JP2020163743A - Method of manufacturing barrier laminate - Google Patents

Abstract

To provide a method of manufacturing a stress resistant barrier laminate having barrier property to a gas such as oxygen, and steam, and an agent and the like in a form of liquid, and maintaining barrier property even if receiving stresses such as bending, and retort treatment, a packaging material produced using the barrier laminate, and a package.SOLUTION: The method of manufacturing a stress resistant barrier laminate 1 is a method of manufacturing a barrier laminate 1 including: laminating a barrier layer 3, and a protective layer 4 composed of a deposited membrane of a polymer of a para-xylene-based compound in this order on the surface of a member 2 by inline treatment in a same vapor deposition chamber, where a plasma-treated surface is formed on the surface of the member 2 using a gas containing 10 vol.% or more and 100 vol.% or less of oxygen, an inorganic deposited membrane including an oxide or a nitride of an element selected from the group consisting of Al, Si, Ti, Nb, Ta, Hf, Zr, and Zn is formed by atomic layer vapor-deposition method (ALD method), as the barrier layer 3, and the protective layer 4 is laminated on the outer most surface of the barrier laminate 1.SELECTED DRAWING: Figure 1

Description

The present invention comprises a barrier layer composed of an ALD inorganic vapor deposition film by an atomic volume deposition method (ALD method) for imparting barrier properties to a gas such as oxygen or water vapor, or a liquid such as a chemical solution, and a polymer vapor deposition film of a paraxylylene compound. The present invention relates to a method for producing a stress-resistant barrier laminate which has a protective layer and maintains a barrier property even when subjected to stress such as bending or retort treatment.

Conventionally, in order to improve the waterproof / moisture-proof property of a tangible object, a liquid resin composition is applied to the surface of the tangible object (Patent Document 1), or a metal or a metal oxide is coated or vapor-deposited to make the tangible object waterproof. A method of laminating a moisture-proof layer has been adopted.
However, in the method of applying the liquid resin composition, the waterproof / moisture-proof layer becomes uneven and thick, and the unlaminated portion remains, the entire narrow gap is filled with the liquid resin composition, and the entire laminate is further formed. It also affected the physical properties of the product.
Since the metal coating layer, the metal oxide coating layer, the metal vapor deposition layer, and the metal oxide vapor deposition layer are hard and brittle, they are cracked or peeled off when the object to be laminated is deformed, so that the use is limited.
Among medical materials, various resin films, molded products such as gaskets for syringes, and substrates such as silicone tubes in which a polyparaxylylene coating is laminated are known (Patent Document 2). Is only for the purpose of enhancing biocompatibility with a polyparaxylylene film, and further, there is a problem that the polyparaxylylene film does not adhere well to the base material and is easily peeled off, so that it can be used sufficiently. Adhesion is difficult to obtain.

JP 2017-109312 Special Table 2001-522652

The present invention has a barrier property against gases such as oxygen and water vapor, gas or liquid chemicals, etc., maintains the barrier property even under stress such as bending or retort treatment, and maintains an arbitrary shape and color of the member. An object of the present invention is to provide a stress-resistant barrier laminate, a packaging material produced by using the barrier laminate, and a method for producing the packaging.

（式中、Ｒは水素原子またはフッ素原子であり、Ｘはハロゲン原子であり、ｎは平均値が０〜４の数である。）
１１．前記パラキシリレン系化合物が下記式で表される化合物を含むことを特徴とする、上記１〜１０の何れかに記載の、耐ストレス性のバリア積層体の製造方法。

１２．前記パラキシリレン系化合物が下記式で表される化合物を含むことを特徴とする、上記１〜１１の何れかに記載の、耐ストレス性のバリア積層体の製造方法。

１３．前記バリア積層体の、未ボイル時の酸素透過率が、１ｃｃ／ｍ²／日／ａｔｍ以下であることを特徴とする、上記１〜１２の何れかに記載の、耐ストレス性のバリア積層体の製造方法。
１４．前記バリア積層体の、１００℃、２０分間ボイルした後の酸素透過率が、１ｃｃ／ｍ²／日／ａｔｍ以下であることを特徴とする、上記１〜１３の何れかに記載の、耐ストレス性のバリア積層体の製造方法。
１５．前記バリア積層体の、未ボイル時の水蒸気透過率が、１ｇ／ｍ²／日以下であることを特徴とする、
上記１〜１４の何れかに記載の、耐ストレス性のバリア積層体の製造方法。
１６．前記バリア積層体の、１００℃、２０分間ボイルした後の水蒸気透過率が、１ｇ／ｍ²／日以下であることを特徴とする、
上記１〜１５の何れかに記載の、耐ストレス性のバリア積層体の製造方法。
１７．前記部材が、樹脂フィルム、樹脂フィルムからなる包装袋、樹脂成形品、医療器材、電子部品、電気部品、回路基板からなる群から選択される１種であることを特徴とする、
上記１〜１６の何れかに記載の、耐ストレス性のバリア積層体の製造方法。
１８．前記部材が樹脂フィルムであり、上記１〜１６の何れかに記載の製造方法によって作製されたバリア積層体から、バリア包装材料を作製することを特徴とする、耐ストレス性のバリア包装材料の製造方法。
１９．上記１８に記載の製造方法によって作製されたバリア包装材料から、バリア包装袋を作製することを特徴とする、耐ストレス性のバリア包装袋の製造方法。
２０．前記部材がラミネートチューブ前駆体であり、上記１〜１６の何れかに記載の製造方法によって作製されたバリア積層体から、ラミネートチューブを作製することを特徴とする、耐ストレス性のバリアラミネートチューブの製造方法。
２１．前記部材が樹脂製注射器シリンジ部であり、上記１〜１６の何れかに記載の製造方法によって作製されたバリア積層体から、樹脂製注射器シリンジ部を作製することを特徴とする、薬剤充填済み注射器用の耐ストレス性のバリア注射器の製造方法。 As a result of various studies, the present inventors have found that a method for producing a laminate having a barrier layer composed of an ALD inorganic vapor deposition film and a protective layer composed of a polymer vapor deposition film of a paraxylylene-based compound can solve the above problems. It is what I found.
The present invention is characterized by the following points.
1. 1. A barrier layer made of an ALD inorganic vapor-deposited film and a protective layer made of a polymer vapor-deposited film of a paraxylylene-based compound are laminated in this order on the surface of the member by in-line treatment in the same vapor deposition chamber to provide stress resistance. A method for producing a stress-resistant barrier laminate, which comprises producing a barrier laminate.
A plasma-treated surface is formed on the surface of the member by plasma treatment using a gas containing 10% by volume or more and 100% by volume or less of oxygen.
The barrier layer is subjected to an oxide or nitride of one or more elements selected from the group consisting of Al, Si, Ti, Nb, Ta, Hf, Zr, and Zn by an atomic volume deposition method (ALD method). The ALD inorganic vapor deposition film containing an object is formed by laminating one layer or two or more layers.
A method for producing a stress-resistant barrier laminate, which comprises laminating the protective layer on the outermost surface of the barrier laminate.
2. The surface of the barrier layer on the protective layer side is plasma-treated with a gas containing 10% by volume or more and 100% by volume or less of oxygen to form a plasma-treated surface. The method for producing a stress-resistant barrier laminate described above.
3. 3. The ALD inorganic vapor deposition film is formed from a gas containing an organometallic compound of one or more elements selected from the group consisting of Al, Si, Ti, Nb, Ta, Hf, Zr, and Zn. Characteristic,
The method for producing a stress-resistant barrier laminate according to 1 or 2 above.
4. The method for producing a stress-resistant barrier laminate according to any one of the above 1 to 3, wherein the protective layer is laminated by a method including the following steps 1 to 3.
Step 1) A step of introducing the paraxylylene compound into a vaporization chamber and vaporizing at 100 to 160 ° C.
Step 2) A step of radicalizing the vaporized paraxylylene-based compound at 600 to 690 ° C. in a pyrolysis chamber furnace.
Step 3) The radicalized paraxylylene-based compound was introduced at 20 to 40 μbar into a vapor deposition chamber reduced to 5 to 15 μbar at 20 to 35 ° C., and the surface of the vapor deposition object separately introduced into the vapor deposition chamber was introduced. A step of laminating the protective layer by vapor deposition and polymerization while maintaining the surface temperature of the vapor deposition object at 20 to 90 ° C.
5. The method for producing a stress-resistant barrier laminate according to any one of 1 to 4, wherein two or more layers of the barrier layer and the protective layer are alternately laminated.
6. The surface of the barrier layer on the protective layer side is plasma-treated to form a plasma-treated surface.
The method for producing a barrier laminate according to any one of 1 to 4 above.
7. The plasma-treated surface is treated by a reactive ion etching method or a direct plasma method plasma treatment under a pressure of 1 to 100 Pa, using a mixed gas of oxygen and an inert gas as a plasma raw material gas, and having a plasma output of 10 to 500 W. The method for producing a stress-resistant barrier laminate according to 6 above, which comprises forming in 5 to 500 seconds.
8. It was formed from a composition containing an organic silicon compound having a polymerizable functional group containing a carbon-carbon double bond and an alkoxy group and / or a silanol group between the barrier layer and the protective layer. It is characterized by laminating an adhesion promoting layer composed of a vapor-deposited film.
The method for producing a stress-resistant barrier laminate according to any one of 1 to 7 above.
9. The polymerizable functional group containing a carbon-carbon double bond is one or more selected from the group consisting of a (meth) acrylic group, a vinyl group, and an allyl group.
The method for producing a stress-resistant barrier laminate according to 8 above.
10. The method for producing a stress-resistant barrier laminate according to any one of 1 to 9 above, wherein the paraxylylene-based compound contains a compound represented by the following formula.

(In the formula, R is a hydrogen atom or a fluorine atom, X is a halogen atom, and n is a number having an average value of 0 to 4.)
11. The method for producing a stress-resistant barrier laminate according to any one of 1 to 10 above, wherein the paraxylylene-based compound contains a compound represented by the following formula.

12. The method for producing a stress-resistant barrier laminate according to any one of 1 to 11 above, wherein the paraxylylene-based compound contains a compound represented by the following formula.

13. The stress-resistant barrier laminate according to any one of 1 to 12 above, wherein the barrier laminate has an oxygen permeability of 1 cc / m ² / day / atm or less when not boiled. Manufacturing method.
14. The stress resistance according to any one of 1 to 13 above, wherein the oxygen permeability of the barrier laminate after boiling at 100 ° C. for 20 minutes is 1 cc / m ² / day / atm or less. A method for producing a sex barrier laminate.
15. The barrier laminate has a water vapor permeability of 1 g / m ² / day or less when not boiled.
The method for producing a stress-resistant barrier laminate according to any one of 1 to 14 above.
16. The barrier laminate has a water vapor transmittance of 1 g / m ² / day or less after boiling at 100 ° C. for 20 minutes.
The method for producing a stress-resistant barrier laminate according to any one of 1 to 15 above.
17. The member is one selected from the group consisting of a resin film, a packaging bag made of a resin film, a resin molded product, a medical device, an electronic component, an electric component, and a circuit board.
The method for producing a stress-resistant barrier laminate according to any one of 1 to 16 above.
18. Production of a stress-resistant barrier packaging material, wherein the member is a resin film, and a barrier packaging material is produced from a barrier laminate produced by the production method according to any one of 1 to 16 above. Method.
19. A method for producing a stress-resistant barrier packaging bag, which comprises producing a barrier packaging bag from the barrier packaging material produced by the production method according to the above 18.
20. A stress-resistant barrier laminate tube, wherein the member is a laminate tube precursor, and a laminate tube is produced from the barrier laminate produced by the production method according to any one of 1 to 16 above. Production method.
21. A drug-filled syringe, wherein the member is a resin syringe syringe portion, and a resin syringe syringe portion is produced from a barrier laminate produced by the production method according to any one of 1 to 16 above. How to make a stress resistant barrier syringe for use.

According to the present invention, a barrier layer made of an ALD inorganic thin-film film and a protective layer made of a polymer-deposited film of a paraxylylene-based compound, which are almost colorless and transparent, are laminated on the surface very thinly by vapor deposition. It has a barrier property against gas such as oxygen and water vapor, gas or liquid chemicals, etc. while maintaining the arbitrary shape and color of the member to be vapor-deposited, and even if it receives stress such as bending or retort treatment. A stress-resistant barrier laminate that maintains its properties can be obtained.
By having the above-mentioned barrier property, the packaging bag produced from the barrier laminate can dissipate and permeate the packed contents packaging bag even after being subjected to stress such as bending or retort treatment. Deterioration of the contents due to the penetration of oxygen and water vapor from the outside can be suppressed.

The cross-sectional view which shows an example of the layer structure of the barrier laminated body of this invention. FIG. 5 is a cross-sectional view showing an example of another aspect of the layer structure of the barrier laminate of the present invention. FIG. 5 is a cross-sectional view showing an example of still another aspect of the layer structure of the barrier laminate of the present invention. The cross-sectional view which shows an example of the structure of the electrode of plasma processing in this invention. FIG. 5 is a cross-sectional view showing an example of another aspect of the configuration of the electrode for plasma treatment in the present invention.

In each figure, the size and ratio may be changed or exaggerated for the sake of clarity. In addition, for the sake of readability, unnecessary parts for explanation and repeated codes may be omitted.

Hereinafter, embodiments of the present invention will be described in detail. Further, the present invention is not limited to the various specific examples and figures listed below.

In the present invention, a barrier layer made of an ALD inorganic vapor deposition film by an atomic volume deposition method (ALD method) and a protective layer made of a polymer vapor deposition film of a paraxylylene-based compound are laminated in this order on the surface of a member to form a barrier. This is a method for producing a stress-resistant barrier laminate in which the protective layer is laminated on the outermost surface of the laminate.
The barrier layer and the protective layer may be one layer each, and two or more layers may be alternately laminated such as a member / barrier layer / protective layer / barrier layer / protective layer / ... ..
Between the barrier layer and the protective layer, if necessary, in order to improve the interlayer adhesiveness between the barrier layer and the protective layer, a polymerizable functional group containing a carbon-carbon double bond and an alkoxy group It is also possible to laminate an adhesion promoting layer composed of a vapor-deposited film formed from a composition containing an organic silicon compound having and / or a silanol group. In this case, the surface of the barrier layer on which the adhesion promoting layer is laminated is preferably a plasma-treated surface.

The barrier laminate produced by the present invention has a high barrier property against gases such as oxygen and water vapor, gas or liquid chemicals, etc., and is subjected to bending treatment such as bending and rolling, retort treatment such as boiling at high temperature, and the like. High barrier properties can be maintained even after being stressed by.
Therefore, the packaging material, the packaging body, and the packaging bag produced by using the barrier laminate have the same high barrier property, and maintain the high barrier property even if stress is applied during each production process or use. However, it is possible to suppress the dissipation of the packed contents permeating the packaging bag and the deterioration of the contents due to the permeation of oxygen and water vapor from the outside.

The oxygen permeability of the barrier laminate, barrier packaging material, barrier packaging, and barrier packaging bag produced by the present invention when not boiled is 0.001 cc / m ² / day / atm or more, 1 cc / m ² / day. It is preferably less than / atm, 0.005 cc / m ² / day / atm or more, 0.
More preferably, it is 5 cc / m ² / day / atm or less.
Then, 100 ° C., oxygen permeability after boiling 20 minutes, 0.001 cc / m ² / day / atm or more is preferably not more than 1 cc / m ² / day / atm, 0.05 cc / m ² / It is preferably 1 day / atm or more and 0.5 cc / m ² / day / atm or less.
The water vapor permeability of the barrier laminate, barrier packaging material, barrier packaging, and barrier packaging bag produced by the present invention when not boiled is 0.0001 g / m ² / day or more and 1 g / m ² / day or less. It is preferably 0.001 g / m ² / day or more, and more preferably 0.5 g / m ² / day or less.
The water vapor transmittance after boiling at 100 ° C. for 20 minutes is preferably 0.0001 g / m ² / day or more and 1 g / m ² / day or less, and 0.001 g / m ² / day or more, 0. More preferably, it is 5.5 g / m ² / day or less.
It is difficult to stably reduce the oxygen permeability and / or the water vapor permeability below the above range, and if it is larger than the above range, it is due to the dissipation of the filled contents and the permeation of oxygen and water vapor from the outside. It tends to be difficult to sufficiently suppress the deterioration of the contents.

The barrier property of a gas or liquid to a drug can be evaluated by the adsorptivity of a drug such as l-menthol or dl-α-tocopherol acetate.
For example, when evaluating drug adsorption using l-menthol, for example, first, a film-like laminate is cut into 10 cm × 10 cm squares, folded in half so that the protective layer is on the outside, and combined. A sealed bag is prepared by sealing the edge of the bag, and its weight (initial weight [g]) is measured.
Then, put 10 g of l-menthol solid in a stainless steel container with a volume of 10 liters, cover the container with l-menthol steam, hang the sealed bag made in it, and store it at 40 ° C. for 7 days. did. After storage, the sealed bag is taken out, the weight (weight after adsorption [g]) is measured, and the adsorption amount of l-menthol is calculated from the difference from the initial weight by the following formula.
Adsorption amount [mg / m ² ] = (weight after adsorption [g] -initial weight [g]) x 1000 / 0.1 ²
The adsorption amount of l-menthol is preferably 0.1 mg / m ² or more and 200 mg / m ² or less, and more preferably 1 mg / m ² or more and 100 mg / m ² or less.
The adsorption amount of l-menthol after boiling at 100 ° C. for 20 minutes is preferably 0.1 mg / m ² or more and 200 mg / m ² or less, and more preferably 1 mg / m ² or more and 100 mg / m ² or less.

Further, for example, when evaluating the drug adsorptivity using dl-α-tocopherol acetate, for example, first, a film-like laminate is cut into 5 cm × 5 cm squares, and the weight (initial weight [g]) thereof is determined. Measure.
Then, a dl-α-tocopherol acetate solution is applied to the protective layer surface, and the glass petri dish is brought into close contact with the applied surface face down, covered, and stored at 40 ° C. for 7 days. After storage, the laminate was taken out, the dl-α-tocopherol acetate solution on the coated surface was wiped off with ethanol, and then the weight (weight after adsorption [g]) was measured. From the difference from the initial weight, acetic acid was obtained by the following formula. The adsorption amount of dl-α-tocopherol is calculated.
Adsorption amount [mg / m ² ] = (weight after adsorption [g] -initial weight [g]) x 1000/0.05 ²
The adsorption amount of dl-α-tocopherol acetate is preferably 0.1 mg / m ² or more and 200 mg / m ² or less, and more preferably 1 mg / m ² or more and 100 mg / m ² or less.
The adsorption amount of dl-α-tocopherol acetate after boiling at 100 ° C. for 20 minutes is preferably 0.1 mg / m ² or more and 200 mg / m ² or less, and 1 mg / m ² or more and 100 mg / m ² or less. More preferred.
It is difficult to stably reduce the adsorption amount of l-menthol and / or dl-α-tocopherol acetate below the above range, and if it is larger than the above range, the medicinal component of the drug which is the filled content It tends to be difficult to sufficiently suppress the decrease and dissipation.

<Members>
[type]
Examples of the member used in the laminate produced by the present invention include a resin film, a packaging bag made of a resin film, a resin molded product, a medical device, an electronic component, an electric component, a circuit board, and the like.
A mask may be applied to the portion of the surface of the member where the plasma-treated surface, the barrier layer, and the protective layer are not to be laminated so that these are not formed.

[shape]
The thickness of the resin film is not particularly limited, as long as it can withstand the process of forming the barrier layer, the protective layer, and the plasma-treated surface in the present invention.
The barrier layer, the protective layer, and the plasma-treated surface may be formed on a resin film or a packaging bag made of a resin film.
When the resin film is used, it is preferable to secure the heat-sealing property by applying a mask or the like to the portion to be heat-sealed.
The resin molded product is not a thin film but a three-dimensional structure, which may be plate-shaped or block-shaped, has a tubular shape with a recess having a high aspect ratio, and has a small opening. May have a wide sake bottle shape, may have large irregularities or fine irregularities on the surface, or may have a narrow open gap.
The surface of the recess and the inner part of the narrow gap can also have a plasma-treated layer, an ALD inorganic vapor-deposited film layer, and a polymer-deposited film layer of a paraxylylene-based compound.
The aspect ratio of the recess is preferably 1 or more and 5000 or less, and more preferably 1 or more and 500 or less.
The diameter of the opening of the recess is preferably 1 mm or more and 1000 mm or less, and more preferably 5 mm or more and 500 mm or less. The depth of the recess is preferably 10 mm or more and 10000 mm or less, and preferably 10 mm or more and 5000 mm or less.
There is no particular limitation on the convex portion, and the present invention can also be applied to a molded product having extremely fine holes or a molded product having a complicated shape.

Examples of the resin molded product having a recess include a laminate tube precursor before sealing, a cup, a medical syringe, and the like.
Since the barrier layer and the protective layer have an extremely thin thickness, the member in which these are laminated has substantially the same shape, size, and color as the original member, and imparts barrier properties without impairing the characteristics of the original member. can do.
For example, when the member is a resin syringe syringe portion, the inner diameter of the syringe is substantially the same as that before stacking, so that it can be used in combination as it is without changing the outer diameter of the piston. It is also possible to assemble a stress-resistant barrier syringe for a finished syringe.
Further, for example, when the member is a laminate tube precursor, it can be bent or folded even after lamination, and the laminate tube can be produced by sealing the opening as usual. Is.
There are no particular restrictions on the shapes of electronic components, electrical components, circuit boards, etc.

[Material]
The material of the member is not particularly limited as long as it can withstand the process of forming the barrier layer, the protective layer and the plasma-treated surface in the invention. For example, resin, leather, paper, cloth, fiber, metal, metal oxide, wood, etc. It can contain various materials such as.
The barrier property in the present invention is most exhibited when the material is a resin.
The type of resin is not particularly limited, and examples thereof include various types of thermoplastic resins, thermosetting resins and cured products thereof, elastomers, silicone-based resins, and the like, and one or more of these are contained. be able to.
In addition, various resin raw materials, elastomer raw materials, organic fillers, inorganic fillers, radical polymerization initiators, vulcanizing agents, vulcanization activators, mold release agents, antiaging agents, and various other additions are added to the resin depending on the application. It can also contain an agent.

The thermoplastic resin is not particularly limited, and a general thermoplastic resin can be included. Specific examples thereof include polyethylene-based resins, polypropylene-based resins, and polystyrene-based resins.
The polyethylene-based resin is a resin mainly using ethylene as a polymerization raw material, and also includes a copolymer in which other polymerization raw materials are used in combination. Specifically, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer, ethylene- Examples thereof include (meth) methyl acrylate copolymers, ethylene- (meth) ethyl acrylate copolymers, ethylene- (meth) acrylate copolymers, ethylene-propylene copolymers and the like, and mixtures of these resins. , Not limited to these.
The polypropylene-based resin is a resin mainly using propylene as a polymerization raw material, and also includes a copolymer in which other polymerization raw materials are used in combination. Specific examples thereof include propylene homopolymers, propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene-butene-1 copolymers and mixtures of these resins. Not limited.
The polystyrene-based resin is a resin using styrene as a polymerization raw material, and includes copolymers using other polymerization raw materials in combination and hydrogenated products thereof.
When the thermosetting resin is contained, the thermosetting resin may be in an uncured state, a B stage state, or a cured product.
The elastomer is not particularly limited, and for example, the above-mentioned thermoplastic resin and thermosetting resin having rubber elasticity are applicable.
Vulcanized products are also included in each resin and elastomer.

[Color pattern]
Since the barrier layer made of the ALD inorganic vapor deposition film and the protective layer made of the polymer vapor deposition film of the paraxylylene compound in the present invention are thin and substantially colorless and transparent, the color pattern on the surface of the member can be maintained. Furthermore, the iridescent color due to the diffracted luster using the prism effect due to the fine uneven pattern can be maintained.

[Plasma processing surface]
The surface on which the barrier layer of the member is laminated is sufficient if it has a normal level of cleanliness, but it is preferably a plasma-treated surface that has been cleaned with a solvent or subjected to plasma treatment, if necessary. The plasma treatment at that time is preferably a plasma treatment using a gas containing 10% by volume or more and 100% by volume or less of oxygen.
Since the surface of the member is the plasma-treated surface, the adhesive strength of the barrier layer can be increased.

<Barrier layer>
In the present invention, the barrier layer is a barrier layer made of an ALD inorganic vapor deposition film obtained by an atomic volume deposition method (ALD method), and imparts a barrier property to a member such as a gas such as oxygen or water vapor or a gas or liquid chemical. It is a layer.
The barrier layer may be provided in one layer or two or more layers in the laminated body, and at least one layer is laminated in contact with the plasma-treated surface of the member surface, but can also be laminated alternately with the protective layer. Two or more layers can be laminated continuously.
When two or more barrier layers are laminated, the composition of each barrier layer may be the same or different.
The ALD inorganic vapor deposition film preferably contains oxides or nitrides of one or more elements selected from the group consisting of Al, Si, Ti, Nb, Ta, Hf, Zr and Zn. Specific examples of the compound include AlO _x , SiO _x , Si ₃ N ₄ , TiO _x , NbO _x , Ta ₂ O, TiN, HfO ₂ , ZrO _x , ZnO and the like. (X is a number from 1 to 5.)

The above-mentioned ALD inorganic vapor deposition film is formed from a gas containing an organometallic compound of one or more elements selected from the group consisting of Al, Si, Ti, Nb, Ta, Hf, Zr, and Zn. Is preferable.
Specific examples of the organometallic compound include trimethylaluminum (TMA), trisdimethylaminosilane (TDMAS), tetrakisdimethylaminotitanium (TDMAT), tetrakisethylmethylaminozirconium (TEMAZ), tetrakisdimethylaminohafnium (TDHA) and the like. ..
The thickness of the barrier layer is preferably 2 nm or more and 50 nm or less, and more preferably 5 nm or more and 30 nm or less. When the thickness is in the above range, it can be firmly adhered to the member and can exhibit sufficient barrier properties.
If it is thinner than the above range, the barrier effect is difficult to be exhibited, and if it is thicker than the above range, it takes a long time to form the barrier layer, so that the production cost increases.
Further, the thickness of the barrier layer is preferably uniform, and the thickness of each portion is preferably within ± 15% of the average thickness value, more preferably within ± 10% of the average thickness value, and the average thickness value. It is more preferably within ± 5%. If it is narrower than the above range, it is difficult to control the formation of the barrier layer, and if it is wider than the above range, it tends to be difficult to form the barrier layer in the fine gaps.

[Plasma processing surface]
It is preferable that the surface on which the protective layer of the barrier layer is laminated is subjected to plasma treatment, if necessary, to form a plasma-treated surface.
Since the surface of the barrier layer is the above-mentioned plasma-treated surface, the adhesive strength of the protective layer can be increased.
The plasma treatment conditions and the like are the same as the formation of the plasma treatment surface on the member surface.

<Adhesion promotion layer>
The adhesion promoting layer is a layer for enhancing the adhesion between the barrier layer and the protective layer, and when the surface of the barrier layer is a plasma-treated surface, the adhesiveness can be further enhanced.
The adhesion promoting layer may be a layer composed of a vapor-deposited film formed of a composition containing a polymerizable functional group containing a carbon-carbon double bond and an organic silicon compound having an alkoxy group and / or a silanol group. preferable.
The polymerizable functional group containing a carbon-carbon double bond is preferably one or more selected from the group consisting of a (meth) acrylic group, a vinyl group, and an allyl group.
By having an alkoxy group and / or a silanol group, it is possible to firmly adhere to the barrier layer made of an ALD inorganic vapor deposition film, and by having the above-mentioned polymerizable functional group containing a carbon-carbon double bond. , Can be firmly adhered to a protective layer made of a polymer vapor-deposited film of a paraxylylene-based compound.

<Protective layer>
The protective layer is a layer made of a polymer vapor deposition film of a paraxylylene-based compound, has a barrier property against gas such as oxygen and water vapor, gas or liquid chemicals, and ALD by the atomic volume deposition method (ALD method). It is a layer that protects the barrier layer made of an inorganic vapor deposition film.
Since the protective layer protects the barrier layer, even if stress such as bending or retort treatment is applied, deterioration of the barrier layer and local peeling of the barrier layer are suppressed, and the protective layer and the barrier layer are separated from each other. It is possible to obtain a stress-resistant barrier laminate capable of maintaining a high barrier property due to a synergistic effect.
For example, when the ALD inorganic vapor deposition film is Al ₂ O ₃ , the water resistance is relatively weaker than that of the ALD inorganic vapor deposition film layers having other compositions, and the ALD inorganic vapor deposition film deteriorates in the long term and has barrier properties. However, by providing the barrier layer on the barrier layer, deterioration of the ALD inorganic vapor deposition film can be suppressed even in a high humidity environment, and the barrier property of the laminated body can be maintained.

In order to obtain high adhesion of the protective layer, the protective layer is composed of a barrier layer composed of an ALD inorganic vapor deposition film by an atomic volume deposition method (ALD method), a plasma-treated surface of the barrier layer, and an adhesion promoting layer. It is preferable that the layers are laminated by in-line treatment in the same vapor deposition chamber in the same apparatus following the previous steps such as lamination.
By the in-line treatment as described above, the object to be laminated can be maintained at high temperature and low pressure without being exposed to the outside air, contamination and oxidation of the surface of the object to be laminated can be suppressed, and high adhesion of the protective layer can be obtained. it can.
In addition, productivity can be increased because the device is small and simplified.

The thickness of the protective layer is preferably 10 nm or more and 5 μm or less, more preferably 20 nm or more and 2 μm or less, and further preferably 50 nm or more and 500 nm or less.
The protective layer can be firmly adhered when the thickness is in the above range, and can exhibit sufficient barrier properties and protective properties.
If it is thinner than the above range, barrier properties and protective properties are difficult to be exhibited, and if it is thicker than the above range, the protective layer itself becomes hard and difficult to handle, and it takes a long time to form a polymer vapor deposition film of a paraxylylene compound. The production cost will also increase.
Further, the thickness of the protective layer is uniform, and the thickness of each portion is preferably within ± 15% of the average thickness value, more preferably within ± 10% of the average thickness value, and the average thickness value is ± 5%. It is more preferably within. If it is smaller than the above range, it is difficult to control the formation of the polymer vapor-deposited film layer of the paraxylylene-based compound, and if it is larger than the above range, it is difficult to form the polymer-deposited film layer of the paraxylylene-based compound in the fine gaps. easy.
The polymer vapor deposition film of the paraxylylene compound has excellent elasticity, and even when the member is deformed by expansion and contraction or bending, it follows the expansion and contraction and bending and deforms without peeling or cracking. Is possible, and the barrier property can be maintained.

[Paraxylylene compound]
The paraxylylene-based compound used in the present invention is preferably a paraxylylene-based compound represented by the following formulas (1), (2) and (3). As these paraxylylene-based compounds, one kind or a mixture of two or more kinds can be used. Commercially available products of these paraxylylene-based compounds include unsubstituted paraxylylene dimer (manufactured by SCS Co., Ltd., parylene N) and monochloroparaxili. Lendimer (SCS Co., Ltd., Parylene C), Dichloroparaxylylene dimer (SCS Co., Ltd., Parylene D), Tetrafluoroparaxylylene dimer (SCS Co., Ltd., Parylene FVT4), α, α, Examples thereof include α', α'-tetrafluoroparaxylylene dimer (manufactured by SCS Co., Ltd., parylene AF4) and the like.
These paraxylylene-based compounds polymerize to produce a paraxylylene-based polymer called parylene.

（式中、Ｒは水素原子またはフッ素原子であり、Ｘはハロゲン原子であり、ｎは平均値が０〜４の数である。）

(In the formula, R is a hydrogen atom or a fluorine atom, X is a halogen atom, and n is a number having an average value of 0 to 4.)

<Lamination of barrier laminate>
[Formation of plasma-treated surface of member surface]
In the present invention, the surface of the member on which the ALD inorganic vapor deposition film layer is laminated can be preliminarily formed with a plasma-treated surface by plasma treatment.
As the plasma treatment, RF plasma discharge treatment, reactive ion etching plasma treatment, or direct plasma plasma treatment can be used. Furthermore, corona treatment can also be used in combination.
By plasma treatment, additives and contamination on the surface of the member are removed, polar groups and functional groups containing oxygen atoms such as OH groups are generated to impart polarity, and appropriate surface roughness can be obtained. Therefore, the adhesiveness between the member surface and the barrier layer can be improved.
When the plasma treatment is performed, for example, it can be performed in a mixed gas atmosphere of oxygen / inert gas. As the inert gas, argon, helium or the like can be used.
The oxygen ratio of the oxygen / inert gas is preferably 10% by volume to 100% by volume. If it is less than the above range, the efficiency of adding polar groups and functional groups containing oxygen atoms to the surface of the molded product deteriorates, and the stackability of the ALD inorganic vapor deposition film layer in the next step deteriorates.
When the corona treatment is performed, the electrode distance is preferably 3 to 6 mm, the voltage is 1 to 20 kV, and the treatment time is preferably 1 to 60 seconds. If the voltage and the processing time are smaller than the above range, the processing effect is difficult to be exhibited, and if it is larger than the above range, the vapor deposition object is likely to be deteriorated.
The plasma treatment is preferably carried out under a pressure of 1 to 100 Pa, using a mixed gas of oxygen and an inert gas as a plasma raw material gas, a plasma output of 10 to 500 W, and a treatment time of 5 to 500 seconds.

[Lamination of ALD inorganic vapor deposition film layer]
The ALD inorganic vapor deposition film layer is formed continuously with the above plasma treatment in the same chamber in the apparatus without exposing the molded product to the outside air in order to suppress recontamination and oxidation of the member surface. Is preferable. As a result, the ALD inorganic vapor deposition film can be more firmly adhered to the member surface.
First, an organometallic group can be added to the plasma-treated surface of the member by reacting the gas containing the organometallic compound with the hydroxyl group. Specifically, for example, a gas containing an organometallic compound is introduced and reacted under a pressure of 1 × 10 ⁻² Pa or more and 1 × 10 ³ Pa or less, and then purged with an inert gas to perform unreacted organic. This can be achieved by removing the gas of the metal compound and the organic gas of the by-product.
Next, steam adds a hydroxyl group to the surface to which the organometallic group has been added. Specifically, for example, water vapor is introduced at an atmospheric pressure of 1 × 10 ⁻² Pa or more and 1 × 10 ³ Pa or less to generate OH groups on the surface of the molded product, and then purged with an inert gas. This can be achieved by removing the unreacted steam. By this operation, the added organic metal is changed to a metal oxide and / or a metal hydroxide.
Further, addition of an organometallic group by introduction of a gas containing the above-mentioned organometallic compound and an inert gas purge treatment, and formation of a metal oxide and / or a metal hydroxide by the above-mentioned introduction of steam and an inert gas purge treatment. The ALD inorganic vapor-deposited film is grown until it reaches the target thickness by alternately repeating it many times.
Here, hydrogen peroxide may be added to water vapor, or Ar or N2 may be used as a carrier gas to generate high-frequency plasma to promote the above reaction.

[Lamination of polymer vapor deposition film of paraxylylene-based compound]
The polymer vapor deposition layer of the paraxylylene-based compound can be formed by laminating, for example, by a method including the following steps 1 to 3.
Step 1) A step of introducing the paraxylylene compound into a vaporization chamber and vaporizing at 100 to 160 ° C.
Step 2) A step of radicalizing the vaporized paraxylylene-based compound at 600 to 690 ° C. in a pyrolysis chamber furnace.
Step 3) The radicalized paraxylylene-based compound was introduced at 20 to 40 μbar into a vapor deposition chamber reduced to 5 to 15 μbar at 20 to 35 ° C., and the surface of the vapor deposition object separately introduced into the vapor deposition chamber was introduced. A step of laminating the protective layer by vapor deposition and polymerization while maintaining the surface temperature of the vapor deposition object at 20 to 90 ° C.

The polymer vapor deposition layer of the paraxylylene-based compound is formed by first vaporizing the paraxylylene-based compound, then radicalizing it, and bringing it into contact with the vapor-deposited object.
In step 1, an appropriate amount of the paraxylylene-based compound is vaporized according to the volume of the vaporization chamber and the vapor deposition chamber. If the amount of the paraxylylene-based compound is too small, the air pressure in the vapor deposition chamber is low, the density of radical monomers is low, and the formation rate of the vapor deposition layer is slow, which is not preferable.
If the amount of the paraxylylene-based compound is too large, the density of the radical monomer becomes too high, and polymerization tends to proceed before reaching the surface of the vapor-deposited object, and the film quality of the formed vapor-deposited layer deteriorates. It is not preferable because the adhesion between the and the vapor deposition layer is lowered.
The temperature at which the paraxylylene-based compound is vaporized in the vaporization chamber is preferably 100 to 160 ° C. When the temperature is lower than 100 ° C., vaporization tends to be insufficient. When the temperature is higher than 160 ° C., the vaporized paraxylylene-based compound tends to be chemically unstable and easily carbonized.

In step 2, the temperature at which the vaporized paraxylylene-based compound is radicalized in the pyrolysis chamber is preferably 600 to 690 ° C. When the temperature is lower than 600 ° C., radicalization tends to be insufficient. When the temperature is higher than 690 ° C., the vaporized paraxylylene-based compound is likely to be carbonized, and the radicalized paraxylylene-based compound is likely to be chemically unstable.

In the vapor deposition chamber before introducing the radicalized paraxylylene-based compound in step 3, the atmospheric pressure is preferably maintained in the range of 5 to 15 μbar in order to obtain a good quality and highly adherent vapor deposition layer.
When the atmospheric pressure is lower than 5 μbar, the density of the radical monomer becomes small, so that the vapor deposition layer forming rate becomes slow and the production efficiency decreases. When it is higher than 15 μbar, the density of the radical monomer becomes too high, polymerization easily proceeds before reaching the surface of the vapor deposition object, the film quality of the formed vapor deposition layer deteriorates, and the vapor deposition target and the vapor deposition object are deposited. This is not preferable because the adhesion to the layer is reduced.
The atmospheric pressure of the radicalized paraxylylene-based compound when introduced into the vapor deposition chamber is preferably 10 to 400 μbar. When it is lower than 10 μbar, the density of the radical monomer becomes small, the formation rate of the vapor-deposited layer becomes slow, and the production efficiency decreases. When the atmospheric pressure is higher than 400 μbar, the density of the radical monomer becomes too high, polymerization easily proceeds before reaching the surface of the vapor deposition object, the film quality of the formed vapor deposition layer deteriorates, and the vapor deposition object It is not preferable because the adhesion between the and the vapor deposition layer is lowered.
Here, the above steps 1 to 3 can be batch-processed.

<Barrier packaging material>
The barrier packaging material is a barrier packaging material produced from the barrier laminate of the present invention in which the member is a resin film, and a barrier packaging produced by laminating a barrier layer, a protective layer, or the like using the packaging material as a member. Materials can be mentioned.

<Barrier packaging>
Examples of the barrier packaging include a barrier packaging made from the barrier packaging material of the present invention and a barrier packaging made by laminating a barrier layer, a protective layer, etc. using the packaging as a member.

<Packaging bag>
Examples of the barrier packaging bag include a barrier packaging bag made of the barrier packaging material of the present invention, and a barrier packaging bag made by laminating a barrier layer, a protective layer, and the like using the packaging bag as a member.

The raw materials used in the examples are as follows.
-PP film 1: A film-forming film with a thickness of 50 μm.
-Polypropylene (PP) cup 1: A polypropylene cup with an inner diameter of 80 mm at the mouth, an inner diameter of 40 mm at the bottom, a height of 50 mm, a capacity of 150 ml, and a wall thickness of 1.5 mm.
-Paraxylylene compound 1: Parylene N manufactured by SCS Co., Ltd. Unsubstituted paraxylylene dimer. In powder form.
-Paraxylylene compound 2: Parylene C manufactured by SCS Co., Ltd. Monochrome loparaxylylene dimer. In powder form.
-Silicone resin A: KR-251 manufactured by Shin-Etsu Chemical Co., Ltd. Conventional moisture-proof coating agent.
-Alkoxysilane 1: γ-methacryloxypropyltrimethoxysilane

[Example 1]
Each of the PP film 1 and the polypropylene cup 1 was subjected to the following treatment as a member, and the barrier layer 1 made of an ALD film and the protective layer 1 made of a polymer vapor deposition film of a paraxylylene-based compound were laminated.
Using a mixing vapor deposition kettle equipped with a pyrolysis furnace and a vaporization chamber in the ALD device, the formation of the plasma processing surface, the formation of the barrier layer, and the formation of the protective layer are performed in-line in the same chamber in one mixing vapor deposition kettle. It was done by processing.
For the PP film 1, as shown in FIG. 4, a parallel plate type electrode for a plasma CVD apparatus was used to form a barrier layer 1 and a protective layer 1 on only one side of the PP film 1.
As shown in FIG. 5, the polypropylene cup 1 has a polypropylene cup 1 in which the upper electrode is a U-shaped plate and the lower electrode is a columnar plasma CVD apparatus electrode inserted into the cup. A barrier layer 1 and a protective layer 1 were formed only on the outside.
However, the ALD film was formed on the PP film 1 and the polypropylene cup 1 under the same conditions.

(Plasma surface treatment)
First, the member was installed in the chamber inside the vapor deposition kettle, and the pressure inside the chamber was reduced to 5.2 × 10 ^-4 Pa.
Next, in an environment of 0.43 Pa of a mixed gas having an oxygen / argon = 50/50 volume ratio, RF plasma discharge for 300 seconds was performed using a plasma excitation power source of 13.56 MHz and 500 W to perform RF plasma discharge on the member surface. A plasma-treated surface was formed on the surface.

(Barrier layer formation)
In succession with the plasma surface treatment, the following treatments a) to d) were continuously carried out in order to form one cycle, which was carried out at 230 seconds / cycle, and a total of 100 cycles were carried out to carry out ALD alumina (Al ₂₎ having a thickness of 10 nm. O ₃ ) A barrier layer 1 made of a vapor-deposited film was formed on the surface of the member.
a) The pressure in the vapor deposition kettle is reduced to 5.8 × 10 ^-4 Pa, and the raw material gas made of trimethylaluminum (TMA) as an organometallic compound is supplied for 30 seconds.
b) Argon (Ar) gas is purged as a purge gas for 50 seconds.
c) Water vapor (H ₂ O) is supplied as a reaction gas for 100 seconds.
d) Argon (Ar) gas is purged as a purge gas for 50 seconds.

(Protective layer formation)
While replacing the inside of the chamber with helium gas, the pressure was reduced to an ultimate vacuum of 4.0 Pa.
Then, the paraxylylene compound 1 is introduced into the vaporization chamber, vaporized at 160 ° C., heated to 670 ° C. in a pyrolysis furnace to be radicalized, introduced into the chamber at a pressure of 4 Pa, and laminated on the surface of the member. On the barrier layer 1, a protective layer 1 having a thickness of 2000 nm made of a polymer vapor deposition film of a paraxylylene-based compound was formed.
The inside of the chamber was returned to normal pressure, a laminated body in which the barrier layer 1 and the protective layer 1 were laminated on the member was taken out, and various evaluations were performed.

[Example 2]
When the barrier layer 1 is formed, a total of 70 cycles are carried out to change the thickness of the barrier layer 1 made of the ALD alumina (Al ₂ O ₃ ) vapor-deposited film to 7 nm, and when the protective layer is formed, the paraxylylene compound 2 is used to form the paraxylylene. A laminate was obtained by the same operation as in Example 1 except that the thickness of the protective layer 1 made of the polymer vapor deposition film of the compound was changed to 1300 nm, and the evaluation was carried out in the same manner.

[Example 3]
With respect to the laminate in Example 1, the surface of the barrier layer 1 on the protective layer 1 side was used as a plasma-treated surface, and a laminate having an adhesion promoting layer was produced and evaluated by the following operation.
(Barrier layer formation)
A barrier layer was formed by operating in the same manner as in Example 1.

(Plasma treatment on the surface of the barrier layer)
The surface of the barrier layer 1 laminated on the member was surface-treated by a reactive ion etching method under the following conditions to form a plasma-treated surface.
Plasma raw material gas: Argon / oxygen = mixed gas with a volume ratio of 1/1 Atmospheric pressure: 10 Pa
Plasma output: 100W
Processing time: 100 seconds

(Adhesion promotion layer formation)
After the above plasma treatment, vacuuming was performed to 1 Pa, and alkoxylan 1 was vapor-deposited on the plasma-treated surface formed above by a thermal CVD method to form an adhesion promoting layer.

(Protective layer formation)
By operating in the same manner as in Example 1, a protective layer 1 made of a polymer vapor deposition film of a paraxylylene-based compound is formed on the organic silane compound layer laminated on the surface of the member, and the barrier layer 1, the plasma-treated surface, and the organic A laminated body in which the silane compound layer and the protective layer 1 were laminated was prepared, and the evaluation was carried out in the same manner.

[Example 4]
A laminate in which two barrier layers and two protective layers were alternately laminated was produced and evaluated by the following operation.
(Barrier layer 1 formation)
The barrier layer 1 was formed in the same manner as in the formation of the barrier layer 1 in Example 2.
(Protection layer 1 formation)
The protective layer 1 was formed by operating in the same manner as in the formation of the protective layer 1 in Example 2.
(Formation of barrier layer 2)
The barrier layer 2 was formed in the same manner as in the formation of the barrier layer 1 in Example 1.
(Formation of protective layer 2)
The protective layer 2 is formed in the same manner as in the formation of the protective layer 1 in the second embodiment to prepare a laminated body in which the barrier layer 1, the protective layer 1, the barrier layer 2, and the protective layer 2 are laminated, and evaluated in the same manner. Was carried out.

[Comparative Example 1]
The barrier layer 1 was formed by the same operation as the formation of the barrier layer 1 in Example 1, but a laminated body was prepared without forming the protective layer 1, and the evaluation was carried out in the same manner.

[Comparative Example 2]
The barrier layer 1 was not formed, and the same operation as in the formation of the protective layer 1 in Example 1 was performed to directly laminate the protective layer 1 on the member to prepare a laminated body, and the evaluation was carried out in the same manner.

[Comparative Example 3]
An evaluation was carried out in the same manner as in Example 1 for an unlaminated member in which neither a barrier layer nor a protective layer was laminated.

[Result Summary]
In all the examples, each of the laminates made from the PP cup 1 and the PP film 1 has good low water vapor permeability, oxygen permeability, and drug adsorption even after boiling due to the lamination of the barrier layer and the protective layer. Indicated.
On the other hand, the laminate prepared from the PP cup 1 and the PP film 1 of Comparative Example 1 in which the protective layer was not laminated showed good low water vapor permeability, oxygen permeability, and drug adsorption before boiling. After boiling, it showed insufficient high water vapor permeability, oxygen permeability, and drug adsorption.
The laminates produced from the PP cup 1 and the PP film 1 in Comparative Example 2 in which the barrier layer was not formed and Comparative Example 3 in which neither the barrier layer nor the protective layer was laminated were insufficient both before and after boiling. It showed high water vapor permeability, oxygen permeability, and drug adsorption.

<Evaluation method>
[Oxygen permeability]
The test piece is boiled as it is or at 100 ° C. for 20 minutes to remove water on the surface, and then oxygen permeability under the conditions of 23 ° C. and 90% RH using OXTRAN2 / 20 manufactured by MOCON, USA. (Cc / m ² / day / atm) was measured.

[Water vapor permeability]
The test piece is boiled as it is or at 100 ° C. for 20 minutes to remove water on the surface, and then water vapor permeability under the conditions of 40 ° C. and 90% RH using PERMATRAN 3/31 manufactured by MOCON, USA. (G / m ² / day) was measured.

[Drug adsorption]
a) A test piece of l-menthol PP film (50 μm thickness) is cut into 10 cm × 10 cm squares, folded in half so that the protective layer is on the outside, and the combined edges are sealed to prepare a sealed bag. The weight (initial weight [g]) was measured.
Then, put 10 g of l-menthol solid (manufactured by Genuine Chemical Co., Ltd.) in a stainless steel container with a volume of 10 liters, cover the container with l-menthol steam, and hang the prepared airtight bag in it. It was lowered and stored at 40 ° C. for 7 days. After storage, the sealed bag was taken out, the weight (weight after adsorption [g]) was measured, and the adsorption amount of l-menthol was calculated from the difference from the initial weight.
Adsorption amount [mg / m ² ] = (weight after adsorption [g] -initial weight [g]) x 1000 / 0.1 ²

b) A test piece of dl-α-tocopherol PP film (50 μm thickness) acetate was cut into 5 cm × 5 cm squares, and the weight (initial weight [g]) was measured. Apply dl-α-tocopherol acetate solution (manufactured by Kanto Chemical Co., Inc., purity:> 98.0%) to the member surface, make it adhere to the glass petri dish with the application surface facing down, cover it, and at 40 ° C. Stored for 7 days. After storage, the laminate is taken out and the dl-α-tocopherol acetate solution on the coated surface is wiped off with ethanol (manufactured by Genuine Chemical Co., Ltd., purity: 99.5%) and then removed by weight (weight after adsorption [g]. ) Was measured, and the adsorption amount of dl-α-tocopherol acetate was calculated from the difference from the initial weight.
Adsorption amount [mg / m ² ] = (weight after adsorption [g] -initial weight [g]) x 1000/0.05 ²

1 Laminate 2 Member 3 Barrier layer made of silicon oxide-based plasma CVD film 4 Protective layer made of polymer-deposited film of paraxylylene-based compound 5 Plasma-treated surface 6 Organic silane compound layer 41 Upper plasma electrode 42 Lower plasma electrode

Claims (21)

A barrier layer made of an ALD inorganic vapor-deposited film and a protective layer made of a polymer-deposited film of a paraxylylene-based compound are laminated in this order on the surface of the member by in-line treatment in the same vapor-film deposition chamber to provide stress resistance. A method for producing a stress-resistant barrier laminate, which comprises producing a barrier laminate.
A plasma-treated surface is formed on the surface of the member by plasma treatment using a gas containing 10% by volume or more and 100% by volume or less of oxygen.
The barrier layer is subjected to an oxide or nitride of one or more elements selected from the group consisting of Al, Si, Ti, Nb, Ta, Hf, Zr, and Zn by an atomic volume deposition method (ALD method). The ALD inorganic vapor deposition film containing an object is formed by laminating one layer or two or more layers.
A method for producing a stress-resistant barrier laminate, which comprises laminating the protective layer on the outermost surface of the barrier laminate. The surface of the barrier layer on the protective layer side is plasma-treated with a gas containing 10% by volume or more and 100% by volume or less of oxygen to form a plasma-treated surface.
The method for producing a stress-resistant barrier laminate according to claim 1. The ALD inorganic vapor deposition film is formed from a gas containing an organometallic compound of one or more elements selected from the group consisting of Al, Si, Ti, Nb, Ta, Hf, Zr, and Zn. Characteristic,
The method for producing a stress-resistant barrier laminate according to claim 1 or 2. The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 3, wherein the protective layer is laminated by a method including the following steps 1 to 3.
Step 1) A step of introducing the paraxylylene compound into a vaporization chamber and vaporizing at 100 to 160 ° C.
Step 2) A step of radicalizing the vaporized paraxylylene-based compound at 600 to 690 ° C. in a pyrolysis chamber furnace.
Step 3) The radicalized paraxylylene-based compound was introduced at 20 to 40 μbar into a vapor deposition chamber reduced to 5 to 15 μbar at 20 to 35 ° C., and the surface of the vapor deposition object separately introduced into the vapor deposition chamber was introduced. A step of laminating the protective layer by vapor deposition and polymerization while maintaining the surface temperature of the vapor deposition object at 20 to 90 ° C. The barrier layer and the protective layer are alternately laminated in two or more layers.
The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 4. The surface of the barrier layer on the protective layer side is plasma-treated to form a plasma-treated surface.
The method for producing a barrier laminate according to any one of claims 1 to 4. The plasma-treated surface is treated by a reactive ion etching method or a direct plasma method plasma treatment under a pressure of 1 to 100 Pa, using a mixed gas of oxygen and an inert gas as a plasma raw material gas, and having a plasma output of 10 to 500 W. The method for producing a stress-resistant barrier laminate according to claim 6, wherein the barrier laminate is formed in a time of 5 to 500 seconds. It was formed from a composition containing an organic silicon compound having a polymerizable functional group containing a carbon-carbon double bond and an alkoxy group and / or a silanol group between the barrier layer and the protective layer. It is characterized by laminating an adhesion promoting layer composed of a vapor-deposited film.
The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 7. The polymerizable functional group containing a carbon-carbon double bond is one or more selected from the group consisting of a (meth) acrylic group, a vinyl group, and an allyl group.
The method for producing a stress-resistant barrier laminate according to claim 8. The paraxylylene-based compound is characterized by containing a compound represented by the following formula.
The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 9.

(In the formula, R is a hydrogen atom or a fluorine atom, X is a halogen atom, and n is a number having an average value of 0 to 4.) The paraxylylene-based compound is characterized by containing a compound represented by the following formula.
The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 10.

The paraxylylene-based compound is characterized by containing a compound represented by the following formula.
The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 11.

The stress resistance according to any one of claims 1 to 12, characterized in that the oxygen permeability of the barrier laminate when not boiled is 1 cc / m ² / day / atm or less. A method for manufacturing a barrier laminate. The one according to any one of claims 1 to 13, wherein the oxygen permeability of the barrier laminate after boiling at 100 ° C. for 20 minutes is 1 cc / m ² / day / atm or less. , A method for manufacturing a stress-resistant barrier laminate. The barrier laminate has a water vapor permeability of 1 g / m ² / day or less when not boiled.
The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 14. The barrier laminate has a water vapor transmittance of 1 g / m ² / day or less after boiling at 100 ° C. for 20 minutes.
The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 15. The member is one selected from the group consisting of a resin film, a packaging bag made of a resin film, a resin molded product, a medical device, an electronic component, an electric component, and a circuit board.
The method for producing a stress-resistant barrier laminate according to any one of claims 1 to 16. A stress-resistant barrier packaging, wherein the member is a resin film, and a barrier packaging material is produced from a barrier laminate produced by the production method according to any one of claims 1 to 16. How to make the material. A method for producing a stress-resistant barrier packaging bag, which comprises producing a barrier packaging bag from the barrier packaging material produced by the production method according to claim 18. A stress-resistant barrier, wherein the member is a laminate tube precursor, and a laminate tube is produced from a barrier laminate produced by the production method according to any one of claims 1 to 16. Manufacturing method of laminated tube. A drug, wherein the member is a resin syringe syringe portion, and the resin syringe syringe portion is produced from a barrier laminate produced by the production method according to any one of claims 1 to 16. A method for manufacturing a stress-resistant barrier syringe for a filled syringe.

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