CN106103838A - Niu Bage sample tablet and its manufacture method - Google Patents
Niu Bage sample tablet and its manufacture method Download PDFInfo
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- CN106103838A CN106103838A CN201580013466.8A CN201580013466A CN106103838A CN 106103838 A CN106103838 A CN 106103838A CN 201580013466 A CN201580013466 A CN 201580013466A CN 106103838 A CN106103838 A CN 106103838A
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- China
- Prior art keywords
- top layer
- sample tablet
- niu bage
- polyurethane resin
- sample
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0007—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0007—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure
- D06N7/0026—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure obtained by moulding, e.g. moulding table (tapis moule)
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Laminated Bodies (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Niu Bage sample tablet (1) is above to be laminated obtained from the top layer (3) comprising polyurethane resin at fibrous substrate (2).Have on the surface (4) of Niu Bage sample tablet protuberance (8) and the difference of height of recess (9) (A) be 20～150 μm, the interval (B) on adjacent projection summit be 20～150 μm fine concavo-convex.In addition, the surface dynamic friction coefficient of surface (4) is 0.20～0.50.
Description
Technical field
The present invention relates to tablet and its manufacture method with Niu Bage sample outward appearance.
Background technology
In the past, the tablet of the outward appearance with the Niu Bage (nubuck) imitating natural leather is used for dress material, suitcase, footwear
The various uses such as son, house decorative material, vehicle interior ornament materials.As Niu Bage sample tablet, by being referred to as wet type
It is main flow that the method for method or dry process manufactures.
For damp process, solvent (organic solvent) solution of coating or impregnation polyurethane resin on fibrous substrate, will
It impregnated in the liquid of the non-solvent comprising polyurethane resin, makes the solvent in polyurethane resin solution move to non-solvent.
Thus, polyurethane resin is made to solidify and form porous layer.Afterwards, outward appearance surface grinding being had pile sample.By this
The tablet that damp process obtains has the outward appearance of very thin pile sample, has the thoughts and feelings of moistening stick-slip sense and the feel of softness, with
The Niu Bage approximation of natural leather.But crisp to external force, it is difficult to obtain disclosure satisfy that and require the field of highly durable property, for example make
Abrasion performance for house decorative material, vehicle interior ornament materials.
On the other hand, for dry process, coating or the solvent solution or the water that are impregnated with polyurethane resin on fibrous substrate
Dispersion liquid so that it is be dried, the outward appearance afterwards surface grinding being had pile sample.The tablet being obtained by this dry process first one
See the outward appearance of pile sample.But, feel coarse and for dry, feel is also hard, is very different with the Niu Bage of natural leather.
In addition, compared with the tablet being obtained by damp process excellent wear resistance, but can not be said to be sufficient.
In the manufacture of Niu Bage sample tablet, above-mentioned 2 methods are main flows, as a scheme of dry process, it is proposed that,
The method that the epidermal area comprising polyurethane resin made on processing release paper is laminated.For example, patent document 1 proposes,
That makes on processing release paper comprises to make on the epidermal area of polyurethane resin the mediopellis comprising polyurethane resin so that it is pass through
Bonding agent is glued with fibrous substrate, peels off processing release paper afterwards, thus has the design of Niu Bage sample.With it, it is permissible
Obtain the design of Niu Bage sample, but sense of touch (particularly stick-slip sense) cannot be reappeared.Therefore, for this problem, in patent document 2
Propose, make the epidermal area comprising polyurethane resin made on processing release paper be fitted with fibrous substrate by bonding agent, it
After by processing release paper peel off, the outward appearance that the surface grinding of epidermal area is had pile sample.With it, Niu Bage can be obtained
The stick-slip sense of sample, but due to grinding skin, therefore not there is abrasion performance.
So, present situation is to obtain the excellent Niu Bage print shape of both Niu Bage sample functional properties and abrasion performance
Thing.
Prior art literature
Patent document
Patent document 1: No. 3078208 publication of Japan's patent
Patent document 2: No. 3062399 publication of Japan's patent
Content of the invention
Problems to be solved by the invention
The present invention makes in view of such present situation, and offer has concurrently and disclosure satisfy that touching as Niu Bage sample tablet
The Niu Bage sample tablet of sense and abrasion performance and its manufacture method.
For solution to problem
Present embodiment the 1st is a kind of ox Ba Ge sample tablet, which is stacking on fibrous substrate and comprises polyurethane tree
Obtained from the top layer of fat, have on the surface of Niu Bage sample tablet protuberance and the difference of height of recess be 20～150 μm, adjacent
Protuberance summit be spaced apart 20～150 μm concavo-convex, and the surface dynamic friction coefficient on surface is 0.20～0.50.
The manufacture method that present embodiment the 2nd is a kind of above-mentioned ox Ba Ge sample tablet, it includes following operation successively:
(1) top layer resin liquid is coated on release property base material, form the operation on top layer；
(2) top layer and the operation of fibrous substrate laminating are made；With,
(3) operation that release property base material is peeled off.
The effect of invention
According to present embodiment, it is provided that have concurrently and disclosure satisfy that sense of touch as Niu Bage sample tablet and abrasion performance
Niu Bage sample tablet and its manufacture method.
Brief description
Fig. 1 is the schematic cross-section of the Niu Bage sample tablet of an embodiment.
Fig. 2 is the schematic cross-section of the Niu Bage sample tablet of other embodiments.
The cross-sectional modes figure of the Niu Bage sample tablet for other embodiments further for the Fig. 3.
Detailed description of the invention
The Niu Bage sample tablet of present embodiment is characterised by, which is stacking on fibrous substrate and comprises polyurethane
Niu Bage sample tablet obtained from the top layer of resin, has fine concavo-convex on the surface of Niu Bage sample tablet, and surface
Surface dynamic friction coefficient be 0.20～0.50.Herein, fine concavo-convex referring to, protuberance is 20～150 μ with the difference of height of recess
M and adjacent projection summit be spaced apart 20～150 μm concavo-convex.
Fig. 1 schematically shows the cross section structure of the Niu Bage sample tablet 1 of an embodiment.In this tablet 1, at fibre
Being laminated with top layer 3 on one face of dimension matter base material 2, the surface on top layer 3 is surface 4, is provided with and comprises protuberance 8 He on this surface 4
Recess 9 fine concavo-convex.In addition, in this example, top layer 3 is laminated in fibrous substrate 2 via adhesive linkage 5, therefore, at cellulosic
It is sequentially laminated with adhesive linkage 5 and top layer 3 on one face of base material 2.
Fig. 2 schematically shows the cross section structure of the Niu Bage sample tablet 10 of other embodiments.In this tablet 10,
The lower section on top layer 3 is provided with anchor coating 6, and is arranged over protective layer 7 on top layer 3.Therefore, in the example of Fig. 2, at cellulosic base
Being sequentially laminated with adhesive linkage the 5th, anchor coating the 6th, top layer 3 and protective layer 7 on one face of material 2, the surface of protective layer 7 becomes having micro-
Thin concavo-convex surface 4.
The difference of height of the protuberance in above-mentioned surface and recess be arbitrary protuberance and with this protuberance the height of immediate recess
Low difference, obtains according to the observation in vertical cross-section as described below.That is, with microscope (KEYENCE CORPORATION manufacture,
Numeral HF microscope VH-8000) observe the vertical cross-section of Niu Bage sample tablet, for the adjacent projection at any 10 and recessed
Portion, measures the difference of height (A with reference in Fig. 1) on the summit of protuberance and the end of recess, is averaged value as protuberance and recess
Difference of height.
In addition, adjacent projection summit in above-mentioned surface be spaced apart arbitrary protuberance and with this protuberance immediate protuberance
Summit spacing, obtain according to the observation in vertical cross-section as described below.That is, with microscope (KEYENCE
CORPORATION manufacture, numeral HF microscope VH-8000) observe Niu Bage sample tablet vertical cross-section, at any 10
Protuberance and with this protuberance immediate protuberance, measure the horizontal range (side vertical with the thickness direction of tablet between summit
The distance between summit upwards, with reference to the B in Fig. 1), be averaged the interval as adjacent projection summit for the value.
According to present embodiment, the protuberance in surface is 20～150 μm with the difference of height of recess, and adjacent projection summit
It is spaced apart 20～150 μm.Remove from office same outward appearance and sense of touch thus, it is possible to obtain Zhen Niuba, be specially stick-slip sense and fine hair sense.In detail
For Xi, if protuberance is more than 20 μm with the difference of height of recess, then can recognize difference of height, Jin Erke with the form of fine hair
To obtain the frictional resistance value of appropriateness.Therefore, it can obtain the same sense of touch of Zhen Niuba leather, stick-slip sense, fine hair sense.If protuberance
Difference of height with recess is less than 150 μm, then frictional resistance value will not become too high, is possible to prevent abrasion performance impaired.In addition,
If adjacent projection summit be spaced apart more than 20 μm, then frictional resistance value will not become too high, is possible to prevent abrasion performance to be subject to
Damage.If adjacent projection summit be spaced apart less than 150 μm, then can obtain appropriateness frictional resistance value, therefore can obtain
The same sense of touch of Zhen Niuba leather, stick-slip sense, fine hair sense.Protuberance is more preferably 50～100 μm with the difference of height of recess.Adjacent projection
The interval on summit is more preferably 80～120 μm.
According to present embodiment, in addition, be 0.20～0.50 by the surface dynamic friction coefficient on above-mentioned surface, become with very
The same surface dynamic friction coefficient of Niu Bage.Therefore, feel the skin resistance of appropriateness when contacting with surface, Zhen Niuba can be obtained
Remove from office same sense of touch, particularly stick-slip sense.Specifically, if surface dynamic friction coefficient is more than 0.20, then surface will not become
For the sense of touch slided glossily, the same stick-slip sense of Zhen Niuba leather can be obtained.If surface dynamic friction coefficient is less than 0.50,
Then surface will not become adhesion and feels strong sense of touch or the strong and coarse sense of touch of resistance, can obtain the same stick-slip of Zhen Niuba leather
Sense.The surface dynamic friction coefficient on surface is more preferably 0.20～0.40.
The surface dynamic friction coefficient on surface can be measured by following method.That is, Niu Bage sample tablet is cut into
The material in 20cm four directions, as test film, uses surface dynamic friction coefficient determination device: KES-SE (Keskato Co., Ltd. system
Make), under temperature 22 ± 2 DEG C, humidity 65 ± 5%RH environment, measure the average surface coefficient of kinetic friction (MIU) on surface.Measure bar
Part is as follows: be set to piano wire sensor 10mm as friction member square, and sample translational speed is set to the 1mm/ second, measures direction and is set to
WARP (warp-wise), measures at any 3, is averaged value as surface dynamic friction coefficient.
As above-mentioned fibrous substrate, can enumerate: cloth and silk, natural leather (the leather bases such as braid, fabric, non-woven fabrics
The end).It on cloth and silk, is coated with or is impregnated with known solvent system, the height of solvent-free system (including water system) furthermore, it is also possible to use
Molecular compound (preferably polyurethane resin or its copolymer or the mixture with polyurethane resin as principal component) simultaneously makes its dry type
Material obtained from solidification or wet type solidification.In addition, the raw material constituting the fiber of fibrous substrate are also not particularly limited, can
To enumerate: the known fibers such as natural fiber, regenerated fiber, semisynthetic fibre, synthetic fibers, they also can combine 2
More than Zhong.Wherein, from the aspect such as heat resistance, light resistance, preferably synthetic fiber, more preferably polyester fiber, particularly preferably poly-
Ethylene glycol terephthalate.The thickness of fibrous substrate from the viewpoint of abrasion performance and feel, preferably 0.3～
1.5mm, more preferably 0.5～1.0mm.It should be noted that fibrous substrate can be for being formed by dyestuff or pigment coloring
Material.
The Niu Bage sample tablet of present embodiment be laminated on above-mentioned fibrous substrate as resin bed comprise gather
Obtained from the top layer of urethane resin.
Polyurethane resin used in the formation on top layer can use known polyurethane resin, from abrasion performance
It from the viewpoint of property and sense of touch (particularly stick-slip sense), is preferably compounded polycarbonate-based polyurethane resin and polyethers system polyurethane tree
Fat.By using polycarbonate-based polyurethane resin, abrasion performance becomes good.By using polyethers system polyurethane resin, touch
Sense, particularly stick-slip sense become good.
Polycarbonate-based polyurethane resin is preferably Merlon with the compounding of polyethers system polyurethane resin than (mass ratio)
It is polyurethane resin: polyethers system polyurethane resin=80:20～20:80, in order to take into account abrasion performance and sense of touch, more preferably
50:50～30:70.Ratio by polycarbonate-based polyurethane resin is more than 20 mass %, is possible to prevent heat resistance, moisture-proof
Hot, light resistance reduces.In addition, be more than 20 mass % by the ratio of polyethers system polyurethane resin, sense of touch, hand can be improved
The improved effect of sense.It should be noted that polyurethane resin accounts for the overall content (being scaled solid constituent) in top layer not especially
Limit, can be 55～93 mass % also can be 70～85 mass %.
From the viewpoint of improving abrasion performance, it is also possible to add smooth agent in top layer.The content of smooth agent (is scaled
Solid constituent) relative to top layer integrally preferably 1～15 mass %, more preferably 3～10 mass %.It is 1 matter by content
Amount more than %, can improve the improved effect of abrasion performance.In addition, by below for 15 mass %, be possible to prevent to ooze out or
The destruction surface grade that scratch is substantially caused.
As smooth agent, silicone compound etc. can be enumerated, for example, can enumerate: dimethyl silscone, acrylic compounds change
Property silicone etc., they can use a kind or combine two or more and use.Wherein, from the aspect of versatility, preferably dimethyl
Silicone.
From the viewpoint of giving stick-slip sense, top layer also can be added sense of touch improver.The content of sense of touch improver
(being scaled solid constituent) is integrally preferably 1～6 mass %, more preferably 2～5 mass % relative to top layer.If content is 1
More than quality %, then can obtain desired stick-slip sense.It in addition, below if 6 mass %, then is possible to prevent to produce by wearing away
The albinism being caused.
As sense of touch improver, wax etc. can be enumerated.For example can enumerate: paraffin, Tissuemat E, polypropylene wax, Brazil
Palm wax, lanolin wax etc., they can use a kind or combine two or more use.Wherein, high from the effect giving stick-slip sense
Aspect set out, preferably paraffin.
In order to colour, in top layer, preferably add pigment.The content (being scaled solid constituent) of pigment is whole relative to top layer
Body is preferably 5～20 mass %, more preferably 10～15 mass %.It when content is more than 5 mass %, is possible not only to coloring and schedules to last
The color hoped and the xanthochromia that can cover resin, therefore can improve light resistance, heat resistance, humidity resistance.If content is
Below 20 mass %, then will not destroy the overlay film intensity on top layer, therefore excellent wear resistance.
For 100% modulus on top layer, become to be easily adapted to from fine concavo-convex and hand, thus can feel as fine hair that
Sample, the aspect that can obtain the Zhen Niuba same sense of touch (particularly fine hair sense) of leather are set out, preferably 1～5MPa, and more preferably 2
～3MPa.When 100% modulus is more than 1MPa, the intensity of gained Niu Bage sample tablet will not be destroyed.In addition, if 5MPa
Hereinafter, then be possible to prevent fine concavo-convex thicker firmly, such that it is able to improve sense of touch.
Herein, 100% modulus value on top layer calculates as described below.That is, use bar coater, become with the thickness of cured film
The composition forming top layer is coated smooth processing release paper (EU130TPD, LINTEC Corporation by the mode of 100 μm
Manufacture) on, at 80 DEG C, carry out heat treatment in 5 minutes with drying machine, then in room temperature 20 ± 2 DEG C, the situation of humidity 65 ± 5%RH
Under carry out 1 day maturation process, make cured film.Gather wide 30mm, the test film 3 of long 100mm size from this cured film, in room
In the case of temperature 20 ± 2 DEG C, humidity 65 ± 5%RH, it is spaced 50mm is installed on cupping machine with pawl width 30mm, pawl
The gripping apparatus of (Autograph AG-X, Shimadzu Scisakusho Ltd manufacture), stretches with draw speed 100m/ minute, surveys
Determine load when stroke distance becomes 50mm.Calculate 100% modulus value by following formula, using 3 mean values as the 100% of top layer
Modulus value.
100% modulus value (MPa)=stroke distance becomes load (N)/test film sectional area (mm during 50mm2)
The thickness on top layer is preferably 20～200 μm, more preferably 50～150 μm.It is more than 20 μm by thickness, Ke Yiti
The abrasion performance of high gained Niu Bage sample tablet.When thickness is less than 200 μm, there is no the feel of gained Niu Bage sample tablet
Thicker hard worry.
Herein, the thickness on top layer calculates as described below.That is, with microscope, (KEYENCE CORPORATION manufactures, counts
Word HF microscope VH-8000) observe the vertical cross-section of Niu Bage sample tablet, will be for measuring protuberance summit and table at any 10
Value obtained from the difference of height of layer foot and obtaining for measuring the end of recess and the difference of height of top layer foot at any 10
The mean value of the value arriving is as the thickness on top layer.
In the Niu Bage sample tablet of present embodiment, in order to improve abrasion performance, it is also possible to arrange protective layer and/or anchor
Coating.As described above, protective layer is laminated in the upper strata on top layer, and anchor coat layer is laminated on the lower floor on top layer.It should be noted that from
From the viewpoint of improving cementability, protective layer and/or anchor coating are preferably formed by polyurethane resin in the same manner as top layer.
As formation protective layer, the polyurethane resin of anchor coating, it is possible to use the polyurethane resin as top layer.Protection
Layer is positioned at the outermost layer on the surface forming Niu Bage sample tablet, becomes people and directly contacts.Therefore, for protective layer, from wear-resisting
The aspect of consumption is set out, and polycarbonate-based polyurethane resin is preferably used, and then from the viewpoint of stick-slip sense, preferably adds and touch
Sense improver, from the viewpoint of abrasion performance, preferably adds smooth agent.
From the viewpoint of abrasion performance and sense of touch, the thickness of protective layer is preferably 2～10 μm, more preferably 2～5 μm.
In addition, the thickness of anchor coating is preferably 10～30 μm from the viewpoint of feel, more preferably 15～20 μm.Protective layer, top layer,
The gross thickness of anchor coating from the viewpoint of abrasion performance and feel, preferably 32～240 μm, more preferably 60～120 μm.
In the Niu Bage sample tablet of present embodiment, adhesive linkage also can be set between top layer and fibrous substrate.
Can by top layer directly with fibrous substrate stacking, but pass through via adhesive linkage, that may cause when can suppress directly to be laminated,
Constitute the excessive immersion to fibrous substrate for the polyurethane resin on top layer, be readily obtained the sense of touch as Zhen Niuba leather, feel.
It as the bonding agent as adhesive linkage, is not particularly limited, polyurethane resin is preferably used, it is possible to use with use in top layer
The same resin of resin.
Fine concavo-convex per unit area (1cm in the surface of Niu Bage sample tablet2) the number of protuberance preferred
It is 4000～80000, more preferably 20000～50000, more preferably 20000～30000.If per unit
The number of the protuberance of area is 4000～80000, then be readily obtained the same sense of touch of Zhen Niuba leather, i.e. stick-slip sense, fine hair sense.
Herein, the fine concavo-convex per unit area (1cm in surface2) the number of protuberance calculate as described below.
That is, microscope (KEYENCE CORPORATION manufacture, numeral HF microscope VH-8000) is used to observe ox bar with multiplying power 500 times
The surface of leather sample tablet, the by visual observation quantity (X) of vertical 500 μm of counting, protuberance in horizontal 250 μm.For the protuberance counting
Quantity (X), use following formula, calculate per unit area (1cm2) the number of protuberance.
Conversion formula: the quantity (X) × 10 of the protuberance of the number of the protuberance of per unit area=count2/0.125
In the range of not damaging the effect of present embodiment, on the surface of Niu Bage sample tablet also can overlapping other
Relief pattern.Other relief patterns refer to, compared with above-mentioned fine concavo-convex protuberance and recess, by height (difference of height) and wide
The relief pattern that the big recess of degree (interval) and protuberance are formed, for example, can enumerate: the pit pattern of natural leather, geometry figure
Case etc..Therefore, in certain embodiment, can be fine concavo-convex recessed more than above-mentioned in the surface configuration of Niu Bage sample tablet
Convex pattern, profile on the basis of this big relief pattern, this big relief pattern is formed above-mentioned fine concavo-convex.By weight
Folded so big relief pattern, it is provided that possess the complicated design of Zhen Niuba leather and other patterns.Furthermore it is possible to make to touch
Sense, stick-slip sense, fine hair sense are removed from office closer to Zhen Niuba.It should be noted that it is thus understood that, above-mentioned fine concavo-convex with one
As the pit pattern of natural leather compare densification, can be for more concavo-convex than more uniform.
Fig. 3 schematically shows the cross section structure of the Niu Bage sample tablet 11 being provided with other relief patterns above-mentioned.At this piece
It is formed the big relief pattern being formed by big recess 12 and protuberance 13 becoming baseline profile on the surface 4 of shape thing 11.?
Have the surface 4 of this big relief pattern be provided with by above-mentioned recess 9 and protuberance 8 formed fine concavo-convex.
The interval of the adjacent recesses of above-mentioned big relief pattern is the extreme lower position and with this recess of arbitrarily large recess
The distance of the extreme lower position of near big recess (referring to the part that difference of height is big compared with above-mentioned fine concavo-convex recess).Greatly
The recess of relief pattern and the difference of height of protuberance be recess big arbitrarily and the height of the big protuberance nearest with this recess
Difference.They are obtained by the observation in vertical cross-section as described below.That is, with microscope (KEYENCE CORPORATION manufacture,
Numeral HF microscope VH-8000) observe the vertical cross-section of Niu Bage sample tablet, for the big recess at any 10 and with
The nearest big recess of this recess, measures end horizontal range each other (in the direction vertical with the thickness direction of tablet
Extreme lower position between distance, with reference to the C in Fig. 3), using its scope (minimum of a value and maximum) as between adjacent big recess
Every.In addition, for the adjacent big recess at any 10 and protuberance, measure the difference of height at the end of recess and the summit of protuberance
(D with reference in Fig. 3), is averaged the difference of height as recess and protuberance for the value.Herein, in order to observe broader scope, permissible
To be set as being compared to fine concavo-convex observe based on microscopical multiplying power when big relief pattern is observed
When multiplying power little.For example, observe fine concavo-convex when multiplying power be 500 times, and multiplying power when observing big relief pattern is permissible
It is set to 50 times.
Then, the manufacture method of above-mentioned ox Ba Ge sample tablet is illustrated.This manufacture method includes following operation:
(1) top layer resin liquid is coated on release property base material, form the operation on top layer；
(2) top layer and the operation of fibrous substrate laminating are made；With,
(3) operation that release property base material is peeled off.
As method top layer resin liquid coated on release property base material, known various side can be used
Method, is not particularly limited.For example can enumerate: use reverse roll coater, flush coater, roll coater, knife type coater, funny spot printing
The method of the devices such as cloth machine.Wherein, from the aspect that can form uniform film layer, preferably by reverse roll coater,
Knife type coater or the coating of comma coater.
Release property base material is not particularly limited, as long as having the base material of release property to polyurethane resin or implementing de-
The base material that mould is processed.For example can enumerate: processing release paper, demoulding treatment cloth, water repellent treatment cloth, by polyvinyl resin or poly-third
The alkene piece of the formation such as olefine resin or the plastic sheeting etc. of film, fluororesin piece or film, band processing release paper.
Release property base material is it is important that have relief pattern.Be 20 by using the difference of height with protuberance and recess～
The release property base material of the relief pattern being spaced apart 20～170 μm of 170 μm and adjacent recesses, can be to ox Ba Ge sample tablet
Surface give desired fine relief pattern.That is, the surface of Niu Bage sample tablet fine concavo-convex by release property base
The relief pattern of material gives.In the range of not damaging fine relief pattern, on release property base material also can have and is equivalent to
State the big relief pattern of big relief pattern.
The coating thickness of top layer resin liquid suitably can set, preferably 40～400 μm according to the thickness on aforementioned top layer,
More preferably 100～300 μm.By coating thickness is set as this scope, become having preferably 20～200 μm, more preferably 50～
The top layer of the thickness of 150 μm.
After top layer resin liquid is coated release property base material, can be heat-treated as required.Heat treatment be in order to
The solvent in the resin liquid of top layer is made to evaporate so that resin is dried and carries out.Cause crosslinking in addition, use by heat treatment
Reaction crosslinking agent situation or use bi-component curing type resin in the case of, be in order to promote reaction, formed have
The overlay film of sufficient intensity and carry out.
Heat treatment temperature can be 50～150 DEG C also can be 60～130 DEG C.When heat treatment temperature is more than 50 DEG C, heat
Process will not excessively expend the time, and therefore, process load will not become excessive.Furthermore it is possible to prevent the crosslinking of resin from becoming not
Fully, accordingly it is possible to prevent abrasion performance becomes bad.It when heat treatment temperature is less than 150 DEG C, is possible to prevent synthetic leather
Feel is thicker firmly.In addition, heat treatment time can be within 2～20 minutes, also can be 2～10 minutes.Heat treatment time is 2 minutes
It when above, is possible to prevent the crosslinking of resin to become insufficient, accordingly it is possible to prevent abrasion performance becomes bad.Heat treatment time
When being within 20 minutes, process load will not become excessive.
Then, top layer and fibrous substrate laminating are made.During laminating, as described above, can fit via adhesive linkage, also may be used
With directly stacking laminating.Preferably it is made to fit via adhesive linkage.When being provided with adhesive linkage, can paste after coating adhesive on top layer
Together in fibrous substrate.
The method of coating adhesive can use known various methods, is not particularly limited.For example can enumerate: use
The devices such as reverse roll coater, flush coater, roll coater, gravure coater, kiss roll coater, knife type coater, comma coater
Method.
Then, release property base material is peeled off from top layer.It is hereby achieved that the Niu Bage sample tablet of present embodiment.But
It is that the method for the Niu Bage sample tablet for manufacturing present embodiment is not limited to said method.
During it should be noted that form anchor coating, on release property base material behind formation top layer before coating adhesive, at table
It is coated with anchor coating resin liquid on layer thus formed.On the other hand, when forming protective layer, after release property base material is peeled off on top layer,
Surface coat protective layer resin liquid on this top layer thus formed.For the heat treatment after the method being coated with and coating, permissible
Use the method as the formation on top layer.
The coating thickness of protective layer used resin liquid suitably can set according to the thickness of aforementioned protective layer, can be 5～25 μ
M also can be 5～13 μm.By coating thickness is set as this scope, become that there are preferably 2～10 μm, more preferably 2～5 μm
The protective layer of thickness.
The coating thickness of anchor coating resin liquid suitably can set according to the thickness of aforementioned anchor coating, can be 50～
150 μm also can be 75～100 μm.By coating thickness is set as this scope, become having preferably 10～30 μm, more preferably 15
The anchor coating of the thickness of～20 μm.
During for the Niu Bage sample tablet of present embodiment, surface has table that is above-mentioned distinctive concavo-convex and that have regulation
The face coefficient of kinetic friction, even if therefore not grinding skin surface also can obtain the sense of touch of Niu Bage sample.That is, the ox of present embodiment
Although surface is not ground in Ba Ge sample tablet, but also give the sense of touch of Niu Bage sample.Therefore, have and disclosure satisfy that conduct
The sense of touch of Niu Bage sample tablet and also can give the abrasion performance that disclosure satisfy that in the field requiring highly durable property.
Embodiment
Hereinafter, illustrate in greater detail the present invention according to embodiment, but the present invention is not limited to below example.Embodiment
In " part " be quality criteria.
[table 1]
[table 2]
[table 3]
[embodiment 1]
Use comma coater, in the way of coating thickness becomes 200 μm, the top layer prepared according to above-mentioned formula 1 is used
Resin liquid coats processing release paper with sheet, carries out heat treatment in 3 minutes with drying machine, form the table of thickness 100 μm at 100 DEG C
Layer.As processing release paper, use and there is the difference of height 115 μm of protuberance and recess, 94 μm of the interval of adjacent recesses, the number of recess
28000/cm2The processing release paper of nick convex pattern.Formed top layer polyurethane resin polycarbonate-based polyurethane resin with
The mass ratio of polyethers system polyurethane resin is 32:68, and the containing ratio (being scaled solid constituent) of pigment is 11 mass %, 100%
Modulus value is 2.5MPa.
Then, comma coater is used, in the way of coating thickness becomes 170 μm, using the carbamic acid as bonding agent
Ester polyisocyanate prepolymers (NH230, solid constituent 100 mass %, Dainippon Ink Chemicals's system) coats aforementioned top layer with sheet
On.This carbamate polyisocyanate prepolymers is made (to utilize with circle latitude cloth and use in the state of having toughness
150dtex/48f polyester multifilament mockrody tissue carry out tissue weave into, thickness 0.7cm, weight per unit area 260g/m2、
70 rows (course)/24.5mm, 33 wales (wale)/25.4mm) laminating, with ironer with 5kg/m2Load
Carry out Guan Bi pressurization.Temperature 23 DEG C, relative humidity 65% atmosphere under carry out 3 days maturation process, peel off processing release paper afterwards,
To Niu Bage sample tablet.
In gained Niu Bage sample tablet, the protuberance on surface and the difference of height of recess are 86 μm, between adjacent projection summit
Being divided into 102 μm, the number of protuberance is 24000/cm2, surface dynamic friction coefficient is 0.38.In addition, Niu Bage sample tablet
The containing ratio (being scaled solid constituent) of the smooth agent in most surface i.e. top layer is 8 mass %, and the containing ratio of sense of touch improver (changes
Calculating is solid constituent) it is 3 mass %.
[embodiment 2]
Remove smooth agent and sense of touch improver from the resin liquid of top layer, in addition, obtain piece similarly to Example 1
Shape thing.Use roll coater, in the way of coating thickness becomes 10 μm, by the protective layer used resin liquid according to formula 2 preparation with piece
Shape is coated on the top layer of gained tablet, carries out heat treatment in 3 minutes with drying machine, form the protection of thickness 4 μm at 100 DEG C
Layer, obtains Niu Bage sample tablet.In gained Niu Bage sample tablet, the protuberance on surface and the difference of height of recess are 54 μm, phase
Adjacent protuberance summit be spaced apart 98 μm, the number of protuberance is 21600/cm2, surface dynamic friction coefficient is 0.26.In addition, ox bar
The containing ratio of the smooth agent in the most surface i.e. protective layer of leather sample tablet is 7 mass %, and the containing ratio of sense of touch improver is 3 matter
Amount %.
[embodiment 3]
In embodiment 1, after processing release paper forms top layer, before coating adhesive, use comma coater, to be coated with thickness
Degree becomes the mode of 150 μm, by coating on this top layer according to the anchor coating resin liquid of formula 3 preparation with sheet, with drying
Machine carries out heat treatment in 3 minutes at 100 DEG C, forms the anchor coating of thickness 30 μm.In addition, all similarly to Example 1
Obtain Niu Bage sample tablet.In gained Niu Bage sample tablet, the protuberance on surface and the difference of height of recess are 84 μm, adjacent convex
Summit, portion be spaced apart 110 μm, the number of protuberance is 24000/cm2, surface dynamic friction coefficient is 0.34.In addition, Niu Bage
The containing ratio (being scaled solid constituent) of the smooth agent in the most surface of sample tablet i.e. top layer is 8 mass %, sense of touch improver
The containing ratio of (being scaled solid constituent) is 3 mass %.
[embodiment 4]
In embodiment 2, after processing release paper forms top layer, before coating adhesive, form thickness similarly to Example 3
The anchor coating of 30 μm.In addition, Niu Bage sample tablet is all obtained similarly to Example 2.Gained Niu Bage print shape
In thing, the protuberance on surface and the difference of height of recess are 55 μm, adjacent projection summit be spaced apart 93 μm, the number of protuberance is
21600/cm2, surface dynamic friction coefficient is 0.25.In addition, smoothing in the most surface i.e. protective layer of Niu Bage sample tablet
The containing ratio (being scaled solid constituent) of agent is 7 mass %, and the containing ratio (being scaled solid constituent) of sense of touch improver is 3 matter
Amount %.
[embodiment 5～11 and comparative example 1～4]
Make Niu Bage sample tablet according to table 4, in addition all make Niu Bage print shape similarly to Example 1
Thing.It should be noted that for the processing release paper using in embodiment 11, take turns on the basis of the big relief pattern of leather pit shape
Exterior feature, have described in table 4 on this relief pattern is fine concavo-convex.The composition of big relief pattern is as follows: recess and protuberance
Difference of height be 235 μm, adjacent projection be spaced apart 0.2～2mm, the number of recess is 63/cm2。
For each ox Ba Ge sample tablet, carry out sense of touch, feel, abrasion performance, humidity resistance, heat-resisting by the following method
Result is recorded in table 4 by property and sunproof evaluation.
[sense of touch]
For the sense of touch on test film surface, carry out sense evaluation, judge according to following benchmark.
A: the thoughts and feelings of moistening stick-slip sense and fine hair sense for there being Niu Bage sample
B: the slightly thoughts and feelings of the one in the moistening stick-slip sense of shortcoming Niu Bage sample or fine hair sense
C: be slightly short of the thoughts and feelings of Niu Bage sample
D: do not have the thoughts and feelings of Niu Bage sample completely, for coarse and dry sense of touch
[feel]
For the hand-held sense of test film, carry out sense evaluation, judge according to following benchmark.
A: there is the softness as Zhen Niuba leather and soft feel
B: there is the softness with Zhen Niuba leather approximation and soft feel, but slightly feel resin sense, core
C: feel difference soft and soft compared with Zhen Niuba leather, feels resin sense, core
D: be substantially different feels with Zhen Niuba leather, feels resin sense, core strongly
[abrasion performance]
Gather the test film 1 of the size of wide 70mm, long 300mm, overleaf configuration width from longitudinal and transverse all directions respectively
70mm, long 300mm, the urethane foam body of size of thickness 10mm.Following central authorities at urethane foam body set
In the state of being equipped with the line of diameter 4.5mm, (Dae Young Co., Ltd.'s science essence device makes to be fixed on plane abrasiometer T-TYPE
Manufactured), to be stamped the abrasion body reciprocating abreast mode with line on line of cotton, to this friction piece imposed load
9.8N, carries out abrasion test.Friction piece speed with 60 round/minutes between 140mm on the surface of test film makes it past
Multiple 3000 times.Observe the surface state of the test film after abrasion test, judge according to following benchmark.
5: be not changed in (not be full of cracks, breakage) in appearance
4: confirm slightly to wear away, but inconspicuous
3: clearly confirming there are abrasion, have fibrous substrate exposes (confirmation has be full of cracks)
2: exposing of fibrous substrate is slightly obvious
1: exposing slightly substantially (confirmation has breakage) of fibrous substrate
[humidity resistance]
The test film being cut into long 50mm × wide 250mm is being adjusted the constant temperature and humidity machine to 70 DEG C, 95%RH: PR-
Stand in 2KTH (ESPEC.CORP manufacture) and carry out humid heat treatment in 5 weeks.With the test film before and after visualization humid heat treatment, for
Test film after humid heat treatment, utilizes the tonal gradation (gray scale) of JIS L-0804 standard to judge.Change is faded 4
It is qualified more than level to be set to.
[heat resistance]
The test film of the size in 10cm four directions will be cut at wide-mouth reagent bottle (the 250mL bottle with stopper, hard glass
System) in along wide-mouth reagent bottle side add, adjust to the drying machine of 110 DEG C standing within 400 hours, be heat-treated.Heat
After process, wide-mouth reagent bottle is taken out from drying machine, after being cooled to room temperature, analoids is taken out from wide-mouth reagent bottle.With visually
Observe the test film before and after being heat-treated, for the test film after heat treatment, utilize the tonal gradation (gray of JIS L-0804 standard
Scale) judge.Fading change more than 4 grades, it is qualified to be set to.
[light resistance]
The test film being cut into long 65mm × wide 150mm is made to fit in the aluminium sheet of thickness 1mm with same size.Use possesses
The promotion xenon Light Resistance Test machine of xenon arc lamp (air-cooled type 8kw): WT-341 (manufacture of Wacom Co., Ltd.), at following bar
Under part, it is tested.
Irradiation cycle: Continuous irradiation
Irradiation time: 144 hours
Exposure intensity: 162W/m2
Black panel temperature: 89 ± 3 DEG C
Relative humidity: 50 ± 5%
Illumination wavelength: 300～400nm
With the test film after visualization pre-irradiation, for the test film after irradiation, utilize the gray scale of JIS L0804 standard
Grade (gray scale) judges light fastness.Fading change more than 4 grades, it is qualified to be set to.[table 4]
Industrial applicability
The Niu Bage sample tablet of present embodiment may be used for dress material, suitcase, shoes, house decorative material, in vehicle
The various uses such as portion's ornament materials, are based particularly on its excellent abrasion performance, for example can be suitable as house decorative material,
Vehicle interior ornament materials uses.
Description of reference numerals
1 ... Niu Bage sample tablet 2 ... fibrous substrate 3 ... top layer
4 ... surface 5 ... adhesive linkage 6 ... anchor coating
7 ... protective layer 8 ... protuberance 9 ... recess
10th, 11 ... Niu Bage sample tablet
Claims (9)
1. an ox Ba Ge sample tablet, which is stacking on fibrous substrate and comprises obtained from the top layer of polyurethane resin,
Have on the surface of Niu Bage sample tablet the difference of height of protuberance and recess be 20～150 μm, being spaced apart of adjacent projection summit
20～150 μm concavo-convex, and the surface dynamic friction coefficient on surface is 0.20～0.50.
2. ox Ba Ge sample tablet according to claim 1, wherein, described polyurethane resin comprises polycarbonate-based poly-ammonia
The quality of ester resin and polyethers system polyurethane resin, described polycarbonate-based polyurethane resin and described polyethers system polyurethane resin
Ratio is 80:20～20:80.
3. ox Ba Ge sample tablet according to claim 1 and 2, its surface is not ground.
4. the Niu Bage sample tablet according to according to any one of claims 1 to 3, wherein, described top layer is contained and is comprised silicone
The smooth agent of based compound.
5. the Niu Bage sample tablet according to according to any one of Claims 1 to 4, wherein, described top layer is contained and is comprised wax
Sense of touch improver.
6. the Niu Bage sample tablet according to according to any one of Claims 1 to 5, wherein, 100% modulus on described top layer is
1～5MPa.
7. the Niu Bage sample tablet according to according to any one of claim 1～6, wherein, being arranged over of described top layer
Comprise the outermost layer as the surface forming Niu Bage sample tablet for the protective layer of polyurethane resin.
8. the Niu Bage sample tablet according to according to any one of claim 1～7, wherein, is provided with in the lower section on described top layer
Comprise the anchor coating of polyurethane resin.
9. a manufacture method for the Niu Bage sample tablet according to any one of claim 1～8, it includes following work successively
Sequence:
Top layer resin liquid is coated and on release property base material, forms the operation on top layer；
Make top layer and the operation of fibrous substrate laminating；With,
The operation that release property base material is peeled off.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-049065 | 2014-03-12 | ||
| JP2014049065 | 2014-03-12 | ||
| PCT/JP2015/001309 WO2015136921A1 (en) | 2014-03-12 | 2015-03-10 | Nubuck-toned sheet-like material and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106103838A true CN106103838A (en) | 2016-11-09 |
| CN106103838B CN106103838B (en) | 2018-02-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580013466.8A Active CN106103838B (en) | 2014-03-12 | 2015-03-10 | Niu Bage samples tablet and its manufacture method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6207717B2 (en) |
| CN (1) | CN106103838B (en) |
| MX (1) | MX2016011454A (en) |
| WO (1) | WO2015136921A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130443A (en) * | 2017-04-21 | 2017-09-05 | 天守(福建)超纤科技股份有限公司 | A kind of preparation method of ox Ba Ge frostings |
| CN110799697A (en) * | 2017-06-27 | 2020-02-14 | 世联株式会社 | Synthetic leather |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102052275B1 (en) * | 2017-09-14 | 2020-01-08 | (주)엘지하우시스 | artificial leather and a method for producing the same |
| JP7377045B2 (en) * | 2018-10-10 | 2023-11-09 | セーレン株式会社 | Synthetic leather and its manufacturing method |
| JP2024017451A (en) * | 2022-07-28 | 2024-02-08 | オカモト株式会社 | Synthetic resin leather and manufacturing method thereof |
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| JP2005220499A (en) * | 2004-02-09 | 2005-08-18 | Dainippon Ink & Chem Inc | Resin composition for artificial leather and the artificial leather |
| CN101133168A (en) * | 2005-03-04 | 2008-02-27 | 巴斯福股份公司 | Die comprising small cup-type depressions |
| JP2012127010A (en) * | 2010-12-13 | 2012-07-05 | Kyowa Leather Cloth Co Ltd | Synthetic leather and method for producing the same |
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| JP4580541B2 (en) * | 2000-11-17 | 2010-11-17 | 大日本印刷株式会社 | Release paper and synthetic leather produced using it |
| KR101158135B1 (en) * | 2004-04-09 | 2012-06-19 | 가부시키가이샤 구라레 | Sheet material excelling in cushion and nonslip properties |
| JP5398451B2 (en) * | 2009-09-28 | 2014-01-29 | セーレン株式会社 | Synthetic leather manufacturing method |
| JP2013011038A (en) * | 2011-06-30 | 2013-01-17 | Kuraray Co Ltd | Leather-like sheet and method for manufacturing the same |
| JP5496389B2 (en) * | 2012-06-06 | 2014-05-21 | セーレン株式会社 | Skin material |
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2015
- 2015-03-10 MX MX2016011454A patent/MX2016011454A/en unknown
- 2015-03-10 WO PCT/JP2015/001309 patent/WO2015136921A1/en active Application Filing
- 2015-03-10 CN CN201580013466.8A patent/CN106103838B/en active Active
- 2015-03-10 JP JP2016507356A patent/JP6207717B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220499A (en) * | 2004-02-09 | 2005-08-18 | Dainippon Ink & Chem Inc | Resin composition for artificial leather and the artificial leather |
| CN101133168A (en) * | 2005-03-04 | 2008-02-27 | 巴斯福股份公司 | Die comprising small cup-type depressions |
| JP2012127010A (en) * | 2010-12-13 | 2012-07-05 | Kyowa Leather Cloth Co Ltd | Synthetic leather and method for producing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130443A (en) * | 2017-04-21 | 2017-09-05 | 天守(福建)超纤科技股份有限公司 | A kind of preparation method of ox Ba Ge frostings |
| CN110799697A (en) * | 2017-06-27 | 2020-02-14 | 世联株式会社 | Synthetic leather |
| CN110799697B (en) * | 2017-06-27 | 2022-11-01 | 世联株式会社 | Synthetic leather |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6207717B2 (en) | 2017-10-04 |
| WO2015136921A1 (en) | 2015-09-17 |
| JPWO2015136921A1 (en) | 2017-04-06 |
| MX2016011454A (en) | 2016-12-02 |
| CN106103838B (en) | 2018-02-23 |
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