KR20180103377A - Manufacturing method for thermoplastic polyurethane film and thermoplastic polyurethane film manufactured by the same - Google Patents

Abstract

According to one embodiment of the present invention, provided is a method for manufacturing a thermoplastic polyurethane film, which comprises the following steps: applying a semi-cured urethane composition onto a base film; heat-treating the semi-cured urethane composition to manufacture a laminate including a polyurethane layer formed on the base film; preparing two laminated bodies; and laminating the polyurethane layers of the laminated bodies so as to be in contact with each other to manufacture a thermoplastic polyurethane film; and removing the base film provided on the outer surface of the thermoplastic polyurethane film. According to one embodiment of the present invention, it is possible to easily manufacture the thermoplastic polyurethane film having highly glossy outer surface and excellent mechanical properties.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a thermoplastic polyurethane film, and a thermoplastic polyurethane film produced by the method. BACKGROUND OF THE INVENTION 1. Field of the Invention < RTI ID =

The present invention relates to a process for producing a thermoplastic polyurethane film and a thermoplastic polyurethane film produced thereby.

Thermoplastic polyurethanes (TPU) are widely used industrially due to their excellent properties such as strength, elongation, toughness, abrasion resistance, and ease of processing. For example, thermoplastic polyurethanes have been used predominantly in the automotive, clothing, and so on.

Films using thermoplastic polyurethane are used in automobile parts, engineering parts, and the like. Particularly, a polyurethane film having a high-gloss surface can be used for protecting a painted surface of an automobile, and a polyurethane film having a gloss not lowering the gloss of the painted surface is required.

Generally, a polyurethane film used for automobile parts, engineering parts, and the like is manufactured by dissolving polyurethane pellets in a high-temperature extruder and then pulling the polyurethane pellets through a die. However, there is a problem that it is difficult to produce a polyurethane film having a high gloss outer surface due to the limitation of the physical properties of the polyurethane resin itself. In order to overcome this problem, additives have been used. However, due to the high temperature at the time of extrusion, the additive is denatured and the function thereof is remarkably deteriorated.

Therefore, there is a need for a technique capable of producing a thermoplastic polyurethane film having a high-gloss outer surface by controlling the molecular weight and solid content of the polyurethane.

The present invention relates to a process for producing a thermoplastic polyurethane film and a thermoplastic polyurethane film produced thereby.

According to one embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: applying a semi-cured urethane composition onto a base film; Heat-treating the semi-cured urethane composition to produce a laminate including a polyurethane layer formed on the base film; Preparing two laminated bodies, and laminating the polyurethane layers of the laminated bodies so as to be in contact with each other to produce a thermoplastic polyurethane film; And removing the base film provided on the outer surface of the thermoplastic polyurethane film. The present invention also provides a method for producing a thermoplastic polyurethane film.

According to another embodiment of the present invention, there is provided a thermoplastic polyurethane film produced by a manufacturing method according to an embodiment of the present invention.

According to one embodiment of the present invention, a thermoplastic polyurethane film having a high gloss outer surface and excellent mechanical properties can be easily produced.

1 is a view illustrating a process for producing a thermoplastic polyurethane film according to an embodiment of the present invention.

The terms used in this specification will be briefly described and the present invention will be described in detail.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments. Also, in certain cases, there may be a term selected arbitrarily by the applicant, in which case the meaning thereof will be described in detail in the description of the corresponding invention. Therefore, the term used in the present invention should be defined based on the meaning of the term, not on the name of a simple term, but on the entire contents of the present invention.

When an element is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements as well, without departing from the spirit or scope of the present invention. Further, when a member is referred to herein as being "on " another member, this includes not only when a member is in contact with another member but also when there is another member between the two members.

According to one embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: applying a semi-cured urethane composition onto a base film; Heat-treating the semi-cured urethane composition to produce a laminate including a polyurethane layer formed on the base film; Preparing two laminated bodies, and laminating the polyurethane layers of the laminated bodies so as to be in contact with each other to produce a thermoplastic polyurethane film; And removing the base film provided on the outer surface of the thermoplastic polyurethane film. The present invention also provides a method for producing a thermoplastic polyurethane film.

1 is a view illustrating a process for producing a thermoplastic polyurethane film according to an embodiment of the present invention. Referring to FIG. 1, a laminated body 100 including a base film 10 and a polyurethane layer 30 formed by heat-treating a semi-cured urethane composition coated on a base film 10 can be formed. Two stacked bodies 100 are prepared and the two polyurethane layers 30 and 40 contained in the stacked body 100 are positioned adjacent to each other and the two stacked bodies 100 are joined together to form a thermoplastic polyurethane A film can be produced. Thereafter, the two base films (10, 20) provided on the outer surface of the thermoplastic polyurethane film are removed to produce the thermoplastic polyurethane film (200).

According to one embodiment of the present invention, a thermoplastic polyurethane film having a high gloss outer surface and excellent mechanical properties can be easily produced. Conventional polyurethane films are produced by dissolving polyurethane pellets in a high-temperature extruder and then drawing them out through a die. Due to the limited physical properties of the formed polyurethane resin itself, a polyurethane film having a high gloss outer surface However, the method for producing a thermoplastic polyurethane film according to an embodiment of the present invention has an advantage that it can overcome this problem.

Generally, a polyurethane film is produced by mixing and dissolving a polyurethane pellet in which a polyurethane is extruded in the form of a pellet, together with additives such as an additive and a hardener, in a high-temperature extruder, do. However, in the conventional polyurethane production method, the polyurethane pellets must be melted using a high-temperature extruder, and the mechanical properties of the polyurethane film produced by decomposition of the polyurethane resin exposed to high temperatures during the dissolving process Degradation and yellowing may occur. In addition, it is not easy to set the extrusion conditions due to the nature of the polyurethane having a large viscosity change with temperature change, and a device capable of discharging bubbles in the polyurethane film must be provided.

In addition, the roughness value of the surface of the polyurethane film may be affected by the physical properties of the polyurethane resin. However, according to the conventional method of producing a polyurethane film, the surface gloss of the polyurethane film depends on the physical properties or leveling of the polyurethane resin itself, and it is not easy to produce a polyurethane film having high gloss. In order to overcome this problem, additives have been used. However, due to the high temperature at the time of extrusion, the additive is denatured and the function thereof is remarkably deteriorated.

On the other hand, according to an embodiment of the present invention, the outer surface gloss of the thermoplastic polyurethane film can be effectively improved, and the molecular weight and solid content of the polyurethane resin contained in the semi-cured urethane composition can be controlled, Can be controlled.

According to one embodiment of the present invention, the semi-cured urethane composition is applied on a base film. As the method of applying the semi-cured urethane composition on the base film, known methods can be used. For example, a spray coating method, a gravure coating method, a microgravure coating method, a roll coating method, a flexo coating method, Coating methods such as spray coating method, spin coating method, flow coating method, knife coating method, nozzle coating method, rotary screen coating method, reverse loss coating method, comma coating method, lip coating method, die coating method, dip coating method, Coating method, dipping method and the like can be used.

According to one embodiment of the present invention, after the semi-cured urethane composition is applied on the base film, the semi-cured urethane composition is heat-treated to form a polyurethane layer. A plurality of stacked bodies each having a polyurethane layer formed on the base film may be prepared and two of the stacked bodies may be prepared so that the polyurethane layers contained in the two stacked bodies face each other. Thereafter, the two polyurethane layers included in the two stacked bodies can be stacked and heated so as to be in contact with each other. In the process of heating the two polyurethane layers, the surfaces to which the two polyurethane layers are bonded can be bonded to each other. Specifically, when the heat of the glass transition temperature or more of the polyurethane layer is applied to the laminate, the surface on which the two polyurethane layers contact is melted to increase the viscosity, whereby the two poly Urethane layer can be bonded.

As the two polyurethane layers are bonded to each other, a polyurethane layer having a single layer shape can be formed. In the specification of the present invention, the shape of the single layer may mean a state in which it is not easy to peel the two bonded polyurethane layers by bonding two polyurethane layers together.

Therefore, according to one embodiment of the present invention, the two polyurethane layers can be bonded together without using an adhesive or an adhesive film, whereby the thickness of the polyurethane layer can be effectively increased.

According to an embodiment of the present invention, the step of preparing the thermoplastic polyurethane film may be performed at 80 ° C or higher and 140 ° C or lower. Specifically, the step of preparing the thermoplastic polyurethane film may be performed at a temperature of 80 ° C or more and 130 ° C or less, and 100 ° C or more and 120 ° C or less.

If the temperature applied during the bonding of the polyurethane layer is less than 80 캜, the bonding strength between the surfaces of the two polyurethane layers contacting with each other may be weak, so that the separation of the two polyurethane layers may easily occur. If the temperature applied during the bonding of the polyurethane layer is more than 140 ° C, the fluidity of the polyurethane layer is increased to thin the thermoplastic polyurethane film to be produced, or the polyurethane layer may be excessively melted, The problem of flowing out of the film may occur. Thus, according to one embodiment of the present invention, in order to produce a thermoplastic polyurethane film strongly bonded to two polyurethane layers, the step of preparing the thermoplastic polyurethane film may be performed at a temperature of 80 ° C or more and 140 ° C or less have.

According to an embodiment of the present invention, in the step of preparing the thermoplastic polyurethane film, the two polyurethane layers may be bonded while passing through a high-temperature press roll heated to 80 ° C or more and 140 ° C or less.

According to an embodiment of the present invention, the base film provided on the outer surface of the thermoplastic polyurethane film in the form of a single layer is removed. Layered thermoplastic polyurethane film is formed in the process of heating and bonding the two laminated bodies, and the surface of the base film, which is in contact with the outer surface of the single-layered thermoplastic polyurethane film, is in contact with the thermoplastic poly The outer surface of the monolayer-shaped thermoplastic polyurethane film from which the base film is removed may have a gloss similar to that of the surface of the base film as it is transferred to the outer surface of the urethane film.

Therefore, according to one embodiment of the present invention, a thermoplastic polyurethane film having a high gloss surface can be easily produced by selecting a film having a high gloss value as a base film.

The semi-cured urethane composition can be prepared by reacting a second raw material comprising a chain extender containing a diol and a first raw material containing a polyol and a first isocyanate curing agent in an organic solvent. According to an embodiment of the present invention, the weight average molecular weight and the mechanical properties of the thermoplastic polyurethane film to be produced can be controlled by adjusting the weight average molecular weight of the polyol and the number of carbon atoms contained in the diol.

According to one embodiment of the present invention, the number average molecular weight of the polyol may be 1,800 g / mol to 2,200 g / mol or less. Specifically, the number average molecular weight of the polyol may be 1,900 g / mol to 2,200 g / mol and 1,900 g / mol to 2,100 g / mol. By using a polyol having a number average molecular weight of 1,800 g / mol or more and 2,200 g / mol or less, it is possible to prevent the problem that the elongation rate of the produced thermoplastic polyurethane film is reduced.

According to one embodiment of the present invention, the polyol may include at least one member selected from the group consisting of a polycarbonate diol, a polycaprolactone diol, a polyester diol, and a polyisodiol.

According to an embodiment of the present invention, a chain extender containing a diol having 4 to 10 carbon atoms may be used. Specifically, a chain extender containing a diol having 4 to 6 carbon atoms can be used.

The chain extender may react with the first isocyanate-based curing agent contained in the second raw material to extend the chain of the first isocyanate-based curing agent. Specifically, when butanediol is used as a chain extender, one hydroxy functional group among the two hydroxy functional groups of butanediol may be reacted with the isocyanate functional group of the first isocyanate based curing agent. The remaining unreacted hydroxy functional groups of the butanediol may then be combined with the isocyanate functional groups of the novel first isocyanate based curing agent. Therefore, when a diol is used as the chain extender, the first isocyanate-based curing agent may be connected to form a first isocyanate-based curing agent having an extended chain. In addition, the process of bonding the unreacted isocyanate functional group of the first isocyanate type curing agent having the extended chain and the hydroxy functional group of the new chain extending agent is repeated, and a longer isocyanate type curing agent . By extending the chain of the first isocyanate-based curing agent, the weight average molecular weight of the semi-cured urethane composition to be produced can be improved.

Therefore, according to one embodiment of the present invention, in order to effectively extend the chain of the first isocyanate-based curing agent, the chain extender may include a diol having 4 to 10 carbon atoms.

According to one embodiment of the present invention, the chain extender is selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, octyleneglycol, 1,10-decanediol, 1,1- Hexane dimethanol, and 1,4-cyclohexane dimethanol.

The second raw material according to one embodiment of the present invention comprises a first isocyanate-based curing agent. According to one embodiment of the present invention, the semi-cured urethane composition can be prepared by reacting the first raw material and the second raw material in an organic solvent to form a semi-cured urethane composition. The semi-cured urethane composition has properties such as solid content and weight average molecular weight Can be easily controlled.

According to one embodiment of the present invention, the polyol and the chain extender contained in the first raw material, and the first isocyanate curing agent contained in the second raw material are dissolved in the organic solvent, and the polyol, the chain extender and the first isocyanate The curing agent may react to polymerize the polyurethane resin. The unreacted hydroxy functional group contained in the polyol may react with an unreacted isocyanate functional group contained in the first isocyanate based curing agent to form a urethane bond. Thus, as the polyol reacts with the first isocyanate-based curing agent, a polyurethane resin containing a urethane bond can be polymerized. In addition, the unreacted isocyanate functional group contained in the first isocyanate-based curing agent having a chain extended by the chain extender reacts with the unreacted hydroxy functional group of the polyol to polymerize a polyurethane resin having a higher molecular weight have.

The polyurethane resin may comprise a soft segment and a hard segment. The soft segment of the polyurethane resin may include a repeating unit in which the polyol and the first isocyanate-based curing agent are polymerized, and the hard segment of the polyurethane resin may include a repeating unit in which the chain-extending agent and the first isocyanate- . ≪ / RTI >

According to an embodiment of the present invention, the polyurethane and the chain extender contained in the first raw material may be separated from each other and reacted with the second raw material to prepare a semi-cured urethane composition. Specifically, a polyurethane contained in the first raw material is reacted with a first isocyanate type curing agent contained in the second raw material to produce a urethane bond-containing polyurethane resin, The first isocyanate-based curing agent contained in the raw material may be reacted to prepare a first isocyanate-based curing agent having a long extended chain. Thereafter, the polyurethane resin and the first isocyanate-based curing agent having the elongated chain are reacted to form a semi-cured urethane composition comprising a polyurethane resin having an increased molecular weight.

The semi-cured urethane composition can be formed by simultaneously reacting the polyol and the chain extender contained in the first raw material with the first isocyanate curing agent contained in the second raw material. The diol used as a chain extender has a lower carbon number than the polyol, and the diol has higher fluidity than the polyol in the organic solvent. Thus, when the polyol, the chain extender and the first isocyanate curing agent are simultaneously reacted, the reaction between the chain extender and the first isocyanate curing agent may occur earlier than the reaction between the polyol and the first isocyanate curing agent. Therefore, the chain extender and the first isocyanate-based curing agent first react to form a first isocyanate-based curing agent having a long elongated chain, and the first isocyanate-based curing agent having a long elongated chain reacts with the polyol, This increased polyurethane resin can be formed. When the semi-cured urethane composition is produced by reacting the polyol and the chain extender contained in the first raw material simultaneously with the first isocyanate-based curing agent contained in the second raw material, during the heat treatment of the semi-cured urethane composition, Can be prevented from being volatilized and lost by the high temperature.

According to an embodiment of the present invention, the content of the polyol may be 50 wt% or more and 75 wt% or less based on the total weight of the first raw material and the second raw material. Specifically, the content of the polyol may be 50 wt% or more and 70 wt% or less based on the total weight of the first raw material and the second raw material.

According to an embodiment of the present invention, by controlling the content of the polyol to 50 wt% to 75 wt% with respect to the total weight of the first raw material and the second raw material, the content of the soft segment of the polyurethane resin Can be prevented from deteriorating in workability of the thermosetting polyurethane resin. Further, the problem that the durability of the thermosetting polyurethane resin is lowered as the content of the soft segment of the polyurethane resin becomes excessively large can be effectively prevented.

Therefore, according to one embodiment of the present invention, in order to produce a thermoplastic polyurethane film having excellent mechanical properties, the semi-cured urethane composition is used in an amount of 50% by weight or more and 75% by weight or less based on the total weight of the first raw material and the second raw material, And the following polyols.

According to an embodiment of the present invention, the content of the chain extender may be 5 wt% or more and 15 wt% or less based on the total weight of the first raw material and the second raw material. Specifically, the content of the chain extender may be 6 wt% or more and 13 wt% or less based on the total weight of the first raw material and the second raw material. The weight average molecular weight of the semi-cured urethane composition can be effectively improved by adjusting the content of the chain extender to 5 wt% or more and 15 wt% or less based on the total weight of the first raw material and the second raw material. Further, by reacting with the first isocyanate-based curing agent to effectively form the hard segment of the polyurethane resin, the mechanical properties of the produced thermoplastic polyurethane resin can be improved.

According to an embodiment of the present invention, the content of the first isocyanate curing agent may be 20 wt% or more and 40 wt% or less based on the total weight of the first raw material and the second raw material. Specifically, the content of the first isocyanate curing agent may be 23 wt% or more and 37 wt% or less based on the total weight of the first raw material and the second raw material.

By controlling the content of the first isocyanate curing agent to 20 wt% to 40 wt% with respect to the total weight of the first raw material and the second raw material, the polyurethane resin can be effectively polymerized, and the thermoplastic polyurethane film The workability and durability of the substrate can be improved.

According to an embodiment of the present invention, the first isocyanate-based curing agent may include an isocyanate functional group having 2 to 6 carbon atoms. Specifically, the first isocyanate-based curing agent may include two isocyanate functional groups.

According to an embodiment of the present invention, the first isocyanate-based curing agent may include isophorone diisocyanate (IPDI), methylenediphenyl-4,4'-diisocyanate, 4,4'-methylenebiscyclohexyldiisocyanate , Xylene diisocyanate (XDI), naphthalene-1,5-diisocyanate, and cyclohexane diisocyanate. In the present invention,

According to an embodiment of the present invention, the organic solvent may include at least one member selected from the group consisting of methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, acetylacetone, and dimethylformamide.

According to an embodiment of the present invention, the first raw material and the second raw material may be mixed and polymerized on an organic solvent to prepare a polyurethane resin. The polyurethane resin to be produced is dissolved in the organic solvent, and additives such as additional heat stabilizer, light stabilizer, defoaming agent or antifoaming agent can be easily added according to the required properties.

It is not necessary to add an additive such as a heat stabilizer, a light stabilizer, a defoaming agent or defoaming agent to the solvent-type polyurethane composition containing the polyurethane resin. Therefore, according to one embodiment of the present invention, by producing a polyurethane resin on an organic solvent, a solvent-type polyurethane composition containing a polyurethane resin can be easily produced, and manufacturing time and manufacturing cost can be reduced .

According to an embodiment of the present invention, since the first raw material, the second raw material, and the first isocyanate curing agent are easily dissolved in an organic solvent, a problem caused by using a highly toxic solvent can be overcome.

According to an embodiment of the present invention, the content of the organic solvent may be 30 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the total of the first raw material and the second raw material. The content of the organic solvent is controlled to be not less than 30 parts by weight and not more than 80 parts by weight based on 100 parts by weight of the total amount of the first raw material and the second raw material, whereby the semi-cured urethane composition is heat- It is possible to prevent the organic solvent from being swollen from the inside of the polyurethane layer due to the rapid drying and forming of the film, and it is possible to prevent the thickness of the polyurethane layer from being thinned.

According to one embodiment of the present invention, a catalyst may be used to produce the semi-cured urethane composition. Specifically, the semi-cured urethane composition can be prepared by mixing and polymerizing the first raw material, the second raw material, the organic solvent, and the catalyst.

As the catalyst, dibutyltin dilaurate (DBTDL) may be used. By using the catalyst, the production time of the semi-cured urethane composition can be reduced, and the polyurethane resin can be polymerized at a relatively low temperature.

According to an embodiment of the present invention, the content of the catalyst may be 0.5 to 2 parts by weight based on 100 parts by weight of the total of the first raw material and the second raw material. By controlling the content of the catalyst for producing the semi-cured urethane composition from 0.5 part by weight to 2 parts by weight based on 100 parts by weight of the total of the first raw material and the second raw material, the production time of the semi-cured urethane composition is reduced And the bonding strength between the two polyurethane layers can be improved.

According to one embodiment of the present invention, the semi-cured urethane composition can be manufactured at a temperature of 55 ° C or more and 65 ° C or less. The semi-cured urethane composition can be formed at a relatively low temperature of 55 占 폚 or more and 65 占 폚 or less, thereby shortening the manufacturing cost and time of the thermoplastic polyurethane film.

According to an embodiment of the present invention, the step of heat-treating the semi-cured urethane composition may be performed at 80 ° C or higher and 140 ° C or lower. After the semi-cured urethane composition is applied on the base film, the organic solvent contained in the semi-cured urethane composition can be volatilized by heat treatment at a temperature of 100 ° C or higher and 150 ° C or lower.

When the semi-cured urethane composition is heat-treated at a temperature of less than 100 ° C, it is not easy to volatilize and remove the organic solvent contained in the semi-cured urethane composition, and the resulting thermoplastic polyurethane film may have yellowing or physical properties The problem may be degraded. Further, when the heat treatment is performed at a temperature exceeding 150 캜, the thermoplastic polyurethane film produced due to excessive oxidation may be discolored. Therefore, according to one embodiment of the present invention, in order to produce a thermoplastic polyurethane film having excellent mechanical properties and optical properties, the semi-cured urethane composition coated on the base film is heat-treated at a temperature of 100 ° C or higher and 150 ° C or lower .

According to one embodiment of the present invention, the semi-cured urethane composition may further include a second isocyanate-based curing agent. The content of the second isocyanate curing agent may be 3 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the total of the first raw material and the second raw material. Specifically, the content of the second isocyanate curing agent may be 5 parts by weight or more and 7 parts by weight or less based on 100 parts by weight of the total of the first raw material and the second raw material.

By adjusting the content of the second isocyanate curing agent to 3 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the total of the first raw material and the second raw material, the weight average molecular weight of the produced thermoplastic polyurethane film can be effectively increased And a thermoplastic polyurethane film excellent in mechanical properties can be produced.

According to an embodiment of the present invention, the second isocyanate-based curing agent may include an isocyanate functional group of 2 or more and 6 or less. Specifically, according to one embodiment of the present invention, a hexahydroxy isocyanate curing agent MHG-80B of Asahi KASEI, a hexafunctional isocyanate curing agent MFA-100 of Asahi KASEI, and a trifunctional isocyanate curing agent TKA of Asahi KASEI Co. are used as the second isocyanate curing agent -100 can be used.

When a bifunctional isocyanate compound containing two isocyanate functional groups is used as the second isocyanate curing agent, a compound used as the first isocyanate curing agent may be used.

According to one embodiment of the present invention, the thermoplastic polyurethane film can be aged to increase the weight average molecular weight. Specifically, a second isocyanate-based curing agent may be added to the semi-cured urethane composition prepared by reacting a first raw material containing a chain extender containing a diol and a polyol and a second raw material containing a first isocyanate curing agent have. The thermoplastic polyurethane film may be prepared using the semi-cured urethane composition to which the second isocyanate-based curing agent is added, and the thermoplastic polyurethane film produced may be aged to increase the weight average molecular weight.

The semi-cured urethane composition may contain a polyol containing an unreacted hydroxy functional group and a chain extender, a first isocyanate-based curing agent containing an unreacted isocyanate functional group, and a second isocyanate-based curing agent. The reaction between the unreacted functional groups of the polyol, the chain extender, the first isocyanate curing agent and the second isocyanate curing agent contained in the semi-cured urethane composition is further progressed by performing a secondary curing step of aging the semi-cured urethane composition A high molecular weight thermoplastic polyurethane film can be produced by polymerizing a polyurethane resin having an improved weight average molecular weight.

According to one embodiment of the present invention, after aging the laminate, the polyurethane layer can be laminated so as to be in contact with the laminate, and the laminate can be aged after being laminated so as to be in contact with the polyurethane layer.

According to an embodiment of the present invention, the base film may be any one selected from the group consisting of a triacetate cellulose film, a cycloolefin polymer film, a polyimide film, and a polyethylene phthalate film.

According to an embodiment of the present invention, the solid content of the semi-cured urethane composition may be 20% or more and 70% or less. Specifically, the solid content of the semi-cured urethane composition may be 30% or more and 60% or less, and 40% or more and 60% or less.

It is possible to control the type and content of the compound used as the first raw material and the second raw material and to polymerize the polyurethane resin on the organic solvent so that the solid content of the semi-cured urethane composition containing the polyurethane resin can be controlled have. The semi-cured urethane composition is coated on the base film in a thick manner to prepare a thermoplastic polyurethane film having a solids content of 20% or more and 70% or less and a solids content of 15% or less, The thickness of the thermoplastic polyurethane film can be made larger.

According to one embodiment of the present invention, the semi-cured urethane composition can be coated by a solution coating method to easily control the thickness of the thermoplastic polyurethane film. The polyurethane resin contained in the semi-cured urethane composition is an organic solvent phase So that a thermoplastic polyurethane film having a homogeneous composition can be produced.

According to another embodiment of the present invention, there is provided a thermoplastic polyurethane film produced by a manufacturing method according to an embodiment of the present invention. The thermoplastic polyurethane film may have a high-gloss surface. Specifically, the surface gloss value of the thermoplastic polyurethane film may be 100 GU or more and 120 GU or less.

According to another embodiment of the present invention, the weight average molecular weight of the thermoplastic polyurethane film may be 20,000 g / mol or more and 100,000 g / mol or less. Specifically, the weight average molecular weight of the thermoplastic polyurethane film may be 40,000 g / mol or more and 70,000 g / mol or less. When the weight average molecular weight of the thermoplastic polyurethane film is less than 20,000 g / mol, the durability is reduced. When the weight average molecular weight exceeds 100,000 g / mol, the processability of the thermoplastic polyurethane film is lowered .

Therefore, according to another embodiment of the present invention, the thermoplastic polyurethane film has a weight average molecular weight of 20,000 g / mol to 100,000 g / mol, which is excellent in durability and processability.

Hereinafter, the present invention will be described in more detail with reference to examples. These embodiments are for illustrative purposes only and are not intended to be limiting of the present invention.

Example  One

As the first raw material, a polyol and a chain extender were used together. A polycarbonate diol (PCDL) having a number average molecular weight of 1,900 g / mol by Asahi Kasei Co., Ltd., 1,4-butanediol 1,4-butanediol (1,4BD) was used as the first isocyanate-based curing agent, isophorone diisocyanate (IPDI) of Evonik was used, and methylethylketone (MEK) Respectively. The content of the polyol, the chain extender and the first isocyanate curing agent was adjusted to 52.6 wt% of PCDL, 12.3 wt% of 1,4BD and 35.1 wt% of IPDI, dissolved in methyl ethyl ketone, and charged into the reactor. The organic solvent was adjusted to 55 parts by weight based on 100 parts by weight of the total of the first raw material and the second raw material. The charged raw materials were heated to 55 ° C. and then 0.5 parts by weight of dibutyl tin dilaurate (DBDTL) was added to 100 parts by weight of the total of the first raw material and the second raw material in an organic solvent And reacted at 57 DEG C for 25 hours to prepare a semi-cured urethane composition. The solid content of the prepared semi-cured urethane composition is about 45%.

7 parts by weight of H12MDI (purchased from Evonik) containing two isocyanate functional groups was added to the semi-cured urethane composition as a second isocyanate-based curing agent based on 100 parts by weight of the raw material in which the first raw material and the second raw material were mixed . A semi-cured urethane composition containing a second isocyanate-based curing agent was applied onto a polyethylene phthalate film as a base film and heat-treated at 100 캜 to prepare a polyurethane layer.

As shown in Fig. 1, two laminates including the polyurethane layer and the base film were prepared and aged at 25 DEG C for 19 hours. The polyurethane layers of each of the two stacks were positioned adjacent to each other. Thereafter, the two adjacent polyurethane layers were brought into contact with each other, and passed between a pair of press rolls heated to 130 캜 to form a laminate. The two polyurethane layers were laminated together to form a single layer thermoplastic polyurethane film, and the two base films on the outer surface of the single layer type thermoplastic polyurethane film were removed to produce a thermoplastic polyurethane film.

Example  2

A thermoplastic polyurethane film was prepared in the same manner as in Example 1, except that the first raw material, the second raw material, the catalyst and the second isocyanate curing agent were prepared as shown in Table 1 below. In Table 1 below, MHG80B contains six isocyanate functional groups, and KS1467 contains two isocyanate functional groups.

The first raw material
(wt%) The second raw material
(wt%) Organic solvent
(Parts by weight) catalyst
(Parts by weight) The second isocyanate-based vulcanizing agent
(Parts by weight) Semi-hardening
Urethane composition Polyol chain
Extenders The first isocyanate-based curing agent Solids
(%) Example 1 PCDL
(52.61) 1.4 BD
(12.33) IPDI
(35.06) MEK
(55) DBDTL
(0.5) H12MDI
(7) 45 Example 2 PCDL
(52.61) 1.4 BD
(12.33) IPDI
(35.06) MEK
(55) DBDTL
(0.5) MHG80B / KS1467
(2 / 3.5) 46

Comparative Example  One

A TPO film IO-403M manufactured by OG Film's extrusion method was prepared.

Comparative Example  2

A TPU film 49510 manufactured by Argotec's extrusion method was prepared.

Thermoplastic Poly  Polishing of urethane film

The surface gloss measurement of the thermoplastic polyurethane films prepared in Examples 1 to 2 and Comparative Examples 1 to 2 was carried out as follows.

Each of the thermoplastic polyurethane films prepared in Examples 1 to 2 and Comparative Examples 1 to 2 was coated with a pressure-sensitive adhesive, laminated on an automobile paint plate, and allowed to stand at room temperature for 2 days so that the thermoplastic polyurethane film adhered to the paint plate Respectively. The gloss value of the initial 60 ° of the thermoplastic polyurethane film left for 2 days after the coating of the coated plate was measured using a gloss measuring device Rhopoint IQ (Rhopoint Instruments). Thereafter, the thermoplastic polyurethane film was further left at 60 DEG C and 85 DEG C for 3 days, respectively, and the gloss value of the surface 60 DEG was measured. Table 2 shows the surface gloss values of the thermoplastic polyurethane films prepared in Example 1 and Comparative Examples 1 and 2 of the present invention.

Table 2 shows the surface gloss values of the thermoplastic polyurethane films prepared in Example 1 and Comparative Examples 1 and 2 of the present invention.

60 ° C 85 ℃ Early
(GU) 3 days
(GU) Early
(GU) 3 days
(GU) Example 1 101.67 102.09 100.67 102.8 Example 2 102.04 101.98 100.88 102.66 Comparative Example 1 96.3 98.4 96 90.9 Comparative Example 2 92.5 93.4 92.0 90.5

Referring to Table 2, it can be seen that the surface gloss value of the thermoplastic polyurethane film produced according to the embodiment of the present invention is higher than the surface gloss value of the thermoplastic polyurethane film produced by the conventional extrusion method.

100:
10, 20: base film
30, 40: polyurethane layer
200: thermoplastic polyurethane film

Claims (12)

Applying a semi-cured urethane composition onto a substrate film;
Heat-treating the semi-cured urethane composition to produce a laminate including a polyurethane layer formed on the base film;
Preparing two laminated bodies, and laminating the polyurethane layers of the laminated bodies so as to be in contact with each other, thereby producing a thermoplastic polyurethane film; And
And removing the base film provided on the outer surface of the thermoplastic polyurethane film.
The method according to claim 1,
Wherein the step of preparing the thermoplastic polyurethane film is carried out at a temperature of from 80 캜 to 140 캜.
The method according to claim 1,
Wherein the semi-cured urethane composition is produced by reacting a first raw material comprising a chain extender containing a diol and a polyol and a second raw material comprising a first isocyanate curing agent on an organic solvent .
The method of claim 3,
Wherein the content of the polyol is 50 wt% or more and 75 wt% or less based on the total weight of the first raw material and the second raw material.
The method of claim 3,
Wherein the content of the chain extender is 5 wt% or more and 15 wt% or less based on the total weight of the first raw material and the second raw material.
The method of claim 3,
Wherein the content of the first isocyanate curing agent is 20 wt% or more and 40 wt% or less based on the total weight of the first raw material and the second raw material.
The method of claim 3,
Wherein the first isocyanate curing agent comprises an isocyanate functional group of 2 or more and 6 or less.
The method according to claim 1,
Wherein the base film is any one selected from the group consisting of a triacetate cellulose film, a cycloolefin polymer film, a polyimide film, and a polyethylene phthalate film.
The method according to claim 1,
Wherein the step of heat-treating the semi-cured urethane composition is performed at a temperature of 80 ° C or more and 140 ° C or less.
The method according to claim 1,
Wherein the semi-cured urethane composition has a solid content of 20% or more and 70% or less.
A thermoplastic polyurethane film produced by the manufacturing method according to claim 1.
The method of claim 11,
Wherein the thermoplastic polyurethane film has a surface gloss value of 100 GU to 120 GU.

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