KR101395815B1 - Color changing laminate products by physical stress and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a laminate product having its surface color changed by bending or stretching which is a physical stress to the product and a manufacturing method thereof. More specifically, when colors are differently made based on a polyurethane resin containing a compound of silica, wax, calcium carbonate, and titanium oxide and a product is formed into multi layers; a high quality product can be more naturally provided by changing the color of a material surface when bending or stretching which is an external stress that is applied. Fiber materials used for artificial leather such as fabric, felt, or thermo plastic polyurethane (TPU) can be applied as a base material in order to be applied to a wide range including sports shoes, clothes, furniture, bags, wallet, accessories, mobile phone case, interior items, natural leather, and others while enabling various visual coloring material and pattern application.

Description

Technical Field [0001] The present invention relates to a color-changing laminate product by physical stress and a manufacturing method thereof,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to a discolorable laminate product and a method of manufacturing the same. More particularly, the present invention relates to a laminate product whose color changes due to physical stress (stretching, bending, etc.) and a method of manufacturing the same.

In the case of a product using a conventional whitening phenomenon, a polyurethane resin including silica and calcium carbonate is coated on a substrate layer to provide a cracking effect that induces whitening of the surface. As a result, it has been limited to only a part of leather products such as shoes, bags, and garments, because it is limited to the consumer's various coloring needs and other patterns. Particularly, in artificial leather products in which the substrate used is mainly composed of fiber materials (woven fabric, nonwoven fabric), the visual and functional characteristics of the surface are not satisfying consumers' desire for a color pattern having various colors The scope of application of the product was further reduced.

Conventional color-changing products include red dispersion of polyaniline or coating of prussian blue-containing nano-dispersion composition to make electrical discoloration (Korean National Publication No. 10-2006-0058513, Korean Registration No. 10-0740324, etc.) , Or a color-changeable coating product according to a temperature change (Korean National Publication No. 10-2001-0103484), but a discoloration product due to physical stress has not yet been developed.

As a result of efforts to solve the problems of the prior art, the present invention has been made to solve the problems of the prior art, and as a result, it has been found that when a laminate composed of a multilayer having colors different from each other with respect to a resin capable of exhibiting whitening phenomenon is stretched or bent, It is possible to provide natural and luxurious laminate products by discoloring. That is, the object of the present invention is to provide a discolorable laminate product by physical stress and a method of manufacturing the same.

The present invention is directed to a discolorable laminate product by physical stress, comprising: a polyurethane skin layer; A polyurethane pull-up coating layer exhibiting bleaching phenomenon; Adhesive layer; And a base layer, wherein the base layer, the polyurethane adhesive layer, the polyurethane peel-up coating layer, and the polyurethane skin coating layer are laminated in this order.

(A) coating a polyurethane skin coating solution on one side of a release paper on which a pattern pattern is formed, and drying the coated polyurethane skin to form a polyurethane skin layer; (b) coating a polyurethane peel-up coating solution on one surface of the polyurethane skin layer to form a polyurethane peel-up coating layer; (d) applying a polyurethane adhesive solution to one side of the polyurethane peel-up coating layer, semi-drying, and then fusing with the substrate; And (e) aging the mixture to form a discolored laminate product by physical stress.

Another method of manufacturing the discolorable laminate product of the present invention comprises the steps of: (a) coating a polyurethane skin coating solution on one side of a release paper on which a patterned pattern is formed and then drying to form a polyurethane skin layer; (b) coating a polyurethane peel-up coating solution on one surface of the polyurethane skin layer to form a polyurethane peel-up coating layer; (c) coating and drying a polyurethane coating solution on one surface of the polyurethane peel-up coating layer to form a polyurethane coating layer; (d) applying a polyurethane adhesive solution to one surface of the polyurethane coating layer, semi-drying and then coating the substrate with the polyurethane coating solution; And (e) aging the mixture to form a discolored laminate product by physical stress.

According to the present invention, when external stress such as stretching or bending is applied, it is possible to induce a variety of excellent surface color discoloration, and it has excellent visual effect, and is suitable for sports shoes, clothes, furniture, bags, It can be applied to a variety of applications such as accessories, cellular phone cases, interior goods, and other miscellaneous goods. Thus, the application of the discolorable laminate product of the present invention can be expected to have an extremely high expansion effect and marketability.

FIG. 1-a is an outline of a cross-sectional photograph and a surface color of the laminate product prepared in Comparative Example 1. FIG.
Fig. 1-b is a photograph showing a cross-sectional photograph of the surface color-changing coating according to Comparative Example 1 and a discoloration test before and after stretching.
Figure 2 is an overview of the color discoloration principle of a surface color-changing coating.
FIG. 3A is a SEM photograph of a cross-sectional photograph of a surface color-changing coating according to Example 1, and FIG. 3B is a photograph showing discoloration test of the discolorable laminate product prepared in Example 1 before and after stretching.
4 is a photograph showing a discoloration test photograph of the discolorable laminate product prepared in Example 2 before and after stretching.
5 is a photograph showing a discoloration test photograph of the discolorable laminate product prepared in Example 3 before and after stretching.
6 is a photograph showing a photograph of discoloration test before and after stretching of the discolorable laminate product produced in Example 4, showing the effect that the actual print pattern disappears as the surface color is discolored.
7 is a photograph showing the color discoloration effect on the surface of the discolorable laminate product prepared in Example 5 before and after stretching.

The present invention relates to a product whose surface color is discolored through stretching or bending, which is a physical stress applied to a product, wherein a polyurethane peeling-up coating layer is whitened due to external stress, To a discolorable laminate product that exhibits various surface color discolorations by the complementary color effect of the disc.

The outline of the color discoloration principle of the discoloration laminate product of the present invention is shown in FIG. 2. In the discolorable laminate product of the present invention, the polyurethane skin layer corresponding to the color discoloration developing layer is yellow, and the polyurethane skin layer When the lower layer is black, it has a dark green color due to the complementary effect. When external stress is applied to the product, the color develops in dark yellow. Further, when the polyurethane skin layer corresponding to the color discoloration developing layer is light magenta and the lower layer of the polyurethane skin layer is green, it has dark purple due to the complementary color effect. When external stress is applied, The color is expressed.

The discolorable laminate article of the present invention comprises a polyurethane skin layer, a polyurethane peel-up coating layer for developing whitening, a polyurethane adhesive layer and a substrate layer, wherein a polyurethane layer is further provided between the polyurethane peel- . The discolorable laminate product may be in the form of a laminate of a polyurethane skin layer, a polyurethane peel-up coating layer for expressing whitening phenomenon, a polyurethane adhesive layer and a base layer as shown in Fig.

In the discoloration laminate product of the present invention, the color of the lower layer of the polyurethane skin layer should be darker and darker than the color of the polyurethane skin layer, so that the complementary color effect can be maximized when the stress is applied. If the polyurethane skin layer is darker and darker in color than the lower layer, the whitening phenomenon due to the cracks in the polyurethane peel-up coating layer is obscured by the surface color and becomes invisible. On the other hand, the most effective arrangement of colors is to make a complementary relationship between the bright colors of the polyurethane skin layer and the deep colors of the lower layer of the polyurethane skin layer, so that the surface discoloration manifestation can visually approach the maximum value will be. This case is a principle in which the coating layer of the substrate is applied to all three or more layers.

[Polyurethane skin layer]

In the color-changeable laminate product of the present invention, the polyurethane skin layer may be formed of a polyurethane skin coating liquid, wherein the polyurethane skin coating liquid comprises 30 to 70% by weight of polyurethane dry resin, dimethylformamide (DMF) Preferably 5 to 20% by weight, and methyl ethyl ketone (MEK) 15 to 50% by weight, preferably 45 to 65% by weight of a polyurethane dry resin and 5 to 15% by weight of dimethylformamide (DMF) , And 15 to 40% by weight of methyl ethyl ketone (MEK).

The polyurethane skin coating solution may further contain 1 to 40 parts by weight, preferably 1 to 20 parts by weight, of toner based on 100 parts by weight of the polyurethane skin coating solution.

In the above polyurethane skin coating solution, it is preferable to use a colorless clear transparent material as the polyurethane dry resin. For example, D-ACE 8301 (Dong Sung Chemical) widely used for skin in artificial leather, UA 501MB (Fine Chemical). If the amount of the polyurethane dry resin used is less than 20% by weight of the total weight of the skin coating solution, the thickness of the coating film after drying the skin coating solution may become thinner and mechanical strength such as abrasion resistance and bending resistance may be lowered. The viscosity of the skin-coating liquid is too high, so that the production stability in the coating process is lowered and the coating layer may be unevenly formed.

If the amount is less than 5% by weight of the total weight of the skin coating solution, the viscosity of the skin coating solution may be too high. If the amount is more than 20% by weight, the drying time may be too long, There may be a problem of deterioration.

The MEK serves to control the viscosity of the coating liquid and to dry the coating layer. The MEK may be used alone or as a mixture of alcohols. When the amount of the MEK is less than 15% by weight based on the total weight of the skin coating liquid, the viscosity of the coating liquid If the amount is more than 50% by weight, it is difficult to form a coating film having a uniform thickness. In addition, there is a problem that the drying rate is lowered, There may be a problem that it occurs excessively, so it is preferable to use it within the above range.

The amount of the toner to be used is not particularly limited. The amount of the toner to be used may be selected from the group consisting of a polyurethane skin coating solution (polyurethane dry resin except toner, DMF , MEK total content) is less than 1 part by weight based on 100 parts by weight of the composition, color development is not smooth, and use of more than 40 parts by weight is uneconomical. The toner may be a toner commonly used in the art. Preferably, the toner may be a SCU COLOR (product name: SCU RED, SCU BLUE, etc.) and / or PF COLOR Song Jung Chemical: product name PF RED, PF BLUE, etc.) Toner can be used.

In the present invention, the polyurethane skin layer may have an average thickness of 10 to 50 mu m, and preferably an average thickness of 15 to 30 mu m. At this time, if the average thickness of the polyurethane skin layer is less than 10 mu m, there is a problem that the thickness is too thin and mechanical strength such as abrasion resistance and bending resistance is weak, and when the thickness exceeds 50 mu m, It is preferable to have an average thickness within the above range.

[Polyurethane Pull-Up Coating Layer]

In the discoloring laminate product of the present invention, the polyurethane peel-up coating layer serves to develop a whitening phenomenon and may be formed of a polyurethane peel-up coating solution, wherein the polyurethane peel- 5 to 20% by weight of DMF and 15 to 45% by weight, preferably 55 to 75% by weight of MEK, 5 to 10% by weight of DMF and 20 to 40% by weight of MEK.

If the amount of the pull-up polyurethane resin used is less than 50% by weight in the polyurethane pull-up coating liquid, there may be a problem that the effect of discoloration of the surface color is visually deteriorated to deteriorate the merchantability. If it exceeds 80% by weight, May be too high and workability may be deteriorated. The pull-up polyurethane resin may contain at least one selected from copolymerized polyols such as 1,4-butanediol having a number average molecular weight of 1,000 to 3,000 and copolymerized polyol with adipic acid, neopentyl glycol and copolymerized polyol with 1,4-butanediol Based polyol; Or a polyether polyol such as polytetramethylene glycol and the like, or a chain extender containing at least one selected from 1,4-butanediol, ethylene glycol, neopentyl glycol, 1,6-hexanediol, and diethylene glycol, Two or more of them are mixed to form a polyol composition. The polyol composition was mixed with isocyanate and subjected to a urethane reaction to synthesize a polyurethane exhibiting a viscosity of 60,000 to 90,000 cps at 25 ° C. Up polyurethane resin exhibiting a viscosity of 15,000 to 25,000 cps at 25 DEG C can be prepared by adding an appropriate amount of waxes, silica, calcium carbonate, titanium oxides, or a mixture of two or more thereof to the polyurethane.

If the amount of the DMF is less than 5% by weight based on the total weight of the skin coating solution, the viscosity of the skin coating solution may be too high. When the amount of the skin coating solution is more than 20% by weight There is a problem that the drying time takes too long and the productivity is lowered.

Also, in the polyurethane pull-up coating liquid, the MEK serves to control the viscosity and the drying of the coating layer, and may be used alone or in combination with alcohols. When the amount of the MEK is less than 15 wt% There may be a problem in that the discoloration of the surface color may be significantly deteriorated due to the decrease of the whitening phenomenon, and when it is used in an amount exceeding 45% by weight, the mechanical properties such as abrasion resistance and bending resistance may be deteriorated. It is good to do.

In addition, the polyurethane pull-up coating liquid may further include an additive containing at least one selected from the group consisting of silica, wax, calcium carbonate and titanium oxide, and they may impart a role of causing a bleaching phenomenon to the polyurethane pull- have. When the additive is used, it is preferable to shorten the period of time after the additive is mixed after considering the viscosity control and stability of the pull-up coating liquid. If the polyurethane pull-up coating solution is left for more than 24 hours, precipitation of the additive may occur. Therefore, it is preferable to use the polyurethane pre-coating solution after 12 hours from the preparation of the mixture.

In the present invention, the viscosity of the polyurethane pull-up coating solution is more preferably 500 cPs to 10,000 cPs at 25 ° C, preferably 1,500 cPs to 6,000 cPs, in view of stability and workability.

On the other hand, since the polyurethane peel-up coating layer formed of the polyurethane peel-up coating solution is a coating layer which causes bleaching caused by cracks and thus has the greatest influence on the discoloration of the surface color, A process of homogeneously mixing at a mixing speed of 2,000 rpm is essential. The more uniform the dispersion is, the more clear and transparent the visual color of the discolorable laminate product can be expressed.

The polyurethane peel-off coating layer of the present invention formed of the polyurethane peel-up coating solution may have an average thickness of 10 to 80 mu m, and preferably an average thickness of 10 to 50 mu m. At this time, if the average thickness is less than 10 탆, there may be a problem that the surface discoloring effect is lowered. If the average thickness exceeds 80 탆, there may be a problem that the physical properties such as stretchability is lowered.

[Polyurethane adhesive layer]

In the discoloring laminate product of the present invention, the polyurethane adhesive layer serves to bond the substrate with the polyurethane skin layer, the polyurethane peel-up coating layer and / or the polyurethane layer as shown in Fig. 3, .

The polyurethane adhesive solution may be a polyurethane adhesive. In the present invention, the polyurethane adhesive may be a one-component adhesive or a two-component adhesive, depending on the required physical properties such as adhesive strength, -component) adhesives can be used. For products requiring high performance mechanical properties such as durability, two-component adhesives are usually used, and other one-component adhesives can be used.

In the case of the two-pack type adhesive, an aromatic isocyanate (trade name: AK-75, Aekyung Chemical) system is generally used as the crosslinking agent and a crosslinking agent based on a fatty isocyanate (trade name: PLHX, .

The polyurethane adhesive solution comprises 50 to 80 wt% of the polyurethane adhesive, 5 to 10 wt% of DMF and 15 to 40 wt% of MEK, preferably 60 to 80 wt% of a polyurethane adhesive, 5 to 10 wt% of DMF, 15 to 30% by weight can be used.

At this time, if the amount of the polyurethane adhesive is less than 50% by weight, the adhesiveness may deteriorate. If the amount of the polyurethane adhesive is more than 80% by weight, the viscosity of the adhesive may be too high.

The polyurethane adhesive solution may further comprise a toner. The amount of the toner to be used is preferably 1 to 15 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the polyurethane adhesive . The color of the toner used in the polyurethane adhesive solution is preferably darker than the color of the toner used in the polyurethane skin layer, and preferably a black-based toner is preferably used.

The polyurethane adhesive layer may have an average thickness of 15 to 80 탆, and preferably an average thickness of 20 to 50 탆. If the average thickness is less than 15 mu m, there may be a problem of poor adhesion. If the average thickness exceeds 80 mu m, bubbles may be excessively generated in the adhesive layer and the aging time may be 72 hours or more, It is preferable to have an average thickness within the above range.

[Other Layers]

As described above, a polyurethane coating layer may be further formed between the polyurethane peel-up coating layer and the polyurethane adhesive layer to increase the surface discoloring effect and to exhibit various surface colors through complementary colors, Urethane coating liquid.

The polyurethane coating solution may contain 40 to 70% by weight of a polyurethane dry resin, 5 to 20% by weight of dimethylformamide (DMF), and 10 to 40% by weight of methyl ethyl ketone (MEK) It is advantageous in view of the appropriate thickness and mechanical strength of the coating layer that it contains 55 to 70% by weight of resin, 5 to 10% by weight of DMF and 20 to 35% by weight of MEK.

The same polyurethane dry resin as used in the polyurethane skin layer can be used.

The polyurethane coating liquid may further contain 5 to 40 parts by weight of toner, preferably 5 to 30 parts by weight, based on 100 parts by weight of the polyurethane coating solution (polyurethane dry resin excluding DMF, DMF and MEK) . The toner may be a toner different from the color of the polyurethane skin layer. Preferably, the toner having a color darker than that of the toner used for the polyurethane skin layer is used in terms of complementary color.

The polyurethane coating layer may have an average thickness of 10 to 50 占 퐉, and preferably an average thickness of 15 to 30 占 퐉. If the average thickness is less than 10 탆, the mechanical properties may deteriorate. If the average thickness exceeds 50 탆, bubbles may excessively occur in the coating layer.

The discoloring laminate article of the present invention comprises a substrate layer, wherein the substrate layer is selected from the group consisting of a thermoplastic polyurethane (TPU) sheet, a thermoplastic polyolefin (TPO) sheet, a fabric, a microfiber cloth, a microfiber cloth, It is preferable to use at least one selected from artificial leather, wet film and natural leather.

The thickness of the substrate layer is varied depending on the substrate, and the average thickness may be 50 to 1,500 占 퐉, preferably 100 to 1,000 占 퐉. If the average thickness is less than 50 탆, the base layer may be too thin to reduce the mechanical properties. If the average thickness exceeds 1,500 탆, the weight of the product may increase, And the average thickness of the film.

A method of manufacturing a discolorable laminate product by physical stress of the present invention will be described below.

The discoloration laminate product of the present invention comprises: (a) coating a polyurethane skin coating solution on one side of a release paper on which a pattern pattern is formed, followed by drying to form a polyurethane skin layer; (b) coating a polyurethane peel-up coating solution on one surface of the polyurethane skin layer to form a polyurethane peel-up coating layer; (d) applying a polyurethane adhesive solution to one side of the polyurethane peel-up coating layer, semi-drying, and then fusing with the substrate; And (e) aging the mixture.

When the discoloration laminating product of the present invention further comprises a polyurethane coating layer, (a) coating a polyurethane skin coating solution on one side of a release paper on which a patterned pattern is formed and drying the polyurethane skin layer to form a polyurethane skin layer; (b) coating a polyurethane peel-up coating solution on one surface of the polyurethane skin layer to form a polyurethane peel-up coating layer; (c) coating and drying a polyurethane coating solution on one surface of the polyurethane peel-up coating layer to form a polyurethane coating layer; (d) applying a polyurethane adhesive solution to one surface of the polyurethane coating layer, semi-drying and then coating the substrate with the polyurethane coating solution; And (e) aging the mixture.

In addition, the two manufacturing methods include (e) aging; Thereafter, various processes such as digital photographic printing, surface light processing, surface color processing, laser etching, laser cutting, and punching can be added for various enlargement of the surface pattern.

In the manufacturing method of the present invention, the polyurethane skin coating solution is applied and coated on one surface of the release paper at a rate of 100 g / m ² to 250 g / m ² and then dried at 70 ° C to 130 ° C for 30 seconds ~ 5 minutes drying can be performed.

Further, in the production method of the present invention, the step (b) the polyurethane coating on the pull-up polyurethane skin layer surface to ^{100 g / m 2 ~ 250 g} / m 2 Coating and coating are preferable in terms of forming a pull-up coating layer with an appropriate thickness.

In step (c), the polyurethane coating solution may be coated on one surface of the polyurethane coating layer at 100 to 250 g / m ² Coating and coating are preferable in terms of formation of a suitable polyurethane coating layer.

In the step (d), the impregnation is preferably carried out at a pressure of 1 to 10 kg / cm ^{2 for} 0.5 to 3 seconds.

The aging in step (e) is carried out to increase the hardenability of the polyurethane adhesive layer, and it is preferable to aged at 50 to 90 ° C. for 12 to 72 hours. When the aging temperature is lower than 50 ° C., There may be a problem that the adhesion increases remarkably due to a delay in the increase of the curing temperature, and when the temperature exceeds 90 ° C, the curing reaction proceeds rapidly, which may lead to excessive bubbles in the polyurethane adhesive layer. If the aging time is less than 12 hours, the increase in hardenability due to aging can not be observed. If the aging time exceeds 72 hours, it is disadvantageous from the commercial viewpoint.

In the above-mentioned two manufacturing methods, a method for producing the polyurethane pull-up coating solution will be described. A copolymer polyol of 1,4-butanediol and adipic acid having a number average molecular weight of 1,000 to 3,000, neopentyl glycol and 1,4- A polyether polyol containing at least one selected from a copolymerized polyol such as a copolymerized polyol; Or a polyether polyol such as polytetramethylene glycol and the like, or a chain extender containing at least one selected from 1,4-butanediol, ethylene glycol, neopentyl glycol, 1,6-hexanediol, and diethylene glycol, Two or more of them are mixed to form a polyol composition. The isocyanate is mixed with the polyol composition to carry out a urethane reaction to prepare a pull-up polyurethane resin having a viscosity of 60,000 to 90,000 cps at 25 ° C.

Next, a polyurethane resin for pulling up and waxes, silica, calcium carbonate, titanium oxide alone or two or more additives; DMF; And MEK can be mixed to prepare a polyurethane pull-up coating liquid exhibiting a viscosity of 15,000 to 25,000 cps at 25 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.

Comparative Example 1

(1) 40% by weight of polyurethane dry resin for skin (trade name D-ACE 8301, Dong Sung Chemical) widely used in the artificial leather industry, 5% by weight of DMF, 30% by weight of MEK, and black toner (trade name: SU7809 BLACK, 25 weight%) were mixed and then mixed with a high-speed stirrer for 30 minutes to prepare a polyurethane coating solution.

(2) 70% by weight of a polyurethane adhesive (trade name UA-5900 70, Fine Chemical), 5% by weight of DMF and 25% by weight of MEK were mixed and mixed with a high-speed stirrer for 30 minutes to prepare a polyurethane adhesive solution.

(3) The polyurethane coating solution was coated on a release paper having a pattern formed thereon with a knife coater at about 150 g / m ² and dried at 120 ° C for 1 minute to form a film.

Next, in order to increase the physical properties of the coating layer in the artificial leather products, an additional coating (secondary coating) is carried out on the primary coated film. Therefore, the polyurethane coating liquid of the same composition coated on the primary side is knife coated , 150 g / m < ² > was coated with a secondary coating and dried at 120 DEG C for 1 minute to form a polyurethane coating layer having a two-layer structure.

After confirming that the polyurethane adhesive solution was completely dried, 180 g / m ² of the polyurethane adhesive solution was applied on the polyurethane coating layer of the two-layer structure using a knife coater, semi-dried at 120 ° C for 1 minute, While maintaining the adhesive properties, laminate products were prepared by using a transparent WINMELT-S TPU sheet (hot melt film) sold by Juwon Tech Co., Ltd. and a compression roll.

A cross section and a surface photograph of the laminate product are shown in FIG. 1A, and it can be confirmed that the surface color is black.

The laminate product of Comparative Example 1 is manufactured in accordance with the conventional artificial leather manufacturing process and can be stretched based on the high elongation of the TPU material but the color of the surface is fixed to a single color, 1b that the surface color does not change even if it works.

Example 1

(1) Preparation of polyurethane skin coating liquid

60% by weight of polyurethane dry resin (trade name: D-ACE 8301, Dong Sung Chemical), 5% by weight of DMF, 30% by weight of MEK and 5% by weight of yellow toner To prepare a yellow polyurethane skin coating solution.

(2) Production of polyurethane pull-up coating liquid

65 wt% of pulling-up polyurethane resin (trade name: BS 109. Baic acid), 5 wt% of DMF and 30 wt% of MEK were mixed and uniformly stirred and mixed for 1 hour by a high-speed stirrer to prepare a polyurethane pull- The viscosity of one coating solution was 2,500 cPs (25 캜).

(3) Production of polyurethane adhesive solution

75% by weight of a polyurethane adhesive (trade name: UA-5900 70, Fine Chemical), 6% by weight of DMF and 19% by weight of MEK were mixed. Then, 100 parts by weight of the polyurethane adhesive was mixed with a black toner (trade name: SU BLACK 7809 , 1 part by weight) was mixed and stirred with a high-speed stirrer for 30 minutes to prepare a polyurethane adhesive solution.

(4) Manufacture of laminate products

The polyurethane skin coating solution of yellow color was applied on a releasing paper having a first pattern on the basis of a knife coater in an amount of about 150 g / m ² and dried at 120 ° C for 1 minute to prepare a polyurethane skin layer (average thickness 20 μm) .

Next, an amount of about 120 g / m < ² > was applied to the polyurethane skin layer using a knife coater and dried at 120 DEG C for 1 minute to obtain a polyurethane peeling layer (average thickness of 15 mu m) / RTI >

Next, after fully dried, the polyurethane adhesive solution was applied to the upper surface of the polyurethane peel-up coating layer at 180 g / m ² using a knife coater, semi-dried at 120 ° C for 1 minute, (Average thickness 200 μm) and a compression roll, which were sold by Juwon Tech Co., Ltd., were used. At this time, the impregnation was carried out under a pressure of 6 kg / cm ^{2 for} 2 to 3 seconds.

The resulting laminate product was aged at 70 < 0 > C for 48 hours to produce a discolorable laminate product.

The names of the various raw materials used in the above embodiments are not limited to the above embodiments.

The above-mentioned object was able to exhibit a visually striking appearance color by exhibiting excellent color discoloration through stretching based on the high elongation characteristic unique to the base material TPU material. FIG. 3A shows SEM measurement photographs of the fabricated discolorable laminate product, and FIG. 3B shows a color change photograph of the fabricated discolorable laminate product upon stretching.

Example 2

(1) Preparation of polyurethane skin coating liquid

60% by weight of a polyurethane dry resin (trade name: BSP-5070, Baic acid), 5% by weight of DMF, 30% by weight of MEK and 5% by weight of a blue toner (trade name: PF BLUE, Song Jeung Chemical) Followed by stirring and mixing to prepare a blue colored polyurethane skin coating solution.

(2) Production of polyurethane pull-up coating liquid

65 wt% of pulling-up polyurethane resin (trade name: BS 109. Baic acid), 5 wt% of DMF and 30 wt% of MEK were mixed and uniformly stirred and mixed for 1 hour by a high-speed stirrer to prepare a polyurethane pull- The viscosity of one coating solution was 2,500 cPs (25 캜).

(3) Production of polyurethane coating liquid

68% by weight of a polyurethane dry resin (trade name: BSP-5070, Baic acid), 7% by weight of DMF and 25% by weight of MEK were mixed to prepare a mixed solution. 100 parts by weight of the mixed solution was mixed with 100 parts by weight of a red toner , Song Jung Chemical Co., Ltd.) were mixed and stirred with a high-speed stirrer for 30 minutes to prepare a red colored polyurethane coating solution.

(4) Manufacture of polyurethane adhesive solution

70% by weight of a polyurethane adhesive (trade name: UA-5900 70, Fine Chemical), 5% by weight of DMF and 25% by weight of MEK were mixed and mixed with a high-speed stirrer for 30 minutes to prepare a polyurethane adhesive solution.

(5) Manufacture of laminate products

The blue polyurethane skin coating solution was coated on the release paper by about 150 g / m ² using a knife coater and dried at 120 ° C for 1 minute to form a polyurethane skin coating layer (average thickness of 20 μm).

Next, about 120 g / m < ² > was applied on the polyurethane skin coating layer using a knife coater and dried at 120 DEG C for 1 minute to form a polyurethane peel-up coating layer (average thickness of 15 mu m).

Next, the red polyurethane coating liquid prepared above was applied to the upper surface of the polyurethane peel-up coating layer at a rate of about 150 g / m ² using a knife coater and dried at 120 ° C for 1 minute to form a polyurethane coating layer Thickness: 20 mu m).

Next, after confirming that the polyurethane adhesive solution was completely dried, 180 g / m ² of the polyurethane adhesive solution was applied to the upper surface of the red polyurethane coating layer using a knife coater, semi-dried at 120 ° C for 1 minute, While keeping the adhesive property, the laminate was prepared by using a WINMELT-S TPU sheet (average thickness 200 mu m) sold by Juwon Tech Co., Ltd. and a compression roll. At this time, the impregnation was carried out under a pressure of 6 kg / cm ^{2 for} 2 to 3 seconds.

The resulting laminate product was aged at 70 < 0 > C for 48 hours to produce a discolorable laminate product. FIG. 4 shows a photograph of the color change caused by the stretching of the discolorable laminate product.

Example 3

(1) Preparation of polyurethane skin coating liquid

A clear polyurethane skin coating solution was prepared by stirring a transparent mixed solution containing 60% by weight of a polyurethane dry resin (trade name: BSP-5070, Baic acid), 5% by weight of DMF and 35% by weight of MEK with a high speed stirrer for 30 minutes.

(2) Production of polyurethane pull-up coating liquid

65 wt% of pulling-up polyurethane resin (trade name: BS 109. Baic acid), 5 wt% of DMF and 30 wt% of MEK were mixed and uniformly stirred and mixed for 1 hour by a high-speed stirrer to prepare a polyurethane pull- The viscosity of one coating solution was 2,500 cPs (25 캜).

(3) Production of polyurethane coating liquid

40% by weight of polyurethane dry resin (trade name UB-501MB, Fine Chemical), 5% by weight of DMF, 35% by weight of MEK and 20% by weight of red toner (trade name SU RED, Followed by stirring and mixing to prepare a red colored polyurethane coating solution.

(4) Manufacture of polyurethane adhesive solution

70% by weight of a polyurethane adhesive (trade name: UA-5900 70, Fine Chemical), 5% by weight of DMF and 25% by weight of MEK were mixed and mixed with a high-speed stirrer for 30 minutes to prepare a polyurethane adhesive solution.

(5) Manufacture of laminate products

The transparent polyurethane skin coating solution was coated on the release paper at a rate of about 150 g / m ² using a knife coater and dried at 120 ° C. for 1 minute to form a polyurethane skin coating layer (average thickness of 20 μm).

Next, about 120 g / m ^{2 was} applied to the polyurethane skin coating layer using a polyurethane pull-up coating knife coater and dried at 120 ° C for 1 minute to form a polyurethane pull-up coating layer (average thickness of 15 μm).

Next, 150 g / m ² of the red color polyurethane coating liquid prepared above was applied to the upper surface of the polyurethane peel-up coating layer using a knife coater and dried at 120 ° C for 1 minute to obtain a polyurethane coating layer (average thickness 20 mu m).

Next, after it was confirmed to be completely dried, a coating solution for polyurethane coating was applied to the upper surface of the polyurethane coating layer at a rate of about 180 g / m ² using a knife coater, semi-dried at 120 ° C. for 1 minute, The lamination was carried out using a WINMELT-S TPU sheet (average thickness 200 μm) sold by Juwon Tech Co., Ltd. and a compression roll. At this time, the impregnation was carried out under a pressure of 6 kg / cm ^{2 for} 2 to 3 seconds.

The resulting laminate product was aged at 70 < 0 > C for 48 hours to produce a discolorable laminate product.

With the above-mentioned implementations, artificial leather materials having no surface color limitation and being visually striking were obtained. FIG. 5 shows a photograph of the color change according to the stretching of the discolored laminate product.

Example 4

(1) Preparation of polyurethane skin coating liquid

60% by weight of a polyurethane dry resin (trade name: BSP-5070, Baic acid), 5% by weight of DMF, 30% by weight of MEK and 5% by weight of a yellow toner (trade name: SCU YELLOW, To prepare a yellow polyurethane skin coating solution.

(2) Production of polyurethane pull-up coating liquid

65 wt% of pulling-up polyurethane resin (trade name: BS 109. Baic acid), 5 wt% of DMF and 30 wt% of MEK were mixed and uniformly stirred and mixed for 1 hour by a high-speed stirrer to prepare a polyurethane pull- The viscosity of one coating solution was 2,500 cPs (25 캜).

(3) Production of polyurethane adhesive solution

75% by weight of a polyurethane adhesive (trade name: UA-5900 70, Fine Chemical), 6% by weight of DMF and 19% by weight of MEK were mixed. Then, 100 parts by weight of the polyurethane adhesive was mixed with a black toner (trade name: SU BLACK 7809 , 1 part by weight) was mixed and stirred with a high-speed stirrer for 30 minutes to prepare a black polyurethane adhesive solution.

(4) Preparation of TPU substrate with pattern on the surface by real printing

A pattern was formed on the surface of the WINMELT-S TPU sheet (average thickness 200 mu m) sold by Juwon Tech Co., Ltd. using the actual print.

(5) Manufacture of laminate products

The yellow polyurethane skin coating solution was coated on the release paper at about 150 g / m ² using a knife coater and dried at 120 ° C for 1 minute to form a polyurethane skin coating layer (average thickness of 20 μm).

Next, about 120 g / m < ² > was applied on the polyurethane skin coating layer using a knife coater and dried at 120 DEG C for 1 minute to form a polyurethane peel-up coating layer (average thickness of 15 mu m).

Next, after confirming that the polyurethane adhesive solution was completely dried, the black polyurethane adhesive solution was applied on the upper surface of the blue polyurethane coating layer at 180 g / m ² using a knife coater and dried at 120 ° C for 1 minute after the happo was performed by using a compression roll and while appropriately maintaining the surface tack, TPU sheet (average thickness 200㎛) that implements the inspection in the print pattern on the surface of the substrate, at this time, happo 2 under 6 kg / cm ² pressure ≪ / RTI > for 3 seconds.

The resulting laminate product was aged at 70 < 0 > C for 48 hours to produce a discolorable laminate product. FIG. 6 shows a photograph of the color change according to the stretching of the manufactured discoloration laminate product, and it was confirmed that the actual print pattern disappears as the surface color is discolored.

The above-mentioned laminate product is a type of linking the surface color-changing coating and the actual print, and the present laminate product has a characteristic in which a vividly expressed surface-realignment pattern has an effect of disappearing naturally when external stress acts on the substrate itself. In addition, in order to give various effects based on the actual print pattern, it is possible to carry out the actual print printing directly on the surface color discoloration coating.

Example 5

(1) Preparation of polyurethane skin coating liquid

60% by weight of a polyurethane dry resin (trade name: BSP-5070, Baic acid), 5% by weight of DMF, 30% by weight of MEK and 5% by weight of a yellow toner (trade name: SCU YELLOW, To prepare a yellow polyurethane skin coating solution.

(2) Production of polyurethane pull-up coating liquid

65 wt% of pulling-up polyurethane resin (trade name: BS 109. Baic acid), 5 wt% of DMF and 30 wt% of MEK were mixed and uniformly stirred and mixed for 1 hour by a high-speed stirrer to prepare a polyurethane pull- The viscosity of one coating solution was 2,500 cPs (25 캜).

(3) Production of polyurethane coating liquid

68% by weight of a polyurethane dry resin (trade name: BSP-5070, Baic acid), 7% by weight of DMF and 25% by weight of MEK were mixed to prepare a mixed solution. Then, 100 parts by weight of the mixed solution was blended with a blue toner , And 33 parts by weight of a polyurethane coating liquid of blue color was prepared by mixing and stirring for 30 minutes with a high-speed stirrer.

(4) Manufacture of polyurethane adhesive solution

70% by weight of a polyurethane adhesive (trade name: UA-5900 70, Fine Chemical), 5% by weight of DMF and 25% by weight of MEK were mixed and mixed with a high-speed stirrer for 30 minutes to prepare a polyurethane adhesive solution.

(5) Manufacture of laminate products

The yellow polyurethane skin coating solution was coated on the release paper at about 150 g / m ² using a knife coater and dried at 120 ° C for 1 minute to form a polyurethane skin coating layer (average thickness of 20 μm).

Next, about 120 g / m < ² > was applied on the polyurethane skin coating layer using a knife coater and dried at 120 DEG C for 1 minute to form a polyurethane peel-up coating layer (average thickness of 15 mu m).

Next, the blue polyurethane coating solution prepared above was applied to the upper surface of the polyurethane peel-up coating layer at a rate of about 150 g / m ² using a knife coater and dried at 120 ° C for 1 minute to form a polyurethane coating layer Thickness: 20 mu m).

Next, after confirming that the polyurethane adhesive solution was completely dried, 180 g / m ² of the polyurethane adhesive solution was applied to the upper surface of the blue polyurethane coating layer using a knife coater, semi-dried at 120 ° C for 1 minute, by using a compression roll and a stay (Day) WINMELT-S TPU sheet (average thickness 200㎛) sold in Joowon Tech while still tacky was performed on the happo, at this time, happo is 2 or 3 under 6 kg / cm ² pressure Lt; / RTI > The resulting laminate product was aged at 70 캜 for 48 hours, and the hotmelt TPU base layer and the stretchable fabric fabric (average thickness 800 탆) included in the product were laminated using a thermocompressor . At this time, the lamination was carried out by applying pressure for 30 seconds under the pressure of 60 kg / cm ² at the upper and lower plates of the thermocompressor at 140 ° C.

The next manufactured laminate product was allowed to stand at room temperature for 1 hour, and then a discolorable laminate product was prepared which can be used as a base fabric.

As a result, an artificial leather material was obtained in which the surface color discoloration was very excellent and the surface color was expressed in various colors.

The surface discoloration of the discoloration laminate product prepared in Example 5 before and after stretching is shown in Fig. It can be seen from the polyurethane skin layer direction that the surface color changes to dark gray (A in FIG. 7) before stretching but bright yellow in the stretched state (FIG. 7B) before stretching.

The present invention can be applied to various substrates (TPU, fabric, nonwoven fabric, microfibers, natural leather, etc.) through the above-described embodiments. In particular, And it was confirmed that the product conformed to the various needs of. Such discolorable laminate products due to physical stresses are excellent in visual discoloration effect, so that they can be used not only for existing sports shoes but also for clothing, furniture, bags, balls, wallets, belts, accessories, automobile interior materials, Products, and other miscellaneous goods.

Claims (23)

A polyurethane skin layer;
A polyurethane pull-up coating layer exhibiting bleaching phenomenon;
A polyurethane adhesive layer; And
And a base layer,
The polyurethane adhesive layer is formed of a polyurethane adhesive solution containing 50 to 80% by weight of a polyurethane adhesive, 5 to 10% by weight of DMF and 15 to 40% by weight of MEK,
Wherein the polyurethane skin layer, the polyurethane peel-up coating layer, the polyurethane adhesive layer, and the base layer are laminated in this order.
The article of claim 1, further comprising a polyurethane coating layer between the polyurethane adhesive layer and the polyurethane peel-up coating layer.
The polyurethane adhesive layer according to claim 1, wherein the polyurethane skin layer has an average thickness of 10 to 50 占 퐉, the polyurethane peel-up coating layer has an average thickness of 10 to 80 占 퐉, the polyurethane adhesive layer has an average thickness of 15 to 80 占 퐉, Is an average thickness of 45 to 210 < RTI ID = 0.0 > pm. ≪ / RTI > 3. The product of claim 2, wherein the polyurethane coating layer has an average thickness of 10 to 50 占 퐉.
The polyurethane skin layer according to claim 1, wherein the polyurethane skin layer
Wherein the polyurethane resin is formed from a polyurethane skin coating liquid containing 30 to 70% by weight of a polyurethane dry resin, 5 to 20% by weight of dimethylformamide (DMF) and 15 to 50% by weight of methyl ethyl ketone (MEK) Discolorable laminate products.
The discoloration product according to claim 1, wherein the polyurethane skin coating solution further comprises 1 to 40 parts by weight of toner based on 100 parts by weight of the polyurethane dry resin.
2. The coating composition of claim 1, wherein the polyurethane < RTI ID = 0.0 >
Characterized in that it is formed from a polyurethane peel-up coating liquid comprising 50 to 80% by weight of a pull-up polyurethane resin, 5 to 20% by weight of DMF and 15 to 45% by weight of MEK, product. 8. The coating composition of claim 7, wherein the polyurethane < RTI ID = 0.0 >
Characterized in that it further comprises at least one additive selected from the group consisting of silica, wax, calcium carbonate and titanium oxide.
9. The method according to claim 8, wherein the polyurethane coating composition is comprised of 5 to 50 parts by weight of at least one additive selected from silica, wax, calcium carbonate and titanium oxide, based on 100 parts by weight of the polyurethane pull- product.
8. The article of claim 7, wherein the polyurethane pull-up coating has an average viscosity of from 500 to 10,000 cPs (25 DEG C).
delete The discoloration laminate product according to claim 1, wherein the polyurethane adhesive further comprises 1 to 15 parts by weight of a black toner based on 100 parts by weight of the polyurethane adhesive.
The article of claim 1, wherein the polyurethane adhesive further comprises at least one crosslinker selected from aromatic isocyanates and aliphatic isocyanates.
The polyurethane coating composition according to claim 2, wherein the polyurethane coating layer
A polyurethane coating liquid comprising 40 to 70% by weight of a polyurethane dry resin, 5 to 20% by weight of dimethylformamide (DMF) and 10 to 40% by weight of methyl ethyl ketone (MEK) Discolorable laminate products.
15. The method according to claim 14, wherein the polyurethane coating liquid
Further comprising 5 to 30 parts by weight of toner based on 100 parts by weight of the polyurethane coating liquid.
2. The method of claim 1, wherein the substrate layer is selected from the group consisting of a thermoplastic polyurethane (TPU) sheet, a thermoplastic polyolefin (TPO) sheet, a fabric, a microfiber cloth, a microfiber cloth, a wet type artificial leather, a dry type artificial leather, ≪ RTI ID = 0.0 > 1, < / RTI >
(a) coating a polyurethane skin coating solution on one side of a release paper on which a pattern pattern is formed, and then drying to form a polyurethane skin layer;
(b) coating a polyurethane peel-up coating solution on one surface of the polyurethane skin layer to form a polyurethane peel-up coating layer;
(d) applying a polyurethane adhesive solution to one side of the polyurethane peel-up coating layer, semi-drying, and then fusing with the substrate; And
(e) aging;
≪ RTI ID = 0.0 > 1, < / RTI >
(a) coating a polyurethane skin coating solution on one side of a release paper on which a pattern pattern is formed, and then drying to form a polyurethane skin layer;
(b) coating a polyurethane peel-up coating solution on one surface of the polyurethane skin layer to form a polyurethane peel-up coating layer;
(c) coating and drying a polyurethane coating solution on one surface of the polyurethane peel-up coating layer to form a polyurethane coating layer;
(d) applying a polyurethane adhesive solution to one surface of the polyurethane coating layer, semi-drying and then coating the substrate with the polyurethane coating solution; And
(e) aging;
≪ RTI ID = 0.0 > 1, < / RTI >
The method of claim 17 or 18, wherein the step (a) comprises coating and coating the polyurethane skin coating solution at 100 g / m ² to 250 g / m ² on one side of the release paper, Followed by drying for 30 seconds to 5 minutes. ≪ RTI ID = 0.0 > 11. < / RTI >
[18] The method of claim 17 or 18, wherein the step (b) comprises applying the polyurethane pulp coating solution on one side of the polyurethane skin layer at a rate of 100 g / m ² to 250 g / m ² A method for producing a discolorable laminate product by physical stress.
19. The method of claim 18, wherein the step (c) comprises applying a polyurethane coating solution to one surface of the polyurethane peel-up coating layer at 100 to 250 g / m ² A method for producing a discolorable laminate product by physical stress.
The method according to claim 17 or 18, wherein the composite of step (d) is performed for 0.5 to 3 seconds under a pressure of 1 to 10 kg / cm ² .
The method according to claim 17 or 18, wherein the aging in step (e) is performed at 50 ° C to 90 ° C for 12 hours to 72 hours.

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