TW202306780A - Optical film, method for manufacturing optical film, optical member, and image display device - Google Patents

Abstract

This optical film comprises a resin film and an easy adhesion layer formed on a surface of the resin film. The easy adhesion layer includes a binder resin, polyamine, and fine particles. The polyamine is a polymer having multiple amino groups. The multiple amine groups include at least one selected from the group consisting of a secondary amino group and a tertiary amino group. The polyamine content of the easy adhesion layer is 0.0090 wt% to 1.4100 wt%.

Description

Optical film, manufacturing method of optical film, optical member, and image display device

The invention relates to an optical film, a manufacturing method of the optical film, an optical component, and an image display device.

Liquid crystal display devices or organic EL display devices are used in various image display applications such as monitors and televisions. A polarizing plate is used in a liquid crystal display device. In an organic EL display device, in order to prevent reflection of external light, a polarizing plate and a 1/4 wavelength plate are used. A polarizing plate usually includes a polarizing element, and a polarizing element protective film bonded to at least one side of the polarizing element through an adhesive layer.

Conventionally, cellulose-based films have been widely used as polarizing element protective films. In recent years, films made of acrylic, polyester, polycarbonate, cyclic polyolefin, etc. have also been used. These films have lower moisture permeability and excellent durability than cellulose-based films, but are inferior in adhesion to PVA-based polarizers compared to cellulose-based films. Therefore, a method of providing an easy-adhesive layer on the surface of these films to improve the adhesion between the film and the polarizing element has been proposed. For example, Patent Document 1 describes that an easy-adhesive layer containing fine particles and an adhesive resin is provided on the surface of an acrylic film, thereby not only improving the adhesion between the acrylic film and a polarizer, but also suppressing sticking.

It is described in Patent Document 2 that alkaline components such as ammonia and amine are included in the easy-adhesive layer; although the excess residual alkaline components in the easily-adhesive layer will deteriorate the polarizer, the basic components can also be used to promote adhesion. It acts as a catalyst for the reaction of the resin (precursor); the alkaline component improves the dispersibility of the inorganic particles present in the easy-adhesive layer. It is described that after coating the easy-adhesive composition on the film base material, heating it can volatilize and remove the alkaline components and reduce the residual alkaline components in the easy-adhesive layer. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2010-55062 [Patent Document 2] Japanese Patent Laid-Open No. 2020-16872

[Problem to be Solved by the Invention]

However, sufficient studies have not been conducted on, for example, the adhesion between the film and the easily-adhesive layer or the uniformity of the easily-adhesive layer. Also, for example, in the technique described in Patent Document 2, it is relatively difficult to adjust the amount of residual alkaline components. [Technical means to solve the problem]

In view of the above circumstances, the inventors of the present invention have diligently studied repeatedly, and as a result, have completed the inventions shown in the following [1] to [10]. [1] An optical film comprising a resin film and an easy-adhesive layer formed on the surface of the resin film, wherein the easy-adhesive layer contains an adhesive resin, a polyamine, and fine particles, and the polyamine has a plurality of amines A polyamine-based polymer, the plurality of amine groups include at least one selected from the group consisting of secondary amine groups and tertiary amine groups, and the content of the above-mentioned polyamine in the above-mentioned easy-adhesive layer is 0.0090% by weight to 1.4100% weight%. [2] The optical film according to [1], wherein the binder resin includes a urethane resin. [3] The optical film according to [1] or [2], wherein the plurality of amine groups include a primary amine group, a secondary amine group, and a tertiary amine group. [4] The optical film according to any one of claims [1] to [3], wherein the polyamine includes polyalkyleneimine. [5] The optical film according to [4], wherein the polyalkyleneimine includes a primary amine group, the secondary amine group, and the tertiary amine group, and has a branched structure. [6] The optical film according to any one of claims [1] to [5], wherein the resin film contains a (meth)acrylic polymer. [7] An optical member comprising the optical film according to any one of [1] to [6]. [8] An image display device comprising the optical film according to any one of [1] to [6]. [9] A method for producing an optical film, which is the method for producing an optical film according to any one of [1] to [6], wherein the surface of the resin film is coated with an adhesive resin, polyamine, and fine particles. Composition to form the coating film of the above-mentioned easy-adhesive composition, the above-mentioned coating film is dried to form an easy-bonding layer comprising the above-mentioned binder resin, the above-mentioned polyamine, and the above-mentioned fine particles on the surface of the above-mentioned resin film. The above-mentioned polyamine has a plurality of A polymer of amine groups, wherein the plurality of amine groups include at least one selected from the group consisting of secondary amine groups and tertiary amine groups. [Effect of Invention]

The optical film of the present invention has a resin film and an easily bonding layer, and these are excellent in adhesion. In addition, the optical film of the present invention is easy to control the amount of alkaline components contained in the easily-adhesive layer because the basic components contained in the easily-adhesive layer are polymers that are not volatile during the production of the optical film.

Unless otherwise specified, "resin" in this specification is a broader concept than "polymer". The resin can be composed of, for example, one or two or more polymers, and can also contain materials other than polymers, such as ultraviolet absorbers, antioxidants, additives such as fillers, compatibilizers, stabilizers, etc., if necessary.

[Optical film] The optical film of this embodiment has a resin film and an easy-adhesive layer formed on the surface of the resin film.

[resin film] The resin film is not particularly limited, and is, for example, a film made of materials such as (meth)acrylic polymers, polyesters, polycarbonates, and cyclic polyolefins. Among them, an acrylic resin film obtained by molding an acrylic resin containing a (meth)acrylic polymer is preferable. The content of the (meth)acrylic polymer in the acrylic resin is usually at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight, particularly preferably at least 90% by weight, most preferably at least 95% by weight %above.

A (meth)acrylic polymer is a polymer having structural units ((meth)acrylate units) derived from (meth)acrylate monomers. The content of (meth)acrylate units in the (meth)acrylic polymer is usually at least 10% by weight, preferably at least 30% by weight, more preferably at least 50% by weight, and most preferably at least 70% by weight. The weight average molecular weight of the (meth)acrylic polymer is preferably from 10,000 to 500,000, more preferably from 50,000 to 300,000.

(Meth)acrylate units are e.g. derived from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylic acid Tertiary butyl ester, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, chloromethyl (meth)acrylate, 2-chloroethyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth)acrylate, (methyl) Structural unit of each monomer of 2,3,4,5-tetrahydroxypentyl acrylate. The (meth)acrylic polymer preferably has a structural unit derived from methyl (meth)acrylate, and in this case, the optical properties and thermal stability of the finally obtained optical film are improved. A (meth)acrylic polymer may have 2 or more types of (meth)acrylate units.

A (meth)acrylic polymer may have a structural unit other than a (meth)acrylate unit. Such structural units are derived, for example, from styrene, vinyltoluene, α-methylstyrene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, 4-methyl-1-pentene, vinyl acetate, 2-hydroxymethyl-1-butene, methyl vinyl ketone, N-vinyl pyrrolidone, N-vinyl carbazole monomers Structural units. A (meth)acrylic polymer may have these structural units of 2 or more types. In the case where the (meth)acrylic polymer has an N-vinylpyrrolidone unit or an N-vinylcarbazole unit, the degree of freedom in controlling the wavelength dispersion of birefringence in the optical film increases. For example, a retardation film exhibiting wavelength dispersion (so-called inverse wavelength dispersion) in which the birefringence becomes smaller (the absolute value of the retardation becomes smaller) in the visible light region is obtained as the wavelength of light is shorter. The retardation film can be preferably used as a positive retardation film.

The (meth)acrylic polymer may have a ring structure in the main chain. Such a (meth)acrylic polymer is obtained by, for example, copolymerizing a (meth)acrylate monomer with a monomer having a ring structure or polymerizing a monomer group containing a (meth)acrylate monomer, followed by cyclization. obtained by the reaction. When the (meth)acrylic polymer has a ring structure in the main chain, the total content of the (meth)acrylate unit and the ring structure may be 50% by weight or more.

Furthermore, when a ring structure is introduced into the main chain by a cyclization reaction after polymerization, the (meth)acrylic polymer is preferably formed by a monomer group containing a monomer having a hydroxyl group and/or a carboxylic acid group. formed by the aggregation. Monomers with hydroxyl groups are, for example, 2-(hydroxymethyl)methyl acrylate, 2-(hydroxymethyl)ethyl acrylate, 2-(hydroxymethyl)isopropyl acrylate, 2-(hydroxymethyl)butyl acrylate ester, 2-(hydroxyethyl)methyl acrylate, methallyl alcohol, allyl alcohol. The monomer having a carboxylic acid group is, for example, acrylic acid, methacrylic acid, crotonic acid, 2-(hydroxymethyl)acrylic acid, 2-(hydroxyethyl)acrylic acid. Two or more of these monomers can also be used. Furthermore, during the cyclization reaction, all of the monomers need not be changed into ring structures, and the (meth)acrylic polymer after the cyclization reaction may also have structural units derived from these monomers.

The (meth)acrylic polymer preferably has a ring structure in the main chain. Thus, the heat resistance and hardness of an acrylic resin film are excellent. In addition, since it exhibits a large retardation when it is made into a stretched film, it can be preferably used as a retardation film or a polarizer protective film having the function of a retardation film.

The ring structure is, for example, at least one selected from an N-substituted maleimide structure, a maleic anhydride structure, a glutarimide structure, a glutaric anhydride structure, and a lactone ring structure. N-substituted maleimide structures are, for example, cyclohexylmaleimide structures, methylmaleimide structures, phenylmaleimide structures, benzylmaleimide structures, and benzylmaleimide structures. Diamide structure. From the viewpoint of the heat resistance of the optical film, the ring structure is preferably a lactone ring structure, a cyclic imide structure (such as an N-alkyl substituted maleimide structure, a glutarimide structure) , Cyclic anhydride structure (such as maleic anhydride structure and glutaric anhydride structure). The optical film of this embodiment can be used as a retardation film. The ring structure is preferably a lactone ring structure, a glutarimide structure, and a glutaric anhydride structure from the viewpoint of imparting a positive phase difference to an optical film as a retardation film. The ring structure is preferably a lactone ring structure from the viewpoint of improving the wavelength dispersion of birefringence in the retardation film.

The glutaric anhydride structure and the glutarimide structure are shown in the following general formula (1).

R ¹ and R ² in the above general formula (1) are independently a hydrogen atom or a methyl group, and X ¹ is an oxygen atom or a nitrogen atom. When X ¹ is an oxygen atom, R ³ does not exist, and when X ¹ is a nitrogen atom, R ³ is a hydrogen atom, a linear alkyl group having 1 to 6 carbons, cyclopentyl, cyclohexyl, benzyl or phenyl.

When X ¹ is an oxygen atom, the ring structure represented by the general formula (1) is a glutaric anhydride structure. The glutaric anhydride structure can be formed, for example, by intramolecular dealcoholization and cyclocondensation of a copolymer of (meth)acrylate and (meth)acrylic acid. When X ¹ is a nitrogen atom, the ring structure represented by the general formula (1) is a glutarimide structure. The glutarimide structure can be formed, for example, by imidating a (meth)acrylate polymer with an imidating agent such as methylamine.

The maleic anhydride structure and the N-substituted maleimide structure are shown in the following general formula (2).

R ⁴ and R ⁵ in the above general formula (2) are independently a hydrogen atom or a methyl group, and X ² is an oxygen atom or a nitrogen atom. When X ² is an oxygen atom, there is no R ⁶ , and when X ² is a nitrogen atom, R ⁶ is a hydrogen atom, a linear alkyl group with 1 to 6 carbons, cyclopentyl, cyclohexyl, benzyl or phenyl.

When X ² is an oxygen atom, the ring structure represented by the general formula (2) is a maleic anhydride structure. The maleic anhydride structure can be formed by copolymerizing maleic anhydride and (meth)acrylate, for example. When X ² is a nitrogen atom, the ring structure represented by the general formula (2) is an N-substituted maleimide structure.

Furthermore, in the method of forming a ring structure exemplified in the description of general formulas (1) and (2), all polymers used to form each ring structure have (meth)acrylate units as structural units, so The obtained resin was an acrylic resin.

The lactone ring structure is shown in the following general formula (3).

In the above general formula (3), R ⁷ , R ⁸ and R ⁹ are independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may also contain oxygen atoms.

The organic residues in the general formula (3) are, for example, unsaturated aliphatic groups with carbon numbers ranging from 1 to 20, such as methyl, ethyl, and propyl, and unsaturated aliphatic groups ranging from 2 to 20, such as vinyl and propenyl. Aromatic hydrocarbon groups ranging from 6 to 20 carbon atoms such as hydrocarbon groups, phenyl groups, naphthyl groups, etc., the above-mentioned alkyl groups, the above-mentioned unsaturated aliphatic hydrocarbon groups, and one or more hydrogen atoms of the above-mentioned aromatic hydrocarbon groups can also be selected from hydroxyl, carboxyl, At least one of ether group and ester group is substituted.

The 6-membered lactone ring structure is shown in the general formula (3) above, but the lactone ring structure is not limited thereto. For example, a 4- to 8-membered ring is also possible. In terms of excellent stability of the ring structure, a 5-membered ring or a 6-membered ring is preferred, and a 6-membered ring is more preferred.

When the (meth)acrylic polymer has a ring structure in the main chain, the content of the ring structure in the polymer is not particularly limited, but it is usually 5 to 90% by weight, preferably 10 to 70% by weight. More preferably, it is 10 to 60 weight%, More preferably, it is 10 to 50 weight%. When the content of the ring structure is large (for example, 10% by weight or more), the heat resistance, solvent resistance, and surface hardness of the film are particularly excellent. When the content of the ring structure is small (for example, 70% by weight or less), the acrylic resin film is particularly excellent in easiness of stretching and handling during production.

When the ring structure of the main chain is other than the lactone ring structure (such as N-substituted maleimide structure, maleic anhydride structure, glutarimide structure and glutaric anhydride structure), the ring The content of the structure is not particularly limited, but is, for example, 5 to 90% by mass, preferably 10 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 10 to 50% by mass.

When the ring structure of the main chain is a lactone ring structure, the content of the ring structure is not particularly limited, for example, 5 to 90% by mass, preferably 10 to 80% by mass, more preferably 10 to 70% by mass , and more preferably 10 to 60% by mass.

The (meth)acrylic polymer which has a ring structure in a main chain can be formed by a well-known method. (Meth)acrylic polymers having a lactone ring structure in the main chain are, for example, JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544 The polymers described in Japanese Patent Publication No. 2005-146084 and JP-A-2005-146084 can be formed by the method described in the publication.

(Meth)acrylic acid polymers having a glutaric anhydride structure in the main chain are, for example, polymers described in JP-A-2006-283013, JP-A-2006-335902, and JP-A-2006-274118. Formed by the method described in the gazette.

(Meth)acrylic polymers having a glutarimide structure in the main chain are, for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328329, JP-A-2006 -328334, JP-A 2006-337491, JP-A 2006-337492, JP-2006-337493, JP-2006-337569, JP-2007-009182 The described polymer can be formed by the method described in this gazette.

Furthermore, when forming various polymers in an acrylic resin, from the viewpoint of reducing foreign matter in the polymer, and in terms of filtering at a low-viscosity stage compared to filtering after polymerization, it is preferable to use When performing polymerization, the monomer raw materials, by-products such as polymerization initiators or catalysts, and solvents used for polymerization are filtered as much as possible before use. As a method of filtration, if it is a liquid, it can be directly filtered, if it is a solid, it can be dissolved in a solvent used for polymerization, etc., and then passed through various filters such as a membrane filter or a hollow fiber membrane filter, and can be filtered separately. Can be made into a mixture and filtered. In addition, the filtration accuracy at this time is preferably 5.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.5 μm or less.

Acrylic resins can be formed by combining (meth)acrylic polymers with other polymers depending on the desired physical properties and applications. Other polymers are not particularly limited, and may be thermoplastic polymers, curable polymers, or combinations thereof. Other polymers can be used alone or in combination of two or more.

Specific examples of other polymers include other (meth)acrylic polymers and olefin-based polymers that differ in composition ratio or molecular weight from (meth)acrylic polymers, or in copolymerization compositions that are different from (meth)acrylic polymers. Polymers (such as polyethylene, polypropylene, ethylene-propylene copolymer, poly(4-methyl-1-pentene), etc.), halogen-based polymers (such as polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride Halogenated vinyl polymers), styrenic polymers [such as polystyrene, styrenic copolymers (such as styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butane ethylene-styrene block copolymer (ABS resin), acrylate-styrene-acrylonitrile copolymer (ASA resin), etc.), polyester-based polymers (such as polyethylene terephthalate, polyethylene terephthalate Aromatic polyesters such as butylene phthalate and polyethylene naphthalate), polyamide-based polymers (such as aliphatic polyamide-based polymers such as polyamide 6, polyamide 66, and polyamide 610) polymer), polyacetal polymer, polycarbonate polymer, polyphenylene ether polymer, polyphenylene sulfide polymer, polyetheretherketone polymer, polysulfide polymer, polyether are polymers, copolymers containing polymer blocks having units derived from dienes and/or olefins and polymer blocks having units derived from aromatic vinyl monomers [e.g. styrene-ethylene/butylene -Styrene block copolymer (SEBS), styrene-butadiene/butylene-styrene block copolymer (SBS), etc.], cellulosic polymers (cellulose derivatives), thermoplastic elastomers (benzene Ethylene elastomers, etc.), etc.

When the acrylic resin contains other polymers besides the (meth)acrylic polymer, the form of the (meth)acrylic polymer and other polymers is not particularly limited, and may be a polymer blend or a The above-mentioned (meth)acrylic polymer is chemically bonded to other polymers. In this case, a block copolymer, a graft copolymer, etc. can also be formed with a (meth)acrylic polymer and another polymer.

When the acrylic resin contains other polymers besides the (meth)acrylic polymer, the content of other polymers may be, for example, 90% by mass or less (for example, 0.1 to 85% by mass), or may be 80% by mass or less ( For example, 0.5 to 70% by mass), preferably less than 60% by mass (eg, 1 to 55% by mass), or less than 50% by mass (eg, 2 to 45% by mass), or less than 30% by mass (eg, 2 to 25% by mass) % by mass), 20% by mass or less (for example, 2 to 15% by mass), etc.

For example, when the acrylic resin contains a styrene-based polymer, the acrylic resin film composed of the acrylic resin is made into a stretched film, whereby the negative phase difference exhibited by the styrene-based polymer can be offset by having a ring structure in the main chain The (meth)acrylic polymer exhibits a positive phase difference. By adjusting the content of the styrene-based polymer in the acrylic resin film, a negative retardation film or a polarizer protection film with low retardation can be produced. When the acrylic resin film contains a styrene polymer, the styrene polymer is preferably a styrene-acrylonitrile copolymer from the viewpoint of compatibility with the (meth)acrylic polymer. When the acrylic resin film contains ABS resin or ASA resin, by adjusting the content of the ABS resin or ASA resin in the acrylic resin film, the acrylic resin film can be made into a negative retardation film or a low retardation film. And flexibility can be improved.

Acrylic resins may also contain materials other than polymers, such as additives. Examples of additives are: hindered phenol (hindered phenol)-based, phosphorus-based, sulfur-based and other antioxidants; light-resistant stabilizers, weather-resistant stabilizers, heat stabilizers and other stabilizers; glass fiber, carbon fiber and other reinforcing materials; phenyl salicylate, (2,2'-Hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone and other ultraviolet absorbers; near-infrared absorbers; ginseng (dibromopropyl) phosphate, triene phosphate Flame retardants such as propyl ester and antimony oxide; antistatic agents composed of anionic, cationic, and nonionic surfactants; coloring agents such as inorganic pigments, organic pigments, and dyes; organic fillers, inorganic fillers; antiblocking agents ; Resin modifier; Organic filler, inorganic filler; Plasticizer; Lubricant; Phase difference reducer.

The content of the additive in the acrylic resin is preferably from 0 to 5% by weight, more preferably from 0 to 2% by weight, and still more preferably from 0 to 0.5% by weight.

The Tg (glass transition temperature) of the acrylic resin is preferably at least 100°C, more preferably at least 110°C, still more preferably at least 115°C, particularly preferably at least 120°C. The upper limit of Tg of the acrylic resin is not particularly limited, but it is preferably 170° C. or lower from the viewpoint of elongation when used as an acrylic resin film.

Acrylic resin films are obtained by shaping acrylic resins. The thickness of the acrylic resin film is not particularly limited, but is preferably 5-200 μm, more preferably 10-100 μm. When the thickness is 5 μm or more, the strength is excellent. Transparency is excellent as this thickness is 200 micrometers or less.

The wetting tension of the surface of the acrylic resin film is preferably at least 40 mN/m, more preferably at least 50 mN/m, still more preferably at least 55 mN/m. When the wetting tension of the surface is 40 mN/m or more, the adhesiveness between the optical film of this embodiment and other members is further improved. In order to adjust the wetting tension of the surface, any appropriate surface treatment may be performed on the surface of the acrylic resin film. Surface treatment is, for example, corona discharge treatment, plasma treatment, ozone blowing, ultraviolet irradiation, flame treatment, and chemical treatment. Among them, corona discharge treatment and plasma treatment are preferred.

[Manufacturing method of (acrylic) resin film] The acrylic resin film can be formed by a known film forming method using an acrylic resin. The film forming method is, for example, a solution casting method, a melt extrusion method, a calendar method, and a compression molding method. Among them, the solution casting method and the melt extrusion method are preferable.

The acrylic resin used for film formation can be formed by a known method. For example, the acrylic resin is formed by thoroughly mixing the (meth)acrylic polymer, other thermoplastic polymers, additives, etc. blended according to the composition of the acrylic resin to be obtained by an appropriate mixing method. The mixing method is, for example, extrusion kneading or mixing in a solution state. Commercially available acrylic resins can also be used for film production. Commercially available acrylic resins are, for example, ACRYPET VH and ACRYPET VRL20A (both manufactured by Mitsubishi Rayon). For extrusion kneading, any appropriate mixer can be used, such as an omni-mixer, a single-screw extruder, a twin-screw extruder, and a pressurized kneader.

烷等醚；二氯甲烷、氯仿、四氯化碳等鹵化烴；二甲基甲醯胺；二甲基亞碸。亦可將2種以上之該等溶劑併用。Devices for implementing the solution casting method are, for example, roll casting machines, belt casting machines, and spin coaters. The solvent used in the solution casting method is not limited as long as it dissolves the acrylic resin. The solvent is, for example: aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as cyclohexane and decahydronaphthalene; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketones such as base ketone; alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, methyl cellosulfur, ethyl cellosulfur, butyl cellosulfur; tetrahydrofuran, di

Alkanes and other ethers; Dichloromethane, chloroform, carbon tetrachloride and other halogenated hydrocarbons; Dimethylformamide; Dimethylsulfoxide. These solvents may be used in combination of two or more.

The melt extrusion method is, for example, a T-die method and an inflation method. The molding temperature during melt extrusion is preferably from 150 to 350°C, more preferably from 200 to 300°C. In the T-die method, for example, a tape-shaped acrylic resin film can be formed by installing a T-die at the front end of a known extruder. The formed strip-shaped acrylic resin film can be wound up on a roll to make a film roll.

The obtained acrylic resin film can be stretched. The extending direction may be any of the longitudinal direction (MD direction) of the acrylic resin film, the width direction (TD direction) perpendicular to the longitudinal direction, and the direction inclined with respect to the longitudinal direction. In the case of stretching in the biaxial direction, stretching in the MD direction (longitudinal stretching) and stretching in the TD direction (transverse stretching) can be performed sequentially, or stretching in the MD direction and TD direction can be performed simultaneously. The extension of the direction extends at the same time. If the glass transition temperature of the acrylic resin film is set as Tg, the temperature during stretching is preferably in the range of (Tg-30) to (Tg+100) ° C, more preferably (Tg-20) to (Tg+80 )°C, more preferably (Tg-5) to (Tg+20)°C. The elongation ratio is not particularly limited, and may be, for example, about 1.1 to 25 times (for example, 1.3 to 10 times) as the elongation ratio defined by the area ratio. It does not specifically limit as stretching speed (unidirectional), For example, it can be about 10-20000%/min (for example, 100-10000%/min). A stretched acrylic resin film is preferably used as a retardation film. The stretching method is not particularly limited, and a known stretching machine can be used for stretching. The extension machine is described below.

When forming an acrylic resin film by melt extrusion, formation of an acrylic resin by material mixing to formation of an acrylic resin film, and stretching can be performed continuously. In the case of forming an acrylic resin film by the T-die method, the temperature of the roll that winds up the formed film can also be adjusted, and the uniaxial stretching in the MD direction and the film winding can be performed simultaneously.

Furthermore, for example, after stretching, the acrylic resin film may be heat-treated (annealed) in order to stabilize the optical homogeneity and mechanical properties of the acrylic resin film. The method and conditions of heat treatment can be selected appropriately.

[easy adhesion layer] The easy-adhesive layer contains an adhesive resin, polyamine, and fine particles. Polyamine is a polymer with multiple amine groups. The plurality of amine groups includes at least one selected from the group consisting of secondary amine groups and tertiary amine groups. The content rate of the polyamine in an easy-adhesive layer is 0.0090 weight% - 1.4100 weight%. Polyamine promotes the dispersion of fine particles in the easy-adhesive layer, improves the adhesion between the resin film and the easy-adhesive layer, the blocking resistance of the optical film, and the uniformity of the easy-adhesive layer.

The physical properties required for optical films include retardation, tear resistance, and folding resistance. In order to obtain a biaxially stretched optical film that satisfies the required physical properties, the stretching temperature must be strictly controlled. The extension temperature is changed according to the subtle differences in the physical properties of each batch of resin, such as molecular weight or composition ratio. Here, in the manufacture of an optical film, the drying of the easily-adhesive layer is often carried out simultaneously with the lateral stretching step. Therefore, changing the stretching temperature means changing the drying temperature of the easily bonded layer. When the basic component contained in the easy-adhesive layer is a low-molecular-weight compound, if the drying temperature of the easy-adhesive layer is changed, the volatilization amount of the basic component will change, and the content of the basic component in the easy-adhesive layer will also change. change. In this case, the desired effect based on the basic component may not be sufficiently obtained. It is difficult to change the extension temperature so that the content of the basic component falls within the desired range. In particular, when an optical film is produced using a resin having a relatively high Tg such as an acrylic resin having a ring structure, the stretching temperature must be increased. Low-molecular-weight basic components with high volatility are easily released to the outside during the extension step at high temperature. In this case, the effect of promoting the dispersion of fine particles by the alkaline component becomes insufficient.

On the other hand, the polyamine of the polymer is not volatile, and can reliably remain in the easy-adhesive layer. Even if the stretching temperature is changed, the polyamine content in the easily-adhesive layer does not change easily. Therefore, the polyamine of the polymer can preferably make the content of the basic component in the easy-adhesive layer fall within a desired range, and can surely promote the dispersion of fine particles. As a result, it can be expected that the blocking resistance of the optical film will be further improved.

In addition, it is also speculated that the cationicity of the polyamine acts on the ester moiety of the acrylic resin. That is, it is presumed that the adhesion between the easily-adhesive layer and the resin film is improved by the interaction between the amine group of the polyamine and the ester moiety of the acrylic resin.

Also, when an acrylic resin having a ring structure in the main chain is used as a material of the resin film, the stretching temperature of the resin film (≒the drying temperature of the easily-adhesive layer) is set higher. It is considered that the adhesive resin of the easy-adhesive layer easily permeates to the surface of the resin film whose temperature is higher than Tg. As a result, the adhesion between the easy-adhesive layer and the resin film can be further improved.

The binder resin should just be a well-known resin with easy adhesiveness, for example, an urethane resin, a cellulose resin, a polyol resin, a polycarboxylic acid resin, a polyester resin, and an acrylic resin. At least one selected from these resins can be used as the binder resin.

The number average molecular weight of the binder resin is preferably from 5,000 to 600,000, more preferably from 10,000 to 400,000.

The binder resin includes, for example, urethane resin. The binder resin is preferably urethane resin. Thus, the adhesiveness of an easily-adhesive layer to an acrylic resin film improves, and the easy-adhesiveness of an optical film to another member improves.

The urethane resin is not particularly limited, and is typically a resin obtained by reacting a polyol and a polyisocyanate. As the polyol, any polyol having two or more hydroxyl groups in the molecule can be used. Polyols are, for example, polyacrylic polyols, polyester polyols, and polyether polyols. You may combine 2 or more types of polyols.

Polyacrylic polyol is typically a copolymer of a (meth)acrylate monomer and a monomer having a hydroxyl group. Examples of (meth)acrylate monomers include methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Monomers with hydroxyl groups are, for example: (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate-3-hydroxypropyl, (meth)acrylate- Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl ester, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypentyl (meth)acrylate; polyols such as glycerin and trimethylolpropane Mono(meth)acrylate; N-methylol(meth)acrylamide.

The polyacrylic acid polyol may also be a copolymer with further other monomers. Other monomers are not limited as long as they can be copolymerized with the above-mentioned (meth)acrylate monomers and monomers having hydroxyl groups. The other monomers are, for example: unsaturated monocarboxylic acids such as (meth)acrylic acid; unsaturated dicarboxylic acids such as maleic acid and their anhydrides and mono- or diesters; unsaturated nitriles such as (meth)acrylonitrile Unsaturated amides such as (meth)acrylamide and N-hydroxymethyl(meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl esters such as methyl vinyl ether Ethers; α-olefins such as ethylene and propylene; halogenated α, β-unsaturated aliphatic monomers such as vinyl chloride and vinylidene chloride; α, β-unsaturated aromatics such as styrene and α-methylstyrene monomer.

Polyester polyol is typically obtained by reacting a polybasic acid component and a polyol component. Polyacid components such as: phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, biphenyl dicarboxylic acid , tetrahydrophthalic acid and other aromatic dicarboxylic acids; oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid Acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, tartaric acid, alkyl succinic acid, linolenic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, icon Aliphatic dicarboxylic acids such as acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. ; or reactive derivatives such as acid anhydrides, alkyl esters, and acid halides.

Polyol components such as: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentylene glycol, 1,6 -Hexanediol, 1,8-octanediol, 1,10-decanediol, 1-methyl-1,3-butanediol, 2-methyl-1,3-butanediol, 1-methyl 1,4-pentanediol, 2-methyl-1,4-pentanediol, 1,2-dimethylneopentyl glycol, 2,3-dimethylneopentyl glycol, 1-methyl 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-dimethylbutanediol, 1,3 -Dimethylbutanediol, 2,3-dimethylbutanediol, 1,4-dimethylbutanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol , 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F.

Typically, polyether polyol is obtained by ring-opening polymerization of alkylene oxide and adding to polyol. Polyhydric alcohols are, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane. Alkylene oxides are, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and tetrahydrofuran.

Polyisocyanates are, for example: tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate Isocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate Aliphatic diisocyanates such as isocyanates; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-cyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate , 1,3-bis(isocyanatomethyl)cyclohexane and other alicyclic diisocyanates; toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene Diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and other aromatic diisocyanates; dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, α,α, Araliphatic diisocyanates such as α,α-tetramethylxylylene diisocyanate.

The urethane resin preferably has a carboxyl group. By having a carboxyl group, the performance (adhesiveness) of an easily-adhesive layer improves. This effect is especially remarkable in the environment of high temperature and high humidity. The urethane resin having a carboxyl group is obtained, for example, by adding to a polyol and polyisocyanate, and reacting a chain length agent having a free carboxyl group. Chain length agents with free carboxyl groups are, for example, dihydroxycarboxylic acids and dihydroxysuccinic acids. Dihydroxycarboxylic acids are, for example, dihydroxymethylalkanoic acids (such as dimethylolacetic acid, dimethylolbutyric acid, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpentanoic acid) and the like. Hydroxyalkylalkanoic acids.

The acid value of the urethane resin is preferably at least 10, more preferably 10-50, particularly preferably 20-45. In these cases, the performance of the easy-adhesive layer (for example, the adhesiveness with other functional films such as polarizing elements) is further improved.

The urethane resin can also be obtained by reacting with other polyols or other chain length agents in addition to the above-mentioned components. Other polyols are, for example, sorbitol, 1,2,3,6-hexanethritol, 1,4-sorbitan, 1,2,4-butanetriol, 1,2,5-pentanetriol, Polyhydric alcohols having three or more hydroxyl groups, such as glycerin, trimethylolethane, trimethylolpropane, and neoerythritol. Other chain length agents are, for example: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol Alcohol, 1,6-hexanediol, propylene glycol and other diols; ethylenediamine, propylenediamine, hexamethylenediamine, 1,4-butylenediamine, aminoethylethanolamine and other aliphatic diamines; Alicyclic diamines such as isophoronediamine and 4,4'-dicyclohexylmethanediamine; aromatic diamines such as xylylenediamine and toluenediamine.

The urethane resin can be formed by a known method. This method is, for example, a one-shot method in which each component is reacted at one time, or a multistage method in which each component is reacted in stages. In terms of easy introduction of carboxyl groups, the urethane resin having carboxyl groups is preferably formed by a multistage method. The catalyst used to form the urethane resin is not particularly limited.

Polyamines may also comprise primary, secondary, and tertiary amine groups. Such polyamine also exhibits the effect of improving the adhesiveness between the resin film and the easy-adhesive layer.

The polyamines may also comprise polyalkyleneimines. Polyalkyleneimine can be preferably used as the basic component of the easy-adhesive layer. The polyalkyleneimine may be linear or may have a branched structure.

As the polyamine, polyalkyleneimines can be preferably used. Examples of polyalkyleneimines include polyalkyleneimines obtained by polymerizing one or more alkyleneimines having 2 to 6 carbon atoms, unsaturated carboxylic acids or cyclic Derivatives obtained by adding oxane to polyalkyleneimine, etc. Examples of alkyleneimines having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1 , 1-Dimethylethylene imine and so on. As the polyalkyleneimines, preferably polyethyleneimine, polypropyleneimine, derivatives of polyethyleneimine, derivatives of polypropyleneimine, more preferably polyethyleneimine imine, polyethylene imine derivatives. As the above-mentioned polyethyleneimine and polyethyleneimine derivatives, for example, Epomin Series manufactured by Nippon Shokubai Co., Ltd., which is already on the market; Epomin SP-003, Epomin SP-006, Epomin SP- 012, Epomin SP-018, Epomin SP-103, Epomin SP-110, Epomin SP-200, Epomin SP-300, Epomin SP-1000, Epomin SP-1020 (all trade names), etc.

The polyalkyleneimine may also contain primary amine groups, secondary amine groups, and tertiary amine groups and have a branched structure. The polyalkyleneimine having such a structure can be preferably used as the basic component of the easy-adhesive layer.

By adjusting the content rate of the polyamine in an easily bonding layer to the said range, the adhesiveness of a resin film and an easily bonding layer can be improved. The content rate of the polyamine in an easy-adhesive layer may be 0.0098 weight% - 1.4098 weight%.

The presence and content rate of the polyamine in an easily-bonding layer can be detected by known analysis methods, such as NMR, for example.

The fine particles may be any of inorganic fine particles and organic fine particles. Inorganic microparticles include, for example, inorganic oxides such as silicon dioxide (silica), titanium oxide, aluminum oxide, and zirconia; calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Microparticles such as magnesium silicate and calcium phosphate. Organic fine particles are, for example, fine particles of silicone resin, fluororesin, and acrylic resin. Among them, silica fine particles are preferable. Silica microparticles improve blocking resistance. In addition, since silica fine particles are excellent in transparency, coloring of the optical film and increase in haze ratio are less likely to occur.

The particle size (average particle size) of the fine particles is preferably from 10 to 1000 nm. By using fine particles of such a particle size, appropriate unevenness can be formed on the surface of the easy-adhesive layer, effectively reducing the adhesion between the acrylic resin film and the easily-adhesive layer, or between the easily-adhesive layers. From the viewpoint of suppressing light scattering by the particles, the average particle size of the microparticles is preferably smaller than the wavelength of visible light, and the smaller the better, and the larger is preferable from the viewpoint of stickiness. Therefore, the upper limit of the average particle diameter is, for example, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, more preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 350 nm or less. Also, the lower limit is 20 nm or more, 40 nm or more, 60 nm or more, 80 nm or more, and 100 nm or more, more preferably 120 nm or more, 140 nm or more, 160 nm or more, 180 nm or more, and 200 nm or more, Furthermore, it is preferably 220 nm or more, 240 nm or more, 260 nm or more, 280 nm or more, 300 nm or more, 320 nm or more, and 340 nm or more in this order. The particle size distribution of the fine particles is preferably from 1.0 to 1.2.

The content of fine particles in the easy-adhesive layer is not particularly limited, but relative to 100 parts by weight of the adhesive resin (solid content: when a crosslinking agent is included, the solid content also includes the crosslinking agent), The upper limit of the content is preferably less than 30 parts by weight, more preferably less than 20 parts by weight, and still more preferably less than 5 parts by weight. If the content rate of fine particles is less than 30 parts by weight, the strength of the easily-adhesive layer will be excellent. The lower limit of the content is preferably at least 0.1 part by weight, more preferably at least 0.2 part by weight, further preferably at least 0.5 part by weight. When the content rate of fine particles is 0.1 part by weight or more, the blocking resistance of the optical film is excellent. Furthermore, if the average particle size is small (for example, less than 100 nm), in order to obtain the effect of improving the blocking resistance, the content of fine particles is preferably more, and the lower limit of the content is preferably 0.5 parts by weight or more, 1.0 parts by weight or more, 5.0 parts by weight or more, and 10.0 parts by weight or more. Also, if the average particle size is large (for example, 200 nm or more), from the viewpoint of suppressing light scattering, the content of fine particles is preferably small, and the upper limit of the content is preferably less than 2.0 parts by weight, Less than 1.0 parts by weight.

The thickness of the easy-adhesive layer is not limited, and varies depending on the thickness of the film. It is preferably 100 nm to 10 μm, more preferably 100 nm to 5 μm, and still more preferably 200 nm to 1.5 μm. Within this range, the adhesiveness of the optical film to other members by the easily bonding layer is favorable. In addition, the easily-adhesive layer itself can be suppressed from exhibiting a phase difference.

The ratio r/d of the thickness d of the easily-adhesive layer to the average particle size r of the fine particles contained in the easily-adhesive layer is preferably 0.3-1.4, more preferably 0.4-1.1, and still more preferably 0.6-1.0. Within this range, the blocking resistance and transparency of the optical film of the present embodiment can be more reliably achieved.

The method of forming the easy-adhesive layer on the surface of the optical film is not limited, and it may follow a known method. The easy-adhesive layer is preferably formed by coating an easily-adhesive composition including an adhesive resin, polyamine, and fine particles on the surface of a resin film to form a coating film of the easily-bond composition, and drying the coating film. The easy-adhesive composition is preferably a water-based composition. Compared with organic solvent-based compositions, water-based compositions have less environmental load when forming an easily-adhesive layer, and have excellent workability. The aqueous composition is, for example, a dispersion of binder resin. The dispersion is typically an emulsion of the binder resin. The emulsion of the binder resin is dried to form a resin layer. The fine particles contained in the emulsion remain directly in the resin layer.

When the easy-adhesive composition is an aqueous system, the fine particles are preferably blended in the form of an aqueous dispersion such as colloidal silicon dioxide. What is necessary is just to satisfy the said range about an average particle diameter and a particle size distribution, and colloidal silica can also be a commercial item.

烷、四氫呋喃、丙二醇單甲醚等醚系溶劑。When the easy-adhesive composition is an aqueous composition containing urethane resin, it is preferable to use an organic solvent that is inactive to polyisocyanate and compatible with water when forming the urethane resin. Organic solvents are, for example: ester-based solvents such as ethyl acetate, butyl acetate, and ethyl cellophane acetate; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone;

Alkanes, tetrahydrofuran, propylene glycol monomethyl ether and other ether solvents.

唑啉基、環氧基、碳二亞胺基，較佳為

唑啉基。具有

唑啉基之交聯劑由於在與胺酯樹脂混合時，於室溫之使用期限較長，且藉由加熱進行交聯反應，故作業性良好。該聚合物例如較佳為（甲基）丙烯酸聚合物、苯乙烯・丙烯酸聚合物，（甲基）丙烯酸聚合物。於交聯劑為（甲基）丙烯酸聚合物之情形時，易接著層之性能進而提高。此外，（甲基）丙烯酸聚合物與水系易接著組成物穩定地相容，使胺酯樹脂良好地交聯。When the easy-adhesive composition contains urethane resin, if a crosslinking agent is further included, the performance of the easily-adhesive layer will be improved. The crosslinking agent is not particularly limited. When the urethane resin has a carboxyl group, the crosslinking agent is preferably a polymer having a group reactive with the carboxyl group. A group that can react with a carboxyl group is, for example, an organic amino group,

Azoline group, epoxy group, carbodiimide group, preferably

Azolinyl. have

The oxazoline-based cross-linking agent has a long service life at room temperature when mixed with urethane resin, and the cross-linking reaction is carried out by heating, so the workability is good. The polymer is preferably, for example, a (meth)acrylic polymer, a styrene-acrylic polymer, or a (meth)acrylic polymer. When the cross-linking agent is a (meth)acrylic polymer, the performance of the easy-adhesive layer is further improved. In addition, the (meth)acrylic polymer is stably compatible with the water-based easy-adhesive composition, so that the urethane resin can be well cross-linked.

When the easy-adhesive composition contains an urethane resin, the content of the urethane resin is preferably 1.5 to 15% by weight, more preferably 2 to 10% by weight. When the content rate is in these ranges, the applicability when the easily-adhesive composition is applied to the surface of an optical film, especially an acrylic resin film, is high. When the composition further includes a crosslinking agent, the content of the crosslinking agent is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the urethane resin (solid content). .

When the easy-adhesive composition contains urethane resin, it is preferable to contain a neutralizing agent. In this case, the stability of the urethane resin in the easy-adhesive composition improves. Neutralizing agents are, for example, ammonia, N-methylmorpholine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, morpholine, tripropylamine, ethanolamine, triisopropanolamine, 2-amine Base-2-methyl-1-propanol.

The adhesive composition may also contain additives. Additives are, for example, dispersion stabilizers, thixotropic agents, antioxidants, ultraviolet absorbers, defoamers, thickeners, dispersants, surfactants, catalysts, and antistatic agents.

[Characteristics and uses of optical film] The optical film of this embodiment is excellent in adhesiveness and blocking resistance to other members. Moreover, it is also excellent in transparency, and usually has a haze ratio of 1.5% or less. According to the structure of the optical film of this embodiment, a haze rate becomes 1.0 % or less, and further becomes 0.5 % or less.

The optical film of this embodiment is, for example, a polarizing element protective film, a retardation film, a viewing angle compensation film, a light diffusion film, a reflection film, an antireflection film, an antiglare film, a brightness improvement film, and a conductive film for a touch panel. The phase difference exhibited by the optical film of this embodiment can be controlled by the composition and stretching state of the film. The optical film of this embodiment may be an optically homogeneous film, or may be a film having optical anisotropy (for example, showing birefringence such as retardation).

When using the optical film of this embodiment as a retardation film, it can be suitably used for image display devices, such as LCD. This retardation film can be used for color tone compensation and viewing angle compensation of LCD, for example.

Since the retardation film has an easy-adhesive layer, it can also be used in forms other than those generally used as retardation films. Specifically, for example, it is considered to be a form used for bonding to a polarizing element included in an LCD. In this case, the retardation film functions as a general retardation film for color tone compensation or viewing angle compensation and as a polarizing element protective film for protecting the polarizing element. This form can omit the protective film for the polarizing element that has no retardation, which is conventionally used separately from the retardation film, and thus contributes to thinning and high-functioning LCDs.

In the case of forming an easy-adhesive layer on only one surface of the optical film, various functional coating layers may be formed on the opposite surface as needed. The functional coating layer is, for example, an antistatic layer, an adhesive layer, an adhesive layer, an easy-to-adhesive layer, an anti-glare (none-glare) layer, a photocatalyst layer, etc. Heat line shielding layer, electromagnetic wave shielding layer, gas barrier layer, etc.

[Optical components] The optical film of this embodiment is suitable, for example, for optical members such as a polarizing plate, a diffuser plate, a light guide, and a patch sheet.

A polarizing plate will be described as an example of the optical member of the present embodiment. In LCD, based on the principle of image display, a pair of polarizers are arranged with a liquid crystal cell sandwiched between them. The polarizing plate has, for example, a structure in which the optical film (polarizing element protective film) of this embodiment is laminated on at least one surface of the polarizing element through an easily adhesive layer.

Conventionally, a triacetyl cellulose (TAC) film has been used as a protective film for polarizing elements. However, the heat-and-moisture resistance of a TAC film is not sufficient, and when using a TAC film as a polarizing element protective film, the characteristic of a polarizing plate may deteriorate in high temperature or high humidity environment. In addition, the TAC film has a phase difference in the thickness direction, and this phase difference will adversely affect the viewing angle characteristics of image display devices such as LCDs, especially large-screen image display devices. On the other hand, when an acrylic resin film is used for a polarizing element protective film, heat-and-moisture resistance and optical characteristics can be improved compared with a TAC film.

Typically, a polarizing plate is manufactured by laminating an optical film and a polarizing element through an adhesive layer. When the optical film has an easily-adhesive layer, both are laminated so that the easily-adhesive layer becomes the polarizing element side. Specifically, for example, after applying an adhesive composition to become an adhesive layer after drying on the surface of any one selected from a polarizing element or an optical film, the two are bonded together and dried. The coating method of the adhesive composition is, for example, a roll coating method, a spray method, or a dipping method. When the adhesive composition contains metal compound colloid, the adhesive composition is applied such that the thickness of the adhesive layer after drying is larger than the average particle diameter of the metal compound colloid particles. The drying temperature is typically 5 to 150°C, preferably 30 to 120°C. The drying time is typically at least 120 seconds, preferably at least 300 seconds.

The polarizing element is not limited, and any appropriate polarizing element can be used according to the required function of the polarizing plate. The polarizing element is, for example, the partial saponification of polyvinyl alcohol (PVA) film, partially formalized PVA film, and ethylene-vinyl acetate copolymer (EVA) by adsorbing dichroic substances such as iodine or dichroic dyes. The film is a hydrophilic polymer film and a film formed by uniaxial stretching; a polyene-based alignment film using a dehydration-treated product of PVA or a dehydrochlorination-treated product of polyvinyl chloride. Among them, a film obtained by adsorbing a dichroic substance on a PVA-based film and stretching it uniaxially is preferred as a polarizing element. The polarizing element exhibits a high polarization dichroic ratio. The thickness of the polarizing element is not limited, and is usually about 1-80 μm. A polarizing element obtained by absorbing iodine on a PVA film and uniaxially stretching it can be produced, for example, by immersing a PVA film in an aqueous solution containing iodine, dyeing it, and stretching it uniaxially at a stretching ratio of 3 to 7 times. . The aqueous solution used for dyeing may also contain boric acid, zinc sulfate, zinc chloride, etc. as needed. As the aqueous solution containing iodine, an aqueous solution of iodide such as potassium iodide can also be used. The PVA film can also be dipped in water for washing before dyeing. By washing the PVA-based film, the stains and anti-blocking agents on the surface of the film can be removed. Furthermore, the PVA-based film is swollen by washing with water, and unevenness at the time of dyeing is suppressed. Extension can be performed before dyeing, after dyeing, or simultaneously with dyeing.

The composition of the adhesive that becomes the adhesive layer after drying is not limited. The following method is not limited, it can be water paste or UV bonding. The adhesive composition preferably includes a PVA-based resin. PVA-based resins include, for example, the following polymers: saponified polyvinyl acetate and its derivatives; saponified copolymers of vinyl acetate and other monomers; acetalization, urination, etherification, and grafting of PVA Modified PVA made by phosphating or phosphating. The above other monomers are, for example: maleic acid (anhydride), fumaric acid, crotonic acid, itaconic acid, (meth)acrylic acid and other unsaturated carboxylic acids and their esters; ethylene, propylene and other α- Olefins; (methyl)allylsulfonic acid (sodium), sodium sulfonate (monoalkylmaleate), sodium disulfonate alkylmaleate, N-methylolacryl Amines, acrylamide alkylsulfonic acid base salts, N-vinylpyrrolidone, N-vinylpyrrolidone derivatives. The PVA-based resin preferably contains acetoacetyl group-containing PVA. In this case, the adhesiveness of a polarizing element and an optical film (especially an acrylic resin film) improves, and the durability of a polarizing plate improves.

From the viewpoint of the adhesiveness of the adhesive composition, the average degree of polymerization of the PVA-based resin is preferably about 100-5000, and more preferably 1000-4000. From the viewpoint of adhesiveness of the adhesive composition, the average degree of saponification of the PVA-based resin is preferably about 85-100 mol%, more preferably 90-100 mol%.

烷等溶劑而成之溶液添加倍羰烯之方法；使倍羰烯氣體或液狀倍羰烯與PVA直接接觸之方法。Acetylacetyl group-containing PVA can be obtained, for example, by reacting PVA with carbocene by any method. Specific examples are: a method of adding carbocene to a dispersion obtained by dispersing PVA in a solvent such as acetic acid;

A method of adding carbocene to a solution made of alkane and other solvents; a method of directly contacting PVA with carbocene gas or liquid carbocene.

The modification degree of acetyl acetyl group in PVA containing acetyl acetyl group is typically 0.1 mol% or more, preferably 0.1-40 mol%, more preferably 1-20%, and more preferably 2 to 7 mole%. By properly adjusting the degree of modification, the effect of modification (such as the improvement of water resistance) can be fully obtained. The modification degree of acetyl acetyl group of PVA can be measured by NMR.

、苯胍

與甲醛之縮合物等胺基-甲醛樹脂；鈉、鉀、鎂、鈣、鋁、鐵、鎳等一價至三價金屬之鹽及氧化物。其中，交聯劑較佳為胺基-甲醛樹脂及二醛。胺基-甲醛樹脂較佳為具有羥甲基，較佳為羥甲基三聚氰胺。二醛較佳為乙二醛。The adhesive composition may also include a crosslinking agent. The crosslinking agent is not limited, and is a compound having at least two functional groups showing reactivity to PVA-based resins. Examples of cross-linking agents are: ethylenediamine, triethylenediamine, hexamethylenediamine and other alkylene diamines with alkylene groups and 2 amine groups; toluene diisocyanate, hydrogenated toluene diisocyanate, trimethylol propane toluene diisocyanate adduct, triphenylmethane triisocyanate, methylene bis(4-phenylmethane triisocyanate), isophorone diisocyanate, and their ketoxime block or phenol block, etc. Isocyanate; Ethylene Glycol Diglycidyl Ether, Polyethylene Glycol Diglycidyl Ether, Glycerin Diglycidyl Ether, Glycerin Triglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether Epoxy such as base ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diglycidylamine; monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; glyoxal, propanediol Aldehyde, succinic dialdehyde, glutaraldehyde, maleic dialdehyde, o-phthalaldehyde and other dialdehydes; methylol urea, methylol melamine, alkylated methylol urea, alkylated methylol melamine, ethiguanide

, benzoguanidine

Amino-formaldehyde resins such as condensation products with formaldehyde; salts and oxides of monovalent to trivalent metals such as sodium, potassium, magnesium, calcium, aluminum, iron, nickel, etc. Among them, the crosslinking agent is preferably amino-formaldehyde resin and dialdehyde. The amino-formaldehyde resin preferably has a methylol group, preferably methylolmelamine. The dialdehyde is preferably glyoxal.

The blending amount of the crosslinking agent in the adhesive composition can be appropriately set according to the type of PVA-based resin. Typically, it is about 10 to 60 parts by weight with respect to 100 parts by weight of the PVA-based resin, preferably 20 to 50 parts by weight. Within this range, good adhesiveness can be obtained. By properly adjusting the compounding amount of the crosslinking agent, gelation of the adhesive composition can be suppressed. In this case, the pot life of the adhesive composition is extended, making it easy to use industrially.

The adhesive composition may also include metal compound colloid. The metal compound colloid may be a colloid in which metal compound particles are dispersed in a dispersion medium. The metal compound colloid can be a colloid that is always stable due to the electrostatic stabilization brought about by the mutual repulsion of the same kind of charges possessed by the particles. By making the adhesive composition contain the metal compound colloid, for example, even when the compounding amount of the crosslinking agent is large, the stability of the adhesive composition is improved.

The average particle size of the colloidal particles in the metal compound colloid can be set within a range that does not adversely affect the optical characteristics (such as polarization characteristics) of the polarizing plate. The average particle diameter of the colloidal particles is preferably from 1 to 100 nm, more preferably from 1 to 50 nm. Within these ranges, the colloidal particles can be uniformly dispersed in the adhesive layer. Thereby, adhesiveness is ensured, and occurrence of crack defects is suppressed. If a knick point defect occurs, for example, light leakage will occur in an image display device incorporating the polarizing plate.

Metal compounds are not limited, for example: alumina, silicon dioxide, zirconia, titanium oxide and other oxides; aluminum silicate, calcium carbonate, magnesium silicate, zinc carbonate, barium carbonate, calcium phosphate and other metal salts; diatoms Soil, talc, clay, kaolin and other minerals. Preferably, it is a metal compound colloid with a positive charge. The metal compound that becomes a positively charged colloid is preferably aluminum oxide and titanium oxide, particularly preferably aluminum oxide.

Typically, the metal compound colloid is a colloidal solution dispersed in a dispersion medium. The dispersion medium is, for example, water or alcohol. The solid content concentration in the colloid solution is typically about 1 to 50% by weight, preferably 1 to 30% by weight. The colloidal solution may also contain acids such as nitric acid, hydrochloric acid, and acetic acid as stabilizers.

The blending amount of the metal compound colloid in the adhesive composition (solid content conversion) is preferably 200 parts by weight or less, more preferably 10 to 200 parts by weight, and still more preferably 20 parts by weight relative to 100 parts by weight of the PVA-based resin. ~175 parts by weight, especially preferably 30~150 parts by weight. Within these ranges, the adhesiveness of the adhesive composition becomes more reliable, and the generation of crack point defects is further suppressed.

The adhesive composition may also include: coupling agents such as silane coupling agents and titanium coupling agents; various adhesion imparting agents; ultraviolet absorbers; antioxidants; heat-resistant stabilizers, hydrolysis-resistant stabilizers and other stabilizers.

The adhesive composition is preferably an aqueous solution (resin solution). From the viewpoint of coating properties and storage stability of the composition, the concentration of the resin in the aqueous solution is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight. The viscosity of the aqueous solution is preferably 1-50 mPa·s. When the adhesive composition contains metal compound colloid, even if the viscosity is as low as 1-20 mPa·s, it can effectively suppress the occurrence of crack point defects. The pH of the aqueous solution is preferably from 2 to 6, more preferably from 2.5 to 5, still more preferably from 3 to 5, especially preferably from 3.5 to 4.5. Usually, the surface charge of the metal compound colloid is adjusted by adjusting the pH of the aqueous solution. The surface charge is preferably a positive charge. By being positively charged, the occurrence of knick point defects can be further suppressed. The surface charge of the metal compound colloid can be confirmed, for example, by measuring the zeta potential with a zeta potential measuring machine.

The adhesive composition which is an aqueous solution (resin solution) can be formed by a well-known method. When the adhesive composition contains a crosslinking agent and a metal compound colloid, for example, a method of mixing a PVA-based resin and a crosslinking agent in a solution adjusted to an appropriate concentration by mixing the metal compound colloid can be used. It is also possible to mix the cross-linking agent at the same time after mixing the PVA-based resin and the metal compound colloid, considering the use period of the adhesive composition. The concentration of the aqueous solution can be adjusted after preparing the aqueous solution.

The thickness of the adhesive layer formed from the adhesive composition can be appropriately set according to the composition of the composition. The thickness is preferably 10-300 nm, more preferably 10-200 nm, especially preferably 20-150 nm. Within this range, the adhesive layer exhibits sufficient adhesive force.

[image display device] The optical film of this embodiment is suitable, for example, for image display devices such as electroluminescent (EL) display panels, plasma display panels (PDP), field emission displays (FED: Field Emission Display), and LCDs. The configuration of the image display device including the optical film of this embodiment is not particularly limited, as long as members such as a power supply, a backlight unit, and an operation unit are appropriately provided as necessary.

[Manufacturing method of optical film] The method for producing an optical film includes: coating a surface of a resin film with an easily bondable composition comprising an adhesive resin, polyamine, and microparticles to form a coating film of the easily bondable composition (coating step); The coating film is dried to form an easy-adhesive layer on the surface of the resin film (drying step). The manufacturing method of the resin film is as above-mentioned.

In the coating step, a coating film of an easy-adhesive composition is formed on at least one surface of the resin film. Typically, the coating film is formed on one surface of the optical film. A known method can be applied to the method of coating the easily-adhesive composition in the coating step.

The method is, for example, a bar coating method, a roll coating method, a gravure coating method, a rod coating method, a slot orifice coating method, a curtain coating method, or a jet coating method. The thickness of the coating film formed in the coating step can be appropriately adjusted according to the thickness required for the coating film to be an easily adhesive layer.

The surface of the resin film to be coated with the easy-adhesive composition is preferably subjected to surface treatment. The surface treatment is as above, but corona discharge treatment and plasma treatment are preferred. The conditions of the corona discharge treatment are not limited. The amount of electron irradiation in the corona discharge treatment is preferably from 50 to 150 W/m ² /min, more preferably from 70 to 100 W/m ² /min.

A known method can be used for the drying step. The drying temperature is typically 50°C or higher, preferably 90°C or higher, more preferably 110°C or higher. By setting the drying temperature within these ranges, for example, an optical film excellent in corrosion resistance (especially in a high-temperature and high-humidity environment) can be obtained. The upper limit of the drying temperature is preferably at most 200°C, more preferably at most 180°C.

Between the coating step and the drying step, the resin film may be stretched simultaneously with the drying step or after the drying step. The stretching of the resin film after applying the easy-adhesive composition can be performed by a known method, and can be uniaxially stretched or biaxially stretched in the same manner as the stretching method of the above-mentioned resin film (before coating the easily-adhesive layer).

The resin film for forming the coating film of the easily bondable composition in the coating step may be an unstretched resin film or a stretched resin film. When the resin film before the coating step is an unstretched film and the finally produced optical film is a biaxially stretched film, what is necessary is just to perform biaxial stretching after the coating step. When the resin film before the coating step is a uniaxially stretched film and the finally produced optical film is a biaxially stretched film, the direction of the uniaxial stretching is set as the MD direction and stretched in the TD direction after the coating step .

A known stretching machine can be used for stretching of the resin film. The longitudinal stretching machine is not particularly limited, but an oven stretching machine is preferred. The oven longitudinal stretching machine usually consists of an oven, and transfer rollers respectively provided on the entrance side and the exit side of the oven. The resin film is stretched in the conveyance direction by giving a peripheral velocity difference between the conveyance roller on the entrance side of the oven and the conveyance roller on the exit side. The transverse stretching machine is not particularly limited, but a tenter stretching machine is preferable. The tenter stretching machine may be of a grip type or a pin type, and the grip type is preferable in terms of less likely to cause tearing of the resin film. The grab-type tenter stretching machine is usually composed of a grip moving device for horizontal stretching and an oven. In the grasping and moving device, the resin film is conveyed in a state in which the lateral ends of the resin film are clamped by the clips. At this time, the guide rail of the grasping and moving device is opened, and the distance between the two rows of clamps on the left and right is enlarged, thereby extending the resin film laterally. In the grip-type tenter stretching machine, the clamps are provided with expansion and contraction functions relative to the conveying direction of the resin film, so that biaxial stretching can be performed simultaneously. In addition, it may be an inclined stretching machine that stretches the resin film in the conveying direction of the film at different speeds on the left and right sides of the stretching direction of the resin film.

The stretching temperature is preferably around Tg of the resin constituting the resin film. Specifically, it is preferably in the range of Tg-30°C to Tg+100°C, more preferably in the range of Tg-20°C to Tg+80°C. By properly adjusting the stretching temperature, a sufficient stretching ratio can be stably achieved.

The elongation ratio defined by the area ratio is preferably 1.1 to 25 times, more preferably 1.3 to 10 times. By properly adjusting the elongation ratio, the characteristics (such as toughness) of the optical film can be improved. Regarding stretching in one direction, the stretching speed is preferably from 10 to 20000%/minute, more preferably from 100 to 10000%/minute. By properly adjusting the stretching speed, the breakage of the optical film can be prevented, and the time required for stretching can be shortened at the same time.

When performing the formation of the easy-adhesive layer and the extension of the resin film at the same time, for example, after the coating step, the resin film formed with the coating film of the easily-adhesive composition may be stretched under a heating environment. The coating film of the easily-adhesive composition formed on the surface of the resin film is dried by heat applied to the resin film for stretching, and becomes an easily-adhesive layer. In addition, Tg of a resin film is 100 degreeC or more normally, and the said stretching temperature is a temperature high enough for forming an easily-bonding layer from the coating film of an easily-bonding composition.

In the case of forming a resin film by melt extrusion, the steps from forming the resin film to obtaining an optical film as a stretched film may be continuously performed. In this case, it is preferable to continuously perform the step of coating the easily-adhesive composition on the surface of the resin film and the step of stretching the film coated with the easily-adhesive composition under a heating environment. This continuous coating step of the easy-to-adhesive composition is called in-line coating. In the case of manufacturing an optical film as a biaxially stretched film by the manufacturing method of this embodiment, it is particularly preferable to carry out continuously: the step of stretching an unstretched film to form a film as a uniaxially stretched film; A step of coating the surface of the film with an easy-adhesive composition; and a step of extending the film coated with the easy-adhesive composition in a heated environment. Furthermore, when surface treatment such as corona discharge treatment and plasma treatment is performed on the film, it is preferable to continuously carry out the following steps: the step of stretching the unstretched film to form a film as a uniaxially stretched film ; the step of surface treating the surface of the film; the step of coating the surface of the surface-treated film with an easy-adhesive composition; and the step of extending the film coated with the easy-adhesive composition in a heated environment.

The manufacturing method of this embodiment may also include arbitrary steps other than the above-mentioned steps. This step is, for example, a step of further laminating a "layer (such as a resin layer)" on the formed optical film, or a step of performing post-processing such as coating treatment and surface treatment on the formed optical film. [Example]

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is of course not limited to the following examples.

(1) Analysis method (1-1) Weight average molecular weight (Mw) The weight average molecular weight was calculated|required by polystyrene conversion using the gel permeation chromatography (GPC). The apparatus and measurement conditions used for the measurement are as follows. -System: GPC system HLC-8220 manufactured by Tosoh Corporation - Determination of side string composition Guard column: manufactured by Tosoh, TSKguardcolumn SuperHZ-L Separation column: manufactured by Tosoh Company, TSKgel SuperHZM-M 2 pieces connected in series -Refer to side string composition Reference column: manufactured by Tosoh, TSKgel SuperH-RC - Developing solvent: Chloroform (manufactured by Wako Pure Chemical Industries, Ltd., special grade) -Flow rate of developing solvent: 0.6 mL/min -Standard sample: TSK standard polystyrene (manufactured by Tosoh, PS-Oligomer set) -Column temperature: 40°C

(1-2) Glass transition temperature (Tg) The glass transition temperature was determined in accordance with the Japanese Industrial Standard JIS K7121. Specifically, by using a differential scanning calorimeter (manufactured by Rigaku, Thermo plus EVO DSC-8230), in a nitrogen atmosphere, about 10 mg of a sample is obtained by raising the temperature from normal temperature (temperature increase rate 20°C/min) to 200°C The DSC curve was evaluated by the starting point method. Reference is made to the use of alpha-alumina.

(1-3) Thickness of optical film The thickness of the optical film was measured using a digital micrometer (manufactured by Mitutoyo). The samples for measuring and evaluating the physical properties of the optical film including the physical properties of the evaluation methods shown below were obtained from the central portion of the film in the width direction.

(1-4) Average particle size and particle size distribution of fine particles The silica particles were added to methanol so as to have a concentration of 1% by mass, and the silica particles were dispersed by an ultrasonic disperser for 10 minutes to prepare a measurement sample. This sample was measured using a laser diffraction analysis/scattering type particle size distribution measuring device (manufactured by Horiba Seisakusho Co., Ltd., LA-920). The arithmetic mean value of the obtained volume-based particle size distribution was defined as the average particle diameter, and the arithmetic maximum value was defined as the maximum particle diameter.

(1-5) Total light transmittance, haze The total light transmittance, haze (total haze), and internal haze of the produced optical film were measured using a nephelometer (manufactured by Nippon Denshoku Industries, NDH5000) based on JIS K7136. In addition, internal haze was measured in the state which immersed the film which is a measurement object in the tetralin in a quartz cell.

(1-6) Adhesiveness between the resin film and the easy-to-adhesive layer The adhesiveness between the prepared resin film and the easy-adhesive layer was subjected to a cross-cut adhesion test according to JIS K5400 3.5, and evaluated by the following points. Use a sharp knife to cut 1 mm square checkerboard-shaped incisions on three parts of the easy-to-adhesive layer of the test sample. Adhere scotch tape (width 24 mm, JIS Z1522) to the incision with a wood chip. Then, the cellophane tape was peeled off, and the presence or absence of peeling of the easily-adhesive layer was confirmed. When the easy-adhesive layer is not peeled off, use the wood chip again to make a new scotch tape adhere to the incision, perform the operation of peeling off the scotch tape, and evaluate the adhesiveness. This evaluation was performed at three sites. The evaluation criteria are as follows. ⊚: Among the 3 locations, the easily-adhesive layer was not peeled even when the peeling test was performed 5 times at the 3 locations. ◯: Among the three locations, the easily-adhesive layer was not peeled even when the peeling test was performed five times at one or two locations. ×: Among the three locations, the adhesive layer was easily peeled when the peeling test was performed 1 to 4 times at the three locations.

(1-7) Blocking resistance of optical film The blocking resistance of the produced optical film was evaluated by the following method. After the produced optical film was wound up on a roll to form a film roll, it was left to stand for 24 hours. After standing, the film roll was visually confirmed, and the optical film was unwound from the film roll, and the surface was visually confirmed over the entire length direction of the optical film at the same time, and the blocking resistance was evaluated. The evaluation criteria are as follows. ◯: Deformation of the film roll and wrinkles of the unwound optical film were not observed. ×: Deformation of the film roll or wrinkles of the unrolled optical film were observed.

(1-8) Uniformity of easy bonding layer In addition, the easy-adhesive layer (coating film) obtained by applying the prepared easily-adhesive composition (coating liquid) to the resin film and drying it was visually observed, and the uniformity of the easily-adhesive composition and the uniformity of the easily-adhesive layer were checked. evaluate. The evaluation criteria are as follows, and expressed as (evaluation of easily-adhesive composition)/(evaluation of easily-adhesive layer). Regarding the evaluation of the easy-to-adhesive composition, A: It is easy to obtain a uniform and easy-to-adhesive composition. B: A uniform easy-to-adhesive composition was obtained after only stirring for less than 6 hours, although inhomogeneous substances such as gel components appeared during the preparation of the easy-to-adhesive composition. C: Inhomogeneous substances such as gel components appear when making the easy-adhesive composition, and a uniform easy-adhesive composition cannot be obtained without filtering.

Regarding the evaluation of the easy-to-adhesive layer, A: Coating unevenness, streaks, and thickness unevenness were not visually confirmed, and a uniform coating film was obtained. B: At least one of coating unevenness, streaks, and thickness unevenness was visually confirmed, and a uniform coating film was not obtained.

(2) Manufacturing example (Manufacturing example 1) Add 40 parts by weight of methyl methacrylate (MMA) and 2-(hydroxymethyl)methyl acrylate (MHMA) to a reactor with an inner volume of 1000 L equipped with a stirring device, a temperature sensor, a condenser tube, and a nitrogen introduction tube 10 parts by weight, 50 parts by weight of toluene as a polymerization solvent, and 0.025 parts by weight of an antioxidant (Adekastab 2112, manufactured by ADEKA), were blown with nitrogen gas while raising the temperature to 105°C. At the beginning of reflux accompanied by temperature rise, 0.05 parts by weight of isononyl peroxide third amyl peroxide (manufactured by Arkema Yoshitomi, trade name: Luperox 570) was added as a polymerization initiator, and the above-mentioned isononyl peroxide was added dropwise over 3 hours. 0.10 parts by weight of tertiary amyl ester, and at the same time carry out solution polymerization under reflux at about 105-110° C., and then carry out aging for 4 hours.

Then, 0.05 parts by weight of 2-ethylhexyl phosphate (manufactured by Sakai Chemical Industries, Phoslex Α-8) was added to the obtained polymerization solution as a catalyst (cyclization catalyst) for the cyclocondensation reaction, and the reaction temperature was about 90- The cyclocondensation reaction to form the lactone ring structure was carried out under reflux at 110° C. for 2 hours. Then, the temperature of the obtained polymerization solution was raised to 240° C. using an autoclave, and the cyclocondensation reaction was further performed at this temperature.

Then, the obtained polymerization solution is introduced into the barrel at a processing speed of 45 kg/hour (resin amount conversion) at a temperature of 240°C, a rotation speed of 100 rpm, a degree of reduced pressure of 13.3 to 400 hPa (10 to 300 mmHg), 1 rear vent and 4 front vents (referred to as the 1st, 2nd, 3rd, and 4th vents from the upstream side), in the third row A side feeder is installed between the air hole and the fourth exhaust hole, and a leaf disk-type polymer filter (filtering precision 5 μm, filtering area 1.5 m ² ) is installed at the front end. The exhaust type spiral double shaft Devolatilization was performed in an extruder (φ=50.0 mm, L/D=30). At this time, drop the mixed solution of antioxidant/cyclization catalyst deactivator prepared in advance from the back of the first exhaust hole at a rate of 0.68 kg/hour, and from the second and Ion-exchanged water is poured into the back of the third vent hole. The mixed solution of antioxidant/cyclization catalyst deactivator is used to make 50 parts by weight of antioxidant (manufactured by Ciba Specialty Chemicals, Irganox1010) and 35 parts by weight of zinc octylate as a deactivator (manufactured by Japan Chemical Industry, Nikka Octhix Zinc 3.6% by weight) dissolved in 200 parts by weight of toluene. In addition, when volatilization was performed, styrene-acrylonitrile copolymer (AS resin: ratio of styrene unit/acrylonitrile unit was 73% by weight/27% by weight, weight Particles with an average molecular weight of 220,000).

After the de-volatilization is completed, the hot-melt resin remaining in the extruder is filtered from the front end of the extruder through a polymer filter, and discharged at the same time, and granulated by a granulator to obtain Transparent particles of acrylic resin containing a (meth)acrylic polymer having a lactone ring structure in the main chain as the main component (75% by weight) and 25% by weight of styrene-acrylonitrile copolymer (1A). The acrylic resin constituting the pellet (1A) had a Tg of 122°C and a weight average molecular weight of 151,000.

Then, using a single-screw extruder (φ=20.0 mm, L/D=25) and a coat-hanger T-die (width 150 mm), the manufactured pellets (1A) were melt-extruded at 280°C to form a 100-μm-thick Acrylic film. During melt extrusion, the resin film was sprayed from a T-die to a cooling roll maintained at 110°C.

Then, using a biaxial stretching machine (manufactured by Toyo Seiki Seisakusho, TYPE EX4), the produced acrylic resin film was stretched 2.0 times at a stretching temperature of 140°C in the MD direction (traveling direction, extrusion direction). Stretching to obtain a stretched acrylic resin film (F1).

(Manufacturing example 2) Add 42.5 parts by weight of MMA, 5 parts by weight of N-phenylmaleimide (PMI), and 0.5 parts by weight of styrene (St) to a stainless steel polymerization tank with an inner volume of 100 L equipped with a liquid tank and a stirring device 50 parts by weight of toluene as a polymerization solvent, 0.2 parts by weight of acetic anhydride as an organic acid, and 0.06 parts by weight of n-dodecylmercaptan as a chain transfer agent, stirring it at a rotational speed of 100 rpm, and simultaneously making Nitrogen was bubbled for 10 minutes. Then, the tank is maintained as a nitrogen atmosphere and the temperature is directly raised. When the temperature in the tank reaches 100 ° C, 0.075 parts by weight of tertiary butyl peroxyisopropyl carbonate is added. into nitrogen. Then, a mixture of 2 parts by weight of styrene and 0.075 parts by weight of tertiary butyl peroxyisopropyl carbonate was added to the tank at a constant speed for 5 hours, and at the same time, it was refluxed at a polymerization temperature of 105 to 110°C for 15 hours. hour polymerization.

Then, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., HCA) as a phosphoric acid-based antioxidant and phenol 0.1 parts by weight and 0.02 parts by weight of [3-(3,5-di-tert-butyl-4-hydroxyphenyl) neopentylthritol propionate] (manufactured by Asahi Denka Co., Ltd., AO-60), which is an antioxidant .

Then, introduce the polymerization solution with antioxidant added at a processing speed of 2.0 kg/hour (resin amount conversion) to a drum temperature of 240°C, a rotation speed of 100 rpm, and a decompression degree of 13.3 to 400 hPa (10 to 300 mmHg). Vented type screw twin-screw extruder with 1 vent hole and 4 front vent holes (Φ=29.75 mm, L/D=30). Then, the resin in the hot-melt state in the extruder is sprayed from the front end of the extruder, and is granulated by a granulator to obtain (formaldehyde) having an N-substituted maleimide structure in the main chain. Base) transparent particles of acrylic resin composed of acrylic polymer (2A). The acrylic resin constituting the particles (2A) had a Tg of 138°C and a weight average molecular weight of 200,000.

Then, using a single-screw extruder (φ=20.0 mm, L/D=25) and a coat-hanger T-die (width 150 mm), the produced pellets (2A) were melt-extruded at 280°C to form a 100-μm-thick Acrylic film. During melt extrusion, the acrylic resin film was sprayed from a T-die to a cooling roll maintained at 110°C.

Then, the produced acrylic resin film was stretched free-end uniaxially in the MD direction (traveling direction, extrusion direction) at a stretching ratio of 2.0 times and a stretching temperature of 155°C using a biaxial stretching machine (manufactured by Toyo Seiki Seisakusho, TYPE EX4). , to obtain a stretched acrylic resin film (F2).

(Manufacturing example 3) Use a single-screw extruder (φ=20 mm, L/D=25) and a coat hanger T-die (width 150 mm) to use a (meth)acrylic polymer with a glutarimide structure in the main chain as the main component An acrylic resin (manufactured by Rohm and Haas, KAMAXT-240) (this resin is referred to as 3A) was melt-extruded at 280° C. to form an acrylic resin film with a thickness of 100 μm. During melt extrusion, the resin film was sprayed from a T-die to a cooling roll maintained at 110°C.

Then, the produced acrylic resin film was stretched free-end uniaxially in the MD direction (traveling direction, extrusion direction) at a stretching ratio of 2.0 times and a stretching temperature of 140°C using a biaxial stretching machine (manufactured by Toyo Seiki Seisakusho, TYPE EX4) , to obtain a stretched acrylic resin film (F3).

(Manufacturing example 4) In place of KAMAX T-240, the procedure was the same as in Production Example 3, except that an acrylic resin mainly composed of a (meth)acrylic anhydride polymer having a glutaric anhydride structure in its main chain (Sumitomo Chemical, Sumipex B-TR) was used instead of KAMAX T-240. The stretched acrylic resin film (F4) was obtained in this way.

(Manufacturing example 5) In place of KAMAX T-240, except that an acrylic resin (manufactured by Asahi Kasei Chemicals, DELPET 980N) mainly composed of a (meth)acrylic anhydride polymer having a maleic anhydride structure in its main chain was used, the method was the same as in Production Example 3. A stretched acrylic resin film (F5) was obtained in the same manner.

(Manufacturing example 6) Add 70 parts by weight of deionized water, 0.5 parts by weight of sodium pyrophosphate, 0.2 parts by weight of potassium oleate, 0.005 parts by weight of ferrous sulfate, 0.2 parts by weight of glucose, and 0.1 parts by weight of p-menthane hydroperoxide to a pressure-resistant reaction vessel equipped with a stirrer. The reaction mixture composed of 28 parts by weight of 1,3-butadiene and 1,3-butadiene was heated up to 65° C. to carry out polymerization reaction. After 2 hours from the start of polymerization, 0.2 parts by weight of hydrogen peroxide was further added to the mixture, and 72 parts by weight of 1,3-butadiene, 1.33 parts by weight of potassium oleate and deionized 75 parts by weight of water. Thereafter, the polymerization reaction was continued, and latex of a butadiene-based rubber polymer having an average particle diameter of 0.240 μm was obtained by polymerization for 21 hours from the start of the polymerization.

Then, 120 parts by weight of deionized water, 50 parts by weight (solid content) of the butadiene rubber polymer latex produced above, 1.5 parts by weight of potassium oleate and methylol, were put into a polymerization container equipped with a cooler and a stirrer. 0.6 parts by weight of sodium sulfonate (SFS), and the inside of the container was fully replaced with nitrogen. Then, after the temperature in the container was raised to 70°C, a mixed monomer solution composed of 36.5 parts by weight of styrene and 13.5 parts by weight of acrylonitrile was mixed with 0.27 parts by weight of cumene hydroperoxide and 20 parts by weight of deionized water. The polymerization initiator solution was continuously added dropwise into the container for 2 hours respectively, and the polymerization reaction was carried out simultaneously. After completion of the dropwise addition, the temperature in the container was raised to 80° C., and the polymerization reaction was continued for 2 hours. Next, after lowering the temperature in the container to 40°C, the contents were passed through a 300-mesh wire mesh to obtain an emulsion polymerization solution of elastic organic fine particles.

Use calcium chloride to salt out and coagulate the emulsion polymerization solution of the obtained elastic organic microparticles, and wash and dry the coagulum to obtain powdery elastic organic microparticles (G1: average particle diameter 0.260 μm, soft polymer layer The refractive index of 1.516).

Next, an acrylic resin (manufactured by Asahi Kasei Chemicals, DELPET 980N) mainly composed of a (meth)acrylic acid polymer having a maleic anhydride structure in its main chain and the elastic organic fine particles produced above were mixed using a twin-screw extruder. (G1) Kneading is carried out in such a manner that acrylic resin/elastic organic fine particles = 90/10 (weight ratio) to produce granules (3A). Then, using a single-screw extruder (φ=20.0 mm, L/D=25) and a coat-hanger T-die (width 150 mm), the produced pellets (3A) were melt-extruded at 280°C to form a 100-μm-thick Acrylic film. During melt extrusion, the resin film was sprayed from a T-die to a cooling roll maintained at 110°C.

Then, the produced acrylic resin film was stretched free-end uniaxially in the MD direction (traveling direction, extrusion direction) at a stretching ratio of 2.0 times and a stretching temperature of 140°C using a biaxial stretching machine (manufactured by Toyo Seiki Seisakusho, TYPE EX4) , to obtain a stretched acrylic resin film (F6).

(Manufacturing example 7) Add 229.6 parts by weight of methyl methacrylate (MMA), 33 parts by weight of 2-(hydroxymethyl)methyl acrylate (MHMA), anti 0.138 parts by weight of an oxidizing agent (manufactured by ADEKA "Adekastab (registered trademark) 2112"), 248.6 parts by weight of toluene as a non-polymerizable organic solvent, and 0.1925 parts by weight of n-dodecylmercaptan, nitrogen gas was introduced thereinto, and simultaneously It was warmed to 105°C. At the beginning of reflux accompanied by temperature rise, 0.2838 parts by weight of tertiary amyl peroxyisononanoate ("Luperox (registered trademark) 570" manufactured by Arkema Yoshitomi Co., Ltd.) was added as a polymerization initiator, and the above-mentioned over 2 hours was added dropwise. Oxidize 0.5646 parts by weight of tertiary amyl isononanoate and 12.375 parts by weight of styrene (St), and carry out solution polymerization under reflux at about 105-110°C at the same time. After the dropwise addition, carry out further aging at this temperature for 4 hours.

Then, 0.206 parts by weight of stearyl phosphate ("Phoslex A-18" manufactured by Sakai Chemical Industry Co., Ltd.) was added to the obtained polymerization solution as a catalyst for the cyclocondensation reaction (cyclization catalyst) at about 90 to 110 The cyclocondensation reaction for forming the lactone ring structure was carried out under reflux at °C for 2 hours. Then, the obtained polymerization solution was passed through a multi-tubular heat exchanger heated to 240°C, and after the cyclocondensation reaction was completed, it was introduced into the exhaust type spiral double shaft at a processing speed of 31.2 parts/hour (resin amount conversion). For the extruder (L/D=52), set the decompression degree of each vent hole to 798 hPa for the rear vent hole, 266 hPa for the first vent hole, and set both the second vent hole to the fourth vent hole. It is 27 hPa, and the volatilization is carried out. The drum temperature of the above-mentioned exhaust type screw twin-screw extruder is 250 ℃, and it is equipped with 1 rear exhaust hole and 4 front exhaust holes (referred to as the first, 2nd, 3rd, 4th vent hole) and a side feeder is provided between the 3rd vent hole and the 4th vent hole, and a leaf disc type polymer filter (filter fineness 5 μm) is arranged at the front end ). At this time, ion-exchanged water was injected from the back of the second and fourth exhaust holes at a rate of 0.47 parts/hour, and octylic acid zinc ("Nikka Octhix Zinc 18%" manufactured by Nippon Chemical Industry Co., Ltd.), Irganox 1010 ( Ciba Specialty Chemicals) 50 parts by weight, Adekastab AO-412S (manufactured by ADEKA) in toluene solution with respect to the thermoplastic resin composition obtained, in terms of mass ratio, zinc octanoate was 160 ppm, Irganox 1010 was 50 ppm, Adekastab AO- 412S is injected at 50 ppm.

After the de-volatilization is completed, the resin composition in a hot-melt state remaining in the extruder is filtered from the front end of the extruder using the above-mentioned polymer filter, and is discharged at the same time, and after passing through the equipped die, Filter through a filter with a pore size of 1 μm ("product name: microporous filter 1EU" manufactured by Organo Co., Ltd.), and cool the strands in a water tank filled with cooling water maintained at a temperature within the range of 30±10°C , and then introduced into a cutting machine (granulator), thereby obtaining granules composed of a resin composition (7A) including a lactone ring polymer having a lactone ring structure in the main chain. The obtained resin composition (7A) had a weight average molecular weight of 132,000, a number average molecular weight of 59,000, a glass transition temperature of 121°C, a thermal decomposition initiation temperature of 335°C, and a refractive index of 1.501.

Next, the produced pellets (7A) were formed into a film by the same method as in Production Example 1, and a stretched acrylic resin film (F7) was obtained.

(Manufacturing example 11) Add the emulsion containing amorphous silica microparticles (Nippon Shokubai, Seahostar KE-W30, average particle size (primary particle size) 0.28 μm, particle size distribution 1.1, solid content 20 wt. %) 0.09% by weight, urethane resin (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., Superflex 210, solid content 35% by weight) 20% by weight, polyamine (manufactured by Nippon Shokubai, Epomin SP-006) 0.0007% by weight and fully mixed, The mixed solution was passed through a 1 μm filter to obtain an easily-adhesive composition (1B) as an emulsion-like dispersion. The remainder after removing urethane resin, silicon dioxide microparticles, and polyamines from the adhesive composition is pure water.

(Manufacturing examples 12 to 83) Using the raw materials shown in Table 1A, Table 1B, and Table 1C below, easily-adhesive compositions (2B to 73B) as emulsion-like dispersions were obtained in the same manner as in Production Example 11. Furthermore, the crosslinking agent is added after the urethane resin and before the polyamine.

[Table 1A] Urethane resin microparticles polyamine Other crosslinkers type weight% type weight% type weight% Content rate of polyamine in the easy-adhesive layer (weight %) type weight% Manufacturing example 11 1B SF210 20 KE-W30 0.09 SP-006 0.0007 0.0100 (Unused) - Manufacturing Example 12 2B SF210 20 KE-W30 0.09 SP-006 0.0035 0.0498 (Unused) - Manufacturing Example 13 3B SF210 20 KE-W30 0.09 SP-006 0.005 0.0712 (Unused) - Manufacturing Example 14 4B SF210 20 KE-W30 0.09 SP-006 0.007 0.0996 (Unused) - Manufacturing Example 15 5B W-5030 18 KE-W30 0.08 SP-006 0.0007 0.0129 (Unused) - Manufacturing Example 16 6B CP-7020 14 KE-W30 0.07 SP-006 0.0007 0.0125 (Unused) - Manufacturing example 17 7B SF620 20 KE-W30 0.3 SP-006 0.0007 0.0115 (Unused) - Manufacturing Example 18 8B SF210 20 The average particle size (primary particle size) of the emulsion containing amorphous silica microparticles is 0.28 μm, the particle size distribution is 1.7, and the solid content is 19% by weight 0.09 SP-006 0.0007 0.0100 (Unused) - Manufacturing Example 19 9B SF210 20 KE-W10 0.12 SP-006 0.0007 0.0100 (Unused) - Manufacturing Example 20 10B SF210 20 KE-W10 1.0 SP-006 0.0007 0.0098 (Unused) - Manufacturing example 21 11B SF210 19 KE-W30 0.09 SP-006 0.0007 0.0100 WS-700 1.3 Manufacturing example 22 12B SF210 19 KE-W30 0.09 SP-006 0.0035 0.0500 WS-700 1.3 Manufacturing example 23 13B AP-40N 19 KE-W30 0.09 SP-006 0.0007 0.0100 WS-700 1.3 Manufacturing Example 24 14B SF210 20 KE-W30 0.09 (Unused) - - (Unused) - Manufacturing example 25 15B W-5030 18 KE-W30 0.08 (Unused) - - (Unused) - Manufacturing Example 26 16B CP-7020 14 KE-W30 0.07 (Unused) - - (Unused) - Manufacturing example 27 17B SF620 20 KE-W30 0.3 (Unused) - - (Unused) - Manufacturing example 28 18B SF210 20 The average particle size (primary particle size) of the emulsion containing amorphous silica microparticles is 0.28 μm, the particle size distribution is 1.7, and the solid content is 19% by weight 0.09 (Unused) - - (Unused) - Manufacturing example 29 19B SF210 20 KE-W10 0.12 (Unused) - - (Unused) - Manufacturing Example 30 20B SF210 20 KE-W10 1.0 (Unused) - - (Unused) - Manufacturing Example 31 21B SF210 19 KE-W30 0.09 (Unused) - - WS-700 1.3 Manufacturing Example 32 22B AP-40N 19 KE-W30 0.09 (Unused) - - WS-700 1.3

[Table 1B] Urethane resin microparticles polyamine Other crosslinkers type weight% type weight% type weight% Content rate of polyamine in the easy-adhesive layer (weight %) type weight% Manufacturing example 33 23B SF210 20 KE-W30 0.09 SP-006 0.0005 0.0071 (Unused) - Manufacturing example 34 24B SF210 20 KE-W30 0.09 SP-006 0.008 0.1139 (Unused) - Manufacturing example 35 25B SF210 20 KE-W30 0.09 SP-006 0.009 0.1281 (Unused) - Manufacturing example 36 26B SF210 20 KE-W30 0.09 SP-006 0.01 0.1423 (Unused) - Manufacturing example 37 27B SF210 20 KE-W30 0.09 SP-006 0.02 0.2842 (Unused) - Manufacturing example 38 28B SF210 20 KE-W30 0.09 SP-006 0.025 0.3550 (Unused) - Manufacturing example 39 29B SF210 20 KE-W30 0.09 SP-006 0.03 0.4257 (Unused) - Manufacturing Example 40 30B SF210 20 KE-W30 0.09 SP-006 0.04 0.5667 (Unused) - Manufacturing Example 41 31B SF210 20 KE-W30 0.09 SP-006 0.05 0.7074 (Unused) - Manufacturing example 42 32B SF210 20 KE-W30 0.09 SP-006 0.06 0.8477 (Unused) - Manufacturing example 43 33B SF210 20 KE-W30 0.09 SP-006 0.07 0.9876 (Unused) - Manufacturing example 44 34B SF210 20 KE-W30 0.09 SP-006 0.08 1.1271 (Unused) - Manufacturing Example 45 35B SF210 20 KE-W30 0.09 SP-006 0.09 1.2662 (Unused) - Manufacturing example 46 36B SF210 20 KE-W30 0.09 SP-006 0.1 1.4049 (Unused) - Manufacturing Example 47 37B SF210 20 KE-W30 0.09 SP-006 0.2 2.7709 (Unused) - Manufacturing Example 48 38B SF210 20 KE-W10 0.12 SP-006 0.005 0.0712 (Unused) - Manufacturing Example 49 39B SF210 20 KE-W10 1.0 SP-006 0.0005 0.0070 (Unused) - Manufacturing Example 50 40B SF210 20 KE-W10 1.0 SP-006 0.0035 0.0489 (Unused) - Manufacturing example 51 41B SF210 20 KE-W10 1.0 SP-006 0.005 0.0699 (Unused) - Manufacturing example 52 42B SF210 20 KE-W10 1.0 SP-006 0.007 0.0978 (Unused) - Manufacturing example 53 43B SF210 20 KE-W10 1.0 SP-006 0.008 0.1118 (Unused) - Manufacturing example 54 44B SF210 20 KE-W10 1.0 SP-006 0.009 0.1257 (Unused) - Manufacturing example 55 45B SF210 20 KE-W10 1.0 SP-006 0.01 0.1397 (Unused) - Manufacturing example 56 46B SF210 20 KE-W10 1.0 SP-006 0.02 0.2789 (Unused) - Manufacturing example 57 47B SF210 20 KE-W10 1.0 SP-006 0.02 0.2789 (Unused) - Manufacturing example 58 48B SF210 20 KE-W10 1.0 SP-006 0.03 0.4178 (Unused) - Manufacturing example 59 49B SF210 20 KE-W10 1.0 SP-006 0.04 0.5563 (Unused) - Manufacturing Example 60 50B SF210 20 KE-W10 1.0 SP-006 0.05 0.6944 (Unused) - Manufacturing example 61 51B SF210 20 KE-W10 1.0 SP-006 0.06 0.8322 (Unused) - Manufacturing example 62 52B SF210 20 KE-W10 1.0 SP-006 0.07 0.9695 (Unused) - Manufacturing Example 63 53B SF210 20 KE-W10 1.0 SP-006 0.08 1.1065 (Unused) - Manufacturing Example 64 54B SF210 20 KE-W10 1.0 SP-006 0.09 1.2431 (Unused) - Manufacturing example 65 55B SF210 20 KE-W10 1.0 SP-006 0.1 1.3793 (Unused) - Manufacturing Example 66 56B SF210 20 KE-W10 1.0 SP-006 0.2 2.7211 (Unused) -

[Table 1C] Urethane resin microparticles polyamine Other crosslinkers type weight% type weight% type weight% Content rate of polyamine in the easy-adhesive layer (weight %) type weight% Manufacturing example 67 57B SF210 19 KE-W30 0.09 SP-006 0.0005 0.0071 WS-700 1.3 Manufacturing example 68 58B SF210 19 KE-W30 0.09 SP-006 0.005 0.0714 WS-700 1.3 Manufacturing example 69 59B SF210 19 KE-W30 0.09 SP-006 0.007 0.1000 WS-700 1.3 Manufacturing example 70 60B SF210 19 KE-W30 0.09 SP-006 0.008 0.1143 WS-700 1.3 Manufacturing example 71 61B SF210 19 KE-W30 0.09 SP-006 0.009 0.1285 WS-700 1.3 Manufacturing Example 72 62B SF210 19 KE-W30 0.09 SP-006 0.01 0.1428 WS-700 1.3 Manufacturing example 73 63B SF210 19 KE-W30 0.09 SP-006 0.02 0.2852 WS-700 1.3 Manufacturing example 74 64B SF210 19 KE-W30 0.09 SP-006 0.025 0.3562 WS-700 1.3 Manufacturing example 75 65B SF210 19 KE-W30 0.09 SP-006 0.03 0.4272 WS-700 1.3 Manufacturing Example 76 66B SF210 19 KE-W30 0.09 SP-006 0.04 0.5687 WS-700 1.3 Manufacturing Example 77 67B SF210 19 KE-W30 0.09 SP-006 0.05 0.7099 WS-700 1.3 Manufacturing Example 78 68B SF210 19 KE-W30 0.09 SP-006 0.06 0.8507 WS-700 1.3 Manufacturing Example 79 69B SF210 19 KE-W30 0.09 SP-006 0.07 0.9911 WS-700 1.3 Manufacturing Example 80 70B SF210 19 KE-W30 0.09 SP-006 0.08 1.1311 WS-700 1.3 Manufacturing Example 81 71B SF210 19 KE-W30 0.09 SP-006 0.09 1.2706 WS-700 1.3 Manufacturing Example 82 72B SF210 19 KE-W30 0.09 SP-006 0.1 1.4098 WS-700 1.3 Manufacturing example 83 73B SF210 19 KE-W30 0.09 SP-006 0.2 2.7805 WS-700 1.3

‧SF210: manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., Superflex 210, solid content 35% by weight ‧W-5030: Made by Mitsui Chemicals Polyurethane, Takelac W-5030, solid content 30% by weight ‧CP-7020: Made by DIC, Hydran CP-7020, solid content 40% by weight ‧SF620: manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., Superflex620, solid content 30% by weight ‧AP-40N: Manufactured by DIC, Hydran AP-40N, solid content 35% by weight ‧KE-W30: Manufactured by Nippon Shokubai, Seahostar KE-W30, average particle size (primary particle size) 0.28 μm, particle size distribution 1.1, solid content 20% by weight ‧KE-W10: Manufactured by Nippon Shokubai, Seahostar KE-W10, average particle size (primary particle size) 0.11 μm, particle size distribution 1.1, solid content 15% by weight ‧SP-006: Manufactured by Nippon Shokubai, Epomin SP-006 ‧WS-700: Manufactured by Nippon Shokubai, Epocros WS-700, solid content 25% by weight

(3) Example (Example 1) The easy-adhesive composition (1B) prepared in Production Example 11 was coated on one surface of the acrylic resin film (F1) produced in Production Example 1 so that the thickness of the dried coating film became 270 nm, and the whole Dry at 100°C for 2 minutes. In this way, an optical film with an easily bonding layer formed on one surface is obtained. The fine particles contained in the formed easy-adhesive layer maintain the shape of the easily-adhesive composition (1B).

(Examples 2-58, Comparative Examples 1-16) The combination of the acrylic resin film and the easy-adhesive composition was changed as shown in Tables 2A-2C below, and an optical film having an easily-adhesive layer formed on one surface was obtained in the same manner as in Example 1.

The evaluation results of the optical films produced in the respective examples and comparative examples are summarized in Table 2A, Table 2B and Table 2C below.

[Table 2A] membrane Easy-to-adhesive composition Haze (%) Closeness Anti-blocking Uniformity of easy-adhesive layer (evaluation of coating solution)/(evaluation of coating film) Example 1 F1 1B 0.2 ○ ○ A/A Example 2 F1 2B 0.2 ○ ○ A/A Example 3 F1 3B 0.2 ○ ○ A/A Example 4 F1 4B 0.2 ○ ○ A/A Example 5 F1 5B 0.2 ○ ○ A/A Example 6 F2 1B 0.2 ○ ○ A/A Example 7 F3 1B 0.2 ○ ○ A/A Example 8 F4 6B 0.2 ○ ○ A/A Example 9 F5 7B 0.6 ○ ○ A/A Example 10 F6 1B 0.4 ○ ○ A/A Example 11 F1 8B 0.6 ○ ○ A/A Example 12 F1 9B 0.2 ○ x A/A Example 13 F1 10B 0.3 ○ ○ A/A

[Form 2B] membrane Easy-to-adhesive composition Haze (%) Closeness Anti-blocking Uniformity of easy-adhesive layer (evaluation of coating solution)/(evaluation of coating film) Example 14 F7 24B 0.2 ○ ○ A/A Example 15 F7 25B 0.2 ○ ○ A/A Example 16 F7 26B 0.2 ○ ○ A/A Example 17 F7 27B 0.2 ○ ○ B/A Example 18 F7 28B 0.2 ◎ ○ B/A Example 19 F7 29B 0.2 ◎ ○ B/A Example 20 F7 30B 0.2 ◎ ○ B/A Example 21 F7 31B 0.2 ◎ ○ B/A Example 22 F7 32B 0.2 ◎ ○ B/A Example 23 F7 33B 0.2 ◎ ○ B/A Example 24 F7 34B 0.2 ◎ ○ B/A Example 25 F7 35B 0.2 ◎ ○ B/A Example 26 F7 36B 0.2 ◎ ○ B/A Example 27 F7 38B 0.2 ○ ○ A/A Example 28 F7 40B 0.3 ○ ○ A/A Example 29 F7 41B 0.3 ○ ○ A/A Example 30 F7 42B 0.3 ○ ○ A/A Example 31 F7 43B 0.3 ○ ○ A/A Example 32 F7 44B 0.3 ○ ○ A/A Example 33 F7 45B 0.3 ○ ○ A/A Example 34 F7 46B 0.3 ○ ○ B/A Example 35 F7 47B 0.3 ◎ ○ B/A Example 36 F7 48B 0.3 ◎ ○ B/A Example 37 F7 49B 0.3 ◎ ○ B/A Example 38 F7 50B 0.3 ◎ ○ B/A Example 39 F7 51B 0.3 ◎ ○ B/A Example 40 F7 52B 0.3 ◎ ○ B/A Example 41 F7 53B 0.3 ◎ ○ B/A Example 42 F7 54B 0.3 ◎ ○ B/A Example 43 F7 55B 0.3 ◎ ○ B/A Example 44 F7 58B 0.2 ○ ○ A/A Example 45 F7 59B 0.2 ○ ○ A/A Example 46 F7 60B 0.2 ○ ○ A/A Example 47 F7 61B 0.2 ○ ○ A/A Example 48 F7 62B 0.2 ○ ○ A/A Example 49 F7 63B 0.2 ○ ○ B/A Example 50 F7 64B 0.2 ◎ ○ B/A Example 51 F7 65B 0.2 ◎ ○ B/A Example 52 F7 66B 0.2 ◎ ○ B/A Example 53 F7 67B 0.2 ◎ ○ B/A Example 54 F7 68B 0.2 ◎ ○ B/A Example 55 F7 69B 0.2 ◎ ○ B/A Example 56 F7 70B 0.2 ◎ ○ B/A Example 57 F7 71B 0.2 ◎ ○ B/A Example 58 F7 72B 0.2 ◎ ○ B/A

[Table 2C] membrane Easy-to-adhesive composition Haze (%) Closeness Anti-blocking Uniformity of easy-adhesive layer (evaluation of coating solution)/(evaluation of coating film) Comparative example 1 F1 14B 0.2 x ○ A/A Comparative example 2 F1 15B 0.2 x ○ A/A Comparative example 3 F2 14B 0.2 x ○ A/A Comparative example 4 F3 14B 0.2 x ○ A/A Comparative Example 5 F4 16B 0.2 x ○ A/A Comparative example 6 F5 17B 0.2 x ○ A/A Comparative Example 7 F6 14B 0.4 x ○ A/A Comparative Example 8 F1 18B 0.6 x ○ A/A Comparative Example 9 F1 19B 0.2 x x A/A Comparative Example 10 F1 20B 0.3 x ○ A/A Comparative Example 11 F7 23B 0.2 x ○ A/A Comparative Example 12 F7 37B 0.2 ○ ○ C/B Comparative Example 13 F7 39B 0.3 x ○ A/A Comparative Example 14 F7 56B 0.3 ○ ○ C/B Comparative Example 15 F7 57B 0.2 x ○ A/A Comparative Example 16 F7 73B 0.2 ○ ○ C/B

(Example 59) The easy-adhesive composition (1B) prepared in Production Example 11 was coated on one surface of the acrylic resin film (F1) produced in Production Example 1 so that the thickness of the dried coating film became 600 nm using a coating tester Thereafter, the whole was dried at 100° C. for 2 minutes. Then, using a biaxial stretching machine (manufactured by Toyo Seiki Seisakusho, TYPE EX4), the film obtained in the above manner was stretched at a stretching ratio of 1.5 times and a stretching temperature of 140°C in the TD direction (the direction perpendicular to the MD direction in the film surface, The width direction during extrusion molding) is uniaxially stretched at the free end to obtain an optical film composed of an acrylic resin film as a biaxially stretched film with an easy-adhesive layer containing urethane resin and fine particles formed on one surface.

(Comparative Example 17) The combination of the acrylic resin film and the easy-adhesive composition was changed as shown in Table 3 below, and an optical film having an easily-adhesive layer formed on one surface was obtained in the same manner as in Example 11.

The evaluation results of the optical films produced in the respective Examples and Comparative Examples are summarized in Table 3 below.

[table 3] membrane Easy-to-adhesive composition Haze (%) Closeness Anti-blocking Uniformity of easy-adhesive layer (evaluation of coating solution)/(evaluation of coating film) Example 59 F1 1B 0.2 ○ ○ A/A Comparative Example 17 F1 14B 0.2 x ○ A/A

(Example 60) Using a single-screw extruder (φ=90.0 mm, L/D=32) equipped with a polymer filter (filter fineness 5 μm) and a T-die at the front end, the pellets of the acrylic resin produced in Production Example 1 ( 1A) Melt and extrude at a processing speed of 200 kg/hour (converted by the amount of resin) and a temperature of 270°C to form a strip-shaped acrylic resin film with a film thickness of 220 μm. Next, the acrylic resin film obtained by film production is continuously supplied to an oven longitudinal stretcher after melt extrusion, and in the stretcher, the acrylic resin film is stretched in the longitudinal direction (travel direction at the time of melt extrusion, MD direction) to Stretching was carried out at a stretching temperature of 142° C. and a stretching ratio of 1.5 times (longitudinal stretching).

Furthermore, the easily-adhesive composition (11B) prepared in Production Example 21 was continuously coated (in-line coating) on the acrylic resin after longitudinal stretching by the gravure coating method so that the thickness of the coated film after drying became 1050 nm. After one surface of the film, the acrylic resin film was directly supplied to a tenter stretcher, and stretched at a stretching temperature of 132° C. and a stretching ratio of 3.0 times the width direction (transverse stretching). In this way, an optical film (thickness 58 μm) composed of an acrylic resin film as a biaxially stretched film in which an easily-adhesive layer (thickness 350 nm) containing urethane resin and fine particles was formed on one main surface was obtained.

(Examples 61 to 79, Comparative Examples 18 to 20) The combination of the resin particles and the easy-adhesive composition was changed as shown in Table 4 below, and an optical film having an easily-adhesive layer formed on one surface was obtained in the same manner as in Example 57.

The evaluation results of the optical films produced in the respective Examples and Comparative Examples are summarized in Table 4 below.

[Table 4] resin Easy-to-adhesive composition Haze (%) Closeness Anti-blocking Uniformity of easy-adhesive layer (evaluation of coating solution)/(evaluation of coating film) Example 60 1A 11B 0.2 ○ ○ A/A Example 61 1A 12B 0.2 ○ ○ A/A Example 62 1A 13B 0.2 ○ ○ A/A Example 63 3A 11B 0.2 ○ ○ A/A Example 64 7A 11B 0.2 ○ ○ A/A Example 65 7A 12B 0.2 ○ ○ A/A Example 66 7A 24B 0.2 ○ ○ A/A Example 67 7A 26B 0.2 ○ ○ A/A Example 68 7A 27B 0.2 ○ ○ B/A Example 69 7A 28B 0.2 ◎ ○ B/A Example 70 7A 29B 0.2 ◎ ○ B/A Example 71 7A 30B 0.2 ◎ ○ B/A Example 72 7A 43B 0.3 ○ ○ A/A Example 73 7A 46B 0.3 ○ ○ B/A Example 74 7A 49B 0.3 ◎ ○ B/A Example 75 7A 59B 0.2 ○ ○ A/A Example 76 7A 60B 0.2 ○ ○ A/A Example 77 7A 62B 0.2 ○ ○ A/A Example 78 7A 65B 0.2 ◎ ○ B/A Example 79 7A 67B 0.2 ◎ ○ B/A Comparative Example 18 1A 21B 0.2 x ○ A/A Comparative Example 19 1A 22B 0.2 x ○ A/A Comparative Example 20 7A 23B 0.2 x ○ A/A

(Example 80) Using a single-screw extruder (φ=90.0 mm, L/D=32) equipped with a polymer filter (filter fineness 5 μm) and a T-die at the front end, the pellets of the acrylic resin produced in Production Example 1 ( 1A) Melt extrusion at a processing speed of 200 kg/hour (resin amount conversion) and a temperature of 270°C to form a strip-shaped film with a film thickness of 220 μm. Then, the film obtained by film production is continuously supplied to the oven longitudinal stretching machine after melt extrusion, and in the stretching machine, the film is stretched at a temperature of 142 ℃, stretching ratio 1.5 times for stretching (longitudinal stretching).

Furthermore, after corona treatment was continuously applied to one main surface of the acrylic resin film stretched longitudinally, the easily-adhesive composition (11B) prepared in Production Example 21 was coated with the thickness of the dried coating film by the gravure coating method. Coating (in-line coating) on the treated surface so as to become 1050 nm. Next, the acrylic resin film was directly supplied to a tenter stretcher, and stretched at a stretching temperature of 132° C. and a stretching ratio of 3.0 times the width direction (transverse stretching). In this way, an optical film (thickness 58 μm) composed of an acrylic resin film as a biaxially stretched film in which an easily-adhesive layer (thickness 350 nm) containing urethane resin and fine particles was formed on one main surface was obtained.

(Examples 81 to 82, Comparative Example 21) The combination of the resin particles and the easily-adhesive composition was changed as shown in Table 5 below, and an optical film having an easily-adhesive layer formed on one main surface was obtained in the same manner as in Example 13.

The evaluation results of the optical films produced in the respective Examples and Comparative Examples are summarized in Table 5 below.

[table 5] resin Easy-to-adhesive composition Haze (%) Closeness Anti-blocking Uniformity of easy-adhesive layer (evaluation of coating solution)/(evaluation of coating film) Example 80 1A 11B 0.2 ○ ○ A/A Example 81 1A 13B 0.2 ○ ○ A/A Example 82 7A 11B 0.2 ○ ○ A/A Comparative Example 21 1A 21B 0.2 x ○ A/A

As shown in Tables 2A to 5, by making the easy-adhesive layer contain an adhesive resin, polyamine, and fine particles, and setting the content of the polyamine in the easily-adhesive layer to 0.0090% by weight to 1.4100% by weight, the resin film and The adhesiveness of the easy-adhesive layer is excellent, and a homogenized easy-adhesive layer can be formed. It is presumed that the use of polyamine as a polymer improves the adhesion between the resin film and the easily bonding layer due to the interaction between the polyamine and the base film. Furthermore, it turned out that blocking resistance is also ensured by making the content rate of a polyamine into 0.0489 mass % or more, for example. The reason for this is presumed to be that by sufficiently adding the polyamine, the viscosity of the easily-adhesive composition increases, and the holding force of the microparticles increases. It is speculated that the addition of polyamine increases the viscosity of the matrix portion of the easily-adhesive layer, thereby inhibiting the microparticles from being buried in the coating solution during the drying process. Furthermore, it is speculated that the effect of suppressing the shedding of fine particles is also imparted by polyamines. In contrast, Comparative Examples 1 to 11, 13, 15, and 17 to 20 using the easily-adhesive compositions (14B to 23B, 39B, and 57B) in which the polyamine content rate was less than 0.0090% by weight failed to satisfy the adhesiveness. In addition, Comparative Examples 12, 14, and 16 using the easily-adhesive compositions (37B, 56B, and 73B) in which the polyamine content exceeds 1.4100% by weight failed to satisfy the uniformity of the easily-adhesive composition or the easily-adhesive layer. It is speculated that the reason is that the viscosity of the easy-adhesive composition becomes too large due to the excessive addition of polyamine. [Industrial availability]

The optical film of the present invention is used in image display devices such as LCDs, and can be preferably used in various protective films such as polarizing element protective films, retardation films, and polarizing films.

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Claims (9)

An optical film comprising a resin film and an easy-adhesive layer formed on the surface of the resin film, and The above-mentioned easy-adhesive layer contains an adhesive resin, polyamine, and fine particles, The above-mentioned polyamine is a polymer having a plurality of amine groups, The above-mentioned plurality of amine groups include at least one selected from the group consisting of secondary amine groups and tertiary amine groups, The content rate of the said polyamine in the said easily-adhesive layer is 0.0090 weight% - 1.4100 weight%. The optical film according to claim 1, wherein the adhesive resin includes urethane resin. The optical film according to claim 1, wherein the plurality of amine groups include primary amine groups, secondary amine groups, and tertiary amine groups. The optical film according to claim 1, wherein the polyamine includes polyalkyleneimine. The optical film according to claim 4, wherein the polyalkyleneimine includes a primary amine group, the secondary amine group, and the tertiary amine group, and has a branched structure. The optical film according to claim 1, wherein the resin film comprises a (meth)acrylic polymer. An optical member comprising the optical film according to any one of claims 1 to 6. An image display device comprising the optical film according to any one of Claims 1 to 6. A method of manufacturing an optical film, which is a method of manufacturing an optical film according to any one of Claims 1 to 6, and coating the surface of the resin film with an easy-adhesive composition comprising an adhesive resin, polyamine, and microparticles to form a coating film of the above-mentioned easily-adhesive composition, drying the coating film to form an easy-adhesive layer comprising the binder resin, the polyamine, and the microparticles on the surface of the resin film, The above-mentioned polyamine is a polymer having a plurality of amine groups, The above-mentioned plurality of amine groups includes at least one selected from the group consisting of secondary amine groups and tertiary amine groups.