, the feel of the flocked product can be improved and the surface quality can be improved, and when it is 3 mm or less, the deterioration of the hair fall resistance and the feel of the flocked product are prevented. be able to. Furthermore, by setting the pile length to 2 mm or less, a flocking product having a surface quality suitable for automobile interiors can be obtained.

When the pile for flocking of the present invention is used for electrostatic flocking in particular, the surface resistance value is preferably in the range of 10 ⁸ to 10 ¹⁰ Ω · cm. By setting the surface resistance value within the range, the dispersibility and flying properties of the short fibers that are gathered can be improved. The surface resistance value within the range can be achieved, for example, by electrodeposition treatment with a treatment liquid of a silicon compound such as sodium silicate or potassium silicate, or a compatible potassium compound such as potassium formate or potassium acetate.

  The electrodeposition treatment is a step of treating the resistance value on the fiber surface to an appropriate resistance value for electrostatic flocking.

When performing electrodeposition process polylactic acid fiber, sodium silicate and, if Ru using a silicon compound such as potassium silicate, without causing hydrolysis of the polylactic acid, can be processed, preferably.

Further, by treating the surface with a tannin compound, a flocked pile having a good texture can be obtained without hydrolyzing polylactic acid.
Before subjecting the pile for flocking of the present invention to flocking processing, it is possible to pass short fibers through a mesh and remove fibers fused with yarn in the spinning process or fibers longer than the specified length. Is preferable in improving the surface quality of the flocked product.

  The pile for flocking of the present invention can be used for various types of flocking processes such as electrostatic flocking, spray flocking, and spray flocking.

  In electrostatic flocking, a high-voltage electrostatic field is generated between the electrodes, a base material coated with an adhesive is placed on one electrode side, charges are applied to the pile for flocking, and the electrode from the opposite side is directed to the base fabric. It is a thing to fly and plant.

  Examples of the material and shape of the base material to be planted include resin materials, woody materials, paper, metal materials, ceramics, or moldings and cloths using these composite materials. Examples of the resin material include polyolefin resin, polystyrene resin, ABS resin, AS resin, AAS resin, polyvinyl chloride resin, methacrylic resin, polyester resin, polyamide resin, polyacetal resin, and polycarbonate resin.

  Moreover, as an adhesive for fixing a pile to such a base material, adhesives such as epoxy, melamine, acrylic, urethane, polyester, vinyl acetate, and synthetic rubber can be used.

  In particular, acrylic and polyester adhesives can be preferably used from the viewpoint of low drying temperature and adhesive strength.

  The flocked product of the present invention can be suitably used for automobile interior materials such as pillar ganish and pillar heater guards, trays, sheets, sun visors, louvers, carpets, toys, air conditioner wind direction plates, and the like.

[Measuring method]
(1) Pile length The pile after cutting was expanded with a magnifying glass (PROFILE PROJECTOR V-12 manufactured by Nikon), its length was measured, and an average value of 200 pieces was calculated.

(2) Pile fineness The fineness was measured in accordance with JIS L 1015: 1999 8.5.1 b) (Method B).
A set of 200 piles was weighed, and the mass was measured. From the average pile length measured above, the fineness (dtex) was calculated by the following formula, and the average value of 5 times was calculated.
F = 10000 × m ÷ (200 × L)
Here, F: Fineness (dtex)
m: Mass of sample (mg)
L: Average pile length.

(3) Pile diameter When the surface of the flocked product is observed with a scanning electron microscope (SEM) and magnified 500 times, and the number of piles in the plane exceeds 30 out of the field of view of 150 μm in length and 200 μm in width The number of n was extracted at random, the crossing of each pile was measured with image analysis software, and the diameter was calculated from the area in terms of a perfect circle.

(4) Hand feeling Measured in four stages by sensory evaluation. Particularly excellent results were evaluated as ◎, excellent results as ◯, slightly inferior results as △, and inferior results as ×.

(5) Napiness Measured in four stages by sensory evaluation. Particularly excellent results were evaluated as ◎, excellent results as ◯, slightly inferior results as △, and inferior results as ×.

(6) Color developability Measured in four stages by sensory evaluation. Particularly excellent results were evaluated as ◎, excellent results as ◯, slightly inferior results as △, and inferior results as ×.

(7) Bacteriostatic activity value According to JIS Z 2801, a bacterial solution prepared with 1/500 ordinary bouillon is dropped onto the surface of the test piece, closely adhered with a film and stored at 35 ° C., and then the bacterial solution on the test piece after 24 hours. The viable cell count was measured.

The bacteriostatic activity value obtained by calculating the bacteriostatic activity value from the measured number of viable bacteria by the following formula = log (A / B)
Here, A: the number of viable bacteria after 24 hours of the unprocessed test piece B: the number of viable bacteria after 24 hours of the test piece.

[Example 1] (Reference Example)
(spinning)
A polylactic acid chip (Cargildau 6201D) was charged into a spinning machine hopper, melted at 220 ° C. with an extruder-type spinning machine, spun at a discharge rate of 505 g / min from a die having 600 holes, and a spinning speed of 1000 m / min. I took it. Similarly, a plurality of spun yarns were combined and received in a can.

(Stretching)
The undrawn yarn was further combined into a 27.7 ktex tow, drawn to 3.1 times in an 80 ° C. water bath, and then crimped by a stuffing box. Next, a relaxing heat treatment was performed at 90 ° C., and an oil agent was applied to obtain a drawn tow having a single fiber fineness of 3.3 dtex.

(Pile cut)
The obtained stretched tow was cut into 0.8 mm with a guillotine cutter.

(Electrodeposition processing)
The obtained short fiber was treated with a disperse dye at 110 ° C. for 30 minutes, washed with hot water, then treated with a colloidal silica dispersion, and a pile length of 0.8 mm, a pile fineness of 3.3 dtex, and a pile diameter of 18.3 μm. Got.

(Flocking)
A polyolefin base material (Toyota TSOP plastic) was treated with a primer (containing 92% toluene, 2% chlorinated PP, and 5% acrylic resin) and dried at 80 ° C. for 30 minutes. Thereafter, an acrylic emulsion adhesive was applied to the substrate, a voltage of 30,000 V was applied to the pile obtained above, electrostatic flocking was carried out by the up method, and drying was performed at 80 ° C. for 30 minutes.

  The obtained flocked product was excellent in touch, feeling of nap, color development, and bacteriostatic activity.

[Example 2] (Reference Example)
(Spinning, drawing, pile cutting, electrodeposition processing)
A pile for flocking having a pile length of 1.2 mm, a pile fineness of 3.3 dtex, and a pile diameter of 18.3 μm was obtained in the same manner as in Example 1 except that the cut length was changed to 1.2 mm.

(Flocking)
A flocked product was obtained in the same manner as in Example 1 except that the flocked pile obtained above was used.

[Example 3] (Reference Example)
(spinning)
A polylactic acid chip (6201D manufactured by Cargill Dow) was charged into a spinning machine hopper, melted at 220 ° C. with an extruder type spinning machine, spun at a discharge rate of 390 g / min from a die having 600 holes, and a spinning speed of 1000 m / min. I took it. Similarly, a plurality of spun yarns were combined and received in a can.

(Stretching)
The undrawn yarn was further combined into a 28 ktex tow, drawn to 3.6 times in a water bath at 80 ° C., and then crimped by a stuffing box. Subsequently, a relaxing heat treatment was performed at 90 ° C., and an oil agent was applied to obtain a drawn tow having a single fiber fineness of 6.6 dtex.

(Pile cut)
The obtained stretched tow was cut into 1.0 mm with a guillotine cutter.

(Electrodeposition processing)
The pile obtained by cutting was subjected to electrodeposition treatment in the same manner as in Example 1 to obtain a pile for flocking having a pile length of 1.0 mm, a pile fineness of 6.6 dtex, and a pile diameter of 28.9 μm.

(Flocking)
A flocked product was obtained in the same manner as in Example 1 except that the flocked pile obtained above was used.

[Example 4] (Reference Example)
(spinning)
A polylactic acid chip (Cargildau 6201D) was charged into a spinning machine hopper, melted at 220 ° C. with an extruder-type spinning machine, spun at a discharge rate of 290 g / min from a base having 600 holes, and a spinning speed of 1000 m / min. I took it. Similarly, a plurality of spun yarns were combined and received in a can.

(Stretching)
The undrawn yarn was further combined into a 28 ktex tow, drawn to 3.1 times in an 80 ° C. water bath, and then crimped by a stuffing box. Subsequently, a relaxing heat treatment was performed at 90 ° C. to apply an oil agent, and a drawn tow having a single fiber fineness of 1.5 dtex was obtained.

(Pile cut)
The obtained stretched tow was cut into 1.0 mm with a guillotine cutter.

(Electrodeposition processing)
The pile obtained by cutting was subjected to electrodeposition treatment in the same manner as in Example 1 to obtain a pile for flocking having a pile length of 1.0 mm, a pile fineness of 1.5 dtex, and a pile diameter of 12.3 μm.

(Flocking)
A flocked product was obtained in the same manner as in Example 1 except that the flocked pile obtained above was used.

[Example 5] (Reference Example)
(spinning)
Polylactic acid chips (Cargil Dow 6201D) and nylon 6 chips are charged into a spinning machine hopper, melted at 255 ° C. with an extruder-type spinning machine, spun at a discharge rate of 350 g / min from a die having 437 holes, spinning speed It was collected at 800 m / min. Similarly, a plurality of spun yarns were combined and received in a can.

(Stretching)
Then, this undrawn yarn was further combined into a 42 ktex tow, drawn 3.5 times in a 90 ° C. steam box, and then an oil agent was applied. Next, crimping was applied with a stuffing box, and relaxed heat treatment was performed at 90 ° C. to obtain a drawn tow having a single fiber fineness of 3.3 dtex.

(Pile cut)
The obtained stretched tow was cut into 1.0 mm with a guillotine cutter.

(Electrodeposition processing)
The pile obtained by cutting was subjected to electrodeposition treatment in the same manner as in Example 1 to obtain a pile for flocking having a pile length of 1.0 mm, a pile fineness of 3.3 dtex, and a pile diameter of 18.7 μm.

(Flocking)
A flocked product was obtained in the same manner as in Example 1 except that the flocked pile obtained above was used.

[Example 6]
(spinning)
A polylactic acid chip (6400D manufactured by Cargill Dow) (melt viscosity 1210 poise) and nylon 6 chip (melt viscosity 580 poise) were kneaded with an extruder at a kneading mass ratio (polylactic acid: nylon) 70:30, kneading temperature 230 ° C., Supplied to the spinning machine.

  The spinning temperature in the spinning machine was 230 ° C., filtered through a metal nonwoven fabric filter having a mesh size of 20 μm in a spinning pack, spun from a die having 600 holes at a discharge rate of 505 g / min, and taken up at a spinning speed of 1000 m / min. Similarly, a plurality of spun yarns were combined and received in a can.

(Stretching)
Then, this undrawn yarn is further combined into a 28 ktex tow, drawn to 3.11 times in a 90 ° C. water bath, then crimped by a stuffing box, and given an oil agent, then at 90 ° C. Relaxed heat treatment was performed to obtain a drawn tow having a single fiber fineness of 3.3 dtex.

(Pile cut)
The obtained stretched tow was cut into 1.0 mm with a guillotine cutter.

(Electrodeposition processing)
The pile obtained by cutting was subjected to electrodeposition treatment in the same manner as in Example 1 to obtain a pile for flocking having a pile length of 1.0 mm, a pile fineness of 3.3 dtex, and a pile diameter of 19.0 μm.

(Flocking)
A flocked product was obtained in the same manner as in Example 1 except that the flocked pile obtained above was used.

[Comparative Example 1]
(spinning)
A polylactic acid chip (Cargildau 6201D) was charged into a spinning machine hopper, melted at 220 ° C. with an extruder-type spinning machine, spun at a discharge rate of 484 g / min from a die having 200 holes, and a spinning speed of 1000 m / min. I took it. Similarly, a plurality of spun yarns were combined and received in a can.

(Stretching)
The undrawn yarn was further combined into a 28.8 ktex tow, drawn in a water bath at 80 ° C. by 3.6 times, and then crimped by a stuffing box. Next, relaxing heat treatment was performed at 110 ° C. to apply an oil agent, and a drawn tow having a single fiber fineness of 9 dtex was obtained.

(Pile cut)
The obtained stretched tow was cut into 0.8 mm with a guillotine cutter.

(Electrodeposition processing)
The pile obtained by cutting was subjected to electrodeposition treatment in the same manner as in Example 1 to obtain a pile for flocking having a pile length of 0.8 mm, a pile fineness of 9 dtex, and a pile diameter of 31.7 μm.

(Flocking)
A flocked product was obtained in the same manner as in Example 1 except that the flocked pile obtained above was used.

  The flocked product of Comparative Example 1 was inferior to the touch and the raised feeling compared with Examples 1 and 2.

[Reference Examples 1 and 2]
In place of polylactic acid fiber, nylon fiber and polyethylene terephthalate fiber were used as Reference Examples 1 and 2, respectively.

  The pile for flocking of the Example using a polylactic acid fiber was inferior in a touch, a nap feeling, and coloring property compared with the conventional petroleum material.

  The pile for flocking and flocking product of the present invention are used for automobiles, air conditioner wind direction plates in household electrical appliances, copy machine parts, anti-slip in furniture applications, scratch prevention covers, sound absorption in audio equipment applications, vibration damping materials, or household goods. It can be suitably used for a decoration material or the like in use.

Claims (4)

It comprises a polylactic acid fiber having a diameter of 0.3 to 31 μm and a pile length of 0.1 to 3 mm, and the polylactic acid fiber is coated with another polymer by a sea-island structure or a polymer blend. A pile for flocking.   A flocking product comprising the filing pile according to claim 1.   The flocked product according to claim 2, which is used for automobile interior materials.   The flocked product of Claim 2 used for the wind direction board use of an air conditioner.