CN100389840C - Skin material for ball and ball - Google Patents
Skin material for ball and ball Download PDFInfo
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- CN100389840C CN100389840C CNB2004800073149A CN200480007314A CN100389840C CN 100389840 C CN100389840 C CN 100389840C CN B2004800073149 A CNB2004800073149 A CN B2004800073149A CN 200480007314 A CN200480007314 A CN 200480007314A CN 100389840 C CN100389840 C CN 100389840C
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- Prior art keywords
- skin material
- ball
- layer
- coating
- described skin
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- 239000000463 material Substances 0.000 title claims abstract description 213
- 229920001971 elastomer Polymers 0.000 claims abstract description 109
- 239000000806 elastomer Substances 0.000 claims abstract description 98
- 238000000576 coating method Methods 0.000 claims description 147
- 239000011248 coating agent Substances 0.000 claims description 143
- 239000000758 substrate Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000853 adhesive Substances 0.000 claims description 17
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- 230000006835 compression Effects 0.000 claims description 14
- 238000007906 compression Methods 0.000 claims description 14
- 239000005060 rubber Substances 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 10
- 239000002250 absorbent Substances 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract 6
- 239000011247 coating layer Substances 0.000 abstract 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- 239000000835 fiber Substances 0.000 description 30
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- 238000000034 method Methods 0.000 description 24
- 239000012530 fluid Substances 0.000 description 21
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- 239000004814 polyurethane Substances 0.000 description 19
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 15
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- 235000011613 Pinus brutia Nutrition 0.000 description 4
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- 239000004698 Polyethylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 238000012545 processing Methods 0.000 description 4
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- KCHCXGVQNDVSKB-UHFFFAOYSA-N 1-cyclohexyl-1-methylhydrazine Chemical compound CN(N)C1CCCCC1 KCHCXGVQNDVSKB-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 208000012886 Vertigo Diseases 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 210000003491 skin Anatomy 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 2
- 206010053567 Coagulopathies Diseases 0.000 description 2
- 239000001836 Dioctyl sodium sulphosuccinate Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229920006218 cellulose propionate Polymers 0.000 description 2
- 230000035602 clotting Effects 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
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- 238000007710 freezing Methods 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- PMDHMYFSRFZGIO-UHFFFAOYSA-N 1,4,7-trioxacyclotridecane-8,13-dione Chemical compound O=C1CCCCC(=O)OCCOCCO1 PMDHMYFSRFZGIO-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002955 Art silk Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- 229940106012 diethylene glycol adipate Drugs 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
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- 238000009423 ventilation Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
Abstract
A skin material for balls which is a sheet-form material comprising a base layer and formed on one side thereof a coating layer made of a polymeric elastomer, characterized in that (1) the coating layer is composed of three layers (C-1), (C-2), and (C-3) disposed in this order from the surface side, (2) the layer (C-3) on the base layer side is made of a porous polymeric elastomer, (3) the layer (C-1) on the surface side is made of a polymeric elastomer containing a pressure-sensitive adhesive, and (4) the coating layer comprises one or more polymeric elastomers which have or do not have fine through-holes extending from the surface side to the base layer; and a ball having the skin material bonded to the surface. The skin material for ball-game balls brings about excellent wet gripping and is excellent also in wearing resistance and impact absorption.
Description
Technical field
The present invention relates to skin material for ball.In more detail, relate to firmly grasping property and excellent in wear resistance when moistening, and soft, the excellent skin material for ball that is suitable for ball for ball game such as basketball, rugby, American football, handball, vollyball, baseball of impact absorbency.
Prior art
As the skin material of ball for ball game, use natural leather since ancient times always, but in recent years because the easness of handling etc. have been extensive use of the so-called dermatine that is formed by fiber and macromolecular elastomer.But, for mar proof with prevent to adhere to spot, form the one side of the epidermal area of macromolecular elastomer formation as ball on the surface of dermatine, therefore easily sliding, particularly in the often manual ball game such as basketball, rugby, American football, handball, vollyball, baseball, when hand is perspired, exist to be easy to produce problem of slip.
As reducing one of this means of improving the promptly property when moistening of skidding, the method for the skin material that the tablet of considering to use the softness with ventilating and moisture-permeable is used as ball.As this sheet material that just had in the past, can enumerate the dermatine of ventilating and moisture-permeable, the general use as disclosed method in the international open WO94/20665 communique, promptly be beneficial to the solvent of the macromolecular elastomer that forms wet type porous layer surface, form open bore on the surface of dermatine in the surface coating.But according to the inventor's etc. research, the open bore of this dermatine is present in the part that contacts with hand or ground, and therefore difficult contaminative and the mar proof as skin material for ball is not met.
As other method, open in the flat 9-250091 communique the spy, the method for the surperficial discontinuous form of dermatine with plush being given the resin of performance skid resistance is disclosed.But, though this method plush partly has water imbibition, but fine hair exist at the very start, durability and mar proof shortcoming also has rete not form on the surface, therefore exist to be easy to pollute, the also low problem of property promptly,
On the other hand, skin material as ball for ball game, for example open and disclose by fiber complexing body in the 2000-328465 communique and be present in the porous matter elastomer in this network and space the spy, and the ball leather-like sheet that forms of porous matter base layer and porous matter superficial layer of forming on its surface.
But, this dermatine is owing to form by fiber with the macromolecular elastomer of its bonding, thereby there is the weak problem of impact absorption power, particularly can not obtain the ball dermatine that impact absorbency and mar proof have both at the same time, like this, just need be suitable for most vollyball, basketball, rugby, American football, baseball etc. often manual ball game, when transmission ball the ball of excellence dermatine skin material aspect the impulsive force minimizing.
Summary of the invention
The skin material that is suitable for the ball for ball game epidermis of all excellent and excellent in wear resistance of firmly grasping property when the 1st purpose of the present invention is drying is provided and when moistening.
The 2nd purpose of the present invention is to provide softness, impact absorbency is excellent and the skin material that is suitable for the ball for ball game epidermis of excellent in wear resistance.
The 3rd purpose of the present invention is to provide ball for ball game, and firmly grasping property is all excellent when promptly dry and when moistening, the ball that excellent in wear resistance and impact absorbency are also excellent.
According to the inventor's research, the purpose of the invention described above is reached by the skin material for ball of following (I)～(III) and ball (IV).
(I) a kind of skin material for ball, it is that the tablet that has the coating that is formed by macromolecular elastomer on base layer one side surface forms, it is characterized in that, (1) this coating forms for these 3 layers by be followed successively by C-1, C-2 and C-3 from face side, (2) the C-3 layer of base layer side is formed by porous matter macromolecular elastomer, (3) the C-1 layer of face side is formed by the macromolecular elastomer that contains adhesive, and (4) coating comprises having from face side and arrives the fine through hole of base layer or the macromolecular elastomer in this hole not.
(II) a kind of skin material for ball, it is that the tablet that has the coating that is formed by macromolecular elastomer on base layer one side surface forms, it is characterized in that, (1) this coating is by being followed successively by C-1 from face side, these 3 layers of formation of C-2 and C-3, (2) the C-3 layer of base layer side is formed by porous matter macromolecular elastomer, (3) the C-1 layer of face side is formed by the macromolecular elastomer that contains adhesive, (4) coating comprises having from face side and arrives the fine through hole of base layer or the macromolecular elastomer in this hole not, (5) there be the concavo-convex of many difference of height 0.1～1.0mm in the surface of coating, and the gross area at the top of (6) this concavo-convex protuberance accounts for 20～70% of coating area.
(III) a kind of skin material for ball, it is that the tablet that has the coating that is formed by macromolecular elastomer on base layer one side surface forms, it is characterized in that, (1) this coating is by being followed successively by C-1 from face side, these 3 layers of formation of C-2 and C-3, (2) the C-3 layer of base layer side is formed by porous matter macromolecular elastomer, (3) the C-1 layer of face side is formed by the macromolecular elastomer that contains adhesive, (4) coating comprises having from face side and arrives the fine through hole of base layer or the macromolecular elastomer in this hole not, and (5) have even surface in fact on the surface of coating.
(IV) a kind of ball is characterized in that, above-mentioned (I)～(III) each skin material for ball is sticked on the surface of spheroid.
Below, the ball with regard to skin material for ball of the present invention and this skin material of use describes in more detail.
The tablet that constitutes skin material for ball of the present invention forms coating and integrated basically on a side surface of base layer.In addition, this coating is formed by macromolecular elastomer and has a 3-tier architecture that is followed successively by C-1 layer, C-2 layer and C-3 layer from face side.Briefly, tablet of the present invention has the structure that is followed successively by C-1 layer/C-2 layer/C-3 layer/base layer from face side.Thereby in the present invention, " face side " is meant as the surface of the most surperficial C-1 layer of tablet (reverse side of base layer).
The base layer that forms tablet of the present invention is the complex layer that fibrous substrate forms with macromolecular elastomer.
Wherein, as the used fiber of fibrous substrate, can enumerate regenerated fiber such as synthetic fibers such as polyamide, polyester, artificial silk, acetate or natural fiber etc. separately or the fiber that mixes.More preferably polyester fibers such as Fypro, PETG, polybutylene terephthalate (PBT) such as nylon 6, nylon 66, nylon 12.
In addition, preferred this fibrous substrate is the complexing fabric nonwoven cloth of this fiber being made with known methods such as combing, one-tenth net, lamination, pin punching presses, the following superfine fibre of 0.2dtex particularly, the fibrous substrate that the superfine fibre of preferred especially 0.0001～0.05dtex forms.As the method that obtains this superfine fibre, for example make the composite fibre or the blend spinning fiber that form by the fiber formation property high molecular polymer more than the different two compositions of solvent solubility, make the complexing fabric nonwoven cloth, 1 kind of composition is removed in extraction, makes superfine fibre complexing fibrous substrate.
The apparent density of this fibrous substrate is 0.05～0.20, preferred 0.1～0.15g/cm
3Proper.Especially for the impact absorbency of the skin material that improves acquisition, the density of optimum fiber matter base material is low, and preferred apparent density is 0.05～0.14g/cm
3, more preferably 0.09～0.12g/cm
3
As the macromolecular elastomer that is applicable to base layer at this moment with fibrous substrate, can enumerate polyurethane elastomer, polyurethane-urea elastomers, SPUA, polyester elastomer and synthetic rubber etc., wherein optimization polyurethane class elastomer.In order to improve the impact absorbency of skin material, 100% elongation stress of preferred macromolecular elastomer is 80～100kg/cm
2More preferably the macromolecular elastomer of base layer is a porous matter, preferably uses the deliquescent wet type of DMF to solidify with polyurethane etc.
In addition, the macromolecular elastomer of base layer with respect to the ratio macromolecular elastomer/fiber (following is R/F) of the fiber in the fibrous substrate by weight preferably in 20/100～40/100 scope.
In order to use as skin material for ball, base layer preferably has 0.3～3mm, the thickness of preferred 0.4～2mm.
Skin material of the present invention has coating on the surface of a side of above-mentioned base layer.In addition, this coating is formed for these 3 layers by C-1 layer, C-2 layer and C-3 layer successively, and the C-3 layer is connected with the surface of base layer and lamination.
C-3 layer in this coating is formed by porous matter macromolecular elastomer.The macromolecular elastomer of this C-3 layer can use the elastomer with the identical type of using in base layer.That is to say,, can enumerate polyurethane elastomer, polyurethane-urea elastomers, SPUA, polyester elastomer, synthetic rubber etc., wherein optimization polyurethane class elastomer as the macromolecular elastomer of C-3 layer.
As the preferred elastomeric instantiation of polyurethanes that uses in C-3 layer and the base layer, can enumerate make molecular weight 800～4000 polyester-diol, PTMEG or PCDL etc. separately or mix two pure and mildly with diphenyl methane 4,4 '-vulcabond is the elastomer that main organic diisocyanate and the chain lengthening agent reaction that comprises low-molecular-weight diol, diamines, hydrazine, hydrazine derivate etc. obtain.
In the present invention, the C-3 layer that is formed by macromolecular elastomer is necessary it is porous matter.And the very unfertile land existence of the epidermal area of preferred C-3 layer, when observing the cross section, have the coniform loose structure of the apex of making towards the face side of this C-3 layer.And it is 10～200 μ m that preferred C-3 layer has major diameter, vertical cavernous structure of preferred 30～100 μ m.The macromolecular elastomer of C-3 layer more preferably of the present invention and base layer has fine through hole.Take this porous matter, can when having intensity, become more soft sheet material, further can give higher ventilation, poisture-penetrability.
The sheet material that has the C-3 layer on this one side that is used for base layer of the present invention can be handled and obtain by fibrous substrate being carried out macromolecular elastomer, the solution of the organic solvent of macromolecular elastomer is penetrated in the fibrous substrate, further behind the elastomeric solution of coated high molecular on this surface, make it to solidify and obtain.Special clotting method as this moment, preferably make macromolecular elastomer be frozen into the method for porous matter shape, as this method, after the solution that can enumerate the organic solvent that for example makes macromolecular elastomer is penetrated in the fibrous substrate and/or is coated on the fibrous substrate, in the non-solvent of macromolecular elastomer, flood, the wet type freezing method that macromolecular elastomer is solidified, perhaps in the organic solvent solution of macromolecular elastomer, the non-solvent that mixes macromolecular elastomer, make emulsion, evaporation afterwards removes the special dry type clotting method that desolvates etc.
Further, especially preferably adopt the wet type freezing method in order to make the C-3 layer finally become structure with fine through hole.At this moment, add in the solvent solution of the macromolecular elastomer that solidifies toward wet type have anionic species or nonionic class, the surfactant of the hydrophilic radical of cationic is effective as the porous conditioning agent.As surfactant, preferred sodium sulfonate dialkyl group succinate, polyoxyethylene modification silicon, polyoxyethylene modified alkylbenzene etc.
The C-3 layer that forms on the one side of base layer has 1～20 μ m, and the thickness of preferred 2～15 μ m is proper.
Skin material of the present invention has the structure that forms C-1 layer and C-2 layer on the surface of the C-3 layer side of the sheet material of above-mentioned C-3 layer and base layer formation.This C-1 layer and C-2 layer are all mainly formed by macromolecular elastomer, but C-1 layer (the most surperficial) has the feature that is formed by the macromolecular elastomer that contains adhesive.
The aggregate thickness of preferred C-1 layer and C-2 is more than the 1 μ m, and more preferably 3～20 μ m most preferably are 5～10 μ m.When aggregate thickness is lower than 1 μ m, the tendency that exists the mar proof of skin material to become not enough.On the other hand, if aggregate thickness surpasses 20 μ m, then there is the decreased number of the required minute aperture of water imbibition in skin material, the tendency of the promptly property reduction when moistening.
For the aggregate thickness of this C-1 layer and C-2 layer, the C-1 layer: the ratio of the thickness of C-2 layer was at 2: 8～4: 6, and preferred 3: 7～5: 5 scope is favourable.
Skin material of the present invention forms the coating that is made of C-1 layer, C-2 layer and C-3 layer on the one side of base layer, the surface configuration of this coating can be level and smooth in fact face, also can be to have many concavo-convex faces.
One of preferred implementation of skin material of the present invention is to have many concavo-convex skin materials on the surface.For this concaveconvex shape that has many concavo-convex skin materials on the surface, specify below.
There is concavo-convex more than the difference of height 0.1mm in skin material with concave-convex surface shape of the present invention on its surface, and the total area at protuberance top exists with 20～70% ratio of coating area.More preferably this difference of height is 0.15～1.2mm, most preferably is 0.2～1.0mm.In addition, the ratio that the area summation at protuberance top accounts for coating (skin material) area is 20～70%, more preferably 30～60%.Wherein, the area of the coating of skin material is the area of skin material itself.That is to say, be meant the projected area when face side is observed skin material, different with the concavo-convex surface area of having considered to be present in the surface.Wherein the top is meant and observes from the side of skin material when concavo-convex, 1/10 the part apart from the top of the distance of protuberance top and the lowest point as the top.Skin material of the present invention has this jog on the surface, thereby can reach promptly property and durability with high level.
For the skin material with concave-convex surface shape of the present invention, in order to increase promptly property, preferred protuberance is formed by protuberance independently.Independently the average area at each top of protuberance is preferably 0.5～7mm
2, more preferably 1.5～4.0mm
2Preferably about 5～100/cm of its number in addition
2More preferably 10～60/cm
2
In addition,, consider from aspects such as durability as the shape of protuberance independently, preferred especially truncated cone shape, and also the diameter at the top of truncated cone shape protuberance is 0.8～3.0mm, preferred 1.2～2.5mm.
And there be C-1 layer and the C-2 layer that forms by macromolecular elastomer at the protuberance top on the surface of skin material.More than the preferred 1 μ m of the aggregate thickness of this C-1 layer and C-2 layer, more preferably 3～20 μ m, most preferably 5～10 μ m.
Preferred its 100% elongation stress of the macromolecular elastomer that uses in C-1 layer and C-2 layer is 30～150kg/cm in addition
2As this macromolecular elastomer, be polyurethane elastomer the best.100% elongation stress of this macromolecular elastomer is lower than at 30 o'clock, exists modulus low, and the tendency that mar proof is not enough on the other hand, surpasses 150kg/cm
2The time, though there is the promptly tendency of property reduction in excellent in wear resistance.100% elongation stress of preferred macromolecular elastomer is 40～100kg/cm
2, 60～80kg/cm most preferably
2
Further, preferred its intensity height of the macromolecular elastomer of C-2 layer, the macromolecular elastomer of preferred C-1 layer contains the high composition of coefficient of friction.
As the macromolecular elastomer that forms the C-2 layer, optimization polyurethane elastomer, its instantiation can be enumerated the polyurethane elastomer that following two pure and mild vulcabond and chain lengthening agent one react and obtain.That is to say,, can enumerate the PTMEG such as polyvinylether glycol (polyethylene ether glycol), polytetramethylene glycol of molecular weight 1000～3000 as glycol; Carbonic ester glycol such as polyhexamethylene carbonic ester glycol, polytetramethylene carbonic ester glycol; Independent or the mixing glycol of polymer diols such as polyester-diol such as polytetramethylene adipate diol, polyhexamethylene adipate diol, as vulcabond, can enumerate dicyclohexyl methyl hydride 4,4 ' vulcabond, 3, alicyclic or aliphatic vulcabonds such as 3,5 trimethyls, 5 isocyanates isocyanatomethyl, hexamethylene diisocyanate; With diphenyl methane 4,4 ' vulcabond is main aromatic diisocyanate.In addition,, can enumerate ethylene glycol, butanediol, propane diamine, butanediamine, hydrazine, hydrazine derivate, amino acid hydrazides, 3,3, low strand elongation agents such as 5 trimethyls, 5 amino methyl cyclo-hexylamine, diamino-dicyclohexyl methane as the chain lengthening agent.Further preferred this diol component is PTMEG, PCDL, at this moment raisings such as hydrolytic resistance, durability.In addition, as vulcabond, preferred alicyclic or aliphatic vulcabond, the tendency that exists discoloration-resistant to improve.When using this polyurethane elastomer,, can easily regulate 100% elongation stress by regulating the content of vulcabond, low strand elongation agent.
As the macromolecular elastomer that forms the C-1 layer, in the above-mentioned polyurethane elastomer of enumerating as the macromolecular elastomer of C-2 layer, preferred 100% elongation stress is 30～150kg/cm
2The low-modulus polyurethane elastomer, more preferably 40～120kg/cm
2There is promptly property raising in 100% elongation stress hour, but the tendency that mar proof reduces, otherwise, when 100% elongation stress is big, exist mar proof to improve, but the tendency of property reduction promptly.
Further preferably in the macromolecular elastomer of C-1 layer, contain adhesive (promptly improving agent).As adhesive, can enumerate abietic resin and aqueous rubber etc., can be used alone or as a mixture.Wherein, be preferably the molecular weight 800～5000 of aqueous rubber, preferred 1000～4000 low-molecular-weight synthetic aqueous rubber, preferred especially low molecular weight polybutadiene, low molecular weight propylene nitrile butadiene copolymer, low-molecular-weight polydicyclopentadiene, low molecular weight phenylethylene butadiene copolymer, low-molecular-weight chlorobutadiene, low-molecular-weight polystyrene etc.In addition, the content of the adhesive in the preferred C-1 layer is 5～100 weight portions with respect to macromolecular elastomer solid content 100 weight portions, more preferably 10 weight portions～85 weight portions, most preferably 20 weight portions～70 weight portions.The addition of adhesive need be according to desired sense of touch, promptly the level of property is determined optimised quantity, when addition is too much, has the intensity reduction that produces the C-1 layer, the tendency of mar proof deficiency etc.In addition, preferred gloss conditioning agent, coloring pigment, stabilizing agent such as mixed silica in this C-1 layer also, the texture such as gloss that can regulate the surface.
In addition, the skin material with surperficial convex-concave shape of the present invention preferably the side surface part between this protuberance top and recess valley portions have 1000/cm
2Above minute aperture.More preferably there is 2000/cm
2Most preferably there is 5000/cm in above hole
2Above hole.In addition, from viewpoints such as durability, preferred 100,000/cm
2Below.In addition, preferred 0.5～50 μ m of the diameter of minute aperture.There are many minute apertures by side surface part like this, can improve the promptly property when moistening and do not reduce durability at skin material.
Wherein, protuberance top, recess valley portions and the side surface part between it are to observe when concavo-convex from the right-angle cross-section of skin material, 1/10 the part apart from the top of the difference of height of protuberance top and recess the lowest point as the top, 2/10 part is as valley portions apart from the lowest point, between it apart from the top 1/10～8/10 part as side surface part.
Further preferred skin material also exists minute aperture beyond side surface part, but the number in the hole of preferred concavo-convex side surface part is more than the number of the minute aperture at protuberance top, further the number of the minute aperture of preferred top is below 80% of side surface part, more preferably below 60%.In addition, also there is minute aperture in the valley portions of preferred recess, and there is 2000/cm in the total of the minute aperture of preferred coatings unit are
2Above minute aperture.In addition, from viewpoints such as durability, preferred 100,000/cm
2Below.By the existence of this minute aperture, its surperficial moisture film is absorbed when moistening, can improve the promptly property when moistening.
In addition, when protuberance independently exists,, be preferably placed at each protuberance on its surface, have the minute aperture of 0.5～50 μ m more than 50 in the side surface part of removing top and valley portions for skin material.In addition, from the viewpoint of anti-soil resistance etc., preferred below 5000.
Further for skin material, preferably the minute aperture that exists in its side surface part leads to as the inside of continuous through hole and skin material, and is preferably in side surface part, many in the number near the minute aperture of the shoulder portion at top.
Skin material with concave-convex surface shape of the present invention can obtain with manufacture method described below.Promptly, the C-3 layer that lamination porous polymer elastomer forms on the surface of base layer, obtain sheet material, this sheet material of impression in the metal die of the jog more than having 0.1mm, the total area that makes it to become the protuberance top accounts for 20～70% sheet material of sheet material area, then, in the C-1 layer of protuberance top coating macromolecular elastomer formation and the method for C-2 layer.Be further used as the difference of height of the jog of metal die, be preferably 0.2～1.5mm, most preferably 0.3～1.0mm.
Impress in the metal die by the jog more than having 0.1mm, will prolong as the part of the side on this concavo-convex inclined-plane, thereby can on the surface of its epidermal area, form minute aperture.Further preferred this metal die has independently recess, further preferably opposite with truncated cone shape protuberance former metal die.By the former metal die, can form jog on the surface of sheet material.The size at the top of protuberance can obtain by the shape of regulating metal die, and the height of jog can be regulated the degree of depth of metal die and impress the pressure, the temperature and time that add man-hour and obtain.
Further, the condition of this impression the softening temperature with the macromolecular elastomer of C-3 layer be SP (℃) time, preferably SP-(SP-40) ℃～(SP+20) ℃, more preferably in the C-3 layer side of the temperature range compacting sheet material of (SP-20) ℃～(SP+5) ℃.
Further, preferably before impression, carry out the photogravure processing with the porous high score that contains epidermal area in the organic solvent of elastomeric solvent in advance.For example use 50～200 orders, preferred 70～100 purpose gravure roll, coating contains the organic solvent of the solvent of the macromolecular elastomer that forms above-mentioned C-3 layer on the sheet material with C-3 layer, forms cortex, with this layer dissolving, forms the method for minute aperture.Take this method, can be pre-formed minute aperture, therefore can further increase the number of minute aperture in epidermal surface.But, before the organic solvent photogravure is handled, for example preferably be not coated with the solution that contains the macromolecular elastomer that forms C-2 layer, C-1 layer.This is to form minute aperture because the macromolecular elastomer layer of coating hinders the present invention by impression, and Tu Bu macromolecular elastomer produces the problem of peeling off because of impressing heat in addition.
In addition, for C-1 layer and the C-2 layer that macromolecular elastomer forms formed on the top at convex-concave surface, adopt the method for coating high polymer elastic liquid solution separately respectively.Preferably be coated with in order to avoid be blocked in the minute aperture of the protuberance formation of shapes such as truncated cone, therefore, preferably reduce concentration, the solution viscosity of coating solution, the thin photogravure roller of order number is used in coating, can suppress each coating weight and hang down.That is to say that the preferred low boiling point organic solvent solution of regulating the macromolecular elastomer separately that constitutes C-1 layer and C-2 layer is in the top coating of the protuberance that impresses processing, xeothermic drying.The further preferably method of carrying out the photogravure coating with 70～98% gap of the thickness of sheet material.By under this condition, being coated with, only at the solution of top coating macromolecular elastomer, can be not at the solution of side and bottom coating macromolecular elastomer.Like this, the solution by at the top coating macromolecular elastomer of protuberance can improve surface abrasion resistance, makes the skin material that is difficult to adhere to dirt.
In addition, C-1 layer and C-2 layer can use photogravure roller, spraying process etc. to be coated with the low boiling point organic solvent solution of macromolecular elastomer separately successively.That is, form the C-2 layer, form the C-1 layer on its surface then.Wherein,, be present in the minute aperture and the top of its side, further compare, also be difficult to stop up with paddy portion owing to produce big concavo-convexly on the surface.
The surface that other embodiment of the present invention is a coating has the skin material for ball of even surface in fact.Wherein, level and smooth in fact face is meant with above-mentioned surface and exists many concavo-convex skin materials different, is not have concavo-convex surface on the surface.Even surface is so long as also can there be very fine decorative pattern or fine concavo-convex in smooth in fact the getting final product in surface.
Have the order formation of the skin material of this smooth surface with C-1 layer/C-2 layer/C-3 layer/base layer.Constitute respectively this skin material C-1 layer, C-2 layer, C-3 layer and base layer composition and thickness with above-mentioned description with skin material of convex-concave surface is compared not too big variation, therefore omit detailed explanation at this.
Skin material with smooth surface can be produced on the base layer that has the C-3 layer on the one side according to the method that above-mentioned skin material with convex-concave surface is described, and forms the C-2 layer successively and the C-1 layer is made on the surface of this C-3 layer.Particularly make the C-1 layer contain adhesive, thereby can obtain promptly property excellence and the also excellent skin material of mar proof.
The skin material that further preferably has even surface, C-1 layer and C-2 layer have the fine through hole and this through hole that arrive the C-3 layer from face side and have 500/cm on the surface
3More than.Further preferred coatings has the fine through hole and this through hole that arrive base layer from face side and has 1000/cm on the surface
3More than.The ways and means of the many fine through holes of this formation can adopt with to the above-mentioned the same ways and means of description with skin material of convex-concave surface.
Further the moistening coefficient of friction on the surface of preferred skin material for ball of the present invention is 1.5～4.5.More preferably 1.8～4.0, most preferably 2.0～3.5, preferred especially 2.3～3.0.When moistening coefficient of friction hangs down, be easy to skid, have the promptly tendency of property reduction, when high, cohesive is strong, the tendency that exists sense of touch and soil resistance to reduce.Preferred in addition dry friction coefficient is 1.5～4.5, more preferably the same with moistening coefficient of friction scope.
In addition, when representing that with absorbent time the water absorbent surface of skin material of the present invention is spent, preferably the trap of measuring with the described method in back is below 500 seconds.Preferred absorbent time is below 300 seconds, most preferably below 200 seconds.Like this, the short skin material of absorbent time absorbs moisture film from surface holes, does not have residual moisture film on the surface, even therefore in the occasion of being got wet by sweat, the promptly property of ball can not reduce yet.
In addition, further the contact angle of preferred surface and water is below 90 degree, and for this reason, making aperture portion surface and macromolecular elastomer clad is that hydrophily gets final product.Therefore, preferably demonstrate hydrophilic surface-active material in the surface and inner existence of the clad that forms by macromolecular elastomer.Can enumerate interpolation anion surfactant, the non-ionic surface active agent more than the HLB10 etc.Be the occasion of polyurethane elastomer at clad perhaps,, preferably have the hydrophilic polyurethane elastomer of polyoxyethylene glycol as segment as the PTMEG composition.
Skin material for ball of the present invention that obtains like this and charged pressure air and the spheroid that expands is bonding can obtain ball for ball game, are applicable to basketball, rugby, American football, handball, vollyball, baseball etc.
In addition, skin material for ball of the present invention also can be used as the skin material that handbag is used.For example can be suitable for the golf handbag, go fishing with gloves, other physical culture gloves.
Embodiment
Describe the present invention in detail with embodiment below.In addition, the present invention is not limited to the scope of embodiment, and not special explanation, and part or % represent weight portion, weight %.
In addition, mensuration project of the present invention is measured according to following.
(1) elongation stress
, under the condition of elongation speed 100%/min, measure as sample with the film of the thickness 0.1mm of JISK63012 type dumb-bell test piece with the constant speed elongation testing machine.
(2) dry friction coefficient
Make 24 hours skin material of damping under the condition of 23 ℃ of temperature, relative humidity 60% (wide 2.5cm, long 5cm) contact placement with stainless steel flat runner surface, apply the load of 500g, frictional force (F) when mensuration is moved with speed 2m/min is obtained dry friction coefficient μ d=F/500.Mean value when in addition, frictional force (F) is the test film motion.
(3) moistening coefficient of friction
The test film of skin material (wide 2.5cm, long 5cm) is placed in 23 ℃ the water after 24 hours, remove the water of surface attachment with paper handkerchief, make it to contact placement with stainless steel flat runner surface, apply the load of 500g, frictional force (F) when mensuration is moved with speed 2m/min (unit: g), obtain moistening coefficientoffriction w=F/500.Mean value when in addition, frictional force (F) is the test film motion.
(4) mar proof
Measure according to JIS L10796.15.3 C method (anti-sliding wear testing).The instrument of 280 purpose sand paper is installed in use on abrasion wheels, increase the weight of 500g, after 100 frictions, with the surface damage state of following grade evaluation test film.
5 grades: color change is few, and is not obvious.
4 grades: be surface-coated layer damage, practical in appearance aspect is no problem.
3 grades: the part damage of porous matter coating.(boundary that allows in the practicality)
2 grades: porous matter coating major injury, the fiber of a part of substrate layer exposes.
1 grade: substrate layer is major injury also, and fiber etc. expose.
(5) hole count of the top of jog, valley portions, side surface part and size
Exist on the surface of skin material when concavo-convex, protuberance top, recess valley portions, the side surface part therebetween that exists is meant from the side surface part of skin material and observes when concavo-convex, 1/10 the part apart from the top of the difference of height of the lowest point of the top of protuberance and recess as the top, as valley portions, 1/10～8/10 the part apart from the top therebetween is as side surface part apart from the part of valley portions 2/10.
In an embodiment, as described below, measure each hole count and size in concavo-convex, its mean value multiply by every 1cm
2The protuberance number calculate.
The hole count at protuberance top and size with 200 times of photograph, are got 5 different protuberance tops with scanning electron microscope, measure hole count, hole dimension, obtain hole count and its mean value of 0.5～50 μ m and represent.
The hole count of valley portions and size make the valley portions of skin material in focus, with 200 times of photograph, measure hole count, hole dimension with scan microscope, obtain hole count and its mean value of 0.5～50 μ m, are converted into every 1cm
2Expression.In addition, when having independently protuberance, around the protuberance of 5 different points, measure, obtain mean value.
The hole count of side surface part and the mensuration of size, because the side becomes the side of three-dimensional protuberance, therefore shine fuzzyly, protuberance 4 five equilibriums or vertically cut apart more than 4 five equilibriums in order to prevent, use scanning electron microscope, take a picture with 200 times of surfaces to the lateral parts of each protuberance.Protuberance to 5 different points is measured hole count, hole dimension, obtains hole count and its mean value of 0.5～50 μ m.
(6) thickness of skin material holostrome
With increasing the weight of 150g/cm
2The spring dial indicator measure.
(7) average thickness of face side coating (C-1, C-2)
The thickness measurement of the coating of face side (C-1, C-2) uses scanning electron microscope, with 2500～3000 times of photograph, measures the average thickness of coating.In the time that multilayer can being differentiated, measure thickness respectively.
(8) difficult dustiness
In 10 innings of matches, use the ball for ball game of making of skin material, afterwards, according to the pollutional condition of following evaluation ball.
5 grades: do not pollute, good.
4 grades: some aberration are arranged, but no problem.
3 grades: pollution is arranged, but use the scope that allows in reality.
2 grades: pollute big slightly.
1 grade: pollute greatly, even wiping also is difficult to drop.
(9) firmly grasp property, sense of touch
Allow the ball for ball game that uses skin material to make become drying regime, to soak the moisture state in water, estimate player's promptly property, 5 stages of adopting are estimated.5 grades are very good, 3 grades of scopes that allow in practicality, and 1 grade for poor.
(10) water absorbent surface degree
On the surface of skin material (being the protuberance top during concavo-convex the existence), from the distance of height 10mm, use biuret, drip 1 (0.02cc), measure time after the dropping at once until suction.
(11) 40% compression stresses
Use elasticity of compression testing machine, (imposed load on the thickness direction of 10cm * 10cm) is measured its thickness with sheet material in test.With load 100g/cm
2The time thickness be benchmark, read the load that thickness reduces at 40% o'clock, be scaled every 1cm
2Load, as 40% compression stress.
Embodiment 1
＜possess the making of the tablet of base layer and coating (C-3) 〉
With 50/50 mixing nylon 6 and low density polyethylene (LDPE), with extruder fusion, mixing,, stretch 290 ℃ of blend spinnings, finish is handled also cutting, obtains the fiber of 5.5dtex, 51mm.Make its operation, obtain heavy 480g/m by combing, intersection winding water cloth, pin type rocker, calender
2, thick 1.6mm, apparent density 0.3g/cm
3The complexing fibrous substrate.
On the other hand, solidify the macromolecular elastomer of usefulness as porous, with dimethyl formamide as solvent, make molecular weight 2050 polytetramethylene ether diol, molecular weight 1950 poly-diethylene glycol adipate 50/50 mix glycol, diphenyl methane 4,4 ' vulcabond, glycol reaction obtain 100% elongation stress 60kg/cm
2, 180 ℃ of thermal softening temperature elastic polyurethane liquid solution (1) (solid content 20%).
The solution (polyurethane concentration 14%) that mixes 100 parts of this elastic polyurethane liquid solutions, 42 parts of dimethyl formamides, 0.5 part of porous conditioning agent (polyoxyethylene modification silicon: FG-10 pine this grease pharmacy (strain) system), 0.5 part of dark brown pigment is as the high polymer elastic liquid solution (maceration extract) of base material dipping usefulness.
In addition, mix 100 parts of above-mentioned elastic polyurethane liquid solutions, 33 parts of dimethyl formamides, 0.5 part of porous conditioning agent, 0.5 part of low-molecular-weight cellulose propionate: FG-220 pine this grease pharmacy (strain)) solution (polyurethane concentration 15%) of 0.5 part of dark brown pigment, as the high polymer elastic liquid solution of coating (C-3) usefulness.
Then, fibrous substrate is immersed in the maceration extract of base material dipping usefulness, after 90% compression with base material thickness, before the compression recovery of base material, the high polymer elastic liquid solution of coating coating (C-3) usefulness makes it to count 180g/m by solid content
2, in containing 40 ℃ of water of 10% dimethyl formamide, the macromolecular elastomer wet type is solidified, wash, drying.Resulting sheet compresses in 90 ℃ hot toluene repeatedly, lax, extract the polyethylene composition of removing in the fiber out, make with the superfine fibre of 0.003 danier tablet with macromolecular elastomer coating (C-3) as fibrous substrate.Coating has the teardrop shaped loose structure of long 50 μ m from the surface.
The making of＜skin material (1) 〉
With the imprinting apparatus that roller platen has been installed, suppress the surface (160 ℃ of roll surface temperatures) of above-mentioned tablet, obtain having the independently tablet of protuberance.As roller platen, but make, use the roller of the thermophore heating with former metal die, this former metal pattern has 24/cm
2The independently recess of truncated cone shape, the maximum gauge at the top of the protuberance of tablet is 1.8mm after the transfer printing, and the maximum gauge of the bottom of protuberance is 2.3mm, and the height of truncated cone is 0.6mm.
Tablet behind the impression has the protuberance of truncated cone shape, and in the side of this protuberance, per 1 protuberance on average exists the fine through hole of 2000 1～20 μ m to exist.In addition, show that this through hole distributes more at the shoulder of the projection of side.
Then, mix polyoxyethylene glycol (molecular weight 2020) with 2: 4: 4 ratio of mol ratio, polytetramethylene ether diol (molecular weight 2000), polyhexamethylene carbonic ester glycol (molecular weight 1980), make and mix the polymer diol and 3 that obtains, 3,5 trimethyls, 5 isocyanates isocyanatomethyl are reacted under the excessive condition of isocyanates, make prepolymer, make it in dimethyl formamide, to dissolve, after concentration is 40%, drip the toluene solution of 3,3,5 trimethyls, 5 amino methyl cyclohexylamine, carry out the chain lengthening reaction, obtain concentration 30%, 25 ℃ of following viscosity are the polyurethane elastomer of coating (C-2) usefulness of 1000 pools.100% elongation stress that the film of the thickness 0.15mm that makes of the solvent of removing this material is measured is 110kg/cm
2
Mix 100 parts of this polyurethane elastomers, MEK: isopropyl alcohol: 1 part of dimethyl formamide=5: 4: 1 200 parts of mixed solvents, dark brown pigment, make the coating fluid (1) of coating (C-2) usefulness of concentration 10.3%, viscosity 140 centipoises (25 ℃).
Formerly on the tablet with protuberance independently of impression, with the gravure coating machine that 200 purpose photogravure rollers have been installed, the coating clearance of dancer rools is 90% of a sheet thickness, is coated with the coating fluid (1) of this coating (C-2) usefulness, obtain the having coating tablet of (C-2).Only in the protuberance top coating of tablet, the through hole that is present in the projection face portion does not have blocked this coating (C-2).
Then, macromolecular elastomer as coating (C-1) usefulness, mix polyoxyethylene glycol (molecular weight 2020) with 3: 3: 4 ratio of mol ratio, polytetramethylene ether diol (molecular weight 2000), polyhexamethylene carbonic ester glycol (molecular weight 1980), make and mix the polymer diol and 3 that obtains, 3,5 trimethyls, 5 isocyanates isocyanatomethyl are reacted under the excessive condition of isocyanates, make prepolymer, make it in dimethyl formamide, to dissolve, after concentration is 40%, further drip 3,3, the toluene solution of 5 trimethyls, 5 amino methyl cyclohexylamine carries out the chain lengthening reaction, obtains concentration 30%, 25 ℃ of following viscosity are the polyurethane elastomer of coating (C-1) usefulness of 1000 pools.100% elongation stress that the film of the thickness 0.15mm that makes of the solvent of removing this material is measured is 100kg/cm
2
100 parts of this polyurethane elastomers of mixed dissolution, MEK: isopropyl alcohol: dimethyl formamide=5: 4: 1 343 parts of mixed solvents, 0.6 part of dark brown pigment, 0.3 part of silica, 15 parts in adhesive (polybutadiene of molecular weight 2000), make the coating fluid (2) of coating (C-1) usefulness of concentration 10.8%, viscosity 150 centipoises (25 ℃).
Formerly have on the tablet of coating (C-2, C-3), with the gravure coating machine that 200 purpose photogravure rollers have been installed, the coating clearance of dancer rools is 90% of a sheet thickness, be coated with the coating fluid (2) of this coating (C-1) usefulness, obtain on the protuberance of tablet, having the sheet skin material of the superficial layer that a plurality of coatings (C-2) (C-1) form.This superficial layer is only in the protuberance top coating, and the through hole that is present in the projection face does not have blocked.The every 1cm of sheet material
2The through hole of area is about 36000/cm
2
The diameter that is positioned at the top of surperficial protuberance is 1.64mm, and area is 2.1mm
2, highly be 0.32mm.The ratio that the area at the top of protuberance accounts for the sheet material area is 50%, and the through hole of concavo-convex side surface part is at the every 1cm of sheet material
2There is about 36000/cm on the area
2(1500 * 24/cm
2).Measure the characteristic of gained skin material (1), the results are shown in the table 1.
In addition, the basketball that expands charging into air is pasted the skin material of gained on spheroid, tests as ball, and sense of touch is good as a result, even and perspire and also be difficult to skid, the mar proof on surface is also excellent.
Comparative example 1
Under the condition the same with embodiment 1, tablet is impressed, obtain having the independently tablet of protuberance.The gained tablet is except that the coating (C-1, C-2) that does not have the surface, be the tablet the same with the skin material of embodiment 1, though sense of touch, promptly property is good, the mar proof on surface is poor, be easy to contaminated, undesirable as the ball for ball game skin material.
The measurement result of tablet is shown in Table 1 in the lump.
Comparative example 2
On the surface of the tablet that embodiment 1 obtains, do not impress processing, respectively under the condition the same with embodiment 1, the coating (C-2) of coating embodiment 1 and coating fluid (1), (2) of coating (C-1) usefulness, afterwards, though process sequence is different, under the condition the same, impress processing with embodiment 1.
The coating of gained tablet superficial layer (C-2, C-1) fusion sticks on the roller platen, strips off from the surface, and the insufficient formability of the protuberance of truncated cone shape not only, and do not form the opening of through hole.The measurement result of this sheet material is shown in Table 1 in the lump.
Embodiment 2
The surface of the tablet of making at embodiment 1 with coating (C-3), use 110 purpose photogravure rollers, coating dimethyl formamide: the mixed solvent of MEK=7: 3, dissolving is present in the cortex of the macromolecular elastomer on surface, make it opening, obtain having the level and smooth sheet material of through hole.1600/the cm in hole that has mean value 15 μ m on the surface of this level and smooth sheet material
2
Then, use the imprinting apparatus the same, under the same conditions, the level and smooth sheet material with this opening is impressed, make the tablet of independent protuberance with truncated cone shape with embodiment 1.Elongate the hole on surface of side surface part of the protuberance of this tablet, major diameter becomes 30 μ m, and the hole of top, paddy portion becomes, and some is little, but has residually, and there are 820 holes in each protuberance.
Then, remove and the embodiment 1 the same coating fluid that uses coating (C-2) usefulness, carry out outside 2 gravures are coated with, under identical condition, form coating (C-2) on the tablet of independent protuberance having.Then, under the condition the same, be coated on the coating fluid (2) of coating (C-1) usefulness of using among the embodiment 1, obtain having the skin material (2) of the sheet of coating with embodiment 1.The every 1cm of sheet material
2The through hole of area is about 20000/cm
2(820 * 24/cm
2).The average diameter at the top of the protuberance of this sheet material is 1.6mm, and area is 2mm
2, highly be 0.29mm.The ratio that the topside area of protuberance accounts for the sheet material area is 50%, and the hole of concavo-convex side surface part is at the every 1cm of sheet material
2There is about 11000/cm on the area
2The measurement result of skin material (2) is shown in Table 1 in the lump.
The same with embodiment 1, as the skin material of ball commentary valency gained, result, water imbibition are good especially, and sense of touch is also excellent.
Embodiment 3
Except that the gravure coating number of times of the coating fluid (1) of the coating of will be among embodiment 1 and the embodiment 2 using (C-2) changes into 3 times from 2 times, the same with embodiment 2, the making skin material.The every 1cm of sheet material
2The through hole of area is about 16000/cm
2(680 * 24/cm
2).The height at the top of the protuberance of this sheet material is 0.29mm.The ratio that the topside area of protuberance accounts for the sheet material area is 50%, and the hole of concavo-convex side surface part is the every 1cm of sheet material
2There is about 11000/cm in area
2The measurement result of this skin material (3) is shown in Table 1 in the lump.
The same with embodiment 2, as the skin material of ball commentary valency gained, result, surface abrasion resistance are good especially, and sense of touch, water imbibition are also good.
Embodiment 4
With PCDL: hexamethylene diisocyanate: (100% elongation stress is 60kg/cm to the polyurethane elastomer that IPD forms
2) be main, with respect to this polyurethane elastomer solid content weight, mix 15% aqueous rubber (low molecular weight propylene nitrile butadiene copolymer), make it to be dissolved in MEK: in the mixed solvent of toluene=3: 7, obtain the solution of concentration 10%, viscosity 150 centipoises (25 ℃), this solution as coating fluid (3), the coating fluid (2) of coating (C-1) usefulness that replacement is used in embodiment 1 and embodiment 2, in addition, under the condition the same, make the skin material (4) of sheet with embodiment 2.
Further this skin material of dipping in 1.0% aqueous solution of hydrophilic surfactant dioctyl sodium sulphosuccinate pushes, and makes it dry.The absorption of water of gained skin material is 180 seconds, is easy to suction, and sense of touch, promptly property is also good, and the surface abrasion resistance during actual the use is also excellent.The every 1cm of sheet material
2The through hole of area is about 19000/cm
2(810 * 24/cm
2), the height at the top of the protuberance of this sheet material is 0.30mm.The ratio that the topside area of protuberance accounts for the sheet material area is 50%, and the hole of concavo-convex side surface part is the every 1cm of sheet material
2There is about 11000/cm in area
2The measurement result of this skin material is shown in Table 1 in the lump.
Embodiment 5
Coating fluid (2) to coating (C-1) usefulness of use in embodiment 1 changes, use is with respect to 100 parts of polyurethane elastomers, the coating fluid (4) that the low-molecular-weight dicyclopentadiene resin of 60 parts of molecular weight 3000 of mixed dissolution replaces the polybutadiene in this coating fluid (2) to obtain, in addition, under the condition the same, make the skin material (5) of sheet with embodiment 1.
The mar proof of gained skin material, promptly property is all good.The every 1cm of sheet material
2The through hole of area is about 35000/cm
2(1450 * 24/cm
2).The height at the top of the protuberance of this sheet material is 0.32mm.The ratio that the area at the top of protuberance accounts for the sheet material area is 50%, and the hole of concavo-convex side surface part is the every 1cm of sheet material
2There is about 35000/cm in area
2The measurement result of this skin material is shown in Table 1 in the lump.
Table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Skin material thickness mm | 1.40 | 1.42 | 1.40 | 1.42 | 1.40 | 1.40 | 1.40 |
| The hole count of jog | |||||||
| The top is individual | 0 | 240 | 40 | 250 | 0 | 0 | 0 |
| Side surface part is individual | 1500 | 460 | 440 | 440 | 1450 | 560 | 0 |
| Valley portions is individual | 0 | 120 | 200 | 120 | 0 | 0 | 0 |
| The average diameter in the hole of jog | |||||||
| Top μ m | - | 1.8 | 1.0 | 2.0 | - | - | - |
| Side surface part μ m | 2.0 | 4.8 | 4.8 | 5.0 | 2.0 | 3.1 | - |
| Valley portions μ m | - | 2.3 | 2.1 | 2.3 | - | - | - |
| The average thickness mm of superficial layer (total of coating (C-2) (C-1)) | 3.0 | 4.6 | 9.5 | 4.5 | 3.0 | Do not have | Come off |
| 100% elongation stress of PU | |||||||
| Coating (C-2) kg/cm 2 | 110 | 110 | 110 | 110 | 110 | 110 | 110 |
| Coating (C-1) kg/cm 2 | 100 | 100 | 100 | 60 | 100 | 100 | 100 |
| Skin material | |||||||
| Water absorbent surface degree second | 300 | 300 | 280 | 180 | 280 | 600 | ＞1000 |
| Dry friction coefficient | 2.4 | 2.6 | 2.3 | 3.8 | 2.5 | 4.5 | 2.1 |
| Moistening coefficient of friction | 2.0 | 1.8 | 1.7 | 2.2 | 1.9 | 3.8 | 1.9 |
| The abrasion resistance level | 4 | 5 | 5 | 3 | 4 | 2 | 4 |
| Difficult dustiness level | 4 | 4 | 5 | 4 | 4 | 2 | 3 |
| The sense of touch level | 4 | 4 | 4 | 4 | 4 | 4 | 3 |
| Dry promptly property level | 4 | 4 | 4 | 4 | 4 | 3 | 3 |
| Moistening promptly property level | 4 | 4 | 4 | 4 | 4 | 3 | 3 |
Embodiment 6
＜possess the making of the tablet of base layer and coating (C-3) 〉
With 50/50 mixing nylon 6 and low density polyethylene (LDPE), fusion in extruder, mixing, in 290 ℃ of blend spinnings, stretching, finish is handled, and cuts out, and obtains the fiber of 5.5dtex, 51mm.Make the operation of this fiber, obtain heavy 400g/m by combing, intersection winding water cloth, pin type rocker, calender
2, thick 1.6mm, apparent density 0.25g/cm
3The complexing fibrous substrate.
On the other hand, solidify the macromolecular elastomer of usefulness, use the 100% elongation stress 60kg/cm the same with the tablet of embodiment 1 as porous
2, 180 ℃ of thermal softening temperature elastic polyurethane liquid solution (1) (solid content: 20%), solution (the PU concentration: 8%), make the high polymer elastic liquid solution (maceration extract) of base material dipping usefulness of mixing (1) 100 part of this elastic polyurethane liquid solution, 150 parts of dimethyl formamides, 0.5 part of porous conditioning agent (polyoxyethylene modification silicon: FG-10 pine this grease pharmacy (strain) system), 0.5 part of dark brown pigment.
In addition, solution (the PU concentration: 13%), make the high polymer elastic liquid solution of coating (C-3) usefulness of mixing 100 parts of above-mentioned elastic polyurethane liquid solutions, 54 parts of dimethyl formamides, 0.5 part of porous conditioning agent, 0.5 part of low-molecular-weight cellulose propionate (this grease pharmacy (strain) of FG-220 pine), 0.5 part of dark brown pigment.
Then, fibrous substrate is immersed in the maceration extract of base material dipping usefulness, after 90% extruding with base material thickness, before the compression recovery of base material, the high polymer elastic liquid solution that the coating coating is used, making solid content is 180g/m
2, in containing 40 ℃ water of 10% dimethyl formamide, wet type is solidified macromolecular elastomer, washes, drying.In 90 ℃ hot toluene to resulting sheet compress repeatedly, lax, extract the polyethylene composition of removing in the fiber out, make with the superfine fibre of 0.003dtex tablet with macromolecular elastomer coating (C-3) as fibrous substrate.Coating has the teardrop shaped loose structure that length is 50 μ m from the surface.
The making of＜skin material (6) 〉
On the surface of above-mentioned tablet, use 110 purpose photogravure rollers, the coating dimethyl formamide: the mixed solvent of MEK=7: 3, make cortex dissolving, the perforate of the macromolecular elastomer that is present in the surface, obtain level and smooth perforate sheet material.1800/the cm in hole that has mean value 15 μ m on the surface of this level and smooth sheet material
2Further, use the roller platen of blood vessel grain pattern, impress, make the tablet of smooth appearance at 140 ℃ on this surface.
In addition, on the tablet of smooth appearance, with the gravure coating machine that 200 purpose photogravure rollers have been installed, the coating clearance of photogravure roller is adjusted to 90% of sheet thickness, the coating fluid (1) (concentration 10.3%) of coating (C-2) usefulness of using among the coating embodiment 1, obtain the having coating tablet of (C-2).
Then, with the gravure coating machine that 200 purpose photogravure rollers have been installed, the coating clearance of photogravure roller is adjusted to 90% of sheet thickness, formerly have the coating fluid (2) (concentration 10.8%) that is coated on coating (C-1) usefulness of using among the embodiment 1 on the tablet of coating (C-2, C-3), obtain on coating (C-3), having sheet skin material (6) by a plurality of coatings (C-2) and the superficial layer that (C-1) forms.
40% compression stress of this sheet material is 1.0kg/cm
2In addition, the 680/cm in hole that on the surface of this level and smooth sheet material, has mean value 5.2 μ m
2, coating of superficial layer (C-2) and thickness (C-1) add up to 3.0 μ m.The measurement result of the characteristic of gained skin material is shown in Table 2.
In addition, the vollyball that expands toward charging into air is tested as ball with the skin material of pasting gained on the spheroid, and the impact when ball transmits as a result is few, even sense of touch is good and perspiration also is difficult to skid, the mar proof on surface is also excellent.
Comparative example 3
Except that the coating (C-1, C-2) on the surface that does not have embodiment 6,, obtain the tablet of smooth appearance with embodiment 6 the same carrying out.The surface abrasion resistance of this sheet material is poor, is easy to pollute, and is undesirable as the ball for ball game skin material.The measurement result of tablet is shown in Table 2.
Embodiment 7
Use with 100% elongation stress 90kg/cm
2The maceration extract (solid content: 13%) replace the usefulness 100% elongation stress 60kg/cm of the base material dipping usefulness of embodiment 6 of polyurethane elastomer
2Polyurethane elastomer maceration extract (PU concentration: 8%), the high polymer elastic liquid solution that the high polymer elastic liquid solution that uses the coating of PU concentration 15% to use replaces the coating of PU concentration 13% to use, in addition the same with embodiment 6, the making tablet.
The mar proof of gained skin material, difficult dustiness excellence.The measurement result of this skin material is shown in Table 2 in the lump.
Embodiment 8
Use is with respect to 100 parts of polyurethane elastomers, the coating fluid (4) of the low-molecular-weight polydicyclopentadiene resin of the molecular weight 3000 that uses among 60 parts of embodiment 5 of mixed dissolution, the coating fluid (2) that replaces coating (C-1) usefulness of use among the embodiment 6, in addition, under the condition identical, make the skin material of sheet with embodiment 6.
40% compression stress of gained skin material (8) is 0.92kg/cm
2In addition, the 700/cm in hole that on the surface of this level and smooth sheet material, has mean value 5.5 μ m
2, coating of superficial layer (C-2) and thickness (C-1) add up to 3.2 μ m.In addition, mar proof, promptly property is all good.The measurement result of this skin material is shown in Table 2 in the lump.
Embodiment 9
＜possess the making of the tablet of base layer and coating (C-3) 〉
Use the fiber the same with embodiment 6, the operation by combing, intersection winding water cloth, pin type rocker, calender obtains weight 480g/m
2, thick 1.9mm, apparent density 0.25g/cm
3The complexing fibrous substrate.Except that using this complexing fibrous substrate, the same with embodiment 6, dipping, coating, wet type are solidified, are extracted out and remove the polyethylene composition, and the superfine fibre made from 0.003dtex is the tablet with macromolecular elastomer coating (C-3) of fibrous substrate.Coating has the teardrop shaped loose structure of long 50 μ m from the surface.
The making of＜base layer 〉
With the imprinting apparatus that roller platen has been installed,, obtain having the tablet of independent protuberance on 160 ℃ of surfaces of suppressing the gained tablet down of roll surface temperature.As roller platen, but make the roller that uses the thermophore heating with former metal die, this former metal pattern has 24/cm
2The independent recess of truncated cone shape, the maximum gauge at the top of protuberance is 1.8mm after the transfer printing, the maximum gauge 2.3mm of the bottom of protuberance, the height of truncated cone are 0.6mm.
Tablet behind the impression has the protuberance of truncated cone shape, and in the side of this protuberance, on average there is the through hole of 2000 1～20 μ m in per 1 protuberance.In addition, show that this through hole distributes more at the shoulder of the projection of side.
Then, the same with embodiment 6, be coated with the coating fluid (1) of this coating (C-2) usefulness and the coating fluid (2) of coating (C-3) usefulness successively, obtain on the protuberance of coating (C-3), having the sheet skin material of a plurality of superficial layers (thickness 3 μ m) of coating (C-2), (C-1).This superficial layer (C-2), (C-1) only are coated on the protuberance top of skin material, and the through hole that is present in the side surface part of protuberance can be not blocked.
40% compression stress of this sheet material is 1.0kg/cm
2In addition, the diameter at the top of protuberance is 1.64mm, and area is 2.1mm
2, highly be 0.32mm.The ratio that the topside area of protuberance accounts for the sheet material area is 50%, and in addition, the hole of concavo-convex side surface part is the every 1cm of sheet material
2There is about 30000/cm in area
2The top of truncated cone shape protuberance and paddy portion do not have through hole to exist, and each protuberance is 1200 of the average through holes that has 2.0 μ m on the surface of side surface part only.The measurement result of the characteristic of gained skin material is shown in Table 2.
Embodiment 10
The surface of the tablet that in embodiment 9, obtains, the same with embodiment 6, use 110 purpose photogravure rollers, coating dimethyl formamide: the mixed solvent of MEK=7: 3, make cortex dissolving, the perforate of the macromolecular elastomer that is present in the surface, obtain level and smooth perforate sheet material.1600/the cm in hole that on the surface of this level and smooth sheet material, has mean value 15 μ m
2
Then, use the imprinting apparatus the same, under identical condition, this level and smooth sheet material with peristome is impressed, make the tablet of independent protuberance with truncated cone shape with embodiment 9.Elongate the hole of side surface of the protuberance of this tablet, the hole of top, paddy portion becomes, and some is little, but has residual.
Then, use has mixed the coating fluid (1) of coating (C-2) usefulness of using among coating fluid (3) (concentration 10%) the replacement embodiment 6 of the aqueous rubber (low molecular weight propylene nitrile butadiene copolymer) that uses among the embodiment 4, in addition, under the condition the same, make the skin material of sheet with embodiment 6.
Further this skin material is immersed in 1.0% aqueous solution of hydrophilic surfactant dioctyl sodium sulphosuccinate, extruding is dry.40% compression stress of this sheet material is 0.9kg/cm
2, the thickness of the coating of superficial layer (C-2), (C-1) adds up to 4.5 μ m.The absorption of water of gained skin material is 180 seconds, is easy to suction, sense of touch, promptly property might as well, the surface abrasion resistance during actual the use is also excellent.The every 1cm of sheet material
2The through hole of area is about 20000/cm
2(840 * 24/cm
2).The height at the protuberance top of this sheet material is 0.30mm.The ratio that the area at protuberance top accounts for the sheet material area is 50%, and in addition, the hole of concavo-convex side surface part is the every 1cm of sheet material
2There is about 11000/cm in area
2Each protuberance is in the mountain top of truncated cone shape protuberance portion, has 250 in the hole of average 3.0 μ m, at side surface, has 460 in the hole of average 5.5 μ m, has 130 in the hole of average 2 μ m in paddy portion.The measurement result of this skin material is shown in Table 2 in the lump.
Toward charging into basketball that air expands with the skin material of pasting gained on the spheroid, test as ball in addition, the impact when ball transmits is few, and sense of touch is good and compare with the tablet of embodiment 6, also is difficult to skid even perspire, and the mar proof on surface is excellence also.
Table 2
| Project | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 3 |
| Thickness mm | 1.32 | 1.35 | 1.30 | 1.40 | 1.42 | 1.35 |
| Water absorbent surface degree second | 280 | ＞1000 | 280 | 260 | 180 | 600 |
| Dry friction coefficient | 2.6 | 2.4 | 2.7 | 2.4 | 3.8 | 4.5 |
| Moistening coefficient of friction | 2.2 | 1.9 | 2.3 | 2.0 | 2.4 | 3.8 |
| The abrasion resistance level | 4 | 4 | 4 | 4 | 3～4 | 2 |
| Difficult dustiness level | 4 | 4 | 4 | 4 | 4 | 2 |
| The sense of touch level | 4 | 3 | 4 | 4 | 4 | 4 |
| Dry promptly property level | 4 | 3 | 4 | 4 | 4 | 3～4 |
| Moistening promptly property level | 4 | 3 | 4 | 4 | 4 | 3 |
| 40% compression stress kg/cm 2 | 1.0 | 2.7 | 0.92 | 1.0 | 0.9 | 1.0 |
Claims (29)
1. skin material for ball, it is that the tablet that has the coating that is formed by macromolecular elastomer on a side surface of base layer forms, it is characterized in that: (1) this coating begins to be formed for these 3 layers by C-1, C-2 and C-3 successively from face side, (2) the C-3 layer of base layer side is formed by porous matter macromolecular elastomer, (3) the C-1 layer of face side is formed by the macromolecular elastomer that contains adhesive, and (4) coating forms by having or do not have the macromolecular elastomer that arrives the fine through hole of base layer from face side.
2. the described skin material for ball of claim 1, wherein said adhesive is aqueous rubber or abietic resin.
3. the described skin material for ball of claim 1, wherein said adhesive is that molecular weight is 800～5000 synthetic aqueous rubber.
4. the described skin material for ball of claim 1, wherein said C-1 layer and C-2 layer have the fine through hole that arrives the C-3 layer from face side, and there is 500/cm from the teeth outwards in this through hole
2More than.
5. the described skin material for ball of claim 1, wherein said coating have the fine through hole that arrives base layer from face side, and there is 1000/cm from the teeth outwards in this through hole
2More than.
6. the described skin material for ball of claim 1, wherein said base layer is the complex layer that is formed by fibrous substrate and macromolecular elastomer.
7. the described skin material for ball of claim 1,40% compression stress of this material is 0.4～2.2kg/cm
2
8. the described skin material for ball of claim 1, its moistening coefficient of friction is 1.5～4.5, and the water absorbent surface degree is below 500 seconds.
9. the described skin material for ball of claim 1, there be the concavo-convex of many difference of height 0.1～1.0mm from the teeth outwards in wherein said coating, and the total area at the top of this concavo-convex protuberance accounts for 20～70% of coating area.
10. the described skin material for ball of claim 9, the top of the protuberance in the jog of wherein said coating is formed by C-1 layer, C-2 layer and C-3 layer, and the valley portions of recess is formed by the C-3 layer.
11. the described skin material for ball of claim 9, wherein said adhesive are aqueous rubber or abietic resin.
12. the described skin material for ball of claim 9, wherein said adhesive are the synthetic aqueous rubber of molecular weight 800～5000.
13. the described skin material for ball of claim 9, wherein said C-1 layer and C-2 layer have the fine through hole that arrives the C-3 layer from face side, and there is 500/cm from the teeth outwards in this through hole
2More than.
14. the described skin material for ball of claim 9, wherein said coating have the fine through hole that arrives base layer from face side, and there is 1000/cm from the teeth outwards in this through hole
2More than.
15. the described skin material for ball of claim 9, wherein said base layer are the complex layers that is formed by fibrous substrate and macromolecular elastomer.
16. the described skin material for ball of claim 9, the average area at each top of protuberance is 0.5～7mm in the jog of wherein said coating
2
17. in the protuberance top of the jog of coating and the side surface part between the recess valley portions, there is 1000/cm in the described skin material for ball of claim 9
2Above hole.
18. the described skin material for ball of claim 17, wherein at the jog of coating, reach the protuberance top the hole number be below 80% of hole number of side surface part.
19. the described skin material for ball of claim 9,40% compression stress of this material is 0.4～2.2kg/cm
2
20. the described skin material for ball of claim 9, its moistening coefficient of friction is 1.5～4.5, and the water absorbent surface degree is below 500 seconds.
21. the described skin material for ball of claim 1 wherein has even surface in fact on the surface of coating.
22. the described skin material for ball of claim 21, wherein said adhesive are aqueous rubber or abietic resin.
23. the described skin material for ball of claim 21, wherein said adhesive are the synthetic aqueous rubber of molecular weight 8000～5000.
24. the described skin material for ball of claim 21, wherein C-1 layer and C-2 layer have the fine through hole that arrives the C-3 layer from face side, and there is 500/cm from the teeth outwards in this through hole
2More than.
25. the described skin material for ball of claim 21, its floating coat have the fine through hole that arrives base layer from face side, and there is 1000/cm from the teeth outwards in this through hole
2More than.
26. the described skin material for ball of claim 21, wherein said base layer are the complex layers that is formed by fibrous substrate and macromolecular elastomer.
27. the described skin material for ball of claim 21,40% compression stress of this material is 0.4～2.2kg/cm
2
28. the described skin material for ball of claim 21, its moistening coefficient of friction is 1.5～4.5, and the water absorbent surface degree is below 500 seconds.
29. a ball is characterized in that: on the surface of this spheroid, have claim 1,9 or 21 described skin material for ball.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003073666A JP4259893B2 (en) | 2003-03-18 | 2003-03-18 | Skin material for ball and method for manufacturing the same |
| JP73666/2003 | 2003-03-18 | ||
| JP170378/2003 | 2003-06-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1761502A CN1761502A (en) | 2006-04-19 |
| CN100389840C true CN100389840C (en) | 2008-05-28 |
Family
ID=33289506
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800073149A Expired - Lifetime CN100389840C (en) | 2003-03-18 | 2004-03-17 | Skin material for ball and ball |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4259893B2 (en) |
| CN (1) | CN100389840C (en) |
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| US7758458B2 (en) * | 2004-04-09 | 2010-07-20 | Kuraray Co., Ltd. | Ball |
| JP4691021B2 (en) * | 2004-04-09 | 2011-06-01 | 株式会社クラレ | Sheet-like material with excellent cushioning and non-slip properties |
| WO2007119478A1 (en) * | 2006-03-27 | 2007-10-25 | Kuraray Co., Ltd. | Composite sheet showing excellent handling properties in wet state and game ball |
| CN101583757B (en) | 2006-06-27 | 2012-08-15 | 可乐丽股份有限公司 | Leather-like sheet and method of producing leather-like sheet |
| EP2044980B1 (en) * | 2006-07-26 | 2022-11-09 | Kuraray Co., Ltd. | Sheet-like object for ball and ball |
| WO2009125758A1 (en) | 2008-04-10 | 2009-10-15 | 株式会社クラレ | Leather-like sheet having excellent grip performance and artificial leather product using the same |
| JP5226407B2 (en) * | 2008-07-15 | 2013-07-03 | 帝人コードレ株式会社 | Method for producing artificial leather for balls with excellent grip |
| JP5443067B2 (en) * | 2009-06-11 | 2014-03-19 | 帝人コードレ株式会社 | Ball skin material |
| JP5202466B2 (en) * | 2009-07-27 | 2013-06-05 | 帝人コードレ株式会社 | Skin material for baseball |
| JP5596411B2 (en) * | 2010-05-20 | 2014-09-24 | 帝人コードレ株式会社 | Ball skin material |
| JP5502596B2 (en) * | 2010-05-20 | 2014-05-28 | 帝人コードレ株式会社 | Skin sheet material |
| CN103550919A (en) * | 2013-11-05 | 2014-02-05 | 泸州市慧江机械制造有限公司 | Tennis ball |
| JP6362340B2 (en) * | 2014-01-30 | 2018-07-25 | 株式会社クラレ | Ball skin material and balls |
| EP3485946B1 (en) * | 2016-07-12 | 2022-03-16 | Molten Corporation | Ball |
| CN106750104A (en) * | 2017-02-24 | 2017-05-31 | 耿佃勇 | Polyurethane baseball and preparation method thereof |
| CN108729251B (en) * | 2018-07-18 | 2021-07-20 | 华伦皮塑（苏州）有限公司 | Environment-friendly PU leather for flower-type basketball and preparation method thereof |
| CN112933557A (en) * | 2021-02-03 | 2021-06-11 | 天长市正牧铝业科技有限公司 | High-sealing-performance PU (polyurethane) veneered football with butyl liner and preparation process of football |
| CN112933559A (en) * | 2021-02-03 | 2021-06-11 | 天长市正牧铝业科技有限公司 | Dry manufacturing process of PU (polyurethane) leather-covered volleyball |
| CN114308576B (en) * | 2022-01-20 | 2022-08-12 | 浙江希尔达汽车零部件有限公司 | Production method for cross flocking of automobile B upper column camera area |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078162A (en) * | 1992-05-05 | 1993-11-10 | 原三藩玩具制造有限公司 | Inflation spheroid and manufacture method thereof with surface layer of down feather |
-
2003
- 2003-03-18 JP JP2003073666A patent/JP4259893B2/en not_active Expired - Fee Related
-
2004
- 2004-03-17 CN CNB2004800073149A patent/CN100389840C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078162A (en) * | 1992-05-05 | 1993-11-10 | 原三藩玩具制造有限公司 | Inflation spheroid and manufacture method thereof with surface layer of down feather |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106178434A (en) * | 2015-05-28 | 2016-12-07 | 阿迪达斯股份公司 | The sport ball of on-inflatable |
| CN106178434B (en) * | 2015-05-28 | 2019-12-13 | 阿迪达斯股份公司 | non-inflatable sport ball |
| US10850165B2 (en) | 2015-05-28 | 2020-12-01 | Adidas Ag | Non-inflatable sports balls |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004277961A (en) | 2004-10-07 |
| JP4259893B2 (en) | 2009-04-30 |
| CN1761502A (en) | 2006-04-19 |
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