KR20020066360A - Laminated Polymer and Manufacturing method of the same - Google Patents

Abstract

PURPOSE: To provide a polymeric laminate enhanced in the adhesiveness of a sheet member formed of polymeric foam and a polymeric sheet member. CONSTITUTION: The polymeric laminate has the sheet member comprising either one of an ethylene/vinyl acetate thermoplastic elastomer foam and a 1,2- polybutadiene type thermoplastic elastomer foam both of which have plasma treated surfaces, the polymeric sheet member and the urethane adhesive layer interposed between both sheet members.

Description

Polymer laminate and its manufacturing method {Laminated Polymer and Manufacturing method of the same}

The present invention relates to a polymer laminate obtained by adhering a sheet member and a polymer sheet member with a urethane-based adhesive, and to a method of manufacturing the same. More specifically, the polymer laminate having improved adhesion between the sheet member and the polymer sheet member and its manufacture The present invention relates to a polymer laminate and a method for producing the same, which specifically improve the adhesion between the midsole member and the outsole member used for the sole.

When manufacturing soles such as tennis shoes, sports shoes and walking shoes, a polymer laminate is formed by laminating an outsole member in contact with the ground and a midsole member positioned above and formed of a polymer foam.

In order to ensure the flexibility of the sole and to maintain the adhesiveness between the outsole member and the midsole member firmly, the adhesion between the outsole member and the midsole member may be adhered by a urethane-based adhesive.

In order to maintain the adhesion between the outsole member and the midsole member, polishing by buffing is performed on the outsole member and the midsole member as a pretreatment, and an organic solvent primer may be applied after surface cleaning with an organic solvent. . Such buffing increases the adhesion area between the outsole member and the midsole member, and gives a fixing effect to the outsole member and removes the oil component deposited on the surface thereof, thereby improving the adhesion between the outsole member and the midsole member. Increase significantly.

However, since buffing is often performed by hand and requires a great deal of labor and time, productivity and running cost were not relatively good. In addition, dust generated during buffing may adversely affect workers and the environment. Further, in buffing, there is a possibility that gaps occur easily in the adhesive state due to uneven processing, and the reliability of the adhesive force between the outsole member and the midsole member may be low. In addition, there was a possibility of adversely affecting the operator and the environment by surface cleaning with an organic solvent and application of an organic solvent primer.

The present invention has been made to solve the above problems, and an object thereof is to provide a polymer laminate having improved adhesion between a sheet member formed of a polymer foam and a polymer sheet member, and a method of manufacturing the same.

As described in claim 1, the polymer laminate according to the present invention may be a plasma-treated ethylene-vinyl acetate-based thermoplastic polymer foam (hereinafter referred to as EVA foam) or a 1,2-polybutadiene-based thermoplastic polymer foam (hereinafter, It is a polymer laminated body which has a sheet member which consists of any one of RB foams), a polymer sheet member, and the urethane type adhesive layer interposed between the said sheet member and the said polymer sheet member.

In addition, as described in claim 2, the polymer laminate according to the present invention is a polymer laminate in which the upper member is adhesively integrated with the sheet member via a second urethane-based adhesive layer.

In the polymer laminate according to the present invention, as described in claim 3, in the invention according to claim 1 or 2, the sheet member is a midsole member used for the sole, and the polymer sheet member is attached to the sole. It is a polymer laminated body which is an outsole member used.

In addition, the method for producing a polymer laminate according to the present invention is, as described in claim 4, a plasma treatment step of performing a plasma treatment on a sheet member made of either an EVA foam or an RB foam, and the sheet member after the plasma treatment process. Joining a first coating step of applying a urethane adhesive to a second coating step, a second coating step of applying a urethane adhesive to a polymer sheet member, a sheet member after the first coating step, and a polymer sheet member after the second coating step It is a manufacturing method of a polymer laminated body which has a sticking process.

Moreover, as for the manufacturing method of the polymer laminated body which concerns on this invention, as described in Claim 5, in the invention of Claim 4, after the 3rd application process of apply | coating a urethane type adhesive agent to an upper member, and after the said 3rd application process It is a manufacturing method of the polymer laminated body which has an upper member and the 2nd bonding process which pastes the sheet member after a said 1st application process.

Moreover, as for the manufacturing method of the polymer laminated body which concerns on this invention, as described in Claim 6, in the invention of Claim 4 or 5, while the said sheet member is a midsole member used for a sole, the said polymer sheet A member is a manufacturing method of a polymer laminated body which is an outsole member used for a sole.

Moreover, as for the manufacturing method of the polymer laminated body which concerns on this invention, as described in Claim 7, the invention of any one of Claims 4-6 WHEREIN: In the said plasma processing process, a plasma irradiation output is 150-250 W In addition, the plasma irradiation time is 1 to 3 seconds, the plasma irradiation distance is 5 to 15 mm, and the method for producing a polymer laminate having a plasma irradiation area of 3 to 7 cm ² .

Moreover, as for the manufacturing method of the polymer laminated body which concerns on this invention, in the invention as described in any one of Claims 4-7, in the said 1st coating process and the said 2nd coating process, as described in Claim 8, It is a manufacturing method of the polymer laminated body which apply | coats the said urethane type adhesive agent so that the application amount of a non volatile component may be 30 g / m <^2> -60 g / m <^2> .

Moreover, as for the manufacturing method of the polymer laminated body which concerns on this invention, in the invention as described in any one of Claims 4-8, in the said 1st coating process and the said 2nd coating process in any one of Claims 4-8, It is a manufacturing method of the polymer laminated body whose ratio of the polyisocyanate-type hardening | curing agent in the said urethane type adhesive agent is 3-7 mass%.

In the method for producing a polymer laminate according to the present invention, as described in claim 10, the polymer according to any one of claims 4 to 9, wherein the plasma treatment in the plasma treatment step is performed in the air. It is a manufacturing method of a laminated body.

The polymer laminate according to the present invention has a sheet member composed of any one of an EVA foam or RB foam subjected to plasma treatment, a polymer sheet member, and a urethane-based adhesive layer interposed between the sheet member and the polymer sheet member.

Plasma treatment is performed on a sheet member made of either an EVA foam or an RB foam. The plasma treatment gives a cleaning effect on the surface of the sheet member. That is, the plasma is bonded to the dirt such as organic matter adhered to the surface of the sheet member, thereby cleaning the organic matter adhered to the surface of the sheet member. Moreover, the roughening effect appears on the surface of the said sheet member by performing a plasma process. That is, atomic level irregularities are produced on the surface of the sheet member by the plasma particles by performing the plasma treatment. In addition, an active effect appears on the surface of the sheet member by performing a plasma treatment. That is, by performing plasma treatment, the molecular bond rings on the surface of the sheet member can be decomposed by the plasma particles. In the case where the molecular bond ring on the surface of the sheet member is decomposed, hydrophilic groups such as hydroxyl groups and carboxyl groups, which tend to become familiar with the liquid, are formed on the surface of the sheet member. When a hydrophilic group is formed on the surface of the sheet member, the adhesive becomes easy to fuse to the surface of the sheet member.

Thus, by performing a plasma process on the said sheet member, the cleaning effect, the roughening effect, and the active effect are expressed on the surface of the said sheet member, and the wettability of the said sheet member surface is improved by these effects. Since the wettability of the surface of the sheet member is improved, when the sheet member and the polymer sheet member are composed of a polymer laminate through a urethane-based adhesive layer, adhesion between the sheet member and the polymer sheet member can be greatly improved. It is.

The sheet member is formed by either EVA foam or RB foam. In addition, EVA can be made by radical copolymerization of ethylene and vinyl acetate under high temperature and high pressure conditions. EVA is, for example, ultracene of Tong Yang procurement industry, Evaflex of Mitsui-Dupont Polychemistry, Sumate of Sumitomo Chemical Industries, Yukaron-Eva of Mitsubishi Emulsion, NUC copolymer-EVA of Japan Yunaka, Japan Synthetic Chemical It is possible to use industrial Sox Rex. RB can make butadiene into solution polymerization by the cobalt type Ziegler type catalyst. For example, RB may use JSR RB made of nitrile rubber.

As the polymer sheet member, a sheet member of TPU or a sheet member of PAE can be used. TPU is a thermoplastic urethane resin. In addition, PAE is a polyamide elastomer.

In the polymer laminate according to the present invention, the upper member can be adhesively integrated through the second urethane-based adhesive layer. The upper member can be formed of any one of natural leather, artificial leather, synthetic leather, natural fiber and synthetic fiber. Natural leather is leather that is tanned, dyed, and processed for animal skins such as cattle, horses, pigs, and kangaroos. In addition, artificial leather is leather which impregnated the polyurethane resin in the nonwoven fabric of synthetic fiber, and applied it to the surface. In addition, synthetic leather is leather which apply | coated polyvinyl chloride, nylon, and polyurethane to the surface of a woven fabric. In addition, natural fibers are fibers collected from plants and animals such as cotton, hemp, silk, wool and the like. In addition, synthetic fibers are artificial fibers such as nylon, polyester and vinylon.

In the polymer laminate according to the present invention, the sheet member is used as the midsole member used for the sole, and the polymer sheet member can be used as the outsole member used for the sole. That is, by performing a plasma treatment on the midsole member, the cleaning effect, the roughing effect and the active effect are expressed on the surface of the midsole member, and the wettability of the surface of the midsole member is improved by these effects. Since the wettability of the surface of the midsole member is improved, when the polymer laminate is composed of the midsole member and the outsole member via the urethane-based adhesive layer, the adhesion between the midsole member and the outsole member can be remarkably improved.

The manufacturing method of the polymer laminated body which concerns on this invention is a plasma processing process which plasma-processes the sheet member which consists of EVA foam or RB foam, and the 1st application | coating process which apply | coats a urethane type adhesive agent to the said sheet member after the said plasma processing process. And a second application step of applying a urethane adhesive to the polymer sheet member, and a pasting step of pasting the sheet member after the first application step and the polymer sheet member after the second application step.

In the plasma treatment step, a plasma treatment is performed on a sheet member made of either an EVA foam or an RB foam. By performing a plasma treatment on the sheet member, a cleaning effect, a roughening effect and an active effect are expressed on the surface of the sheet member, and the wettability of the surface of the sheet member is improved by these effects. In the first coating step, a urethane-based adhesive is applied to the sheet member subjected to the plasma treatment. In the second coating step, a urethane-based adhesive is applied to the polymer sheet member. Thereafter, in the pasting step, the sheet member after the first coating step and the polymer sheet member after the second coating step are pasted together. In the plasma treatment step, since the wettability of the surface of the sheet member is improved, the adhesiveness of the sheet member and the polymer sheet member can be remarkably improved through a urethane adhesive.

The manufacturing method of the polymer laminated body which concerns on this invention is the 2nd pasting process which joins the 3rd application process which apply | coats a urethane type adhesive agent to an upper member, the upper member after the said 3rd application process, and the sheet member after the said 1st application process. It is possible to have a process.

The sheet member after the said 1st coating process has already improved wettability by a plasma processing process. Therefore, the urethane-based adhesive is applied to the upper member by the third coating step, and the upper member after the third coating step and the sheet member after the first coating step are bonded together by the second bonding step. The sheet member and the upper member can be improved remarkably through their urethane adhesive.

The manufacturing method of the polymer laminated body which concerns on this invention can be set as the midsole member used for a sole, and the outsole member used for a said sole, and the said polymer sheet member. That is, by performing a plasma treatment process on a midsole member, the washing | cleaning effect, the roughening effect, and the active effect are expressed on the surface of a midsole member, and these effects improve the wettability of the surface of a midsole member. Since the wettability of the surface of the midsole member is improved, the adhesion between the midsole member and the outsole member can be remarkably improved through the urethane adhesive.

In the method for producing a polymer laminate according to the present invention, in the plasma processing step, the plasma irradiation output is 150 to 250 W, the plasma irradiation time is 1 to 3 seconds, and the plasma irradiation distance is 5 to 15 mm, It is also possible to set the plasma irradiation area to 3 to 7 cm ² .

Plasma irradiation output can be 150-250W. This is because the adhesion improvement effect may be low when the plasma irradiation output is smaller than 150W. This is because deterioration of the material surface may occur when the plasma irradiation output is larger than 250W.

The plasma irradiation time can be 1 to 3 seconds. This is because a decrease in the adhesion improving effect may occur when the plasma irradiation time is shorter than 1 second. This is because deterioration of the surface of the material may be seen when the plasma irradiation time is longer than 3 seconds.

The plasma irradiation distance can be 5 to 15 mm. This is because deterioration of the surface of the material may be seen when the plasma irradiation distance is smaller than 5 mm. This is because, when the plasma irradiation distance is larger than 15 mm, the adhesion improving effect may be lowered.

It is possible to make plasma irradiation area into 3-7 cm <^2> . This is because the irradiation efficiency may decrease when the plasma irradiation area is smaller than 3 cm ² . When the plasma irradiation area is larger than 7 cm ² , the effect of improving adhesion may decrease.

In the method for producing a polymer laminate according to the present invention, in the first coating step and the second coating step, it is possible to apply the urethane-based adhesive so that the coating amount of the nonvolatile component is 30 g / m ² to 60 g / m ² . Do. This is because when the coating amount in the nonvolatile component of the urethane-based adhesive is smaller than 30 g / m ² , the adhesive layer of the convex portion on the surface of the material becomes thin and the adhesive force may decrease. Moreover, when the application amount in the non volatile component of the said urethane type adhesive agent is larger than 60 g / m <^2> , it is because the adhesive layer of the recessed part of a material surface may become thick, and adhesive force may fall by lack of drying of an adhesive surface.

In the manufacturing method of the polymer laminated body which concerns on this invention, in the said 1st application | coating process and the said 2nd application | coating process, it is possible to make the ratio of the polyisocyanate-type hardening | curing agent in the said urethane type adhesive agent 3-7 mass%. It is because when the ratio of the polyisocyanate-type hardening | curing agent in the said urethane type adhesive agent is less than 3 mass%, there exists a possibility that it may become the hardening of an adhesive agent, and also the adhesiveness with respect to a material may fall. Moreover, when the ratio of the polyisocyanate-type hardening | curing agent in the said urethane type adhesive agent is more than 7 mass%, when the usable time of an adhesive agent is shortened, application | coating workability may fall, or cost may increase. to be.

In the method for producing a polymer laminate according to the present invention, the plasma treatment in the plasma treatment step can be performed in the air. By carrying out the plasma treatment in the air, it is possible to easily configure the polymer laminate. In other words, since the plasma treatment can be performed without providing a shield for preventing the atmosphere from contacting the plasma treatment portion, the polymer laminate can be simply configured. Moreover, the polymer laminate is manufactured by a simple facility. As a result, the running cost can be prevented from rising.

Therefore, the result of having experimented with the effect of the plasma process on various sole materials is shown. Various sole materials as test materials were prepared by EVA sponge bottom, RB sponge bottom, vulcanized rubber bottom, PAE molded bottom, and TPU molded bottom, respectively. The surface condition is EVA sponge bottom is ski side, RB sponge bottom is skin side, vulcanized rubber bottom is buff side, PAE molded bottom is skin side, and TPU molded bottom is skin side. In addition, a skin surface means the surface which contacted the injection mold or a thermoforming mold, and a ski surface means the surface cut | disconnected with the sharp blade in the thickness direction, and a buff surface means the surface cut and roughened by the rough grindstone.

An aqueous urethane adhesive was applied to the various soles described above, and an aqueous urethane adhesive was also applied to artificial leather. Various soles coated with the water-based urethane adhesive and artificial leather coated with the water-based urethane adhesive were bonded together to measure peel strength and material breakage rate, respectively.

The measurement results of the peel strength and the material breakdown rate in the various soles are shown in Table 1 below.

Test material Surface condition Peel Strength [N / cm] Material destruction rate [%] Untreated Plasma treatment Untreated Plasma treatment EVA sponge bottom Ski surface 6 32 0 100 RB Sponge Bottom Skin cotton One 33 0 100 Vulcanized Rubber Bottom Buff cotton 9 4 0 0 PAE molding bottom Skin cotton 13 15 0 0 TPU molding bottom Skin cotton 58 45 0 5

In the case of the EVA sponge bottom, the peel strength was 6 N / cm when the plasma treatment was not treated and 32 N / cm when the plasma treatment was applied. In the case of the bottom of the RB sponge, the peel strength was 1 N / cm when the plasma treatment was not treated and 33 N / cm when the plasma treatment was used. In the case of the vulcanized rubber bottom, the peel strength was 9 N / cm when the plasma treatment was not treated and 4 N / cm when the plasma treatment was applied. In the case of the PAE molded bottom, the peel strength was 13 N / cm when the plasma treatment was not treated and 15 N / cm when the plasma treatment was applied. In the case of the bottom of the TPU molding, the peel strength was 58 N / cm when the plasma treatment was not treated and 45 N / cm when the plasma treatment was applied.

In the case of the EVA sponge bottom, the material destruction rate was 0% when the plasma treatment was untreated and 100% when the plasma treatment was performed. In the case of the bottom of the RB sponge, the material destruction rate was 0% when the plasma treatment was not treated and 100% when the plasma treatment was applied. In the case of the vulcanized rubber bottom, the peel strength was 0% when the plasma treatment was not treated and 0% when the plasma treatment was performed. In the case of PAE molding bottom, the peel strength was 0% when the plasma treatment was not treated and 0% when the plasma treatment was applied. In the case of the bottom of the TPU molding, the peel strength was 0% when the plasma treatment was not treated and 5% when the plasma treatment was applied.

From the results in Table 1, it is understood that the peeling strength and the material breakdown rate of the EVA sponge bottom and the RB sponge bottom are significantly improved in the effects of the plasma treatment and the adhesion with the aqueous urethane adhesive.

Next, experiments were conducted on the effect of plasma treatment by the surface state of the bottom of the EVA sponge. As for the surface state of the EVA sponge bottom, the skin surface, the ski surface, and the buff surface were prepared, respectively. The aqueous urethane adhesive was apply | coated to the sole of various surface states mentioned above, and the aqueous urethane adhesive was also apply | coated also to artificial leather. Peel strength and material failure rate were measured by bonding various soles coated with an aqueous urethane adhesive and artificial leather coated with an aqueous urethane adhesive.

In the case of the skin surface, the peeling strength was 4 N / cm when the plasma treatment was not treated and 41 N / cm when the plasma treatment was applied. In the case of the ski surface, the peeling strength was 19 N / cm when the plasma treatment was not treated and 28 N / cm when the plasma treatment was applied. In the case of the buff surface, the peeling strength was 25 N / cm when the plasma treatment was not treated and 29 N / cm when the plasma treatment was applied.

In the case of the skin surface, the material destruction rate was 0% when the plasma treatment was not treated and 100% when the plasma treatment was applied. In the case of the ski surface, the material destruction rate was 5% when the plasma treatment was not treated and 100% when the plasma treatment was applied. In the case of the buff surface, the peeling strength was 50% when the plasma treatment was not treated and 100% when the plasma treatment was applied.

These results are shown in Table 2 below.

Test material Surface condition Peel Strength [N / cm] Material destruction rate [%] Untreated Plasma treatment Untreated Plasma treatment EVA sponge bottom Skin cotton 4 41 0 100 Ski surface 19 28 5 100 Buff cotton 25 29 50 100

It is understood that the plasma treatment and the adhesion method using an aqueous urethane adhesive are effective not only on the buff surface and the ski surface of the EVA sponge bottom, but also on the skin surface which is extremely difficult to adhere.

Next, a comparative experiment was conducted with respect to the effect of plasma treatment on the bottom of the EVA sponge, depending on the type of urethane adhesive and the presence or absence of a curing agent. The EVA sponge bottom used the skin side. The urethane adhesive used the aqueous thing and the solvent type thing. In addition, the urethane adhesive used what mixed the hardening | curing agent and the thing which did not mix the hardening | curing agent was used. The various urethane adhesives described above were applied to the bottom of the EVA sponge, and urethane adhesive was also applied to the artificial leather. Various soles coated with a urethane adhesive and artificial leather coated with a urethane adhesive were bonded together, and peel strength and material breakage rate were measured, respectively.

In the case of the aqueous urethane adhesive containing a curing agent, the peeling strength was 4 N / cm as the surface treatment untreated, 37 N / cm as the plasma treatment, and 29 N / cm in the conventional treatment. In the case of the aqueous urethane adhesive containing no curing agent, the surface treatment was 1 N / cm as the untreated, and 11 N / cm when the plasma was treated. In the case of the solvent-based urethane adhesive containing a curing agent, the peeling strength was 8 N / cm for the surface treatment untreated, 29 N / cm for the plasma treatment, and 26 N / cm for the conventional treatment. In the case of the solvent-based urethane adhesive containing no curing agent, the peel strength was 1 N / cm as the surface treatment was untreated, and 14 N / cm when the plasma treatment was performed.

In the case of the aqueous urethane adhesive containing a curing agent, the material destruction rate was 0% as the surface treatment was untreated, 100% when the plasma treatment was applied, and 100% when the conventional treatment was used. In the case of the aqueous urethane adhesive containing no curing agent, the material destruction rate was 0% when the surface treatment was untreated and 0% when the plasma treatment was performed. In the case of the solvent-based urethane adhesive containing a curing agent, the material destruction rate was 0% when the surface treatment was not treated, 100% when the plasma treatment was applied, and 100% when the treatment was conventional. In the case of the solvent-based urethane adhesive containing no curing agent, the material destruction rate was 0% when the surface treatment was untreated and 0% when the plasma treatment was performed. In addition, the conventional process means the pretreatment of the adhesion | attachment which cuts and roughens a surface with a grindstone, wash-drys with an organic solvent, and performs primer application drying of an organic solvent. Next, these results are shown in Table 3 below.

Urethane Adhesive Hardener mixture Peel Strength [N / cm] Material destruction rate [%] Untreated Plasma treatment Conventional treatment Untreated Plasma treatment Conventional treatment Mercury has exist 4 37 29 0 100 100 Mercury none One 11 - 0 0 - Solvent system has exist 8 29 26 0 100 100 Solvent system none One 14 - 0 0 -

It can be understood that a significant improvement in peel strength and material breakdown rate is recognized by mixing the curing agent with the urethane adhesive applied to the bottom of the EVA sponge subjected to plasma treatment. In addition, it is understood that the type of the urethane adhesive to be mixed is more advantageous in peel strength than in the aqueous type. This is accomplished by plasma treatment, while the surface of the material is washed and roughened, hydroxyl groups and carboxyl groups are generated, and the surface of the material is changed to a hydrophilic surface. On the other hand, while the wettability of an aqueous urethane adhesive improves, it is considered that the isocyanate group of the hardening | curing agent mixed in the adhesive reacts not only with the hydroxyl group in an adhesive, but also with the hydroxyl group and carboxyl group of a material surface.

In addition, the said aqueous urethane adhesive agent is an adhesive agent which disperse | distributed the urethane polymer which has a hydroxyl group in the terminal in water, and makes a non-volatile component 50%. In addition, the said solvent-type urethane adhesive is an adhesive which melt | dissolved the urethane polymer which has a hydroxyl group in the terminal in the organic solvent, and makes a non-volatile component 20%. In addition, the hardening | curing agent mixed with the urethane adhesive is a polyisocyanate type hardening | curing agent which has an isocyanate group at the terminal. In addition, the mixture of a urethane adhesive and a hardening | curing agent used what mixed and stirred the mixing ratio of a urethane adhesive and a hardening agent in the ratio of 100: 5 by weight ratio. The coating method of the urethane adhesive which mixed the urethane adhesive or hardening | curing agent to the bottom of EVA sponge was apply | coated by hand with a brush, and was apply | coated. The application amount of the urethane adhesive mixed with the urethane adhesive or the curing agent to the bottom of the EVA sponge was about 50 g / m ² when converted into a nonvolatile component. The drying after apply | coating the urethane adhesive which mixed the urethane adhesive or the hardening | curing agent to the EVA sponge bottom was performed by heating for about 10 minutes in about 55 degreeC atmosphere. In addition, bonding between the sole coated with the urethane adhesive and the artificial leather coated with the urethane adhesive was performed immediately after drying (heating), followed by pressing with a hand roller. In addition, the peeling evaluation method used the T-type peeling test method prescribed | regulated to JISK6854-3. In addition, the peeling speed was 50 mm / min. In addition, the material failure rate was evaluated by the area ratio of the failure of the test material which occupies the whole adhesive surface.

In addition, it should be thought that embodiment disclosed this time is an illustration and restrictive at no points. The scope of the present invention is shown by above-described not description but Claim, and it is intended that the meaning of a claim and equality and all the changes within a range are included.

The polymer laminate according to the present invention has a sheet member composed of any one of a plasma foamed EVA foam or an RB foam, a polymer sheet member, and a urethane-based adhesive layer interposed between the sheet member and the polymer sheet member. By adopting the constitution, the adhesion between the sheet member and the polymer sheet member could be dramatically improved. Since the adhesiveness between the sheet member and the polymer sheet member can be improved remarkably, soles such as tennis shoes using the polymer laminate according to the present invention can secure the flexibility of the sole and the outsole member and the midsole member. The adhesiveness with can be maintained firmly. In addition, compared to the conventional buffing of the surface treatment, buffing, air blowing, surface cleaning with an organic solvent, and application of the adhesive after drying are sufficiently secured by the application of the adhesive immediately after the plasma treatment. Not only does it reduce the cost by shortening the process, but also does not adversely affect the worker and the environment by the organic solvent. As such, the benefits of the present invention are immeasurable.

Claims (10)

A sheet member made of either ethylene-vinyl acetate-based thermoplastic polymer foam or 1,2-polybutadiene-based thermoplastic polymer foam subjected to plasma treatment; A polymer sheet member, And a urethane-based adhesive layer interposed between the sheet member and the polymer sheet member. The method of claim 1, A polymer laminate, wherein the upper member is adhesively integrated through a second urethane-based adhesive layer on the sheet member. The method according to claim 1 or 2, While the seat member is a midsole member used for the sole, The polymer laminate according to claim 1, wherein the polymer sheet member is an outsole member used for the sole. A plasma treatment step of performing a plasma treatment on a sheet member made of either an ethylene-vinyl acetate-based thermoplastic polymer foam or a 1,2-polybutadiene-based thermoplastic polymer foam; A first coating step of applying a urethane adhesive to the sheet member after the plasma processing step; A second coating step of applying a urethane adhesive to the polymer sheet member, And a pasting step of pasting the sheet member after the first coating step and the polymer sheet member after the second coating step. The method of claim 4, wherein A third application step of applying a urethane adhesive to the upper member, And a second pasting step of pasting the upper member after the third coating step and the sheet member after the first coating step. The method according to claim 4 or 5, While the seat member is a midsole member used for the sole, The polymer sheet member is a method for producing a polymer laminate, characterized in that the outsole member used for the sole. The method of claim 4, wherein In the plasma treatment process, Plasma irradiation power is 150-250W, In addition, the plasma irradiation time is 1 to 3 seconds, In addition, the plasma irradiation distance is 5 to 15 mm, In addition, the method for producing a polymer laminate, characterized in that the plasma irradiation area is 3 to 7 cm ² . The method of claim 4, wherein In the first coating step and the second coating step, Method for producing a polymer laminate, characterized in that the urethane-based adhesive is applied so that the coating amount of the nonvolatile component is 30g / m ² to 60g / m ² The method of claim 4, wherein In the first coating step and the second coating step, The ratio of the polyisocyanate-type hardener in the said urethane type adhesive agent is 3-7 mass%, The manufacturing method of the polymeric laminated body characterized by the above-mentioned. The method of claim 4, wherein A method for producing a polymer laminate, wherein the plasma treatment in the plasma treatment step is performed in the atmosphere.