CN108883596A - Liquid-repellant resin sheet and the article that the liquid-repellant resin sheet is utilized - Google Patents
Liquid-repellant resin sheet and the article that the liquid-repellant resin sheet is utilized Download PDFInfo
- Publication number
- CN108883596A CN108883596A CN201780016423.4A CN201780016423A CN108883596A CN 108883596 A CN108883596 A CN 108883596A CN 201780016423 A CN201780016423 A CN 201780016423A CN 108883596 A CN108883596 A CN 108883596A
- Authority
- CN
- China
- Prior art keywords
- liquid
- resin
- convex form
- repellant
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 230000000007 visual effect Effects 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- ZENKESXKWBIZCV-UHFFFAOYSA-N 2,2,4,4-tetrafluoro-1,3-benzodioxin-6-amine Chemical group O1C(F)(F)OC(F)(F)C2=CC(N)=CC=C21 ZENKESXKWBIZCV-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXUDJAVFUJMRFG-UHFFFAOYSA-N COC(C=C)=O.[C] Chemical compound COC(C=C)=O.[C] UXUDJAVFUJMRFG-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000227653 Lycopersicon Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ROPXFXOUUANXRR-YPKPFQOOSA-N bis(2-ethylhexyl) (z)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C/C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-YPKPFQOOSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- GHPKXHUHROFDQP-UHFFFAOYSA-N hydrazinylmethanol Chemical compound NNCO GHPKXHUHROFDQP-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HOWGUJZVBDQJKV-UHFFFAOYSA-N n-propyl-nonadecane Natural products CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Bag Frames (AREA)
- Wrappers (AREA)
Abstract
By using the resin sheet with convex form layer (1) and liquid repellent layer (2), it can obtain the liquid-repellant resin sheet with the liquid-repellant stable for the pressure from liquid, and, convex form layer (1) has at least one kind of fine convex form (1a) and contains thermoplastic resin composition, there is the liquid repellent layer (2) containing hydrophobic inorganic particle and binder resin in the face with above-mentioned convex form (1a), the content of hydrophobic inorganic particle in above-mentioned liquid repellent layer (2) is more than 80 mass % and is 95 mass % or less, the content of binder resin is 5 mass % or more and less than 20 mass %.
Description
Technical field
The present invention is about the resin sheet for having liquid-repellant and utilizes the article of the resin sheet for having liquid-repellant.
Background technique
Use paper material, high molecular material as food, life such as cold drink water, fruit drink, hobby diet products in the past
Apply flexibly product packaging material.Concaveconvex shape is set on resin sheet and then is applied on its surface for example, proposing in patent document 1
The cloth resin sheet for having liquid-repellant of water repellent.
However, the liquid-repellant resin sheet recorded in patent document 1 can be because the pressure given from liquid, leads to liquid
It is affine in the liquid-repellant resin sheet surface the phenomenon that, that is to say, that the decline or loss that liquid-repellant can be generated, in the stabilization of liquid-repellant
It is problematic in property.
Patent document 1：International Publication No. 2014/087695.
Summary of the invention
The issue of the present invention is to provide the resin sheet for having the liquid-repellant stable for the pressure from liquid and utilizations
The article of the resin sheet.
The present inventor is studied for the various means for showing liquid-repellant, as a result, it has been found that, by being assigned on piece surface
Fine convex form is given, and the liquid repellent layer containing hydrophobic inorganic particle and binder resin at a specific ratio is set, from
And the liquid-repellant stable for the pressure from liquid can be assigned to piece surface, complete the present invention.
The present invention for solving the above subject, is made up of the following contents.
(1) a kind of liquid-repellant resin sheet, wherein it has at least 1 with convex form layer and liquid repellent layer, the convex form layer
It plants fine convex form and contains thermoplastic resin composition, have in the face with convex form of the convex form layer containing thin
The content of the liquid repellent layer of aqueous inorganic particle and binder resin, the hydrophobic inorganic particle in the liquid repellent layer is more than 80 matter
It measures % and is 95 mass % hereinafter, the content of binder resin is 5 mass % or more and less than 20 mass %.
(2) the liquid-repellant resin sheet as described in (1), wherein it has liquid-repellant for the water system liquid containing sugar.
(3) the liquid-repellant resin sheet as described in (1) or (2), wherein the thermoplastic resin composition is in 230 DEG C of conditions
Under melt mass flow rate be 5g/10 minutes or more.
(4) the liquid-repellant resin sheet as described in any one of (1) to (3), wherein the thermoplastic resin composition is contained
Polyolefin resin composite.
(5) the liquid-repellant resin sheet as described in (4), wherein the polyolefin resin composite contain 35 mass %~
The polyolefin-based resins of 100 mass %.
(6) the liquid-repellant resin sheet as described in any one of (1) to (5), wherein the hydrophobic inorganic particle is in table
Face has the hydrophobic silica particle of trimethyl silyl.
(7) the liquid-repellant resin sheet as described in any one of (1) to (6), wherein the hydrophobic inorganic particle is averaged
Primary particle size is 5nm~1000nm.
(8) the liquid-repellant resin sheet as described in any one of (1) to (7), wherein the binder resin includes to be selected from alkene
The resin of one or more of hydrocarbon system copolymer and fluorine system copolymer.
(9) the liquid-repellant resin sheet as described in any one of (1) to (8), wherein the convex form by the 1st convex form and
2nd convex form is constituted, and the height of the 1st convex form and the height of the 2nd convex form are respectively 20 μm~150 μm, adjacent convex form
Vertex spacings be 20 μm~100 μm.
(10) the liquid-repellant resin sheet as described in any one of (1) to (9), wherein the convex form layer with a thickness of 50 μ
M~200 μm.
(11) the liquid-repellant resin sheet as described in any one of (1) to (10), wherein the side with the liquid repellent layer
Contact angle when surface and the liquid containing carbohydrate contact is 130 ° or more, and rolling angle is 40 ° or less.
(12) the liquid-repellant resin sheet as described in any one of (1) to (11), wherein on the surface of the convex form layer,
Even if the pressure for applying 866Pa from liquid still maintains liquid-repellant.
(13) the liquid-repellant resin sheet as described in any one of (1) to (12), wherein convex in having for the convex form layer
1 layer or more of substrate layer has been laminated in the another side in the face of shape, and the substrate layer includes to be selected from phenylethylene resin series, olefin-based tree
The tree of one or more of rouge, polyester based resin, nylon system resin, ethylene-vinyl alcohol copolymer resin and acrylic resin
Rouge.
(14) the liquid-repellant resin sheet as described in (13), wherein formed between the convex form layer and the substrate layer
Encapsulant resins layers, the encapsulant resins layer contain in modified olefin based polymer resin and thermoplastic elastomer (TPE)
At least one kind of resin.
(15) a kind of article, wherein it uses the liquid-repellant resin sheets described in any one of (1) to (14).
(16) article as described in (15), wherein it is daily necessity, packaging material or building materials.
(17) article as described in (16), wherein it is food containers, sack, raincoat, umbrella, wallpaper or with the structure at water
Part.
In accordance with the invention it is possible to provide the liquid-repellant resin sheet for having the liquid-repellant stable for the pressure from liquid and
The article of the resin sheet is utilized.
Detailed description of the invention
Fig. 1 be indicate the first embodiment of the present invention is related to liquid-repellant resin sheet outline longitudinal side sectional view.
Fig. 2 is the approximate vertical view of the liquid-repellant resin sheet of Fig. 1.
Fig. 3 be the first embodiment of the present invention is related to liquid-repellant resin sheet other forms outline longitudinal side section
Figure.
Fig. 4 is the approximate vertical view of the liquid-repellant resin sheet of Fig. 3.
Fig. 5 is that the outline longitudinal side of the stepped construction for the liquid-repellant resin sheet for indicating that second embodiment of the present invention is related to is cutd open
Face figure.
Fig. 6 is that the outline longitudinal side of the stepped construction for the liquid-repellant resin sheet for indicating that third embodiment of the present invention is related to is cutd open
Face figure.
Fig. 7 is that the outline longitudinal side of the stepped construction for the liquid-repellant resin sheet for indicating that the 4th embodiment of the invention is related to is cutd open
Face figure.
Fig. 8 is the figure for indicating the evaluation criteria of applied voltage test of the invention.
Specific embodiment
[first embodiment]
The liquid-repellant resin sheet of first embodiment of the invention has convex form layer (1) and liquid repellent as shown in fig. 1
Layer (2), convex form layer (1) has at least one kind of fine convex form (1a) and contains thermoplastic resin composition, with above-mentioned
The face of convex form (1a) has the liquid repellent layer (2) containing hydrophobic inorganic particle and binder resin, dredging in above-mentioned liquid repellent layer
The content of aqueous inorganic particle is more than 80 mass % and is 95 mass % hereinafter, the content of binder resin is 5 mass % or more
And less than 20 mass %, liquid-repellant resin sheet has liquid-repellant.
<Convex form layer>
Thermoplastic resin composition can be used to be formed in convex form layer.For thermoplastic resin composition, it can enumerate poly-
Olefin-based resin, polystyrene resin, polyester based resin, polyvinylidene fluoride resin etc..For example, when being used as food containers,
Preferred polyolefm system resin particularly preferably contains 35 mass % of polyolefin-based resins or more.By making polyolefin-based resins 35
The transferability of convex form can be improved in quality % or more.In addition, melt quality of the polyolefin resin composite in 230 DEG C of conditions
Flow rate is preferably 5g/10 minutes or more, and more preferably 15g/10 minutes or more.By making melt mass flow rate
5g/10 minutes, the transferability of convex form can be improved.It should be noted that melt mass flow rate passes through survey according to JIS K 7210
Outflow quality (g/10 minutes) at regular intervals is determined to calculate.As the condition of standard, melt mass flow rate is in examination
Test 190 DEG C to 230 DEG C of temperature, load 2.16kg~10.00kg is measured.
Polyolefin-based resins refer to the resin mainly contained comprising alpha-olefin as the polymer of monomer, particularly preferably contain
Polyethylene-based resin and polypropylene-based resin.For polyvinyl resin, can enumerate high density polyethylene (HDPE), low density polyethylene (LDPE),
Straight-chain low density polyethylene (LDPE), straight-chain medium density polyethylene, using ethylene as copolymer obtained by principal component or graft copolymerization
Object also includes their mixture.For above-mentioned copolymer, such as vinyl-vinyl acetate copolymer, ethylene-can be enumerated
Acrylic copolymer, vinyl-acrylate copolymer, ethylene-methyl acrylate copolymer, ethane-acetic acid ethyenyl ester-chloroethene
Alkene copolymer etc. can enumerate such as styrene-ethylene graft copolymer for above-mentioned graft copolymer.
In addition, homo-polypropylene, random polypropylene, block polypropylene etc. can be enumerated for acrylic resin.Use homopolymerization
When propylene, the structure of the homo-polypropylene can be any one of isotaxy, atactic, syndiotaxy.Use random poly- third
When alkene, for the alhpa olefin being copolymerized with propylene, preferred carbon number 2~20 can be enumerated, more preferable carbon number 4~12 can example citing
Such as ethylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 1- octene, 1- nonene, 1- decene.It, can when using block polypropylene
Enumerate block copolymer (block polypropylene), the block copolymer containing rubber constituent or graft copolymer etc..These alkene trees
Other olefin-based resins also can be used together other than being used alone in rouge.
Thermoplastic resin composition can contain other additives in the range of not harming effect of the invention.With regard to it
For his additive, stabilizer, surfactant, lubricant, filler, foaming agent, colorant, nucleating agent can be enumerated
Deng.
(convex form)
Convex form layer has a kind or more of fine convex form.Convex form can be a kind of convex as illustrated in figure 1
Shape preferably has different 1st convex form of shape and the 2nd convex form as illustrated.In addition, convex form can also have
There is different 3 kinds of shape or more of convex form.When convex form has the 1st convex form and 2 convex form herein, the 1st convex form
Height it is higher than the height of the 2nd convex form.To the configuration of the 1st convex form and the 2nd convex form there is no limit, the 1st convex form with
2nd convex form alternately configures preferred from liquid-repellant aspect.There is no particular limitation for the configuration of convex form, has vertical
The gridiron pattern configured breadthways configures, is interconnected.It is preferably interconnected to further maintain liquid-repellant.Wherein, convex form layer
Forming method there is no particular limitation, well known method can be used.It can enumerate and for example resin sheet surface is passed through with use
The method that laser engraving method forms the transfer roll of concaveconvex shape and contact roller is cast (casting) to be formed；Utilize band
Shape mold heats piece, and concave-convex method etc. is transferred by pressurizeing.
The height (h) of convex form is preferably 20 μm~150 μm.It, can be fully by making 20 μm of convex form height or more
Ensure liquid-repellant, by making 150 μm of convex form height or more, the convex form ruler in the mold for assigning convex form can be made
Very little stabilization.It should be noted that added the thickness (100nm~4000nm) of aftermentioned liquid repellent layer in convex form height.With regard to convex
For the thickness of shape layer, there is no particular limitation, the height comprising above-mentioned convex form, can be 50 μm~1000 μm.
The vertex spacings (t) of adjacent convex form are preferably 20 μm~100 μm.Wherein, vertex spacings refer to adjacent place
It is the convex form but as long as being neighbor even if mutual convex form is not identical in the interval of the convex form of the shortest distance
Interval.By making 20 μm of vertex spacings or more, the convex form dimensionally stable in the mold for assigning convex form can be made.
In addition, can prevent liquid-repellant from reducing by being 100 μm or more.
Wherein, convex form height and the vertex spacings of convex form can be used laser microscope (for example, Keyemce company
(KEYENCE CORPORATION) VK-X100 processed) it is measured.
When using 2 kinds of convex form, the ratio between the height of the 2nd convex form relative to the 1st convex form be preferably 0.4 or more and
0.8 or less.By making the ratio between height for 0.4 or more and 0.8 hereinafter, can get more effective liquid-repellant.
The bottom surface of convex form can for the cone-shapeds such as triangular pyramid, rectangular pyramid, hexagonal pyramid, eight pyramids, circular cone, frustum of a pyramid shape,
Truncated cone shape, the present inventor to the structure of resin sheet of the present embodiment carry out after various researchs as a result, knowing spy
Not not preferably hexagonal pyramid shaped convex form.
<Liquid repellent layer>
Liquid repellent layer is formed on the surface of convex form layer with substantially certain thickness, so as to substantially remain convex as former state on piece surface
The convex form of shape layers.Even if liquid repellent layer is arranged to still maintain liquid-repellant after for molding component, using hydrophobicity without
Machine particle and binder resin are formed.The thickness of liquid repellent layer is preferably 100nm~4000nm, as long as obtaining effect of the invention just
There is no particular limitation.Wherein, " liquid-repellant " adheres to referred to herein as carbohydrate system liquid (liquid containing carbohydrate) is substantially prevented from
In the liquid-repellant of the degree of resin sheet, specifically, it is intended that the liquid of these liquid for resin sheet contact angle be 130 ° with
Upper and/or rolling angle is 40 ° or less.Wherein, contact angle and rolling angle can for resin sheet using automatic contact angle meter (for example,
Consonance surface chemistry Co. Ltd. system DM-501) it is measured.In addition, " even if the pressure for applying 866Pa from liquid still maintains
Liquid-repellant " refers to the liquid-repellant stable for the pressure from liquid, it is intended that even if being applied with pressure for example for liquid
Liquid-repellant is still maintained in the case where the pressure of 866Pa.
The feature of liquid repellent layer is that the content of hydrophobic inorganic particle is more than 80 mass % and is 95 mass % hereinafter, binder
The content of resin is 5 mass % or more and not up to 20 mass %.Furthermore it is preferred that the content of hydrophobic inorganic particle is 85 mass %
~95 mass %, the content of binder resin are 5 mass of mass %~15 %.By the composition for the range, even if can get
The still stable liquid-repellant in the case where giving pressure from liquid.In contrast, if the content of hydrophobic inorganic particle is 80
Quality % can not obtain substantially stabilized liquid-repellant when hereinafter, then from liquid giving pressure sometimes, if hydrophobic inorganic particle
Content is more than 95 mass %, and hydrophobic inorganic particle peels off sometimes.
As the method for forming liquid repellent layer in convex form face, with the following method：It is previously prepared to add in isopropanol (IPA)
Dispersion liquid made of hydrophobic inorganic particle is added, has then been mixed with binder resin with arbitrary ratio, in above-mentioned convex form
Face is coated by spreader etc..
(hydrophobic inorganic particle)
As hydrophobic inorganic particle, as long as there is hydrophobic group person, it can be for by being surface-treated through hydrophobization person.
For example, it is preferable to which there is trimethyl silyl, dimethyl siloxane, aIkylsilyl groups, aminoalkylsilane on surface
Base, methylacryloyl silicyl, dimethylpolysiloxane--based or dimetylsilyl hydrophobic silica particle.
Furthermore, it is possible to use the applications such as hydrophilic inorganic particle silane coupling agent are surface-treated, surface state is made to become hydrophobicity
Particle.As long as the type of inorganic matter is also just not limit with hydrophobicity person.In them, it can be used hydrophobic fumed
Silica, fused silica, aluminium oxide, titanium dioxide etc. it is at least one kind of.For these particles as long as having hydrophobicity
Just there is no limit the shape of spherical, aspherical (broken shape) can be used shape.Average primary particle diameter be preferably 5nm~
1000nm, more preferably 7nm~200nm, further preferably 7nm~25nm.By make average primary particle diameter 5nm~
1000nm, while acquisition meets the liquid-repellant of condition of the invention, the dispersibility in binder resin becomes good.Its
In, average primary particle diameter refers to using scanning electron microscope, changes the visual field and shoots multiple images, soft using image analysis
The diameter for 3000~5000 hydrophobic inorganic particles that part measurement is arbitrarily extracted out is worth obtained by average value by calculating.Make
For their concrete example, such as silica, product name " AEROSIL R972 ", " AEROSIL can be enumerated
R972V ", " AEROSIL R972CF ", " AEROSIL R974 ", " AEROSIL RX200 ", " AEROSIL RY200 " (the above are
Japanese Ai Luoxier company (NIPPON AEROSIL CO., LTD.) system), " AEROSIL R202 ", " AEROSIL R805 ",
" AEROSIL R812 ", " AEROSIL R812S ", " AEROSIL RY300 " (the above are Evonik Degussa Corp. (EVONIK
Degussa Co., Ltd.) system) etc..For titanium dioxide, the product name that can illustrate out " AEROXIDE TiO2 T805 " (wins wound
Goldschmidt chemical corporation system) etc..For aluminium oxide, it can illustrate product name " AEROXIDEAlu C " (Evonik Degussa Corp.'s system)
Particle surface is set to become hydrophobic particle Deng processing is carried out with silane coupling agent.
(binder resin)
Binder resin indicates to be scattered in dispersion obtained by water for wantonly a kind or more of olefin copolymer and fluorine system copolymer
Liquid.In the present specification, the content of binder resin indicates the solid using resin as main body in the binder resin used
The content of ingredient.
Olefin copolymer refers to the polymer for containing alpha-olefin as monomer, includes polyethylene-based polymer, polypropylene
Based polymer.Such as low density polyethylene (LDPE), ultra-low density polyethylene (copolymer of ethylene and alpha-olefin), ethylene-second can be enumerated
Vinyl acetate copolymer (EVA), ethylene-acrylic acid alkyl ester copolymer, ethylene alkyl methacrylate copolymer, ethylene-
The ionomers such as acrylic copolymer, ethylene-methacrylic acid copolymer, low density polyethylene (LDPE), propylene-based elastomers material etc..Make
For the commercially available product for corresponding to it, " CHEMIPEARL S-100 " (Mitsui Chemicals, Inc's system), " AQUATEX AC- can be enumerated
3100 ", " AQUATEX EC-3500 " (Japanese coating Resins Corporation (Japan Coating Resin Corporation) system),
(Japanese You Niqika is public by " Arrow base SE-1200 ", " Arrow base SD-1200 ", " Arrow base YA-4010 "
Take charge of (UNITIKA LTD.) system) etc..
Fluorine system copolymer is the hydrocarbon system resin containing fluorine, preferably comprises copolymer as described below (1) and copolymer (2).
Copolymer (1) and copolymer (2) contain structural unit (a)~(d) as described below.But, copolymer (1) contains structure list
First (a) and structural unit (b), copolymer (2) contain structural unit (a) and structural unit (c).Copolymer (1) is mainly for tree
Showing for the liquid-repellant of rouge piece is made contributions, and copolymer (2) is made contributions mainly for the durability of resin sheet.
Structural unit (a) is that some or all of hydrogen atom of alkyl is substituted by group obtained by fluorine atom, carbon atom
Number is 1~6.Structural unit (a) can also be the chain polyfluohydrocarbon with unsaturated groups such as 1 or more carbon-to-carbon unsaturated double-bonds
Base.As unsaturated group, preferred (methyl) acrylate.
Structural unit (b) is preferably the monomer for the saturated hydrocarbyl for being 16~40 with carbon atom number, more preferably contains carbon
(methyl) acrylate of the alkyl of atomicity 16~40, further preferably (methyl) stearyl acrylate, (methyl) propylene
Sour docosane ester.
Structural unit (c) is the monomer from the monomer without fluorine atom and with crosslinkable functional group.With regard to cross-linking
Functional group for, preferred isocyanate base, blocked isocyanate base, alkoxysilyl, amino, methylolamide
Base, silanol group, ammonium, amide groups, epoxy group, hydroxyl, oxazolinyl, carboxyl, alkenyl, sulfonic group etc..In addition, more preferable ring
Oxygroup, hydroxyl, blocked isocyanate base, alkoxysilyl, amino, carboxyl.
For forming the monomer of structural unit (c), preferably enumerates (methyl) esters of acrylic acid, there are 2 or more
Copolymerizable group compound, ethylene ethers or vinyl esters.
Structural unit (c) may be from mixture of more than two kinds.Structural unit (c) mainly influences making film property, refusing for liquid repellent film
The cementability with substrate of fluidity composition, adaptation are made contributions for improving durability.
Structural unit (d) be from structural unit (a), (b) and (c) other than polymerizable group monomer structure
Unit.Furthermore it is preferred that from making, film property is good, obtains the monomer of uniform copolymer solution or dispersion liquid.With regard to structural unit (d)
For, particularly preferably from vinyl chloride, vinylidene chloride, cyclohexyl methacrylate, polyoxyethylene two (methyl) acrylate,
The alkyl ether, di-2-ethylhexyl maleate of polyoxyethylene two (methyl) acrylate.Structural unit (d) can be for composition for base
The improvement of the adaptation of material, the improvement of dispersibility are made contributions.
For corresponding to its commercially available product, " AsahiGuard AG-E070 ", " AsahiGuard AG- can be enumerated
E550D " (Asahi Glass corporation), " UNIDYNE TG-5546 ", " UNIDYNE TG-5671 ", " UNIDYNE TG-6071 " are (big
Golden industrial group (DAIKIN INDUSTRIES, LTD.) system) etc..
<Water system liquid>
Water system liquid in present embodiment be using water as solvent and the liquid with mobility, to the viscosity of liquid without
Limitation.It especially include the liquid of the food such as the liquid containing carbohydrate.Specifically comprising Yoghourt, jelly, pudding, jam, syrup,
Tomato sauce, fruit juice, congee, honey, molasses, liquid sugar etc..
[second embodiment]
As the example for the resin sheet that second embodiment of the present invention is related to, for as shown in figure 5 in superficial layer
The resin sheet that encapsulant resins layer (3) are formed between the convex form layer (1) of liquid repellent layer (2) and substrate layer (4) is folded.Namely
It says, the layer structure for the resin sheet that second embodiment is related to is liquid repellent layer (2), convex form layer (1), encapsulant resins from the top down
Layer (3), substrate layer (4).Herein, liquid repellent layer and convex form layer are because identical as person illustrated in the first embodiment, Gu Sheng
Slightly illustrate.But, the thickness of convex form layer is preferably 50 μm~200 μm.By being 50 μm or more, the transfer of convex form can be prevented
Become bad.In addition, can prevent production cost from getting higher by being 200 μm or more.
<Substrate layer>
(impact resistance polystyrene, polybutadienes-polystyrene-polyacrylonitrile connect substrate layer optimization styrene system resin
Branch polymer etc.), olefin-based resin (polyethylene, polypropylene etc.), polycarbonate, polyester based resin (poly terephthalic acid second two
Alcohol ester, polybutylene terephthalate (PBT) etc.), nylon system resin (nylon 6, nylon -66 etc.), ethylene-vinyl alcohol copolymer, third
The thermoplastic resins such as olefin(e) acid system resin.In addition, when being laminated, have the stacking by co-extrusion modling, used tensionless winkler foundation film,
Extrusion laminate molding, the stacking of dried layer synthesis type of biaxially-stretched film.
As substrate layer, preferably polyester based resin.For example, poly- terephthaldehyde can be used in the polyester based resin for becoming substrate layer
Sour glycol ester, polybutylene terephthalate (PBT), poly- 2,6-naphthalenedicarboxylic acid glycol ester, poly terephthalic acid methylene glycol ester,
And it will the diol component such as diethylene glycol (DEG), neopentyl glycol, polyalkylene glycol, adipic acid, decanedioic acid, phthalic acid, isophthalic
Polyester resin obtained by dicarboxylic acid components such as dioctyl phthalate, 2,6- naphthalenedicarboxylic acid etc. are copolymerized as copolymer composition etc..
In substrate layer, as needed, the coloring such as pigment, dyestuff can be added in the range that does not impair the effects of the present invention
The colorants such as fibee reinforced dose of the release agents such as agent, silicone oil, glass fibre etc., talcum, clay, silica, sulfonic acid and alkali gold
Additive as the antistatic agents such as salt compound, the polyalkylene glycol of category etc. and ultraviolet absorbing agent, antibacterial agent.In addition,
Generated spent resin in multi-layer resinous manufacturing step of the invention can also be used in mixed way.
<Encapsulant resins layer>
Encapsulant resins layer shows the cementability of convex form layer and substrate layer.For resin component, there is 100 mass %'s
The thermoplastic elastomer (TPE) of modified olefin based polymer resin, 100 mass parts.
For encapsulant resins layer, preferred modified olefin based polymer.For modified olefin based polymer resin, make
It can enumerate to represent by the alkene of the carbon numbers such as ethylene, propylene, 1- butylene 2~8 or so, these alkene and ethylene, propylene, 1- fourth
The carbon numbers such as alkene, 3-methyl-1-butene, 1- amylene, 4-methyl-1-pentene, 1- hexene, 1- octene, 1- decene 2~20 or so its
The copolymer of his alkene, these alkene and vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylate, methyl-prop
The olefin-based resins such as the copolymer of the vinyl compounds such as olefin(e) acid ester, styrene；Ethylene-propylene copolymer, ethylene-propylene-two
The olefin-baseds rubber such as alkene copolymer, ethylene-butene-1 copolymer, propene-1-butene copolymer acrylic acid, methacrylic acid,
The unsaturated carboxylic acids such as crotonic acid, iso-crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid or its acyl
The derivatives such as halogen, amide, acid imide, acid anhydrides, ester, specifically malenyl chloride, maleimide, maleic anhydride, citraconic acid
Acid anhydride, monomethyl maleate, dimethyl maleate, maleic acid polyglycidyl is modified equal under the conditions of graft reaction and obtains person.
Wherein, preferably with unsaturated dicarboxylic or the ethylene-the third of its acid anhydrides, especially maleic acid or its anhydride modified mistake
Alkene-diene copolymers or ethylene-propylene or butene-1 copolymer rubber.
The thickness of encapsulant resins layer is preferably 20 μm~90 μm, more preferably 40~80 μm.If not existing sometimes up to 20 μm
It is removed between convex form layer and substrate interlayer generating layer, in addition, if production cost is got higher sometimes more than 90 μm.
[third embodiment]
The resin sheet that third embodiment of the present invention is related to is without using second embodiment as shown in Figure 6
Shown in encapsulant resins layer (3), the resin sheet that convex form layer (1) and substrate layer (4) are directly laminated.Namely
It says, the layer structure for the resin sheet that third embodiment is related to is liquid repellent layer (2), convex form layer (1), substrate layer (4) from the top down,
With from the thermoplastic resin sheet that second embodiment is related to remove encapsulant resins layer made of layer structure.Herein, liquid repellent
Layer and convex form layer are because identical as the layer in first embodiment and second embodiment, and description will be omitted.On the other hand,
Substrate layer (4) in present embodiment preferably has sufficient cementability with convex form layer.
Therefore, it is preferable to use benzene excellent in adhesion with convex form layer in the resin sheet that third embodiment is related to
Vinylite is as substrate layer.As phenylethylene resin series, preferably 60 mass of mass %~15 %, more preferable 55 are preferably comprised
The polystyrene resin of the mass of quality %~15 % and 40 mass of mass %~85 %, the more preferable 45 mass mass of %~85 %
Polystyrene substrate layer made of polystyrene resin of impact resistance.Furthermore, it is possible to use be added to hydrogenated styrene system thermoplastic
Styrene resin composite obtained by property elastomer.And with polystyrene resin and hydrogenated styrene based thermoplastic elastomer
When, the hydrogenation of benzene second of polystyrene resin and 5 mass of mass %~10 % preferably containing 90 mass of mass %~95 %
Styrene resin composite made of alkene based thermoplastic elastomer.At this point, if hydrogenated styrene based thermoplastic elastomer
Additive amount is sometimes insufficient with the cementability of convex form layer not up to 5 mass %, splitting is generated, if having more than 10 mass %
When production cost get higher.
[the 4th embodiment]
The resin sheet that 4th embodiment of the invention is related to is as shown in Figure 7, for by liquid repellent layer (2), convex form layer
(1), the sequential layer of the 1st encapsulant resins layer (3a), oxygen barrier substrate layer (5), the 2nd encapsulant resins layer (3b), substrate layer (4)
Resin sheet made of folded.1st encapsulant resins layer and the composition of the 2nd encapsulant resins layer can it is identical can also be different.Convex form
The thickness of layer is preferably 50~250 μm.If convex form transfer sometimes becomes bad not up to 50 μm.In addition, if having more than 200 μm
When production cost get higher.
<Substrate layer>
With regard to being used as in the 4th embodiment used in substrate layer for resin, preferably nylon system resin or methacrylic acid
Ester system resin.For nylon system resin, can enumerate the lactam polymers such as caprolactam, lauric lactam, 6- amino oneself
Polymer, hexamethylene diamine, decamethylene diamine, ten dimethylenes two of the amino carboxylic acids such as acid, 11- aminoundecanoic acid, 12-aminolauric acid
It is the aliphatic diamines such as amine, 2,2,4- or 2,4,4- trimethylhexane diamine, 1,3- or bis- (amino methyl) hexamethylenes of 1,4-, bis- (right
Aminocyclohexylmethane) etc. the diamine units such as aromatic diamines such as ester ring types diamines, m-xylene diamine or p dimethylamine and oneself
The ester ring types such as the aliphatic dicarboxylic acids such as diacid, suberic acid, decanedioic acid, cyclohexane dicarboxylic acid dicarboxylic acids, terephthalic acid (TPA), isophthalic two
The condensation polymer of the dicarboxylic acid units of the aromatic dicarboxylic acids such as formic acid etc. and their copolymer etc..Specifically there are nylon 6, nylon
9, nylon 11, nylon 12, nylon66 fiber, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD 6, nylon 6/
66, nylon 6/610, nylon 6/6T, nylon 6I/6T etc., wherein it is preferred that nylon 6, nylon MXD 6.
As long as polyvinyl of the methacrylate ester resin based on methacrylate monomers, ties it
Structure etc. is not particularly limited.For the methacrylate monomers, such as methyl methacrylate, methyl-prop can be enumerated
Olefin(e) acid ethyl ester, propyl methacrylate, butyl methacrylate, pentylmethacrylate and hexyl methacrylate etc..They
In, particularly preferred methyl methacrylate.In addition, the alkyl such as propyl, butyl, amyl and hexyl in methacrylate monomers
It can be straight chain, it can also branch.In addition, blending can be methyl in the methacrylate resin of the resin combination of present embodiment
The copolymer of the independent polymers of acrylate monomer, a variety of methacrylate monomers.Or can have from as methyl-prop
The ethylene of well known vinyl compound other than olefin(e) acid ester, propylene, butadiene, styrene, α-methylstyrene, acrylonitrile and
The monomeric unit of acrylic acid etc..
<Oxygen obstructs substrate layer>
For oxygen obstructs substrate layer, such as ethylene-vinyl alcohol copolymer resin, nylon system resin can be enumerated.Wherein, from
It sets out in terms of processability, mouldability, optimal ethylene-vinyl alcohol copolymer resin.
Ethylene-vinyl alcohol copolymer resin is usually obtained from being saponified vinyl-vinyl acetate copolymer, to be
Have oxygen barrier performance, processability, mouldability, ethylene contents are 10 moles of %~65 mole %, preferably 20 moles of %~50
Mole %, saponification degree are 90% or more, preferably 95% or more.
In addition, the lactam polymers such as caprolactam, lauric lactam, 6- ammonia can be enumerated for nylon system resin
Polymer, hexamethylene diamine, decamethylene diamine, ten dimethylenes of the amino carboxylic acids such as base caproic acid, 11- aminoundecanoic acid, 12-aminolauric acid
It is the aliphatic diamines such as diamines, 2,2,4- or 2,4,4- trimethylhexane diamine, 1,3- or bis- (amino methyl) hexamethylenes of 1,4-, double
The diamine units such as the aromatic diamines such as the ester ring types such as (to aminocyclohexylmethane) diamines, m-xylene diamine or p dimethylamine with
The ester ring types such as the aliphatic dicarboxylic acids such as adipic acid, suberic acid, decanedioic acid, cyclohexane dicarboxylic acid dicarboxylic acids, terephthalic acid (TPA), isophthalic
The condensation polymer of the dicarboxylic acid units of the aromatic dicarboxylic acids such as dioctyl phthalate etc. and their copolymer etc..
As nylon system resin, specifically there are nylon 6, nylon 9, nylon 11, nylon 12, nylon66 fiber, nylon 610, Buddhist nun
Dragon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD 6, nylon 6/66, nylon 6/610, nylon 6/6T, nylon 6I/6T etc.,
Wherein, preferably nylon 6, nylon MXD 6.
<Encapsulant resins layer>
For encapsulant resins layer, preferred modified olefin based polymer.For modified olefin based polymer resin, make
It can enumerate to represent by the alkene of the carbon numbers such as ethylene, propylene, 1- butylene 2~8 or so, these alkene and ethylene, propylene, 1- fourth
The carbon numbers such as alkene, 3-methyl-1-butene, 1- amylene, 4-methyl-1-pentene, 1- hexene, 1- octene, 1- decene 2~20 or so its
The copolymer of his alkene, these alkene and vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylate, methyl-prop
The olefin-based resins such as the copolymer of the vinyl compounds such as olefin(e) acid ester, styrene；Ethylene-propylene copolymer, ethylene-propylene-two
The olefin-baseds rubber such as alkene copolymer, ethylene-butene-1 copolymer, propene-1-butene copolymer acrylic acid, methacrylic acid,
The unsaturated carboxylic acids such as crotonic acid, iso-crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid or its acyl
The derivatives such as halogen, amide, acid imide, acid anhydrides, ester, specifically malenyl chloride, maleimide, maleic anhydride, citraconic acid
Acid anhydride, monomethyl maleate, dimethyl maleate, maleic acid polyglycidyl is modified equal under the conditions of graft reaction and obtains person.
Wherein, preferably with the ethylene system tree of unsaturated dicarboxylic or its acid anhydrides, especially maleic acid or its anhydride modified mistake
Rouge, propylene resin or ethylene-propylene or butene-1 copolymer rubber.
For the thickness of encapsulant resins layer, either side is preferably 10 μm~50 μm, more preferably 20 μm~40 μm.
If sufficient layers cementing intensity can not be obtained sometimes not up to 10 μm, in addition, if production cost is got higher sometimes more than 50 μm.
[manufacture of liquid-repellant resin sheet]
The manufacturing method of resin sheet of the invention is not limited, any means can be used, includes following steps typically
Suddenly：It is produced on the one side single-layer sheet of the convex form at least one or more or the stacking resin of the layer comprising this with convex form
Piece finally forms liquid repellent layer on the surface of convex form.
Firstly, being produced on the single-layer sheet of convex form of the one side at least one or more or containing this with convex form
When the stacking resin sheet of layer, arbitrary resin sheet forming method can be used.For example following method can be enumerated：In the case where single layer
Using 1 single screw extrusion machine, using plural platform single screw extrusion machine in the case where plural layer, each material resin is melted
It squeezes out, resin sheet is obtained by T-die.In the case of multiple layers, branch manifold die head can be used.Wherein, resin of the invention
The layer structure of each embodiment of piece basically described above, if in addition, for example, physical property etc. will not show deterioration, can will
The useless raw material generated in the manufacturing step of resin sheet, component of the invention is added to substrate layer, also can be used as additional layer and carries out
Stacking.
Then, convex form is formed in single-layer or multi-layer resin sheet, this method is also not particularly limited, and this field can be used
Any means known to technical staff.Such as have using the method that extrusion molding mode is manufactured, using photolithographicallpatterned
(phtolithography) method that is manufactured is solidified using the method that hot pressing mode is manufactured, using pattern roller and UV
The method etc. that resin is manufactured.
Finally, forming refusing for the hydrophobic inorganic particle containing certain content and binder resin on the surface of convex form layer
Liquid layer.The method for forming liquid repellent layer is not particularly limited, such as roller coating cloth, intaglio plate coating, stick coating, scraper can be used
Coating method well known to coating, hairbrush coating, powder electrostatic method etc..In addition, to solvent when preparing coating fluid also without special
Restriction, in addition to water, can also suitably select for example alcohol (ethyl alcohol), hexamethylene, toluene, acetone, IPA, propylene glycol, oneself two
The organic solvents such as alcohol, butyldiglycol (butyl diglycol), pentanediol, pentane, n-hexane, hexanol.At this point, can also be simultaneously
With micro dispersing agent, colorant, antisettling agent, viscosity modifier etc..
[article]
Liquid-repellant resin sheet of the invention be applicable to need it is above-mentioned shown in liquid-repellant article.Remember in detail below
It carries.
Liquid-repellant resin sheet of the invention can be used as the daily necessities such as the packaging materials such as food containers, sack, raincoat, umbrella,
Kitchen, bathroom, lavatory etc. with building materials applications such as component, wallpapers at water.
For example, can get prevents content by using liquid-repellant resin sheet of the invention in food containers, sack etc.
Be attached to the inner wall of container etc., make content the last effect for being easy to have used completely, in garbage classification when reduce cleaning and hold
The effect etc. of the effort of device.
For example, also can get by using liquid-repellant resin sheet of the invention in the rain gears such as raincoat, umbrella and be difficult to attached water
Drop, when folding, water droplet etc. is difficult to be attached to the effect of hand.
For example, can get by using liquid-repellant resin sheet of the invention in the siding in bathroom and be difficult to adhere to water droplet etc.
Effect.
For example, can get by using liquid-repellant resin sheet of the invention in built-in material etc. and be difficult to adhere to dirt etc.
Effect.
Embodiment
The present invention is specifically described below by way of Examples and Comparative Examples are enumerated, but there is no because of embodiment etc. by the present invention
Content and have any restriction.
Various raw materials used in embodiment etc. are as described below.
(1) convex form layer
(A) random polypropylene " PM921V " (sun allomeric company (SunAllomer Ltd.) system), melt quality
Flow rate：25g/10min (test temperature：230 DEG C, load：2.16kg).
(2) liquid repellent layer
(B) hydrophobic inorganic particle：Hydrophobic silica " AEROSIL R812S " (Evonik Degussa Corp.'s system) is put down
Equal primary particle size：7nm, trimethyl silyl are modified.
(C) hydrophobic inorganic particle：Hydrophobic silica " AEROSIL R8200 " (Evonik Degussa Corp.'s system) is put down
Equal primary particle size：12nm, trimethyl silyl are modified.
(D) hydrophobic inorganic particle：Hydrophobic silica " AEROSIL NAX50 " (Japanese Ai Luoxier corporation),
Average primary particle diameter：30nm, trimethyl silyl are modified.
(E) binder resin：Olefin copolymer " AQUATEX AC-3100 " (Japanese coating Resins Corporation system), ethylene-
Methacrylic copolymer resins.
(F) binder resin：Fluorine system copolymer " AsahiGuard AG-E550D " (Asahi Glass Co., Ltd's system), (first
Base) acrylic ester fluo-copolymer resin.
For resin sheet made in embodiment etc. various characteristics evaluation method is as follows described.
(1) convex form is observed
The convex form of piece uses laser microscope VK-X100 (Keyemce corporation) measurement convex form height, convex form
Vertex spacings.In addition, making convex form section sample using slicer to measure convex form height and vertex spacings.Convex
The height of shape is to measure 10 height of same shape respectively from any the 3 of resin sheet, flat using the arithmetic of its 30 measured values
Mean value.When convex form is two or more, distinctly acquired in the same way for the height of the 1st convex form and the 2nd convex form.
For vertex spacings, from any the 3 of resin sheet, the vertex spacings of 10 adjacent convex forms is measured, its 30 measured values are used
Arithmetic mean of instantaneous value.When convex form is two or more, the vertex spacings of the 1st convex form and the 2nd convex form are measured, use its 30
The arithmetic mean of instantaneous value of measured value.
(2) contact angle and rolling angle
For resin sheet, contact angle is measured using automatic contact angle meter DM-501 (consonance interface science society system) and is tumbled
Angle.In addition, experimental liquid uses pure honey (Xin honey society system), tomato sauce (Kagome K. K. (カ go メ society) system),
Dripping quantity is 8 μ L in contact angle determination, is 20 μ L in rolling angle measurement.It is can determine that if contact angle is 130 ° or more to refuse
Fluidity is high, can prevent the attachment of liquid.In addition, can determine that if rolling angle is 40 ° or less for liquid-repellant height, liquid can be prevented
Attachment.
(3) applied voltage test
1g experimental liquid is placed on resin sheet, and cylindric polypropylene shell is further placed from liquid (hereinafter referred to as
For circular cylindrical shell) carry out applied voltage test.Circular cylindrical shell is diameter 32mm, weight 70g, and the pressure applied for liquid is
866Pa.After pressurization, for the residual liquid being attached to when taking circular cylindrical shell away on resin sheet, as illustrated in fig. 8, if
The state absolutely not adhered to is " 5 ", and adhering to most states is " 1 ", is evaluated by visual observation with 5 grades.In 5 grade
In evaluation, as long as to be just judged as that attachment is suppressed more than " 4 ".
<Embodiment 1 (the layer structure of Fig. 1)>
Using 1 65mm single screw extrusion machine, pass through T-die method extrusion resin piece.For the extrudate piece, by with adopting
The transfer roll of concaveconvex shape is imparted for surface with laser engraving method and contact roller is cast, obtaining has in surface imparting
The resin sheet of the convex form layer of convex form.
Then, it in order to form liquid repellent layer on the surface of convex form layer, has made hydrophobic silica and binder tree
Rouge becomes 90 volume %, binder resin as the ratio of components of 10 mass % to mix with the hydrophobic silica in liquid repellent layer
Made of dispersion liquid (solvent is Purified Water/isopropanol mixed liquor).The mixed dispersion liquid is coated on using rod coaters convex
It is formed liquid repellent layer in 90 DEG C of dryings by shape layer surface.
<Embodiment 2~8, the Comparative Examples 1 to 5>
The presence or absence of the presence or absence of the composition of liquid repellent layer, liquid repellent layer and convex form are set like that as shown in table 1, remove this
In addition, the resin sheet that embodiment 2~8 and the Comparative Examples 1 to 5 are related to is made similarly to Example 1 and is evaluated.By liquid repellent layer
Composition it is shown in table 1, show the result in table 2.
It should be noted that change the silicon dioxide microparticle content and binder resin content in liquid repellent layer in comparative example 1~3,
Liquid repellent layer, no imparting convex form in comparative example 5 are not formed in comparative example 4.
[table 1]
[table 2]
The result shown in the table 2 may know that content below.
About the liquid-repellant (contact angle, rolling angle, applied voltage test) on piece for each liquid, Examples 1 to 8 is all obtained
Obtain the result of 130 ° of contact angle or more, 40 ° of rolling angle or less, 4 or more applied voltage test.In contrast, pressurizeing in comparative example 1
Liquid repellent layer peels off in test, is unable to maintain that the liquid repellent layer to be formed.In comparative example 2, although obtaining 130 ° of contact angle or more, rolling angle
40 ° below as a result, but becoming 3 or less in applied voltage test.In comparative example 3, although obtain 130 ° of contact angle or more as a result,
But rolling angle is 40 ° or more, becomes 2 or less in applied voltage test.In addition, in comparative example 4 and 5, about contact angle, rolling angle and
Any one of applied voltage test all there is no effect.
Although illustrating the present invention using various embodiments above, technical scope of the invention is not limited to certainly
Range documented by above embodiment.To those skilled in the art, above embodiment can be made various changes
Or improvement is obvious.In addition, from form obtained by such change or improvement is subject to known to the record of claim
It may be included in technical scope of the invention.
Description of symbols
1a convex form；The protrusion 1b vertex；The 1st protrusion vertex 1c；The 2nd protrusion vertex 1d；H convex form height；T convex form top
Point interval；2 liquid repellent layers；3 encapsulant resins layers；The 1st encapsulant resins layer of 3a；The 2nd encapsulant resins layer of 3b；4 substrate layers；5 oxygen
Barrier property substrate layer.
Claims (17)
1. a kind of liquid-repellant resin sheet, wherein
It has at least one kind of fine convex form and contains thermoplastic resin with convex form layer and liquid repellent layer, the convex form layer
Oil/fat composition has in the face with convex form of the convex form layer and refuses containing hydrophobic inorganic particle and binder resin
Liquid layer,
The content of hydrophobic inorganic particle in the liquid repellent layer is more than 80 mass % and is 95 mass % hereinafter, binder resin
Content be 5 mass % or more and less than 20 mass %.
2. liquid-repellant resin sheet according to claim 1, wherein
It has liquid-repellant for the water system liquid containing sugar.
3. liquid-repellant resin sheet according to claim 1 or 2, wherein
Melt mass flow rate of the thermoplastic resin composition under the conditions of 230 DEG C is 5g/10 minutes or more.
4. liquid-repellant resin sheet described in any one of claim 1 to 3, wherein
The thermoplastic resin composition contains polyolefin resin composite.
5. liquid-repellant resin sheet according to claim 4, wherein
The polyolefin resin composite contains the polyolefin-based resins of 35 mass of mass %~100 %.
6. liquid-repellant resin sheet according to any one of claims 1 to 5, wherein
The hydrophobic inorganic particle is the hydrophobic silica particle for having trimethyl silyl on surface.
7. liquid-repellant resin sheet described according to claim 1~any one of 6, wherein
The average primary particle diameter of the hydrophobic inorganic particle is 5nm~1000nm.
8. liquid-repellant resin sheet according to any one of claims 1 to 7, wherein
The binder resin includes the resin selected from one or more of olefin copolymer and fluorine system copolymer.
9. liquid-repellant resin sheet described according to claim 1~any one of 8, wherein
The convex form is made of the 1st convex form and the 2nd convex form, the height of the 1st convex form and the height difference of the 2nd convex form
It is 20 μm~150 μm, the vertex spacings of adjacent convex form are 20 μm~100 μm.
10. liquid-repellant resin sheet described according to claim 1~any one of 9, wherein
The convex form layer with a thickness of 50 μm~200 μm.
11. liquid-repellant resin sheet described according to claim 1~any one of 10, wherein
The contact angle when surface of side with the liquid repellent layer and the liquid containing carbohydrate contact is 130 ° or more, and is rolled
The angle of fall is 40 ° or less.
12. liquid-repellant resin sheet described according to claim 1~any one of 11, wherein
On the surface of the convex form layer, even if the pressure for applying 866Pa from liquid has still maintained liquid-repellant.
13. liquid-repellant resin sheet described according to claim 1~any one of 12, wherein
1 layer or more of substrate layer, the substrate layer packet has been laminated in another side in the face with convex form of the convex form layer
Containing selected from phenylethylene resin series, olefin-based resin, polyester based resin, nylon system resin, ethylene-vinyl alcohol copolymer resin and third
The resin of one or more of olefin(e) acid system resin.
14. liquid-repellant resin sheet according to claim 13, wherein
Encapsulant resins layer is formd between the convex form layer and the substrate layer, the encapsulant resins layer, which contains, to be selected from
At least one kind of resin in modified olefin based polymer resin and thermoplastic elastomer (TPE).
15. a kind of article, wherein
It uses the liquid-repellant resin sheets described in any one of claim 1~14.
16. article according to claim 15, wherein
It is daily necessity, packaging material or building materials.
17. article according to claim 16, wherein
It is food containers, sack, raincoat, umbrella, wallpaper or with the component at water.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016050225 | 2016-03-14 | ||
| JP2016-050225 | 2016-03-14 | ||
| PCT/JP2017/010114 WO2017159654A1 (en) | 2016-03-14 | 2017-03-14 | Liquid-repellent resin sheet and article using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108883596A true CN108883596A (en) | 2018-11-23 |
| CN108883596B CN108883596B (en) | 2021-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780016423.4A Active CN108883596B (en) | 2016-03-14 | 2017-03-14 | Liquid-repellent resin sheet and article using same |
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| Country | Link |
|---|---|
| JP (1) | JP6941597B2 (en) |
| CN (1) | CN108883596B (en) |
| TW (1) | TW201800224A (en) |
| WO (1) | WO2017159654A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113543964A (en) * | 2019-03-07 | 2021-10-22 | 东洋纺株式会社 | Laminated film |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019073331A (en) * | 2017-10-19 | 2019-05-16 | 住友ベークライト株式会社 | Packing material and packing body |
| KR102374818B1 (en) * | 2017-11-28 | 2022-03-15 | 주식회사 엘지에너지솔루션 | Laminate Sheet with Modified Internal Surface and Pouch-Type Battery Comprising the Same |
| KR20210023854A (en) | 2018-06-20 | 2021-03-04 | 도판 인사츠 가부시키가이샤 | Liquid-repellent structure and its manufacturing method, and packaging material and release sheet |
| EP3829868A1 (en) * | 2018-08-03 | 2021-06-09 | Cryovac, LLC | Super-hydrophobic thermoplastic films for packaging and packages made therefrom |
| US20210309428A1 (en) * | 2018-09-21 | 2021-10-07 | Toppan Printing Co., Ltd. | Liquid repellent layer-forming resin composition, and liquid repellent film, liquid repellent laminate, packaging material, and container using same |
| WO2021182043A1 (en) * | 2020-03-12 | 2021-09-16 | 凸版印刷株式会社 | Liquid-repellant structure, production method for liquid-repellant structure, coating liquid for liquid repellant layer formation, and packaging material |
| EP4119604A4 (en) * | 2020-03-12 | 2023-08-30 | Toppan Inc. | Liquid-repellant structure, production method for liquid-repellant structure, coating liquid for liquid-repellant layer formation, and packaging material |
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- 2017-03-14 WO PCT/JP2017/010114 patent/WO2017159654A1/en active Application Filing
- 2017-03-14 CN CN201780016423.4A patent/CN108883596B/en active Active
- 2017-03-14 JP JP2018505935A patent/JP6941597B2/en active Active
- 2017-03-14 TW TW106108362A patent/TW201800224A/en unknown
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| JP2003001736A (en) * | 2001-06-27 | 2003-01-08 | Toto Ltd | Water repellent highly bright transparent material |
| JP2013035559A (en) * | 2011-08-05 | 2013-02-21 | Showa Denko Packaging Co Ltd | Content sticking preventive lid material and method of manufacturing the same |
| JP2013208816A (en) * | 2012-03-30 | 2013-10-10 | Toppan Printing Co Ltd | Heat sealing film |
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| CN113543964A (en) * | 2019-03-07 | 2021-10-22 | 东洋纺株式会社 | Laminated film |
| CN113543964B (en) * | 2019-03-07 | 2024-05-10 | 东洋纺株式会社 | Laminated film |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017159654A1 (en) | 2017-09-21 |
| CN108883596B (en) | 2021-06-18 |
| TW201800224A (en) | 2018-01-01 |
| JP6941597B2 (en) | 2021-09-29 |
| JPWO2017159654A1 (en) | 2019-01-17 |
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