CN106103838B - Niu Bage samples tablet and its manufacture method - Google Patents
Niu Bage samples tablet and its manufacture method Download PDFInfo
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- CN106103838B CN106103838B CN201580013466.8A CN201580013466A CN106103838B CN 106103838 B CN106103838 B CN 106103838B CN 201580013466 A CN201580013466 A CN 201580013466A CN 106103838 B CN106103838 B CN 106103838B
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- Prior art keywords
- top layer
- sample tablets
- sense
- niu bage
- polyurethane resin
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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 samples tablet (1) is to be laminated on fibrous substrate (2) obtained from the top layer (3) comprising polyurethane resin.To have difference of height (A) of convex portion (8) and recess (9) in the surface of Niu Bage sample tablets (4) be 20~150 μm, the fine bumps that the interval (B) on adjacent projection summit is 20~150 μm.In addition, the surface dynamic friction coefficient of surface (4) is 0.20~0.50.
Description
Technical field
The present invention relates to the tablet with Niu Bage sample outward appearances and its manufacture method.
Background technology
In the past, the tablet with the outward appearance for the Niu Bage (nubuck) for 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 tablets, by being referred to as wet type
The method of method or dry process is main flow to manufacture.
For damp process, solvent (organic solvent) solution of polyurethane resin is coated with or is impregnated with fibrous substrate, will
It is impregnated in the liquid of the non-solvent comprising polyurethane resin, the solvent in polyurethane resin solution is moved to non-solvent.
Thus, polyurethane resin is made to solidify and form porous layer.Afterwards, surface is ground and there is the outward appearance of 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 stick-slip sense and the feel of softness of moistening, with
The Niu Bage of natural leather is approximate.It is but crisp to external force, it is difficult to obtain disclosure satisfy that the field of highly durable property that requires, for example make
For house decorative material, the abrasion performance of vehicle interior ornament materials.
On the other hand, for dry process, the solvent solution or water of coating or impregnation polyurethane resin on fibrous substrate
Dispersion liquid, make its drying, surface is ground afterwards and there is the outward appearance of pile sample.The tablet obtained by the dry process first one
See the outward appearance of pile sample.However, thoughts and feelings is coarse and is what is done, feel is also hard, is very different with the Niu Bage of natural leather.
In addition, the excellent wear resistance compared with the tablet obtained by damp process, but can not be said to be sufficient.
Above-mentioned 2 methods are main flows in the manufacture of Niu Bage sample tablets, a scheme as dry process, it is proposed that,
By the method for the epidermis layer stackup comprising polyurethane resin made on processing release paper.For example, proposed in patent document 1,
The mediopellis for including polyurethane resin is made on the epidermis comprising polyurethane resin made on processing release paper, is passed to
Bonding agent is glued with fibrous substrate, afterwards peels off processing release paper, so as to the design of Niu Bage samples.With it, can be with
The design of Niu Bage samples is obtained, but sense of touch (particularly stick-slip sense) can not be reappeared.Therefore, for the problem, in patent document 2
Proposing, the epidermis comprising polyurethane resin for making to make on processing release paper is bonded by bonding agent with fibrous substrate, it
Processing release paper is peeled off afterwards, the surface of epidermis is ground and there is the outward appearance of pile sample.With it, Niu Bage can be obtained
The stick-slip sense of sample, but due to grinding skin, therefore do not have abrasion performance.
In this way, present situation is can not to obtain the excellent Niu Bage print shapes of both Niu Bage samples 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
The content of the invention
Problems to be solved by the invention
The present invention be in view of such present situation and make, there is provided have concurrently disclosure satisfy that as Niu Bage sample tablets touch
Sense and the Niu Bage samples tablet and its manufacture method of abrasion performance.
The solution used to solve the problem
Present embodiment the 1st is a kind of ox Ba Ge sample tablets, and it is that stacking includes polyurethane tree on fibrous substrate
Obtained from the top layer of fat, have on the surface of Niu Bage sample tablets the difference of height of convex portion and recess for 20~150 μm, it is adjacent
Convex portion summit at intervals of 20~150 μm of bumps, and the surface dynamic friction coefficient on surface is 0.20~0.50.
Present embodiment the 2nd is a kind of manufacture method of above-mentioned ox Ba Ge sample tablets, and it includes following process successively：
(1) top layer is coated on to the process for forming top layer on release property base material with resin liquid；
(2) process for making top layer and fibrous substrate fitting；With,
(3) process for peeling off release property base material.
The effect of invention
According to present embodiment, the sense of touch and abrasion performance that has concurrently and disclosure satisfy that as Niu Bage sample tablets can be provided
Niu Bage samples tablet and its manufacture method.
Brief description of the drawings
Fig. 1 is the schematic cross-section of the Niu Bage sample tablets of an embodiment.
Fig. 2 is the schematic cross-section of the Niu Bage sample tablets of other embodiment.
Fig. 3 is the cross-sectional modes figure of the Niu Bage sample tablets of further other embodiment.
Embodiment
The Niu Bage sample tablets of present embodiment are characterised by that it is that stacking includes polyurethane on fibrous substrate
Niu Bage samples tablet obtained from the top layer of resin, there is fine bumps, and surface on the surface of Niu Bage sample tablets
Surface dynamic friction coefficient be 0.20~0.50.Herein, fine bumps refer to, the difference of height of convex portion and recess is 20~150 μ
M, and adjacent projection summit at intervals of 20~150 μm of bumps.
Fig. 1 schematically shows the cross section structure of the Niu Bage samples tablet 1 of an embodiment.In the tablet 1, in fibre
Top layer 3 is laminated with one face of dimension matter base material 2, the surface on top layer 3 is surface 4, is provided with the surface 4 and includes the He of convex portion 8
The fine bumps of recess 9.In addition, in the example, top layer 3 is laminated in fibrous substrate 2 via adhesive linkage 5, therefore, in cellulosic
Adhesive linkage 5 and top layer 3 are sequentially laminated with one face of base material 2.
Fig. 2 schematically shows the cross section structure of the Niu Bage samples tablet 10 of other embodiment.In the tablet 10,
The lower section on top layer 3 is provided with anchor coating 6, and is provided with protective layer 7 in the top on top layer 3.Therefore, in Fig. 2 example, in cellulosic base
It is sequentially laminated with adhesive linkage 5, anchor coating 6, top layer 3 and protective layer 7 on one face of material 2, the surface of protective layer 7 is changed into having micro-
Thin concavo-convex surface 4.
The difference of height of convex portion and recess in above-mentioned surface is arbitrary convex portion and the height with the immediate recess in the convex portion
Low difference, the as described below observation in vertical cross-section are obtained.That is, with microscope (KEYENCE CORPORATION manufacture,
Digital HF microscope VH-8000) observation Niu Bage sample tablets vertical cross-section, for the adjacent projection at any 10 and recessed
Portion, the difference of height (A in reference picture 1) at the summit of convex portion and the bottom of recess is determined, be averaged value as convex portion and recess
Difference of height.
In addition, adjacent projection summit in above-mentioned surface at intervals of arbitrary convex portion and with the immediate convex portion in the convex portion
Summit between distance, the observation in vertical cross-section as described below obtains.That is, with microscope (KEYENCE
CORPORATION manufacture, digital HF microscope VH-8000) observation Niu Bage sample tablets vertical cross-section, at any 10
Convex portion and with the immediate convex portion in the convex portion, determine summit between the horizontal range (side vertical with the thickness direction of tablet
The B in distance, reference picture 1 between upward summit), it is averaged interval of the value as adjacent projection summit.
According to present embodiment, the difference of height of convex portion and recess in surface is 20~150 μm, and adjacent projection summit
At intervals of 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 thin, if the difference of height of convex portion and recess is more than 20 μm, difference of height, Jin Erke can be recognized in the form of fine hair
To obtain appropriate frictional resistance value.Therefore, Zhen Niuba can be obtained and remove from office same sense of touch, stick-slip sense, fine hair sense.If convex portion
Difference of height with recess is less than 150 μm, then frictional resistance value will not become too high, abrasion performance can be prevented to be damaged.In addition,
If adjacent projection summit at intervals of more than 20 μm, frictional resistance value will not become too high, can prevent abrasion performance by
Damage.If adjacent projection summit at intervals of less than 150 μm, appropriate frictional resistance value can be obtained, therefore can obtain
Zhen Niuba removes from office same sense of touch, stick-slip sense, fine hair sense.The difference of height of convex portion and recess is more preferably 50~100 μm.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, be changed into very
Surface dynamic friction coefficient same Niu Bage.Therefore, appropriate skin resistance is felt when being contacted 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, surface will not become
For the sense of touch glossily slided, Zhen Niuba can be obtained and remove from office same stick-slip sense.If surface dynamic friction coefficient is less than 0.50,
Then surface will not be changed into adhesion and feel strong sense of touch or the strong and coarse sense of touch of resistance, can obtain Zhen Niuba and remove from office same stick-slip
Sense.The surface dynamic friction coefficient on surface is more preferably 0.20~0.40.
The surface dynamic friction coefficient on surface can be determined by following method.That is, Niu Bage sample tablets are cut into
The material in 20cm four directions uses surface dynamic friction coefficient determination device as test film：KES-SE (Keskato Co. Ltd. systems
Make), the average surface coefficient of kinetic friction (MIU) on measure surface under 22 ± 2 DEG C of temperature, humidity 65 ± 5%RH environment.Determine bar
Part is as follows：Piano wire sensor 10mm square is set to as friction member, sample translational speed is set to the 1mm/ seconds, and measure direction is set to
WARP (warp-wise), determine at any 3, be averaged value as surface dynamic friction coefficient.
As above-mentioned fibrous substrate, can enumerate：The cloth and silks such as braid, fabric, non-woven fabrics, natural leather (leather base
Bottom).Furthermore, it is also possible to using be coated with or be impregnated with cloth and silk known solvent system, it is solvent-free system (including water system) height
Molecular compound (preferably polyurethane resin or its copolymer or the mixture using polyurethane resin as principal component) simultaneously makes its dry type
Material obtained from solidification or wet type solidification.In addition, the raw material for forming the fiber of fibrous substrate are also not particularly limited, can
To enumerate：The known fiber such as natural fiber, regenerated fiber, semisynthetic fibre, synthetic fibers, they can also combine 2
More than kind.Wherein, from heat resistance, light resistance etc., preferably synthetic fiber, more preferably polyester fiber are 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 to be formed by dyestuff or pigment coloring
Material.
The Niu Bage sample tablets of present embodiment are that stacking is poly- as including for resin bed on above-mentioned fibrous substrate
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
Property and sense of touch (particularly stick-slip sense) from the viewpoint of, be 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.
The mix ratio (mass ratio) of polycarbonate-based polyurethane resin and polyethers system polyurethane resin is preferably makrolon
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.It is more than 20 mass % by the ratio of polycarbonate-based polyurethane resin, heat resistance, moisture-proof can be prevented
Hot, light resistance reduces.In addition, the ratio for passing through polyethers system polyurethane resin is more than 20 mass %, 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 without special
Limit, can be that 55~93 mass % can also be 70~85 mass %.
From the viewpoint of abrasion performance is improved, smooth agent can also be added in top layer.The content of smooth agent (is scaled
Solid constituent) relative to top layer integrally be preferably 1~15 mass %, more preferably 3~10 mass %.It is 1 matter by content
More than % is measured, the improved effect of abrasion performance can be improved.In addition, by for below 15 mass %, can preventing from oozing out or
Destruction surface grade caused by scratch is obvious.
As smooth agent, silicone compound etc. can be enumerated, such as can enumerate：Dimethyl silscone, acrylic compounds change
Property silicone etc., they can use a kind or combine two or more use.Wherein, from versatility aspect, preferably dimethyl
Silicone.
From the viewpoint of stick-slip sense is assigned, sense of touch improver can also be added in top layer.The content of sense of touch improver
(being scaled solid constituent) is preferably integrally 1~6 mass %, more preferably 2~5 mass % relative to top layer.If content is 1
More than quality %, then it can obtain desired stick-slip sense.In addition, if being below 6 mass %, then can prevent by wearing away
Caused albinism.
As sense of touch improver, wax etc. can be enumerated.Such as it 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, it is high from the effect for assigning stick-slip sense
Aspect set out, preferred paraffin.
In order to colour, pigment is preferably added in top layer.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 %.When content is more than 5 mass %, it can not only colour by a definite date
The color of prestige and the xanthochromia that resin can be covered, therefore light resistance, heat resistance, humidity resistance can be improved.If content is
Below 20 mass %, then it will not destroy the film intensity on top layer, therefore excellent wear resistance.
For 100% modulus on top layer, become to be easily adapted to hand from fine bumps, it is possible thereby to feel as fine hair that
Sample, it can obtain setting out in terms of Zhen Niuba removes from office same sense of touch (particularly fine hair sense), preferably 1~5MPa, more preferably 2
~3MPa.When 100% modulus is more than 1MPa, the intensity of gained Niu Bage sample tablets will not be destroyed.In addition, if it is 5MPa
Hereinafter, then it can prevent fine bumps from becoming thick and stiff, so as to improve sense of touch.
Herein, 100% modulus value on top layer calculates as described below.That is, using bar coater, it is changed into the thickness of cured film
100 μm of mode, the composition for forming top layer is coated on flat processing release paper (EU130TPD, LINTEC Corporation
Manufacture) on, at 80 DEG C be heat-treated within 5 minutes with drying machine, then in 20 ± 2 DEG C of room temperature, 65 ± 5%RH of humidity situation
1 day maturation process of lower progress, is made cured film.From the cured film gathers wide 30mm, the test film 3 of long 100mm sizes is opened, in room
In the case of 20 ± 2 DEG C of temperature, 65 ± 5%RH of humidity, it is installed on cupping machine with the wide 30mm of pawl, pawl interval 50mm
The gripping apparatus of (Autograph AG-X, Shimadzu Scisakusho Ltd's manufacture), is stretched with draw speed 100m/ minutes, is surveyed
Determine load when stroke distance is changed into 50mm.100% modulus value is calculated with following formula, using 3 average values as the 100% of top layer
Modulus value.
100% modulus value (MPa)=stroke distance is changed into 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 tablets.When thickness is less than 200 μm, without the feel of gained Niu Bage sample tablets
Become thick and stiff worry.
Herein, the thickness on top layer calculates as described below.That is, with microscope, (KEYENCECORPORATION is manufactured, numeral
HF microscope VH-8000) observation Niu Bage sample tablets vertical cross-section, will be for determining convex portion summit and top layer at any 10
Value obtained from the difference of height of foot and obtained for determining the bottom of recess and the difference of height of top layer foot at any 10
Value thickness of the average value as top layer.
In the Niu Bage sample tablets of present embodiment, in order to improve abrasion performance, protective layer and/or anchor can also be set
Coating.As described above, protective layer is laminated in the upper strata on top layer, and anchor coating is laminated in 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 in the same manner as top layer by polyurethane resin.
As the polyurethane resin for forming protective layer, anchor coating, the polyurethane resin same with top layer can be used.Protection
Layer becomes and directly contacted into people positioned at the outermost layer on the surface for forming Niu Bage sample tablets.Therefore, for protective layer, from wear-resisting
Set out in terms of consumption, preferably using polycarbonate-based polyurethane resin, and then from the viewpoint of stick-slip sense, preferably addition is touched
Feel improver, from the viewpoint of abrasion performance, preferably add 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, more preferably 15~20 μm from the viewpoint of feel.Protective layer, top layer,
The gross thickness of anchor coating is from the viewpoint of abrasion performance and feel, preferably 32~240 μm, more preferably 60~120 μm.
In the Niu Bage sample tablets of present embodiment, adhesive linkage can also be set between top layer and fibrous substrate.
Top layer can be directly laminated with fibrous substrate, but by via adhesive linkage, when can suppress directly to be laminated may caused by,
Excessive immersion of the polyurethane resin on top layer to fibrous substrate is formed, is readily obtained and removes from office same sense of touch, feel with Zhen Niuba.
As the bonding agent as adhesive linkage, it is not particularly limited, preferably using polyurethane resin, can uses and be used in top layer
The same resin of resin.
Fine concavo-convex per unit area (1cm in the surface of Niu Bage sample tablets2) convex portion number it is preferred
For 4000~80000, more preferably 20000~50000, more preferably 20000~30000.If per unit
The number of the convex portion of area is 4000~80000, then is readily obtained Zhen Niuba and removes from office same sense of touch, i.e. stick-slip sense, fine hair sense.
Herein, the fine concavo-convex per unit area (1cm in surface2) the number of convex portion calculate as described below.
That is, using microscope (KEYENCE CORPORATION manufactures, digital HF microscope VH-8000) with 500 times of observation oxen bar of multiplying power
The surface of sample tablet is removed from office, counts the quantity (X) of convex portion vertical 500 μm, in 250 μm of horizontal stroke by visual observation.For the convex portion counted
Quantity (X), using following formula, calculate per unit area (1cm2) convex portion number.
Conversion formula：The quantity (X) × 10 of the convex portion for the number of the convex portion of per unit area=count2/0.125
In the range of the effect of present embodiment is not damaged, the surface of Niu Bage sample tablets can also it is overlapping other
Relief pattern.Other relief patterns refer to, compared with above-mentioned fine concavo-convex convex portion and recess, by height (difference of height) and width
(interval) big recess and the relief pattern of convex portion formation are spent, such as can be enumerated：Pit pattern, the geometry figure of natural leather
Case etc..Therefore, in some embodiment, can be set on the surface of Niu Bage sample tablets be more than it is above-mentioned fine concavo-convex recessed
Convex pattern, profile on the basis of the relief pattern big by this, forms above-mentioned fine bumps on the big relief pattern.Pass through weight
Folded so big relief pattern, the complicated design for possessing Zhen Niuba leather and other patterns can be provided.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 bumps and one
As natural leather pit pattern compared to densification, can be for than more uniform bumps.
Fig. 3 schematically shows the cross section structure of the Niu Bage samples tablet 11 provided with other above-mentioned relief patterns.In the piece
Formed with the big relief pattern formed by big recess 12 and convex portion 13 for being changed into baseline profile on the surface 4 of shape thing 11.
Surface 4 with the big relief pattern is provided with the fine bumps formed by above-mentioned recess 9 and convex portion 8.
The interval of the adjacent recesses of above-mentioned big relief pattern be the extreme lower position of arbitrarily large recess and with the recess most
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 convex portion be arbitrary big recess and the height of the big convex portion nearest with the recess
Difference.They are obtained by the observation in vertical cross-section as described below.That is, with microscope (KEYENCE CORPORATION manufacture,
Digital HF microscope VH-8000) observation Niu Bage sample tablets vertical cross-section, for the big recess at any 10 and with
The nearest big recess of the recess, the horizontal range between bottom is determined (in the direction vertical with the thickness direction of tablet
Extreme lower position between distance, the C in reference picture 3), using its scope (minimum value and maximum) as between adjacent big recess
Every.In addition, for the adjacent big recess at any 10 and convex portion, the difference of height on the bottom of recess and the summit of convex portion is determined
(D in reference picture 3), value is averaged as recess and the difference of height of convex portion.Herein, can be with order to observe broader scope
It will be set as when being observed for big relief pattern based on microscopical multiplying power than being observed for fine bumps
When multiplying power it is small.For example, multiplying power during the fine bumps of observation is 500 times, and multiplying power when observing big relief pattern can be with
It is set to 50 times.
Then, the manufacture method of above-mentioned ox Ba Ge sample tablets is illustrated.The manufacture method includes following process：
(1) top layer is coated on to the process for forming top layer on release property base material with resin liquid；
(2) process for making top layer and fibrous substrate fitting；With,
(3) process for peeling off release property base material.
As the method being coated on top layer with resin liquid on release property base material, known various sides can be used
Method, it is not particularly limited.Such as it can enumerate：Applied using reverse roll coater, flush coater, roll coater, knife type coater, comma
The method of the devices such as cloth machine.Wherein, from uniform film layer aspect can be formed, preferably by reverse roll coater,
The coating of knife type coater or comma coater.
Release property base material is not particularly limited, as long as to have the base material of release property to polyurethane resin or implementing de-
The base material of mould processing.Such as it can enumerate：Processing release paper, it is stripped treatment cloth, water repellent treatment cloth, by polyvinyl resin or poly- third
The alkene piece or film of the formation such as olefine resin, fluororesin piece or film, plastic sheeting with processing release paper etc..
Release property base material is it is important that have relief pattern.By using the difference of height with convex portion and recess be 20~
The release property base material at intervals of 20~170 μm of relief pattern of 170 μm and adjacent recesses, can be to ox Ba Ge sample tablets
Surface assign desired fine relief pattern.That is, the fine bumps on the surface of Niu Bage samples tablet are by release property base
The relief pattern of material assigns.In the range of fine relief pattern is not damaged, release property base material can also have equivalent to upper
State the big relief pattern of big relief pattern.
Top layer can suitably be set, preferably 40~400 μm with the coating thickness of resin liquid according to the thickness on foregoing top layer,
More preferably 100~300 μm.By will coating thickness be set as the scope, be changed into have preferably 20~200 μm, more preferably 50~
The top layer of 150 μm of thickness.
After top layer is coated on into release property base material with resin liquid, it can be heat-treated as needed.Heat treatment be in order to
Make top layer with the solvent evaporation in resin liquid so that resin is dry and carries out.In addition, cause crosslinking using by heat treatment
In the case of the situation of the crosslinking agent of reaction or the resin of use bi-component curing type, had to promote to react, formed
The overlay film of sufficient intensity and carry out.
It can also be 60~130 DEG C that heat treatment temperature, which can be 50~150 DEG C,.When heat treatment temperature is more than 50 DEG C, heat
Processing will not excessively expend the time, and therefore, process load will not become too much.Furthermore it is possible to preventing the crosslinking of resin becomes not
Fully, accordingly it is possible to prevent abrasion performance becomes bad.When heat treatment temperature is less than 150 DEG C, synthetic leather can be prevented
Feel becomes thick and stiff.In addition, heat treatment time can also be able to be 2~10 minutes for 2~20 minutes.Heat treatment time is 2 minutes
During the above, can prevent the crosslinking of resin becomes insufficient, accordingly it is possible to prevent abrasion performance becomes bad.Heat treatment time
During within 20 minutes, process load will not become too much.
Then, it is bonded top layer and fibrous substrate.During fitting, as described above, it can be bonded via adhesive linkage, also may be used
To be directly laminated fitting.It is preferred that make its fitting via adhesive linkage.During provided with adhesive linkage, it can be pasted on top layer after coating adhesive
Together in fibrous substrate.
The method of coating adhesive can use known various methods, be not particularly limited.Such as it 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 tablets of present embodiment.But
It is to be not limited to the above method for manufacturing the method for Niu Bage sample tablets of present embodiment.
It should be noted that when forming anchor coating, formed on release property base material behind top layer before coating adhesive, in table
Anchor coating resin liquid is coated with layer so as to be formed.On the other hand, when forming protective layer, after peeling off release property base material from top layer,
In the surface coat protective layer resin liquid on the top layer so as to being formed.The heat treatment after method and coating for coating, can be with
Using the method same with the formation on top layer.
The coating thickness of protective layer used resin liquid can suitably be set according to the thickness of foregoing protective layer, can be 5~25 μ
M can also be 5~13 μm.By the way that coating thickness is set as into the scope, it is changed into preferably 2~10 μm, more preferably 2~5 μm
The protective layer of thickness.
Anchor coating resin liquid coating thickness can suitably be set according to the thickness of foregoing anchor coating, can be 50~
150 μm can also be 75~100 μm.By will coating thickness be set as the scope, be changed into have preferably 10~30 μm, more preferably 15
The anchor coating of~20 μm of thickness.
For present embodiment Niu Bage sample tablets when, surface is with above-mentioned distinctive concavo-convex and with defined table
The face coefficient of kinetic friction, therefore can also obtain the sense of touch of Niu Bage samples even if skin surface is not ground.That is, the ox of present embodiment
Although surface is not ground in Ba Ge sample tablets, the sense of touch of Niu Bage samples is also assigned.Therefore, have and disclosure satisfy that conduct
The sense of touch of Niu Bage sample tablets and the abrasion performance that disclosure satisfy that can also be assigned in the field for requiring highly durable property.
Embodiment
Hereinafter, the present invention is described in more detail according to embodiment, but the present invention is not limited to following embodiment.Embodiment
In " part " be quality criteria.
[table 1]
[table 2]
[table 3]
[embodiment 1]
Using comma coater, in a manner of coating thickness is changed into 200 μm, the top layer prepared according to above-mentioned formula 1 is used
Resin liquid is coated on processing release paper with sheet, at 100 DEG C be heat-treated within 3 minutes with drying machine, forms the table of 100 μm of thickness
Layer.As processing release paper, using 115 μm of the difference of height with convex portion and recess, 94 μm of the interval of adjacent recesses, recess number
28000/cm2Nick convex pattern processing release paper.Formed top layer polyurethane resin polycarbonate-based polyurethane resin with
The mass ratio of polyethers system polyurethane resin is 32：68, the containing ratio (being scaled solid constituent) of pigment is 11 mass %, 100%
Modulus value is 2.5MPa.
Then, using comma coater, in a manner of coating thickness is changed into 170 μm, using as the carbamic acid of bonding agent
Ester polyisocyanate prepolymers (NH230, the mass % of solid constituent 100, Dainippon Ink Chemicals's system) are coated on foregoing top layer with sheet
On.The carbamate polyisocyanate prepolymers are made (to utilize use with circle latitude cloth in the state of with toughness
150dtex/48f polyester multifilaments 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) fitting, with ironer with 5kg/m2Load
Carry out closure pressurization.3 days maturation process are carried out under 23 DEG C of temperature, the atmosphere of relative humidity 65%, processing release paper is peeled off afterwards, obtains
To Niu Bage sample tablets.
In gained Niu Bage sample tablets, the convex portion on surface and the difference of height of recess are 86 μm, between adjacent projection summit
102 μm are divided into, the number of convex portion is 24000/cm2, surface dynamic friction coefficient is 0.38.In addition, Niu Bage sample tablets
Most surface is that the containing ratio (being scaled solid constituent) of the smooth agent in top layer is 8 mass %, and the containing ratio of sense of touch improver (changes
Calculate as solid constituent) it is 3 mass %.
[embodiment 2]
Smooth agent and sense of touch improver are removed from the resin liquid of top layer, in addition, obtains piece similarly to Example 1
Shape thing.Using roll coater, in a manner of coating thickness is changed into 10 μm, by the protective layer used resin liquid prepared according to formula 2 with piece
Shape is coated on the top layer of obtained sheet, at 100 DEG C be heat-treated within 3 minutes with drying machine, is formed the protection of 4 μm of thickness
Layer, obtains Niu Bage sample tablets.In gained Niu Bage sample tablets, the convex portion on surface and the difference of height of recess are 54 μm, phase
Adjacent convex portion summit at intervals of 98 μm, the number of convex portion is 21600/cm2, surface dynamic friction coefficient is 0.26.In addition, ox bar
The most surface of leather sample tablet is that the containing ratio of the smooth agent in protective layer is 7 mass %, and the containing ratio of sense of touch improver is 3 matter
Measure %.
[embodiment 3]
In embodiment 1, on processing release paper behind formation top layer, before coating adhesive, using comma coater, to be coated with thickness
Degree is changed into 150 μm of mode, and the anchor coating resin liquid prepared according to formula 3 is coated on the top layer with sheet, uses drying
Machine carries out being heat-treated for 3 minutes at 100 DEG C, forms the anchor coating of 30 μm of thickness.In addition, all similarly to Example 1
Obtain Niu Bage sample tablets.In gained Niu Bage sample tablets, the convex portion on surface and the difference of height of recess are 84 μm, adjacent convex
Portion summit at intervals of 110 μm, the number of convex portion is 24000/cm2, surface dynamic friction coefficient is 0.34.In addition, Niu Bage
The most surface of sample tablet is that the containing ratio (being scaled solid constituent) of the smooth agent in 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, on processing release paper behind formation top layer, before coating adhesive, thickness is formed similarly to Example 3
30 μm of anchor coating.In addition, Niu Bage sample tablets are all obtained similarly to Example 2.Gained Niu Bage print shapes
In thing, the convex portion on surface and the difference of height of recess are 55 μm, adjacent projection summit at intervals of 93 μm, the number of convex portion is
21600/cm2, surface dynamic friction coefficient is 0.25.In addition, the most surface of Niu Bage sample tablets is smooth in protective layer
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
Measure %.
[embodiment 5~11 and comparative example 1~4]
Niu Bage sample tablets are made according to table 4, in addition all make Niu Bage print shapes similarly to Example 1
Thing.It should be noted that for the processing release paper used in embodiment 11, taken turns on the basis of the big relief pattern of leather pit shape
Exterior feature, there are the fine bumps described in table 4 on the relief pattern.The composition of big relief pattern is as follows：Recess and convex portion
Difference of height be 235 μm, adjacent projection at intervals of 0.2~2mm, the number of recess is 63/cm2。
For each ox Ba Ge sample tablets, sense of touch, feel, abrasion performance, humidity resistance, heat-resisting is carried out by the following method
Property and sunproof evaluation, table 4 is recorded in by result.
[sense of touch]
For the sense of touch on test film surface, sense evaluation is carried out, is judged according to following benchmark.
A：To there is the thoughts and feelings of the stick-slip sense of the moistening of Niu Bage samples and fine hair sense
B：Slightly it is short of the stick-slip sense of moistening or the thoughts and feelings of one of fine hair sense of Niu Bage samples
C：Slightly it is short of the thoughts and feelings of Niu Bage samples
D：It is coarse and dry sense of touch completely without the thoughts and feelings of ox Ba Ge samples
[feel]
Sense is taken for the hand of test film, sense evaluation is carried out, is judged according to following benchmark.
A：With the soft and soft feel same with Zhen Niuba leather
B：With with the approximate soft and soft feel of Zhen Niuba leather, but slightly feel resin sense, core
C：Soft and soft feel is poor compared with Zhen Niuba is removed from office, and feels resin sense, core
D：It is substantially different feels from Zhen Niuba leather, feels resin sense, core strongly
[abrasion performance]
From longitudinal and transverse all directions gather wide 70mm respectively, the long 300mm test film 1 of size is opened, overleaf configuration is wide
70mm, long 300mm, thickness 10mm size urethane foam body.Center is set below urethane foam body
It is equipped with the state of diameter 4.5mm line, being fixed on plane abrasiometer T-TYPE, (Dae Young Co., Ltd.'s science essence device makes
It is manufactured), by be stamped the abrasion body of cotton on line with line it is abreast reciprocating in a manner of, load is applied to the friction piece
9.8N, carry out abrasion test.Friction piece makes its past between 140mm on the surface of test film with the speed of 60 round/minutes
It is multiple 3000 times.The surface state of the test film after abrasion test is observed, is judged according to following benchmark.
5：(it is not cracked, damaged) without change in appearance
4：Confirmation is slightly worn away, but unobvious
3：Clearly confirm there are abrasion, there is exposing (confirmation has cracking) for fibrous substrate
2：Exposing for fibrous substrate is slightly obvious
1：Fibrous substrate exposes slightly obvious (confirmation has breakage)
[humidity resistance]
The test film for being cut into long 50mm × wide 250mm is being adjusted to the constant temperature and humidity machine of 70 DEG C, 95%RH：PR-
5 weeks, which are stood, in 2KTH (ESPEC.CORP manufactures) carries out humid heat treatment.Visually to observe the test film before and after humid heat treatment, for
Test film after humid heat treatment, judged using the tonal gradation (gray scale) of JIS L-0804 standards.Change is faded 4
More than level it is set to qualified.
[heat resistance]
The test film of the size in 10cm four directions will be cut into wide-mouth reagent bottle (250mL bottles, hard glass with plug
System) in added along the side of wide-mouth reagent bottle, in the drying machine adjusted to 110 DEG C standing 400 hours is heat-treated.Heat
After processing, wide-mouth reagent bottle is taken out from drying machine, after being cooled to room temperature, test film taken out from wide-mouth reagent bottle.With visual
The front and rear test film of observation heat treatment, for the test film after heat treatment, utilizes the tonal gradation (gray of JIS L-0804 standards
Scale) judged.Change is faded more than 4 grades and is set to qualified.
[light resistance]
The test film for being cut into long 65mm × wide 150mm is set to fit in thickness 1mm aluminium sheet with identical size.Using possessing
The promotion xenon Light Resistance Test machine of xenon arc lamp (air-cooled type 8kw)：WT-341 (manufacture of Wacom Co., Ltd.s), at following
It is tested under part.
Irradiation cycle：Continuous irradiation
Irradiation time：144 hours
Exposure intensity：162W/m2
Black flour plate temperature：89±3℃
Relative humidity：50 ± 5%
Illumination wavelength：300~400nm
Visually to observe the test film after pre-irradiation, for the test film after irradiation, the gray scale of JIS L0804 standards is utilized
Grade (gray scale) judges light fastness.Change is faded more than 4 grades and is set to qualified.
[table 4]
Industrial applicability
The Niu Bage sample tablets of present embodiment can be used for dress material, suitcase, shoes, house decorative material, in vehicle
The various uses such as portion's ornament materials, be 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 samples tablet 2 ... fibrous substrate 3 ... top layer
4 ... surface 5 ... adhesive linkage 6 ... anchor coatings
7 ... protective layer 8 ... convex portion 9 ... recesses
10th, 11 ... Niu Bage sample tablets
Claims (8)
1. a kind of ox Ba Ge sample tablets, it is to be laminated on fibrous substrate obtained from the top layer comprising polyurethane resin,
Have on the surface of Niu Bage sample tablets the difference of height of convex portion and recess for 20~150 μm, adjacent projection summit at intervals of
20~150 μm of bumps, and the surface dynamic friction coefficient on surface is 0.20~0.50,
The polyurethane resin includes polycarbonate-based polyurethane resin and polyethers system polyurethane resin, described polycarbonate-based poly-
The mass ratio of urethane resin and polyethers system polyurethane resin is 80：20~20：80.
2. ox Ba Ge sample tablets according to claim 1, its surface is not ground.
3. ox Ba Ge sample tablets according to claim 1 or 2, wherein, the top layer is contained comprising silicone compound
Smooth agent.
4. ox Ba Ge sample tablets according to claim 1 or 2, wherein, the sense of touch comprising wax is contained on the top layer to be improved
Agent.
5. ox Ba Ge sample tablets according to claim 1 or 2, wherein, 100% modulus on the top layer is 1~5MPa.
6. ox Ba Ge sample tablets according to claim 1 or 2, wherein, it is provided with the top on the top layer and includes poly- ammonia
Outermost layer of the protective layer of ester resin as the surface for forming Niu Bage sample tablets.
7. ox Ba Ge sample tablets according to claim 1 or 2, wherein, it is provided with the lower section on the top layer and includes poly- ammonia
The anchor coating of ester resin.
8. a kind of manufacture method of ox Ba Ge sample tablets according to any one of claims 1 to 7, it includes following work successively
Sequence：
Top layer is coated on to the process for forming top layer on release property base material with resin liquid；
The process for making top layer and fibrous substrate fitting；With,
The process that release property base material is peeled off.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2014049065 | 2014-03-12 | ||
| JP2014-049065 | 2014-03-12 | ||
| PCT/JP2015/001309 WO2015136921A1 (en) | 2014-03-12 | 2015-03-10 | Nubuck-toned sheet-like material and manufacturing method thereof |
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| CN106103838A CN106103838A (en) | 2016-11-09 |
| CN106103838B true CN106103838B (en) | 2018-02-23 |
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| JP (1) | JP6207717B2 (en) |
| CN (1) | CN106103838B (en) |
| MX (1) | MX2016011454A (en) |
| WO (1) | WO2015136921A1 (en) |
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| 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 |
| WO2019004180A1 (en) * | 2017-06-27 | 2019-01-03 | セーレン株式会社 | Synthetic leather |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101133168A (en) * | 2005-03-04 | 2008-02-27 | 巴斯福股份公司 | Die comprising small cup-type depressions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| JP2005220499A (en) * | 2004-02-09 | 2005-08-18 | Dainippon Ink & Chem Inc | Resin composition for artificial leather and the artificial leather |
| 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 |
| JP5718038B2 (en) * | 2010-12-13 | 2015-05-13 | 共和レザー株式会社 | Synthetic leather and method for producing the same |
| 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
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|---|---|---|---|---|
| CN101133168A (en) * | 2005-03-04 | 2008-02-27 | 巴斯福股份公司 | Die comprising small cup-type depressions |
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| JP6207717B2 (en) | 2017-10-04 |
| JPWO2015136921A1 (en) | 2017-04-06 |
| WO2015136921A1 (en) | 2015-09-17 |
| CN106103838A (en) | 2016-11-09 |
| MX2016011454A (en) | 2016-12-02 |
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