TW201711860A - Laminated film and method for manufacturing same - Google Patents

Abstract

Provided is a laminated polyester film having a polyester layer and a resin layer, wherein the laminated film, in which at least one surface layer is a resin layer, and the resin layer provided as a surface layer has a microsurface roughness (Ra-1) of 1-20 nm, inclusive, as determined by atomic force microscopy (AFM), and a macrosurface roughness (Ra-2) of 1-50 nm, inclusive, as determined by a three-dimensional surface roughness meter, yields exceptional transparency, scratch resistance, and anti-blocking properties.

Description

Laminated film and method of manufacturing same

The present invention relates to a laminated film having a laminated film of a polyester layer and a resin layer, and at least one side of which is a resin layer.

The thermoplastic resin film, in which the biaxially stretched polyester film has excellent properties such as mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance, is widely used in many applications such as magnetic recording materials and packaging materials. use. In particular, in recent years, various optical films have been used for display members such as touch panels, liquid crystal display panels (LCDs), plasma display panels (PDPs), and organic electroluminescence (organic EL).

Many of these optical films are formed by laminating a layer having a different refractive index on a polyester film (hereinafter, an optical adjustment layer), and then a conductive layer is provided as a conductive film. Here, in general, when the optical adjustment layer is laminated, a functional coating agent is applied onto a base film wound in a roll shape to be cured, and then rolled into a roll-like so-called roll to roll. Form processing. Further, the conductive layer is formed by forming a metal oxide film on the roll film by sputtering in a vacuum environment.

For this reason, in such an application, in order to prevent scratches when the film roll is conveyed, a laminated film in which a scratch-resistant layer is laminated on the polyester film is used.

As the laminated film, a hard coat film which is a laminated layer containing a UV curable resin as a scratch resistant layer is used. In the case of being used for optical use, since the transparency is required, the surface of the resin layer is smoothed in order to improve the transparency. However, when the surface of the resin layer is made smooth, adhesion (attachment) occurs when the film roll is formed. . For this reason, a laminated film having adhesive resistance is required in recent years.

Further, in the laminated film used for optical applications, in addition to scratch resistance, adhesion to a substrate, transparency, and the like are required not only at normal temperature but also under high temperature and high humidity. Moreover, since it is often used for the surface of a display, etc., it is required for visibility and designability in the laminated film used for optical use.

In order to meet this requirement, Patent Document 1 proposes a method of reducing the contact area of a hard coat film by laminating a coating film containing particles thicker than a coating film to form an anti-adhesion property. Further, Patent Document 2 proposes a method of obtaining a laminated film excellent in antiglare property and scratch resistance by coating a coating film containing acrylic particles having a thickness smaller than that of a coating film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2014-228833

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-186287

However, in the method described in Patent Document 1, since the particle diameter of the particles existing in the coating layer is large, scattering of light occurs, which is damaged. The issue of transparency. Further, in the method described in Patent Document 2, the particle size of the acrylic particles present in the coating layer having a thickness of 6 to 8 μm is as large as about 2 to 5 μm, and is a region where light is scattered, so that it is required to be high. The optical use of transparency has a problem in terms of transparency.

Therefore, the present invention has been made to provide a laminated film which is excellent in transparency, scratch resistance, and anti-adhesion property, and which solves the above-mentioned disadvantages.

In order to solve the above problems, the laminated film of the present invention has the following constitution.

[I] A laminated film comprising a laminate film of a polyester layer and a resin layer, wherein at least one surface layer is a resin layer, and the surface layer has a resin layer obtained by an AFM (Atomic Force Microscope) microscopic surface The roughness (Ra-1) is 1 nm or more and 20 nm or less, and the macroscopic surface roughness (Ra-2) obtained by a ternary surface roughness meter is 1 nm or more and 50 nm or less.

[II] The laminated film according to [I], wherein the resin layer of the surface layer has a macroscopic surface roughness (Ra-2) determined by a ternary surface roughness meter of 5 nm or more and 50 nm or less.

[III] The laminated film according to [I] or [II], wherein the surface layer has a ratio of a microscopic surface roughness (Ra-1) to a macroscopic surface roughness (Ra-2) of the resin layer (Ra-2/Ra) -1) is 3 or more and 30 or less.

[IV] The laminated film according to any one of [1], wherein the surface layer has a resin layer containing particles, and the surface of the resin layer from the thickness direction of the resin layer is observed to the thickness of the resin layer. The particle presence ratio (P-1) in the range of 10% of the position is greater than that from the surface of the resin layer The particle existence ratio (P-2) in the range of 40% of the thickness of the resin layer to the position of 60%.

[V] The laminated film according to [IV], wherein a ratio of particles (P-1) in a range from a position of the surface of the aforementioned resin layer to a position of 10% of a thickness of the resin layer, and a thickness of the resin layer from the surface of the resin layer The ratio (P-1/P-2) of the particle existence ratio (P-2) in the range from 40% of the position to 60% of the position is 1.1 or more and 5.0 or less.

[VI] The laminated film according to [IV] or [V], wherein the surface layer has a resin layer having a thickness (t) of 100 nm or more and 5000 nm or less.

[VII] The laminated film according to [VI], wherein the resin layer of the surface layer has a particle average particle diameter (d) of 1 nm or more and 100 nm or less, and a thickness (t) of the resin layer and an average particle diameter (d) of the resin layer. The ratio (t)/(d) is 2 or more and 1000 or less.

[VIII] The laminated film according to any one of [I] to [VII], which is formed by directly laminating a polyester layer and a resin layer.

[9] A method for producing a laminated film according to any one of [1] to [VIII], comprising the step of coating a polyfunctional acrylic resin and particles on at least one side of the polyester film before the end of the crystal alignment. Then, the polyester film is stretched in at least a uniaxial direction, and heat treatment is applied to the polyester film to complete the crystal alignment of the polyester film.

The laminated film of the present invention is excellent in transparency, scratch resistance, and adhesion resistance, and can improve conveyability at the film processing step, and can suppress scratches on the film.

[Formation of the Invention]

Hereinafter, the laminated film of the present invention will be described in detail.

The present invention is a laminated film having a laminated film of a polyester layer and a resin layer, wherein at least one surface layer is a resin layer, and the resin layer of the surface layer is obtained by AFM (Atomic Force Microscope) The obtained microscopic surface roughness (Ra-1) is 1 nm or more and 20 nm or less, and the macroscopic surface roughness (Ra-2) obtained by a ternary surface roughness meter is 1 nm or more and 50 nm or less.

The microscopic surface roughness in the present invention means the roughness of the surface of the resin layer in a region of 10 μm × 10 μm measured by AFM (Atomic Force Microscope) manufactured by BRUKER. The microscopic surface roughness is a property that imparts an influence on the transparency and scratch resistance of the resin layer. The details of the measurement method will be described later.

When the microscopic surface roughness of the resin layer in the surface layer of the laminated film is 1 nm or more and 20 nm or less, since the resin layer does not have large unevenness of diverging light, the transparency of the laminated film can be improved. Moreover, since the relationship of the resin layer is small, the scratch resistance can be improved. More preferably, it is 1 nm or more and 15 nm or less. In the method of setting the microscopic surface roughness of the resin layer to be 1 nm or more and 20 nm or less, a curable resin containing an acrylic resin excellent in fluidity is applied to a polyester layer having a microscopic surface roughness of 1 nm or more and 20 nm or less. And hardening the method of forming the resin layer, or by coating comprising containing an average particle diameter of 100 nm or less A method of forming a resin layer by hardening a curable resin of an acrylic resin of a nanoparticle. Among them, a method of applying and curing a curable resin containing an inorganic resin having excellent fluidity and containing nano particles is preferable from the viewpoint of excellent transparency.

The macroscopic surface roughness in the present invention means the roughness of the surface of the resin layer in the region of 400 μm × 900 μm measured using a three-dimensional roughness meter manufactured by Otaru Laboratory. The macroscopic surface roughness is a property that imparts an influence on the adhesion resistance and transparency of the resin layer. The details of the measurement method will be described later.

When the macroscopic surface roughness of the resin layer of the surface layer of the laminated film is in the range of 1 nm or more and 50 nm or less, since the surface of the resin layer has a stable concavo-convex structure, the anti-adhesive property and transparency of the laminated film can be improved. It is preferably 5 nm or more and 50 nm or less, more preferably 5 nm or more and 30 nm or less. In the method of setting the macroscopic surface roughness to 1 nm or more and 50 nm or less, the resin layer is formed by using a curable resin containing an acrylic resin, and the resin layer is made to contain particles having an average particle diameter larger than that of the resin layer. Or a so-called nanoimprint method in which a mold having a concave-convex shape is transferred onto a coating film in which the acrylic resin has not been cured, and then the acrylic resin is hardened to form a resin layer, after coating a curable resin containing an acrylic resin After the application of the curable resin containing the acrylic resin, the resin layer is subjected to the stretching treatment in a state where the acrylic resin is not yet cured, thereby imparting a fine unevenness in stretching or the like. In particular, after the application of the curable resin containing the acrylic resin, the resin layer is subjected to the stretching treatment in a state where the acrylic resin has not been hardened, and a smooth concave is formed on the surface of the resin layer by fine uneven stretching. The method of the convex structure is preferably from the point of excellent adhesion prevention. Moreover, since it is a smooth concavo-convex structure, scattering of light can be suppressed, and it is preferable from the point which is excellent in transparency.

Further, in the laminated film of the present invention, the ratio (Ra-2/Ra-1) of the microscopic surface roughness (Ra-1) to the macroscopic surface roughness (Ra-2) of the resin layer of the surface layer is 3 or more and 30 or less. , it is better to improve the anti-adhesion. It is preferably 5 or more and 25 or less, more preferably 5 or more and less than 10. The ratio of the surface roughness (Ra-1) to the macroscopic surface roughness (Ra-2) (Ra-2/Ra-1) can be achieved by adjusting the average particle diameter of the particles contained in the resin layer. Specifically, when the average particle diameter of the particles contained in the resin layer is increased, the microscopic surface roughness (Ra-1) and the macroscopic surface roughness (Ra-2) tend to increase together. In particular, since the macroscopic surface roughness (Ra-2) is a surface roughness in a wide field of view, if the average particle diameter of the particles contained in the resin layer is increased, there is a micro surface roughness (Ra-1). The tendency to increase the value.

In addition, the resin layer of the surface layer of the laminated film of the present invention contains particles, and is preferably a particle existence ratio in a range from the surface of the resin layer when the cross section of the resin layer is observed in the thickness direction to 10% of the thickness of the resin layer. (P-1) is larger than the particle existence ratio (P-2) in a range from a position at which the surface of the resin layer is from 40% of the thickness of the resin layer to 60%. By making (P-1) larger than (P-2), the scratch resistance can be improved. When the ratio (P-1/P-2) of (P-1) to (P-2) is 1.1 or more and 5.0 or less, the scratch resistance is particularly preferably improved. More preferably, it is 1.1 or more and 2.0 or less. In the method of making (P-1) larger than (P-2), a method of using particles having a small specific gravity as particles contained in the resin layer, or using fluorine or A method in which particles having a low surface energy component such as polyoxymethylene are modified and the particles are arranged on the air side.

In addition, when the thickness (t) of the resin layer of the surface layer is 100 nm or more, the laminated film of the present invention is excellent in the scratch resistance of the surface layer of the resin layer and is excellent in scratch resistance. The upper limit of the thickness of the resin layer is not limited, but it is preferably 5,000 nm or less in terms of transparency and productivity. Further, it is more preferably 300 nm or more and 3000 nm, and still more preferably 500 nm or more and 1500 nm.

Further, in the laminated film of the present invention, the average particle diameter (d) of the resin layer contained in the surface layer is 1 nm or more and 100 nm or less, and the thickness (t) of the resin layer and the average particle diameter (d) of the nanoparticle. When the ratio (t)/(d) is 2 or more and 1000 or less, the diffusion of light due to the particles is suppressed, and the transparency of the laminated film is improved, which is preferable. More preferably, it is 2 or more and 100 or less. The above range can be achieved by designing the film thickness of the resin layer and the average particle diameter of the particles contained in the resin layer.

[Acrylic]

In the laminated film of the present invention, it is preferred that the resin layer of the surface layer contains an acrylic resin. It is particularly preferable to contain an acrylic resin (A) and/or an acrylic resin (F) and/or an acrylic resin (G) which will be described later. By using the acrylic resin (A) and/or the acrylic resin (F) and/or the acrylic resin (G), transparency can be maintained and the hardness of the surface of the resin layer can be improved. As a result, it is possible to improve the scratch resistance of the laminated film.

The acrylic resin (A) in the present invention is a hardened composition composed of a monomer component (a) having an acrylonitrile group in the molecule. Among them, the monomer component (a) has three or more propylene groups in the molecule. Functional acrylates are preferred. The polyfunctional acrylate is a monomer or oligomer having 3 (more preferably 4, more preferably 5 or more) (meth)acryl fluorenyl groups in one molecule. In the above-mentioned composition, the hydroxyl group having a polyhydric alcohol having three or more alcoholic hydroxyl groups in one molecule and a compound of three or more esters of (meth)acrylic acid are exemplified.

As a specific example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol IV can be used. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate hexane methylene II An isocyanate urethane polymer or the like. These monomers may be used alone or in combination of two or more. In addition, a commercially available polyfunctional acrylic composition is exemplified by Mitsubishi Rayon Co., Ltd.; (trade name "Diabeam" (registered trademark) series), Nagase Industrial Co., Ltd.; (trade name "DENACOL" "(registered trademark) series, etc.), Shin-Nakamura Co., Ltd.; (trade name "NK ESTER" series, etc.), Dainippon Ink Chemical Industry Co., Ltd.; (trade name "UNIDIC" (registered trademark), etc.), East Asia Synthesis Chemical Industry Co., Ltd.; ("ARONIX" (registered trademark) series, etc.), Japan Oil & Fats Co., Ltd.; ("BLEMMER" (registered trademark) series, etc.), Nippon Kayaku Co., Ltd.; (trade name "KAYARAD" ( Registered trademarks, etc.), Kyoeisha Chemical Co., Ltd.; (trade name "LIGHT ESTER" series, etc.), etc., can use such products.

In the present invention, if the acrylic resin (A) obtained by using an acrylic monomer component having a guanamine bond is used as the acrylic resin (A), scratch resistance is obtained. It is better to improve the sex. The reason for this is estimated by the inventors of the present invention. In the case where an oxygen monomer having an acrylonitrile group is hardened in the presence of an oxygen atom in the atmosphere, the radical polymerization reaction of the acrylonitrile group may hinder the reaction due to an oxygen atom in the atmosphere, and as a result, There is a case where the hardening is insufficient and the scratch resistance is deteriorated. In the case where the acrylic monomer component containing an acrylonitrile group has a guanamine bond, it is estimated that an oxygen atom in the atmosphere interacts with a highly polar guanamine bond, so that the propylene sulfhydryl radical is caused by oxygen in the atmosphere. The hardening inhibition of the polymerization reaction is suppressed, and as a result, the acrylic resin continues to be hardened, and the scratch resistance is particularly improved. The acrylic monomer component having a guanamine bond may, for example, be a compound having a structure represented by the following formula (1).

The acrylic resin (F) in the present invention is a resin having a monomer unit (f ₃ ) represented by (Formula 2).

(In the formula 2, the R ₃ group represents a hydrogen atom or a methyl group. Further, the R ₅ group represents a hydroxyl group, a carboxyl group, a tertiary amino group, a 4- to ammonium group, a sulfonic acid group, or a phosphoric acid group)

When an acrylic resin having a monomer unit having an R ₅ group of (Formula 2) and having no hydroxyl group, carboxyl group, tertiary amino group, 4- to ammonium group, sulfonic acid group, or phosphoric acid group is used, The compatibility of the acrylic resin in an aqueous solvent is insufficient, and the acrylic resin (F) is unevenly distributed in the resin composition, and as a result, scratch resistance is deteriorated in a part of the resin layer. Not good.

Further, the inorganic particles (B) to be described later are aggregated or sedimented, or the inorganic particles (B) are aggregated in the drying step, and the pressure on the resin layer is locally enhanced when rubbed, and as a result, the resin layer may be broken to give a flaw. .

Further, since the aggregate is larger than the wavelength of visible light, there is a case where a laminated film having good transparency is not obtained. The acrylic resin (F) in the present invention must have a (meth) acrylate monomer (f ₃ ') represented by (Formula 3) in order to have a monomer unit (f ₃ ) represented by the following (Formula 2). The polymerization is carried out as a raw material.

The following compounds can be exemplified as the (meth) acrylate monomer (f ₃ ') represented by the formula (3).

Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2,3-(meth)acrylate. a polyhydric alcohol such as dihydroxybutyl ester, 4-hydroxybutyl (meth)acrylate or polyethylene glycol mono(meth)acrylate, and a monoester of (meth)acrylic acid, or a ring-opening of the monoester Polymerization of ε-caprolactone The compound or the like is particularly preferably 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

Examples of the (meth) acrylate monomer having a carboxyl group include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, or (methyl). A half esterified product of a hydroxyalkyl acrylate and an acid anhydride is particularly preferably acrylic acid or methacrylic acid.

Examples of the monomer having a tertiary amino group include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate. N,N-dialkylaminoalkyl (meth)acrylate, N,N-dimethylaminoethyl (meth) propylene hydride, etc., N,N-dimethylaminopropyl acrylate N,N-dialkylamino group such as amine, N,N-diethylaminoethyl (meth) acrylamide, N,N-dimethylaminopropyl (meth) acrylamide The alkyl (meth) acrylamide or the like is particularly preferably N,N-dimethylaminoethyl (meth)acrylate.

In the case of a monomer having a quaternary ammonium salt group, a level 4 agent such as epihalohydrin, a halogenated benzyl group or a halogenated alkyl group is preferably used for the above-mentioned monomer having a tertiary amino group. Specific examples of the surfactant include 2-(methacryloyloxy)ethyltrimethylammonium chloride and 2-(methylpropenyloxy)ethyltrimethylammonium bromide, 2 (Meth) propylene decyloxyalkyltrialkylammonium salt such as -(methacryloxy)ethyltrimethylammonium dimethyl phosphate, methacrylamidopropyl propyl chloride (Meth)acryloylaminoalkyltrialkylammonium salt such as trimethylammonium or bromomethacrylamidopropyltrimethylammonium chloride, tetrabutylammonium (meth)acrylate, etc. Trialkylbenzylammonium (meth)acrylate such as tetraalkyl (meth)acrylate or trimethylbenzylammonium (meth)acrylate, particularly preferably 2-(methyl) chloride C Iridinyloxy)ethyltrimethylammonium.

The sulfonic acid group-containing monomer may, for example, be a (meth) acrylamide-alkanesulfonic acid such as butyl acrylamide sulfonamide or 2-propenylamine-2-methylpropane sulfonic acid, or A sulfoalkyl (meth) acrylate such as 2-sulfoethyl (meth) acrylate or the like is particularly preferably 2-sulfoethyl (meth) acrylate.

The acrylic acid group containing a phosphoric acid group may, for example, be an acid phosphoxy ethyl ester of (meth)acrylic acid, and particularly preferably an acid phosphonium oxyethyl (meth)acrylate.

In particular, the acrylic resin (F) is a resin having the monomer unit (f ₃ ) represented by the above formula (2), and the inorganic particles (B) to be described later have an increased adsorption force, and a stronger film can be formed and resistant. In the point of improving the scratching property, the R ₅ group in the formula (2) is preferably a hydroxyl group or a carboxyl group. In the method of using the acrylic resin (F) to have a macroscopic surface roughness of 1 nm or more and 50 nm or less, a method of imparting a fine extension unevenness by extending the resin layer in a state where the acrylic resin is not cured is mentioned. At this time, it is important that the thickness of the resin layer is 300 nm or more. By the thickness as described above, the fine unevenness of the fineness exhibits an appropriate height, and the anti-adhesion property can be improved.

In the present invention, the content of the acrylic resin in the resin layer is preferably from 10 to 90% by weight, and by this range, the scratch resistance of the resin layer can be improved.

In particular, when the acrylic resin (A) is used as the acrylic resin, the content of the acrylic resin (A) is preferably 40% by weight or more and 90% by weight or less based on the entire resin layer, and the acrylic resin (A) in the resin layer. The content is preferably 40% by weight or more and 80% by weight or less, more preferably 45% by weight or more and 70% by weight or less.

When the acrylic resin (F) is used as the acrylic resin, the content of the acrylic resin (F) in the resin layer is preferably 20% by weight or more and 80% by weight or less based on the entire resin layer, and more preferably 40% by weight or more. 80% by weight or less, more preferably 45% by weight or more and 70% by weight or less.

In the present invention, the content in the resin layer means the content of the solid component ([(mass of resin composition) - (mass of solvent))) of the resin composition forming the resin layer.

[Inorganic Particles]

The laminated film of the present invention preferably contains inorganic particles (B) in the resin layer of the surface layer. Examples of the inorganic particles (B) include fine particles such as cerium oxide ( vermiculite), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Among these, fine particles of cerium oxide ( vermiculite), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferred. These may be used alone or in combination of two or more.

Further, the inorganic particles (B) of the present invention are preferably a composition (B-2) obtained by combining inorganic particles (B-1) and a resin component containing an acrylonitrile group, or inorganic particles (B-1). One or all of the surface of the surface has the composition (B-3) of the acrylic resin (G). The so-called binding here may be covalent bonding or non-covalent bonding (physical adsorption).

Examples of the resin composition (B-2) obtained by combining the inorganic particles (B-1) and the acryl-containing sulfonic acid-containing resin component include inorganic particles (B-1) and acryl-containing groups. Resin component bonding (surface modification). By combining the inorganic particles (B-1) and the resin component containing the acrylonitrile group, it is possible to suppress the fall of the inorganic particles when the resin layer is applied with strength, and to improve the scratch resistance.

In the specific method of combining the inorganic particles (B-1) with the lipid component containing the acrylonitrile group, it is preferred that the resin component containing the acryl oxime group be a resin component having a decyl group or form a hydrazine by hydrolysis. Alcohol based resin component.

Next, the propylene group-containing resin component contained in the resin composition (B-2) containing the inorganic particles (B) will be described. The resin component containing an acrylonitrile group is a compound having an acrylonitrile group and a hydrolyzable decyl group. The hydrolyzable decyl group means a group which reacts with water to form a sterol group, and for example, one or more methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, and the like are bonded to hydrazine. An alkoxy group, an aryloxy group, an ethoxylated group, an amine group, or a halogen atom.

The particles obtained by combining the inorganic particles (B-1) and the resin component containing the acrylonitrile group may be composed of a resin component (B-2) containing an acrylic sulfonyl group having a hydrolyzable alkylene group and inorganic particles (B-1). Mixing and hydrolysis, and combining the two. When the particles thus obtained are reacted with the acrylic resin (A), the inorganic particles are less likely to fall off when the resin layer is rubbed, so that the scratch resistance is excellent.

The ratio of the inorganic particles (B-1) contained in the resin composition (B-2) containing the inorganic particles (B) to the resin component containing the acrylonitrile group, and the inorganic particles (B-1) and the acryl-containing group When the resin component is 100 parts by weight, the resin component (B-2) containing an acrylonitrile group is preferably 0.1 part by weight or more and 50 parts by weight or less. By being in this range, the inorganic particles do not fall off, and the scratch resistance, the transparency, and the anti-adhesion property can be achieved. When the resin component containing an acrylonitrile group exceeds 50 parts by weight, the density of the inorganic particles contained in the resin layer may be lowered, and the scratch resistance may be deteriorated.

Further, a part (or all) of the surface of the inorganic particles (B-1) of the present invention having the acrylic resin (G) is preferably a part or all of the surface of the inorganic particles (B-1). The particles of the aforementioned acrylic resin (G).

Here, the term acrylic resin (G) having lines (formula 4) monomer units (g ₁₎ as shown, the resin (Formula 5) monomer units (g ₂₎ as shown in the.

(In the formula 4, the R ₁ group represents a hydrogen atom or a methyl group. Further, n represents an integer of 9 or more and 34 or less.).

(In the formula 5), the R ₂ group represents a hydrogen atom or a methyl group. Further, the R ₄ group represents a group containing two or more saturated carbocyclic rings).

Here, the acrylic resin (G) in the present invention is preferably a resin having a monomer unit (g ₁ ) represented by (Formula 4). When the acrylic resin (G) has the monomer unit (g ₁ ) represented by (Formula 4), since the surface energy of the resin layer becomes low, the friction coefficient associated with the resin layer at the time of performing the rubbing treatment becomes small, and Improves scratch resistance.

In the formula (4), when the acrylic resin having a monomer unit having n of less than 9 is used, the dispersibility of the inorganic particles (B) in the aqueous solvent (described later in the detailed description of the aqueous solvent) becomes unstable. When an acrylic resin having a monomer unit having n of less than 9 in (Formula 4) is used, the inorganic particles (B) in the resin composition may aggregate or precipitate, or the inorganic particles (B) may aggregate in the drying step. As a result, the transparency of the laminated film may be impaired and the scratching property may be deteriorated. On the other hand, the acrylic resin having a monomer unit in which n in n in (Formula 4) exceeds 34, and the solubility in an aqueous solvent is remarkably low, so that aggregation of the acrylic resin is likely to occur in an aqueous solvent. Since this aggregate is larger than the wavelength of visible light, there is a case where a laminated film having good transparency cannot be obtained.

In the acrylic resin (G) of the present invention, in order to have a monomer unit (g ₁ ) represented by (Formula 4), it is necessary to use a (meth) acrylate monomer (g ₁ ' represented by the following (Formula 6). ) Polymerization is carried out as a raw material.

The (meth) acrylate monomer (g ₁ ') is preferably a (meth) acrylate monomer represented by an integer of 9 or more and 34 or less in the formula (6), and more preferably The (meth) acrylate monomer of 11 or more and 32 or less is more preferably a (meth) acrylate monomer of 13 or more and 30 or less.

The (meth) acrylate monomer (g ₁ ') is not particularly limited as long as it is a (meth) acrylate monomer in which n is 9 or more and 34 or less in the formula (6), and specific examples thereof include Ethyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, 1-methyltridecyl (meth)acrylate Ester, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosanyl (meth) acrylate, behenyl (meth) acrylate, (meth) acrylate Tetraalkyl ester, trialkyl (meth)acrylate, etc., particularly preferably dodecyl (meth)acrylate or tridecyl (meth)acrylate. These may be used alone or in combination of two or more.

Further, the acrylic resin (G) in the present invention is preferably a resin having the monomer unit (g ₂ ) represented by the above (Formula 5). By having the acrylic resin (G) having the monomer unit (g ₂ ) represented by (Formula 5), the resin layer becomes straight due to the influence of the steric hindrance of the saturated carbon ring, and the scratch resistance can be improved.

In the formula (5), when an acrylic resin containing only one monomer unit of a saturated carbocyclic ring is used, the function as a steric hindrance may be insufficient, and the inorganic particles (B) may be in the resin composition. Aggregation or sedimentation, the inorganic particles (B) will agglomerate during the drying step.

Since this aggregate is larger than the wavelength of visible light, there is a case where a laminated film having good transparency cannot be obtained. In the acrylic resin (G) of the present invention, in order to have a monomer unit (g ₂ ) represented by (Formula 5), it is necessary to use a (meth) acrylate monomer (g ₂ ' represented by the following (Formula 7). ) Polymerization is carried out as a raw material.

The (meth) acrylate monomer (g ₂ ') represented by (Formula 7) may be exemplified by having a crosslinked condensed ring type (having two or more rings each having 2 atoms in combination and bonding Various structures such as a structure, a spiro ring type (a structure having a single carbon atom and a structure in which two ring structures are bonded), specifically, a compound such as a bicyclic ring, a tricyclic ring or a tetracyclic group, and particularly From the viewpoint of compatibility with the binder, a (cyclo) group-containing (meth) acrylate is preferred.

As the (meth) acrylate containing the above bicyclic group, (meth)acrylic acid is exemplified Ester, (meth)acrylic acid Ester, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl hydroxyalkyl (meth) acrylate, etc. Acrylic ester.

By having the acrylic resin (G) on the surface of the inorganic particles (B-1), the interface between the inorganic particles (B-1) and the acrylic resin (G) in the resin layer is then firmed, and the particles during the rubbing treatment are subjected to the treatment. The shedding is suppressed and the scratch resistance is excellent. Further, it is possible to suppress the aggregation of the inorganic particles (B) during the drying process, and to set the microscopic surface roughness and the macroscopic surface roughness of the resin layer to a predetermined range.

In addition, the method of producing the inorganic particles (B-1) is not particularly limited, and examples thereof include a method of surface-treating the inorganic particles (B-1) with an acrylic resin (G), and specifically, the following (i)~ can be exemplified. (iv) method. Further, in the present invention, the surface treatment refers to a treatment in which all or a part of the surface of the inorganic particles (B-1) is adsorbed and the acrylic resin (G) is attached.

(i) A method of dispersing a mixture of the inorganic particles (B-1) and the acrylic resin (F) in advance and adding them to a solvent.

(ii) sequentially adding inorganic particles (B-1) and propylene to the solvent A method of dispersing an acid resin (G).

(iii) A method of dispersing the inorganic particles (B-1) and the acrylic resin (G) in advance in a solvent and mixing the obtained dispersion.

(iv) A method of adding an acrylic resin (G) to the obtained dispersion after dispersing the inorganic particles (B-1) in a solvent.

The desired effect can be obtained by any of the methods described above.

Further, as the apparatus for dispersing, a dissolver, a high-speed mixer, a homomixer, a kneader, a ball mill, a roll mill, a sand mill, a paint mixer, an SC mill, a ring mill, and a corner column can be used. Type grinders, etc.

Further, in the dispersion method, the rotating shaft is rotated at a peripheral speed of 5 to 15 m/s by using the above-described apparatus. The rotation time is 5 to 10 hours.

Further, the use of dispersed beads such as glass beads in the dispersion is more preferable from the viewpoint of improving dispersibility. The bead size is preferably from 0.05 to 0.5 mm, more preferably from 0.08 to 0.5 mm, and particularly preferably from 0.08 to 0.2 mm.

The mixing and stirring method can be carried out by shaking the container by hand, using a magnetic stirrer or a stirring blade, and performing ultrasonic irradiation, vibration dispersion, and the like.

Further, the presence or absence of adsorption or adhesion of all or a part of the acrylic resin (G) on the surface of the inorganic particles (B-1) can be confirmed by the following analysis method. The object to be measured (for example, the composition (B-3) containing the inorganic particles (B-1)) is centrifuged by a Hitachi desktop ultracentrifuge (manufactured by Hitachi Kogyo Co., Ltd.: CS150NX) (number of rotations) 3,0000 rpm, separation time 30 minutes), in the inorganic particles (B-1) (and already After the acrylic resin (G) adsorbed on the surface of the inorganic particles (B-1) was allowed to settle, the supernatant was removed, and the precipitate was concentrated and dried. The precipitates fixed by concentration and drying were analyzed by X-ray photoelectron spectroscopy (XPS) to confirm the presence or absence of the acrylic resin (F) in the surface of the inorganic particles (B-1). In the case where the surface of the inorganic particles (B-1) is 100% by mass based on the total of the inorganic particles (B-1), and the acrylic resin (G) is present at 1% by mass or more, the inorganic particles (B-1) are present. Surface adsorption ‧ adhered to acrylic resin (G).

Here, the number average particle diameter of the inorganic particles (B-1) will be described. The number average particle diameter referred to herein means a particle diameter obtained by a transmission electron microscope (TEM). The magnification was set to 500,000 times, and the number average particle diameter of the total of 100 particles was measured for 10 fields on the outer diameter of the 10 particles present on the screen. Here, the outer diameter means the maximum diameter of the particles (that is, the long diameter of the particles, indicating the longest diameter in the particles), and the case where the particles have voids in the same manner also indicates the maximum diameter of the particles.

When the number average particle diameter of the inorganic particles (B) becomes less than 1 nm, the van der Waals force of the particles increases, and the particles aggregate with each other, and as a result, light is scattered, and transparency is lowered. On the other hand, when the number average particle diameter of the inorganic particles (B) becomes larger than 100 nm, from the viewpoint of transparency, it becomes a starting point of light scattering, and transparency may be deteriorated. Moreover, the filling of the inorganic particles in the coating film cannot be sufficiently performed, and the scratch resistance is lowered. For this reason, the inorganic particles (B) preferably have a coefficient average particle diameter of 5 nm or more and 100 nm or less. It is preferably 10 nm or more and 80 nm or less, more preferably 20 nm or more and 60 nm or less.

In the present invention, the inorganic particles (B) contained in the resin layer (X) With respect to 100 parts by weight of the acrylic resin (A), it is preferably in the range of 10 to 50 parts by weight, more preferably in the range of 15 to 50 parts by weight. By setting it in the said range, it can have both transparency and a scratch resistance.

Furthermore, in the present invention, the inorganic particles (B) contained in the resin layer (X) are preferably in the range of 50 to 200 parts by weight based on 100 parts by weight of the total of the acrylic resin (F) and the acrylic resin (G). More preferably, it is in the range of 100 to 200 parts by weight. By setting it in the said range, it can have both transparency and a scratch resistance.

[Polyester layer]

In the laminated film of the present invention, a polyester layer used as a base material layer (hereinafter, a polyester film used as a base material layer is referred to as a polyester film) will be described. First, the so-called polyester is a general term for a polymer having an ester bond in the main chain, and preferably used may be selected from the group consisting of ethylene terephthalate, propylene terephthalate, and naphthalene dicarboxylate. 2,6-ester, butylene terephthalate, propane-2,6-ester naphthalate, ethyl-α,β-bis(2-chlorophenoxy)ethane-4,4' At least one of a dicarboxylic acid ester or the like is considered as a constituent component.

The above polyester film using polyester is preferably a biaxial alignment. The biaxially oriented polyester film means that the polyester sheet or the film in an unstretched state is generally extended by about 2.5 to 5 times in the longitudinal direction and the width direction orthogonal to the longitudinal direction, and then heat treatment is performed. When the crystal alignment is terminated, a person who displays the biaxial alignment pattern by wide-angle X-ray diffraction. In the case of biaxial alignment of the polyester film, thermal stability, especially dimensional stability or mechanical strength, is sufficient, and planarity is also good.

Also, in the polyester film, it can be deteriorated without making its characteristics To various degrees, various additives such as an antioxidant, a heat stabilizer, a weathering stabilizer, a UV absorber, an organic slip agent, a pigment, a dye, organic or inorganic fine particles, a filler, an antistatic agent, a nucleating agent and the like are added.

The thickness of the polyester film is not particularly limited and may be appropriately selected depending on the use or the kind, and is usually preferably from 10 to 500 μm, more preferably from 15 to 250 μm, most preferably from 20 in terms of mechanical strength and handleability. ~100μm. Further, the polyester film may be a composite film obtained by co-extrusion, or may be a film obtained by laminating the obtained film in various methods.

[Method for Producing Resin Layer]

In the following, the method for producing the resin layer of the laminated film of the present invention is exemplified, and the materials, the amounts, the ratios, the contents of the treatment, the treatment procedures, and the like described below can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the invention should not be construed as limited by the examples shown below.

When the resin layer of the present invention contains at least one type of acrylic resin selected from the group consisting of an acrylic resin (A) and an acrylic resin (F), and the inorganic particles (B), the resin layer has transparency, scratch resistance, and anti-adhesion property. Excellent and better.

Further, the resin layer may contain other compounds other than (A), (F), and (B), such as a polymer resin such as a polyester resin, an acrylic resin, or a urethane resin; Amine compound, A titanate coupling agent such as an oxazoline compound, an aziridine compound, or a titanium chelate compound; a melamine compound which is methylolated or alkylated. Further, various additives such as an organic slip agent, organic or inorganic fine particles, an antistatic agent, and the like can be added to such an extent that the properties are not deteriorated.

Particularly, as compounds other than (A), (F) and (B), it is preferably The oxazoline compound and or the melamine compound preferably contain a melamine compound.

As the melamine-based compound, for example, a methylolated melamine derivative obtained by condensing melamine, melamine and formic acid, a compound partially or completely etherified by reacting a lower alcohol with methylolated melamine, and the like can be used. Mixtures, etc. Specifically, the special series has three A compound with a methylol group. Further, the melamine-based compound may be either a monomer or a condensate containing a polymer of a dimer or more, or a mixture thereof. As the lower alcohol used for the etherification, methanol, ethanol, isopropanol, n-butanol, isobutanol or the like can be used. In the case of a group, an alkoxymethyl group having an imido group, a methylol group, or a methoxymethyl group or a butoxymethyl group in one molecule is an imidomethylated melamine resin, A methylol type melamine resin, a methylol type methylated melamine resin, a completely alkyl type methylated melamine resin, or the like. Among them, the best is methylolated melamine resin. Further, in order to promote thermal hardening of the melamine-based compound, an acidic catalyst such as p-toluenesulfonic acid can be used.

When such a melamine-based compound is used, not only the hardness of the coating film due to self-condensation of the melamine-based compound is improved, but also the scratch resistance is improved, and the hydroxyl group or the carboxylic acid group and the melamine-based compound contained in the acrylic resin are also observed. By carrying out the reaction, a stronger resin layer can be obtained, and a film excellent in scratch resistance can be obtained. Further, by the effect of suppressing the fall of the inorganic particles (B) in the resin layer, it is possible to prevent the anti-adhesive property from being exhibited. The detachment of the convex portion of the concave-convex structure necessary for the sex.

[Manufacturing method of laminated film]

In the following, the method for producing the laminated film of the present invention will be described as an example. However, the materials, the amounts, the ratios, the contents of the treatment, the treatment procedures, and the like described below can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the invention should not be construed as limited by the examples shown below.

The laminated film of the present invention can be applied to the polyester film by the acrylic monomer (a) constituting the acrylic resin (A) and the resin composition (b) containing the inorganic particles (B), and the resin composition contains the solvent. In this case, a resin layer is formed on the polyester film by drying the solvent.

Further, the acrylic resin (F) constituting the acrylic resin (F) and the resin composition (b) containing the inorganic particles (B) may be applied to the polyester film, and the resin composition may contain a solvent. It is obtained by forming a resin layer on a polyester film by drying a solvent.

Further, in the present invention, in the case where the resin composition contains a solvent, it is preferred to use an aqueous solvent as a solvent. By using an aqueous solvent, not only the evaporation of the solvent in the drying step can be suppressed, but also a uniform composition layer can be formed, and it is excellent also from the point of environmental load.

Here, the aqueous solvent means water, alcohol such as methanol, ethanol, isopropanol or butanol, ketones such as acetone or methyl ethyl ketone, ethylene glycol, diethylene glycol, and the like. A water-soluble organic solvent such as a glycol such as propylene glycol is mixed at an arbitrary ratio.

Further, in the case of using an aqueous solvent in the present invention, it is preferred to apply an acrylic monomer (f) containing an acrylic resin (A) or an acrylic monomer (f) constituting an acrylic resin (F), and containing inorganic particles ( B) A water-based paint for the resin composition (b). This is because, by applying it as a water-based paint, compared with the organic solvent-based paint, the water-dispersing agent or the emulsifier is disposed on the surface layer of the coating film in a state where the solvent is dried, so that the above-mentioned propylene-based group The hardening inhibition of the radical polymerization reaction is suppressed, and the thickness of the resin layer is excellent even in the case of a film.

In addition, the method of performing aqueous coating of the acrylic monomer (a) constituting the acrylic resin (A) or the resin composition (b) containing the inorganic particles (B) is exemplified as the acrylic resin (A). The acrylic monomer (a) or the resin composition (b) containing the inorganic particles (B) contains a hydrophilic group such as a carboxylic acid or a sulfonic acid, or a method of emulsification using an emulsifier.

The method of applying the resin composition to the polyester film is preferably an in-line coating method. The so-called in-line coating method is a coating method in a production step of a polyester film. Specifically, it refers to a method of applying a polyester resin after melt-extruding and then heat-treating to a roll-up stage after biaxial stretching, and is usually applied to a substantially amorphous state obtained by quenching after melt extrusion. Uniaxially stretched (unaligned) polyester film (A film), then uniaxially stretched (uniaxially oriented) polyester film (B film) extending in the longitudinal direction, or biaxially oriented before heat treatment extending further in the width direction Any film that extends (biaxially aligned) polyester film (C film).

Preferably, the present invention employs a resin composition coated on any of the above-mentioned A film and B film before the end of crystal alignment, and then extends the polyester film in a uniaxial direction or a biaxial direction to a boiling point of a solvent. The heat treatment is performed at a high temperature to terminate the crystal alignment of the polyester film and to provide a resin layer. If it is this method, since it can be aggregated at the same time The film formation of the ester film and the application drying of the resin composition (that is, the formation of the resin layer) have an advantage in manufacturing cost. Further, since the stretching is performed after the application, the thickness of the resin layer is easily made thinner.

Among them, a film composition (B film) which is uniaxially stretched in the longitudinal direction is coated with a resin composition, and then stretched in the width direction, and the method of heat treatment is excellent. After application to the unstretched film, since the stretching step is less than once in the biaxial stretching method, defects or cracks in the composition layer due to stretching are less likely to occur, and a composition excellent in transparency or smoothness can be formed. Layer of matter.

Further, by providing the resin layer in an in-line coating method, it is possible to extend the resin layer before the resin layer is completely cured, and a smooth uneven structure can be easily formed. In addition, the uneven structure is such that the thickness of the resin layer is 300 nm or more, and a more remarkable uneven structure can be formed. As a result, even if a large protrusion is not formed in the resin layer, the anti-adhesion property of the film can be exhibited. Further, the smooth uneven structure means that the macroscopic surface roughness measured by a three-dimensional roughness meter manufactured by Kosaka Research Institute is 5 to 50 nm.

In the present invention, the resin layer is preferably provided by an in-line coating method due to various advantages described above. Here, as a form of coating the resin composition on the polyester film, a known coating method such as a bar coating method, a reverse coating method, a gravure coating method, a die casting method, a knife coating method, or the like can be used.

Therefore, the method for forming the resin layer which is the best in the present invention is a method in which a resin composition using an aqueous solvent is applied onto a polyester film by an in-line coating method, followed by drying and heat treatment. also More preferably, it is a method of in-line coating of a resin composition on a B film after uniaxial stretching. In the method for producing a laminated film of the present invention, the drying is carried out in a temperature range of 80 to 130 ° C in order to complete the removal of the solvent of the resin composition. Further, the heat treatment is carried out in a temperature range of 160 to 240 ° C in order to complete the thermal alignment of the resin composition and complete the formation of the resin layer in order to complete the crystal alignment of the polyester film.

Next, the method for producing a laminated film of the present invention will be described by using a polyethylene terephthalate (hereinafter referred to as PET) film as a polyester film as an example, but the invention is not limited thereto. First, the pellets of PET were sufficiently vacuum-dried, and then supplied to an extruder, melt-extruded into a sheet shape at about 280 ° C, and cooled and solidified to prepare an unstretched (unaligned) PET film (A film). The film was stretched 2.5 to 5.0 times in the longitudinal direction by a roll heated to 80 to 120 ° C to obtain a uniaxially oriented PET film (B film). A resin composition of the present invention having a predetermined concentration is applied to one side of the B film.

At this time, the surface of the PET film to be coated may be subjected to a surface treatment such as corona discharge treatment before coating. By performing surface treatment such as corona discharge treatment, the wettability of the resin composition to the PET film can be improved, and shrinkage of the resin composition can be prevented to form a resin layer having a uniform coating thickness. After coating, the end of the PET film was held by a jig and guided to a heat treatment zone (preheating zone) of 80 to 130 ° C to dry the solvent of the resin composition. After drying, it extends 1.1 to 5.0 times in the width direction. Then, the heat treatment zone (heat-fixing zone) of 160 to 240 ° C is guided to heat treatment for 1 to 30 seconds to complete the crystallization alignment.

In the heat treatment step (heat setting step), as needed Perform a 3 to 15% relaxation treatment in the width direction or the long side direction. The laminated film obtained in this way is a laminated film which is excellent in transparency, scratch resistance, and anti-adhesion property.

Further, the laminated film of the present invention may be provided with an intermediate layer between the resin layer and the polyester layer, and in the case where the intermediate layer is provided, when the film of the intermediate layer is wound, or after the resin of the present invention is provided In the step of the layer, there is a case where the film is scratched. Therefore, in the present invention, it is preferred to directly laminate the resin layer and the polyester layer.

[Method for measuring characteristics and method for evaluating effects]

The method for measuring the characteristics and the method for evaluating the effects in the present invention are as follows.

(1) Haze (transparency)

The haze was measured in a normal state (23 ° C, relative humidity: 50%), and the laminated film sample was allowed to stand for 40 hours, and then a haze meter "NDH5000" manufactured by Nippon Denshoku Industries Co., Ltd. was used in accordance with JIS K 7136. The method of obtaining the haze of a transparent material (2000 edition) is carried out. Moreover, it measured by irradiating light from the resin laminated layer side of a sample. For the sample, 10 square samples of 50 mm were prepared, and the average value of each of 10 times and the total of 10 times was taken as the haze value of the sample.

Further, the transparency was evaluated in four stages based on the haze value. × is a practically problematic level, △ is a practical level, and A and S are good.

S: 0.6% or less

A: more than 0.6% and less than 1.0%

B: more than 1.0% and less than 2.0%

C: More than 2.0%.

(2) Scratch resistance

Steel wool (Bonstar #0000, manufactured by Nippon Steel Wool Co., Ltd.) was rubbed 10 times at a load of 200 g/cm ² to visually confirm the occurrence of scratches on the surface of the laminated film, and the following evaluation was carried out.

S: no scars

A: 1~5 scars

B: 6~10 scars

C: More than 11 scars.

(3) Anti-adhesion

The resin layers of the laminated film were bonded to each other and pressurized at a load of 1 kg/cm ² . Store at room temperature for 24 hours. Then, the presence or absence of adhesion (attachment) of the film at the time of peeling the laminated film was visually confirmed, and the following evaluation was performed.

A: No adhesive

B: Some of them are adhesive.

C: Fully adhesive

(4) Adhesiveness

100 cross-cuts of 1 mm ² were placed on the resin layer side of the laminated film, and "Cycari tape" (registered trademark) (manufactured by Nichiban Co., Ltd., CT405AP) was attached, and the hand was pressed to 1.5 kg/ After the load of cm ² was pressed, the laminated film was rapidly peeled off in the direction of 90 degrees. The adhesiveness was evaluated in four stages based on the number of remaining lattices. The evaluation was carried out by performing an average of 10 times. The C system is practically problematic, the B system is practical, and the A and S are good.

S: 90~100 surviving

A: 80~89 remaining

B: 50~79 remaining

C: 0~ less than 50 residuals.

(5) The average particle size of the particles contained in the resin layer

The number average particle diameter of the particles contained in the resin layer was determined by observing the cross-sectional structure of the laminated film by a transmission electron microscope (TEM). The magnification was set to 500,000 times, and a total of 100 particles were measured for 10 fields on the outer diameter of the 10 particles present on the screen, and the average particle diameter was determined. When there are no 10 particles in the screen, the other places are observed under the same conditions, and the outer diameter of the particles existing on the screen is measured, and the outer diameter of the total of 100 particles is measured and averaged. Here, the outer diameter means the maximum diameter of the particles (that is, the long diameter of the particles, indicating the longest diameter in the particles), and the case where the particles have voids therein also shows the maximum diameter of the particles.

(6) Film thickness of the resin layer

The thickness of the resin layer on the polyester film was measured by observing the cross section using a transmission electron microscope (TEM). The thickness of the resin layer was read from the image taken by the TEM at a magnification of 100,000 times to read the thickness of the resin layer. The thickness of the resin layer of 20 points in total was measured and averaged.

Sample adjustment: RuO ₄ staining FIB method

SMI3200SE (SIINT (share) system)

FB-2000A II Micro Sampling System (Hitachi (share) system)

Strata400S (made by FEI)

Observation device: High resolution penetrating electron microscope (Hitachi H9000 UHR II)

Observation conditions: Accelerating voltage 300kV

(7) Microscopic surface roughness (Ra-1)

The surface of the resin layer side of the laminated film was measured using a ScanAsyst Air mode of AFM (Atomic Force Microscope) and a Dimension Icon Scan Asyst, manufactured by BRUKER, with a measurement range of 10 μm × 10 μm, a measured number of 512, and a measurement rate of 1.0 Hz. The obtained surface information was calculated by the method specified in JIS-B-0601-1994 to calculate the arithmetic mean roughness (Ra). Specifically, use "NanoScope Analysis" as the software, and select "3rd" of "Flatten Order" to perform the three-dimensional fluctuation processing. Then select "Roughness" and use the value described in "Image Ra" of the screen as the arithmetic mean roughness. Further, the total value of the total of eight data values other than the maximum value and the minimum value was measured 10 times, and the arithmetic mean roughness (Ra) of the sample was taken as the micro surface roughness (Ra-1).

(8) Macro surface roughness (Ra-2)

The surface of the resin layer side of the laminated film was measured by a stylus method using a three-dimensional surface roughness meter (ET-4000A, manufactured by Otaru Laboratory) under the following conditions, and the obtained center line surface roughness (SRa) was obtained. It is obtained as a macro surface roughness (Ra-2).

Further, the measurement was changed to the sampling place, and 10 samples were measured, and the average value of 8 points other than the maximum value and the minimum value was removed.

Needle diameter 0.5 (μmR)

Needle pressing pressure 100 (μN)

Vertical magnification 20000 (times)

Low field CUT OFF 200 (μm)

Wide area CUT OFF 0 (μm)

Measuring speed 100 (μm / s)

Measurement interval X direction 1 (μm), Y direction 5 (μm)

Number of records 81

Hysteresis width 0.000 (μm)

The reference area is 1 mm in the X direction and 0.4 mm in the Y direction.

(9) Particle existence ratio

For the image of the cross-sectional TEM obtained by the method described in (6) (100,000 times magnification), adjust the white balance with software (image processing software ImageJ/development source: National Institute of Satellite Research (NIH)) to restore the most The upper part and the darkest part are 8-bit tone curves. Further, the contrast is adjusted in such a manner that the black portion (inorganic particles) is clearly recognized.

Then, the ratio of the black portion in the range from the surface of the resin layer to the position of 10% of the thickness of the resin layer in the obtained image is the particle existence ratio (P-1), and the surface of the resin layer is 40% of the thickness of the resin layer. The ratio of the black portion in the range from the position to the position of 60% is set as the particle existence ratio (P-2).

<Reference Example 1> Emulsion (EM-5) containing an acrylic monomer (a-1) constituting the acrylic resin (A) component

In a flask equipped with a stirrer, 100 parts by weight of acrylic monomer (a-1) (Dipentahexaacrylate (KAYARAD DPHA, manufactured by Nippon Chemical Co., Ltd.)), and 79 parts by weight of polyoxyethylene polycyclic phenyl group as an emulsifier were charged. 10% by weight aqueous solution of ether sulfate salt (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.), 2.1 parts by weight of polyoxyethylene lauryl ether (King) Emulgen 104P), 128.9 parts by weight of ion-exchanged water, and stirred and mixed. Then, while cooling with an ice bath, ultrasonic wave irradiation was performed three times for 120 seconds using an ultrasonic disperser (UH-600S manufactured by SMT Co., Ltd.) to obtain an emulsion.

Subsequently, the above emulsion was subjected to a refining treatment under a pressure of 70 MPa by a high pressure homogenizer (Microfluidizer M110Y manufactured by Mizuho Co., Ltd.) to obtain an emulsion (EM-5) containing an acrylic monomer (a-1). The solid content concentration of the emulsion (EM-5) was 30% by weight.

<Reference Example 2> Resin composition containing inorganic particles (B) (b-2)

For a solution containing 221 parts by weight of mercaptopropyltrimethoxydecane, 1 part of dibutyltin dilaurate and methyl ethyl ketone, 222 parts by weight of isophorone was dropped at 50 ° C for 1 hour while stirring. After isocyanate and 30 parts by weight of perfluoropolyether diol (FLUOROLINK D10H manufactured by Solvaysolexis Co., Ltd.), the mixture was stirred under heat at 70 ° C for 3 hours. After 549 parts by weight of a polyfunctional acrylate ("NK ESTER" A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.) was dropped at a temperature of 30 ° C for 1 hour, stirring was carried out at 60 ° C for 10 hours. The acrylonitrile-containing particle modifier (b-1) was obtained.

Next, 50 parts by weight of the propylene group-containing particle modifier (b-1), 50 parts by weight of a colloidal vermiculite aqueous dispersion ("SNOWTEX OL" manufactured by Nissan Chemical Co., Ltd. having a particle size of 40 nm), and 0.12 weight were obtained. A mixture of ion-exchanged water and 0.01 part by weight of p-hydroxyphenyl monomethyl ether was stirred at 60 ° C for 4 hours, and then 1.36 parts by weight of methyl orthoformate was added, and further at the same temperature for 1 hour. Stir overheating to obtain inorganic particles The propylene group-containing resin composition (b-2) of the sub- (B).

<Reference Example 3> An emulsion (EM-1) containing an acrylic monomer (a-1) constituting the acrylic resin (A) component and a resin composition (b-2) containing the inorganic particles (B)

80 parts by weight of acrylic monomer (a-1) (Dipentahexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)) and 20 parts by weight of an acrylic-containing group containing inorganic particles (B) were added to a flask equipped with a stirrer. Resin composition (b-2), 79 parts by weight of a polyoxyethylene polycyclic phenyl ether sulfate salt as an emulsifier (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.), and 2.1 parts by weight of polyoxygen Ethylene lauryl ether (Emulgen 104P, manufactured by Kao) was charged with 128.9 parts by weight of ion-exchanged water and stirred and mixed. Then, while cooling with an ice bath, ultrasonic wave irradiation was performed three times for 120 seconds using an ultrasonic disperser (UH-600S manufactured by SMT Co., Ltd.) to obtain an emulsion.

Then, the above emulsion was subjected to a refining treatment under a pressure of 70 MPa by a high pressure homogenizer (Microfluidizer M110Y manufactured by Mizuho Co., Ltd.) to obtain an acrylic monomer (a-1) containing a component constituting the acrylic resin (A). An emulsion (EM-1) with a resin composition (b-2) containing inorganic particles (B). The solid content concentration of the emulsion (EM-1) was 30% by weight.

<Reference Example 4> An emulsion containing an amide bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) component and a resin composition (b-2) containing the inorganic particle (B) (EM-2) )

In a flask equipped with a stirrer, 0.024 g of 2,6-di-t-butyl-p-cresol, 15 g of ethylene glycol, and 12 g of 2.4-toluene diisocyanate (Mitsui Chemical Polyurethane) were fed. Ester company "TOLDY-100") and methyl b After adding 0.080 g of dibutyltin dilaurate, the base was heated to 60 ° C and heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and 35 g of tetramethylolethane triacrylate ("NK ESTER" A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) was added as methyl ethyl ketone. Dilute to a solid concentration of 50% by mass. The temperature was raised to 60 ° C and heated for 4 hours to obtain an acrylic monomer (a-2) represented by Formula 1.

In a flask equipped with a stirrer, 30 parts of Dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 50 parts by weight of an acrylic monomer (a-2) represented by the following formula 1, and 20 parts by weight of an inorganic substance were charged. a resin composition (b-2) of the particles (B), a 10% by weight of a polyoxyethylene polycyclic phenyl ether sulfate salt (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.) as an emulsifier, and 2.1 parts by weight A portion of polyoxyethylene lauryl ether (Emulgen 104P manufactured by Kao) and 128.9 parts by weight of ion-exchanged water were mixed and stirred. Then, while cooling with an ice bath, ultrasonic wave irradiation was performed three times for 120 seconds using an ultrasonic disperser (UH-600S manufactured by SMT Co., Ltd.) to obtain an emulsion.

Then, the above emulsion was subjected to a refining treatment under a pressure of 70 MPa by a high pressure homogenizer (Microfluidizer M110Y manufactured by Mizuho Co., Ltd.) to obtain an emulsion (EM-2) containing an acrylic monomer (a-3). The solid content concentration of the emulsion (EM-2) was 30% by weight.

(Formula 1) Acrylic monomer (a-2)

<Reference Example 5> An emulsion containing an indole bond-containing acrylic monomer (a-3) constituting the acrylic resin (A) component and a resin composition (b-2) containing the inorganic particle (B) (EM-3) )

In a flask equipped with a stirrer, 0.024 g of 2,6-di-t-butyl-p-cresol, 15 g of ethylene glycol, and 12 g of 3-isocyanate methyl-3,5,5-three were fed. Methylcyclohexyl isocyanate (made by Sumitomo Chemical Bayer Aurethane Co., Ltd., DESMODUR I) and methyl ethyl ketone, after adding 0.080 g of dibutyltin dilaurate, the temperature was raised to 60 ° C, and heated for 1.5 hours. . Next, the reaction mixture was cooled in a water bath, and 35 g of tetramethylolethane triacrylate ("NK ESTER" A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) was added as methyl ethyl ketone. Dilute to a solid concentration of 50% by mass. The temperature was raised to 60 ° C and heated for 4 hours to obtain an acrylic monomer (a-3) obtained in Formula 8.

Next, 30 parts of Dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Chemical Co., Ltd.), 50 parts by weight of acrylic monomer (a-3), and 20 parts by weight of inorganic particles (B) were placed in a flask equipped with a stirrer. Resin composition (b-2), 79 parts by weight of a polyoxyethylene polycyclic phenyl ether sulfate salt as an emulsifier (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.), a 10% aqueous solution, and 2.1 parts by weight of polyoxyethylene laurel Ethyl ether (Emulgen 104P, manufactured by Kao), 128.9 parts by weight of ion-exchanged water, and stirred and mixed. Then, while cooling with an ice bath, ultrasonic wave irradiation was performed three times for 120 seconds using an ultrasonic disperser (UH-600S manufactured by SMT Co., Ltd.) to obtain an emulsion.

Next, the above emulsion was subjected to a high pressure homogenizer (Microfluidizer M110Y manufactured by Mizuho Industries Co., Ltd.) under a pressure of 70 MPa. The refining treatment was carried out to obtain an emulsion (EM-3) containing the acrylic monomer (a-3). The concentration of the emulsion (EM-3) was 30%.

(Formula 8) Acrylic monomer (a-3)

<Reference Example 6> Emulsion (EM-4) containing a amide bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) component

30 parts by weight of Dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Chemical Co., Ltd.), 50 parts by weight of the obtained acrylic monomer (a-2), and 79 parts by weight of polyoxygen as an emulsifier were placed in a flask equipped with a stirrer. 10% by weight aqueous solution of ethylene polycyclic phenyl ether sulfate salt (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.), 2.1 parts by weight of polyoxyethylene lauryl ether (Emulgen 104P manufactured by Kao), and 128.9 parts by weight of ion exchange Water and mix and stir. Then, while cooling with an ice bath, ultrasonic wave irradiation was performed three times for 120 seconds using an ultrasonic disperser (UH-600S manufactured by SMT Co., Ltd.) to obtain an emulsion.

Then, the above emulsion was subjected to a refining treatment under a pressure of 70 MPa by a high pressure homogenizer (Microfluidizer M110Y manufactured by Mizuho Co., Ltd.) to obtain an emulsion (EM-4) containing an acrylic monomer (a-2).

<Reference Example 7> An acrylic monomer (a-2) containing a guanamine bond constituting the component of the acrylic resin (A) and a resin containing the inorganic particle (B) Emulsion of composition (b-2) (EM-6)

In a flask equipped with a stirrer, 30 parts of Dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 50 parts by weight of an acrylic monomer (a-2), and 40 parts by weight of a resin containing inorganic particles (B) were charged. (b-2), 79 parts by weight of a polyoxyethylene polycyclic phenyl ether sulfate salt as an emulsifier (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.), a 10% by weight aqueous solution, and 2.1 parts by weight of polyoxyethylene lauryl Ether (Emulgen 104P, manufactured by Kao), 128.9 parts by weight of ion-exchanged water, and stirred and mixed. Then, while cooling with an ice bath, ultrasonic wave irradiation was performed three times for 120 seconds using an ultrasonic disperser (UH-600S manufactured by SMT Co., Ltd.) to obtain an emulsion.

Then, the above emulsion was subjected to a refining treatment under a pressure of 70 MPa by a high pressure homogenizer (Microfluidizer M110Y manufactured by Mizuho Co., Ltd.) to obtain an emulsion (EM-6) containing an acrylic monomer (a-2). The solid content concentration of the emulsion (EM-6) was 30% by weight.

<Reference Example 8> Resin composition containing inorganic particles (B) (b-3)

50 parts by weight of a propylene group-containing particle modifier (b-1), 50 parts by weight of a vermiculite particle water dispersion ("Sicastar" 43-02-103 particle size 1000 nm manufactured by Micromod Co., Ltd.), 0.12 A mixture of 0.1 part by weight of ion-exchanged water and 0.01 part of p-hydroxyphenyl monomethyl ether was stirred at 60 ° C for 4 hours, then 1.36 parts of methyl orthoformate was added, and further stirred at the same temperature for 1 hour. The resin composition (b-3) containing the inorganic particles (B) was obtained.

<Reference Example 9> The acrylic monomer (a-1) constituting the acrylic resin (A) component and the resin composition (b-3) containing the inorganic particle (B) Emulsion (EM-7)

80 parts by weight of acrylic monomer (a-2) (Dipentahexaacrylate (KAYARAD DPHA, manufactured by Nippon Chemical Co., Ltd.)) and 20 parts by weight of a resin composition containing inorganic particles (B) were placed in a flask equipped with a stirrer ( B-3), 79 parts by weight of a polyoxyethylene polycyclic phenyl ether sulfate salt as an emulsifier (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.), a 10% by weight aqueous solution, and 2.1 parts by weight of polyoxyethylene lauryl ether ( Emulgen 104P), 128.9 parts by weight of ion-exchanged water, and stirred and mixed. Then, while cooling with an ice bath, ultrasonic wave irradiation was performed three times for 120 seconds using an ultrasonic disperser (UH-600S manufactured by SMT Co., Ltd.) to obtain an emulsion.

Then, the above emulsion was subjected to a refining treatment under a pressure of 70 MPa by a high pressure homogenizer (Microfluidizer M110Y manufactured by Mizuho Co., Ltd.) to obtain an emulsion (EM-7) containing an acrylic monomer (a-2). The solid content concentration of the emulsion (EM-7) was 30% by weight.

<Reference Example 10> Resin composition containing inorganic particles (B) (b-4)

50 parts by weight of a propylene group-containing particle modifier (b-1), 50 parts by weight of a vermiculite particle aqueous dispersion ("Sicastar" 43-02-503 particle size 5000 nm manufactured by Micromod Co., Ltd.), 0.12 A mixture of 0.01 part by weight of ion-exchanged water and 0.01 part by weight of p-hydroxyphenyl monomethyl ether was stirred at 60 ° C for 4 hours, and then 1.36 parts of methyl orthoformate was added, and further heated at the same temperature for 1 hour. The mixture was stirred to obtain a resin composition (b-4) containing the inorganic particles (B).

<Reference Example 11> An emulsion (EM-8) containing an acrylic monomer (a-1) constituting the acrylic resin (A) component and a resin composition (b-4) containing the inorganic particles (B)

80 parts by weight of acrylic monomer (a-1) (Dipentahexaacrylate (KAYARAD DPHA, manufactured by Nippon Chemical Co., Ltd.)) and 20 parts by weight of a resin composition containing inorganic particles (B) were placed in a flask equipped with a stirrer ( B-4), a 10% aqueous solution of a 10% aqueous solution polyoxyethylene polycyclic phenyl ether sulfate salt (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.) as an emulsifier, and 2.1 parts of polyoxyethylene lauryl ether (Emulgen 104P manufactured by Kao), 128.9 parts by weight of ion-exchanged water, and stirred and mixed. Then, while cooling with an ice bath, ultrasonic wave irradiation was performed three times for 120 seconds using an ultrasonic disperser (UH-600S manufactured by SMT Co., Ltd.) to obtain an emulsion.

Then, the above emulsion was subjected to a refining treatment under a pressure of 70 MPa by a high pressure homogenizer (Microfluidizer M110Y manufactured by Mizuho Co., Ltd.) to obtain an emulsion (EM-8) containing an acrylic monomer (a-2). The solid content concentration of the emulsion (EM-8) was 30% by weight.

<Reference Example 12> An emulsion (EM-10) comprising a composition (B-3) of an acrylic resin (G) and an acrylic resin (F) on the surface of the inorganic particles (B)

In a usual acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux cooling tube, 100 parts of isopropyl alcohol as a solvent was fed, and the mixture was heated and stirred at 100 °C.

In this case, 50 parts of n=19 of decyl methacrylate as 50 parts of (meth) acrylate (g'1) and 50 parts of (meth) acrylate (g'2) were dropped in 3 hours. Methacrylic acid with 2 rings ester. After the end of the dropping, heating at 100 ° C for 1 hour, and then the feed contains 1 part of t-butyl peroxide 2 Add a catalyst mixture. Then, after heating at 100 ° C for 3 hours, it was cooled to obtain an acrylic resin (G1).

In addition, 100 parts of isopropyl alcohol as a solvent was charged in a usual acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux cooling tube, and the mixture was heated and stirred, and kept at 100 °C. 40 parts of 2-hydroxyethyl acrylate as a hydroxyl group-containing (meth) acrylate (f'3), 20 parts of other ethyl (meth) acrylate, 20 parts of A were dropped in 3 hours. Methyl acrylate. After the end of the dropping, heating at 100 ° C for 1 hour, and then the feed contains 1 part of t-butyl peroxide 2 Add a catalyst mixture. Then, after heating at 100 ° C for 3 hours, it was cooled to obtain an acrylic resin (F-1).

In the aqueous solvent, inorganic particles (B) ("NanoTek" Al ₂ O ₃ slurry (quantitative average particle diameter: 30 nm manufactured by CI Kasei Co., Ltd.) and the above acrylic resin (G-1) were sequentially added by the following method. This was dispersed, and then an acrylic resin (F1) was added to obtain an emulsion (EM-10) containing the mixed composition (B-3) of the particles (B), the acrylic resin (G), and the acrylic resin (F). (ii) method)

The addition ratio (mass ratio) of the inorganic particles (B), the acrylic resin (F1), and the acrylic resin (G-1) is (B) / (F-1) / (G-1) = 50 / 40 / 10 (In addition, the mass ratio is obtained by rounding off the first decimal place). The dispersion treatment was carried out using a homomixer, and was rotated at a peripheral speed of 10 m/s for 5 hours. Further, the mass ratio of the particles (B), the acrylic resin (F-1), and the acrylic resin (G) in the finally obtained composition (B-3) is (B)/(F-1)/(G)=50/50 (In addition, the mass ratio is obtained by rounding off the first decimal place).

In addition, the obtained composition (B-3) was subjected to centrifugal separation by a Hitachi desktop type ultracentrifuge (manufactured by Hitachi Kogyo Co., Ltd.: CS150NX) (rotation number: 3000 rpm, separation time: 30 minutes) to cause inorganic particles ( B) (and the acrylic resin (F-1) adsorbed on the surface of the inorganic particles (B)), the supernatant is removed, and the sediment is concentrated and dried. As a result of analysis by X-ray photoelectron spectroscopy (XPS), the precipitate which was fixed by concentration and drying was confirmed to have an acrylic resin (F-1) on the surface of the inorganic particles (B). That is, it is clear that the acrylic resin (F-1) is adsorbed on the surface of the inorganic particles (B), and the obtained composition (B-3) corresponds to having an acrylic resin on the surface of the inorganic particles (B) ( Particles of F-1).

<Reference Example 13> An emulsion (EM-11) comprising a composition (B-3) of an acrylic resin (G) and an acrylic resin (F) on the surface of the inorganic particles (B)

The ratio (mass ratio) of the addition amount of the inorganic particles (B) and the acrylic resin (F-1) acrylic resin (G-1) is set to (B) / (F-1) / (G-1) = 32.5. In the same manner as in Reference Example 12 of /37.5/30, an emulsion (EM-11) containing the mixed composition (B-3) of the particles (B) and the acrylic resin (F-1) was obtained.

<Reference Example 14> An emulsion (EM-12) containing a composition (B-3) having an acrylic resin (G) and an acrylic resin (F) on the surface of the inorganic particles (B-1)

A particle (B) was obtained in the same manner as in Reference Example 13 except that the inorganic particles ("NanoTek" TiO ₂ slurry (the number average particle diameter of 36 nm manufactured by CI Chem Co., Ltd.) was used as the inorganic particles (B). The surface of the emulsion (EM-12) having a mixture of the composition (B-3) of the acrylic resin (G) and the acrylic resin (F-1) (EM-3).

[Examples]

In addition, the characteristics and the like of the laminated film obtained in the following examples or comparative examples are shown in the table.

<Example 1>

First, the resin composition 1 was prepared as follows.

<Resin composition>

The above emulsion was mixed in an aqueous solvent at a ratio described in the table to obtain a resin composition 1.

‧ Emulsion (EM-5) containing acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight

‧Inorganic particles (B) "SNOWTEX OL" (colloidal vermiculite, particle size 40 nm) manufactured by Nissan Chemical Industry Co., Ltd.: 20 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-5))

<Laminated film>

Next, PET pellets (extreme viscosity 0.63 dl/g) containing substantially no particles were sufficiently vacuum-dried, and then supplied to an extruder and melted at 285 ° C, and extruded into a sheet shape by a T-shaped nozzle. The electrostatic application casting method was wound around a mirror drum casting machine having a surface temperature of 25 ° C to be cooled and solidified. The unstretched film was heated to 90 ° C and extended 3.4 times in the longitudinal direction to form a uniaxially stretched film (B film).

Next, the resin composition 1 was applied to a corona discharge treated surface of a uniaxially stretched film by using a bar coater at a coating thickness of about 6 μm. The both ends of the uniaxially stretched film of the coating resin composition were held by a jig and guided to the preheating zone. After the ambient temperature became 75 ° C, the ambient temperature was set to 110 ° C using a radiant heater, and then the ambient temperature was set to The resin composition was dried at 90 ° C to form a resin layer. Subsequently, the heating zone (extension zone) of 120 ° C was continuously extended 3.5 times in the width direction, followed by heat treatment in a heat treatment zone (heat setting zone) of 230 ° C for 20 seconds to obtain a laminated film in which crystal alignment was completed. In the obtained laminated film, the thickness of the PET film was 50 μm, and the thickness of the resin layer was 1000 nm.

The characteristics and the like of the obtained laminated film are shown in the table.

It is excellent in transparency, scratch resistance, anti-adhesion, and adhesion.

<Example 2>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ Emulsion (EM-5) comprising an acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight

‧Inorganic particles (B): "Sphaerica 140" (starlet particles, particle size: 140 nm): 20 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-5))

<Example 3>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below.

The characteristics and the like of the obtained laminated film are shown in the table.

‧ Emulsion (EM-5) comprising an acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight

‧Inorganic particles (B) (SEAHOSTAR KEW-50, manufactured by Nippon Shokubai Co., Ltd. (the vermiculite particles, particle size: 500 nm)): 20 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-5))

<Example 4>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below.

The characteristics and the like of the obtained laminated film are shown in the table.

‧ Emulsion (EM-5) comprising an acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight

‧Inorganic particles (B) (SNOWTEXS O (manufactured by Nissan Chemical Industries Co., Ltd.) (20 nm particle size): 20 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-5))

<Example 5>

In addition to changing the resin composition in the coating liquid as described below, A laminate film was obtained in the same manner as in Example 1. The characteristics and the like of the obtained laminated film are shown in the table.

‧ an emulsion (EM-1) comprising an acrylic monomer (a-1) constituting the acrylic resin (A) component and a resin composition (b-2) containing the inorganic particles (B): 100 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-1))

<Example 6>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ an emulsion (EM-2) containing a amide bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) and a resin composition (b-2) containing the inorganic particles (B): 100 weight Share

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-2))

<Example 7>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ Contains decylamine containing the component of acrylic resin (A) An emulsion (EM-3) of a bond acrylic monomer (a-2) and a resin composition (b-2) containing inorganic particles (B): 100 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-3))

<Example 8>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ Emulsion (EM-4) containing a decyl bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) component: 80 parts by weight

‧Inorganic particles (B) (SNOWTEX OL) (colloidal vermiculite, particle size 40 nm) manufactured by Nissan Chemical Industries Co., Ltd.): 20 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-3))

<Examples 9 to 15>

A laminated film was obtained in the same manner as in Example 6 except that the film thickness of the resin layer was changed to the thickness described in the table. The characteristics and the like of the obtained laminated film are shown in the table.

<Example 16>

A laminate film was obtained in the same manner as in Example 6 except that the resin composition in the coating liquid was changed as described below. The resulting laminated film Characteristics and the like are shown in the table.

‧ an emulsion (EM-6) containing a guanamine bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) component and a resin composition (b-2) containing the inorganic particles (B): 100 weight Share

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-2))

<Example 17>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ an emulsion (EM-10) comprising an acrylic resin (G) composition (B-3) and an acrylic resin (F) on the surface of the inorganic particles (B): 100 parts by weight

<Example 18>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ an emulsion (EM-11) comprising an acrylic resin (G) composition (B-3) and an acrylic resin (F) on the surface of the inorganic particles (B): 100 parts by weight

<Example 19>

In addition to changing the resin composition in the coating liquid as described below, A laminate film was obtained in the same manner as in Example 1. The characteristics and the like of the obtained laminated film are shown in the table.

‧ an emulsion (EM-12) comprising an acrylic resin (G) composition (B-3) and an acrylic resin (F) on the surface of the inorganic particles (B-1): 100 parts by weight

<Example 20>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ an emulsion (EM-11) comprising an acrylic resin (G) composition (B-3) and an acrylic resin (F) on the surface of the inorganic particles (B): 80 parts by weight

‧ Melamine compound "BECKAMINE" (registered trademark) APM (made by Dainippon Ink Co., Ltd.): 20 parts by weight

<Examples 21, 22>

A laminate film was obtained in the same manner as in Example 17 except that the film thickness of the resin layer was changed to the thickness described in the table. The characteristics and the like of the obtained laminated film are shown in the table.

<Example 23>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as described below.

The characteristics and the like of the obtained laminated film are shown in the table.

‧ Emulsion (EM-5) comprising an acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight

‧Inorganic particles (B) (Nissan Chemical Industry Co., Ltd.) "SNOWTEXS O" ( vermiculite particles, particle size 10 nm): 20 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-5))

<Comparative Example 1>

A laminate film was obtained in the same manner as in Example 1 except that the composition of the resin composition in the coating liquid was changed as shown in the table. The characteristics and the like of the obtained laminated film are shown in the table.

‧ Emulsion (EM-5) comprising an acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight

‧Inorganic particles (B) (SNOWTEX OXS, manufactured by Nissan Chemical Industries Co., Ltd. (colloidal vermiculite, particle size 5 nm)): 20 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-5))

<Comparative Example 2>

The resin composition used in Example 6 was applied to one side of a PET film ("LUMIRROR (registered trademark)" U34) manufactured by Toray Industries Co., Ltd., having a thickness of 50 nm after drying, using hot air. The oven was dried at 100 ° C for 2 minutes and then dried again at 230 ° C for 20 seconds to obtain a laminated film. The characteristics and the like of the obtained laminated film are shown in the table.

<Comparative Example 3>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ an emulsion (EM-7) comprising an acrylic monomer (a-1) constituting the acrylic resin (A) component and a resin composition (b-3) containing the inorganic particles (B): 100 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-7))

<Comparative Example 4>

A laminate film was obtained in the same manner as in Example 1 except that the resin composition in the liquid was changed as described below. The characteristics and the like of the obtained laminated film are shown in the table.

‧ an emulsion (EM-8) comprising an acrylic monomer (a-1) constituting the acrylic resin (A) component and a resin composition (b-3) containing the inorganic particles (B): 100 parts by weight

‧Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulgen 104P, manufactured by Kao)

(The above emulsifier is accompanied by (EM-8))

<Comparative Example 5>

A laminate film was obtained in the same manner as in Example 17 except that the film thickness of the resin layer was changed to the thickness described in the table. The characteristics and the like of the obtained laminated film are shown in the table.

[Industrial availability]

The present invention is a laminate film which is excellent in transparency, scratch resistance, handleability, and anti-adhesion property, and can be used as a hard coat film used for conventional display applications and a hard coat film used for molding and decoration.

Claims (9)

A laminated film having a laminated film of a polyester layer and a resin layer, wherein at least one surface layer of the surface is a resin layer, and the surface layer has a microscopic surface roughness of the resin layer obtained by AFM (Atomic Force Microscope) Ra-1) is 1 nm or more and 20 nm or less, and the macroscopic surface roughness (Ra-2) obtained by a ternary surface roughness meter is 1 nm or more and 50 nm or less. The laminated film according to claim 1, wherein the resin layer of the surface layer has a macroscopic surface roughness (Ra-2) of 5 nm or more and 50 nm or less as determined by a ternary surface roughness meter. The laminated film according to claim 1, wherein the surface layer has a ratio of a microscopic surface roughness (Ra-1) to a macroscopic surface roughness (Ra-2) of the resin layer (Ra-2/Ra-1) of 3 or more and 30 the following. The laminated film according to any one of claims 1 to 3, wherein the surface layer has a resin layer containing particles and is at a position from the surface of the resin layer when the cross section of the resin layer is observed in the thickness direction to 10% of the thickness of the resin layer. The particle existence ratio (P-1) in the range is larger than the particle existence ratio (P-2) in the range from the position of the resin layer surface from the position of 40% of the thickness of the resin layer to 60%. The laminated film of claim 4, wherein a ratio of particles (P-1) in a range from a surface of the resin layer to a position of 10% of a thickness of the resin layer, and 40% of a thickness of the resin layer from a surface of the resin layer The ratio (P-1/P-2) of the particle existence ratio (P-2) in the range of the position to 60% is 1.1 or more and 5.0 or less. A laminate film according to claim 4 or 5, wherein the surface layer has a resin layer The thickness (t) is 100 nm or more and 5000 nm or less. The laminate film according to claim 6, wherein the surface layer has a resin layer having an average particle diameter (d) of from 1 nm to 100 nm, and a ratio of a thickness (t) of the resin layer to an average particle diameter (d) of the resin layer (t) ) / (d) is 2 or more and 1000 or less. The laminated film according to any one of claims 1 to 7, which is formed by directly laminating a polyester layer and a resin layer. A method for producing a laminated film according to any one of claims 1 to 8, comprising the steps of: coating a coating liquid containing a polyfunctional acrylic resin and particles on at least one side of the polyester film before the end of the crystal alignment, and then applying a coating liquid containing the polyfunctional acrylic resin and the particles, followed by The polyester film is stretched in at least a uniaxial direction, and heat treatment is applied to the polyester film to terminate the crystal alignment of the polyester film.