CN120603711A - Laminated body, method for producing laminated body, and polarizing plate with gas barrier layer - Google Patents
Laminated body, method for producing laminated body, and polarizing plate with gas barrier layerInfo
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- CN120603711A CN120603711A CN202480008118.0A CN202480008118A CN120603711A CN 120603711 A CN120603711 A CN 120603711A CN 202480008118 A CN202480008118 A CN 202480008118A CN 120603711 A CN120603711 A CN 120603711A
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- barrier layer
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- oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/42—Silicides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/02—Metal coatings
- D21H19/08—Metal coatings applied as vapour, e.g. in vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
层叠体1a具备基材2和阻气层3。阻气层3形成于基材2上，且含有硅、碳和氧。阻气层3在阻气层3的厚度方向上朝向基材2依次包含层状的第一部位3a、层状的第二部位3b和层状的第三部位3c。第一部位3a和第三部位3c中的碳的原子数基准的含量相对于硅、碳和氧的原子数基准的含量和之比R1为0.1％～20％。第二部位3b中的比R1小于0.1％。
The laminate 1a includes a substrate 2 and a gas barrier layer 3. The gas barrier layer 3 is formed on the substrate 2 and contains silicon, carbon, and oxygen. The gas barrier layer 3 includes, in order from the thickness of the gas barrier layer 3 toward the substrate 2, a layered first portion 3a, a layered second portion 3b, and a layered third portion 3c. The ratio R1 of the carbon content based on the number of atoms in the first portion 3a and the third portion 3c to the sum of the contents based on the number of atoms of silicon, carbon, and oxygen is 0.1% to 20%. The ratio R1 in the second portion 3b is less than 0.1%.
Description
Technical Field
The present invention relates to a laminate, a method for producing the laminate, and a polarizing plate with a gas barrier layer.
Background
Conventionally, as a laminate having gas barrier properties, a laminate having a thin film layer formed on a substrate including a layer containing silicon, oxygen, and carbon has been known.
For example, patent document 1 describes a gas barrier laminated film comprising a substrate and at least 1 film layer formed on at least a single surface of the substrate. At least 1 of the thin film layers contains silicon, oxygen, and carbon. The silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, which respectively show the relationship between the distance from the surface in the film thickness direction of the layer and the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon, satisfy predetermined conditions. This demonstrates that the gas barrier laminated film has sufficient gas barrier properties, and can sufficiently suppress the decrease in the gas barrier properties even when the film is bent. In patent document 1, the water vapor permeability of a sample is evaluated in order to confirm the gas barrier properties.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2011-73430
Disclosure of Invention
Problems to be solved by the invention
The carbon distribution curve of the gas barrier laminated film described in patent document 1 is understood to have a maximum value because the atomic ratio of carbon is relatively high at a predetermined position in the thickness direction of the layer containing silicon, oxygen, and carbon.
In view of such circumstances, the present invention provides a novel laminate which is advantageous from the standpoint of gas barrier properties.
Solution for solving the problem
The present invention provides a laminate comprising a substrate and a gas barrier layer formed on the substrate, wherein the gas barrier layer contains silicon, carbon and oxygen,
The gas barrier layer includes a layered first portion, a layered second portion, and a layered third portion in this order toward the base material in the thickness direction of the gas barrier layer,
The ratio of the content of the atomic number reference of carbon in the first and third sites to the sum of the contents of the atomic number references of silicon, carbon and oxygen is 0.1% -20%,
The ratio of the content of the atomic number reference of carbon in the second site to the sum of the contents of the atomic number references of silicon, carbon and oxygen is less than 0.1%.
The present invention also provides a laminate comprising a substrate and a gas barrier layer formed on the substrate, wherein the gas barrier layer contains silicon, carbon and oxygen,
The gas barrier layer includes a portion in which the ratio of the content of the atomic number reference of carbon to the sum of the contents of the atomic number references of silicon, carbon and oxygen is less than 0.1% in a region in which the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer is 5% -95% with respect to the thickness of the gas barrier layer.
The present invention also provides a method for producing the laminate, comprising:
an organosilicon compound and oxygen are supplied between a pair of rollers facing each other, and a gas barrier layer is formed on a substrate transported by the pair of rollers by a chemical vapor deposition method.
The present invention also provides a polarizing plate with a gas barrier layer, comprising the laminate and a polarizing material.
ADVANTAGEOUS EFFECTS OF INVENTION
The laminate is a novel laminate which is advantageous from the viewpoint of exhibiting gas barrier properties.
Drawings
Fig. 1A is a cross-sectional view showing an example of a laminate.
Fig. 1B is a cross-sectional view showing another example of the laminate.
Fig. 2 is a schematic diagram illustrating an example of a method for producing a laminate.
Fig. 3 is a cross-sectional view showing another example of the laminate.
Fig. 4 is a cross-sectional view showing an example of a polarizing plate with a gas barrier layer.
Fig. 5A is a graph showing the relationship between the ratio of the content of the atomic number reference of carbon to the sum of the contents of the atomic number references of carbon, silicon and oxygen and the ratio of the distance from the film surface to the film thickness in the sample described in example 1.
Fig. 5B is a graph showing the relationship between the ratio of the content of the atomic number reference of carbon to the sum of the content of the atomic number references of carbon, silicon and oxygen and the ratio of the distance from the film surface to the film thickness in the sample described in example 2.
Fig. 6A is a graph showing the relationship between the ratio of the sum of the content of atomic number references of carbon to the content of atomic number references of carbon, silicon and oxygen to the ratio of the distance from the film surface to the film thickness in the sample described in comparative example 1.
Fig. 6B is a graph showing the relationship between the ratio of the sum of the content of atomic number references of carbon to the content of atomic number references of carbon, silicon and oxygen and the ratio of the distance from the film surface to the film thickness in the sample described in comparative example 2.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is described below by way of example, and the present invention is not limited to the following embodiments.
As shown in fig. 1A, the laminate 1A includes a base material 2 and a gas barrier layer 3. The gas barrier layer 3 is formed on the substrate 2 and contains silicon, carbon, and oxygen. The gas barrier layer 3 includes a layered first portion 3a, a layered second portion 3b, and a layered third portion 3c in this order toward the base material 2 in the thickness direction of the gas barrier layer 3. The ratio R1 of the sum of the atomic number reference contents of carbon in the first part 3a and the third part 3c to the atomic number reference contents of silicon, carbon and oxygen is 0.1% to 20%. On the other hand, the ratio R1 in the second portion 3b is less than 0.1%. The ratio R1 is determined according to the result of depth analysis by, for example, X-ray Electron Spectroscopy (ESCA).
The gas barrier laminated film described in patent document 1 satisfies the condition that the carbon distribution curve has at least 1 extremum and the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 atomic% or more. For example, according to the carbon distribution curve of the gas barrier laminated film of example 1 of patent document 1, a maximum of about 20 atomic% was confirmed at a distance of around 90nm and around 200nm from the surface of the film layer. On the other hand, according to the studies by the present inventors, it has been found that a desired gas barrier property can be exhibited by making a gas barrier layer containing silicon, carbon and oxygen satisfy the following conditions.
There are lamellar sites within the layer that are less than 0.1% of R1.
The layer portions having a ratio R1 of less than 0.1% in the layer are present between a pair of layer portions having a ratio R1 of 0.1% to 20% in the thickness direction.
The ratio R1 is a value at a specific position in the thickness direction of the gas barrier layer 3. The ratio R1 is 0.1% to 20% in the entire thickness direction of the first portion 3a and the third portion 3 c. The ratio R1 is less than 0.1% in the entire thickness direction of the second portion 3 b.
As shown in fig. 1A, for example, the first portion 3a, the second portion 3b, and the third portion 3c are continuously present in the thickness direction of the gas barrier layer 3.
The ratio R1 in one end of the first portion 3a adjacent to the second portion 3b in the thickness direction of the gas barrier layer 3 is lower than the ratio R1 in the other end of the first portion 3a in the thickness direction of the gas barrier layer 3. The ratio R1 in the other end in the thickness direction of the first portion 3a may be the largest in the first portion 3 a. The ratio R1 in one end of the third portion 3c adjacent to the second portion 3b in the thickness direction of the gas barrier layer 3 is lower than the ratio R1 in the other end of the third portion 3c in the thickness direction of the gas barrier layer 3. The ratio R1 in the other end in the thickness direction of the third portion 3c may be the largest in the third portion 3 c.
The ratio R2 of the content of the atomic number reference of silicon to the sum of the contents of the atomic number references of silicon, carbon and oxygen in each of the first portion 3a, the second portion 3b and the third portion 3c is not limited to a specific value. The ratio R2 in each of the first portion 3a, the second portion 3b, and the third portion 3c is, for example, 28.0% to 38.0%. The ratio R3 of the content of the atomic number reference of oxygen to the sum of the contents of the atomic number references of silicon, carbon and oxygen in each of the first portion 3a, the second portion 3b and the third portion 3c is not limited to a specific value. The ratio R3 in each of the first portion 3a, the second portion 3b, and the third portion 3c is, for example, 42.0% to 72.0%. With this structure, the laminated body 1a can more easily exhibit desired gas barrier properties.
In the laminated body 1a, the ratio r1 of the thickness of the first portion 3a to the thickness of the gas barrier layer 3 is not limited to a specific value. The ratio r1 is, for example, 1% to 49%, and may be 1% to 40% or 1% to 20%.
In the laminated body 1a, the ratio r2 of the thickness of the second portion 3b to the thickness of the gas barrier layer 3 is not limited to a specific value. The ratio r2 is, for example, 2 to 98%, and may be 5 to 98% or 5 to 60%.
In the laminated body 1a, the ratio r3 of the thickness of the third portion 3c to the thickness of the gas barrier layer 3 is not limited to a specific value. The ratio r3 is, for example, 1% to 49%, and may be 1% to 40% or 1% to 20%.
As shown in fig. 1A, the first portion 3a forms, for example, a surface 3s of the gas barrier layer 3. The third portion 3c is, for example, adjacent to the substrate 2.
The laminate 1B shown in fig. 1B may also be provided. The laminate 1b includes a base material 2 and a gas barrier layer 3. The gas barrier layer 3 is formed on the substrate 2 and contains silicon, carbon, and oxygen. The gas barrier layer 3 includes a region 3d in the region 3 p. The region 3p is a region in which the distance from the surface 3s of the gas barrier layer 3 in the thickness direction of the gas barrier layer 3 is 5% to 95% with respect to the thickness of the gas barrier layer 3. As shown in fig. 1B, the region 3p is defined between a plane corresponding to the distance D 5 and a plane corresponding to the distance D 95 to the inside of the gas barrier layer 3. The distance D 5 is a distance from the surface 3s of the gas barrier layer 3 corresponding to 5% of the thickness of the gas barrier layer 3. The distance D 95 is a distance from the surface 3s of the gas barrier layer 3 corresponding to 95% of the thickness of the gas barrier layer 3. At position 3d, the ratio R1 is less than 0.1%. According to the studies by the present inventors, it has been found that a desired gas barrier property can be exhibited by providing a region 3d having less than 0.1% of R1 in the region 3p inside the gas barrier layer 3 in the gas barrier layer containing silicon, carbon and oxygen.
The gas barrier layer 3 may include the site 3D in a region determined to correspond to any one selected from the group consisting of the distance D 5, the distance D 10, the distance D 15, and the distance D 20, and a plane corresponding to any one selected from the group consisting of the distance D 95, the distance D 90, the distance D 85, and the distance D 80. The distances D 10, D 15, D 20, D 90, D 85, and D 80 are distances from the surface 3s of the gas barrier layer 3 corresponding to 10%, 15%, 20%, 90%, 85%, and 80% of the thickness of the gas barrier layer 3, respectively.
The site 3d is, for example, a lamellar site. The ratio r4 of the thickness of the portion 3d to the thickness of the gas barrier layer 3 is not limited to a specific value. The ratio r4 may be, for example, 2% to 98%,5% to 79%, 10% to 79%, 15% to 79%, 20% to 79%, 25% to 79%, 30% to 79%, 40% to 79%, 50% to 79%, or 62% to 79%.
In the gas barrier layer 3 of the laminate 1b, the ratio R1 in the portions other than the portion 3d is, for example, 0.1% to 20%. With this structure, the desired gas barrier property can be more easily exhibited.
In the laminate 1a or 1b, the base material 2 is not limited to a specific base material. The substrate 2 is, for example, a film or sheet having insulation properties. The substrate 2 may be a film or sheet containing an organic polymer, or may be paper. When the substrate 2 is a film or sheet containing an organic polymer, examples of the material of the substrate 2 include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin resins such as Polyethylene (PE), polypropylene (PP) and cyclic polyolefin, polyether Sulfone (PEs), polyamide resins, polycarbonate resins, polystyrene resins, polyvinyl alcohol resins, saponified products of ethylene-vinyl acetate copolymers, polyacrylonitrile resins, acetal resins and polyimide resins.
The thickness of the base material 2 is not limited to a specific value. The thickness of the base material 2 is, for example, 5 μm or more and 500 μm or less. The thickness of the base material 2 may be 50 μm or more and 300 μm or less, and may be 50 μm or more and 200 μm or less.
In the laminate 1a or 1b, the thickness of the gas barrier layer 3 is not limited to a specific value. The thickness is, for example, 1nm to 1000nm, may be 5nm to 500nm or 30nm to 300nm.
In the laminate 1a or 1b, the gas barrier layer 3 is, for example, a CVD layer. Thus, the laminated body 1a more easily exhibits desired gas barrier properties.
The water vapor permeability of the laminate 1a or 1b is not limited to a specific value. The laminate 1a or 1b has a water vapor transmission rate of, for example, 0.10 g/(m 2 -24 h) or less. The water vapor permeability was measured in accordance with Japanese Industrial Standard (JIS) K7129-4:2019 under conditions of a temperature of 40 ℃, a humidity of 0% RH in the low humidity chamber and a humidity of 90% RH in the high humidity chamber. The water vapor permeability of the laminate 1a or 1b is preferably 0.05 g/(m 2 ·24 h) or less, more preferably 0.02 g/(m 2 ·24 h) or less.
In the laminate 1a or 1b, the arithmetic average roughness Ra of the surface 3s of the gas barrier layer 3 is not limited to a specific value. The surface 3s has an arithmetic average roughness Ra of, for example, 0.1nm to 2.0nm. With this structure, the desired gas barrier property can be more easily exhibited. It is considered that when the arithmetic average roughness Ra of the surface 3s is small, the surface area of the surface 3s tends to be small, and the gas component adsorbed to the gas barrier layer 3 tends to be small. Further, it is considered that when the arithmetic average roughness Ra of the surface 3s is small, pinholes in the gas barrier layer 3 are small, and local permeation of the gas component is less likely to occur. The arithmetic average roughness Ra of the surface 3s can be determined in accordance with Japanese Industrial Standard (JIS) B0601:2001 using, for example, a roughness curve obtained by observation of the surface 3s based on an Atomic Force Microscope (AFM). The arithmetic average roughness Ra of the surface 3s is desirably 0.1nm to 1.0nm, more desirably 0.1nm to 0.5nm.
The method of manufacturing the laminate 1a or 1b is not limited to a specific method. The method for producing the laminate 1a or 1b includes, for example, supplying an organosilicon compound and oxygen between a pair of rollers facing each other, and forming a gas barrier layer 3 on a substrate 2 conveyed by the pair of rollers by a chemical vapor deposition method. According to this method, the laminate 1a or 1b can be continuously produced, and the laminate 1a or 1b can be easily mass-produced.
As shown in fig. 2, the laminate 1a or 1b is manufactured by, for example, the manufacturing apparatus 100. The manufacturing apparatus 100 includes a first roller 11 and a second roller 12 as the pair of rollers. The manufacturing apparatus 100 includes, for example, a first magnetic field generator 21, a second magnetic field generator 22, a first gas supply port 31, and a second gas supply port 32. The first roller 11 and the second roller 12 are disposed such that a first axis x1, which is an axis of the first roller 11, is parallel to a second axis x2, which is an axis of the second roller 12. The first magnetic field generator 21 is disposed inside the first roller 11, and generates a magnetic field between the first roller 11 and the second roller 12. The second magnetic field generator 22 is disposed inside the second roller 12, and generates a magnetic field between the second roller 12 and the first roller 11. The first gas supply port 31 supplies gas between the first roller 11 and the second roller 12. The second gas supply port 32 supplies gas between the first roller 11 and the second roller 12. The first gas supply port 31 and the second gas supply port 32 are disposed on opposite sides with respect to the plane P1 in a direction perpendicular to the plane P1. The plane P1 is a plane having the first axis x1 and the second axis x2 as ends.
As shown in fig. 2, the manufacturing apparatus 100 includes, for example, a power supply 70. One electrode of the power supply 70 is connected to the first roller 11, and the other electrode of the power supply 70 is connected to the second roller 12. A high-frequency ac or pulse-like voltage is applied to the first roller 11 and the second roller 12 by the power supply 70. Thereby, glow discharge occurs between the first roller 11 and the second roller 12, and plasma is generated.
The magnetic field is formed by the first magnetic field generator 21 such that magnetic lines of force extend from a specific position inside the first roller 11 across the surface of the first roller 11 to other positions inside the first roller 11, for example. The magnetic field is formed by the second magnetic field generator 22 such that magnetic lines of force extend from a specific position inside the second roller 12 across the surface of the second roller 12 to other positions inside the second roller 12. These magnetic fields may be formed along the axis x1 and the axis x2 between the first roller 11 and the second roller 12. The plasma generated by glow discharge between the first roller 11 and the second roller 12 can be converged between the first roller 11 and the second roller 12 toward the vicinity of the surface of the first roller 11 and the vicinity of the surface of the second roller 12 by the magnetic fields generated by the first magnetic field generator 21 and the second magnetic field generator 22.
As shown in fig. 2, the substrate 2 can be continuously conveyed by rotating the first roller 11 and the second roller 12. The manufacturing apparatus 100 further includes, for example, a conveying roller 13 and a conveying roller 14. The conveying roller 13 and the conveying roller 14 are disposed such that these axes are parallel, for example. The plane having the axes of the conveying roller 13 and the conveying roller 14 as the end portions is parallel to the plane P1. The substrate 2 is conveyed by the rotation of the conveying roller 13 and the conveying roller 14 while the first roller 11 and the second roller 12 are rotated.
As described above, the gas is supplied from the first gas supply port 31 and the second gas supply port 32 to between the first roller 11 and the second roller 12. Plasma CVD is performed by interaction of plasma generated between the first roller 11 and the second roller 12 in the vicinity of the surface of the first roller 11 and the vicinity of the surface of the second roller 12 with the gas supplied from the first gas supply port 31 and the second gas supply port 32. As a result, the gas barrier layer 3 derived from the gas supplied from the first gas supply port 31 and the second gas supply port 32 is formed on the surface of the substrate 2 passing between the first roller 11 and the second roller 12.
The gas supplied from the first gas supply port 31 and the second gas supply port 32 contains an organosilicon compound and oxygen. Therefore, the gas barrier layer 3 contains silicon, carbon, and oxygen.
The organosilicon compound is not limited to a specific organosilicon compound. Examples of organosilicon compounds are Hexamethyldisiloxane (HMDSO), 1, 3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane and octamethylcyclotetrasiloxane.
From various viewpoints, the laminate 1a or 1b may be changed. The laminate 1a or 1b may be modified as in the laminate 1c shown in fig. 3, for example. The laminate 1c is configured in the same manner as the laminate 1a or 1b except for the portions specifically described. The same reference numerals are given to the constituent elements of the laminated body 1c corresponding to the constituent elements of the laminated body 1a or 1b, and detailed description thereof will be omitted. The description of the laminate 1a or 1b is applicable to the laminate 1c as long as it is not technically contradictory.
As shown in fig. 3, the laminate 1c further includes an adhesive layer 4. In the laminate 1c, the base material 2 is disposed between the gas barrier layer 3 and the adhesive layer 4 in the thickness direction of the gas barrier layer 3. According to this structure, the laminate 1c can be attached to another article by bringing the adhesive layer 4 into contact with the other article.
The adhesive layer 4 is not limited to a specific adhesive layer. The adhesive layer 4 is, for example, an acrylic adhesive, a silicone adhesive, or a rubber adhesive.
The thickness of the adhesive layer 4 is not limited to a specific value. The thickness is, for example, 1 μm to 1000 μm.
The use of the laminate 1a, 1b, or 1c is not limited to a specific use. For example, as shown in fig. 4, the laminate 1c may be used to provide a polarizing plate 6 with a gas barrier layer. The polarizing plate 6 with a gas barrier layer includes a laminate 1c and a polarizer 5. With this structure, the polarizer 5 can be protected by the gas barrier property of the laminate 1 c.
As shown in fig. 4, in the polarizing plate 6 with a gas barrier layer, for example, a polarizer 5 is disposed between the pair of laminated bodies 1 c. For example, in the polarizing plate 6 with the gas barrier layer, the adhesive layer 4 of the laminate 1c contacts the polarizer 5.
The polarizer 5 is not limited to a specific polarizer. The polarizer 5 is, for example, a resin polarizer. Examples of the polarizing material made of resin include a polarizing material obtained by subjecting a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene-vinyl acetate copolymer partially saponified film to a dyeing treatment and a stretching treatment with a dichroic material such as iodine or a dichroic dye, and a polyvinyl alcohol-dehydrated product and a polyvinyl chloride-desalted product-oriented film. The polarizer 5 is preferably a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching the film.
The thickness of the polarizer 5 is not limited to a specific value. The thickness of the polarizer 5 is, for example, 0.5 μm to 80 μm, and may be 70 μm or less, 50 μm or less, or 40 μm or less.
The laminate 1a, 1b, or 1c can be used for protecting optical elements other than polarizers, electronic devices, foods, medicines, and the like.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. First, an evaluation method for each sample will be described.
(Measurement of elemental composition in the thickness direction)
For each sample, the content of silicon, carbon, and oxygen in the atomic number standard of the film formed on the substrate in the thickness direction was measured by performing a depth analysis by an X-ray Electron Spectroscopy (ESCA) under the following conditions. The measurement results of the samples described in example 1 are shown in fig. 5A, and the measurement results of the samples described in comparative example 1 are shown in fig. 5B.
Etching ion species argon ion (Ar +)
The etching rate of the thermal oxide film converted to SiO 2 was 4/60 nm/sec
An etching interval of 5nm in terms of SiO 2
Quantera SXM manufactured by ALVAC PHI Co., ltd
Irradiation of X-rays, monochromatic Al K alpha
Shape and size of spot of X-ray, circular shape, diameter 100 μm
(Measurement of arithmetic average roughness Ra)
The roughness profile of the surface of the film formed on the substrate of each sample was measured using AFM5500M manufactured by hitachi high new science co. From this roughness curve, the arithmetic average roughness Ra of the surface of the film formed on the substrate of each sample was determined in accordance with JIS B0601:2001. The results are shown in Table 1.
(Measurement of WVTR)
The WVTR of each sample was measured in accordance with JIS K7129-4:2019 using a water vapor transmittance measuring device PERMATRAN-W model3/34 manufactured by mocon. The measurement was performed in an environment at a temperature of 40 ℃, the humidity in the low humidity chamber was adjusted to 0% rh, and the humidity in the high humidity chamber was adjusted to 90% rh. Each sample was configured in such a way that the substrate contacted the low humidity chamber. The results are shown in Table 1.
Example 1 ]
Using a plasma CVD apparatus shown in fig. 2, a substrate, which is a PET film having a thickness of 50 μm, was subjected to plasma CVD while being conveyed, to obtain a sample of example 1 in which a film was formed on the substrate. The thickness of the film was about 200nm. HMDSO as a material gas is supplied from the first gas supply port 31 and the second gas supply port 32, and oxygen is supplied as a reactive gas. The conditions of plasma CVD were adjusted as follows. The distance between the second gas supply port 32 and the plane P1 in the direction perpendicular to the plane P1 is equal to the distance between the first gas supply port 31 and the plane P1 in the direction perpendicular to the plane P1.
Flow rate of material gas in the first gas supply port 31 is 5sccm (Standard cube CENTIMETER PER minutes)
The flow rate of the reactive gas in the first gas supply port 31 was 140sccm
Flow rate of the material gas in the second gas supply port 32 is 20sccm
Flow rate of the reactive gas in the second gas supply port 32 is 560sccm
The vacuum degree of the interior of the plasma CVD apparatus was about 1Pa
The applied power from the power supply 70 was 0.5kW
The frequency of the alternating voltage generated by the power supply 70 is 80kHz
The transport speed of the substrate was 0.2 m/min
Example 2 ]
The same procedure as in example 1 was repeated except that the conditions of plasma CVD were changed as described below to obtain samples as described in example 2.
Flow rate of the material gas in the first gas supply port 31 is 10sccm
The flow rate of the reactive gas in the first gas supply port 31 was 140sccm
Flow rate of the material gas in the second gas supply port 32 is 40sccm
Flow rate of the reactive gas in the second gas supply port 32 is 560sccm
The vacuum degree of the interior of the plasma CVD apparatus was about 1Pa
The applied power from the power supply 70 was 0.6kW
The frequency of the alternating voltage generated by the power supply 70 is 80kHz
The transport speed of the substrate was 0.3 m/min
Comparative example 1 ]
The sample of comparative example 1 was obtained in the same manner as in example 1 except that the conditions of plasma CVD were changed as follows. In comparative example 1, only the gas for film formation was supplied from the first gas supply port 31. The thickness of the film was about 200nm.
Flow rate of the material gas in the first gas supply port 31 is 25sccm
The flow rate of the reactive gas in the first gas supply port 31 was 700sccm
The flow rate of the material gas in the second gas supply port 32 was 0sccm
The flow rate of the reactive gas in the second gas supply port 32 was 0sccm
The vacuum degree of the interior of the plasma CVD apparatus was about 1Pa
The applied power from the power supply 70 is 1.0kW
The frequency of the alternating voltage generated by the power supply 70 is 80kHz
The transport speed of the substrate was 0.5 m/min
Comparative example 2 ]
The same procedure as in example 2 was repeated except that the conditions of plasma CVD were changed as described below to obtain samples as described in comparative example 2. In comparative example 2, only the gas for film formation was supplied from the first gas supply port 31.
The flow rate of the material gas in the first gas supply port 31 was 50sccm
The flow rate of the reactive gas in the first gas supply port 31 was 700sccm
The flow rate of the material gas in the second gas supply port 32 was 0sccm
The flow rate of the reactive gas in the second gas supply port 32 was 0sccm
The vacuum degree of the interior of the plasma CVD apparatus was about 1Pa
The applied power from the power supply 70 was 1.5kW
The frequency of the alternating voltage generated by the power supply 70 is 80kHz
The transport speed of the substrate was 1.0 m/min
As shown in FIGS. 5A and 5B, it is suggested that the films of the samples of examples 1 and 2 have layered sites a, B and c in this order from the surface of the film. In the parts a and c, the ratio of the content of the atomic number reference of carbon to the sum of the contents of the atomic number references of carbon, silicon and oxygen is 0.1% -20%. On the other hand, in the portion b, the ratio is less than 0.1%. In the film of the sample of example 1, the portion b is present in a region in which the distance from the surface of the film in the thickness direction of the film is 5% to 95% with respect to the thickness of the film, more specifically, in a region of 11% to 89%. In the film of the sample of example 1, the ratio of the thickness of the portion a to the thickness of the film was 11%, the ratio of the thickness of the portion b to the thickness of the film was 78%, and the ratio of the thickness of the portion c to the thickness of the film was 11%. In the film of the sample of example 2, the portion b is present in a region in which the distance from the surface of the film in the thickness direction of the film is 5% to 95% with respect to the thickness of the film, more specifically, in a region of 17% to 76%. In the film of the sample of example 2, the ratio of the thickness of the portion a to the thickness of the film was 17%, the ratio of the thickness of the portion b to the thickness of the film was 59%, and the ratio of the thickness of the portion c to the thickness of the film was 24%.
As shown in fig. 6A and 6B, in the films of the samples of comparative examples 1 and 2, there was a portion in the film in the thickness direction where the ratio of the content of the atomic number reference of carbon to the sum of the contents of the atomic number references of carbon, silicon and oxygen showed the maximum.
As shown in table 1, the WVTR of the samples described in examples 1 and 2 was smaller than that of the samples described in comparative examples 1 and 2. From comparison of examples 1 and 2 with comparative examples 1 and 2, it is considered that in the films of the samples of examples 1 and 2, layered sites a, sites b and sites c exist in this order from the surface of the film, or sites b exist in the region where the distance from the surface of the film in the thickness direction of the film is 5% to 95% with respect to the thickness of the film, whereby the gas barrier properties of the films of the samples of examples 1 and 2 become high and the WVTR of the samples of examples 1 and 2 becomes low.
TABLE 1
A first aspect of the present invention provides a laminate comprising a substrate and a gas barrier layer formed on the substrate, wherein the gas barrier layer contains silicon, carbon, and oxygen,
The gas barrier layer includes a layered first portion, a layered second portion, and a layered third portion in this order toward the base material in the thickness direction of the gas barrier layer,
The ratio of the content of the atomic number reference of carbon in the first and third sites to the sum of the contents of the atomic number references of silicon, carbon and oxygen is 0.1% -20%,
The ratio of the content of the atomic number reference of carbon in the second site to the sum of the contents of the atomic number references of silicon, carbon and oxygen is less than 0.1%.
The second side of the present invention provides a laminate comprising a substrate and a gas barrier layer formed on the substrate, wherein the gas barrier layer contains silicon, carbon and oxygen,
The gas barrier layer includes a portion in which the ratio of the content of the atomic number reference of carbon to the sum of the contents of the atomic number references of silicon, carbon and oxygen is less than 0.1% in a region in which the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer is 5% -95% with respect to the thickness of the gas barrier layer.
A third aspect of the present invention provides the laminate of the first aspect, wherein,
The ratio of the content of the atomic number reference of silicon to the sum of the contents of the atomic number references of silicon, carbon and oxygen in each of the first, second and third portions is 28.0% -38.0%,
The ratio of the atomic number reference content of oxygen to the sum of the atomic number reference contents of silicon, carbon and oxygen in each of the first, second and third sites is 42.0% -72.0%.
A fourth side of the present invention provides the laminate according to any one of the first to third sides, wherein the gas barrier layer is a CVD layer.
A fifth aspect of the present invention provides the laminate according to any one of the first to fourth aspects, wherein the laminate has a water vapor transmission rate of 0.10 g/(m 2. 24 h) or less,
The water vapor permeability was measured in accordance with Japanese Industrial Standard (JIS) K7129-4:2019 under conditions of a temperature of 40 ℃, a humidity of 0% RH in the low humidity chamber and a humidity of 90% RH in the high humidity chamber.
The seventh side of the present invention provides the laminate according to any one of the first to fifth sides, wherein the surface of the gas barrier layer has an arithmetic average roughness of 0.1 to 2.0 nm.
The seventh side of the present invention provides the laminate according to any one of the first to sixth sides, further comprising an adhesive layer,
The base material is disposed between the gas barrier layer and the adhesive layer in the thickness direction of the gas barrier layer.
An eighth side of the present invention provides the method for producing a laminate according to any one of the first to seventh sides, comprising:
an organosilicon compound and oxygen are supplied between a pair of rollers facing each other, and a gas barrier layer is formed on a substrate transported by the pair of rollers by a chemical vapor deposition method.
A ninth aspect of the present invention provides a polarizing plate with a gas barrier layer, comprising:
The laminate according to any one of the first side surface to the seventh side surface, and
A polarizing member.
Claims (9)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2023026658 | 2023-02-22 | ||
| JP2023-026658 | 2023-02-22 | ||
| PCT/JP2024/001359 WO2024176674A1 (en) | 2023-02-22 | 2024-01-18 | Laminate, laminate production method, and polarizer with gas-barrier layer |
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| CN120603711A true CN120603711A (en) | 2025-09-05 |
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| CN202480008118.0A Pending CN120603711A (en) | 2023-02-22 | 2024-01-18 | Laminated body, method for producing laminated body, and polarizing plate with gas barrier layer |
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| JP (1) | JPWO2024176674A1 (en) |
| KR (1) | KR20250153205A (en) |
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| WO (1) | WO2024176674A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5513959B2 (en) | 2009-09-01 | 2014-06-04 | 住友化学株式会社 | Gas barrier laminated film |
| WO2012046767A1 (en) * | 2010-10-08 | 2012-04-12 | 住友化学株式会社 | Layered film |
| WO2014123201A1 (en) * | 2013-02-08 | 2014-08-14 | コニカミノルタ株式会社 | Gas barrier film and method for manufacturing same |
| US20140242367A1 (en) * | 2013-02-25 | 2014-08-28 | Au Optronics Corporation | Barrier film and methods of making same |
| JP6007829B2 (en) * | 2013-03-05 | 2016-10-12 | コニカミノルタ株式会社 | Gas barrier film and method for producing gas barrier film |
| JPWO2015182623A1 (en) * | 2014-05-26 | 2017-04-20 | コニカミノルタ株式会社 | Gas barrier film and electronic device using the same |
| JP6342776B2 (en) * | 2014-10-09 | 2018-06-13 | 住友化学株式会社 | Manufacturing method of laminate |
| JP2017119362A (en) * | 2015-12-28 | 2017-07-06 | 凸版印刷株式会社 | Gas barrier film and production method of the same |
| JP7133904B2 (en) * | 2016-03-31 | 2022-09-09 | 住友化学株式会社 | LAMINATED FILM AND METHOD FOR MANUFACTURING THE SAME |
| TWI789351B (en) * | 2016-05-20 | 2023-01-11 | 日商住友化學股份有限公司 | Gas barrier film, optical film, and flexible display |
| WO2018168671A1 (en) * | 2017-03-17 | 2018-09-20 | コニカミノルタ株式会社 | Gas barrier coating, gas barrier film, method for producing gas barrier coating, and method for producing gas barrier film |
| JP2020116942A (en) * | 2019-01-23 | 2020-08-06 | 東レ株式会社 | Laminate |
| US20210032275A1 (en) * | 2019-07-30 | 2021-02-04 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Cyclic germanium silylamido precursors for ge-containing film depositions and methods of using the same |
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| JPWO2024176674A1 (en) | 2024-08-29 |
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