CN104760370A - COLOR CHANGING LAMINATE PRODUCTS based on PHYSICAL STRESS AND MANUFACTURING METHOD THEREOF - Google Patents
COLOR CHANGING LAMINATE PRODUCTS based on PHYSICAL STRESS AND MANUFACTURING METHOD THEREOF Download PDFInfo
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- CN104760370A CN104760370A CN201410196112.9A CN201410196112A CN104760370A CN 104760370 A CN104760370 A CN 104760370A CN 201410196112 A CN201410196112 A CN 201410196112A CN 104760370 A CN104760370 A CN 104760370A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D3/00—Book covers
- B42D3/12—Book covers combined with other articles
- B42D3/16—Book covers combined with other articles with means for holding books open
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D1/00—Books or other bound products
- B42D1/06—Books or other bound products in which the fillings and covers are united by other means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42P—INDEXING SCHEME RELATING TO BOOKS, FILING APPLIANCES OR THE LIKE
- B42P2241/00—Parts, details or accessories for books or filing appliances
- B42P2241/20—Protecting; Reinforcing; Preventing deformations
Abstract
The present invention relates to a color changing laminate product based on physical stress and a manufacturing method thereof. The color changing laminate product includes a polyurethane surface layer, a polyurethane pull-up coating layer causing weathering phenomen, an adhesive layer, and a substrate layer, wherein the substrate layer, the adhesive layer, the polyurethane pull-up coating layer, and the polyurethane surface layer are laminated in order.
Description
Technical field
The present invention relates to a kind of changeable colour multi-layer product and preparation method thereof.More specifically, the present invention relates to a kind of multi-layer product by physical stress (such as extend or bend) changeable colour and preparation method thereof.
Background technology
According to correlation technique, the product of weathering phenomenon can be utilized after applying polyurethane resin (comprising silica and calcium carbonate) on the base layer simply to produce weathering phenomenon on surface, thus crack effect (crack) is provided.Therefore, this series products can not meet the demand that consumer changes for shades of colour, thus has limitation.And this series products does not combine with various pattern.For this reason, the manufacture of this series products is limited in field of leather, as footwear and handbag and some clothes.Especially, when main material is limited to the dermatine goods of fiber (as fabric or adhesive-bonded fabric), if just present monochromatic weathering phenomenon, then make the vision of product surface and functional character cannot meet the demand of consumer to various multicolour pattern, thus the range of application of product is reduced greatly.
According in the off-color product of disclosed prior art, the dispersion again comprising Prussian blue nano-dispersed composition or use polyaniline by coating is had to change (the Korean unexamined patent of publication number 10-2006-0058513 of color electrically, be the Korean Patent of No.10-0740324 with the patent No.), or the color of variable color coated product is according to variations in temperature (publication number is the Korean unexamined patent of No.10-2001-0103484).But, not yet develop the product changing color because of physical stress.
Summary of the invention
The present invention is to solve the problems referred to above occurred in prior art.According to the present invention, when external stress (as extended or bending) is applied to multi-layer product from outside, this multilayer comprises causing each layer centered by the resin of weathering phenomenon, that have mutual different colours, therefore the color on the surface of material can change, thus provides natural and luxurious multi-layer product.That is, changeable colour multi-layer product that an object of the present invention is to provide a kind of physically based deformation stress and preparation method thereof.
For achieving the above object, according to an aspect of the present invention, provide a kind of changeable colour multi-layer product of physically based deformation stress, it comprises: polyurethane skin layer; For generation of the general coat in polyurethane pula of weathering phenomenon; Adhesive phase; And basalis, wherein said polyurethane skin layer, the general coat in polyurethane pula, adhesive phase and basalis stack gradually.
According to another aspect of the invention, a kind of method preparing the changeable colour multi-layer product of physically based deformation stress is provided.The method comprises the following steps: (a) applies and drying polyurethane surface coating liquid on the surface of peeling paper being formed with floral designs, to form polyurethane skin layer; B () applies the general coating liquid in polyurethane pula on a surface of described polyurethane skin layer, to form the general coat in polyurethane pula; D () applies and partial desiccation polyurethane adhesive solution on a surface of the general coat in described polyurethane pula, and the general coat in described polyurethane pula and substrate are combined; And (e) solidifies the structure produced.
According to another aspect of the invention, a kind of method preparing the changeable colour multi-layer product of physically based deformation stress is provided.The method comprises the following steps: (a) applies and drying polyurethane surface coating liquid on the surface of peeling paper being formed with floral designs, to form polyurethane skin layer; B () applies the general coating liquid in polyurethane pula on a surface of described polyurethane skin layer, to form the general coat in polyurethane pula; (c) coating on a surface of the general coat in described polyurethane pula drying polyurethane coating liquid and form polyurethane-coated layer; D () applies and partial desiccation polyurethane adhesive solution on a surface of described polyurethane-coated layer, and described polyurethane-coated layer and substrate are combined; And (e) solidifies the structure produced.
According to the present invention, when applying stress (such as extend or bend) from outside, the color of changeable colour multi-layer product can be changed to the surface color of various beauty.In addition, because the present invention has excellent visual effect, so can be applicable to various product, as sport footwear, clothes, furniture, handbag, wallet, belt, accessory and mobile phone outer casing, decoration material or general commodity, thus the application of changeable colour multi-layer product can be expanded, and marketability also can increase.
Accompanying drawing explanation
Fig. 1-a is the photo of multi-layer product prepared according to comparative example 1, and schematically illustrates the schematic diagram of surface color of this multi-layer product.
Fig. 1-b is the photo of cross section of the surface discolouration coating material prepared according to comparative example 1, and the photo of the change of the color before and after extending test result is shown.
Fig. 2 is the schematic diagram of the metachromatic principle schematically illustrating surface discolouration coating.
Fig. 3 a is that the SEM of the cross section of changeable colour multi-layer product according to the embodiment of the present invention 1 measures photo, and Fig. 3 b is the photo of the discoloration test before and after the elongation of changeable colour multi-layer product prepared by embodiments of the invention 1.
Fig. 4 is the photo before and after the elongation of the changeable colour multi-layer product illustrated prepared by embodiments of the invention 2.
Fig. 5 is the photo of the discoloration test before and after the elongation of the changeable colour multi-layer product illustrated prepared by embodiments of the invention 3.
Fig. 6 is the photo of the discoloration test before and after the elongation of the changeable colour multi-layer product illustrated prepared by embodiments of the invention 4, and shows the existence of the effect that realistic printing floral designs disappear according to surface discolouration.
Fig. 7 is the photo of the discoloration test before and after the elongation of the changeable colour multi-layer product illustrated prepared by embodiments of the invention 5.
Detailed description of the invention
The present invention relates to a kind of by physical stress (as extended or bending) thus the product that changes of surface color.More specifically, the present invention relates to a kind of changeable colour multi-layer product, wherein, weathering phenomenon occurs in polyurethane pula general (pull up) coat, owing to cracking when being applied to the general coat in this polyurethane pula when external pressure, thus by the complementary color effect by polyurethane skin layer, surface color is changed to shades of colour.
The principle changed is carried out, as shown in Figure 2 according to the color of changeable colour multi-layer product of the present invention.According to changeable colour multi-layer product of the present invention, when the color of polyurethane skin layer (it is equivalent to photochromic layer) is yellow, and when the color of layer below this polyurethane skin layer is black, due to complementary color effect, this product is rendered as dirty-green.Then, when external stress is applied on product, the color of this product presents buff.In addition, when the color of this polyurethane skin layer (it is equivalent to photochromic layer) is fuchsin, and the color of layer below this polyurethane skin layer is green, due to complementary color effect, product is rendered as darkmagenta, then, when external stress is applied on product, the color of this product is changed to bright carmetta.
Changeable colour multi-layer product according to the present invention can comprise polyurethane skin layer, for causing the general coat in polyurethane pula of weathering phenomenon, polyurethane adhesive layer and basalis.Changeable colour multi-layer product can also comprise the layer of polyurethane between the general coat in polyurethane pula and polyurethane adhesive layer.As shown in Figure 3, changeable colour multi-layer product can be by polyurethane skin layer, for causing the general coat in polyurethane pula of weathering phenomenon, the form that polyurethane adhesive layer is mutually stacked with basalis.
According to changeable colour multi-layer product of the present invention, the color of the cutting optimal of polyurethane skin layer than polyurethane skin layer color more deeply and comparatively dark, thus when applying stress to it, complementary colours effect is easy to realization, makes various color present maximization thus.If the color of this polyurethane skin layer is darker than the color of the cutting optimal of polyurethane skin layer, the weathering phenomenon that the crackle due to the general coat in polyurethane pula produces just can not be easily visible to the naked eye, this is because weathering phenomenon may cover by surface color.Meanwhile, the most effective color alignment can be complimentary to one another compared with the pass between dark colour by what make the polyurethane skin layer of bright color and polyurethane skin layer cutting optimal, thus the changeability of surface color is realized close to maximum.Even when the coat of substrate comprises three layers or more, this principle is also applicable.
polyurethane skin layer
In changeable colour multi-layer product according to the present invention, described polyurethane skin layer can realize by using polyurethane surface coating liquid, this polyurethane surface coating liquid comprises the polyurethane dried resin of 30 to 70wt.% (% by weight), the dimethyl formamide (DMF) of 5wt.% to 20wt.% and the MEK (MEK) of 15wt.% to 50wt.%.Preferably, described polyurethane surface coating liquid can comprise the polyurethane dried resin of 45wt.% to 65wt.%, the DMF of 5wt% to 15wt.% and the MEK of 15wt.% to 40wt.%.
In addition, relative to the polyurethane dried resin of 100 weight portions, this polyurethane surface coating liquid can comprise the toner (toner) of 1 ~ 40 weight portion further.Preferably, relative to the polyurethane dried resin of 100 weight portions, this polyurethane skin layer can comprise the toner of 1 ~ 20 weight portion further.
In this polyurethane surface coating liquid, preferably, use cleaning, transparent polyurethane dried resin using as polyurethane dried resin.Such as, D-ACE8301 (Dong Sung chemical company) can be used for the top layer of dermatine, or UA501MB (fine chemistry company) can be used as polyurethane dried resin.If relative to the gross weight of this surperficial coating liquid, when the use amount of polyurethane dried resin is lower than 20wt.%, after desiccated surface coating liquid, the lower thickness of coat, thus mechanical strength (as wearability or elasticity) may be reduced.When the gross weight relative to surperficial coating liquid, when the use amount of polyurethane dried resin is more than 70wt.%, the viscosity of surperficial coating liquid is too high, and the production stability of coating engineering is deteriorated, and such coat also can be irregularly formed.
In addition, when the gross weight relative to surperficial coating liquid, when the use amount as the DMF of solvent is less than 5wt.%, the viscosity of surperficial coating liquid may be too high.When the use amount of DMF is more than 20% of the gross weight of surperficial coating liquid, drying time is just considered as long, thus productivity ratio may reduce.
MEK, it is used for controlling the viscosity of coating liquid, and makes coat dry, can be used alone or used in combination with alcohol.If relative to the gross weight of this surperficial coating liquid, when MEK amount used is less than 15wt.%, the viscosity of coating liquid increases, and the fluid ability of coating liquid is reduced, and therefore makes coat produce scrambling.If relative to the gross weight of this surperficial coating liquid, the use amount of MEK is more than 50wt.%, then the viscosity of coating liquid too declines, and is therefore difficult to be formed the layer with uniform thickness.In addition, in the case, because rate of drying reduces, a lot of bubble may be produced.Therefore, preferably in above-mentioned scope, MEK is used.
In addition, correspond to the color that will show for the toner presenting color, but the present invention is not limited to cited toner here.If relative to the polyurethane surface coating liquid (the polyurethane dried resin except toner, the gross weight of DMF and MEK) of 100 weight portions, the use amount of toner is less than 1 weight portion, be then not easy to present color.Because it is uneconomic for using more than the toner of 40 weight portions, preferably in above-mentioned scope, use toner.All toners of known available are in the art all available, and, preferably, (commodity of Ilsam chemical company are called SCU RED can to use SCU COLOR, the product of SCU BLUE etc.) and/or PF COLOR (commodity of Song-Jeong chemical company are called PF RED, the product of PF BLUE etc.).
In addition, according to the present invention, described polyurethane skin layer can have at 10 ~ 50 μm, or preferably, the average thickness within the scope of 15 ~ 30 μm.Here, when the average thickness of this polyurethane skin layer is less than 10 μm, thickness is excessively thin, thus makes its mechanical strength, and such as mar proof or elasticity can reduce.When the average thickness of polyurethane skin layer is greater than 50 μm, because too much bubble may produce in top layer.Therefore this polyurethane skin layer is preferably made to have the average thickness in above-mentioned scope.
the general coat in polyurethane pula
In changeable colour multi-layer product according to the present invention, for causing the general coat in polyurethane pula of weathering phenomenon, can be formed by using the general coating liquid in polyurethane pula.The general coat in polyurethane pula comprises the general polyurethane resin in pula of 50 ~ 80wt.%, the DMF of 5 ~ 10wt.% and the MEK of 20 ~ 40wt.%.
When the use amount of the general polyurethane resin in pula in the general coating liquid in polyurethane pula is less than 50wt.%, surface discolouration effect may be deteriorated, thus make commodity performance degradation.If the use amount of polyurethane resin is more than 80wt.%, then the viscosity due to resin is too high, and machinability is reduced.Therefore the resin in above-mentioned scope is preferably used in.The general polyurethane resin in pula is by by one or at least two kinds of chain extenders, (this chain extender comprises and is selected from by 1,4-butanediol, ethylene glycol, neopentyl glycol, at least one of the group that 1,6-hexylene glycol and diethylene glycol (DEG) form) and form glycol composition based on the polyalcohol of polyester, this polyalcohol comprises copolymer polyols, and (such as number-average molecular weight is 1, BDO in the scope of 000 to 3,000 and the copolymer polyols of adipic acid; With the copolymer polyols of neopentyl glycol and BDO) or polyester-based polyol (such as polyethylene glycol).This glycol composition mixes with isocyanates, and then through urethane reaction, thus synthesis has 60,000 ~ 90, the polyurethane of the viscosity of 000 centipoise (cps) at 25 DEG C.The general polyurethane resin in pula with 15000 ~ 25000 centipoises (25 DEG C) viscosity by under suitable environment by a kind of or at least two kinds wax, silica, calcium carbonate and titanium dioxide are mixed into polyurethane, then add solvent in the mixture and prepare.
In addition, in the general coating liquid in polyurethane pula, when the gross weight relative to surperficial coating liquid, when the use amount as the dimethyl formamide of solvent is less than 5wt.%, the viscosity of surperficial coating liquid may be too high.When the gross weight relative to surperficial coating liquid, when the use amount of dimethyl formamide is more than 20wt.%, drying time is oversize, thus productivity ratio can reduce.
In the general coating liquid in polyurethane pula, MEK (it is used for controlling the viscosity of coating liquid, and makes coat dry), can be used alone or used in combination with alcohol.If relative to the gross weight of this surperficial coating liquid, MEK amount used is less than 15wt.%, and weathering phenomenon reduces, thus surface discolouration effect is reduced.If the use amount of MEK is more than 45wt.%, mechanical strength such as wearability or elasticity reduce.Therefore, preferably in above-mentioned scope, MEK is used.
In addition, the general coating liquid in polyurethane pula can comprise at least one additive further, and this additive is selected from silica, wax, calcium carbonate and titanium dioxide, and the general coat in polyurethane pula can be caused to produce weathering phenomenon.When additive uses, consider that the viscosity of the general coating liquid in pula controls and stability, preferably, after the general coating liquid in additive and pula mixes, reduce the time of placing the general coating liquid in pula.If the general coating liquid in polyurethane pula is placed 24 hours or the longer time, additive precipitation may be there is.Preferably, what use mixture within 12 hours after mixture prepares is stable, can prevent precipitation.
According to the present invention, 25 DEG C time, the viscosity of the general coating liquid in described polyurethane pula is in the scope of 500 centipoise to 10000 centipoises.Preferably, when the viscosity of the general coating liquid in polyurethane pula is in the scope of 1500 centipoises to 6000 centipoises, this general coating liquid in polyurethane pula is more effective in stability and machinability.
Simultaneously, because the general coat in polyurethane pula formed by the general coating liquid in polyurethane pula, weathering phenomenon can be produced based on crackle, thus make the general coat in polyurethane pula present most important impact for the color of surface color, when preparing this coating liquid, dispersion must be very even.Therefore, generally need with the mixing speed in the scope of 500 ~ 2000rpm, mix coating liquid at least one hour equably.When being uniformly dispersed, the vision color sensation of changeable colour multi-layer product is clean and transparent.
In addition, the average thickness that the general coat in polyurethane pula formed according to the present invention can have, in the scope of 10 ~ 80 μm, is preferably 10 ~ 50 μm.When average thickness is for being less than 10 μm, the effect of surface discolouration may deterioration.If average thickness is more than 80 μm, physical property such as elasticity may reduce.Therefore, preferably make the average thickness of the general coat in polyurethane pula in above-mentioned scope.
polyurethane adhesive layer
As shown in Figure 3 according in changeable colour multi-layer product of the present invention, make polyurethane skin layer by polyurethane adhesive layer, the general coat in polyurethane pula and/or layer of polyurethane bond mutually, and this polyurethane adhesive layer can be formed by polyurethane adhesive solution.
Polyurethane binder can be used for polyurethane adhesive solution.According to the present invention, can according to the purposes of such as this product, attribute and sense of touch, and bonding strength, use one pack system (one-component) adhesive or bi-component (two-component) adhesive.Generally speaking, two component adhesive is for requiring the product of durability and high-performance mechanical attribute, and one-package adhesive can be used for other products.
For two component adhesive, based on aromatic isocyanate (trade name: the AK-75 produced by Aekyung chemistry) reagent, can as crosslinking agent.Concrete requirement is had to the application of excellent light, the mixture that also can to use with aliphatic isocyanates (trade name: the PLHK by Keonseol Chemical Manufacture) be host.
Polyurethane adhesive solution can comprise polyurethane binder of 50 ~ 80wt.%, the DMF of 5 ~ 10wt.%, and the MEK of 15 ~ 40wt.%.Preferably, described polyurethane adhesive solution can comprise polyurethane binder of 60 ~ 80wt.%, the DMF of 5 ~ 10wt.%, and the MEK of 15 ~ 30wt.%.
When the use amount of polyurethane binder is less than 50wt.%, cohesive may deterioration.When the use amount of polyurethane binder is more than 80wt.%, the viscosity of adhesive is too high, and adhesive may be condensed.
In addition, polyurethane adhesive solution may further include toner.Relative to 100 weight portions of polyurethane binder, the use amount of toner is in the scope of 1 ~ 15 weight portion, preferably 5 ~ 15 weight portions.Preferably, the color for the toner in polyurethane adhesive solution is darker than the color of the toner being used for polyurethane skin layer.Preferably, for polyurethane adhesive solution, use the toner of black class.
The average thickness that polyurethane adhesive layer can have, in the scope of 15 ~ 80 μm, is preferably 20 ~ 50 μm.When average thickness is less than 15 μm, cohesive may deterioration.If when average thickness is more than 15 μm, excessive bubble can produce within the adhesive layer, in addition, if more than 72 hours hardening time, then productivity ratio may reduce.Therefore, polyurethane adhesive layer preferably has the average thickness in above-mentioned scope.
other layer
As mentioned above, according to the present invention, polyurethane-coated layer can be formed further between the general coat in polyurethane pula and polyurethane sticking layer, to improve the color changeable effect on surface, and present various surface color by phase complementary colours.Polyurethane-coated layer can by utilizing polyurethane-coated liquid to be formed.
Polyurethane-coated liquid comprises: the polyurethane dried resin of 40wt% to 70wt.%, and the scope with percentage by weight is the DMF of 5% to 20%, and the scope with percentage by weight is the MEK of 10% to 40%.Preferably, polyurethane-coated liquid comprise percentage by weight be 55% ~ 70% scope in polyurethane dried resin, percentage by weight is the DMF in 5% to 10% scope, percentage by weight be 20% to 35% scope in MEK time, be favourable in the coat and mechanical strength of suitable thickness.
Polyurethane dried resin may be used for polyurethane skin layer equally.
In addition, polyurethane-coated liquid may further include the toner of 5 ~ 40 weight portions.Preferably, relative to the polyurethane-coated liquid (comprising the gross weight of the polyurethane dried resin except toner, DMF and MEK) of 100 weight portions, the toner of 5 ~ 30 weight portions is comprised.Use has with the toner of polyurethane skin layer different colours better, preferably uses and has the toner darker than the toner color for polyurethane skin layer.
Polyurethane-coated layer can have the average thickness in the scope of 10 ~ 50 μm, preferably 15 ~ 30 μm.When average thickness is less than 10 μm, mechanical performance may be deteriorated.If average thickness is more than 50 μm, excessive bubble may produce in coat.In addition, solidification (aging) time is 72 hours or longer time, and productivity ratio can reduce.Therefore, preferably, the average thickness of described polyurethane-coated layer is in above-mentioned scope.
Changeable colour multi-layer product according to the present invention comprises basalis.Preferably, use at least one being selected from the group that following material is formed as basalis: thermoplastic polyurethane (TPU) sheet material, TPO (TPO) sheet material, fabric, superfine fibre, ultra-fine adhesive-bonded fabric, wet type artificial leather, dry type artificial leather, wet film and natural leather.
Different with average thickness according to the kind of base material, the thickness of basalis can be within the scope of 50 μm ~ 1,500 μm, is preferably 100 μm ~ 1,000 μm.When average thickness is less than 50 μm, when basalis is too thin, make mechanical degradation.If average thickness is more than 1500 μm, then the weight of product increases, thus is also difficult to apply it to a lightweight product, therefore, preferably, makes basalis have the average thickness in above-mentioned scope.
Hereinafter, the method for the changeable colour multi-layer product of manufacture physically based deformation stress according to the present invention is described.
Can be prepared by the flow process comprised the following steps according to changeable colour multi-layer product of the present invention: (a) applies and drying polyurethane surface coating liquid on the surface of peeling paper being formed with floral designs, to form polyurethane skin layer; B () applies the general coating liquid in polyurethane pula on a surface of polyurethane skin layer, to form the general coat in polyurethane pula; D () applies and partial desiccation polyurethane adhesive solution on a surface of the general coat in polyurethane pula; And general for polyurethane pula coat and substrate are combined; E () solidifies the structure produced.
In addition, when changeable colour multi-layer product according to the present invention also comprises polyurethane-coated layer, changeable colour multi-layer product can be prepared by the process comprised the following steps: (a) applies and drying polyurethane surface coating liquid on the surface of peeling paper being formed with floral designs, to form polyurethane skin layer; B () applies the general coating liquid in polyurethane pula on a surface of polyurethane skin layer, to form the general coat in polyurethane pula; (c) coating on a surface of the general coat in polyurethane pula drying polyurethane coating liquid and form polyurethane-coated layer; D () be polyurethane coating binder solution on a surface of polyurethane-coated layer, partial desiccation is coated in the polyurethane adhesive solution on a surface of polyurethane-coated layer, and polyurethane-coated layer and substrate is combined; E () solidifies the structure produced.
In addition, above-mentioned two kinds of manufacture methods can comprise further after curing schedule (e): the step of the realistic printing of the numeral for variegated surface decorative pattern, surface light process, surface color process, laser-induced thermal etching, laser cutting and punching.
In step (a), polyurethane surface coating liquid can be applied according to 100 grams/m ~ 250 grams/m on of a peeling paper surface, then, at the temperature of 70 DEG C to 130 DEG C, the drying polyurethane surface coating liquid time of 30 seconds to 5 minutes.
In addition, in step (b), by applying and apply the general coating liquid in polyurethane pula according to 100 grams/m ~ 250 grams/m on a surface of polyurethane skin layer, the general coat in pula forming suitable thickness is made it possible to.
In addition, in step (c), by applying and apply polyurethane-coated liquid according to 100 grams/m ~ 250 grams/m on a surface of the general coat in polyurethane pula, polyurethane-coated layer can suitably be formed.
Further, preferably, under the pressure of 1,000 grams/cm to 10,000 grams/cm, step (d) 0.5 second to 3 seconds is performed.
Step (e), for improving the Thermocurable of polyurethane adhesive layer, is under the scope of 50 DEG C to 90 DEG C in temperature, performs step (e) 12 to 72 hours.When solidification temperature is lower than 50 DEG C, cohesive may decline significantly.In contrast, when solidification temperature is more than 90 DEG C, due to rapid thermosetting reaction, a large amount of bubble can produce in polyurethane adhesive layer.Be less than 12 constantly little when solidified, the solidification effect produced because of solidification cannot be obtained, if more than 72 hours, be then unfavorable for commercialization hardening time.
In two kinds of manufacture methods, by by one or at least two kinds of chain extenders, (this chain extender comprises and is selected from by 1,4-butanediol, ethylene glycol, neopentyl glycol, 1, the at least one of the group that 6-hexylene glycol and diethylene glycol (DEG) form) and form glycol composition based on the polyalcohol of polyester, this polyalcohol comprises copolymer polyols, and (such as number-average molecular weight is 1,000 to 3, BDO in the scope of 000 and the copolymer polyols of adipic acid; With the copolymer polyols of neopentyl glycol and BDO) or polyester-based polyol (such as polyethylene glycol).This glycol composition mixes with isocyanates, and then through urethane reaction, thus synthesis has 60,000 ~ 90, the general polyurethane in pula of the viscosity of 000 centipoise at 25 DEG C.
Then, the general polyurethane resin in pula with 15000 ~ 25000 centipoises (25 DEG C) viscosity by by additive, the general polyurethane resin in pula, DMF and MEK mixing and preparing, above-mentioned additive comprises a kind of or at least two kinds wax, silica, calcium carbonate and titanium dioxide.
Hereinafter, will be described in detail embodiments of the invention, but the present invention is not limited to this.
Comparative example 1
(1) preparation of polyurethane-coated liquid: mixing is widely used in the polyurethane dried resin (trade name: D-ACE8301 of the 40wt.% on the surface of artificial leather, Dong-Sung chemical company), the DMF of 5wt.%, the MEK of 30wt.%, with the black toner (trade name: SU7809 black of 25wt.%, Ilsam chemical company), and by using high speed agitator to stir the mixture 30 minutes.
(2) preparation of polyurethane adhesive solution: by using high speed agitator, stir by mixing polyurethane binder (trade name: UA-590070, fine chemistry company), the DMF of 5wt.%, and the MEK of 25wt.% and the mixture that obtains 30 minutes.
(3) by using blade coater, according to about 150 grams/m, polyurethane-coated liquid being coated in and having on the peeling paper of floral designs, and dry one minute, to form film.
Utilize extra coating (secondary coating), the film of primary applies several times again, to improve the physical property of the coat on general dermatine, with the solution for primary, there is the polyurethane-coated liquid of same composition, by using blade coater, again be coated on initial application layer according to 150 grams/m, and 120 DEG C of dryings 1 minute, make to be formed the polyurethane-coated layer with double-layer structure.
After confirming coating liquid bone dry, by using blade coater, with 180 grams/m, polyurethane adhesive solution being coated in and having on the polyurethane-coated layer of double-layer structure, then 120 DEG C of partial desiccations 1 minute.After this, transparent WINMELT-S sheet (hot melt adhesive film) and mixture are combined by pressure roller, keeps suitable surface viscosity, thus obtained multi-layer product, wherein this WINMELT-S sheet can obtain from Juwontech company.
The cross section of multi-layer product and surface picture are shown in Fig. 1 a, can determine that its surface color is black.
Multi-layer product because of comparative example 1 is based on according to correlation technique, prepares according to the method for the dermatine on preparation market, although can realize extending based on the high extensibility of described TPU material, surface color is fixed as solid color.Therefore, can be known by Fig. 1 b, even if apply external stress, its surface color does not also change.
Embodiment 1
(1) polyurethane surface coating liquid is prepared
Yellow polyurethane surface coating liquid is prepared by following steps: the polyurethane dried resin (trade name: D-ACE8301 of mixing 60wt.%, Dong-Sung chemical company), the DMF of 5wt.%, the MEK of 30wt.%, with the Yellow toner (being produced by Ilsam chemical company) of 5wt.%, and by using high speed agitator to stir the mixture 30 minutes.
(2) the general coating liquid in polyurethane pula is prepared
The general coating liquid in polyurethane pula is prepared by following steps: the pula general polyurethane resin (trade name: BS109 of mixing 65wt.%, Backsann company), the MEK of the DMF of 5wt.%, 30wt.%, and by using high speed agitator to stir the mixture equably 1 hour.Prepared coating liquid has the viscosity of 2500 centipoises at the temperature of 25 DEG C.
(3) polyurethane adhesive solution is prepared
Polyurethane adhesive solution is prepared by following steps: polyurethane binder (trade name: UA-590070, fine chemistry company) of mixing 75wt.%, the DMF of 6wt.%, and the MEK of 19wt.% and obtain mixture.Again the black toner (trade name: SU7809 black, Ilsam company) of 14.5 weight portions is joined in polyurethane binder of 100 weight portions, and by using high speed agitator to stir the mixture 30 minutes.
(4) multi-layer product is prepared
Yellow polyurethane surface coating liquid is according to about 150 grams/m, and by using blade coater, primary is on the peeling paper with floral designs.Then, at 120 DEG C, dry 1 minute, thus form polyurethane skin layer (there is the average thickness of 20 μm).
Then, in polyurethane skin layer, by using blade coater, according to about 120 grams/m, the general coating liquid in coating polyurethane pula, then, at 120 DEG C, dry 1 minute, forms the general coat in polyurethane pula (having the average thickness of 15 μm).
Then, after confirming polyurethane pula general coat bone dry, by using blade coater, by polyurethane adhesive solution, according to 180 grams/m, be coated on the upper surface of the general coat in polyurethane pula, then, 120 DEG C of partial desiccations 1 minute.After this, the TPU sheet material (having the average thickness of 200 μm) of WINMELT-S and mixture are combined by pressure roller, keep suitable surface viscosity, thus obtained multi-layer product, wherein this TPU sheet material can obtain from Juwontech company.In this case, under the pressure of 6,000 grams/cm, 2 ~ 3 seconds are carried out, to combine.
Then, prepared multi-layer product solidifies 48 hours at the temperature of 70 DEG C, thus obtained changeable colour multi-layer product.
The raw material used in various embodiment can be not limited to above-mentioned trade name.
According to the product of above-described embodiment, by the high extensibility based on the TPU material as substrate, present the very excellent surface discolouration based on stretching.Fig. 3 a shows the SEM photo of the cross section of prepared changeable colour multi-layer product.Fig. 3 b shows the color change photo caused according to the elongation of prepared changeable colour multi-layer product.
Embodiment 2
(1) polyurethane surface coating liquid is prepared
Blue polyurethane surface coating liquid is prepared by following steps: the polyurethane dried resin (trade name: BSP-5070 of mixing 60wt.%, Backsan company), the DMF of 5wt.%, the MEK of 30wt.%, with blue toner (trade name: the PF blueness of 5wt.%, Song-Jeog company), and by using high speed agitator to stir the mixture 30 minutes.
(2) the general coating liquid in polyurethane pula is prepared
The general coating liquid in polyurethane pula is prepared by following steps: the pula general polyurethane resin (trade name: BS109 of mixing 65wt.%, Backsann company), the MEK of the DMF of 5wt.%, 30wt.%, and by using high speed agitator to stir the mixture equably 1 hour.Prepared coating liquid has the viscosity of 2500 centipoises at the temperature of 25 DEG C.
(3) polyurethane-coated liquid is prepared
Afterwards, polyurethane dried resin (the trade name: BSP-5070 of mixing 68wt.%, Backsan company), the DMF of 7wt.%, the red toner (trade name: PF is red, Song-Jeog chemical company) of 25 weight portions, with obtained mixed solution, then joins in the above-mentioned mixed solution of 100 weight portions by the MEK of 25wt.%, and by using high speed agitator to stir the mixture 30 minutes, to prepare red polyurethane-coated liquid.
(4) polyurethane adhesive solution is prepared
Polyurethane binder (trade name: UA-590070 of mixing 70wt.%, fine chemistry company), the DMF of 5wt.%, and the MEK of 25wt.% and obtain mixture, and stir the mixture 30 minutes by using high speed agitator, to prepare polyurethane adhesive solution.
(5) multi-layer product is prepared
Blue polyurethane surface coating liquid is according to about 150 grams/m, and by using blade coater, primary is on the peeling paper with floral designs.Then, at 120 DEG C, dry 1 minute, thus form polyurethane skin layer (there is the average thickness of 20 μm).
Then, in polyurethane skin layer, by using blade coater, according to about 120 grams/m, the general coating liquid in coating polyurethane pula, then, at 120 DEG C, dry 1 minute, forms the general coat in polyurethane pula (having the average thickness of 15 μm).
Then, by using blade coater, according to about 150 grams/m, the polyurethane-coated liquid of prepared redness is coated on the upper surface of the general coat in polyurethane pula.Then, at 120 DEG C, dry 1 minute, thus form polyurethane coating layer (there is the average thickness of 20 μm).
Then, after confirming polyurethane pula general coat bone dry, by using blade coater, by polyurethane adhesive solution, according to 180 grams/m, be coated on the upper surface of red polyurethane-coated layer, then, 120 DEG C of partial desiccations 1 minute.After this, the TPU sheet material (having the average thickness of 200 μm) of WINMELT-S and mixture are combined by pressure roller, keep suitable surface viscosity, thus obtained multi-layer product, wherein this TPU sheet material can obtain from Juwontech company.In this case, under the pressure of 6,000 grams/cm, 2 ~ 3 seconds are carried out, to combine.
Then, prepared multi-layer product solidifies 48 hours at the temperature of 70 DEG C, thus obtained changeable colour multi-layer product.Fig. 4 shows the photo causing color to change because of elongation of prepared changeable colour multi-layer product.
Embodiment 3
(1) polyurethane surface coating liquid is prepared
Transparent polyurethane surface coating liquid is prepared by following steps: the polyurethane dried resin (trade name: BSP-5070 of mixing 60wt.%, Backsan company), the MEK of DMF and 35wt.% of 5wt.%, and by using high speed agitator to stir the mixture 30 minutes.
(2) the general coating liquid in polyurethane pula is prepared
The general coating liquid in polyurethane pula is prepared by following steps: the pula general polyurethane resin (trade name: BS109 of mixing 65wt.%, Backsann company), the MEK of the DMF of 5wt.%, 30wt.%, and by using high speed agitator to stir the mixture equably 1 hour.Prepared coating liquid has the viscosity of 2500 centipoises at the temperature of 25 DEG C.
(3) polyurethane-coated liquid is prepared
Polyurethane dried resin (the trade name: UB-501MB of mixing 40wt.%, fine chemistry company), the DMF of 5wt.%, the MEK of 35wt.%, with red toner (trade name: the SU redness of 25wt.%, Ilsam company), and by using high speed agitator to stir the mixture 30 minutes, to prepare polyurethane-coated liquid.
(4) polyurethane adhesive solution is prepared
Polyurethane binder (trade name: UA-590070 of mixing 70wt.%, fine chemistry company), the DMF of 5wt.%, and the MEK of 25wt.% and obtain mixture, and stir the mixture 30 minutes by using high speed agitator, to prepare polyurethane adhesive solution.
(5) multi-layer product is prepared
Transparent polyurethane surface coating liquid is according to about 150 grams/m, and by using blade coater, primary is on the peeling paper with floral designs.Then, at 120 DEG C, dry 1 minute, thus form polyurethane surface coat (there is the average thickness of 20 μm).
Then, on polyurethane surface coat, by using blade coater, according to about 120 grams/m, the general coating liquid in coating polyurethane pula, then, at 120 DEG C, dry 1 minute, form the general coat in polyurethane pula (there is the average thickness of 15 μm).
Then, by using blade coater, according to about 150 grams/m, the polyurethane-coated liquid of prepared redness is coated on the upper surface of the general coat in polyurethane pula.Then, at 120 DEG C, dry 1 minute, thus form polyurethane coating layer (there is the average thickness of 20 μm).
Then, after confirming polyurethane pula general coat bone dry, by using blade coater, by polyurethane adhesive solution, according to 180 grams/m, be coated on the upper surface of polyurethane-coated layer, then, 120 DEG C of partial desiccations 1 minute.After this, the TPU sheet material (having the average thickness of 200 μm) of WINMELT-S and mixture are combined by pressure roller, keep suitable surface viscosity, thus obtained multi-layer product, wherein this TPU sheet material can obtain from Juwontech company.In this case, under the pressure of 6,000 grams/cm, 2 ~ 3 seconds are carried out, to combine.
Then, prepared multi-layer product solidifies 48 hours at the temperature of 70 DEG C, thus obtained changeable colour multi-layer product.The present invention does not limit for the exterior color of the visual appearance that surface color and the dermatine of product obtains.Fig. 5 shows the photo causing color to change because of elongation of prepared changeable colour multi-layer product.
Embodiment 4
(1) polyurethane surface coating liquid is prepared
Yellow polyurethane surface coating liquid is prepared by following steps: the polyurethane dried resin (trade name: BSP-5070 of mixing 60wt.%, Backsan company), the DMF of 5wt.%, the MEK of 30wt.%, with Yellow toner (trade name: the SCU yellow of 5wt.%, produced by Ilsam company), and by using high speed agitator to stir the mixture 30 minutes.
(2) the general coating liquid in polyurethane pula is prepared
The general coating liquid in polyurethane pula is prepared by following steps: the pula general polyurethane resin (trade name: BS109 of mixing 65wt.%, Backsann company), the MEK of the DMF of 5wt.%, 30wt.%, and by using high speed agitator to stir the mixture equably 1 hour.Prepared coating liquid has the viscosity of 2500 centipoises at the temperature of 25 DEG C.
(3) polyurethane adhesive solution is prepared
Polyurethane adhesive solution is prepared by following steps: polyurethane binder (trade name: UA-590070, fine chemistry company) of mixing 75wt.%, the DMF of 6wt.%, and the MEK of 19wt.% and obtain mixture.Again the black toner (trade name: SU7809 black, Ilsam company) of 14.5 weight portions is joined in polyurethane binder of 100 weight portions, and by using high speed agitator to stir the mixture 30 minutes.
(4) preparation has the TPU substrate being produced surface detail pattern by realistic printing
On the surface of WINMELT-S sheet material (having the average thickness of 200 μm), form floral designs by realistic printing, this WINMELT-S sheet material can be bought from Juwontech company.
(5) multi-layer product is prepared
Yellow polyurethane surface coating liquid is according to about 150 grams/m, and by using blade coater, primary is on the peeling paper with floral designs.Then, at 120 DEG C, dry 1 minute, thus form polyurethane skin layer (there is the average thickness of 20 μm).
Then, on polyurethane surface coat, by using blade coater, according to about 120 grams/m, the general coating liquid in coating polyurethane pula, then, at 120 DEG C, dry 1 minute, form the general coat in polyurethane pula (there is the average thickness of 15 μm).
Then, after confirming polyurethane pula general coat bone dry, by using blade coater, by the polyurethane adhesive solution of black, according to 180 grams/m, be coated on the upper surface of the general coat in polyurethane pula, then, 120 DEG C of partial desiccations 1 minute.After this, TPU sheet material (having the average thickness of 200 μm) and mixture are combined by pressure roller, keep suitable surface viscosity, thus obtained multi-layer product, wherein this TPU sheet material has the floral designs produced by realistic printing.In this case, under the pressure of 6,000 grams/cm, 2 ~ 3 seconds are carried out, to combine.
Then, prepared multi-layer product solidifies 48 hours at the temperature of 70 DEG C, thus obtained changeable colour multi-layer product.Fig. 4 shows the photo causing color to change because of elongation of prepared changeable colour multi-layer product.Thus, can confirm, because surface discolouration, the floral designs of realistic printing disappear.
Above-mentioned multi-layer product is the combination of surface discolouration coating material and realistic printing.Multi-layer product according to the present invention has following characteristics: the realistic floral designs being clearly presented at surface, may disappear when external stress is applied to substrate.In addition, in order to increase the various effects of the floral designs based on realistic printing, a kind of method likely realized is: be printed on directly realistic for floral designs on surface discolouration coating substance.
Embodiment 5
(1) polyurethane surface coating liquid is prepared
Yellow polyurethane surface coating liquid is prepared by following steps: the polyurethane dried resin (trade name: BSP-5070 of mixing 60wt.%, Backsan company), the DMF of 5wt.%, the MEK of 30wt.%, with Yellow toner (trade name: the SCU yellow of 5wt.%, Ilsam company), and by using high speed agitator to stir the mixture 30 minutes.
(2) the general coating liquid in polyurethane pula is prepared
The general coating liquid in polyurethane pula is prepared by following steps: the pula general polyurethane resin (trade name: BS109 of mixing 65wt.%, Backsann company), the MEK of the DMF of 5wt.%, 30wt.%, and by using high speed agitator to stir the mixture equably 1 hour.Prepared coating liquid has the viscosity of 2500 centipoises at the temperature of 25 DEG C.
(3) polyurethane-coated liquid is prepared
Afterwards, polyurethane dried resin (the trade name: BSP-5070 of mixing 68wt.%, Backsan company), the DMF of 7wt.%, the blue toner (trade name: SCU is blue, Ilsam company) of 25 weight portions, with obtained mixed solution, then joins in the above-mentioned mixed solution of 100 weight portions by the MEK of 25wt.%, and by using high speed agitator to stir the mixture 30 minutes, to prepare blue polyurethane-coated liquid.
(4) polyurethane adhesive solution is prepared
Polyurethane binder (trade name: UA-590070 of mixing 70wt.%, fine chemistry company), the DMF of 5wt.%, and the MEK of 25wt.% and obtain mixture, and stir the mixture 30 minutes by using high speed agitator, to prepare polyurethane adhesive solution.
(5) multi-layer product is prepared
Yellow polyurethane surface coating liquid is according to about 150 grams/m, and by using blade coater, primary is on the peeling paper with floral designs.Then, 120 DEG C of dryings 1 minute, thus form polyurethane skin layer (there is the average thickness of 20 μm).
Then, in polyurethane skin layer, by using blade coater, according to about 120 grams/m, the general coating liquid in coating polyurethane pula, then, 120 DEG C of dryings 1 minute, forms the general coat in polyurethane pula (having the average thickness of 15 μm).
Then, by using blade coater, according to about 150 grams/m, the polyurethane-coated liquid of prepared blueness is coated on the upper surface of the general coat in polyurethane pula.Then, 120 DEG C of dryings 1 minute, thus form polyurethane coating layer (there is the average thickness of 20 μm).
Then, after confirming polyurethane pula general coat bone dry, by using blade coater, by polyurethane adhesive solution, according to 180 grams/m, be coated on the upper surface of red polyurethane-coated layer, then, 120 DEG C of partial desiccations 1 minute.After this, the TPU sheet material (having the average thickness of 200 μm) of WINMELT-S and mixture are combined by pressure roller, keep suitable surface viscosity, thus obtained multi-layer product, wherein this TPU sheet material can obtain from Juwontech company.In this case, under the pressure of 6,000 grams/cm, 2 ~ 3 seconds are carried out, to combine.Then, prepared multi-layer product solidifies 48 hours at the temperature of 70 DEG C.By using hot pressurizer, the hot melt TPU substrate be included in goods and elastic textiles (having the average thickness of 800 μm) are bonded to each other.By using upper plate and the lower plate of hot pressurizer, under the pressure of 60,000 grams/cm, and at the temperature of 140 DEG C, carry out 30 seconds, to combine.
Then, at a normal temperature, prepared multi-layer product is placed one hour, textile can be used just to have prepared as the changeable colour multi-layer product of substrate.
According to prepared product, there occurs surface discolouration very well, and obtain the dermatine can expressing kinds of surface color.
Surface discolouration before and after the elongation of the changeable colour multi-layer product prepared in embodiment 5 is shown in Fig. 7.Can confirm, when viewed from the direction of polyurethane skin layer, before elongation, surface color is Dark grey (see Fig. 7 A), just becomes glassy yellow (see Fig. 7 B) after then extending.
As above by described in embodiment, the present invention is applicable to various base material (TPU, fabric, non-woven fabrics, ultra-fine fabrics, natural leather etc.).Particularly, exceed restriction color representation in the related because very excellent surface discolouration effect provides, the various demands of consumer can be met according to product of the present invention.The changeable colour multi-layer product of physically based deformation stress presents the surface discolouration effect with good vision properties, therefore estimates that this changeable colour multi-layer product can be widely used in industrial circle, such as clothes, furniture, sack, ball, wallet, belt, accessory, car room finishing material, mobile phone housing, interior trim article, natural leather product or other groceries and sport footwear.
Claims (23)
1. a changeable colour multi-layer product for physically based deformation stress, described changeable colour multi-layer product comprises:
Polyurethane skin layer;
For generation of the general coat in polyurethane pula of weathering phenomenon;
Adhesive phase; With
Basalis,
Wherein said polyurethane skin layer, the general coat in polyurethane pula, adhesive phase and basalis stack gradually.
2. changeable colour multi-layer product according to claim 1, is also included in the polyurethane-coated layer between the general coat of described adhesive phase and polyurethane pula.
3. changeable colour multi-layer product according to claim 1, wherein, the average thickness of described polyurethane skin layer is 10 μm to 50 μm, the average thickness of the general coat in described polyurethane pula is 10 μm to 80 μm, the average thickness of described adhesive phase is 15 μm to 80 μm, and the average thickness of described basalis is 45 μm to 210 μm.
4. changeable colour multi-layer product according to claim 2, wherein, the average thickness of described polyurethane-coated layer is 10 μm to 50 μm.
5. changeable colour multi-layer product according to claim 1, wherein, described polyurethane skin layer formed by polyurethane surface coating liquid, described polyurethane surface coating liquid comprises the polyurethane dried resin of 30 ~ 70wt.%, the dimethyl formamide (DMF) of 5 ~ 20wt.%, and the MEK of 15 ~ 50wt.% (MEK).
6. changeable colour multi-layer product according to claim 5, wherein, relative to the polyurethane dried resin of 100 weight portions, described polyurethane skin layer also comprises the toner of 1 ~ 40 weight portion.
7. changeable colour multi-layer product according to claim 1, wherein, the general coat in described polyurethane pula formed by the general coating liquid in polyurethane pula, the general coating liquid in described polyurethane pula comprises the general resin in polyurethane pula of 50 ~ 80wt.%, the DMF of 5 ~ 20wt.%, and the MEK of 15 ~ 45wt.%.
8. changeable colour multi-layer product according to claim 7, wherein, described polyurethane draws coating liquid to comprise at least one additive further, and described additive is selected from: silica, wax, calcium carbonate and titanium dioxide.
9. changeable colour multi-layer product according to claim 8, wherein, relative to the general coating liquid in polyurethane pula of 100 weight portions, add at least one additive of 5-50 weight portion, described additive is selected from: silica, wax, calcium carbonate and titanium dioxide.
10. changeable colour multi-layer product according to claim 7, wherein, the average viscosity of the general coating liquid in described polyurethane pula is 500 ~ 10,000 centipoise 25 DEG C time.
11. variable color multi-layer products according to claim 1, wherein, described adhesive phase comprises polyurethane adhesive layer, and described polyurethane adhesive layer formed by polyurethane adhesive solution, described polyurethane adhesive solution comprises: polyurethane binder of 50 ~ 80wt.%, the DMF of 5 ~ 10wt.% and the MEK of 15 ~ 40wt.%.
12. changeable colour multi-layer products according to claim 11, wherein, relative to polyurethane binder of 100 weight portions, described polyurethane binder comprises the black class toner of 1 ~ 15 weight portion further.
13. changeable colour multi-layer products according to claim 11, wherein, described polyurethane binder comprises at least one crosslinking agent further, and described crosslinking agent is selected from: aromatic isocyanate and aliphatic isocyanate.
14. changeable colour multi-layer products according to claim 2, wherein, described polyurethane-coated layer formed by polyurethane-coated liquid, and described polyurethane-coated liquid comprises the polyurethane dried resin of 40 ~ 70wt.%, the DMF of 5 ~ 20wt.%, and the MEK of 10 ~ 40wt.%.
15. changeable colour multi-layer products according to claim 14, wherein, relative to the polyurethane-coated liquid of 100 weight portions, described polyurethane-coated layer also comprises the toner of 5 ~ 30 weight portions.
16. changeable colour multi-layer products according to claim 1, wherein, described basalis comprises at least one being selected from the group that following material is formed: thermoplastic polyurethane (TPU) sheet material, TPO (TPO) sheet material, fabric, superfine fibre, ultra-fine adhesive-bonded fabric, wet type artificial leather, dry type artificial leather, wet film and natural leather.
17. 1 kinds of methods preparing the changeable colour multi-layer product of physically based deformation stress, said method comprising the steps of:
A () applies and drying polyurethane surface coating liquid on the surface of peeling paper being formed with floral designs, to form polyurethane skin layer;
B () applies the general coating liquid in polyurethane pula on a surface of described polyurethane skin layer, to form the general coat in polyurethane pula;
D () applies and partial desiccation polyurethane adhesive solution on a surface of the general coat in described polyurethane pula, and the general coat in described polyurethane pula and substrate are combined; And
E () solidifies the structure produced.
18. 1 kinds of methods preparing the changeable colour multi-layer product of physically based deformation stress, said method comprising the steps of:
A () applies and drying polyurethane surface coating liquid on the surface of peeling paper being formed with floral designs, to form polyurethane skin layer;
B () applies the general coating liquid in polyurethane pula on a surface of described polyurethane skin layer, to form the general coat in polyurethane pula;
(c) coating on a surface of the general coat in described polyurethane pula drying polyurethane coating liquid and form polyurethane-coated layer;
D () applies and partial desiccation polyurethane adhesive solution on a surface of described polyurethane-coated layer, and described polyurethane-coated layer and substrate are combined; And
E () solidifies the structure produced.
19. methods according to claim 17 or 18, wherein, in step (a), a surface of described peeling paper applies described polyurethane surface coating liquid according to 100 grams/m ~ 250 grams/m, and at the temperature of 70 DEG C to 130 DEG C, the dry described polyurethane surface coating liquid time of 30 seconds to 5 minutes.
20. methods according to claim 17 or 18, wherein, in step (b), on a surface of described polyurethane skin layer, apply the general coating liquid in described polyurethane pula according to 100 grams/m ~ 250 grams/m.
21. methods according to claim 18, wherein, in step (c), on a surface of the general coat in described polyurethane pula, apply described polyurethane-coated liquid according to 100 grams/m ~ 250 grams/m.
22. methods according to claim 17 or 18, wherein, under the pressure of 1 to 10 thousand gram/cm, perform 0.5 second to 3 seconds to described step (d).
23. methods according to claim 17 or 18, wherein, are under the scope of 50 DEG C to 90 DEG C in temperature, perform 12 to 72 hours to described step (e).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2014-0002143 | 2014-01-08 | ||
| KR1020140002143A KR101395815B1 (en) | 2014-01-08 | 2014-01-08 | Color changing laminate products by physical stress and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104760370A true CN104760370A (en) | 2015-07-08 |
| CN104760370B CN104760370B (en) | 2017-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410196112.9A Expired - Fee Related CN104760370B (en) | 2014-01-08 | 2014-05-09 | COLOR CHANGING LAMINATE PRODUCTS based on PHYSICAL STRESS AND MANUFACTURING METHOD THEREOF |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101395815B1 (en) |
| CN (1) | CN104760370B (en) |
| TW (1) | TWI513579B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110952340A (en) * | 2019-12-09 | 2020-04-03 | 福建省睿星纺织科技有限公司 | Novel fabric with stretching, twisting and color changing effects and production process thereof |
| CN111619257A (en) * | 2020-04-21 | 2020-09-04 | 东莞市雄林新材料科技股份有限公司 | Pyrograph film and production process thereof |
| WO2021072807A1 (en) * | 2019-10-16 | 2021-04-22 | 清远市腾翔皮革有限公司 | New-type leather |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101680627B1 (en) | 2016-03-18 | 2016-11-30 | 대원화성 주식회사 | Displaying polyurethane synthetic leather sheet with functions that transmits light |
| CN117470825B (en) * | 2023-12-28 | 2024-04-19 | 纳琳威纳米科技南通有限公司 | Performance detection method and system for electrochromic material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001311911A (en) | 2000-04-27 | 2001-11-09 | Nitto Denko Corp | Laminated sheet |
| JP4925025B2 (en) | 2004-07-12 | 2012-04-25 | 独立行政法人物質・材料研究機構 | Structural color expression elastic body |
| KR20110031615A (en) * | 2009-09-21 | 2011-03-29 | 세바플러스 주식회사 | Interior sheet coated with polyurethane skin layer |
| CN102409551A (en) * | 2011-08-01 | 2012-04-11 | 吴江三辉纺织有限公司 | Color-changing velvet-feel synthetic leather with high brightness |
| CN203229817U (en) * | 2013-05-21 | 2013-10-09 | 清远市齐力合成革有限公司 | Stress color-changing synthetic leather |
-
2014
- 2014-01-08 KR KR1020140002143A patent/KR101395815B1/en active IP Right Grant
- 2014-05-09 CN CN201410196112.9A patent/CN104760370B/en not_active Expired - Fee Related
- 2014-05-15 TW TW103117156A patent/TWI513579B/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021072807A1 (en) * | 2019-10-16 | 2021-04-22 | 清远市腾翔皮革有限公司 | New-type leather |
| CN110952340A (en) * | 2019-12-09 | 2020-04-03 | 福建省睿星纺织科技有限公司 | Novel fabric with stretching, twisting and color changing effects and production process thereof |
| CN111619257A (en) * | 2020-04-21 | 2020-09-04 | 东莞市雄林新材料科技股份有限公司 | Pyrograph film and production process thereof |
| CN111619257B (en) * | 2020-04-21 | 2021-12-14 | 东莞市雄林新材料科技股份有限公司 | Pyrograph film and production process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI513579B (en) | 2015-12-21 |
| CN104760370B (en) | 2017-04-12 |
| KR101395815B1 (en) | 2014-05-19 |
| TW201527101A (en) | 2015-07-16 |
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