JP2007238666A - Method for producing polymer composite film, polymer composite film, and packaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a new polymer composite film, in which a functional film having excellent performances can be formed on various kinds of polymer films and to provide a polymer composite film having excellent functional film. <P>SOLUTION: The method for producing the polymer composite film comprises applying alternating-current voltage to a pair of electrodes arranged in mutually opposite state in the presence of gaseous organometallic compound, bringing the generated plasma into contact with a polymer film and forming a film on the polymer film. The polymer composite film has the film formed by plasma treatment. The packaging material is composed of the polymer composite film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer composite film, a polymer composite film, and a packaging material.

  Conventionally, packaging materials for packaging foodstuffs, pharmaceuticals, various medical-related products, various machines, etc., sealing materials for display materials, sealing materials for solar cell-related materials, displays, printed wiring boards, capacitors, etc. Polymer films are used in many applications such as electrical materials, solar cell materials, medical materials, decorative materials, building materials, heat insulation materials, various sundry materials, and the like.

  In particular, in these various applications, in order to lower the oxygen permeability, water vapor permeability, etc. and increase the gas barrier properties, various coating layers are often formed on the polymer film and used as a polymer composite film. .

  As a method for producing a polymer composite film by forming various coating layers on a polymer film, various methods have been studied, for example, vinylidene chloride or vinyl alcohol polymer on a polypropylene or polyester film. A method of coating a resin with excellent gas barrier properties (see Patent Documents 1 and 2 below), and a method of forming a film of silicon oxide or magnesium oxide on a polyester film or the like by vacuum deposition, sputtering, or plasma CVD (See Patent Documents 3 to 5 below) and the like.

  However, among these methods, the resin coating method has a large temperature dependency of the permeability of gases such as water vapor and oxygen, and the gas barrier property may be impaired particularly at high temperatures. There is a drawback that heat resistance is not sufficient.

In the case of forming an inorganic film such as silicon oxide, there are methods such as a vacuum deposition method, a sputtering method, a plasma CVD method, etc., but the vacuum deposition method and the sputtering method have a sufficient gas barrier against oxygen and water vapor. It is difficult to get sex. In addition, when a plasma CVD method using an RF power source (high frequency power source), a microwave power source, or the like is used, a dense film can be obtained. However, if the film is formed to a thickness of 200 nm or more, cracks tend to occur, In the case of the above plasma CVD method using an organometallic compound, since it is high energy, it forms an inorganic film such as silicon oxide among the active species such as ions and radicals generated. There is a possibility that a large amount of unnecessary active species may be generated, and it is impossible to control the generation of the most important active species for obtaining a film having excellent gas barrier properties. Is difficult.
Japanese Patent Publication No. 50-28120 Japanese Patent Publication No.59-47996 Japanese Patent Publication No.53-12953 JP-A 63-257630 Japanese Patent No. 3511325

  The present invention has been made in view of the current state of the prior art described above, and its main purpose is a novel film capable of forming a functional film having excellent performance on various polymer films. It is to provide a method for producing a polymer composite film and a polymer composite film having an excellent functional film.

  The present inventor has intensively studied to achieve the above-described object. As a result, a plasma generated by applying a pulsed alternating voltage in the presence of a gaseous organometallic compound is brought into contact with the polymer film to form a film on the polymer film. According to the manufacturing method, the positive voltage and the negative voltage to be applied can be set individually, so depending on the type of organometallic compound used, depending on the respective processes of film deposition and surface activation when forming a film It was found that the optimum pulse waveform can be selected and various functional films having excellent characteristics can be formed on the polymer film. In particular, when an organosilicon compound is used as the organometallic compound, it has been found that a film having excellent gas barrier properties against oxygen, water vapor and the like is formed, and the present invention has been completed here.

That is, the present invention provides the following method for producing a polymer composite film, polymer composite film and packaging material.
1. In the presence of a gaseous organometallic compound, a plasma generated by applying a pulsed alternating voltage to a pair of electrodes arranged in opposition to each other is brought into contact with the polymer film on the polymer film. A method for producing a polymer composite film, comprising forming a film.
2. Item 2. The method for producing a polymer composite film according to Item 1, wherein the pulsed alternating voltage is a pulsed alternating voltage having different positive and negative absolute values.
3. Item 2. The method for producing a polymer composite film according to Item 1, wherein the pulsed alternating voltage is a pulsed alternating voltage in which the rate at which the negative pulse is delayed from the rising edge of the positive pulse is set to 10 to 90%.
4). Item 4. The method for producing a polymer composite film according to any one of Items 1 to 3, wherein plasma is generated in the presence of an active gas and / or an inert gas in addition to the gaseous organometallic compound.
5). In the presence of a gaseous organometallic compound and in the presence or absence of an active gas and / or inert gas, a pulsed alternating voltage is applied to a pair of electrodes arranged opposite to each other. The plasma is brought into contact with the polymer film to form a film on the polymer film, and then in the presence of an active gas and / or an inert gas, a pair of electrodes arranged in opposition to each other are pulsed. A method for producing a polymer composite film, characterized in that plasma generated by applying an alternating voltage is brought into contact with a film formed on the polymer film.
6). After forming a film on the polymer film by the manufacturing method according to any one of Items 1 to 5, one or more layers are further formed on the formed film by the manufacturing method according to any one of Items 1 to 5 above. A method for producing a polymer composite film, comprising:
7). Item 7. The method for producing a polymer composite film according to any one of Items 1 to 6, wherein the organometallic compound is an organosilicon compound.
8). A polymer composite film obtained by the production method according to any one of items 1 to 7 and having one or more layers on the polymer film.
9. Item 9. The polymer composite film according to Item 8, wherein the film formed on the polymer film is a film formed using an organosilicon compound as the organometallic compound.
10. A polymer composite film in which at least one gas barrier coating containing 20 to 40 atomic% Si, 50 to 75 atomic% O, and 0 to 15 atomic% C is formed on the polymer film.
11. A stress relaxation coating containing 25 to 35 atomic percent Si, 20 to 30 atomic percent O, and 40 to 50 atomic percent C, 20 to 40 atomic percent Si, 50 to 75 atomic percent O, and C Item 11. The polymer composite film according to Item 10, wherein a composite film having at least one gas barrier film containing 0 to 15 atom% is formed on the polymer film, and the thickness of the composite film is 20 nm to 2 μm. .
12 Item 12. The polymer composite film according to Item 11, wherein the composite film formed on the polymer film is a composite film in which one or more layers of a stress relaxation film and a gas barrier film are laminated in this order from the polymer film side.
13. A composite film formed on a polymer film is applied with a pulsed alternating voltage applied to a pair of electrodes arranged opposite to each other in the presence of an organosilicon compound alone or an organosilicon compound and an inert gas. After the generated plasma is brought into contact with the polymer film to form a film on the polymer film, it is generated by applying a pulsed alternating voltage to a pair of electrodes arranged opposite to each other in the presence of oxygen. Item 13. The composite film according to Item 12, which is a composite film formed by repeating the method of forming a composite film by bringing the plasma that has been brought into contact with the film formed on the polymer film once or twice or more. Molecular composite film.
14 14. A packaging material comprising the polymer composite film according to any one of items 8 to 13.

  Hereinafter, the present invention will be specifically described.

Production method of polymer composite film (1) Polymer film In the polymer composite film production method of the present invention, the type of polymer film is not limited, and excellent adhesion to various polymer films is obtained. A film having the characteristics can be formed.

  As an example of the polymer film, polyester film such as polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyolefin resin film such as polybutene, amorphous polyolefin resin film such as cyclic polyolefin, polyamide film, polyacetal film, Polyimide film, polyvinylidene chloride film, polyethersulfone film, polyacrylate film, polymethacrylate film, polyvinyl alcohol film, polystyrene film, acrylic resin film, fluorine resin film, vinyl resin film, etc. be able to.

  In addition, the polymer film may be any of non-stretched, uniaxially stretched, biaxially stretched, and may be further subjected to hairline processing, mat processing, and the like. Further, it may contain an antistatic agent, an ultraviolet absorber, a colorant, a heat stabilizer and the like. Although the thickness of a polymer film is not specifically limited, For example, the thickness of about 3-300 micrometers can be used.

  When the polymer composite film of the present invention is used as a sealing material for an organic EL material which is one of packaging materials, among the above-described polymer films, in particular, amorphous polyolefins such as polycarbonate films and cyclic polyolefins. It is more preferable to use a polyester film such as a polyethylene resin film or a polyethylene terephthalate film.

(2) Organometallic compound In the present invention, the type of the organometallic compound to be used is not particularly limited, and a plasma treatment to be employed (a pair of electrodes arranged in a mutually opposing manner in the presence of a gaseous organometallic compound) In a plasma processing apparatus (a processing apparatus containing a pair of electrodes arranged opposite to each other) under conditions where a plasma generated by applying a pulsed alternating voltage is contacted with a polymer film As long as it can exist in a gaseous state. From such an organometallic compound, an organometallic compound may be appropriately selected according to the type of the target film. For example, when an organosilicon compound is used as the organometallic compound, a film having excellent gas barrier properties against oxygen, water vapor, and the like can be formed. In addition, when using organic tin compounds, organic titanium compounds, organic aluminum compounds, organic copper compounds, organic zinc compounds, organic indium compounds, organic nickel compounds, etc., various types such as optical thin films, antibacterial films, insulating films, conductive films, etc. A functional film can be formed.

  Among these organometallic compounds, for example, acetoxytrimethylsilane, allyloxytrimethylsilane, allyltrimethylsilane, bistrimethylsilyl are effective when forming a film having excellent gas barrier properties against oxygen, water vapor and the like. Adipate, butoxytrimethylsilane, butyltrimethoxysilane, cyclohexyloxytrimethylsilane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, diacetoxydimethylsilane, diacetoxymethylvinylsilane, diethoxydimethylsilane, diethoxydiphenylsilane, diethoxy-3 -Glycidoxypropylmethylsilane, diethoxymethyloctadecylsilane, diethoxymethylsilane, diethoxymethylphenylsilane, diethoxymethyl Vinylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dimethylethoxyphenylsilane, dimethylethoxysilane, dimethylisopentyloxyvinylsilane, 1,3-dimethyl-1,1,3,3-tetraphenyldisiloxane, diphenyl Ethoxymethylsilane, diphenylsilanediol, 1,3-divinyl-1,1,3,3-tetramethyldisilaxane, 2- (3,4-epoxycyclophenylethyl) trimethoxysilane, ethoxydimethylvinylsilane, ethoxytrimethyl Silane, ethyltriacetoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethylsilane, 3-glycidoxypropyltrimethoxysilane, 1,1,1,3,5 , 5-heptamethyltrisiloxane, hexamethylcyclotrisiloxane, hexamethyldisilane, hexamethyldisilazane, hexamethyldisiloxane, hexyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Methoxytrimethylsilane, methyltriacetoxysilane, methyltriethoxysilane, methyltrimethoxysilane, methylisopropenoxysilane, methylpropoxysilane, octadecyltriethoxyethoxysilane, octamethylcyclotetrasiloxane, 1,1,1,3,5 , 7,7,7-octamethyltetrasiloxane, octamethyltrisiloxane, octyltriethoxysilane, 1,3,5,7,9-pentamethylcyclopentasiloxane, Pentamethyldisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, phenyltriethoxysilane, phenyltrimethoxysilane, phenyltrimethylsilane, propoxytrimethylsilane, propyltriethoxysilane , Tetraacetoxysilane, tetrabutoxysilane, tetrateethoxysilane, tetraisopropoxysilane, tetramethoxysilane, 1,3,5,7-tetramethoxycyclotetrasiloxane, 1,1,3,3-tetramethyldioxane , Tetramethylsilane, 1,3,3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetra Siloxane, tetrapropoxysilane, triacetoxy Vinylsilane, triethoxyvinylsilane, triethylsilane, trihexylsilane, trimethoxysilane, trimethoxyvinylsilane, trimethylsilanol, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, trimethylvinylsilane, triphenylsilanol And tris (2-methoxyethoxy) vinylsilane. Of these, hexamethyldisilane, hexamethyldisilazane, hexamethyldisiloxane and the like are particularly preferable.

  Similarly, as for other organometallic compounds, various compounds that can exist in a gaseous state in the plasma processing apparatus under the plasma processing conditions employed can be used.

(3) Plasma treatment conditions In the present invention, a pulsed alternating voltage is applied to a pair of electrodes arranged opposite to each other in the presence of a gaseous organometallic compound using the various organometallic compounds described above. Thus, plasma may be generated and the plasma may be brought into contact with the polymer film. Thereby, an excellent functional film can be formed on the polymer film.

  According to the plasma processing method applied in the present invention, active species generated from an organometallic compound are deposited on a polymer film by generating a plasma by applying a pulsed alternating voltage, and the film is formed by so-called plasma CVD. A shaped deposit is formed. At this time, if the potential between the electrodes is reversed, electrons or ions having a potential opposite to the potential of the electrode on which the polymer film is installed collide with the polymer film, resulting in a charge-up mitigating effect or the surface portion of the deposited film. The film surface is activated by the detachment of the attached matter. In addition, depending on the type of organometallic compound, a large amount of negative ions may be formed by adsorbing free electrons from positive ions. In that case, the positive voltage and negative voltage to be applied can be set individually, so it is possible to select the optimum pulse waveform for the role of positive and negative ions according to each process, film deposition and surface activation. Yes, film deposition and surface activation are repeated, and high-quality film formation proceeds continuously. As a result, the formed film has excellent adhesiveness and excellent physical properties such as flexibility, smoothness, and denseness.

  Specific plasma treatment conditions are not particularly limited, and may be set as conditions in which plasma is appropriately generated between a pair of electrodes arranged to face each other depending on the type of the organometallic compound to be used.

The polymer film is usually placed on one of the electrodes. The size of the electrode is not particularly limited, and can be appropriately set according to the size of the polymer film, the number of treatments, and the like. For example, the electrode area can be set from a wide range of about 1 cm ^{2 to} 100 m ^2, but an electrode area of about 4 cm ^{2 to 1} m ² is suitable for practical use. The distance between the electrodes is not particularly limited. For example, it can be set from a distance of about 0.1 to 1000 mm, but about 1 to 50 mm is suitable for practical use.

  The pulsed alternating voltage used for generating plasma can be generated from, for example, an inverter power supply having a high-voltage DC power supply and a switching circuit. As the switching circuit, for example, a circuit composed of a small semiconductor element such as a MOSFET element or a TTL element can be used.

  The magnitude of the voltage is not particularly limited, and may be set so that stable plasma is generated according to the type of the organometallic compound to be used, the pressure in the plasma processing apparatus, and the like. For example, when the positive pulse voltage Vp is applied to the counter electrode with reference to the potential of the electrode on which the polymer film is installed, the magnitude of the positive pulse voltage Vp can be about 5 V to 10 kV. About 100V-5kV is preferable. The magnitude of the negative pulse voltage Vn applied to the counter electrode is not particularly limited, but is usually about −5 V to −10 kV, and practically about −100 V to −5 kV. The magnitudes of the positive pulse voltage Vp and the negative pulse voltage Vn are not particularly limited, but the absolute values of the positive pulse voltage Vp and the negative pulse voltage Vn are preferably different. For example, an organic silicon compound is used for gas barrier properties. In the case of forming an excellent film, it is preferable to make the absolute value of the positive pulse voltage Vp larger than the absolute value of the negative pulse voltage Vn. FIG. 1 shows an example of a pulse waveform in which the absolute value of the positive pulse voltage Vp is larger than the absolute value of the negative pulse voltage Vn.

The pulse width T ₁ of the positive pulse and the pulse width T ₂ of the negative pulse may be, for example, about ₁ n seconds ≦ T ₁ ≦ 1 second, and about 1 n seconds ≦ T ₂ ≦ 1 second, respectively. 0.1 μsec ≦ T ₁ ≦ 10 msec and 0.1 μsec ≦ T ₂ ≦ 10 msec. During each pulse period of the positive pulse width T ₁ and the negative pulse width T ₂ , the voltage value may not be constant, and may vary somewhat within the above range.

The pulsed alternating voltage having such a pulse waveform, if one cycle is the total time of _{T 1} and _{T 2} was _{T 3,} the frequency f represented by 1 / _{T 3} is normally 1Hz~10GHz In practical terms, about 100 Hz to 1 MHz is preferable.

Further, as shown in FIG. 2, no-voltage periods T ₄ and T ₅ may be provided between the positive pulse period T ₁ and the negative pulse period T ₂ . In this case, one period T ₃ is T ₃ = T ₁ + T ₂ + T ₄ + T ₅ . The frequency f (1 / T ₃ (T ₃ = T ₁ + T ₂ + T ₄ + T ₅ )) is preferably about 1 Hz to 10 GHz, and more practically about 100 Hz to 1 MHz, as described above. In addition, the rate (%) at which the start portion of the negative pulse is delayed from the rising edge of the positive pulse when one cycle is 100% is referred to as delay (TD) (corresponding to T ₁ + T ₄ / T ₃ in FIG. 2). However, the delay value can be set arbitrarily. For example, it can be set arbitrarily from a range of about 10 to 90%.

  In addition, the positive pulse voltage Vp and the negative pulse voltage Vn are not alternately applied, and the negative pulse voltage Vn is applied after the positive pulse voltage Vp is applied n times continuously as shown in FIG. May be.

T ₁ / T ₃ is generally called a duty ratio. The value is not particularly limited, but is usually preferably about 0.5 to 10 ⁻³ .

The pressure in the plasma processing apparatus is not particularly limited, and may be in a pressure range in which plasma is generated according to the type of organometallic compound to be used, voltage application conditions, and the like. Usually, it can be set as the range of about 10 < ^-4 > Pa-100MPa, and what is necessary is just about 1-1000Pa practically.

  When introducing the organometallic compound described above into the plasma processing apparatus, the organometallic compound can be directly introduced as a gaseous organometallic compound by heating as necessary. Further, when introducing the organometallic compound, an inert gas such as He or Ar may be added. When the inert gas is added, the flow ratio of the organometallic compound to be introduced and the inert gas is not particularly limited. For example, the organometallic compound / inert gas is about 0.1 to 10, preferably The flow rate ratio can be about 0.5 to 5.

  In addition to the organometallic compound, an active gas such as oxygen or nitrogen may be added. By adding the active gas, the composition, physical properties, etc. of the formed film can be changed as compared with the case where only the organometallic compound is used. For example, when oxygen is added, a film having a higher oxygen content can be formed. When nitrogen is added, a film having a higher nitrogen content can be formed. Further, oxygen and nitrogen may be added simultaneously. When these active gases are used, the flow ratio of the organometallic compound to be introduced and the active gas is not particularly limited. For example, the organometallic compound / active gas is about 0.1 to 10, preferably about 0.1. The flow rate ratio can be about 3-4. Further, the active gas and the inert gas may be added simultaneously. In that case, for example, organometallic compound / (active gas + inert gas) = about 0.1 to 10, preferably 0.5 to 5 The flow rate ratio can be about.

  In the production method of the present invention, the plasma treatment time is not particularly limited, and may be appropriately determined according to the target film thickness and the like. Usually, it can be in the range of about 1 second to 100 minutes, and may be practically in the range of about 5 seconds to 30 minutes. The thickness of the film to be formed is not particularly limited and may be appropriately determined depending on the purpose, but is usually about 20 nm to 500 nm.

  In the production method of the present invention, after the plasma treatment using the organometallic compound alone or the organometallic compound and the active gas and / or inert gas by the above-described method, the active gas and / or the inert gas is further continued. In the presence of the active gas, the second plasma treatment may be performed by the same method as the plasma treatment method described above. As the active gas and the inert gas, the same ones as described above can be used. By performing such two-stage plasma treatment, the composition, structure, etc. of the film surface portion formed by the first plasma treatment can be changed (modification of the film surface portion), and the surface layer portion of the film can be changed. A composite film having a two-layer structure that is different in composition, structure, and the like from the lower layer can be obtained.

  The specific conditions for the second plasma treatment may be the same as those for the first plasma treatment except that the treatment is performed in the presence of an active gas and / or an inert gas. The time of the second plasma treatment may be appropriately determined according to the target degree of modification, and is usually about 5 seconds to 30 minutes.

  Furthermore, after forming a film by the above-mentioned organic metal compound alone, or by a film formation method (one-step treatment method) by performing plasma treatment using an organic metal compound and an active gas and / or an inert gas simultaneously, A method of performing plasma treatment in the presence of an active gas and / or an inert gas after performing a plasma treatment using a metal compound alone or an organometallic compound and an active gas and / or an inert gas (2) After the composite coating is formed by the step treatment method), the above-mentioned one-step treatment method or two-step treatment method is repeated once or twice or more to form a composite film having a multilayer structure of two layers or three layers or more. May be. At this time, the types of the organometallic compound, the active gas, the inert gas, and the like can be the same or different. According to the plasma treatment method employed in the present invention, the activation of the coating surface is repeatedly performed. Therefore, even when a composite coating is formed, the adhesion between layers of each layer becomes good, and a functional coating having excellent physical properties is obtained. It is formed.

  The thickness of the composite film is usually about 20 nm to 2 μm.

Polymer Composite Film As described above, a film is formed on the polymer film by the plasma CVD method in which plasma treatment is performed using an inverter power supply, and a polymer composite film having a film on the surface can be obtained. According to the production method of the present invention, film deposition and activation occur repeatedly, so that the resulting polymer composite film has a high-quality film with excellent adhesion.

  The polymer composite film obtained by the production method of the present invention has such excellent properties. For example, depending on the type of film formed, for example, foodstuffs, pharmaceuticals, various medical products, various machines Packaging film, packaging materials for display materials, packaging materials such as sealing materials for solar cells, electrical materials such as displays, printed wiring boards, capacitors, solar cells, medical materials, decorations It can be used for various applications such as materials, construction-related materials, thermal insulation materials, and various sundry materials.

  For example, when an organosilicon compound is used, a film having excellent gas barrier properties against oxygen, water vapor and the like can be formed. In addition, when using organic tin compounds, organic titanium compounds, organic aluminum compounds, organic copper compounds, organic zinc compounds, organic indium compounds, organic nickel compounds, etc., various types such as optical thin films, antibacterial films, insulating films, conductive films, etc. A film can be formed.

  Hereinafter, as a specific example of the polymer composite film of the present invention, a polymer composite film in which a film having excellent gas barrier properties is formed using an organosilicon compound will be described.

  For example, when plasma treatment is performed by simultaneously introducing an organosilicon compound and oxygen within the range of the above-described organometallic compound / active gas ratio, the formed film has a Si content of about 20 to 40 atomic%, O About 50-75 atomic%, C is about 0-15 atomic%, preferably, Si is about 20-40 atomic%, O is about 50-75 atomic%, and C is about 0.5-15 atomic%. It will be a thing. This film has good gas barrier properties against oxygen, water vapor, and the like, and also has excellent adhesion to the polymer film.

  In the present invention, at least a film containing about 20 to 40 atomic% of Si, about 50 to 75 atomic% of O, and about 0 to 15 atomic% of C (hereinafter sometimes referred to as “gas barrier film”) is used. By forming a single layer on the polymer film, a polymer composite film having excellent gas barrier properties can be obtained. In this case, only one layer of the gas barrier film may be formed, or the gas barrier film may be laminated with another film or another gas barrier film having the above composition range to form a composite film.

  As another film that can be laminated with the gas barrier film, only an organosilicon compound is used and plasma treatment is performed in accordance with the above-described conditions, and Si is about 25 to 35 atomic%, and O is 20 to 30. Examples thereof include a film containing about 40% by atom of C and about 40 to 50 atom% of C (hereinafter sometimes referred to as “stress relaxation film”). This film has a good adhesion to the polymer film and is a soft film that is difficult to crack even if bent. Therefore, by having a structure in which the stress relaxation coating and the gas barrier coating are laminated, the gas barrier property is good, and when bending stress is applied, the effect of relaxing the stress is excellent. A composite film having excellent physical properties can be obtained.

  The gas barrier film and the stress relaxation film may be formed at least one layer each, and the stacking order is arbitrary, but in particular, the structure should be laminated in the order of the stress relaxation film and the gas barrier film from the side in contact with the polymer film. Thus, a stress relaxation effect is effectively exhibited, and a composite film having excellent physical properties with little deterioration in gas barrier properties even when used for a long period of time is obtained. In addition to laminating only these two layers, the stress relaxation film and the gas barrier film may have a multilayer structure in which the stress relaxation film and the gas barrier film are repeatedly laminated in this order, thereby further improving the gas barrier property. .

  Further, for example, the outermost surface of the formed film may be a stress relaxation film.

  The thickness of each layer of the gas barrier film and the stress relaxation film is preferably about 20 nm to 500 nm, and more preferably about 40 to 250 nm. The total thickness of the composite film including the gas barrier film is preferably about 20 nm to 2 μm, and more preferably about 50 nm to 1 μm.

  The composite film having a structure in which the gas barrier film and the stress relaxation film are laminated is formed by forming a stress relaxation film by plasma treatment using only an organosilicon compound, and then using an organosilicon compound and oxygen on the stress relaxation film. Although it can be formed by a method of forming a gas barrier film by plasma treatment, it can also be formed by, for example, the above-described two-stage treatment method. That is, after forming a stress relaxation film by performing a plasma treatment using an organosilicon compound alone or an organosilicon compound and an inert gas, the plasma treatment is performed in the presence of oxygen, and the oxygen content in the surface portion of the stress relaxation film By increasing the rate, the composite film having a structure in which the gas barrier film is laminated on the stress relaxation film can also be formed by modifying the surface portion of the stress relaxation film to form the gas barrier film. This method is excellent in production efficiency because a composite film having a two-layer structure of a gas barrier film and a stress relaxation film can be formed by a continuous plasma treatment method. In this method, it is preferable that the thickness of the stress relaxation film is about 50 to 250 nm and the thickness of the gas barrier film is about 5 to 40 nm.

  Further, by repeating this two-step treatment method, a composite film having a multilayer structure in which the laminated structure of the stress relaxation film and the gas barrier film is repeated can be formed.

  In addition, according to the above-described two-stage treatment method, an interface film with a gradually changing composition may be formed at the interface portion between the gas barrier film and the stress relaxation film, but the gas barrier film and the stress relaxation film are separately provided. It becomes a composite film having the same excellent performance as the composite film obtained by the sequential lamination method.

Packaging material The film obtained by performing plasma treatment with an organosilicon compound by the above-described method has good adhesion to various polymer films, and has oxygen permeability, water vapor permeability. Etc. are low, and the gas barrier properties are excellent. Therefore, a polymer composite film in which such a film is formed on the surface of the polymer film is particularly suitable for use as a packaging material. By using this as a packaging material, the contents are in good condition. Can be stored for a long time. For example, the use as a packaging material can be exemplified by food films, pharmaceuticals, various medical-related products, packaging films for packaging various machines, sealing materials for display materials, sealing materials for solar cell-related materials, and the like. Among these, it is useful as a sealing material for organic EL materials that are particularly sensitive to moisture, a sealing material for liquid crystal display devices, foods for long-term storage, foods used for boil / retort processing, and the like.

  As an aspect of using the polymer composite film of the present invention as a packaging material, the polymer composite film can be used as a packaging material as it is, but the polymer composite film is laminated with a sealant film such as a polyethylene film or a polypropylene film. For example, it may be laminated with another polymer film. Moreover, what is necessary is just to determine suitably by the objectives to be used, such as making a bag shape.

  According to the method for producing a polymer composite film of the present invention, a polymer in which various functional films that can be used for various applications are formed on the surface of the polymer film by changing the type of the organometallic compound to be used. A composite film can be obtained. For example, when an organosilicon compound is used, a polymer composite film in which a film having good gas barrier properties against oxygen, water vapor, etc. and excellent film properties such as flexibility can be obtained. A polymer composite film having such a film is very useful as a packaging material.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Examples 1-3
A pair of electrodes arranged oppositely in a plasma processing apparatus using a polycarbonate film (GE Co., Ltd .: Lexan) having a thickness of 180 μm or a polyolefin film (Nippon Zeon Co., Ltd .: ZEONOR) having a thickness of 188 μm as a polymer film. Of these, the polycarbonate film or the polyolefin film was placed on the electrode on the ground side.

  Hexamethyldisiloxane (HMDSO), which is an organosilicon compound, and oxygen were used, and HMDSO and oxygen were introduced into the plasma processing apparatus under the conditions shown in Table 1 below. A pulsed alternating voltage under the conditions shown in Table 1 is applied to the electrode facing the ground side electrode on which the polycarbonate film or polyolefin film is placed, and plasma is generated to form a film on the surface of the polycarbonate film or polyolefin film. Thus, a polymer composite film of the present invention was obtained.

  Among the formed films, the film formed in Example 2 has a thickness of 400 nm and contains 34.9 atomic% Si, 62.4 atomic% O, and 2.7 atomic% C. It was a film to do.

  In addition, the atomic ratio of Si, O, and C was measured by the following method.

Moreover, about the polymer composite film which formed the film | membrane by the above-mentioned method, the oxygen transmission rate and the water vapor transmission rate were measured with the following method. The results are shown in Table 1 below.
[Atomic ratio of Si, O, and C]
Measurement was performed using ESCA (JPS-9010MC manufactured by JEOL Ltd.).
[Oxygen permeability]
It measured based on JIS K 7126 (B method). Measurement was performed at an ambient temperature of 23 ° C. and a humidity of 75%. For the measurement, an oxygen permeability measuring device (“MOCONOX-TRAN” manufactured by Mocon, USA) was used.
(Water vapor transmission rate)
It measured based on JISK7129 (A method). Measurement was performed at an ambient temperature of 40 ° C. and a humidity of 90%. For the measurement, a water vapor transmission rate measuring device (“L80-4000J” manufactured by Swiss Rissy) was used.

Example 4
A polycarbonate film having a thickness of 180 μm (GE Co., Ltd .: Lexan) was used as the polymer film, and a two-step treatment method was performed using the same plasma treatment apparatus as in Examples 1 to 3 under the conditions shown in Table 2 below. A composite film was formed on the surface of the film to obtain a polymer composite film of the present invention. Hexamethyldisiloxane (HMDSO) was used alone in the first stage treatment, and oxygen alone was used in the second stage treatment.

  The formed composite film had a thickness of 150 nm, and in order from the polycarbonate film side, the stress relaxation film containing 33.3% Si, 23.6% O, and 43.1% C, and 28 Si. It consisted of a gas barrier film containing 4%, O 59.1%, and C 12.5%.

For this polymer composite film, the oxygen transmission rate and the water vapor transmission rate were measured in the same manner as in Examples 1 to 3. As a result, the oxygen transmission rate was 0.05 cc / m ² · day, the water vapor transmission rate was 0.06 g / m ² · day, and excellent gas barrier properties were obtained.

Example 5
Similar to Example 4, the process of forming a film by a two-step treatment method was repeated three times to form a six-layer composite film in which the laminated structure of the stress relaxation film and the gas barrier film was repeated three times on the surface of the polycarbonate film. The polymer composite film of the present invention was obtained.

For this polymer composite film, the oxygen transmission rate and the water vapor transmission rate were measured in the same manner as in Examples 1 to 3. As a result, the oxygen permeability was 0.01 cc / m ² · day or less, the water vapor permeability was 0.01 g / m ² · day or less, and the gas barrier property was extremely excellent.

Comparative Example 1
Using the same polycarbonate film as that used in Examples 1 and 2, a silicon oxide film was formed on the surface of the polycarbonate film by a sputtering method by the following method to obtain a polymer composite film.

First, a polycarbonate film was set in the sputtering apparatus, and after reducing the pressure to 10 ⁻⁵ torr, argon as a discharge gas and oxygen as a reaction gas were introduced at a partial pressure ratio of 1: 1. When the atmospheric pressure was stabilized at 0.4 Pa, discharge was started, plasma was generated on the Si target, and sputtering was started.

  When the process was stabilized, the shutter was opened, and a 50 nm thick silicon oxide film was formed on the polycarbonate film.

  For this polymer composite film, the oxygen transmission rate and the water vapor transmission rate were measured in the same manner as in Examples 1 to 3.

  The sputtering conditions and the oxygen permeability and water vapor permeability of the resulting polymer composite film are shown in Table 3 below.

Comparative Example 2
Using the same polycarbonate film as used in Examples 1 and 2, RF plasma CVD using an RF power source was performed by the following method to form a silicon oxide film on the surface of the polycarbonate film, and a polymer composite film Got.

Hexamethyldisiloxane (HMDSO), N ₂ , and O ₂ were introduced at a partial pressure ratio of 1: 5: 1.8, respectively, and when the inside of the chamber was stabilized at 0.13 torr, discharge was started, A silicon oxide film having a thickness of 200 to 300 nm was formed.

  For this polymer composite film, the oxygen transmission rate and the water vapor transmission rate were measured in the same manner as in Examples 1 to 3.

  Table 4 below shows the conditions of RF plasma CVD and the oxygen transmission rate and water vapor transmission rate of the obtained polymer composite film.

Evaluation of gas barrier properties after bending test About each polymer composite film of the present invention obtained in Examples 1, 2, 4 and 5 and each polymer composite film obtained in Comparative Examples 1 and 2, respectively, a polycarbonate film Was wound around a cylindrical rod having a diameter of 15 mm (bending test). Thereafter, the oxygen transmission rate and the water vapor transmission rate were measured in the same manner as in Examples 1 to 3. The measurement results before and after the bending test are shown in Table 5 below.

  As is clear from the above results, the polymer composite film of the present invention maintained good gas barrier properties even after the bending test.

The figure which shows an example of the waveform of the pulse-like alternating voltage applied to the counter electrode of the electrode which installed the sample. The figure which shows an example of the waveform of the pulse-like alternating voltage applied to the counter electrode of the electrode which installed the sample. The figure which shows an example of the waveform of the pulse-like alternating voltage applied to the counter electrode of the electrode which installed the sample.

Claims (14)

In the presence of a gaseous organometallic compound, a plasma generated by applying a pulsed alternating voltage to a pair of electrodes arranged in opposition to each other is brought into contact with the polymer film on the polymer film. A method for producing a polymer composite film, comprising forming a film. The method for producing a polymer composite film according to claim 1, wherein the pulsed alternating voltage is a pulsed alternating voltage having different positive and negative absolute values. 2. The method for producing a polymer composite film according to claim 1, wherein the pulsed alternating voltage is a pulsed alternating voltage in which a rate at which the negative pulse is delayed from the rising edge of the positive pulse is set to 10 to 90%. The method for producing a polymer composite film according to any one of claims 1 to 3, wherein plasma is generated in the presence of an active gas and / or an inert gas in addition to the gaseous organometallic compound. In the presence of a gaseous organometallic compound and in the presence or absence of an active gas and / or inert gas, a pulsed alternating voltage is applied to a pair of electrodes arranged opposite to each other. The plasma is brought into contact with the polymer film to form a film on the polymer film, and then in the presence of an active gas and / or an inert gas, a pair of electrodes arranged in opposition to each other are pulsed. A method for producing a polymer composite film, characterized in that plasma generated by applying an alternating voltage is brought into contact with a film formed on the polymer film. After a film is formed on the polymer film by the production method according to any one of claims 1 to 5, one or more layers are further formed on the formed film by the production method according to any one of claims 1 to 5. A method for producing a polymer composite film, comprising: The method for producing a polymer composite film according to any one of claims 1 to 6, wherein the organometallic compound is an organosilicon compound. A polymer composite film having one or more layers of a coating on a polymer film, obtained by the production method according to claim 1. The polymer composite film according to claim 8, wherein the film formed on the polymer film is a film formed using an organosilicon compound as an organometallic compound. A polymer composite film in which at least one gas barrier coating containing 20 to 40 atomic% Si, 50 to 75 atomic% O, and 0 to 15 atomic% C is formed on the polymer film. A stress relaxation coating containing 25 to 35 atomic percent Si, 20 to 30 atomic percent O, and 40 to 50 atomic percent C, 20 to 40 atomic percent Si, 50 to 75 atomic percent O, and C 11. The polymer composite film according to claim 10, wherein a composite film having at least one gas barrier film containing 0 to 15 atomic% is formed on the polymer film, and the thickness of the composite film is 20 nm to 2 μm. . The polymer composite film according to claim 11, wherein the composite film formed on the polymer film is a composite film in which one or more layers of a stress relaxation film and a gas barrier film are laminated in this order from the polymer film side. A composite film formed on a polymer film is applied with a pulsed alternating voltage applied to a pair of electrodes arranged opposite to each other in the presence of an organosilicon compound alone or an organosilicon compound and an inert gas. After the generated plasma is brought into contact with the polymer film to form a film on the polymer film, it is generated by applying a pulsed alternating voltage to a pair of electrodes arranged opposite to each other in the presence of oxygen. 13. The composite film formed by repeating the method of forming a composite film by bringing the plasma that has been brought into contact with the film formed on the polymer film once or twice or more. Molecular composite film. A packaging material comprising the polymer composite film according to claim 8.

Images