WO2014097999A1 - 積層シート及びその製造方法 - Google Patents
積層シート及びその製造方法 Download PDFInfo
- Publication number
- WO2014097999A1 WO2014097999A1 PCT/JP2013/083530 JP2013083530W WO2014097999A1 WO 2014097999 A1 WO2014097999 A1 WO 2014097999A1 JP 2013083530 W JP2013083530 W JP 2013083530W WO 2014097999 A1 WO2014097999 A1 WO 2014097999A1
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- WIPO (PCT)
- Prior art keywords
- layer
- laminated sheet
- woven fabric
- resin
- base fabric
- Prior art date
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- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/0054—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by mechanical perforations
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- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
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- D10B2505/08—Upholstery, mattresses
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- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3854—Woven fabric with a preformed polymeric film or sheet
Definitions
- the present invention relates to a laminated sheet and a manufacturing method thereof.
- synthetic leather is roughly classified into dry synthetic leather that is bonded to the skin without processing the base fabric, and wet synthetic leather that is wet processed to the base fabric to form a wet base and then bonded to the skin.
- the decorative laminated sheet provided with two or more holes which can visually recognize the color of the colored layer under an opaque skin layer when it sees from the skin layer side is disclosed.
- the laminated sheet used as synthetic leather is perforated (perforation).
- perforation reduces the strength of the synthetic leather, including the tear strength and flat wear strength.
- strength may not be sufficiently obtained due to the physical properties of the base fabric serving as a base material, and air permeability increases due to the formation of holes, and flame retardancy tends to decrease accordingly.
- the base fabric is impregnated with a urethane resin to form a wet base, the flame retardant performance tends to decrease because the urethane resin enters the base fabric.
- the appearance defect that the fray of the base fabric is visible from the hole and the hole is distorted because the synthetic leather is soft is likely to occur.
- a roughening process (buffing) is performed before the skin layer is bonded to the base fabric, the strength of the base fabric may be reduced due to damage to the yarn constituting the base fabric.
- wear resistance tends to be insufficient due to rubbing of the edge of the hole.
- the present invention provides a laminated sheet having high tear strength, moisture permeability, breathability, and flame retardancy and excellent appearance of a vent and a laminated sheet manufacturing method capable of producing the laminated sheet by a simple process. The purpose is to do.
- the present inventors have perforated a laminate including a base fabric layer having a porous structure in which a specific woven fabric is impregnated with a resin solution containing a polyurethane resin and an organic flame retardant. It has been found that a laminated sheet having high tear strength, moisture permeability, breathability, and flame retardancy, and excellent appearance of the vents can be obtained. That is, in order to achieve the above object, the following invention is provided.
- a base fabric layer having a porous structure obtained by impregnating a resin composition containing a polyurethane-based resin and an organic flame retardant into a woven fabric having a tear strength by a trapezoid method of 150 N or more and horizontal 100 N or more; A laminated sheet having a plurality of air holes penetrating in the thickness direction.
- the woven fabric is a woven fabric twilled using a single yarn of 5 to 30 as warp and two to four twisted yarns of 10 to 40 as weft.
- the organic flame retardant is an organic phosphate flame retardant.
- ⁇ 4> The laminated sheet according to any one of ⁇ 1> to ⁇ 3>, further comprising an abrasion-resistant layer on the skin layer.
- ⁇ 5> a step of impregnating a woven fabric having a tear strength by a trapezoid method of 150N or more and a width of 100N or more with a resin solution containing a polyurethane-based resin, an organic flame retardant, and a solvent; Immersing the woven fabric impregnated with the resin solution in water to remove the solvent contained in the woven fabric and coagulating the polyurethane resin; Drying the woven fabric solidified with the polyurethane-based resin to form a base fabric layer having a porous structure; Roughening one side of the base fabric layer; Forming a laminate in which a skin layer is laminated on the roughened surface of the base fabric layer; Drilling a plurality of air holes penetrating in the thickness direction of the laminate; and The manufacturing method of the lamination sheet which has this
- a laminated sheet having high tear strength, moisture permeability, breathability, and flame retardancy and excellent appearance of the vent holes. Moreover, according to this invention, the manufacturing method of the lamination sheet which can manufacture the said lamination sheet by a simple process is provided.
- FIG. 3 is a diagram showing the appearance of the air holes of the laminated sheet produced in Example 1.
- 6 is a view showing an appearance of a vent hole of a laminated sheet produced in Comparative Example 2.
- FIG. 6 is a view showing the appearance of a vent hole of a laminated sheet produced in Comparative Example 3.
- the laminated sheet of the present invention is a base fabric layer having a porous structure formed by impregnating a resin composition containing a polyurethane-based resin and an organic flame retardant into a woven fabric having a tear strength by a trapezoid method of 150 N or more and horizontal 100 N or more. And a skin layer laminated on the base fabric layer, and has a plurality of ventilation holes penetrating in the thickness direction.
- FIG. 1 schematically shows a cross section in the thickness direction of an example of the laminated sheet of the present invention
- FIG. 2 schematically shows an example of the arrangement of the air holes of the laminated sheet of the present invention.
- a base fabric layer 12 an adhesive layer 14, a skin layer 16, an abrasion-resistant layer 18, and a tactile sensation treatment layer 20 are sequentially laminated, and a through-penetrating process penetrates in the thickness direction.
- a large number of pores 30 are provided.
- the adhesive layer 14, the abrasion resistant layer 18, and the tactile sensation treatment layer 20 are omitted.
- the lamination sheet 10 which concerns on this invention is not limited to the structure shown in these figures.
- the wear-resistant layer 18 and the tactile sensation treatment layer 20 may be provided as necessary, and an intermediate layer for providing elasticity, flexibility and the like is provided between the adhesive layer 14 and the skin layer 16. Also good.
- the base fabric layer 12 has a porous structure in which a resin composition containing a polyurethane resin and an organic flame retardant is impregnated into a woven fabric having a tear strength by a trapezoid method of 150 N or more in length and 100 N or more in width.
- a woven fabric having a high tear strength of 150N or more and a horizontal strength of 100N or more according to JIS L1096 8.15.4 C method is used.
- the woven fabric preferably has a tear strength of 180 N or more and a width of 120 N or more, and more preferably a length of 200 N or more and a width of 150 N or more.
- the tear strength by JIS L1096: 1999 8.15.4 C method is specifically measured as follows. Three sample pieces of 7.5 cm ⁇ 15 cm are taken in each of the vertical and horizontal directions, and an isosceles trapezoidal mark is marked on the test piece as shown in FIG.
- the base fabric strength is weak and the tear strength when the hole 30 is opened may be insufficient.
- the warp and weft include polyester / rayon (65/35), polyester (100%), and the like.
- the thickness of the single yarn depends on the material of the yarn, but for example, the warp is 5 to 30 and the weft is 10 to 40.
- a twill-woven fabric using a single yarn of 5 to 30 as the warp and two to four twists of 10 to 40 as the weft is preferable. If two to four twisted yarns are used as the weft, the base fabric has a tear strength of 110 N or more, and a sufficient tear strength can be easily obtained even if a hole is made.
- a woven fabric twilled using two to four twisted yarns as the weft will give sufficient tear strength, and the base fabric has less irregularities (waviness) than the five-twisted yarn, and the surface Abrasion deterioration is suppressed.
- the number of yarns in the woven fabric depends on the material and thickness (count) of the yarn, but to achieve a tear strength of 150 N or more and 100 N or more in width, for example, the warp yarn is 40 to 80 yarns / inch.
- the weft is preferably 20 to 50 yarns / inch.
- Polyurethane resin The polyurethane resin contained in the base fabric layer 12 is impregnated into the woven fabric to form a porous structure together with the woven fabric.
- the polyurethane resin contained in the base fabric layer 12 include polycarbonate polyurethane, polyether polyurethane, and polyester polyurethane. From the viewpoints of hydrolysis resistance, heat deterioration resistance, etc., polycarbonate polyurethane and polyether polyurethane are preferred.
- the content of the polyurethane resin in the base fabric layer 12 is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the woven fabric. If the content of the polyurethane-based resin is 10 parts by mass or more with respect to 100 parts by mass of the woven fabric, the base fabric layer 12 can be given an appropriate hardness, and deformation of the holes 30 can be prevented when the holes 30 are opened. If it is 40 mass parts or less, the softness
- An organic flame retardant is used as the flame retardant contained in the base fabric layer 12. Examples thereof include phosphorus flame retardants, nitrogen-phosphorus flame retardants, halogen flame retardants, etc., organic phosphoric acid flame retardants are preferred, and organic phosphates are more preferred.
- the flame retardant there is an inorganic flame retardant such as aluminum hydroxide, but when an inorganic flame retardant is used, an effect of lowering the combustion temperature is obtained, but a laminate having a vent hole and easily burned. In the seat, the effect of suppressing combustion is small. On the other hand, if it is an organic flame retardant, it is easy to dissolve or disperse in the resin solution. can get.
- the strength of the base fabric layer is likely to be higher than when an inorganic flame retardant is used.
- the organic flame retardant is also available as a commercial product, and examples thereof include a commercial product using triphenyl phosphate or tricresyl phosphate.
- the content of the organic flame retardant in the base fabric layer 12 is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyurethane resin. If the content of the organic flame retardant in the base fabric layer 12 is 10 parts by mass or more with respect to 100 parts by mass of the polyurethane-based resin, high flame retardancy is exhibited even if it is perforated, and 30 parts by mass or less. If this is the case, a decrease in flexibility due to excessive amount can be suppressed. From the above viewpoint, the content of the organic flame retardant in the base fabric layer 12 is more preferably 15 to 25 parts by mass, and particularly preferably 17 to 23 parts by mass with respect to 100 parts by mass of the polyurethane resin.
- the base fabric layer 12 may contain other additives in addition to the woven fabric, the polyurethane resin, and the organic flame retardant.
- a coloring agent such as a pigment, a leveling agent, and the like can be given.
- Examples of the colorant that can be included in the base fabric layer 12 include a colored organic material in which organic resin fine particles selected from urethane resin particles, acrylic resin particles, silicone resin particles, polycarbonate resin particles, and the like are included. Examples include resin particles. Among them, it is preferable to contain polycarbonate-based colored resin particles from the viewpoints of affinity and uniform dispersibility with respect to the polyurethane-based resin serving as a dispersion medium. In general, the average particle size of such colored resin particles is preferably in the range of 0.5 ⁇ m to 100 ⁇ m, more preferably in the range of 3 ⁇ m to 50 ⁇ m.
- the thickness of the base fabric layer 12 is preferably 0.5 to 1.5 mm. If the thickness of the base fabric layer 12 is 0.5 mm or more, the laminated sheet 10 having high tear strength can be obtained, and if it is 1.5 mm or less, the flexibility of the laminated sheet 10 can be maintained. From the above viewpoint, the thickness of the base fabric layer 12 is more preferably 0.7 to 1.3 mm, and particularly preferably 0.9 to 1.1 mm.
- the adhesive layer 14 is made of an adhesive and adheres the base fabric layer 12 and the skin layer 16.
- Examples of the material constituting the adhesive layer 14 include polyurethane-based resins, flame retardants, and pigments.
- the thickness of the adhesive layer 14 is preferably 40 to 80 ⁇ m, more preferably 50 to 70 ⁇ m, and particularly preferably 55 to 65 ⁇ m.
- the skin layer 16 is provided mainly for imparting designability, strength, abrasion resistance, and the like to the laminated sheet 10 and includes a resin and a colorant.
- the resin constituting the skin layer 16 is appropriately selected according to the purpose of use of the laminated sheet 10.
- polycarbonate resin, water-based polyurethane resin, silicon-modified polyurethane resin, polyether-modified polyester resin, etc. are used, and polycarbonate resin is preferable from the viewpoint of good heat resistance and chemical resistance.
- the colorant contained in the skin layer 16 examples include a colored organic resin in which a colorant is contained in organic resin fine particles selected from urethane resin particles, acrylic resin particles, silicone resin particles, polycarbonate resin particles, and the like. And particles. Among them, it is preferable to contain polycarbonate-based colored resin particles from the viewpoints of affinity and uniform dispersibility with respect to the polyurethane-based resin serving as a dispersion medium.
- the average particle diameter of the organic resin fine particles used as the colorant is preferably in the range of 0.5 ⁇ m to 100 ⁇ m, more preferably in the range of 3 ⁇ m to 50 ⁇ m.
- the content of the colorant in the skin layer 16 may be selected according to the purpose of use of the laminated sheet 10.
- the thickness of the skin layer 16 is preferably 15 to 60 ⁇ m, more preferably 20 to 50 ⁇ m, and particularly preferably 30 to 40 ⁇ m.
- the wear-resistant layer 18 is provided as needed mainly to impart wear resistance.
- the abrasion-resistant layer 18 includes, for example, a resin, a lubricant, and a crosslinking agent, and further includes other additives such as a matting agent as necessary.
- the resin contained in the wear-resistant layer 18 is a main component of the wear-resistant layer 18, and examples thereof include polycarbonate urethane.
- silicon is suitable, and as a commercial product, for example, BYK (registered trademark) -306 (manufactured by Big Chemie Japan) can be mentioned.
- the content of the lubricant in the wear resistant layer 18 is, for example, 5 to 15% by mass.
- Examples of the crosslinking agent contained in the wear resistant layer 18 include a carbodiimide crosslinking agent.
- Examples of commercially available products include Carbodilite (registered trademark) E-02 (manufactured by Nisshinbo Chemical Co., Ltd.).
- the content of the crosslinking agent in the wear-resistant layer 18 is, for example, 5 to 20% by mass as the amount added before crosslinking.
- silica and beads are suitable.
- examples of commercially available products include CERACOL (registered trademark, manufactured by Big Chemie Japan), TK-600T (manufactured by Negami Kogyo Co., Ltd.), C -100 (manufactured by Negami Kogyo Co., Ltd.).
- additives that may be included in the abrasion resistant layer 18 include pigments.
- the total content of the matting agent and other additives in the wear-resistant layer 18 is, for example, 5 to 30% by mass.
- the thickness of the wear-resistant layer 18 is preferably 2 to 15 ⁇ m, more preferably 4 to 13 ⁇ m, and particularly preferably 6 to 10 ⁇ m.
- the tactile sensation treatment layer 20 is provided as necessary to give a smooth touch.
- the tactile sensation treatment layer 20 includes a resin, a lubricant, and a matting agent.
- Examples of the resin constituting the tactile sensation treatment layer 20 include silicon-modified polycarbonate polyurethane.
- the thickness of the tactile sensation treatment layer 20 is preferably 0.5 to 5.0 ⁇ m, more preferably 1.0 to 4.0 ⁇ m, and 1.5 to 3.5 ⁇ m. Is particularly preferred.
- the laminated sheet 10 is provided with a plurality of vent holes 30 penetrating in the thickness direction.
- the shape of each vent hole 30 is not particularly limited, and may be circular or polygonal in plan view depending on the purpose of use.
- the circular ventilation holes 30 are provided in the plan view, that is, in the thickness direction of the laminated sheet 10.
- the arrangement pattern of the air holes 30 is not particularly limited, and may be provided regularly or irregularly, but from the viewpoint of exhibiting uniform air permeability and tear strength over the entire laminated sheet.
- the vent holes 30 are preferably arranged regularly at a predetermined interval.
- the hole diameter D of each air hole 30 is preferably 0.5 to 2.0 mm, preferably 1.0 to 1.5 mm from the viewpoint of achieving both the air permeability and strength of the entire laminated sheet, although it depends on the application. More preferably.
- the interval P between the vent holes 30 is preferably 3.0 to 8.0 mm, preferably 4.0 to 7.0 mm from the viewpoint of achieving both the air permeability and strength of the entire laminated sheet, although it depends on the application. It is more preferable.
- the opening ratio of the laminated sheet 10 (total area of the vent holes 30 / area of the laminated sheet 10) is 5 to 20% from the viewpoint of achieving both the air permeability and strength of the entire laminated sheet, although it depends on the application. It is preferably 10 to 15%.
- the tear strength (according to the trapezoid method) of the resin solution containing a polyurethane-type resin, an organic flame retardant, and a solvent is 150N or more in length, and the woven cloth of 100N or more in width. Immersing the woven fabric impregnated with the resin solution in water to remove the solvent contained in the woven fabric and coagulating the polyurethane resin; and coagulating the polyurethane resin.
- ⁇ Impregnation step> a resin solution containing a polyurethane resin, an organic flame retardant, and a solvent is impregnated into a woven fabric having a tear strength by a trapezoid method of 150 N or more and horizontal 100 N or more.
- the solvent used for preparing the resin solution is not particularly limited as long as it can dissolve or disperse the polyurethane-based resin, the organic flame retardant, and the additive added as necessary.
- examples include methyl ethyl ketone (MEK), toluene, tetrahydrofuran (THF), dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), isopropyl alcohol (IPA), N-methyl-2-pyrrolidone (NMP), and the like.
- Polyurethane resins and organic flame retardants, at the base fabric layer 12 in a dry state for example, woven fabric 370 ⁇ 30g / m 2, a polyurethane resin is 105 ⁇ 10g / m 2, the flame retardant 50 ⁇ 5g / m 2 Impregnate the woven fabric so that
- the method of impregnating the woven fabric with the resin solution is not limited.
- the resin solution may be applied to the woven fabric by a known method and impregnated, or the woven fabric is placed in a container containing the resin solution for impregnation. You may let them.
- a base fabric layer (wet microporous layer) 12 having a porous structure is formed by dehydrating a woven fabric containing solidified polyurethane resin and water with mangles and then drying it under hot air at 100 ° C. to 120 ° C. Is done.
- one side of the base fabric layer 12 is roughened.
- one side of the base fabric layer 12 is slightly raised by roughening one side of the base fabric layer 12 with a buffing machine.
- a laminate in which the skin layer 16 is laminated on the roughened surface of the base fabric layer 12 is formed.
- a silicon-modified polyurethane is applied onto a release paper with drawing and heat-dried to form a silicon-modified polyurethane skin layer 16 having a desired thickness.
- a polyurethane adhesive is applied on the skin layer 16 and then dried by heating to form a polyurethane adhesive layer 14 having a desired thickness.
- an intermediate layer that provides elasticity or flexibility is provided between the adhesive layer 14 and the skin layer 16 the intermediate layer is formed on the skin layer 16 before the adhesive layer 14 is formed.
- the method of applying the coating solution for forming the skin layer 16, the intermediate layer, and the adhesive layer 14 is not particularly limited, and a known method may be applied.
- the knife coating method, the lip coating method, the die coating method and the like are particularly preferable from the viewpoint of being suitable for thick coating properties for achieving a sufficient layer thickness by one application.
- the raised surface of the base fabric layer 12 is faced on the surface of the adhesive layer 14, and is aged by thermocompression bonding, so that the adhesive is reacted and solidified.
- the release paper is peeled off to obtain a laminate.
- a wear-resistant layer 18 is provided on the skin layer 16 as necessary.
- a coating solution for forming an abrasion-resistant layer in which a polyurethane resin, a lubricant, a cross-linking agent, a matting agent, and other additives are added in a desired amount to a solvent is prepared, and the skin is coated by a known coating method such as roll coating. After coating on layer 16, it is dried.
- a tactile sensation treatment layer 20 is provided on the skin layer 16 or the abrasion resistant layer 18 as necessary.
- a coating solution for forming a tactile sensation treatment layer in which a polyurethane resin, a solvent, and an additive are respectively added in a desired amount to a solvent is prepared and applied on the skin layer 16 or the abrasion-resistant layer 18 by a known coating method such as roll coating. And dried.
- a plurality of vent holes 30 penetrating in the thickness direction of the laminate are drilled.
- the air holes 30 having a desired diameter are drilled in the laminated body at a desired interval by a punching roll.
- the laminated sheet 10 having a large number of air holes 30 penetrating in the thickness direction is manufactured.
- the base fabric layer 12 serving as a support is reinforced by impregnating a polyurethane resin into a woven fabric, so that the laminate is not easily deformed during drilling, and the opening is a perfect circle.
- a close vent 30 can be formed.
- yarn which comprises the woven fabric of the base fabric layer 12 is cut
- the laminated sheet 10 of the present invention produced through the above steps has high tear strength, moisture permeability, breathability, and flame retardancy, and is excellent in the appearance of the vent holes.
- the laminated sheet 10 of the present invention has high texture, moisture permeability and breathability, so that it does not stuffy even when used in contact with the human body, has excellent comfort, and is mainly used for automobile interior materials and shoes. It can be used as a synthetic leather suitable for footwear and chair upholstery.
- Example 1 (Formation of base fabric layer) A woven fabric twilled using yarns having the structure shown in Table 1 below was prepared as a base fabric. The tear strength of the woven fabric by the trapezoid method was measured with a Tensilon tester (trade name: UNIVERSAL TESTING INSTRUMENT model RTG-1310, manufactured by Orientec Co., Ltd.).
- the woven fabric was immersed in the resin solution for 1 minute and impregnated, and then immersed in water for 10 minutes to remove the solvent and solidify the polyurethane. Subsequently, the base fabric layer (thickness: 1.1 mm) which has a porous structure was formed by making it dry under hot air of 120 degreeC for 10 minutes. Next, using a buffing machine (trade name: A-5, manufactured by Meinan Seisakusho Co., Ltd.), one side of the base fabric layer was buffed to be roughened to obtain a raised surface.
- the above-mentioned skin layer forming coating solution is applied onto a surface-released release release paper (Dai Nippon Printing Co., Ltd., DE-41: paper thickness average 140 ⁇ m) having a release layer.
- a silicon-modified polyurethane skin layer (thickness: 40 ⁇ m, coating amount after drying: 35 g / m 2 ) was formed by heating and drying at 0 ° C. for 1 minute.
- a coating solution for forming an adhesive layer having the following constitution was prepared.
- Polycarbonate-based polyurethane resin manufactured by DIC, trade name: Crisbon TA205FT
- 100 parts by mass Crosslinking agent manufactured by DIC, trade name: Barnock DN-950
- 12 parts by mass Crosslinking accelerator manufactured by DIC, trade name
- Crisbon Axel T-81E 1 part by mass / solvent
- DMF solvent
- the raised surface of the base fabric layer was faced on the surface of the adhesive layer, and aged by thermocompression bonding at 150 ° C. for 1 second to solidify the adhesive. After the adhesive was solidified, the release paper was peeled from the skin layer.
- a coating solution for forming an abrasion resistant layer having the structure shown in Table 2 below was prepared.
- each component is as follows.
- a coating solution for forming an abrasion resistant layer was applied on the skin layer by roll coating, and dried by heating under hot air at 130 ° C. for 1 minute. This formed an abrasion-resistant layer (thickness: 7 ⁇ m, coating amount after drying: 4.5 g / m 2 ).
- Tear strength The tear strength of the laminated sheet was measured by the JIS L1096 8.15.4 C method, and evaluated in the following 5 points, 1 to 5 points. 5 points: tear strength of 100 N or more, 4 points: tear strength of 80 N or more and less than 100 N, 3 points: tear strength of 60 N or more and less than 80 N, 2 points: tear strength of 40 N or more and less than 60 N, 1 point: tear strength of less than 40 N
- the air permeability of the laminated sheet was measured by JIS L1096 8.27.1 A method, and evaluated in 5 stages from 1 point to 5 points.
- Example 2 A laminated sheet was prepared in the same manner as in Example 1 except that the warp yarn was changed from 20th to 30th and the weft yarn was changed from 20th 4 twists to 20th 3 twists. Note that the tear strength of the woven fabric used as the base fabric by the trapezoid method was length 160N and width 130N. The obtained laminated sheet was evaluated in the same manner as in Example 1.
- Example 3 In the resin solution impregnated into the woven fabric, lamination was performed in the same manner as in Example 1 except that the flame retardant having a particle size of 3 ⁇ m was changed to a flame retardant having a particle size of 20 ⁇ m (trade name: Pecoframe ATC, manufactured by Arkroma Japan). A sheet was produced. The obtained laminated sheet was evaluated in the same manner as in Example 1.
- Example 4 A laminated sheet was produced in the same manner as in Example 1 except that the abrasion-resistant layer was not formed on the skin layer. The obtained laminated sheet was evaluated in the same manner as in Example 1.
- Example 1 A laminated sheet was produced in the same manner as in Example 1 except that the organic phosphate compound was changed to aluminum hydroxide in the resin solution impregnated into the woven fabric. The obtained laminated sheet was evaluated in the same manner as in Example 1.
- Example 2 A resin solution obtained by removing the organic phosphate from the resin solution impregnated in the woven fabric used in Example 1 was prepared and impregnated into the woven fabric in the same manner as in Example 1, and a flame retardant (phosphorus compound, product on the back surface) Synthetic leather was produced in the same manner as in Example 1 except that name: nonenen R031-5, manufacturer: Maruhishi Oil Chemical Co., Ltd.) was applied. The obtained laminated sheet was evaluated in the same manner as in Example 1.
- Table 3 shows the evaluation results of the laminated sheets produced in the examples and comparative examples.
- FIG. 4, and FIG. 5 show the appearance of the vent holes of the laminated sheets produced in Example 1, Comparative Example 2, and Comparative Example 3, respectively.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
穿孔加工を施すことにより、乾式合成皮革では基布の種類により孔の歪み、強度の著しい低下が起こり易い。
湿式合成皮革においても、基材となる基布の物性により強度が十分得られない場合があり、また、孔を開けたことにより通気性が上がり、それに伴い難燃性能が低下する傾向になる。また、基布にウレタン樹脂を含浸させて湿式ベースとする場合、ウレタン樹脂が基布に入り込むため、難燃性能が低下する傾向がある。
また、基布に表皮層を貼り合わせる前に粗面化加工(バフ加工)を施す際、基布を構成する糸が傷つくことにより、強度が低下する場合がある。
更に、磨耗耐久性の面において、孔の縁が擦れることにより、耐摩耗性が不十分となり易い。
すなわち、上記目的を達成するため、以下の発明が提供される。
<2> 前記織布が、縦糸として5~30番手の単糸を、横糸として10~40番手の二本~四本撚り糸を用いて綾織した織布である<1>に記載の積層シート。
<3> 前記有機難燃剤が、有機リン酸系難燃剤である<1>又は<2>に記載の積層シート。
<4> 前記表皮層上にさらに耐摩耗層を有する<1>~<3>のいずれかに記載の積層シート。
<5> ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液をトラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させる工程と、
前記樹脂溶液が含浸した前記織布を水中に浸漬して前記織布に含まれる前記溶媒を除去するとともに前記ポリウレタン系樹脂を凝固させる工程と、
前記ポリウレタン系樹脂を凝固させた前記織布を乾燥させて多孔質構造を有する基布層を形成する工程と、
前記基布層の片面を粗面化する工程と、
前記基布層の粗面化した面上に表皮層が積層した積層体を形成する工程と、
前記積層体の厚さ方向に貫通する複数の通気孔を穿孔する工程と、
を有する積層シートの製造方法。
[積層シート]
本発明の積層シートは、ポリウレタン系樹脂及び有機難燃剤を含む樹脂組成物を、トラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させてなる多孔質構造を有する基布層と、前記基布層上に積層された表皮層と、を有し、厚さ方向に貫通する複数の通気孔を有する。
基布層12はポリウレタン系樹脂及び有機難燃剤を含む樹脂組成物を、トラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させてなる多孔質構造を有する。
基布層12を構成する基布として、JIS L1096 8.15.4 C法(トラペゾイド法)による引裂き強度がタテ150N以上かつヨコ100N以上の強度が高い織布を用いる。織布は、引裂き強度がタテ180N以上かつヨコ120N以上であることが好ましく、タテ200N以上かつヨコ150N以上であることがより好ましい。
ここで、JIS L1096:1999 8.15.4 C法(トラペゾイド法)による引裂き強度は、具体的には以下のようにして測定される。
7.5cm×15cmの試料片をタテ方向及びヨコ方向にそれぞれ3枚採取し、試験片上に図6のように等脚台形の印を付け、この印の短辺の中央に辺と直角に1cmの切れ目を入れ、幅7.5cm以上のクランプをもつ引張試験機を用い、図7に示すように試験片のつかみ間隔を2.5cmとして、等脚台形の印(点線部分)に沿って、試験片の台形の短辺を張り、長辺は緩めてクランプに挟む。引張速度は、1分間当たり20cmとし、タテ方向及びヨコ方向に引き裂くときに示す最大荷重(引裂強さ)(N{kgf})を測り、横糸引裂強さ及び縦糸引裂強さ(N{kgf})のそれぞれの平均値を算出し、小数点以下1けたに丸める。
例えば、縦糸として5~30番手の単糸を用い、横糸として10~40番手の二本~四本撚り糸を用いて綾織した織布が好適である。横糸として二本~四本撚り糸を用いれば、基布の引裂強度が110N以上となり、孔をあけても十分な引裂き強度が得られ易い。
横糸として二本~四本撚り糸を用いて綾織した織布であれば、十分な引裂き強度が得られるとともに、五本撚り糸を用いた場合に比べ、基布の凹凸(うねり)が小さく、表面の摩耗性の低下が抑制される。また、五本撚り糸を用いた織布に場合に比べ、穿孔しやすく、毛羽やほつれ糸が出難いため、外観の良い孔を形成し易い。
また、織布における糸の本数は、糸の材質、太さ(番手)にもよるが、タテ150N以上かつヨコ100N以上の引裂き強度を達成するため、例えば、縦糸は40~80本/インチであり、横糸は20~50本/インチであることが好ましい。
基布層12に含まれるポリウレタン系樹脂は前記織布に含浸されて織布とともに多孔質構造を形成する。基布層12に含まれるポリウレタン系樹脂としては、ポリカーボネート系ポリウレタン、ポリエーテル系ポリウレタン、及びポリエステル系ポリウレタンが挙げられる。耐加水分解性、耐熱劣化性等の点から、ポリカーボネート系ポリウレタン、及びポリエーテル系ポリウレタンが好ましい。
ポリウレタン系樹脂の含有量が、織布100質量部に対して10質量部以上であれば基布層12に適度な硬さを与え、孔30を開ける際に孔30の変形を防ぐことができ、40質量部以下であれば基布層12の柔軟性を保つことができる。
上記観点から、基布層12におけるポリウレタン系樹脂の含有量は、織布100質量部に対して15~35質量部であることがより好ましく、20~30質量部であることが特に好ましい。
基布層12に含まれる難燃剤としては、有機難燃剤を用いる。例えば、リン系難燃剤、窒素-リン系難燃剤、ハロゲン系難燃剤などが挙げられ、有機リン酸系難燃剤が好ましく、有機リン酸塩化物がより好ましい。
なお、難燃剤としては、水酸化アルミニウムなどの無機難燃剤があるが、無機難燃剤を用いた場合には、燃焼温度を低下させる効果は得られるものの、通気孔を有し、燃焼し易い積層シートにおいては燃焼を抑制する効果は小さい。一方、有機難燃剤であれば樹脂溶液中に溶解又は分散し易く、樹脂溶液を織布に含浸させたときにポリウレタン系樹脂とともに織布全体に行きわたって積層シートの燃焼を抑制する高い効果が得られる。また、有機難燃剤を用いることで、無機難燃剤を用いた場合に比べて基布層の強度が高くなり易い。
有機難燃剤は市販品としても入手可能であり、例えば、トリフェニルホスフェートやトリクレジルホスフェートなどを用いた市販品が挙げられる。
上記観点から、基布層12における有機難燃剤の含有量は、ポリウレタン系樹脂100質量部に対して15~25質量部であることがより好ましく、17~23質量部であることが特に好ましい。
基布層12は、織布、ポリウレタン系樹脂、有機難燃剤のほかに、他の添加剤を含んでもよい。例えば、顔料等の着色剤、レベリング剤などが挙げられる。
このような着色樹脂粒子の平均粒径は、一般的には、0.5μm~100μmの範囲であることが好ましく、より好ましくは、3μm~50μmの範囲である。
上記観点から、基布層12の厚みは0.7~1.3mmであることがより好ましく、0.9~1.1mmであることが特に好ましい。
接着層14は接着剤によって構成され、基布層12と表皮層16を接着する。接着層14を構成する材料としては、ポリウレタン系樹脂、難燃剤、顔料等が挙げられる。
表皮層16は、主に積層シート10に意匠性や強度、耐摩耗性などを付与するために設けられるものであり、樹脂及び着色剤を含んで構成される。
着色剤として用いられる有機樹脂微粒子の平均粒径は、一般的には、0.5μm~100μmの範囲であることが好ましく、より好ましくは、3μm~50μmの範囲である。
なお、表皮層16における着色剤の含有量は、積層シート10の使用目的に応じて選択すればよい。
耐摩耗層18は、主に耐摩耗性を付与するために必要に応じて設けられる。耐摩耗層18は、例えば、樹脂、滑剤、及び架橋剤を含み、さらに必要に応じて艶消し剤などの他の添加剤を含んで構成される。
耐摩耗層18における滑剤の含有量は、例えば、5~15質量%である。
耐摩耗層18における架橋剤の含有量は、架橋前の添加量として、例えば、5~20質量%である。
耐摩耗層18における艶消し剤及びその他の添加剤の総含有量は、例えば、5~30質量%である。
触感処理層20は、滑らかな肌触りを付与するために必要に応じて設けられる。触感処理層20は、樹脂、滑剤、艶消し剤を含んで構成される。
積層シート10には、厚さ方向に貫通する通気孔30が複数設けられている。
各通気孔30の形状は特に限定されず、使用目的に応じて、平面視において円形でもよいし、多角形でもよい。なお、積層シート10により高い強度を発揮させる観点から平面視において円形、すなわち、積層シート10の厚さ方向に円筒形の通気孔30が設けられていることが好ましい。
通気孔30の間隔Pは、用途にもよるが、積層シート全体の通気性と強度を両立させる観点から、3.0~8.0mmであることが好ましく、4.0~7.0mmであることがより好ましい。
次に、本実施形態に係る積層シート10を製造する方法について説明する。本実施形態に係る積層シート10の製造方法は特に限定されないが、ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液を引裂き強度(トラペゾイド法による)がタテ150N以上かつヨコ100N以上の織布に含浸させる工程と、前記樹脂溶液が含浸した前記織布を水中に浸漬して前記織布に含まれる前記溶媒を除去するとともに前記ポリウレタン系樹脂を凝固させる工程と、前記ポリウレタン系樹脂を凝固させた前記織布を乾燥させて多孔質構造を有する基布層12を形成する工程と、前記基布層12の片面を粗面化する工程と、前記基布層12の粗面化した面上に表皮層16が積層した積層体を形成する工程と、前記積層体の厚さ方向に貫通する複数の通気孔30を穿孔する工程と、を有する方法によって好適に製造することがきる。
まず、ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液をトラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させる。
樹脂溶液を織布に含浸させる方法は限定されず、例えば、樹脂溶液を織布に公知の方法により塗布して含浸させてもよいし、樹脂溶液を収容した容器内に織布を入れて含浸させてもよい。
ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液が含浸した織布を水中に浸漬することで、織布に含まれる樹脂溶液中の溶媒が水と置換して除去(脱溶媒)されるとともにポリウレタン系樹脂が凝固する。
次いで、含浸したポリウレタン系樹脂を凝固させた織布を乾燥させて多孔質構造を有する基布層12を形成する。例えば、凝固したポリウレタン系樹脂と水を含む織布をマングルによって脱水した後、100℃~120℃の熱風下で乾燥させることで多孔質構造を有する基布層(湿式ミクロポーラス層)12が形成される。
次いで、前記基布層12の片面を粗面化する。例えば、基布層12の片面をバッフィングマシンによって粗面化することにより基布層12の片面がわずかに起毛する。
次いで、前記基布層12の粗面化した面上に表皮層16が積層した積層体を形成する。
例えば絞付き離型紙上にシリコン変性ポリウレタンを塗布し、加熱乾燥して所望の厚みのシリコン変性ポリウレタン表皮層16を形成する。
次にこの表皮層16の上にポリウレタン系接着剤を塗布した後、加熱乾燥し所望の厚みのポリウレタン接着層14を形成する。
なお、接着層14と表皮層16との間に弾力性あるいは柔軟性を付与する中間層を設ける場合は、接着層14を形成する前に、表皮層16上に中間層を形成する。
必要に応じて、表皮層16上に耐摩耗層18を設ける。例えば、溶媒にポリウレタン系樹脂、滑剤、架橋剤、艶消し剤、その他の添加剤をそれぞれ所望の量で添加した耐摩耗層形成用塗布液を調製し、ロールコート等の公知の塗布方法によって表皮層16上に塗布した後、乾燥させる。
また、必要に応じて、表皮層16又は耐摩耗層18上に触感処理層20を設ける。例えば、溶媒にポリウレタン樹脂、溶剤、添加剤をそれぞれ所望の量で添加した触感処理層形成用塗布液を調製し、ロールコート等の公知の塗布方法によって表皮層16又は耐摩耗層18上に塗布した後、乾燥させる。
次いで、前記積層体の厚さ方向に貫通する複数の通気孔30を穿孔する。例えば、パンチングロールにより積層体に所望の間隔で所望の径を有する通気孔30を穿孔する。これにより厚さ方向に貫通した多数の通気孔30を有する積層シート10が製造される。
また、穿孔により基布層12の織布を構成する糸が切断されるが、固化したポリウレタン系樹脂によって補強されているため、切断されたほつれ糸が通気孔30の内部や外に飛び出して外観を損ねることが抑制される。
さらに、基布層12における通気孔30の内壁には有機難燃剤が存在するため、通気孔30においても高い難燃性を発揮する。
(基布層の形成)
基布として下記表1に示す構成の糸を用いて綾織した織布を用意した。この織布のトラぺゾイド法による引裂き強度をテンシロン試験機(オリエンテック社製、商品名:UNIVERSAL TESTING INSTRUMENT モデル RTG-1310)で測定したところ、タテ200N、ヨコ150Nであった。
・ポリカーボネート系ポリウレタン
(DIC社製、商品名:MP-865PS):40質量部
・有機リン酸塩化合物(難燃剤)
(アークロマジャパン社製、商品名:ペコフレームSTC、粒径:3μm):10質量部
・ジメチルホルムアミド:60質量部
次いで、120℃の熱風下で10分乾燥させることにより、多孔質構造を有する基布層(厚み:1.1mm)を形成した。
次いで、バッフィングマシン(名南製作所社製、商品名:A-5)を用い、基布層の片面にバフ加工を施して粗面化し、起毛面とした。
下記に示す構成の表皮層形成用塗布液を調製した。
・シリコン変性ポリウレタン樹脂(DIC社製、商品名: NY-373):60質量部
・顔料(DIC社製、商品名:DIALAC BLACK L-1770S):40質量部
・溶剤(日産化学工業社製、商品名:DMF):10質量部
下記に示す構成の接着層形成用塗布液を調製した。
・ポリカーボネート系ポリウレタン樹脂(DIC社製、商品名:クリスボンTA205FT)100質量部
・架橋剤(DIC社製、商品名:バーノックDN-950):12質量部
・架橋促進剤(DIC社製、商品名:クリスボンアクセルT-81E):1質量部
・溶剤(日産化学工業社製、商品名:DMF):60質量部
次に表皮層の上に上記接着層形成用塗布液を塗布した後、130℃で1分加熱乾燥してポリウレタン接着層(厚み:40μm、乾燥後の塗布量:35g/m2)を形成した。
接着剤を固化した後、表皮層から離型紙を剥離した。
下記表2に示す構成の耐摩耗層形成用塗布液を調製した。なお、各成分は以下の通りである。
・ポリカーボネート系ウレタン(主剤):スタール・ジャパン社製、商品名:WF-13-139
・シリコン(滑剤):ビックケミー・ジャパン社製、商品名:BYK-306
・カルボジイミド(架橋剤):日清紡ケミカル社製、商品名:E-02
上記工程を経て得られた基布層、接着層、表皮層、耐摩耗層が積層された積層体(合成皮革)にパンチングロールにより孔を開けて通気孔を有する積層シートを得た。
積層シートにおける通気孔の径、間隔P及び開孔率は以下の通りである。
孔径:1.4mm
ピッチP:5.0mm
開孔率:14%
得られた積層シートについて、孔の外観、引裂き強度、難燃性、通気性について以下の評価を行った。
積層シートに形成された通気孔のうち10個について開口部の円の歪を目視により1点~5点の5段階で評価した。点数が高いほど本皮に穿孔加工した場合と同等の円形に近く、点数が低いほど歪が大きいことを示す。
積層シートに形成された通気孔のうち10個について通気孔の縁部の毛羽を目視で評価し、1点~5点の5段階で評価した。点数が高いほど本皮に穿孔加工した場合と同等に毛羽が少なく、点数が低いほど毛羽を多いことを示す。
積層シートに形成された通気孔のうち10個について通気孔内のほつれ糸を目視で評価し、1点~5点の5段階で評価した。点数が高いほどほつれ糸が少ないことを示す。
積層シートをJIS L1096 8.15.4 C法によって引裂き強度を測定し、以下の1点~5点の5段階で評価した。
5点:引裂き強度が100N以上
4点:引裂き強度が80N以上100N未満
3点:引裂き強度が60N以上80N未満
2点:引裂き強度が40N以上60N未満
1点:引裂き強度が40N未満
積層シートの難燃性をFMVSS No.302 燃焼試験(ISO3795,JIS D1201)により測定し、1点~5点の5段階で評価した。
5点:燃焼速度=0mm/min
4点:0mm/min<燃焼速度≦50mm/min
3点:50mm/min<燃焼速度≦80mm/min
2点:80mm/min<燃焼速度≦100mm/min
1点:100mm/min<燃焼速度
積層シートの通気性をJIS L1096 8.27.1 A法により測定し、1点~5点の5段階で評価した。
5点:130cc/cm2・s以上
4点:100cc/cm2・s以上130cc/cm2・s未満
3点:80cc/cm2・s以上100cc/cm2・s未満
2点:60cc/cm2・s以上80cc/cm2・s未満
1点:60cc/cm2・s未満
縦糸を20番手から30番手に、横糸を20番手4本撚りから20番手3本撚りにそれぞれ変更して基布を作製したこと以外は実施例1と同様にして積層シートを作製した。なお、基布として用いた織布のトラぺゾイド法による引裂き強度は、タテ160N、ヨコ130Nであった。
得られた積層シートについて実施例1と同様に評価した。
織布に含浸させる樹脂溶液において、粒径3μmの難燃剤を粒径20μmの難燃剤(アークロマジャパン社製、商品名:ペコフレームATC)に変更したこと以外は実施例1と同様にして積層シートを作製した。
得られた積層シートについて実施例1と同様に評価した。
表皮層上に耐摩耗層を形成しないこと以外は実施例1と同様にして積層シートを作製した。
得られた積層シートについて実施例1と同様に評価した。
織布に含浸させる樹脂溶液において、有機リン酸塩化合物を水酸化アルミニウムに変更したこと以外は実施例1と同様にして積層シートを作製した。
得られた積層シートについて実施例1と同様に評価した。
実施例1で用いた織布に含浸させる樹脂溶液から有機リン酸塩化物を除いた樹脂溶液を調製して実施例1と同様に織布に含浸させ、裏面に難燃剤(リン系化合物、商品名:ノンネンR031-5、製造元:丸菱油化工業株式会社)を塗工したこと以外は実施例1と同様にして合皮を作製した。
得られた積層シートについて実施例1と同様に評価した。
基布をトリコットサテン組織(コース/ウェル=53/45、トラペゾイド法による引裂き強度がタテ170N以上かつヨコ150N以上)に変更したこと以外は実施例1と同様して積層シートを作製した。
得られた積層シートについて実施例1と同様に評価した。
また、図3、図4、図5に、実施例1、比較例2、比較例3でそれぞれ作製した積層シートの通気孔の外観を示す。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (5)
- ポリウレタン系樹脂及び有機難燃剤を含む樹脂組成物を、トラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させてなる多孔質構造を有する基布層と、前記基布層上に積層された表皮層と、を有し、厚さ方向に貫通する複数の通気孔を有する積層シート。
- 前記織布が、縦糸として5~30番手の単糸を、横糸として10~40番手の二本~四本撚り糸を用いて綾織した織布である請求項1に記載の積層シート。
- 前記有機難燃剤が、有機リン酸系難燃剤である請求項1又は請求項2に記載の積層シート。
- 前記表皮層上にさらに耐摩耗層を有する請求項1~請求項3のいずれか一項に記載の積層シート。
- ポリウレタン系樹脂、有機難燃剤、及び溶媒を含む樹脂溶液をトラペゾイド法による引裂き強度がタテ150N以上かつヨコ100N以上の織布に含浸させる工程と、
前記樹脂溶液が含浸した前記織布を水中に浸漬して前記織布に含まれる前記溶媒を除去するとともに前記ポリウレタン系樹脂を凝固させる工程と、
前記ポリウレタン系樹脂を凝固させた前記織布を乾燥させて多孔質構造を有する基布層を形成する工程と、
前記基布層の片面を粗面化する工程と、
前記基布層の粗面化した面上に表皮層が積層した積層体を形成する工程と、
前記積層体の厚さ方向に貫通する複数の通気孔を穿孔する工程と、
を有する積層シートの製造方法。
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US9885148B2 (en) | 2018-02-06 |
US20150299944A1 (en) | 2015-10-22 |
JPWO2014097999A1 (ja) | 2017-01-12 |
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