JP2011245743A - Laminate and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for forming a laminate by joining a functional film to the top of a polymer base material.SOLUTION: The laminate includes a layer A composed of a polymer material, and a layer B whose one surface is set in contact with a surface of the layer A. The layer B has a thickness of 15 nm or more to 70 nm or less, and is formed by subjecting the surface of the layer A to an atmospheric plasma process using a rare gas containing acrylic acid steam of 0.1 percent by volume or more and cleansing the surface with a solvent.

Description

  The present invention relates to a laminate, and more particularly, to a technique for forming a laminate based on a polymer material.

  Polyolefin resin materials typified by polyethylene and polypropylene have hydrophobic surface characteristics and have poor interaction with other materials. Therefore, it is difficult to join with metal, metal oxide, or other polymer films.

  Therefore, by using polyolefin resin as the main material and adding maleic acid modification to this, it is well compatible with the base polyolefin and has polar groups. Alternatively, adhesives that can be bonded to other polymer films have been developed and widely used. In particular, when polyethylene or polypropylene is used as a base material, a low molecular weight soft polyethylene obtained by maleic acid modification is often used.

  However, in general, in order to use these adhesives, it is necessary to perform primer treatment on the substrate. The primer is for interposing between the base material and the adhesive to improve the adhesive force. When polyolefin is used as the base material, a metal chelate compound or a silane coupling material is used.

  On the other hand, there is an attempt to obtain an equivalent adhesive strength without using an adhesive. This is intended to reduce the thickness of the adhesive layer of the film obtained by bonding in order to reduce the weight of the member. Some are intended to reduce the cost required for the primer treatment, and others are intended to reduce the cost required for the post-treatment associated with the primer treatment.

  Specifically, by using a polyolefin film as a base film and laminating a film formed by a method such as vapor deposition of a metal oxide, an oxygen or water barrier can be used without using an adhesive, and thus without performing primer treatment. Trying to form a film.

  In Non-Patent Document 1 (J. Friedrich et al., Plasma Processes and Polymers, Volume 1, Issue 1, 2004, p. 28-50), a plasma polymerized film is formed on a polypropylene film using an acrylic acid monomer. At the same time, attempts have been made to improve the adhesion of alumina (aluminum oxide) using the plasma polymerized film. In this document, alumina is formed by a vacuum deposition method on a polypropylene film in which a plasma polymerization film is formed using a vacuum plasma apparatus using a mixed gas of acrylic acid and butadiene. In the same document, the concentration of COOH groups present on the surface of the plasma polymerized film is measured by XPS, and the maximum peel strength is exhibited when the COOH groups are 5% or more compared to the total carbon. It has been shown.

  However, this is only related to the vapor-deposited alumina thin film, and in order to put the laminated film thus obtained into practical use, it is necessary to bond a polymer film to protect the alumina layer. For this reason, the process which uses the adhesive agent is needed when bonding together.

  In general, a deposited aluminum thin film has a high bonding force because aluminum atoms jump into the deposition surface in a high energy state during deposition. Therefore, the peel strength is usually increased.

Other surface treatment techniques for the substrate by plasma treatment include the following.
Patent Document 1 (Japanese Patent Laid-Open No. 2001-192070) discloses a method of forming a gas barrier film by performing sol-gel coating after atmospheric pressure plasma treatment.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2001-246660) and Patent Document 3 (Japanese Patent Application Laid-Open No. 2001-260297) disclose a technique for manufacturing a laminate made of a base material and an extruded laminate resin. This document describes that a surface activation treatment is performed on a base material for adhesion without using an anchor coat material. As the surface activation treatment method, a process including atmospheric pressure or low pressure plasma treatment is cited. As the plasma technique, a normal method is disclosed.

  Patent Document 4 (Japanese Translation of PCT International Publication No. 2002-528568) discloses a technique of performing plasma treatment by attaching a photoinitiator having an ethylenically unsaturated group on a substrate.

  Patent Document 5 (Japanese Patent Laid-Open No. 8-7870) discloses a method of graft polymerizing acrylic acid or the like to a polyolefin resin subjected to plasma treatment.

  Patent Document 6 (Japanese Patent Laid-Open No. 2000-117880) discloses that a functional structure is obtained by forming a plasma polymerized film of an acrylic acid compound on a base material made of an organic polymer. This structure is said to have antifouling, deodorizing, antibacterial and antifungal properties.

  Patent Document 7 (Japanese Patent Application Laid-Open No. 2000-319010) discloses a technique relating to a polymer molded counterpart having a structure in which a hydroxyapatite layer is coated on the surface. This document describes that the surface of a polymer molded body is subjected to plasma treatment, a monomer such as acrylic acid is brought into contact with the treated surface and graft polymerization is performed, and a hydroxyapatite layer is formed thereon. .

  Patent Document 8 (Japanese Patent Publication No. 2001-515143) also discloses a method of forming a plasma polymer coupling layer containing acrylic acid or the like after plasma treatment.

  Patent Document 9 (International Publication No. 01/048065 pamphlet) discloses a method of treating a polymer material with a hydrophilic polymer after being activated by plasma treatment or the like. In addition, grafting acrylic acid or the like is described. It is said that the adhesiveness of a polymer film can be improved by the technique described in the document.

  In Patent Document 10 (Japanese Patent Laid-Open No. 2008-265088) and Patent Document 11 (Japanese Patent Laid-Open No. 2008-291051), an acrylic polymer is added to a cyclic polyolefin-based addition (co) polymerized film after plasma treatment. A method of forming is disclosed.

  Patent Document 12 (Japanese Translation of PCT International Publication No. 2002-510340) discloses a method in which an additive containing a carboxyl group is attached and plasma treatment is performed as an additional step in order to improve adhesion to a polyolefin molded article. Has been.

  Patent Document 13 (Japanese Patent Application Laid-Open No. 2004-314322) discloses a method of forming an optical polymerization film after imparting a carboxyl group or the like to the surface of an inorganic film such as a silica film by atmospheric pressure plasma treatment. Yes.

  Patent Document 14 (Japanese Patent Laid-Open No. 2006-116708) discloses a multilayer deposited film in which a polymer layer and a ceramic deposited layer are formed via a plasma treatment layer.

  In addition, an example in which a metal film is formed on a polymer film subjected to plasma treatment using a method that has been reported so far (Patent Document 4), or a metal oxide material is applied to a polymer film that has been subjected to plasma treatment. A coated example (Patent Document 1) has been reported.

JP 2001-192070 A JP 2001-246660 A JP 2001-260297 A Special table 2002-528568 gazette JP-A-8-7870 JP 2000-117880 A JP 2000-319010 A Special table 2001-515143 gazette International Publication No. 01/048065 Pamphlet JP 2008-265088 A JP 2008-291051 A Japanese translation of PCT publication No. 2002-510340 JP 2004-314322 A JP 2006-116708 A

J. Friedrich, G. Kuhn, R. Mix, W. Unger, `` Formation of Plasma Polymer Layers with Functional Groups of Different Type and Density at Polymer Surfaces and their Interaction with Al Atoms '', Plasma Processes and Polymers, Volume 1, Issue 1, 2004, p. 28-50

  However, even when these methods are used, a polymer film that has been subjected to plasma treatment and a laminated film in which a functional film such as a metal or metal oxide is formed on the polymer film are bonded without using an adhesive. There are no reports.

  Therefore, as a result of the study by the present inventor, when a polymer film subjected to such a plasma treatment is to be bonded without using adhesion to a functional film laminated on the polymer film, it is improved in terms of bonding strength. It became clear that there was room.

According to the present invention,
A laminate comprising an A layer made of a polymer material and a B layer provided on one surface in contact with the surface of the A layer,
The thickness of the B layer is 15 nm or more and 70 nm or less,
The B layer is formed by subjecting the surface of the A layer to atmospheric pressure plasma treatment using a rare gas containing 0.1% by volume or more of acrylic acid vapor, and further washing with a solvent. A laminate is also provided.

Moreover, according to the present invention,
A method for producing a laminate including a step of forming a B layer on the surface of an A layer composed of a polymer material,
In the step of forming the layer B, the surface of the layer A is subjected to an atmospheric pressure plasma treatment using a rare gas containing 0.1% by volume or more of acrylic acid vapor, and further washed with a solvent. Provides a method for manufacturing a laminate including a step of forming the B layer having a thickness of 15 nm to 70 nm.

  According to the present invention, by providing the B layer having a specific configuration on the surface of the A layer made of the polymer material, it becomes possible to bond the functional film to the upper part of the A layer via the B layer. The bonding strength can be improved.

It is a schematic diagram which shows the structure of the plasma processing apparatus in embodiment. It is a figure which shows the relationship between the thickness of the process layer (B layer) in an Example, and peeling strength. It is a figure which shows the relationship between the C (= O) -O group density | concentration in a process layer (B layer) in an Example, and peeling strength.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
In addition, when defining a numerical range using “to” in this specification, upper and lower limit values are included. For example, “10 to 100” is 10 or more and 100 or less.

(First embodiment)
The laminated body in this embodiment consists of A layer and B layer. The B layer is obtained by a specific method and has a specific thickness. Hereinafter, the A layer and the B layer will be specifically described.
The A layer is made of a polymer material.
Examples of the polymer material used as the A layer include the following resins. That is, polyolefin resin such as polyethylene, polypropylene, polymethylpentene;
Halogen-based resins such as polyvinyl chloride and polytetrafluoroethylene;
Polyester resins such as polyethylene terephthalate;
Polystyrene, acrylic resin, polyvinyl acetate, polycarbonate, aromatic polyether ketone resin;
Polyacetal;
Polyamide resin;
Polyimide resin;
Polyurethane resin;
Polyphenylene sulfide,
Such as polysulfone. These materials can be used alone or in combination of two or more.

  More specifically, examples of the material for the A layer include polyolefin resins, halogen resins, and polyimide resins. Moreover, it is preferable that A layer consists of polyolefin resin from a viewpoint of improving the joining strength of a laminated body more reliably. The layer A may be a polymer substrate made of these materials. There is no restriction | limiting in particular in the form of a base material, For example, it is set as a film and a board | substrate.

  Although there is no restriction | limiting in particular in the thickness of A layer, From a viewpoint of intensity | strength, it is good also as 2 micrometers or more, for example. Further, from the viewpoint of workability, it may be, for example, 2000 μm or less.

  The B layer is provided in contact with the surface of the A layer on one surface. B layer consists of a homopolymer or a copolymer of acrylic acid.

  The B layer may cover the whole of one surface of the A layer, or may cover a part of the region. From the viewpoint of further reliably improving the bonding strength of the laminate, it is preferable that the B layer is provided on the entire one surface of the A layer. Further, the B layer may be formed, for example, in the form of a film on the surface of the A layer.

Moreover, in the laminated body of this embodiment, the thickness of B layer is a very thin structure. Specifically, by setting the B layer to the following specific thickness, as described later in Examples, it is possible to obtain a configuration with excellent peel strength.
That is, from the viewpoint of stably improving the bonding strength of the laminate, the thickness of the B layer is set to 70 nm or less, preferably 60 nm or less. Moreover, the thickness of B layer shall be 15 nm or more from a viewpoint of improving the joining strength of a laminated body reliably.

The B layer having the above thickness is subjected to an atmospheric pressure plasma treatment using a rare gas containing 0.1% by volume or more of acrylic acid vapor on the surface of the A layer, and further washed with a solvent. It is formed.
Moreover, the manufacturing method of the laminated body in this embodiment includes the process of forming B layer 15-70 nm in thickness on the surface of A layer comprised with the polymeric material. The step of forming the B layer is a step of forming the B layer by subjecting the surface of the A layer to atmospheric pressure plasma treatment using a rare gas containing 0.1% by volume or more of acrylic acid vapor, and After the step of forming the B layer, a step of washing the B layer using a solvent is included.

Hereinafter, the plasma processing method in the step of performing the atmospheric pressure plasma processing will be described in detail.
The plasma processing method may be a so-called direct method in which the substrate to be processed is placed in the discharge plasma space for surface treatment, or the substrate to be processed is placed outside the discharge plasma space and generated in the plasma space. A so-called remote method may be employed in which the activated species are sprayed onto the surface of the substrate to be treated to perform the treatment.

In the present embodiment, the plasma treatment is performed by an atmospheric pressure plasma apparatus.
FIG. 1 is a schematic view showing an example of a plasma processing apparatus used in the present embodiment.

  The plasma processing apparatus of FIG. 1 is a so-called direct type apparatus, in which a voltage application electrode 50 and a ground electrode 55 are arranged to face each other. A dielectric 70 and a dielectric 75 are disposed on the electrode facing surfaces of the voltage application electrode 50 and the ground electrode 55, respectively. In the present embodiment, for example, aluminum oxide is used as the dielectrics 70 and 75. The dielectric 70 and the dielectric 75 are arranged with a specific distance (gap) therebetween, and this space becomes a plasma space 80.

  A pulse power supply 60 is connected to the voltage application electrode 50, and the ground electrode 55 is grounded. Since the voltage application electrode 50 is connected to the gas supply unit 40 and the gas exhaust unit 45 and integrally moves, it is possible to process a wide range of the substrate 90 to be processed disposed on the ground electrode 55. In addition, it is possible to process a narrow range for a long time.

  Main gas is injected from the bubbling main gas supply line 11 into the liquid raw material of the processing agent 20 that has entered the bubbling device 30. The processing agent vaporized inside the bubbling apparatus 30 by the vapor pressure is accompanied by the bubbling main gas, passes through the processing gas addition line 12 as a processing gas, and is mixed with the main gas from the main gas supply line 10. Further, the gas is supplied to the plasma space 80 through the gas supply line 13 and the gas supply unit 40. The gas that has passed through the plasma space 80 is exhausted through the gas exhaust part 45 and the gas exhaust line 14. In addition, the supply amount of the main gas and the processing agent can be controlled by installing a flow meter in the line and installing a ribbon heater in the line and the bubbling device to control the temperature.

  The plasma apparatus used in the present embodiment preferably includes temperature adjusting means for adjusting the temperature of the gas line, the plasma processing space, and the surface of the workpiece from room temperature to about 100 ° C. Thereby, the processing agent can be introduced into the plasma processing space without causing condensation.

  The plasma processing method of the present invention includes a step of generating active species by exciting a gas component into a plasma under atmospheric pressure or a pressure in the vicinity thereof.

  In the present invention, the atmospheric pressure or the pressure in the vicinity thereof means that the present invention can be used by being opened to the atmosphere, and is used in a sealed container to reduce the pressure slightly or to increase slightly compared to the atmospheric pressure. It is used in the sense that it can be used even in a pressure state. Here, the pressure near the atmospheric pressure refers to a pressure of 100 to 800 Torr (0.013 to 0.105 MPa). A range of 700 to 780 Torr (0.092 to 0.103 MPa) is preferable because the apparatus is simple.

  The gas component to be excited and converted to plasma refers to a mixed gas obtained by adding a main gas essential for forming discharge plasma and an additive gas containing a vaporized product of the processing agent to the main gas.

  Here, the main gas specifically refers to one or more kinds of single or mixed gases selected from rare gases such as helium, neon, argon, and xenon. It is desirable that helium and / or argon be the main component because of the ease with which a discharge is formed.

  The treating agent contained in the processing gas added to the main gas is acrylic acid. The amount of acrylic acid added is 0.1% by volume or more with respect to the main gas. Moreover, it is preferable to set it as 0.2 volume% or more from a viewpoint of improving the joining strength of a laminated body reliably. Moreover, although there is no restriction | limiting in particular in the upper limit of the addition amount of acrylic acid, from a viewpoint of improving safety | security further, it shall be less than 2.9 volume% of the explosion lower limit, for example.

  As a means for adding the processing agent to the main gas, for example, a part of the main gas is injected into the liquid containing the processing agent, and the processing gas is added to the main gas as the processing gas depending on the temperature of the liquid raw material and the injection amount of the main gas. A so-called bubbling method for controlling the amount of the treatment agent can be mentioned, but is not limited thereto.

  Examples of the means for introducing the processing gas and / or the main gas into the discharge plasma space include a pipe, a pipe, a joint such as a joint, a mass flow controller, and the like. The flow rate of the gas to be introduced is not particularly limited and can be appropriately set, but is usually preferably 1 L / min to 100 L / min.

  Various types of voltage application means can be used as the voltage application means in the plasma treatment, and the voltage application means is not limited to these types. Preferably, the voltage applying means includes at least a means for applying a pulse-modulated high-frequency voltage or a means for applying a periodic pulse voltage.

  The gas introduced into the plasma space is turned into plasma by application of a voltage to form radicals and become active species.

  Specific examples of the method for transporting the active species to the polymer surface include a method in which the active species are generated and then moved along with the main gas, and a method in which the active species is moved by diffusion of the active species. However, it is not particularly limited.

  The atmosphere in the plasma space preferably does not contain a large amount of oxygen. This is because oxygen generates active species having a strong oxidizing power and the desired functional group is not maintained by reaction with the treating agent, and the polymer surface constituting the A layer is eroded. From such a viewpoint, the oxygen concentration in the atmosphere is preferably 10,000 ppm or less.

Next, the process of cleaning the B layer will be described.
Specifically, the laminate obtained by performing the plasma treatment by the above-described method is a polymer film. In order to remove low molecular weight components generated on the film surface, the surface to be treated is washed with a solvent. By washing, even when a low molecular weight component remains, adverse effects on adhesion can be suppressed. Moreover, a low molecular weight component can be easily removed by using a solvent at the time of washing.

The cleaning solvent can be selected from those that do not attack the polymer film. Specific examples of the solvent include water, methanol, and ethanol.
Further, the cleaning method is not particularly limited, and examples thereof include ultrasonic cleaning.

The laminated body in this embodiment is obtained by the above process.
According to the present embodiment, a separately formed metal oxide vapor deposited film, which has been difficult in the prior art, can be joined as it is without using an adhesive. For this reason, for example, it is possible to form a laminated film in which a functional film of metal or metal oxide is sandwiched between polymer films without using an adhesive.

In addition, the B layer can be configured to include C (═O) —O groups at a specific ratio on the surface.
Here, the ratio of C (= O) -O groups on the surface of the B layer is determined by X-ray photoelectron spectroscopy (XPS or Electron Spectroscopy for Chemical Analysis: ESCA) on the surface of the B layer. The measured carbon 1s spectrum is experimentally determined as the ratio [C (= O) -O] / [C] of the C (= O) -O group to the total number of carbons in the relative abundance ratio obtained by waveform analysis. .

  By analyzing the waveform of the carbon 1s spectrum measured by XPS, the abundance ratio of each carbon bond can be estimated. Here, the main peak existing on the lowest energy side was 285.0 eV derived from carbon of C—C bond. The peak at about 286.5 eV was derived from C—O bond, the peak at about 288.0 eV was derived from C═O bond, and the peak at about 289.2 eV was derived from carbon of C (═O) —O bond. By determining the area ratio of these peaks, the abundance ratio of each bond can be estimated.

From the viewpoint of reliably improving the bonding strength of the laminate, the ratio of C (═O) —O groups on the surface of the B layer is set to, for example, 4.5% or more.
Further, the upper limit of the ratio of C (═O) —O groups on the surface of the B layer is not particularly limited, but is 33% or less, for example, from the viewpoint of layer stability.

XPS may be measured under normal conditions. For example, X-ray source: monochromatic AlKα, degree of vacuum: 1 × 10 ⁻⁹ mbar, output: 16 mA-10 kV. The waveform analysis may be performed by a normal method. For example, the obtained spectrum is curve-fitted and the peaks are separated.

Hereinafter, a description will be given focusing on differences from the first embodiment.
(Second embodiment)
The present embodiment relates to a laminate having a configuration in which a functional film is further bonded to the laminate in the first embodiment.
Here, as shown in Patent Document 7, it is not necessary to separately protect the functional film when the functional film is exposed like a photocatalyst, but the purpose is to provide a gas barrier layer or electrical conduction. In the case of a functional film that generates a function such as, it is necessary to coat with a polymer film in order to protect the functional film itself. Therefore, a laminated film composed of a polymer film having sufficient adhesive strength on both sides across the functional film is required. However, there is no report of forming such a laminated film having sufficient adhesive strength without using an adhesive.

By using the laminated film in the first embodiment, such a laminated film can be formed even when an adhesive is not used.
The laminated body (laminated film) in the present embodiment further includes a C layer and a D layer provided on the other surface of the B layer. That is, the B layer, the C layer, and the D layer are stacked in this order on the A layer.

C layer consists of 1 or more types selected from the group which consists of a metal compound and a metal oxide compound, for example. The C layer is provided in contact with the other surface of the B layer.
Specific examples of the metal compound include aluminum.
Specific examples of the metal oxide compound include aluminum oxide (alumina) and zinc oxide.

  The D layer is provided in contact with the back surface of the surface in contact with the B layer of the C layer. The D layer is made of a polymer material. Examples of the polymer material include those described above as the material of the A layer in the first embodiment. More specifically, examples of the material for the D layer include PMMA, polyethylene, polyethylene terephthalate, and the like. The materials of the A layer and the D layer may be the same or different.

The manufacturing method of the laminated body in this embodiment is
After the step of preparing the laminated body described in the first embodiment, the step of preparing the structure in which the C layer and the D layer are laminated, and the step of forming the B layer, the B layer and the C layer are joined. Process.

  A lamination method in which a laminate composed of an A layer and a B layer and a laminate composed of a C layer and a D layer are formed as an integral laminate: A layer / B layer / C layer / D layer is a commonly used method. May be used, and examples thereof include, but are not limited to, heat sealing and hot pressing.

  According to this embodiment, it is possible to stably obtain a laminate of polymer films sandwiching a functional film composed of metal, metal oxide, or the like.

In addition, although the specific material of A layer / B layer / C layer / D layer can be selected according to the use etc. of a laminated body, the following are mentioned as a specific combination.
A layer: polyethylene / B layer: plasma treatment layer with acrylic acid / C layer: aluminum oxide / D layer: polyethylene terephthalate

  The present invention has been described based on the embodiments. It should be understood by those skilled in the art that these are merely examples, and that various modifications are possible and that such modifications are within the scope of the present invention.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

(Method of measuring the thickness of the plasma treatment layer)
The film thickness of the plasma treatment layer formed by the plasma treatment is determined by measuring the weight difference of the polymer substrate before and after the plasma treatment and ultrasonic cleaning with pure water using an electronic balance. It was determined by making the density the same as the density of the polymer substrate. The substrate to be treated was subjected to plasma treatment after ultrasonic cleaning with pure water.

(Method of quantitative determination of functional groups on the surface of the plasma treatment layer)
The functional group on the surface of the plasma treatment layer formed by the plasma treatment was quantified by a peak separation method of a spectrum obtained from X-ray photoelectron spectroscopy. The apparatus used was ESCALAB 220iXL made by VG, and the conditions were X-ray source: monochromatic AlKα, vacuum: 1 × 10 ⁻⁹ mbar, output: 16 mA-10 kV.

Example 1
In this example, the discharge plasma treatment was performed using an atmospheric pressure plasma surface treatment apparatus (AP-T02-L) manufactured by Sekisui Chemical Co., Ltd. A parallel plate direct type was used as the type of electrode. The distance between the electrodes was 1 mm. A treated substrate made of polyethylene (PE) having a size of 2 cm × 8 cm and a thickness of 230 μm was fixed and held on the ground electrode so that the longitudinal direction of the voltage application electrode and the longitudinal direction of the substrate were parallel to each other. The voltage application electrode was fixed on the substrate to be treated to perform plasma treatment.

  Argon gas was used as the main gas, and the flow rate was 20 L / min. Acrylic acid was used as a treating agent, and a gas obtained by vaporizing this was used as an additive gas. The mixing ratio at 23 ° C. and a pressure of 760 Torr with respect to the argon gas of the additive gas in which acrylic acid was vaporized was 0.2 vol%. The mixing ratio of acrylic acid is controlled by controlling the flow rate of argon gas introduced into the bubbling device and the temperature of the bubbling device to control the amount of acrylic acid vaporized by the bubbling device and supplied to the electrode. did.

  The conditions of time modulation of the pulse power source were a frequency of 10 kHz, an applied voltage of 40 V, and a discharge plasma treatment was performed for 60 seconds. The substrate subjected to the discharge plasma treatment was subjected to ultrasonic cleaning of the surface to be treated in pure water, thereby removing water-soluble low molecular weight components generated on the surface by the plasma treatment. In the surface functional group quantitative evaluation by XPS, the ratio of C (═O) —O groups to the total number of carbon atoms was 6%. Moreover, the thickness of the plasma treatment layer formed by the plasma treatment was 51 nm. The results are shown in Table 1.

A PE film (TL-PET H # 12 manufactured by Tosero Co., Ltd.) having an alumina layer of about 5 nm formed on one surface of the PE film on which the plasma treatment layer thus obtained was formed was subjected to plasma treatment. Heat sealing was performed so that the layer and the alumina layer were in contact with each other, and a laminate composed of PE film / plasma-treated layer / alumina layer / PET film was formed. TP-701-B manufactured by Tester Sangyo Co., Ltd. was used as the heat sealer used for heat sealing. The seal bar temperature was set to 140 ° C. on the PET film side and 70 ° C. on the PE film side, and pressure bonding was performed at a pressure of 3 kg / cm ² and a sealing time of 1 second to form a laminate.

  The laminate was subjected to a 180 ° peel peel test at a peel speed of 10 mm / min and measured for peel strength. As shown in Table 1 and FIG. 2, a peel strength of 130 N / m could be obtained. It was. Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

(Example 2)
The plasma power treatment was performed in the same manner as in Example 1 except that the pulse power supply time modulation conditions were a frequency of 30 kHz, the applied voltage was 80 V, and the discharge plasma treatment was performed for 1 second, a laminate was formed, and a peel peel test was conducted. It was. In the surface functional group quantitative evaluation by XPS, the ratio of C (═O) —O groups to the total number of carbon atoms was 5%. Moreover, the thickness of the plasma treatment layer formed by the plasma treatment was 22 nm. The results are shown in Table 1.
The peel strength was 190 N / m (FIG. 2). Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

(Comparative Example 1)
Except not performing plasma processing with respect to PE, the laminated body was formed similarly to Example 1 and the peel peeling test was done. The plasma treatment layer was not formed, and in the surface functional group quantitative evaluation by XPS, the ratio of C (═O) —O groups to the total number of carbons was 0%. The results are shown in Table 2.
The peel strength was 0 N / m (FIG. 2). Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

(Comparative Example 2)
No treatment agent is used, the time modulation condition of the pulse power supply is set to a frequency of 30 kHz, the applied voltage is set to 80 V, and a discharge plasma treatment is performed for 60 seconds to form a laminate, as in Example 1, A peel peel test was performed. In the quantitative evaluation of the surface functional groups by XPS, the ratio of C (═O) —O groups to the total number of carbons was 1.5%. Moreover, the film thickness of the PE base material decreased and decreased by 12 nm. The results are shown in Table 2.
The peel strength was 26 N / m. Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

(Comparative Example 3)
A plasma treatment was performed in the same manner as in Example 2 except that the discharge plasma treatment was performed for 60 seconds to form a laminate, and a peel peel test was performed. In the surface functional group quantitative evaluation by XPS, the ratio of C (═O) —O groups to the total number of carbon atoms was 4%. The thickness of the plasma treatment layer formed by the plasma treatment was 77 nm. The results are shown in Table 2.
The peel strength was 20 N / m (FIG. 2). Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

(Comparative Example 4)
A plasma treatment was performed in the same manner as in Example 2 except that the time modulation condition of the pulse power supply was set to a frequency of 10 kHz and the discharge plasma treatment was performed for 60 seconds, a laminate was formed, and a peel peel test was performed. In the surface functional group quantitative evaluation by XPS, the ratio of C (═O) —O groups to the total number of carbon atoms was 4%. Moreover, the thickness of the plasma treatment layer formed by the plasma treatment was 100 nm. The results are shown in Table 2.
The peel strength was 30 N / m (FIG. 2). Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

(Comparative Example 5)
A plasma treatment was performed in the same manner as in Example 1 except that the mixing ratio of the additive gas in which acrylic acid was vaporized to the argon gas was 0.02% by volume, a laminate was formed, and a peel peel test was performed. The thickness of the plasma treatment layer formed by the plasma treatment was 12 nm. The results are shown in Table 2.
The peel strength was 34 N / m (FIG. 2).

(Comparative Example 6)
A plasma treatment was performed in the same manner as in Example 2 except that the plasma treatment was performed for 90 seconds and the surface to be treated was not washed with a solvent, a laminate was formed, and a peel peel test was performed.
The thickness of the plasma treatment layer formed by the plasma treatment was 522 nm. The results are shown in Table 3.
The peel strength was 13 N / m.

(Comparative Example 7)
The plasma treatment was performed in the same manner as in Example 1 except that 2-propanol was used as the treatment agent, the mixing ratio of the additive gas vaporized from 2-propanol to 2% by volume, and the applied voltage was 30 kHz. A body was formed and a peel peel test was performed.
In the surface functional group quantitative evaluation by XPS, the ratio of C (═O) —O groups to the total number of carbon atoms was 0%. Moreover, the thickness of the plasma treatment layer formed by the plasma treatment was 10 nm. The results are shown in Table 3.
The peel strength was 9 N / m (FIG. 2). Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

(Comparative Example 8)
Using cis-2-butene-1,4-diol as a treating agent, the mixing ratio of the additive gas obtained by vaporizing cis-2-butene-1,4-diol to argon gas is 0.06% by volume, and the applied voltage is A plasma treatment was performed in the same manner as in Example 1 except that the frequency was 1 kHz, a laminate was formed, and a peel peel test was performed.
In the surface functional group quantitative evaluation by XPS, the ratio of C (═O) —O groups to the total number of carbon atoms was 1%. The thickness of the plasma treatment layer formed by the plasma treatment was 5 nm. The results are shown in Table 3.
The peel strength was 30 N / m (FIG. 2). Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

(Comparative Example 9)
The plasma treatment was performed in the same manner as in Example 2 except that acetic acid was used as the treating agent, the mixing ratio of the additive gas in which acetic acid was vaporized to argon gas was 1.0% by volume, and the discharge plasma treatment was performed for 60 seconds. A body was formed and a peel peel test was performed.
In the surface functional group quantitative evaluation by XPS, the ratio of C (═O) —O groups to the total number of carbons was 2%. The thickness of the plasma treatment layer formed by the plasma treatment was 16 nm. The results are shown in Table 3.
The peel strength was 47 N / m (FIG. 2). Further, FIG. 3 shows the relationship between the surface C (═O) —O group concentration and the peel strength.

  In the above-described embodiments, the example using PE as the treatment base material has been mainly described. However, when other polymer materials including other polyolefin resins are used, the above-described specific method is used. By forming the B layer having a specific thickness, a laminate having excellent peel strength can be obtained.

DESCRIPTION OF SYMBOLS 10 Main gas supply line 11 Main gas supply line 12 for bubbling Process gas addition line 13 Gas supply line 14 Gas exhaust line 20 Processing agent 30 Bubbling apparatus 40 Gas supply part 45 Gas exhaust part 50 Voltage application electrode 55 Ground electrode 60 Pulse power supply 70 Dielectric 75 Dielectric 80 Plasma space 90 Substrate to be processed

Claims (9)

A laminate comprising an A layer made of a polymer material and a B layer provided on one surface in contact with the surface of the A layer,
The thickness of the B layer is 15 nm or more and 70 nm or less,
The B layer is formed by subjecting the surface of the A layer to atmospheric pressure plasma treatment using a rare gas containing 0.1% by volume or more of acrylic acid vapor, and further washing with a solvent. Laminated body.   The ratio of C (= O) -O groups to the total number of carbons [C (= O)-in the relative abundance ratio obtained by waveform analysis of the carbon 1s spectrum obtained by measuring the surface of the B layer by X-ray photoelectron spectroscopy. The laminate according to claim 1, wherein O] / [C] is 4.5% or more.   The laminate according to claim 1 or 2, wherein the A layer is made of a polyolefin resin. Further comprising a C layer and a D layer provided on the other surface of the B layer;
The C layer is in contact with the other surface of the B layer;
The laminate according to any one of claims 1 to 3, wherein the D layer is made of a polymer material and is provided in contact with a back surface of a surface of the C layer that is in contact with the B layer.   The laminate according to claim 4, wherein the C layer is composed of one or more selected from the group consisting of a metal compound and a metal oxide compound. A method for producing a laminate including a step of forming a B layer on the surface of an A layer composed of a polymer material,
In the step of forming the layer B, the surface of the layer A is subjected to an atmospheric pressure plasma treatment using a rare gas containing 0.1% by volume or more of acrylic acid vapor, and further washed with a solvent. The manufacturing method of a laminated body including the process of forming the said B layer of 15 nm or more and 70 nm or less in thickness. Preparing a structure in which the C layer and the D layer are laminated;
After the step of forming the B layer, the step of bonding the B layer and the C layer;
Further including
The manufacturing method of the laminated body of Claim 6 with which the said D layer consists of polymeric materials.   The manufacturing method of the laminated body of Claim 6 or 7 in which the said A layer consists of polyolefin resin.   The method for producing a laminate according to claim 7 or 8, wherein the C layer comprises one or more selected from the group consisting of a metal compound and a metal oxide compound.

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