JP5285189B1 - LAMINATED FILM MANUFACTURING METHOD AND LAMINATED FILM - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a laminated film capable of improving interlayer adhesion between a base material and a functional layer exhibiting a specific function laminated on the surface by providing a carbon cored layer in advance on the surface of the base material. A method and a laminated film according to the manufacturing method are provided.
SOLUTION: At least a surface of a plastic film as a base material is subjected to a plasma treatment in advance under an environment of an atmospheric pressure of 1 × 10 ⁻³ Torr to 1 × 10 ⁻¹ Torr under introduction of an inert gas. And a functional layer laminating step in which a functional layer having a specific function is laminated on the surface after performing the plasma treatment step, the plasma treatment being a glow discharge plasma treatment, and a glow discharge plasma The treatment was performed by generating a carbon-containing plasma by a sputtering method using a carbon target as a cathode, and was a method for producing a laminated film.
[Selection figure] None

Description

  The present invention relates to a method for producing a laminated film and a laminated film obtained by the production method, and specifically, a method for producing a laminated film exhibiting a specific function capable of suppressing and preventing the occurrence of delamination and The present invention relates to a laminated film obtained by the production method.

  Conventionally, various laminated films formed by laminating a functional layer exhibiting a specific function on a polymer resin film have been developed and proposed. For example, a plastic film imparted with a gas barrier property (hereinafter also simply referred to as a “gas barrier film”) for protecting substances that do not like oxygen and moisture is widely used in various scenes. For example, it is used as a packaging material for food or as a packaging material for electronic component materials. In such use, the packaging material is strongly required to have the property of suppressing or preventing the alteration of the contents. In particular, there has recently been a need for packaging materials that can easily protect articles that are so delicate that they are easily altered by oxygen, water vapor, and the like and that require careful handling from oxygen and water vapor.

  Conventionally, plastic films made of polyvinylidene chloride, polyacrylonitrile, or the like have been used as films having gas barrier properties, but these films are no longer used because they discharge environmental harmful substances upon disposal. From the viewpoint of environmental problems, it seems that it is preferable to use a plastic film made of polyvinyl alcohol, but this film has a high gas barrier humidity dependency, that is, a gas barrier property under high humidity, particularly water vapor. Since the barrier property is remarkably and easily deteriorated, it cannot be used in a scene that requires a high gas barrier property.

  Therefore, a film in which an inorganic substance such as silicon oxide or aluminum oxide is provided on the surface of a plastic film by physical vapor deposition or chemical vapor deposition is used as a packaging material as a gas barrier film. However, these gas barrier films have durability against bending. In other words, cracks are easily generated in the vapor deposition layer at the time of bending, so that there is a problem that the barrier property is easily lowered. In addition, since the interlayer adhesion between the plastic film and the inorganic material deposited on the surface is small, if the film is repeatedly bent, the inorganic material cannot follow the flexibility of the film. Since there was a loss of sex, there was a problem in practical use.

  Therefore, various proposals for improving the interlayer adhesion have been made to deal with such problems. For example, in Patent Document 1, before an aluminum oxide layer is laminated on the surface of a base material made of a plastic material, a carbon vapor deposition layer is laminated on the surface of the plastic base material in advance. The carbon deposition layer is a processed surface using reactive ion etching (RIE) mode plasma and is diamond-like carbon (DLC).

JP 2006-315359 A

  In the case of the laminate described in Patent Document 1, by providing the DLC layer using RIE, the interlayer adhesion between the surface of the plastic base film and the aluminum oxide layer is improved compared to the conventional one. At the same time, according to the invention described herein, by performing RIE, carbon having a weak binding force is removed by ion bombardment by RIE mode plasma. Carbon is not contributing to the improvement of interlayer adhesion.

  Certainly, if the invention described in Patent Document 1 is used, the interlayer adhesion can be improved, but for that purpose, the RIE process must be carried out and the DLC layer must be laminated accordingly. However, it was not always preferable. That is, it is desired to more easily secure the interlayer adhesion.

As a simple method, a so-called “nuclear attachment” method is sometimes used.
Here is a brief explanation of this attachment.

  Normally, when a gas barrier material such as aluminum oxide is to be deposited on a base film made of an untreated polymer resin film, aluminum oxide molecules are laminated on the base film surface all at once. However, the aluminum oxide molecules are first laminated on the substrate film surface in a dispersed state on the substrate film surface. Then, with the molecule as a “base point”, the aluminum oxide molecule further adheres to the periphery of the aluminum oxide molecule at the “base point” position, and eventually becomes layered.

  However, in this case, if the bond between the aluminum oxide molecule that is the first base point and the base film is weak in the first place, the state is as if the same molecule has gathered around the base aluminum oxide molecule and has grown as a crystal. Even if it eventually becomes a layered state, it is not easy to achieve a superior so-called interlayer adhesion.

  Therefore, molecules that can easily bond to both the base film and the material to be laminated on the surface and can increase the binding force are scattered on the surface of the base film in advance, and this is used as a base point for lamination. As a result, the act of improving the interlaminar adhesion force and dispersing the molecules as the base point for that purpose on the surface of the base film is referred to as “nucleation”.

  If this nucleation is performed, it can be said that it is theoretically possible to improve the interlayer adhesion without taking the trouble of laminating the DLC layer by RIE.

  The present invention has been made in view of such problems, and the purpose thereof is to provide a base material and its surface in spite of a simple technique by providing a carbon-attached layer on the base material surface in advance. It is providing the laminated film by the manufacturing method of the laminated film which made it possible to improve the interlayer adhesive force with the functional layer which exhibits the specific function laminated | stacked by this, and the manufacturing method concerned.

In order to solve the above-mentioned problem, the invention according to claim 1 of the present invention is at least 1 × 10 ⁻³ Torr or more and 1 × 10 6 in an inert gas introduction with respect to the surface of the plastic film serving as a base material. ^A plasma processing step of performing plasma processing in advance under an environment of ^-1 Torr or less, a functional layer stacking step in which a functional layer having a specific function is stacked on the surface after performing the plasma processing step; The plasma treatment is a glow discharge plasma treatment, and the glow discharge plasma treatment is performed by generating a carbon-containing plasma by a sputtering method using a carbon target as a cathode. .

  Invention of Claim 2 of this invention is a manufacturing method of the laminated | multilayer film of Claim 1, Comprising: The said inert gas is argon, It is characterized by the above-mentioned.

  Invention of Claim 3 of this invention is a manufacturing method of the laminated | multilayer film of Claim 1 or Claim 2, Comprising: After the said plasma treatment process, before the said functional layer lamination process, the said plasma treatment A first polymer resin laminating step is performed by laminating a first polymer resin layer made of a first polymer resin on the surface of the substrate subjected to the above.

  Invention of Claim 4 of this-application invention is a manufacturing method of the laminated | multilayer film of Claim 3, Comprising: After performing the said 1st polymeric resin lamination process, the said plasma treatment process is again made into said 1st high process. It is characterized by being performed on the surface of the molecular resin layer.

  Invention of Claim 5 of this-application invention is a manufacturing method of the laminated | multilayer film of any one of Claim 1 thru | or 4, Comprising: After the said functional layer lamination | stacking process, It is characterized by performing a second polymer resin laminating step in which a second polymer resin is laminated on the surface.

  Invention of Claim 6 of this invention is a manufacturing method of the laminated | multilayer film of any one of Claim 3 thru | or 5, Comprising: Said 1st polymer resin layer or said 2nd polymer resin Either one or both of the layers is made of an epoxy silane coupling agent, or is a polymer resin mainly composed of an epoxy silane coupling agent.

  Invention of Claim 7 of this invention is a manufacturing method of the laminated | multilayer film of any one of Claim 3 thru | or 6, Comprising: Said 1st polymer resin layer or said 2nd polymer resin A curing catalyst is added to one or both of the layers.

  Invention of Claim 8 of this invention is a manufacturing method of the laminated | multilayer film of Claim 7, Comprising: The said curing catalyst is iron acetylacetonate, zinc acetylacetonate, aluminum acetonate, a tin tetrachloride, It is one or more of diisopropoxybisacetylacetonato titanium and dihydroxybis lactato titanium.

  Invention of Claim 9 of this invention is a manufacturing method of the laminated | multilayer film of Claim 5 or Claim 6, Comprising: Said 2nd polymer resin layer is a water-soluble polymer, metal alkoxide, and its hydrolysis. It is resin formed by mix | blending a decomposition product.

  Invention of Claim 10 of this invention is a manufacturing method of the laminated | multilayer film of Claim 9, Comprising: The said water-soluble polymer is polyvinyl alcohol, It is characterized by the above-mentioned.

  Invention of Claim 11 of this invention is a manufacturing method of the laminated | multilayer film of Claim 9 or Claim 10, Comprising: The said metal alkoxide is tetraethoxysilane, It is characterized by the above-mentioned.

  Invention of Claim 12 of this invention is a manufacturing method of the laminated | multilayer film of any one of Claim 1 thru | or 11, Comprising: The substance which comprises the said functional layer is silicon, titanium, Any one of the group consisting of tin, zinc, aluminum, indium, or an oxide or compound thereof, or a plurality of or a plurality of oxides or compounds of each of the group, or a plurality of any of the group and other The functional layer is formed by a vacuum deposition method.

  The invention related to the laminated film according to claim 13 of the present invention is characterized by being obtained by the method for producing a laminated film according to any one of claims 1 to 12.

  As described above, in the conventional laminated film, in comparison with a technique that has been used variously to ensure the interlayer adhesion between the base film and the functional layer, if it is a method for producing a laminated film according to the present invention, By performing the nucleation process in which carbon (carbon: C) atoms are scattered on the surface of the base film, the interlayer adhesion can be easily secured.

  Embodiments of the present invention will be described below. The embodiment shown here is merely an example, and is not necessarily limited to this embodiment.

(Embodiment 1)
A method for manufacturing a gas barrier film according to the present invention will be described as a first embodiment.

The manufacturing method of the gas barrier film according to the present embodiment is an environment in which an atmospheric pressure is 1 × 10 ⁻³ Torr or more and 1 × 10 ⁻¹ Torr or less with an inert gas introduced at least on the surface of a plastic film serving as a substrate. A manufacturing method comprising: a plasma processing step for performing plasma processing in advance below; and a gas barrier layer stacking step in which a gas barrier layer having a gas barrier property is stacked on the surface after performing the plasma processing step.

  In this embodiment, the plasma treatment is a glow discharge plasma treatment, and the glow discharge plasma treatment is performed by generating carbon-containing plasma by a sputtering method using a carbon target as a cathode.

Hereinafter, description will be made sequentially.
The plastic film that is the base material to be subjected to the plasma treatment is not particularly limited in the present embodiment, and any plastic film that is conventionally used as a base film for a gas barrier film may be used. For example, polyethylene terephthalate (PET) film, nylon film, unstretched polypropylene (CPP) film, linear low density polyethylene (LLPDE) film, polyethylene naphthalate (PEN) film, cyclic polyolefin (COP) film, polycarbonate (PC) film, poly Any ether sulfone (PES) film may be used.

  The thickness of the film to be used is not particularly limited, but in the present embodiment, it is necessary to have a thickness that does not cause damage even if plasma treatment is performed, and when a gas barrier film having high barrier properties is finally obtained. Of course, if a certain degree of flexibility is required, it is necessary to make the thickness not more than a level that can ensure such flexibility, as a matter of course. If this point is considered more specifically, it can be said that the thickness of the film is preferably 5 μm or more and 200 μm or less. It is because it is highly likely to break without being able to withstand the above treatment, and when it is 200 μm or more, the flexibility of the actually obtained film becomes poor, and as a result, it becomes unsuitable as a packaging material. Because. In this embodiment, it is assumed that the PET film has a thickness of 12 μm, but it is not necessarily limited thereto.

  The material of the plastic film used in the present embodiment is not particularly limited, but this film is not subjected to any pretreatment such as corona treatment or easy adhesion coating on its surface, so-called plain type. It is desirable to be a film. That is, even if a plasma treatment is performed on a surface that has been subjected to a treatment such as a corona treatment or an easy adhesion coating, it is highly likely that a harmful surface condition will appear in the present embodiment. This point will be described in detail again.

The plasma treatment is performed on the surface of the plastic film serving as the base material while introducing an inert gas. In this embodiment, the range of atmospheric pressure is 1 × 10 ⁻³ Torr or more and 1 × 10 6 in this embodiment. ^-1 Torr or less. The plasma treatment in this embodiment is a glow discharge plasma treatment with an inert gas introduced. (Hereinafter, it is also simply referred to as “plasma treatment”.) The inert gas used is not particularly limited, but is argon gas in this embodiment.

As described above, the atmospheric pressure range of the plasma treatment in the present embodiment is preferably 1 × 10 ⁻³ Torr or more and 1 × 10 ⁻¹ Torr or less as described above. This is because plasma discharge is likely to occur when the plasma treatment is performed, and the desired effect described later can be reliably obtained. In order to obtain the effect of the plasma treatment more reliably, the atmospheric pressure range may be 1 × 10 ⁻³ Torr or more and 1 × 10 ⁻² Torr or less.

The description will be further continued on the assumption that the plasma treatment is performed on the above-described conditions, that is, on the PET film having a film thickness of 12 μm under the condition that the atmospheric pressure under argon gas is set to 2 × 10 ⁻³ Torr. Further, in the following description, the description is continued assuming that a gas barrier layer exhibiting gas barrier properties is laminated as a functional layer having the functionality to be laminated.

The plasma treatment and the state of the substrate film surface corresponding thereto will be described.
In the present embodiment, the plasma treatment is performed on the surface of the PET film, which is the base film, so that the surface of the PET film that was initially “smooth” is the “activated state” after the plasma treatment. It becomes.

This is further described as follows.
Even if any lamination is performed on the surface of the PET film whose surface is untreated (plain), the laminate is not fixed on the surface of the PET film having a “smooth” surface, and a phenomenon called “repel” occurs. Lamination with a desired level of adhesion cannot be performed.

  Therefore, when the conventional plasma treatment is performed on the surface of the PET film having a smooth surface, the following state is obtained.

  When the PET film is expressed strictly, reaction terminals such as a carbonyl group appear on the surface in some places. The surface of the soil is dirty by touching the atmosphere. Therefore, even if a reaction terminal appears, even if some lamination is attempted as it is, the presence of dirt becomes an obstacle and a suitable lamination cannot be obtained.

  On the other hand, generally, when the plasma treatment is performed, such dirt can be physically removed, that is, the surface of the base material is cleaned and no physical dirt such as dust exists.

  However, when a general plasma treatment is performed, the reaction terminals present on the surface of the PET film described above simultaneously react with each other, which becomes a new impediment to improving adhesion.

  On the surface of the PET film, surface functional groups such as carbonyl groups which are reaction terminals are present in an oxidized or nitrided state by performing normal plasma treatment. When a laminate is laminated on the oxidized (nitrided) carbonyl group, the oxidized (nitrided) carbonyl group and the laminate first form an oxygen (nitrogen) bond. It looks like it ’s improved. However, when the laminated body obtained in this way passes a certain period of time, the oxygen (nitrogen) bond portion is easily cut, for example, by hydrolysis. This is caused by a reaction between moisture in the atmosphere and an oxygen (nitrogen) bonding portion. The fact that this oxygen (nitrogen) bond is broken means that delamination easily occurs, that is, the phenomenon that the function provided by the laminate is weakened or disappears due to delamination. Will occur.

  In other words, the laminated body obtained by performing the lamination after performing the conventional plasma treatment is exposed to the moisture in the atmosphere immediately after it is completed as a laminated body, and the oxygen (nitrogen) bond in the laminated part is caused by the moisture. Hydrolysis occurs in the portion, and therefore, the bonded portion is cut, resulting in delamination, resulting in a phenomenon that the interlayer adhesion as intended in the present invention is reduced and lost.

  In order to avoid this phenomenon, in this embodiment, instead of performing the conventional plasma treatment, a glow discharge plasma treatment is selected, and a plasma treatment is performed by a sputtering method using a carbon target as a cathode. By doing so, carbon-containing plasma can be generated, and in particular, the present embodiment becomes more effective by using argon gas as the inert gas used at this time.

  By using argon gas as the introduced gas, it is possible to suppress or prevent the phenomenon of oxidation or nitridation of the carbonyl group, which is the surface functional group of the PET film, seen when performing the general plasma treatment described above. That is, by performing the plasma treatment according to the present embodiment, dust and other physical obstacles are removed, and the reaction terminal appearing on the PET film surface continues to exist without being oxidized or nitrided. Let it be in a state. That is, since the PET film surface is in an activated state, if any resin or the like is laminated to the state, the laminate is not bonded by oxygen (nitrogen) bonds as in the past, but directly PET. It can be combined with reaction terminals present on the film surface. Therefore, when this is exposed to moisture in the atmosphere, hydrolysis does not occur at the bonded portion, and as a result, delamination does not occur. Therefore, the interlayer adhesion after lamination can be maintained as it is, that is, the function can be maintained.

  Although the same effect can be expected by introducing an inert gas other than argon gas, detailed description thereof is omitted here.

  The plasma treatment in this embodiment is a glow discharge plasma treatment as described above. In this embodiment, carbon-containing plasma is generated by a sputtering method using a carbon target as a cathode.

  That is, in the above basic structure, the plasma generated during the reaction contains carbon, so that the carbon is bonded to the surface of the PET film, more specifically, the reaction terminal is bonded to the carbon. A phenomenon occurs. On the opposite side of the carbon atom bonded to the reaction terminal, an additional bonding arm remains, which firmly bonds to the material to be laminated.

  In the base film from which physical bonding inhibiting factors such as dust have been removed from the surface by plasma cleaning, the presence of such a carbon bond further increases the base film and the substance to be laminated on the surface. Interlayer adhesion is ensured and improved.

This phenomenon will be briefly described.
Normally, when a gas barrier material such as SiOx is to be deposited on a PET film having an untreated surface, the portions where SiOx is deposited first are scattered on the surface of the PET film.

  However, in the case of a PET film that has been subjected to plasma treatment, since carbon is already scattered on the surface as described above, SiOx is deposited first at the place where this carbon exists.

  That is, SiOx molecules are not deposited on the surface of the PET film suddenly and densely, but are first deposited from the locations where carbon is scattered in the form of dots on the surface of the PET film. If further SiOx is subsequently deposited in this state, the SiOx molecules will be further deposited on the SiOx molecules that are already present on the PET film surface and bonded to the carbon arms that are firmly bonded to the PET film, and In fact, such deposition is performed. That is, SiOx molecules bonded to carbon existing as dots on the surface of the PET film are used as nuclei, and SiOx is deposited one after another as if the nuclei are growing.

  Eventually, SiOx molecules grown from adjacent nuclei are bonded together, and eventually a film of SiOx molecules on one side, that is, a gas barrier layer made of SiOx, is formed. Since it is firmly bonded to the PET film, as a result, the film made of SiOx molecules is firmly bonded to the PET film, that is, exhibits a strong interlayer adhesion.

  In this embodiment, it is assumed that a glow discharge plasma process is used instead of a plasma process, and that a carbon-containing plasma is generated by performing a sputtering method using a carbon target as a cathode. This is because oxygen and nitrogen present in the atmosphere during the plasma treatment react with the reaction terminal on the surface of the PET film first, and the above-described useless oxygen bond or the like is generated.

  When the gas barrier layer that has reached this state is observed in a substantially side view, the distance from the PET film surface to the gas barrier layer by SiOx that has reached a dense state is approximately 3 nm to 5 nm, and further, the gas barrier layer is, for example, 10 nm on the surface. It is in a laminated state.

  In other words, there is a non-dense, sparse SiOx layer in the 3 nm to 5 nm gap between the dense gas barrier layer and the PET film surface. In this case, since there are a large number of voids in which no gas barrier substance is present, the presence of this portion is a major factor for reducing the gas barrier property.

  However, in the method according to the present embodiment, SiOx aggregates around the carbon bond portion, and the aggregated and grown SiOx directly bonds to the substrate surface in a clean state. As a result, the voids in the part are also filled with SiOx. That is, SiOx is densely laminated in a state dense with the substrate surface. It can be said that this dense SiOx layer structure contributes to the improvement of gas barrier properties.

  Although the above description has been made assuming that SiOx is deposited, the same applies to a resin such as a silane coupling agent used as the first polymer resin described later. In other words, even if a silane coupling agent is applied directly to the surface of a plain PET film that has not been subjected to any treatment, and a layer is formed by this, the silane coupling agent is repelled on the surface of the PET film, resulting in sufficient adhesion. Lamination in the secured state is difficult, but by applying plasma treatment in advance, the silane coupling agents are laminated one after another without being repelled in the same manner as described above, and eventually in a dense state The state that the silane coupling agent is laminated appears.

(Embodiment 2)
In the first embodiment described above, the first polymer resin as the first layer is laminated as the first polymer resin layer before the functional layer is laminated on the plasma-treated surface. You may perform a 1st polymeric resin lamination process. Here, the description will be continued assuming that the first polymer resin lamination step is executed. Moreover, although the function which the functional layer assumed here shall be gas barrier property, it should be noted that the present invention is not necessarily limited to the laminated film exhibiting gas barrier property.

  Although it does not specifically limit as 1st polymeric resin, A silane coupling agent is the most suitable. More preferable are epoxy silane coupling agents, amino silane coupling agents, methacrylic silane coupling agents, and ureido silane coupling agents. In this embodiment, epoxy silanes are used. A coupling agent is used as the first polymer resin.

The reason for providing the first polymer resin layer is as follows.
In general, a metal or a metal oxide is often used as a substance exhibiting a functional layer such as gas barrier properties and transparent conductivity assumed in the present invention. In addition, they are not well known to be familiar with the base film, which is a polymer resin. In other words, the elastic modulus, rigidity modulus, and linear expansion coefficient of both are different, and in the case of a laminated film that is simply laminated, delamination easily occurs when subjected to heat, humidity, and physical stress. There was a problem that it was likely to occur.

  Therefore, in the present invention, as described above, nucleation with carbon is used to cope with this delamination. However, in this embodiment, the first polymer resin layer is provided to further improve the adhesion. In addition, by laminating the first polymer resin layer, it is possible to further improve the functionality exhibited by the functional layer further laminated on the surface. Are laminated.

  If the first polymer resin has the properties of both an organic component and an inorganic component, this intervenes between the base film made of the polymer resin and the functional layer that is a ceramic. The familiarity is expected to be good, and the familiarity can be good.

  However, if the coating surface of the first polymer resin layer is smoothed by providing the first polymer resin layer, the functional layer further laminated on the surface may be smooth as a result. It becomes possible easily, and it improves the denseness of the functional layer, and as a result, the function and interlayer adhesion of the functional layer can be dramatically improved.

  In the present invention, as described above, the adhesion is already improved by the plasma treatment. By providing the first polymer resin layer in this way, the function exhibited by the functional layer is improved in addition to the interlayer adhesion. It is possible to make it.

  The functional layer in the present embodiment assumes gas barrier properties. From this point of view, by providing the first polymer resin layer, the gas barrier layer laminated on the surface thereof becomes denser. Thus, not only the adhesion between the base film and the gas barrier layer is improved by nucleation, but also the adhesion is improved by the presence of the first polymer resin layer, and the gas barrier property is further enhanced. It can be done.

  Therefore, it can be said that it is more preferable to provide the first polymer resin layer in order to achieve such an object. Furthermore, if the first polymer resin layer itself has the same properties as those of the functional layer, it can further contribute to improving the functionality of the laminated film as a whole.

  For example, a silane coupling agent or a polymer resin mainly composed of a silane coupling agent is suitable as a material suitable for such purposes. In this embodiment, an epoxy is used as the first polymer resin. A silane coupling agent is used, and in the following embodiment, description will be continued assuming that this is used.

  The technique for laminating the first polymer resin may be a conventionally known technique, but in this embodiment, the coating method is used, and the thickness of the lamination is 0.2 μm. Incidentally, the thickness of the layer is preferably 0.03 μm or more and 2 μm or less, but if this is 0.03 μm or less, the above-mentioned effect is difficult to obtain, and if it is 2 μm or more, the laminate obtained by this embodiment is obtained. The thickness of the whole film will increase and the flexibility will be lacking. In addition, this is because cracks are generated, and it is difficult to control the cost because the drying process takes time during actual production, so that it is not suitable as a final product.

  When the first polymer resin laminating step of laminating the first polymer resin layer with the epoxy-based silane coupling agent on the plasma-treated surface of the PET film subjected to the plasma treatment in this way is performed next. Although it hardens | cures, the method may be a conventionally well-known thing. However, it is also conceivable to accelerate the curing by adding a curing catalyst.

  The curing catalyst used here may be a conventionally known one, but examples of the curing catalyst used include iron acetylacetonate, zinc acetylacetonate, aluminum acetonate, tin tetrachloride, and diisopropoxybisacetylacetonatotitanium. , Dihydroxybislactotitanium, one or more of them, the polymer resin mainly composed of the epoxy-based silane coupling agent is effectively cured, and will be described later. Depending on the situation, it can be very suitable. In addition, what is necessary is just to select and determine an effective amount suitably about addition amount.

(Embodiment 3)
Next, in the second embodiment described above, after completing all the steps, a second polymer resin laminating step of laminating a second polymer resin on the surface of the functional layer is further performed. A method for manufacturing a laminated film will be described as a second embodiment.

  Regarding the second polymer resin, if the desired laminated film is a gas barrier film and the second polymer resin is a substance having a gas barrier property, this is laminated on the surface of the functional layer having the gas barrier property. Thus, it is possible to further supplement the gas barrier property, that is, it is considered that a higher barrier property can be obtained, and it is expected to play a role as a top coat layer for protecting the gas barrier layer itself.

  That is, when the second polymer resin layer using a material having a property exhibiting a function equivalent to that of the functional layer is used, it is considered that a desired function is more emphasized, and a suitable one can be obtained.

  As for the second polymer resin, as in the case of the first polymer resin described above, if the desired function is a gas barrier property, it is more preferable if it is a polymer resin having a gas barrier property. For example, an epoxy-based silane coupling agent is preferable. If the same epoxy-based silane coupling agent as that of the first polymer resin is used as the second polymer resin, the same substance can be used in the manufacturing process to facilitate the work. In order to stabilize the physical properties of the obtained high-barrier film, it can be said that it is preferable that the number of constituent materials is as small as possible. Therefore, in this embodiment, the desired function is the gas barrier property, which is the same as the first layer. The description will be made on the assumption that the material is an epoxy silane coupling agent. And by laminating this second polymer resin layer, the gas barrier property can be further improved.

  The thickness of the second polymer resin layer is preferably 0.03 μm or more and 2 μm or less, but if this is 0.03 μm or less, the purpose of improving the gas barrier property cannot be achieved. This is because the flexibility of the film becomes poor. In the present embodiment, this thickness is 0.3 μm.

  The second polymer resin layer is also described in the first embodiment in order to promote the curing of the silane coupling agent, as described in the section relating to the first polymer resin layer. It is conceivable to add a curing catalyst similar to the above. The details are the same as described above, and the description thereof is omitted here.

  The second polymer resin is not particularly limited, but is most preferably a silane coupling agent. More preferable are epoxy silane coupling agents, amino silane coupling agents, methacrylic silane coupling agents, and ureido silane coupling agents. In this embodiment, epoxy silanes are used. A coupling agent is used as the second polymer resin.

  According to the method for producing a gas barrier film according to the present embodiment executed in this way, a gas barrier film having a configuration of base film / first polymer resin layer / gas barrier layer / second polymer resin layer is provided. Can be obtained.

  Although not described in detail here, it is conceivable to perform plasma treatment again after laminating the first polymer resin layer and before laminating the functional layer on the surface thereof. This is because it can be considered that the interlaminar adhesion between the first polymer resin layer and the functional layer is further improved. Similarly, it is conceivable to perform plasma treatment before laminating the second polymer resin layer on the surface of the functional layer, but here, whether or not the function exhibited by the functional layer is reduced by performing plasma treatment. What is necessary is just to determine the presence or absence of execution after consideration.

(Embodiment 4)
In the manufacturing method of the laminated film in the second or third embodiment described above, the case where the curing catalyst is added to either one or both of the first or second polymer resin has been described. Description will be made on the case where the two-polymer resin contains one or more of a water-soluble polymer, a metal alkoxide and a hydrolyzate thereof.

  When these are contained in the second polymer resin, the effect of improving the gas barrier property can be expected if the functional layer exhibits gas barrier properties. Furthermore, the effect as a protective layer of the whole laminated film can also be expected. In particular, if there is no first polymer resin layer and only the second polymer resin layer is configured, it is particularly effective when the second polymer resin layer is designed as a so-called Top coat layer.

  Further, when the laminated film according to the present embodiment is assumed to be a gas barrier film, and if polyvinyl alcohol is used as the water-soluble polymer in this embodiment, the oxygen barrier property required for retort application is improved. Therefore, when a polyvinyl alcohol resin is selected as the water-soluble polymer, it can be made suitable.

  If the metal alkoxide is tetraethoxysilane in the present embodiment and polyvinyl alcohol is used at the same time, the reaction rate of the resin layer containing them increases, that is, the time required for curing can be shortened. It can be expected to be more suitable.

The reason why the reaction speed is increased is that the lamination process can be executed only by the Si—O crosslinking reaction. In other words, hydrolysis of tetraethoxysilane (C ₂ H ₅ O) ₄ Si changes the (XO) part to —OH, followed by dehydration condensation with —OH of polyvinyl alcohol to form a three-dimensional crosslinking reaction of O—Si—O. Therefore, a simple structure having no extra organic chain has a higher reaction rate without causing steric hindrance.

(Embodiment 5)
In the four embodiments described above, the functional layer laminating step for laminating the functional layers is executed, but this step will be briefly described. Here, it is assumed that the gas barrier property is desired, that is, the laminated film is a gas barrier film.

  As a gas barrier substance constituting the gas barrier layer in the present embodiment, for example, one of a group consisting of silicon, titanium, tin, zinc, aluminum, indium, and magnesium, or an oxide, nitride, or compound thereof Or a plurality of oxides, nitrides, or compounds thereof in the group. More specifically, for example, silicon may be used, silicon oxide or silicon nitride may be used, and a silicon compound may be used. Further, it may be an oxide or nitride of an alloy of tin and indium. In other words, the gas barrier layer may be made of a material using these group of metals as raw materials.

  Alternatively, the gas barrier layer may be made of silicon oxide represented by SiOx, and x may satisfy 1.0 ≦ x ≦ 2.0.

  As will be described later, the SiOx layer is basically transparent, and the high barrier obtained by the present embodiment can be obtained by using all the materials used for the high barrier film according to the present embodiment that are basically transparent. The entire protective film becomes transparent, and if such a high-barrier film is used as a packaging material, the contents can be easily seen, so the contents are not only protected from gas but also the state of the contents is also visible. It can be said that the use of SiOx is advantageous in this respect.

  When laminating SiOx, the laminating method may be a conventionally known one. In this embodiment mode, the vacuum deposition method is used. However, the method is not necessarily limited to this, and a so-called physical vapor deposition method, chemical vapor deposition method, or other known methods may be used.

  The thickness of the gas barrier layer is preferably 70 to 1000 mm. This is because if the gas barrier layer is 70 mm or less, the gas barrier layer itself has insufficient gas barrier properties, and if it is 1000 mm or more, the flexibility of the entire gas barrier film is poor. . In the present embodiment, this thickness is 120 mm.

  The method for producing a laminated film according to the present invention and the resulting laminated film will be further described below with examples, but the present invention is not limited to these examples. Moreover, the laminated film used for each Example was obtained by the manufacturing method already demonstrated in 1st Embodiment-5th Embodiment, and what was used for the comparative example was also manufactured according to it. Note that it was obtained by the method. Further, in the following description, the desired function is assumed to be gas barrier property, that is, the case of a gas barrier film will be described, but from the viewpoint of improving interlayer adhesion, it is not necessarily explained on the assumption that it is limited to a gas barrier film. I refuse.

(Description of each member and device)
<Polymer resin film as substrate>
PET film (“NS” thickness 12 μm, manufactured by Teijin Ltd.)
<Explanation on glow discharge plasma treatment>
Gas introduced during plasma treatment: Argon Vacuum degree during plasma treatment: 2 × 10 ⁻³ Torr
<Gas barrier layer (functional layer)>
SiOx (1.0 ≦ x ≦ 2.0) Thickness 0.015 μm

<First polymer resin> manufactured by Shin-Etsu Chemical Co., Ltd.
Product Name: KBM403
Lamination thickness: 0.2 μm
(Preparation of the first polymer resin layer)
KBM403 50 parts by weight Water 50 parts by weight Hydrochloric acid (35%) 0.07 parts by weight After preparing a mixture of these and hydrolyzing,
Add IPA / n-butanol = 575/575 (parts by weight) and dilute.
Further, 2 parts by weight of a curing catalyst (aluminum acetylacetonate) is added to complete the preparation.

<Second polymer resin> manufactured by Shin-Etsu Chemical Co., Ltd.
Product name: KBE403
Lamination thickness: 0.2 μm
(Preparation of second polymer resin layer)
KBE403 50 parts by weight Water 50 parts by weight Hydrochloric acid (35%) 0.07 parts by weight After preparing a mixture of these and hydrolyzing them,
Add IPA / n-butanol = 575/575 (parts by weight) and dilute.
Further, 2 parts by weight of a curing catalyst (aluminum acetylacetonate) is added to complete the preparation.

(Configuration of each example and comparative example)
Example 1 Base material / gas barrier layer Example 2-1 Base material / first polymer resin layer / gas barrier layer Example 2-2 Base material / first polymer resin layer / gas barrier layer Example 3-1 Base material / First polymer resin layer / gas barrier layer / second polymer resin layer Example 3-2 Base material / first polymer resin layer / gas barrier layer / second polymer resin layer Example 4 Base material / gas barrier layer / second 2 polymer resin layer

As mentioned above, in each Example, the laminated body was laminated | stacked after performing the vacuum plasma processing by performing the vacuum plasma processing process with respect to the surface of a base material.
In Example 2-2 and Example 3-2, the surface of the first polymer resin layer was again subjected to vacuum plasma treatment, and then further laminated.

Comparative example 1 Base material / gas barrier layer comparative example 2 Base material / first polymer resin layer / gas barrier layer comparative example 3 Base material / first polymer resin layer / gas barrier layer / second polymer resin layer comparative example 4 Base material / Gas barrier layer / second polymer resin layer comparative example 5 base material / first polymer resin layer / gas barrier layer / first polymer resin layer / gas barrier layer

In Comparative Examples 1 and 4, the gas barrier layer was laminated on the substrate surface without any pretreatment.
In Comparative Examples 2, 3 and 5, the substrate surface was subjected to simple plasma treatment without using a carbon target.

For each example and each comparative example, the barrier property was examined as follows.
<Explanation regarding measurement of gas barrier properties>
A sample obtained by dry-laminating a laminated film of each example and comparative example with a CPP (manufactured by Toyobo Co., Ltd .: trade name “CT-P1146”) having a thickness of 60 μm by a conventionally known method was used as a sample.
The obtained sample was immersed in hot water at 125 ° C. for 30 minutes / 120 minutes.
For each sample, (A) Before immersion (B) After 30 minutes immersion (C) After 120 minutes immersion, 1) at each time point 1) WVTR (water vapor permeability)
2) OTR (Oxygen permeability)
3) Change in laminate strength with sealant was measured.

The obtained gas barrier film was subjected to a permeation humidity test according to JIS Z 0208. (Cup method)
The measurement of moisture permeability was performed according to JIS K 7129. (Mocon method moisture permeability)
The measurement regarding oxygen permeability was performed according to JIS K7126. (Mocon oxygen)

  As can be seen from the above results, it can be seen that the laminated film produced by the method for producing a laminated film according to the present invention can exhibit the desired performance at a high level.

  That is, in any example, the values of WVTR and OTR are not changed so much, and the laminate strength is not changed (all are broken), so that the performance is maintained. It can be seen that, as long as it is a comparative example, the values of WVTR and OTR are deteriorated over time, or the laminate strength is reduced.

  If it says by the example of the said gas barrier film, it will be far more preferable for the interlayer adhesiveness by the manufacturing method which concerns on this invention by performing the lamination after performing the plasma treatment to the base film. I understand. Incidentally, it can be seen that the interlaminar adhesion is further improved when the first polymer resin layer is subjected to plasma treatment.

  Moreover, in this invention, it turns out that it is not a mere plasma processing but the plasma processing which used argon gas as introduction gas, and it turns out that interlayer adhesiveness is favorable compared with the case where the plasma processing of a comparative example is performed. As already explained, this is a proof that when oxygen or nitrogen is used for plasma treatment, oxygen bonds that have been inadvertently broken are broken by water vapor, resulting in delamination. Think of things.

  Incidentally, in this embodiment, an example in which the first polymer resin is directly laminated without performing plasma treatment on the surface of the base material is not shown, but this causes a phenomenon called “repellency” even if such lamination is attempted. This is because it was impossible to stack the layers, that is, as a result, a stacked body could not be obtained.

  As described in the beginning, the description was made assuming the case of a gas barrier film. However, for example, it is a laminated film such as a transparent conductive film and the like, as long as improvement in interlayer adhesion is required. Since the result is derived, the description by further examples is omitted.

  With the laminated film manufacturing method described above, even when exposed to a high temperature and high humidity environment, the property change of the transparent conductive layer, that is, the change in conductivity, and the increase in sheet resistance value are small. It can be a product with its own heat and moisture resistance. Therefore, it is useful as a transparent electrode used for various displays such as liquid crystal displays, solar cells, touch panels and the like. Moreover, the transparent conductive agent which is a material of the transparent conductive layer which comprises this film can be useful by using this for an electromagnetic wave shielding material.

Claims (13)

at least,
A plasma treatment step in which a plasma treatment is performed in advance in an environment of an atmospheric pressure of 1 × 10 ⁻³ Torr or more and 1 × 10 ⁻¹ Torr or less under introduction of an inert gas on the surface of a plastic film as a substrate;
After performing the plasma treatment step, a functional layer stacking step in which a functional layer having a specific function is stacked on the surface;
With
The plasma treatment is a glow discharge plasma treatment;
The glow discharge plasma treatment is performed by generating a carbon-containing plasma by a sputtering method using a carbon target as a cathode,
A method for producing a laminated film. A method for producing a laminated film according to claim 1,
The inert gas is argon;
A method for producing a laminated film. It is a manufacturing method of the lamination film according to claim 1 or 2,
After the plasma treatment step and before the functional layer lamination step,
Performing a first polymer resin laminating step of laminating a first polymer resin layer made of a first polymer resin on the surface of the base material subjected to the plasma treatment;
A method for producing a laminated film. It is a manufacturing method of the lamination film according to claim 3,
After performing the first polymer resin lamination step, the plasma treatment step is performed again on the surface of the first polymer resin layer,
A method for producing a laminated film. It is a manufacturing method of the laminated film of any one of Claims 1 thru | or 4, Comprising:
After the functional layer lamination step,
Performing a second polymer resin lamination step in which a second polymer resin is laminated on the surface of the functional layer;
A method for producing a laminated film. A method for producing a laminated film according to any one of claims 3 to 5,
Either or both of the first polymer resin layer and the second polymer resin layer are made of an epoxy silane coupling agent, or a polymer mainly composed of an epoxy silane coupling agent. Being resin,
A method for producing a laminated film. A method for producing a laminated film according to any one of claims 3 to 6,
A curing catalyst is added to one or both of the first polymer resin layer and the second polymer resin layer;
A method for producing a laminated film. A method for producing a laminated film according to claim 7,
The curing catalyst is one or more of iron acetylacetonate, zinc acetylacetonate, aluminum acetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, or dihydroxybislactotitanium,
A method for producing a laminated film. A method for producing a laminated film according to claim 5 or 6,
The second polymer resin layer is a resin comprising one or more of a water-soluble polymer, a metal alkoxide and a hydrolyzate thereof,
A method for producing a laminated film. It is a manufacturing method of the lamination film according to claim 9,
The water-soluble polymer is polyvinyl alcohol;
A method for producing a laminated film. It is a manufacturing method of the lamination film according to claim 9 or 10,
The metal alkoxide is tetraethoxysilane;
A method for producing a laminated film. A method for producing a laminated film according to any one of claims 1 to 11,
The substance constituting the functional layer is any one of a group consisting of silicon, titanium, tin, zinc, aluminum, and indium, or an oxide or compound thereof, or a plurality of or a plurality of each oxidation in the group An object or a compound, or any one of a plurality of members in a group and other oxides or compounds,
The functional layer is formed by a vacuum deposition method;
A method for producing a laminated film. It is obtained by the manufacturing method of the laminated | multilayer film of any one of Claim 1 thru | or 12.
A laminated film characterized by