WO2008020570A1 - Film de résine acrylique - Google Patents

Film de résine acrylique Download PDF

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Publication number
WO2008020570A1
WO2008020570A1 PCT/JP2007/065701 JP2007065701W WO2008020570A1 WO 2008020570 A1 WO2008020570 A1 WO 2008020570A1 JP 2007065701 W JP2007065701 W JP 2007065701W WO 2008020570 A1 WO2008020570 A1 WO 2008020570A1
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Prior art keywords
acrylic resin
resin film
film
mass
parts
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PCT/JP2007/065701
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English (en)
Japanese (ja)
Inventor
Shigetoshi Maekawa
Akimitsu Tsukuda
Takuya Kuma
Susumu Hirama
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Toray Industries, Inc.
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Priority to JP2007540438A priority Critical patent/JPWO2008020570A1/ja
Publication of WO2008020570A1 publication Critical patent/WO2008020570A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers

Definitions

  • the present invention relates to an acrylic resin film excellent in industrially useful transparency, weather resistance, heat resistance and toughness.
  • the acrylic resin film of the present invention is a surface of an object such as a display material such as a flat display panel, a vehicle interior material and exterior material, an electrical appliance, a building material interior material and an exterior material.
  • the present invention relates to an acrylic resin film excellent in transparency, weather resistance, heat resistance and toughness used for the skin.
  • Acrylic resin films are excellent in transparency, surface gloss, and light resistance, so liquid crystal display sheets or films, optical materials such as light guide plates, vehicle interior materials and exterior materials, Used for the surface skin of objects such as vending machine exterior materials, electrical appliances, interior materials for building materials, and exterior materials.
  • R 2 represents the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
  • Patent Document 4 discloses a composition comprising a composition of an acrylic resin and elastic particles, and having improved transparency by making the difference in refractive index between the resin and the particles 0.03 or less. It is disclosed (Patent Document 4).
  • the film formed using this composition by the solution casting method has both low haze and high toughness, but has a problem that productivity is low because it is based on solution casting.
  • this composition can be used in the melt film-forming method in order to increase productivity. When such a film is formed, the film surface becomes uneven and haze increases.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-2711
  • Patent Document 2 Japanese Patent Laid-Open No. 7-268036
  • Patent Document 3 JP-A-60-67557
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-284816
  • An object of the present invention is to provide an acrylic resin film excellent in transparency, heat resistance and toughness.
  • An acrylic resin film comprising at least three layers, wherein at least one layer comprises an acrylic resin (A) containing a dartaric anhydride unit represented by the following structural formula (1) and an elastic particle ( B), and the total of the acrylic resin (A) and the inorganic particles (B) is 100 parts by mass, and the acrylic resin (A) is 50 to 95 parts by mass, 5 to 50 parts by mass of the inorganic particles (B), and at least two layers sandwiching at least one layer are made of the acrylic resin (A) and do not contain the elastic particles (B).
  • An acrylic resin film characterized by this.
  • R 2 represents the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
  • R 2 represents the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
  • the inner layer is a rubber elastic body containing an alkyl acrylate unit and / or an aromatic bur
  • the outer layer is a glutaric acid represented by the structural formula (1).
  • the acrylic resin (A) comprises 50 to 90 parts by mass of methyl methacrylate units and 10 to 50 parts by mass of glutaric anhydride units, with the acrylic resin (A) as a whole being 100 parts by mass.
  • At least one of the at least two layers has a hard coat layer and / or an antireflective film on its surface! /, Or [1] to [; 13]! / Acrylic resin film according to crab.
  • a polarizing plate protective film comprising the acrylic resin film according to any one of [1] to [; 15].
  • an acrylic resin film having excellent transparency and heat resistance and high toughness can be obtained.
  • acrylics with dramatically improved performance such as total light transmittance of 91% or higher, haze of 1.0% or lower, heat distortion temperature of 110 ° C or higher, and elongation at break of 4% or higher. It is also possible to obtain a resin film.
  • the acrylic resin film which is suitable for the present invention, can be preferably used as an industrial material such as an optical filter that requires a high temperature processing step. Furthermore, since the acrylic resin film according to the present invention has good surface hardness, thickness uniformity, and surface adhesiveness, it can be used well in various applications other than optical filters.
  • the acrylic resin (A) used in the present invention is required to contain a gnorethalic anhydride unit represented by the following general formula (1) in the molecule.
  • IT represents the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
  • the heat resistance of the resin film such as the glass transition temperature (Tg) and the heat distortion temperature, is determined by the flexibility of the resin structure, and it has a low degree of freedom, for example, a rigid benzene ring force, an aromatic bonded with a rigid imide bond
  • Polyimide has a Tg of over 400 ° C.
  • Tg of polymethyl methacrylate (PMMA) which is a flexible aliphatic polymer with a high degree of freedom, does not reach 100 ° C.
  • the heat resistance can be remarkably improved by adding a dartaric anhydride unit having an alicyclic structure to an acrylic resin.
  • a small phase difference is required.
  • the heat resistance is improved more than the introduction of the alicyclic structure, but at the same time, there is a problem that the birefringence increases and the phase difference is easily developed.
  • the alicyclic structure include a dartal anhydride structure, a rataton ring structure, a norbornene structure, and a cyclopentane structure.
  • optical isotropy and heat resistance the same effect can be obtained regardless of the structure used.
  • expensive raw materials having these structures are used. This is industrially disadvantageous because it is necessary to use an expensive raw material that is a precursor of these structures or to undergo the reaction in several steps to obtain the desired structure.
  • dartaric anhydride units are industrially very advantageous because they are obtained from a general acrylic raw material through a single-stage dehydration and / or dealcoholization reaction.
  • specific examples include polarizing plate protective films, lenses, and optical waveguide cores. Two polarizing plates are used in LCD TVs.
  • the polarizing plate protective film used for the polarizing plate is not optically isotropic, for example, dark purple is displayed when displaying black, and yellowish white is displayed when displaying white. This coloring varies depending on the anisotropy of the polarizing plate protective film.
  • the polarizing plate protective film does not exist optically, but is indispensable for the purpose of protecting the polarizer from external force and moisture.
  • the lens In the case of a lens, the lens must have a force S that is intended to refract light at the interface, and the light must travel uniformly through the lens. If the lens is not optically isotropic, there are problems such as image distortion.
  • optical waveguide core In the case of an optical waveguide core, if it is not optical isotropic This causes a difference in the transmission speed of the wave signal, which causes noise and interference problems.
  • Other optical isotropic applications include prism sheet substrates, optical disk substrates, flat panel display substrates, and the like.
  • an unsaturated carboxylic acid monomer (i) and an unsaturated carboxylic acid alkyl ester monomer (which give a dartaric anhydride unit represented by the general formula (1) by a subsequent heating step ( In the case of containing other bulle monomer units, ii) is polymerized with bur monomer (iii) giving the units to give copolymer (a). Thereafter, force, such copolymer (a) is heated in the presence or absence of an appropriate catalyst, and an intramolecular cyclization reaction is carried out by dealcoholization and / or dehydration. By doing so, it is possible to produce an acrylic resin ( ⁇ ) containing a gnorethalic anhydride unit represented by the general formula (1).
  • the carboxyl group of the unsaturated carboxylic acid unit of 2 units is dehydrated, and there is! /, which is the adjacent unsaturated carboxylic acid unit and the unsaturated carboxylic acid unit.
  • One unit of the glutaric anhydride unit is generated by elimination of the alcohol from the acid alkyl ester unit.
  • the unsaturated carboxylic acid monomer (i) used in this case is not particularly limited, and can be copolymerized with another vinyl monomer (iii), and is represented by the following general formula (3). Unsaturated carboxylic acid monomers can be used.
  • R 3 represents hydrogen or an alkyl group having 1 to 5 carbon atoms
  • the unsaturated carboxylic acid monomer (i) represented by the general formula (3) is copolymerized to give an unsaturated carboxylic acid unit having a structure represented by the following general formula (4). [0028] [Chemical 6]
  • R represents hydrogen or an alkyl group having 1 to 5 carbon atoms
  • methyl methacrylate is required as the unsaturated carboxylic acid alkyl ester monomer (ii) from the viewpoint of transparency and weather resistance of the resulting film. Furthermore, it is possible to use one or more unsaturated carboxylic acid alkyl ester monomers together with methyl methacrylate.
  • unsaturated carboxylic acid alkyl ester monomers are not particularly limited, but preferred examples include those represented by the following general formula (5).
  • R 4 represents hydrogen or an aliphatic or alicyclic hydrocarbon group having 1 to 5 carbon atoms, and R 5 represents an optional substituent other than hydrogen.
  • R 5 is particularly preferably an acrylate ester and / or a methacrylate ester having an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms or a hydrocarbon group having a substituent.
  • the unsaturated carboxylic acid alkyl ester monomer represented by the general formula (5) gives an unsaturated carboxylic acid alkyl ester unit having a structure represented by the following general formula (6) when copolymerized.
  • R 4 represents hydrogen or an aliphatic or alicyclic hydrocarbon group having 1 to 5 carbon atoms
  • R 5 represents an optional substituent other than hydrogen.
  • the unsaturated carboxylic acid alkyl ester monomer (ii) other than methyl methacrylate include (meth) acrylate ethyl, (meth) acrylate n-propyl, (meth) acrylic acid n —Butyl, (meth) acrylic acid t-butyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid chloromethyl, (meth) acrylic acid 2-chloroethyl, ( 2-Methyl) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2, 3, 4, 5, 6-pentahydroxyhexyl and (meth) acrylic acid 2, 3, 4 , 5-tetrahydroxypentyl and the like.
  • bull monomers (iii) may be used within a range not impairing the effects of the present invention.
  • other bulle monomers (iii) include styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, ⁇ -ethyl styrene, and p-t-butyl styrene.
  • Aromatic butyl monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, allyl glycidyl ether, styrene —p-glycidyl ether, p-glycidyl styrene, maleic anhydride, Itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-fuelmaleimide, atalinoleamide, methacrylolamide, N-methylacrylamide, butoxymethylacranolamide, N-propyl Methacrylamide, aminoethyl acrylate, alcohol Propylaminoethyl crylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl meth
  • the polymerization method of the acrylic resin (A) a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or the like basically by radical polymerization can be used. Solution polymerization, bulk polymerization, and suspension polymerization are particularly preferred in terms of fewer points.
  • the polymerization temperature is not particularly limited, but from the viewpoint of color tone, a monomer mixture containing an unsaturated carboxylic acid monomer and an unsaturated carboxylic acid alkyl ester monomer is used at a polymerization temperature of 95 ° C or lower. It is preferable to polymerize with.
  • a preferable polymerization temperature is 85 ° C or lower, and particularly preferably 75 ° C or lower.
  • the lower limit of the polymerization temperature is not particularly limited as long as the polymerization proceeds, but is usually 50 ° C or higher, preferably 60 ° C or higher from the viewpoint of productivity in consideration of the polymerization rate.
  • the upper limit temperature is controlled to 95 ° C or less.
  • the polymerization initiation temperature is preferably a relatively low temperature of 75 ° C or lower.
  • the polymerization time is not particularly limited as long as it is sufficient to obtain the required degree of polymerization, but is preferably in the range of 60 to 360 minutes from the viewpoint of production efficiency. 90 to; Particularly preferred.
  • the acrylic resin (A) used in the acrylic resin film of the present invention preferably has a weight average molecular weight of 50,000 to 150,000.
  • the copolymer (a) is previously controlled to have a desired molecular weight, that is, a weight average molecular weight of 50,000 to 150,000 at the time of producing the copolymer (a).
  • a desired molecular weight that is, a weight average molecular weight of 50,000 to 150,000 at the time of producing the copolymer (a).
  • Can achieve the power S When the weight average molecular weight exceeds 150,000, there is a tendency to color during heat deaeration in the subsequent process. On the other hand, when the weight average molecular weight is less than 50,000, the toughness of the acrylic resin film tends to decrease.
  • the method for controlling the molecular weight of the copolymer (a) is not particularly limited.
  • a known technique can be applied.
  • the addition amount of radical polymerization initiators such as azo compounds and peroxides, or chain transfer of alkyl mercabtan, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethinorenolemamide, triethylamine, etc. It can be controlled by the amount of agent added.
  • a method of controlling the addition amount of the alkyl mercabtan, which is a chain transfer agent can be preferably used from the viewpoint of stability of polymerization and ease of handling.
  • alkyl mercaptan used in the present invention examples include ⁇ -octyl mercaptan, t-decyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, and the like. Above all, t-dodecyl mercaptan N-dodecyl mercaptan is preferably used.
  • the addition amount of these alkyl mercabtans is not particularly limited as long as the acrylic resin (A) is controlled to have a specific molecular weight as described above, but usually the total amount of the monomer mixture is 100.
  • the amount is 0.2 to 5.0 parts by mass, preferably 0.3 to 4.0 parts by mass, and more preferably 0.4 to 3.0 parts by mass with respect to parts by mass.
  • the method of heating the copolymer (a) and performing an intramolecular cyclization reaction by dehydration or dealcoholization to obtain an acrylic resin (A) containing a glutaric anhydride unit is not particularly limited. From the viewpoint of productivity, a method in which the copolymer (a) is passed through a heated extruder having a vent or heated and degassed under an inert gas atmosphere or under vacuum is preferable. In particular, when an intramolecular cyclization reaction is performed by heating in the presence of oxygen, the yellowness tends to deteriorate. Therefore, it is preferable to sufficiently substitute the inside of the system with an inert gas such as nitrogen.
  • a single screw extruder equipped with a “unimelt” type screw, a twin screw, a three screw extruder, a continuous or batch kneader type kneader, etc. can be used.
  • a machine can be preferably used. It is preferable to provide a structure capable of introducing an inert gas such as nitrogen.
  • an inert gas such as nitrogen
  • a pipe for introducing an inert gas stream of about 10 to 100 liters / minute is connected to the upper and / or lower part of the hopper.
  • the temperature at which heat degassing is performed by the above method is not particularly limited as long as it is a temperature at which an intramolecular cyclization reaction is caused by dehydration or dealcoholization, but is preferably in the range of 180 to 300 ° C, particularly 200 A range of ⁇ 280 ° C is preferred.
  • the heating and degassing time at this time is not particularly limited, and can be appropriately set according to the desired copolymer composition.
  • the time is 1 minute to 60 minutes, preferably 2 minutes to 30 minutes. The range of 3 to 20 minutes is preferable.
  • the length / diameter ratio (L / D) of the extruder screw is preferably 40 or more in order to ensure a sufficient heating time for advancing the intramolecular cyclization reaction using an extruder.
  • the copolymer (a) when the copolymer (a) is heated by the above method or the like, one or more acids, alkalis and salt compounds are added as a catalyst for promoting the cyclization reaction to dartaric anhydride.
  • the addition amount is not particularly limited, but is suitably about 0.0;! To 1 part by mass per 100 parts by mass of the copolymer (a).
  • the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphorous acid, phenylphosphonic acid, and methyl phosphate.
  • Examples of the basic catalyst include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, and ammonium hydroxide salts.
  • examples of the salt catalyst include acetic acid metal salt, stearic acid metal salt, and carbonate metal salt.
  • the compound power containing an alkali metal can be preferably used because it exhibits an excellent reaction promoting effect with a relatively small addition amount.
  • hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide
  • alkoxides such as sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, and potassium phenoxide.
  • organic carboxylates such as compounds, lithium acetate, sodium acetate, potassium acetate and sodium stearate, and sodium hydroxide, sodium methoxide, lithium acetate and sodium acetate are particularly preferably used.
  • the content of the dartaric acid anhydrous unit represented by the general formula (1) in the acrylic resin (A) used in the present invention is 10 to 50 parts per 100 parts by mass of the acrylic resin (A). Part by mass, more preferably 15 to 45 parts by mass, most preferably 20 to 25 parts by mass.
  • the dartal anhydride unit is less than 10 parts by mass, the heat resistance improvement effect may be reduced. If the glutaric anhydride unit exceeds 50 parts by mass, the toughness may deteriorate. Improvement in heat resistance and improvement in toughness are in a trade-off relationship and can be adjusted by the content of dartaric anhydride units. For this reason, the content of the dartaric anhydride unit should be any value from 10 to 50 parts by mass, depending on the application.
  • the Tg of 120 ° C or higher is required for the polarizing plate protective film.
  • the content of dartaric anhydride units is most preferably 20-25 parts by mass! /. If the content of the dartaric anhydride unit is 20-25 parts by mass, it will be 120- after the elastic particles are added; Tg of 130 ° C and sufficient toughness
  • a force such as a methyl methacrylate unit and a metataric acid unit is preferably contained. And it is preferable that it is content of the quantity S methyl methacrylate unit which remove
  • a methacrylic acid unit which is a precursor of a dartaric anhydride unit, is included in addition to the dartaric anhydride unit and the methyl methacrylate unit. If a methacrylolic acid unit or a methyl methacrylate unit is adjacent to a methacrylic acid unit, dehydration or dealcoholization reaction may occur during heating in film formation or stretching, which may cause foaming, which is not preferable. However, if the dartal anhydride units are adjacent, no dehydration or dealcoholization reaction can occur! /, So methacrylic acid units are included! /.
  • an infrared spectrophotometer or a proton nuclear magnetic resonance (HNMR) measuring instrument is used to quantify each component unit in the acrylic resin (A) used in the present invention.
  • HNMR proton nuclear magnetic resonance
  • Darutaru anhydride units, 1800Cm- 1 and 1760Cm- 1 of the absorption force S characteristic can be force to ward different from the unsaturated carboxylic acid unit and an unsaturated carboxylic acid alkyl ester unit.
  • the spectral assignment in a dimethyl sulfoxide heavy solvent is 0.5 to 5; Peak force S ⁇ methyl group hydrogen in methacrylic acid, methyl methacrylate and glutaric anhydride ring compounds, 1.6-2 lppm peak is methylene group hydrogen in polymer main chain, 3.5 ppm peak Is the power of methyl methacrylate, hydrogen of norebonic acid ester (one COOCH), 12.4 ppm peak is the methacrylic acid cal
  • the copolymer composition can be determined from the hydrogen of boric acid and the integral ratio of the spectrum. Also,
  • the acrylic resin (A) used in the present invention contains an unsaturated carboxylic acid unit and / or another copolymerizable bull monomer unit in the acrylic resin (A). But it can.
  • the amount of the unsaturated carboxylic acid unit is 10 parts by mass or less, ie 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, and most preferably 100 parts by mass with respect to 100 parts by mass of the acrylic resin (A). Is 0 to 1 part by mass. When the unsaturated carboxylic acid unit exceeds 10 parts by mass, colorless transparency and residence stability tend to be lowered.
  • the amount of other bur monomer units copolymerizable with the acrylic resin (A) is acrylic resin.
  • (A) It is preferably 5 to 5 parts by mass, more preferably 0 to 3 parts by mass with respect to 100 parts by mass.
  • an aromatic bule monomer unit such as styrene
  • the content exceeds the above range, colorless transparency, optical isotropy, and chemical resistance tend to decrease.
  • the acrylic resin (A) has a melt viscosity of 260 ° C and a shear rate of lOOsec- 1 o'clock.
  • the melt viscosity referred to in the present invention is a value measured using a die having a die length of 10 mm and a die diameter of 1.0 mm in accordance with 13-1 ⁇ 7210-1976 (reference test).
  • the elastic particle (B) is a particle containing a rubbery polymer.
  • the elastic particles (B) As a specific form of the elastic particles (B), it is composed of a layer containing one or more rubbery polymers and one or more layers composed of different polymers, and each of these layers is composed of Adjacent structures of the so-called core-shell type polymer (B-1), or a graft copolymer obtained by copolymerizing a rubber polymer with a monomer mixture such as a bull monomer. (B-2) and the like can be preferably used.
  • the core-shell type multilayer structure polymer (B-1) is not particularly limited in the number of layers constituting the core-shell type polymer (B-1). However, it has at least one rubber polymer layer inside.
  • the rubbery polymer is a polymer composed of a polymer component having rubber elasticity! /
  • the polymer used for the core-shell type multilayer polymer (B-1) is an acrylic component.
  • An example is a rubber composed of a polymer obtained by polymerizing at least one component selected from the group consisting of a component, a propylene component and an isobutene component.
  • preferable rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, and styrene components such as styrene units and ⁇ -methylstyrene units. It is a rubber composed of at least one component selected from the group consisting of nitrile components such as talaronitrile units and metathalonitrile units, and conjugation component components such as butane units and isoprene units. A rubber composed of one of these components may be used, but a rubber composed of a combination of two or more types is also preferred.
  • an acrylic such as an ethyl acrylate unit or a butyl acrylate unit.
  • Components and rubber composed of silicone components such as dimethylsiloxane units and phenylmethylsiloxane units; (2) from acrylic components such as ethyl acrylate and butyl acrylate units and styrene components such as styrene units and a-methylstyrene units Constructed rubber, (3) Rubber composed of acrylic components such as ethyl acrylate units and butyl acrylate units, and Conjugated components such as butane units and isoprene units, and (4) Ethyl acrylate units And acrylic components such as butyl acrylate units, dimethylsiloxane units and Examples thereof include rubbers composed of silicone components such as dimethylsiloxane units and styrene components such as styrene units and ⁇ -methylstyrene units.
  • a rubber obtained by crosslinking a copolymer composed of a crosslinkable component such as a dibutylbenzene unit, a arylarylate unit and a butylene glycol diacrylate unit is also preferred.
  • the type of layer other than the rubbery polymer layer is not particularly limited as long as it is composed of a polymer component having thermoplasticity.
  • the glass transition temperature is higher than that of the layer, preferably a polymer component.
  • the thermoplastic polymer include unsaturated carboxylic acid alkyl ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, unsaturated dicarboxylic anhydride units, aliphatic bur units, and aromatics.
  • a polymer containing at least one unit It is selected from forces such as bulle units, cyanide bulle units, maleimide units, unsaturated dicarboxylic acid units, and other bulle units.
  • a polymer containing at least one unit polymers containing at least one unit selected from unsaturated carboxylic acid alkyl ester units, unsaturated glycidyl group-containing units and unsaturated dicarboxylic anhydride units are preferred and unsaturated.
  • a polymer containing at least one unit selected from glycidyl group-containing units and unsaturated dicarboxylic anhydride units is preferred.
  • the monomer used as the raw material for the unsaturated carboxylic acid alkyl ester unit is not particularly limited, but (meth) acrylic acid alkyl ester is preferably used. Specifically, to methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and (meth) acrylate n Xylyl, 2-methylhexyl (meth) acrylate, cyclohexanol (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic acid Benzyl, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acryl
  • Examples of the monomer used as the raw material for the unsaturated carboxylic acid unit include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, and further a hydrolyzate of maleic anhydride.
  • acrylic acid and methacrylic acid are more preferable than methacrylic acid because they are excellent in thermal stability. These can be used alone or in combination.
  • the monomer that is a raw material of the unsaturated glycidyl group-containing unit is not particularly limited, and is glycidyl (meth) acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, Examples thereof include styrene-4-glycidyl ether and 4-glycidino styrene. From the viewpoint that the effect of improving impact resistance is great, (meth) glycidyl acrylate is preferably used. These units can be used alone or in combination of two or more. Use with power S.
  • Examples of the monomer used as the raw material for the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, and aconitic anhydride.
  • maleic anhydride is preferably used from the viewpoint that the effect of improving impact resistance is great.
  • These units can be used alone or in combination of two or more.
  • ethylene, propylene, butadiene, and the like are used as the raw material for the aliphatic bulle unit, and styrene, ⁇ - Methyl styrene, 1-Burnaphthalene, 4-Methyl styrene, 4-Propylene styrene, 4-Cyclohexyl styrene, 4-Dodecyl styrene, 2-Ethyl 4-1 Benzyl styrene, 4 (Phenylbutyl) styrene, Halogenated styrene, etc. Acrylonitrile, methacrylonitrile, etalonitrile, etc.
  • maleimide ⁇ ⁇ ⁇ methylmaleimide, ethyl maleimide, ⁇ are used as the raw material for the maleimide unit.
  • maleimide, ⁇ ⁇ ⁇ methylmaleimide, ethyl maleimide, ⁇ are used as the raw material for the maleimide unit.
  • Monomers such as chlorohexyl maleimide, ⁇ phenyl maleimide, ⁇ bromophenyl maleimide, and ⁇ - (black phenyl) maleimide are raw materials for the above unsaturated dicarboxylic acid units.
  • Monomers such as acid monoethyl ester, itaconic acid, and phthalic acid that can be used as raw materials for the other above-mentioned units are acrylamide, methacrylamide, ⁇ ⁇ ⁇ methyl acrylamide, butoxymethyl acrylamide, ⁇ ⁇ ⁇ ⁇ propyl methacrylamide, ⁇ ⁇ ⁇ vinyl.
  • Jetylamine ⁇ Acetinolevinoleamine, Alinoleamine, Metalinoleamine, ⁇ Methylenolinoleamine, ⁇ -Aminostyrene, 2-Isopropenyl oxazoline, 2-Bureuxoxazoline, 2-acroyloxazoline and 2-sti Ruokisazorin etc., can Rukoto include each of these monomers alone to be able to use two or more kinds.
  • the type of the outermost layer is not particularly limited.
  • the unsaturated carboxylic acid alkyl ester unit, the unsaturated carboxylic acid unit, the unsaturated glycidyl Group-containing unit, aliphatic bull unit, aromatic bull unit, cyanated bull unit, maleimide unit, unsaturated dicarboxylic acid unit, unsaturated dicarbo At least one selected from a polymer containing an acid anhydride unit and other bulle units is preferred.
  • At least one selected from polymers containing unsaturated carboxylic acid alkyl ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, and unsaturated dicarboxylic anhydride units is preferred.
  • a polymer containing an unsaturated carboxylic acid alkyl ester unit or an unsaturated carboxylic acid unit is preferred.
  • the outermost layer in the multilayer polymer (B-1) is a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit
  • the intramolecular cyclization reaction proceeds and the dartaric anhydride unit represented by the general formula (1) is generated. Therefore, a multilayer structure polymer (B-1) having a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit in the outermost layer is blended with the above-mentioned copolymer (a) and appropriately used.
  • the acrylic resin (A), which is a continuous phase (matrix phase), can be substantially heated and melt-kneaded under various conditions, and the acrylic resin (D) represented by the above general formula (1) is contained in the acrylic resin (A). It is possible to disperse a multilayer structure polymer (B-1) having a resin-based polymer as the outermost layer. At this time, since the affinity between the acrylic resin (A) and the outermost layer of the multilayer structure polymer (B-1) is good, a good dispersion state without agglomeration becomes possible, and impact resistance, etc. Along with the improvement of mechanical properties, it is considered that extremely high transparency can be expressed.
  • the term “main component” refers to a component containing 50 parts by mass or more with respect to 100 parts by mass of the outermost polymer layer.
  • the monomer used as a raw material for the unsaturated carboxylic acid alkyl ester unit here is not particularly limited, but (meth) acrylic acid alkyl ester is more preferable. Methyl acrylate is more preferably used. Further, the monomer used as a raw material for the unsaturated carboxylic acid unit is not particularly limited, but (meth) acrylic acid is preferred, and methacrylic acid is more preferably used.
  • the core layer is a rubber elastic body containing an allylic acid alkyl ester unit and / or an aromatic bur
  • the outer layer is the above-described one.
  • Acrylic resin containing dartal anhydride unit represented by general formula (1) Is a polymer mainly composed of The refractive index difference between the multilayer structure polymer (B-1), which is an elastic particle, and the acrylic resin (A) is preferably 0.01 or less.
  • the core layer is represented by butyl acrylate / styrene polymer
  • the outermost layer is represented by methyl methacrylate / the above general formula (1).
  • Copolymers consisting of dartaric anhydride units, or methyl methacrylate / daltaric anhydride units represented by the general formula (1) / methacrylic acid polymer, and the core layer is dimethylsiloxane / acrylic acid A butyl polymer whose outermost layer is a methyl methacrylate polymer, whose core layer is a butane / styrene polymer, whose outermost layer is a methyl methacrylate polymer, and whose core layer is a butyl acrylate polymer.
  • Examples include those which are outer layer methyl acrylate polymers ("/" indicates copolymerization).
  • a preferable example is a polymer containing a glycidyl acrylate unit in either one or both of the core layer and the outermost layer.
  • the core layer is a butyl acrylate / styrene polymer
  • the outermost layer is a methyl methacrylate / copolymer composed of a dartal anhydride unit represented by the above general formula (1), or methyl methacrylate / the above general formula.
  • the dartaric anhydride unit / methacrylic acid polymer represented by (1) approximates the refractive index with the acrylic resin (A) that is the continuous phase (matrix phase), and Therefore, it is possible to obtain a good dispersion state, and the transparency that can satisfy the demand for more advanced in recent years is exhibited.
  • the weight average particle diameter of the multilayer structure polymer (B-1) is preferably 50 to 400 nm, more preferably 100 to 200 nm. If the weight average particle size is less than 50 nm, the toughness may not be improved sufficiently, and if it exceeds 400 nm, the Tg may decrease.
  • the weight ratio of the core to the shell is not particularly limited, but the core layer is 50 parts by mass or more with respect to 100 parts by mass of the whole multilayer polymer. 90 parts by mass or less is preferable, and 60 parts by mass or more and 80 parts by mass or less is more preferable.
  • the multilayer structure polymer (B-1) a commercially available product that satisfies the above-described conditions may be used, and it may be prepared by a known method.
  • Examples of commercially available multi-layer polymer include “Metaprene” manufactured by Mitsubishi Rayon Co., “Kaneace” manufactured by Kaneka Chemical Co., Ltd., Kureha “Paraloid” by Gaku Kogyo Co., “Atariroid” by Rohm and Haas, “Staffroid” by Gantz Kasei Kogyo, and “Parapet SA” by Kuraray Co., Ltd. Can be used.
  • graft copolymer (B-2) that can be used as the elastic particles (B) include a rubbery polymer, an unsaturated carboxylic acid ester monomer, Examples include a graft copolymer obtained by copolymerizing a monomer mixture comprising a carboxylic acid monomer, an aromatic bulle monomer, and, if necessary, other bulle monomers copolymerizable therewith. It is done.
  • the rubbery polymer used in the graft copolymer (B-2) is obtained by polymerizing at least one component selected from the group consisting of a gen-based rubber, an talyl-based rubber and an ethylene-based rubber.
  • gum comprised can be illustrated.
  • polybutadiene examples include polybutadiene, styrene-butadiene copolymer, block copolymer of styrene butadiene, acrylonitrile-butadiene copolymer, butyl butadiene acrylate copolymer, polyisoprene, butadiene-methyl methacrylate copolymer, Examples include butyl acrylate-methyl methacrylate copolymer, butadiene acrylate acrylate copolymer, ethylene propylene copolymer, ethylene propylene gen copolymer, ethylene isoprene copolymer, and ethylene methyl acrylate copolymer. It is done.
  • These rubbery polymers can be used alone or in a mixture of two or more.
  • the weight average particle diameter of the graft copolymer (B-2) is 50 to 400 nm. S is more preferably 100 to 200 nm. If the weight average particle size is less than 50 nm, the toughness may not be improved sufficiently, and if it exceeds 400 nm, the Tg may decrease.
  • the weight average particle diameter of the elastic particles (B) is as described in "Rubber Age, Vol. 88, p. 484-490 (1960), by E. Schmidt, PH Biddison J. In other words, using the fact that the polybutadiene particle size to be creamed differs depending on the concentration of sodium alginate, it is measured by the method of determining the particle size of 50% cumulative weight fraction from the weight proportion of cream and the cumulative weight fraction of sodium alginate concentration. can do.
  • the graft copolymer ( ⁇ -2) is produced by adding 100 parts by weight of the graft copolymer ( ⁇ -2) to the rubber.
  • Polymer 10-80 parts by weight, preferably 20-70 parts by weight, more preferably 30-60 parts by weight, and the above monomer (mixture) 20-90 parts by weight, preferably 30-80 parts by weight Preferably, it is obtained by copolymerizing 40 to 70 parts by mass. If the ratio of the rubbery polymer is less than the above range or exceeds the above range, impact strength and surface appearance may be lowered.
  • the graft copolymer (B-2) may contain an ungrafted copolymer that is produced when the monomer mixture is graft copolymerized with the rubbery polymer.
  • the graft ratio is preferably 10 to 100%.
  • the graft ratio is a weight ratio of the grafted monomer mixture to the rubbery polymer.
  • the intrinsic viscosity measured at 30 ° C of a methyl ethyl ketone solvent of an undrafted copolymer is not particularly limited, but it has a strength of 0.;! ⁇ 0.6 dl / g S, impact It is preferably used from the viewpoint of the balance between strength and moldability.
  • the intrinsic viscosity of the graft copolymer (B-2) measured at 30 ° C in a methyl ethyl ketone solvent is not particularly limited, but is 0.2 to 1; It is preferably used from the viewpoint of balance with moldability, and more preferably 0.3 to 0.7 dl / g.
  • the method for producing the graft copolymer (B-2) is not particularly limited, and can be obtained by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • the difference in refractive index is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.
  • the difference in refractive index is determined by adjusting the composition ratio of each monomer unit in the acrylic resin (A) and / or the composition ratio of the rubbery polymer or monomer used in the elastic particles (B).
  • the core layer is a butyl acrylate / styrene polymer
  • the outermost layer is a methyl methacrylate / copolymer composed of dartaric anhydride units represented by the general formula (1), or a methacrylate.
  • the difference in refractive index referred to here is a solution in which the attalinole resin film of the present invention is sufficiently dissolved in a solvent in which the acrylic resin (A) is soluble under appropriate conditions to obtain a cloudy solution, which is centrifuged, etc.
  • the solvent-soluble part and the insoluble part are separated, the soluble part (acrylic resin (A)) and the insoluble part (elastic particles (B)) are purified, and the measured refractive index ( 23 ° C, measurement wavelength: 550 nm).
  • the actual copolymer composition of the acrylic resin (A) and the elastic particles (B) in the acrylic resin film is determined by separating the soluble component and the insoluble component with the above-described solvent. Components can be analyzed individually.
  • the acrylic resin film of the present invention has at least two layers (I) made of the acrylate resin (A) not containing the elastic particles (B) as described above.
  • a layer (II) composed of an acrylic resin composition (C) containing a novel attalinole resin (A) and elastic particles (B) is sandwiched.
  • the layer (II) containing the elastic particles (B) improves the toughness in addition to the heat resistance, reduces the cracks during slitting and punching, and improves the workability and handleability.
  • a single-layer film made of the acrylic resin composition (C) as described above is formed by a melt film forming method, fine irregularities are formed on the film surface and the haze of the film is deteriorated, which is not suitable for optical use.
  • a film can be formed by a solution casting method.
  • the film obtained has a low haze and is good as an optical film, has poor productivity, and is difficult to industrialize.
  • the elastic particles (B) as described above are not included! / And the acrylic particles including the elastic particles (B) between at least two layers (I) made of the acrylic resin (A).
  • the acrylic resin (A) in the layer (I) and the layer (II) need not be completely the same as long as it contains the gnoretalic anhydride unit represented by the structural formula (1). Nare ,.
  • the acrylic resin composition (C) comprises 100 parts by mass of the total of the elastic particles (B) and the acrylic resin (A), 50 to 95 parts by mass of the acrylic resin (A), and elastic particles (B). 5 to 50 parts by mass More preferably, the acrylic resin (A) is 70 to 90 parts by mass and the elastic particles (B) are 10 to 30 parts by mass.
  • the content of elastic particles (B) is less than 5 parts by mass! /, And the film has sufficient toughness, and it is difficult to perform slitting and punching. There's a problem. If the content of the elastic particles (B) is more than 50 parts by mass, the heat resistance is lowered and the yellow color of the film increases, making it suitable as an optical film.
  • the thickness of layer (I) must be at least 0.1 am. Preferably it is 0.6 m or more, more preferably 1.0 ⁇ 0 m or more. If the thickness is less than 0.1 m, it is not preferable because irregularities are formed on the surface of the laminated film and there is no effect of improving haze.
  • the thickness of the layer (I) may be thick, but is preferably 20 111 or less in order not to deteriorate the optical isotropy of the film. More preferably, lO ⁇ m or less, still more preferably 6111 or less.
  • the layer (II) containing the elastic particles (B) is preferably 50% or more of the total thickness. If it is less than 50%, the toughness becomes insufficient.
  • the upper limit of the layer (II) is particularly preferably about 95% as long as a sufficient thickness can be secured with respect to the layer (I).
  • the layer thickness can be adjusted by the discharge amount of the resin and the resin composition constituting the layer thickness.
  • the thickness of the acrylic resin film varies depending on the application. For example, when used as a polarizing plate protective film, 20 Hm to 100 Hm is preferred. Preferred for
  • the laminated thickness is obtained by cutting a film with a single blade and observing the cross section with an optical microscope, or when the film thickness is 80 m or less and observation with a microscope is difficult, a thin film section is prepared with a microtome.
  • TEM transmission electron microscope
  • the layered structure introduces a layer (III) composed of other components as long as the effects of the present invention are not impaired.
  • layer (I) and layer Layers (I) / layers ( ⁇ ) / layers (I) / layers ( ⁇ ) / ⁇ / layers ( ⁇ ) / layers (I) are stacked in layers of five or more layers (II) alternately. Also good.
  • the acrylic resin film of the present invention as described above can be obtained by basically using a known method except that the resin as described above is used.
  • the melt film forming method includes an infusion method, a T-die method, a calendar method, a hot press method, a cutting method, and the like
  • the solution film forming method includes a casting method, an emulsion method, and the like.
  • the inflation method and the T-die method can be preferably used from the viewpoint of productivity.
  • the melt extrusion temperature is preferably 150 to 350. C, more preferably 200-300. C. The most preferable temperature is 240 to 270 ° C. Melt shear rate is preferably LOOOsec 1 or more 5000Sec 1 or less.
  • the raw material used is dry.
  • the moisture content is preferably 200 ppm or less, more preferably 150 ppm.
  • Examples of a method for reducing the moisture content of the raw material to 200 ppm or less include a method of drying for 3 hours in a 100 ° C vacuum dryer. Further, from the viewpoint of suppressing coloring, it is preferable to use a vent to perform melt kneading under reduced pressure or melt kneading under a nitrogen stream.
  • the casting method includes at least an acrylic resin (A) for forming layer (I) melted by using a melt extruder, and an acrylic resin (A) and elastic particles (B) for forming layer (II).
  • a method using a feed block is preferable from the viewpoint of stacking accuracy of the apparatus and maintainability. It is preferable to install the feed block part immediately before the base in order to increase the stacking accuracy.
  • the resin is preferably discharged from the die onto a cooled drum by these methods and rapidly cooled to a glass transition temperature (Tg) or lower to obtain an unstretched film.
  • the resin discharged on the cooling drum is rapidly cooled to the glass transition temperature (Tg) or lower, the resin is used as a cooling medium by electrostatic application method, air chamber method, air knife method, press roll method, etc. It is preferable to make it adhere to a certain drum.
  • the ratio of the lip gap of the T die to the film thickness is preferably 20 or less.
  • the lip gap of the T die is preferably 0.8 mm or less.
  • the polymer temperature immediately after the mouthpiece lip is preferably 270 ° C or lower.
  • the polymer may be colored, foaming rather than glue, and bubbles may be formed in the film, making it unsuitable for films for optical applications.
  • the method of setting the force and polymer temperature to 270 ° C or less the method of setting the extrusion set temperature to 260 ° C or less, or the method of setting the lip land length of the die to 30mm or less Etc. It is also effective to lower the polymer temperature and keep the humidity near the extrusion below 70% RH.
  • the acrylic resin film of the present invention obtained as described above has a total light transmittance of 91% or more, a haze of 1.0% or less, and an elongation at break of 4% by adopting the structure described so far. It is possible to satisfy all of the above characteristics at the same time.
  • the total light transmittance and haze of the acrylic resin film are values measured according to JIS-K7361-1 1997 and JIS-K7136-2000.
  • the acrylic resin film of the present invention is suitably used for optical isotropy applications.
  • optical isotropic applications it is required to protect the protected object from external stress, heat, chemicals, etc. without incidenting any optical effects on the incident light. It is done.
  • the total light transmittance is 100% in terms of optical characteristics. If the total light transmittance is low, there is a problem of darkening when a polarizing plate protective film, a prism sheet, or a lens is used, and there is a problem of signal attenuation when the optical waveguide or the core of the optical fiber is used. Therefore, in the present invention, the total light transmittance is preferably 91% or more, more preferably 92% or more. Although there is no upper limit to the total light transmittance, the upper limit is generally about 99% because loss due to interface reflection is unavoidable.
  • the haze is preferably 1.0% or less. If the haze exceeds 1.0%, the total light transmittance may be less than 91%.
  • the haze is preferably 0.7% or less, and more preferably 0.3% or less.
  • the haze can be reduced to L. 0% or less.
  • the haze can be reduced to 0.7% or less by setting the surface roughness R to 20 nm or less, and more preferably, the haze is set to 0.3% or less by setting the surface roughness R to 10 nm or less. It becomes possible.
  • the surface roughness R has no particular lower limit from the viewpoint of reducing haze, but is preferably 3 nm or more from the viewpoint of film winding properties!
  • the elastic particles (B) are included as described above.
  • the layer (I) composed of the acrylic resin (A) and the layer (II) composed of the acrylic resin composition (C) containing the acrylic resin (A) and the elastic particles (B) are sandwiched, for example, Acrylic resin (A) Thickness of layer (I) that also has force is 0.1 l rn or more, and ratio of lip gap of T die to film thickness in melt extrusion using T die (T die lip gap / film The thickness is preferably 20 or less. In order to reduce the surface roughness R to 20 or less, the thickness of the layer (I) should be 1.
  • O ⁇ m or more and the ratio of (T-die lip gap / film thickness) should be 15 or less. Is preferred.
  • the oxygen concentration in the hopper is made 1 ppm or less during melt extrusion. To reduce the oxygen concentration in the hopper to 1 ppm or less, it is preferable to depressurize the hopper or purge nitrogen at a flow rate of 20 ml / min or more.
  • the acrylic resin film of the present invention has a strength S of preferably 4% or more in at least one direction, and more preferably 15% or more. Further, the elongation at break in the orthogonal direction is more preferably 4% or more. When the elongation at break of the acrylic resin film is 4% or more, the acrylic resin film has appropriate flexibility, film tearing during film formation and processing is reduced, and workability such as slitting is improved. Therefore, it is preferable.
  • the elongation at break of such an acrylic resin film is measured by a method based on JIS-C2318-2002.
  • the upper limit of the elongation at break of the acrylic resin film is not particularly limited, but it is considered to be about 50% in practice.
  • the molecular weight of the acrylic resin, the content of cyclic units, the composition of the elastic particles, the particle diameter, the added amount, The dispersion state and the like may be adjusted as appropriate.
  • the elongation at break is 2% force
  • the elongation at break can be made 4%. Therefore, also in the resin film of the present invention, the elongation at break can be increased by adjusting the particle diameter and the amount of the elastic particles added to the layer (II).
  • the acrylic resin film of the present invention contains a dartal anhydride unit, it has excellent heat resistance with a heat distortion temperature of 110 ° C or higher.
  • Upper limit of heat distortion temperature Although there is no particular limit, the upper limit is about 200 ° C in view of the toughness preferred to be 130 ° C or higher and the elongation at break. To improve heat resistance, it is preferable to increase the content of dartaric anhydride units.
  • the thermal deformation temperature is obtained by using thermomechanical analysis (TMA).
  • TMA thermomechanical analysis
  • TMA thermomechanical analysis
  • TMA thermomechanical analysis
  • TMA thermal analysis station
  • TM-9400 sample measurement module
  • the in-plane phase difference with respect to a light beam having a wavelength of 590 nm is preferably lOnm or less, more preferably 5 nm or less, and still more preferably Inm or less.
  • the retardation in the film surface with respect to a light beam having a wavelength of 590 nm is lOnm or less, it can be suitably used as an optical isotropic film in protective film applications such as polarizing plates and optical disks.
  • the retardation in the film surface with respect to light with a wavelength of 590 nm is smaller, but the lower limit is considered to be about 0.1 nm in practice.
  • a film having a thickness of 41 Hm and a retardation of 0.1 nm can be obtained by adjusting the film so that (the lip gap of the T die / film thickness) is 15. This is because stretching between the lip of the T die and the cooling drum can be suppressed, and the occurrence of phase difference can be suppressed.
  • the refractive index in the direction of the orthogonal axis in the acrylic resin film plane with respect to light having a wavelength of 590 nm is n and n (where n ⁇ n), respectively, and the wavelength is 590 ⁇ y x y.
  • n is the refractive index in the thickness direction of the acrylic resin film for m rays
  • z is the refractive index in the thickness direction of the acrylic resin film for m rays
  • the force is preferably S, more preferably 8 nm or less, still more preferably 5 nm or less, and most preferably 2 nm or less. Thickness direction retardation of acrylic resin film R force Onm or less
  • the acrylic resin film has excellent optical isotropy in the thickness direction as well as optical isotropy in the thickness direction. Therefore, it is more suitable for use in protective film applications such as polarizing plates and optical disks. be able to. In applications where optical isotropy in the thickness direction is required, it is preferable that the retardation R in the thickness direction is small, but the lower limit is practically about 0.1 nm.
  • Thickness direction retardation R (nm) d X ⁇ (n + n) / 2— n ⁇
  • V and so on are effective.
  • Gnorethalic anhydride unit: methyl methacrylate unit: methacrylic acid 32: 66: 20 parts by mass of a two-layer particle having a particle size of 155 nm is added to a polymer having 2 parts by mass to obtain a solution.
  • the lip gap of the T die so that the (Die lip gap / film thickness) is 50 by the film formation method, a film with a thickness of 41 ⁇ m and a thickness direction retardation of 4.5 nm is obtained. End up.
  • a film with a thickness of 4 m and a thickness difference of 0.4 nm can be obtained. Obtainable. This is because stretching between the lip of the T-die and the cooling drum is suppressed, and the occurrence of phase difference can be suppressed.
  • the acrylic resin film of the present invention has a photoelastic coefficient of ⁇ 2 X 1 for light having a wavelength of 589 m. It is preferably 0- 12 / Pa ⁇ 2 X 10_ 12 / Pa.
  • ⁇ 2 X 1 for light having a wavelength of 589 m. It is preferably 0- 12 / Pa ⁇ 2 X 10_ 12 / Pa.
  • Photoelastic coefficient of the acrylic resin film is - a 2 X can 10_ is 12 / Pa ⁇ 2 X 10_ 12 / Pa , the force, the change in phase difference even when given the mowing stress preferably small. More photoelastic coefficient is small, the properly preferred over preferred for the phase difference change is small tool to stress - a 1 X 10- 12 / Pa ⁇ l X 10_ 12 / Pa.
  • the photoelastic coefficient of an acrylic resin film is generally small, but if the styrene or maleimide is copolymerized or an aromatic substituent is introduced to improve heat resistance, the photoelastic coefficient also increases. However, the acrylic resin film of the present invention can achieve both improved heat resistance and reduced photoelastic coefficient due to the dartal anhydride structure.
  • an ultraviolet absorber depending on the application.
  • benzotriazole-based, salicylic acid ester-based, benzophenone-based, oxybenzophenone-based, cyanoacrylate-based, polymer-based, and inorganic-based ones can be used as ultraviolet absorbers.
  • commercially available ultraviolet absorbers include Adeka Stub of Asahi Denka Kogyo Co., Ltd. represented by the following general formula (7), TINUVIN (registered trademark), Uvinul of BASF Co., Ltd., and UV absorber of Johoku Chemical Co., Ltd.
  • Aromatic polymer absorbs ultraviolet rays by the aromatic units of the main chain, so the main chain is cleaved by ultraviolet rays and has the problem of degradation.
  • the acrylic resin film of the present invention deteriorates because the main chain portion does not absorb ultraviolet rays.
  • Less UV absorbers to add Depending on the type and amount, a desired UV-cutting function can be imparted, which is preferable.
  • the ultraviolet absorber to be added is an aromatic compound, it will be present in the acrylic resin film at random, so that the phase difference is hardly exhibited. Therefore, the ultraviolet absorber may be an aromatic compound or an aliphatic compound.
  • the addition amount of the ultraviolet absorber is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the acrylic resin film. If the amount is less than 1 part by mass, the desired effect may not be obtained. When the amount exceeds 5 parts by mass, problems such as non-uniform dispersion, a decrease in total light transmittance, and an increase in haze may occur. More preferably, it is 1 part by mass or more and 2 parts by mass or less.
  • the light transmittance of light having a wavelength of 380 nm of the acrylic resin final is 10% or less by adding an ultraviolet absorber as described above. More preferably, it is 5% or less.
  • the light transmittance of 380 nm light can be reduced by increasing the amount of UV absorber and can be increased by reducing it. By sufficiently cutting ultraviolet rays (light with a wavelength of 380 nm or less), materials that dislike ultraviolet rays can be protected.
  • the light transmittance at a wavelength of 380 nm is measured using the following apparatus.
  • T is the intensity of light that has passed through the sample
  • T is the same distance except that it does not pass through the sample.
  • UV measuring instrument U— 3410 manufactured by Hitachi Keiki Co., Ltd.
  • the acrylic resin film of the present invention includes other thermoplastic resins (for example, polyethylene, polypropylene, acrylic resin, polyamide, polyethylene sulfide resin, polyether ether ketone resin, Polyester, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyetherimide, etc.) and thermosetting resins (eg phenol resin, melamine resin, polyester resin, silicone resin, epoxy resin, etc.) And / or laminating I can do it.
  • thermoplastic resins for example, polyethylene, polypropylene, acrylic resin, polyamide, polyethylene sulfide resin, polyether ether ketone resin, Polyester, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyetherimide, etc.
  • thermosetting resins eg phenol resin, melamine resin, polyester resin, silicone resin, epoxy resin, etc.
  • hindered phenol, benzoate, and cyanoacrylate antioxidants such as lubricants and plasticizers, montanic acid and its salts, and esters Release agents such as half esters, stearyl alcohol, stearamide and ethylene wax, anti-coloring agents such as phosphites and hypophosphites, halogen flame retardants, phosphorus and silicone non-halogen flame retardants
  • additives such as nucleating agents, amine-based, sulfonic acid-based, anti-static agents such as polyethers, and colorants such as pigments may be optionally added.
  • the color of the additive does not adversely affect the thermoplastic polymer and the transparency is not lowered!
  • the method of blending optional components such as elastic particles (B) or other additives into acrylic resin (A) and acrylic resin (A) and others are no particular restrictions on the method of blending optional components such as elastic particles (B) or other additives into acrylic resin (A) and acrylic resin (A) and others.
  • a method is preferably used in which after arbitrary blending of these components, the mixture is uniformly melt-kneaded by a single-screw or twin-screw extruder usually at 200 to 350 ° C.
  • the cyclization reaction of the copolymer (a) obtained during the production of the acrylic resin (A) can be simultaneously performed.
  • a cyclization reaction may be performed simultaneously when a part of the elastic particles ( ⁇ ) contains a copolymer composed of an unsaturated rubonic acid monomer unit and an unsaturated carboxylic acid alkyl ester monomer unit. it can.
  • the acrylic resin (wax) is preferably filtered for the purpose of removing foreign substances.
  • the film can be usefully used as an optical application film with strict standards.
  • a resin dissolved in a solvent such as tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, ⁇ ⁇ ⁇ -methylpyrrolidone, etc. is 25 ° C or higher and 100 ° C or lower.
  • a filter such as sintered metal, porous ceramic, sand, wire mesh, etc.
  • the acrylic resin film of the present invention preferably has a hard coat layer and / or an antireflection film on the surface of at least one of the at least two layers. Her When forming both the coat coat layer and the antireflection film, it is preferable to stack an antireflection film on the hard coat layer.
  • the method for forming the hard coat layer is not particularly limited, and any known method can be used.
  • a method using a polyfunctional acrylate can be exemplified.
  • the polyfunctional acrylates include 1,6-hexanediol diatalate, 1,4 butanediol diatalate, ethylene glycol diatalate, diethylene glycol diatalate, tetreethylene glycol diatalate, tripropylene glycolate.
  • the antireflection film can also be formed by a known method without limitation. That is, the antireflection film is preferably a dry type using an inorganic compound or a wet type using an organic compound. Even if only one low refractive index layer is formed, a high refractive index layer, a low refractive index is used. Arbitrary layers of layers and intermediate refractive index layers may be laminated.
  • the optical filter is a member for a display device, and particularly indicates a member used for a flat panel display such as a liquid crystal display, a plasma display, a field emission display, or an electoluminescence display.
  • a flat panel display such as a liquid crystal display, a plasma display, a field emission display, or an electoluminescence display.
  • this A plastic substrate provided with a transparent conductive film and / or a gas-nolia film on a bright acrylic resin film, a lens obtained by processing and molding the acrylic resin film of the present invention, a polarizing plate protective film bonded to a polarizing plate via an adhesive,
  • optical filters include various terminal boards, printed wiring boards, speakers, microscopes, binoculars, cameras, covers for various devices represented by watches, and the like.
  • the acrylic resin film was dissolved in acetone, and this solution was centrifuged at 9000 rpm for 30 minutes to separate into an acetone soluble component and an acetone insoluble component. Acetone-soluble components were dried under reduced pressure at 60 ° C for 5 hours, and each component unit was quantified to identify each component composition of the acrylic resin.
  • a sample in which a layer to be measured based on the thickness of each layer measured with a transmission electron microscope (TEM) was shaved with a single blade was used.
  • TEM transmission electron microscope
  • force S which can be quantified by infrared spectroscopy, in this case, measure each layer of the fracture surface of the film by microscopic FT-IR.
  • the haze value (%) and total light transmittance (%) at 23 ° C. were measured using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., JIS-K7361 1997 and JIS-K7136-2000. Measurements were taken three times and averaged.
  • the tensile Young's modulus was determined from the tangent of the rising portion of the obtained load elongation curve. Also, the elongation at break was calculated by multiplying the length at the time of film rupture by subtracting the distance between chucks and dividing it by the distance between chucks. In addition, the breaking strength was determined by dividing the load at the breaking point by the cross-sectional area. The measurement was performed 5 times and the average value was taken.
  • the phase difference for the light with a wavelength of 480.4 nm the phase difference for the light with a wavelength of 548.3 nm
  • the phase difference for a light beam with a wavelength of 68.2 nm Measure the phase difference for a light beam with a wavelength of 752.7 nm.
  • the wavelength dispersion formula (R () a + b / 2 + c / 4 + d / 6)
  • the refractive index ⁇ ⁇ , ny (where ⁇ ⁇ ⁇ ⁇ ) of the acrylic resin film in the plane of the acrylic resin film is measured, and the refractive index ⁇ in the thickness direction of the acrylic resin film for the light of wavelength 590 nm is measured.
  • the thickness was determined from the following formula when the thickness of the resin film was d (nm). The measurement was performed once.
  • Thickness direction retardation R (nm) d X ⁇ (n + n) / 2— n ⁇
  • Measurement was performed using the following apparatus, and transmittance corresponding to light of each wavelength was determined. The measurement was performed once.
  • T is the intensity of light that has passed through the sample
  • T is the same distance except that it does not pass through the sample.
  • UV measuring instrument U— 3410 manufactured by Hitachi Keiki Co., Ltd.
  • thermo-mechanical analysis when the temperature of the measurement sample was raised and the deformation amount plotted against the measurement temperature, the temperature at which the deformation amount changed by 2% or more was taken as the heat deformation temperature.
  • TMA thermo-mechanical analysis
  • MMS-9000 thermal analysis station
  • TM-9400 sample measurement module
  • the thermal deformation temperature was measured by applying a bow I tension load of 150 MPa per unit cross-sectional area of the measurement sample. The measurement was performed once.
  • Acetone is added to the acrylic resin film and refluxed for 4 hours. This solution is centrifuged at 9, OOOrpm for 30 minutes to obtain acetone-soluble components (components of acrylic resin (A)) and insoluble components (elastic particles (B)). Component). These were dried under reduced pressure at 60 ° C. for 5 hours. Each solid material obtained was press-molded at 250 ° C to form a 0.1 mm thick film, and then refracted at 23 ° C at a wavelength of 550 nm by an Abbe refractometer (manufactured by Atago Co., Ltd., DR-M2). The rate was measured. The absolute value of the difference in refractive index between the acrylic resin (A) component and the elastic particle (B) component was used. The measurement was performed once.
  • DAWN— DSP type multi-angle light scattering photometer Weight average molecular weight (absolute molecular weight) was measured using a gel permeation chromatograph equipped with Wyatt Technology (pump: 515 type, manufactured by Waters, column: TSK-gel-GMHXL, manufactured by Tosoh Corporation).
  • a differential scanning calorimeter (DSC-7 type manufactured by Perkin Elmer) was used, and the measurement was performed at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere. The measurement was performed once. Note that the glass transition temperature (Tmg) of JIS K7121-1987 is used as the glass transition temperature (Tg).
  • the surface pencil hardness was measured in accordance with JIS K 5400-1990. For measurement, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B in the Japan Paint Inspection Association Marked Test Pencil manufactured by Mitsubishi Pencil Co., Ltd. , 5B, 6B hardness pencils were used. It also means hard in this order! [0135] (15) Folding resistance (times):
  • test piece dimensions were 15 ⁇ 0.03 mm wide and 110 ⁇ 5 mm long, and the load was 8.14 MPa per cross-sectional area.
  • Centerline average roughness R was measured using a Keyence laser microscope (VK-9500). The measurement conditions are as follows. The average value of 20 measurements was taken as the value.
  • Cut age 0.08mm.
  • Thin film slices were prepared with a microtome, stained with ruthenium, observed with a transmission electron microscope (TEM), and the laminate thickness was measured with photographs. For the measurement, three different places were measured and the average value was used.
  • TEM transmission electron microscope
  • a solution of 0.05 part of methyl methacrylate / acrylamide copolymer suspension in 165 parts of ion-exchanged water is supplied to a stainless steel autoclave with a capacity of 5 liters and equipped with a baffle and a fudra-type stirring blade. The mixture was stirred at 400 rpm and the system was replaced with nitrogen gas.
  • the methyl methacrylate / acrylamide copolymer suspension was prepared by the following method: methyl methacrylate 20 parts by mass, acrylamide 80 parts by mass, potassium persulfate 0.3 parts by mass, ion Charge 1500 parts by mass of exchange water into the reactor, keep the reactor at 70 ° C while replacing with nitrogen gas, and react until the monomer is completely converted to polymer.
  • An aqueous solution of a copolymer of acrylamide and acrylamide was used as a suspension.
  • the copolymer (a-1) had a polymerization rate of 98% and a weight average molecular weight of 68,000.
  • a pellet-shaped acrylic resin (A1) was obtained.
  • the composition ratio of the dartal anhydride unit was 31 parts by mass, and the weight average molecular weight was 65,000.
  • An acrylic resin (A2) was obtained in the same manner as in Reference Example 1 except that the amount of 2,2′-azobisisobutyronitrile used was changed to 0.5 parts by mass.
  • This acrylic resin had a composition ratio of dartaric anhydride units of 31 parts by mass and a weight average molecular weight of 80,000.
  • the core-shell polymer obtained by the following was used.
  • the acrylic resin composition (C1) pellets dried at 100 ° C for 3 hours were obtained in the above Reference Example 2 using a 45mm ⁇ single screw extruder (S 1) (set temperature 250 ° C).
  • the obtained acrylic resin (A2) was extruded using a single-screw extruder (S2) of 40 ⁇ (set temperature: 250 ° C (the lip portion also has the same temperature)).
  • S1 and the acrylic resin (A2) are laminated through a feed block whose laminated structure is acrylic resin (A2) / acrylic resin composition (C1) / acrylic resin (A2) Extruded into a sheet through a T-die (set temperature 250 ° C).
  • the film was cooled with a single side of the film being completely adhered to a 130 ° C cooling roll to obtain an unstretched acrylic resin film.
  • the stack thickness ratio of each layer was adjusted so that the discharge amount was adjusted so that acrylic resin (A2): acrylic resin composition (C1): acrylic resin (A2) was 1: 5: 1.
  • the acrylic resin film obtained by strength and strength had excellent heat resistance, transparency and toughness, and excellent processing characteristics! Table 1 shows the film characteristics.
  • the acrylic resin film obtained by applying strength and strength had excellent heat resistance, transparency and toughness, and excellent processing characteristics.
  • Table 1 shows the film characteristics.
  • Example 1 except that the cooling roll speed was adjusted so that the total film thickness was 73 m. A film was formed in the same manner.
  • the acrylic resin film obtained by applying strength and strength was excellent in heat resistance, transparency and toughness, and also in processing characteristics.
  • Table 1 shows the film characteristics.
  • a film was formed in the same manner as in Example 1 except that the hopper was purged with nitrogen at a flow rate of 20 ml / min during extrusion and the temperature of the lip portion of the T die was set to 230 ° C.
  • the acrylic resin film obtained by applying strength and strength had excellent heat resistance, transparency and toughness, and excellent processing characteristics.
  • Table 1 shows the film characteristics.
  • the acrylic resin film obtained by applying strength and strength had excellent heat resistance, transparency and toughness, and excellent processing characteristics.
  • Table 1 shows the film characteristics.
  • the acrylic resin film obtained by applying strength and strength had excellent heat resistance, transparency and toughness, and excellent processing characteristics.
  • Table 1 shows the film characteristics.
  • Atalinole resin composition (C1) and acrylic resin (A2) are composed of acrylic resin (A2) / acrylic resin composition (C1) / acrylic resin (A2) / acrylic resin composition (C1) / After lamination through a feed block to be an acrylic resin (A2), it was extruded into a sheet through a T die (set temperature 250 ° C, only the lip portion was set temperature 230 ° C).
  • the acrylic resin film obtained by strength and strength has excellent heat resistance, transparency, and toughness, and excellent processing characteristics! Table 2 shows the film characteristics.
  • a film was formed in the same manner as in Example 4 except that the lamination thickness ratio was 1: 5:... 5: 1 so that the acrylic resin (A2) was thin.
  • the acrylic resin film obtained by applying force has excellent heat resistance, transparency and toughness, and excellent processing characteristics! Table 2 shows the film characteristics.
  • the mixture was kneaded to obtain a pellet-shaped acrylic resin composition (C2), and the lamination thickness ratio was 1: 5: 1 acrylic resin (A2) / acrylic resin composition (C2) / acrylic resin (A2).
  • the film was formed in the same manner as in claim 4 except that the layers were laminated so that [0166]
  • the acrylic resin film obtained by applying strength and strength has excellent heat resistance, transparency and toughness, and excellent processing characteristics! Table 2 shows the film characteristics.
  • a film was formed in the same manner as in Example 4 except that the discharge amount of the two extruders was adjusted so that the acrylic resin (A2) was thin, and the thickness of the acrylic resin (A2) layer was 0.08 m.
  • the acrylic resin film obtained by strength and strength had excellent heat resistance and toughness. The transparency was slightly inferior. Table 2 shows the film characteristics.
  • the acrylic resin composition (C1) pellets dried for 3 hours at 100 ° C were extruded using a 45mm ⁇ single screw extruder (S 1) (set temperature 250 ° C), and T-die (set temperature) 250 ° C.).
  • This film was cooled with a single face of a 130 ° C. cooling roll being completely adhered to obtain an unstretched acrylic resin film having a thickness of 40 m.
  • the acrylic resin film obtained by applying force has a large haze and is not suitable as an optical filter.
  • Table 2 shows the film characteristics.
  • the acrylic resin film obtained by applying strength and strength had excellent heat resistance and transparency, and the toughness was poor and the additive properties were poor.
  • Table 2 shows the film characteristics.
  • the hoppers of both extruders were purged with nitrogen at a flow rate of 20 ml / min.
  • the stacking structure was Sumipec LG2 / Sumipec HT50Y / Sumipec LG2
  • Only the lip and the lip part were extruded into a sheet through a set temperature of 210 ° C.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Number of layers 3 layers 3 layers 3 layers 3 layers 3 layers 3 layers 3 layers 3 layers Overall thickness (m) 39
  • 34 73 40
  • 41 Acrylic Resin A2 or
  • Example 8 Example 9 Example 1 0 Example 1 1 Comparative example 1 Comparative example 2 Comparative example 3 Stack factor 5 layers 9 layers 3 layers 3 layers 1 layers 1 layers 1 layers Overall thickness (im) 40 40 40 40 40 40 80 40 Acrylic resin A2 or 3.1 1.6 5.7 0.08 0 0 5.7 Sumipec LG2 thickness (m)
  • Acrylic resin film that can be obtained through strength and strength makes use of its excellent transparency, heat resistance, light resistance, and toughness to make use of optical filters, electrical and electronic parts, automotive parts, mechanical mechanisms used in display equipment. It can be used for various applications such as covers for parts, OA equipment, home appliances, etc. and their parts and general goods.

Landscapes

  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film de résine acrylique qui présente d'excellentes caractéristiques en terme de transparence, de résistance à la chaleur et de solidité. L'invention concerne spécifiquement un film de résine acrylique composé d'au moins trois couches, qui est caractérisé en ce que au moins une couche renferme une composition de résine acrylique contenant une résine acrylique (A) ayant une unité anhydride glutarique représentée par la formule structurale (1) ci-après et des particules élastiques (B), la résine acrylique (A) étant contenue dans des proportions égales à 50-95 parties en masse et les particules élastiques (B) étant contenues dans des proportions égales à 5-50 parties en masse lorsque le total de la résine acrylique (A) et des particules élastiques (B) est de 100 parties en masse. Le film de résine acrylique est en outre caractérisé en ce que au moins deux couches prenant en sandwich la ou les couches susmentionnées sont composées de résine acrylique (A) et ne contiennent pas de particules élastiques (B). (1)
PCT/JP2007/065701 2006-08-18 2007-08-10 Film de résine acrylique WO2008020570A1 (fr)

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JP2006-223018 2006-08-18

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Cited By (12)

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JP2009263566A (ja) * 2008-04-28 2009-11-12 Sumitomo Chemical Co Ltd メタクリル樹脂組成物の製造方法
JP2009280750A (ja) * 2008-05-26 2009-12-03 Kaneka Corp 光学用フィルムおよび偏光板
JP2009292871A (ja) * 2008-06-02 2009-12-17 Fujifilm Corp アクリルフィルムおよびその製造方法、並びに、偏光板、光学補償フィルム、反射防止フィルムおよび液晶表示装置
JP2010024338A (ja) * 2008-07-18 2010-02-04 Asahi Kasei Chemicals Corp 光学フィルム
JP2010096919A (ja) * 2008-10-15 2010-04-30 Asahi Kasei Chemicals Corp 光学フィルム
JP2010231015A (ja) * 2009-03-27 2010-10-14 Sumitomo Chemical Co Ltd 偏光子保護フィルム、偏光板及び液晶表示装置
JP2012180423A (ja) * 2011-02-28 2012-09-20 Sumitomo Chemical Co Ltd アクリル系樹脂フィルムの製造方法及び該方法で製造されたアクリル系樹脂フィルム並びに偏光板
JP2015221903A (ja) * 2015-07-06 2015-12-10 富士フイルム株式会社 アクリルフィルムおよびその製造方法
WO2016084740A1 (fr) * 2014-11-26 2016-06-02 三菱レイヨン株式会社 Film de stratifié de résine, procédé de fabrication correspondant, et panneau décoratif de mélamine
JPWO2015115537A1 (ja) * 2014-01-29 2017-03-23 日立化成株式会社 樹脂組成物、樹脂組成物を用いた半導体装置の製造方法、及び固体撮像素子
JP2017187619A (ja) * 2016-04-06 2017-10-12 東レ株式会社 光学フィルム
US10358580B2 (en) 2014-01-29 2019-07-23 Hitachi Chemical Company, Ltd. Adhesive composition, resin cured product obtained from adhesive composition, method for manufacturing semiconductor device using adhesive composition, and solid-state imaging element

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KR101293902B1 (ko) 2008-07-01 2013-08-06 주식회사 엘지화학 점착제 조성물，편광판용 보호 필름，편광판 및 액정표시장치
JP2013061600A (ja) * 2011-09-15 2013-04-04 Keiwa Inc ３ｄメガネ用光学シート及び３ｄメガネ
EP3467047B1 (fr) * 2016-05-27 2021-11-03 Kuraray Co., Ltd. Résine thermoplastique, produit moulé, film, et produit en couches

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JP2004051946A (ja) * 2002-05-31 2004-02-19 Toray Ind Inc シートおよびその積層シート
WO2005105918A1 (fr) * 2004-04-28 2005-11-10 Toray Industries, Inc. Films de résine acrylique et procédé de fabrication desdits films

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JP2004051946A (ja) * 2002-05-31 2004-02-19 Toray Ind Inc シートおよびその積層シート
WO2005105918A1 (fr) * 2004-04-28 2005-11-10 Toray Industries, Inc. Films de résine acrylique et procédé de fabrication desdits films

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009263566A (ja) * 2008-04-28 2009-11-12 Sumitomo Chemical Co Ltd メタクリル樹脂組成物の製造方法
JP2009280750A (ja) * 2008-05-26 2009-12-03 Kaneka Corp 光学用フィルムおよび偏光板
JP2009292871A (ja) * 2008-06-02 2009-12-17 Fujifilm Corp アクリルフィルムおよびその製造方法、並びに、偏光板、光学補償フィルム、反射防止フィルムおよび液晶表示装置
JP2010024338A (ja) * 2008-07-18 2010-02-04 Asahi Kasei Chemicals Corp 光学フィルム
JP2010096919A (ja) * 2008-10-15 2010-04-30 Asahi Kasei Chemicals Corp 光学フィルム
JP2010231015A (ja) * 2009-03-27 2010-10-14 Sumitomo Chemical Co Ltd 偏光子保護フィルム、偏光板及び液晶表示装置
JP2012180423A (ja) * 2011-02-28 2012-09-20 Sumitomo Chemical Co Ltd アクリル系樹脂フィルムの製造方法及び該方法で製造されたアクリル系樹脂フィルム並びに偏光板
JPWO2015115537A1 (ja) * 2014-01-29 2017-03-23 日立化成株式会社 樹脂組成物、樹脂組成物を用いた半導体装置の製造方法、及び固体撮像素子
US10358580B2 (en) 2014-01-29 2019-07-23 Hitachi Chemical Company, Ltd. Adhesive composition, resin cured product obtained from adhesive composition, method for manufacturing semiconductor device using adhesive composition, and solid-state imaging element
US10808150B2 (en) 2014-01-29 2020-10-20 Hitachi Chemical Company, Ltd. Resin composition, method for manufacturing semiconductor device using resin composition, and solid-state imaging element
WO2016084740A1 (fr) * 2014-11-26 2016-06-02 三菱レイヨン株式会社 Film de stratifié de résine, procédé de fabrication correspondant, et panneau décoratif de mélamine
JPWO2016084740A1 (ja) * 2014-11-26 2017-08-31 三菱ケミカル株式会社 樹脂積層フィルム及びその製造方法、並びにメラミン化粧板
JP2018171935A (ja) * 2014-11-26 2018-11-08 三菱ケミカル株式会社 積層フィルム、保護フィルム、メラミン化粧板表面保護用フィルム、及びメラミン化粧板
JP2015221903A (ja) * 2015-07-06 2015-12-10 富士フイルム株式会社 アクリルフィルムおよびその製造方法
JP2017187619A (ja) * 2016-04-06 2017-10-12 東レ株式会社 光学フィルム

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