JP2006328334A - Resin composition, optical film and polarizer protection film using the same - Google Patents

Resin composition, optical film and polarizer protection film using the same Download PDF

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JP2006328334A
JP2006328334A JP2005159341A JP2005159341A JP2006328334A JP 2006328334 A JP2006328334 A JP 2006328334A JP 2005159341 A JP2005159341 A JP 2005159341A JP 2005159341 A JP2005159341 A JP 2005159341A JP 2006328334 A JP2006328334 A JP 2006328334A
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film
ultraviolet absorber
resin composition
nm
carbon atoms
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Hiroyuki Iwamoto
Hirosuke Kawabata
博之 岩本
裕輔 川端
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Kaneka Corp
株式会社カネカ
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which has a small phase difference, is excellent in optical homogeneity, and efficiently absorbs a light of 380 nm or less. <P>SOLUTION: The resin composition comprises (A) an imide resin and (B) at least one ultraviolet absorber selected from the group consisting of a triazine-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber and has a haze of 1.0% or lower, a total light transmission of 85% or higher, and a light transmission at 380 nm of 10% or lower. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition and an optical film comprising the resin composition.

  In recent years, electronic devices have become increasingly smaller, and liquid crystal display devices that take advantage of light weight and compactness, such as notebook computers, word processors, mobile phones, and personal digital assistants, have come to be widely used. Yes. In these liquid crystal display devices, various films such as a polarizing film are used in order to maintain the display quality. In order to further reduce the weight of liquid crystal display devices for portable information terminals and mobile phones, liquid crystal display devices using a resin film (sheet) instead of a glass substrate have been put into practical use.

  Similarly to liquid crystal display devices, conventional glass used in various photographing devices such as cameras, film-integrated cameras, video cameras, optical pickup devices such as CDs and DVDs, OA equipment such as projectors, etc. has been used. Lenses are also being replaced with resin to reduce weight. Such plastic lenses are easily affected by phase difference due to focal length shift due to distortion due to temperature, humidity, and other usage environments, and stress during processing such as injection molding. It is demanded that it is difficult to change as well as film.

  When handling polarized light as in a liquid crystal display device, the resin film to be used (sheet; hereinafter, unless otherwise specified, the sheet and film are not distinguished and may be described as a film) is optically transparent. In addition to low birefringence, optical homogeneity is required. For this reason, in the case of a film substrate for a plastic liquid crystal display device in which the glass substrate is replaced with a resin film, the phase difference represented by the product of birefringence and thickness is required to be small, and the film may be affected by external stress. It is required that the phase difference hardly changes.

  As the plastic film used in the liquid crystal display device, an amorphous thermoplastic resin is a suitable material, and engineering plastics such as polycarbonate, polyarylate, polysulfone, and polyethersulfone, and celluloses such as triacetylcellulose. A film made of plastic is known. When these plastic films are produced, various stresses are generated in the film being molded due to melt flow of the plastic, solvent drying shrinkage, heat shrinkage, conveyance stress, and the like. Therefore, a phase difference is likely to remain in the obtained film due to birefringence due to molecular orientation induced by these stresses. Therefore, there is a problem that a special process is applied to the film such as thermal annealing as necessary to reduce the remaining phase difference and the manufacturing process becomes complicated.

  Further, even when a film having a reduced remaining retardation is used, a new retardation is generated due to stress or deformation generated during the subsequent processing of the film. Furthermore, when a plastic film is used as a polarizer protective film, it is known that an unfavorable phase difference occurs in the film due to the contraction stress of the polarizer, which adversely affects the polarizing performance of the polarizing film.

  In order to solve these problems, an attempt has been made to obtain a plastic film having a smaller polarization, that is, a phase difference due to molecular orientation is less likely to occur. For example, a cyclic olefin film has been proposed.

  However, the cyclic olefin-based resin composition as it is passes through the ultraviolet region of about 270 nm and has an insufficient effect of absorbing ultraviolet rays. In such a state, when used as, for example, a polarizer protective film in an optical component, for example, a liquid crystal display device utilizing the characteristics of the present material system, it is possible to prevent deterioration of the liquid crystal compound or the polyvinyl alcohol-based polarizer due to ultraviolet rays. Can not.

  In such a case, an ultraviolet absorber is usually used. For example, Patent Document 1 describes an example in which a triazole-based ultraviolet absorber is used for triacetyl cellulose frequently used as an optical material. Patent Document 2 describes an example in which a triazole ultraviolet absorber or a benzophenone ultraviolet absorber is similarly added to polycarbonate.

  However, triacetyl cellulose and polycarbonate are materials that are difficult to obtain optical homogeneity because they tend to generate birefringence, resulting in phase difference unevenness and a decrease in the contrast of the peripheral part due to the increase in the size of liquid crystal display devices. This is not sufficient as a resin composition for optical films. Further, the cyclic olefin-based resin is a resin composition that is less likely to generate birefringence as compared with the above materials, but it is not yet sufficient.

These problems are not limited to films and sheets, but are often the same in various forms such as fibers and lenses (hereinafter, sometimes simply referred to as molded articles including films and sheets).
JP-A-9-90101 JP-A-9-166711

  The problem to be solved by the present invention is to provide a resin composition that has a small phase difference, excellent optical homogeneity, and efficiently absorbs light of 380 nm or less.

  In order to solve the above problems, the present inventors have conducted extensive research. As a result, it comprises (A) an imide resin, and (B) one or more ultraviolet absorbers selected from the group consisting of triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers. Is 1.0% or less, the total light transmittance is 85% or more, and the light transmittance at 380 nm is 10% or less.

  That is, according to the present invention, the following compositions, films and methods are provided.

(1) It is formed containing the following components (A) and (B), and the haze of the film molded product is 1.0% or less, the total light transmittance is 85% or more, and the light transmittance at 380 nm is 10%. The resin composition characterized by the following.
(A) An imide resin having a unit represented by the following general formula (1) and a unit represented by the following general formula (2) and / or a unit represented by the following general formula (3)

(However, R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(However, R 4 and R 5 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 6 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(However, R 7 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 8 represents an aryl group having 6 to 10 carbon atoms.)
(B) One or more UV absorbers selected from the group consisting of triazine-based UV absorbers, benzotriazole-based UV absorbers, and benzophenone-based UV absorbers (2) (B) in the imide resin of (A) The resin composition according to item (1), wherein the content of the ultraviolet absorber is from 0.1 to 5% by weight.

  (3) The resin composition according to the above item (1) or (2), which contains an ultraviolet absorber having a 10% weight loss temperature of 300 ° C. or more as the ultraviolet absorber of (B). (4) The resin composition according to any one of (1) to (3) above, which contains a benzotriazole ultraviolet absorber as the ultraviolet absorber of (B).

  (5) 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] as the ultraviolet absorber of (B) The resin composition according to item (4), comprising:

  (6) The resin composition as described in (4) above, which contains 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole as the ultraviolet absorber of (B). object.

  (7) The above item containing 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol as the ultraviolet absorber of (B). The resin composition according to any one of (1) to (3).

  (8) The item (1) containing at least one of 2,2′-dihydroxy-4,4′-dimethoxybenzophenone or 2-hydroxy-4-n-octyloxybenzophenone as the ultraviolet absorber of (B). The resin composition according to any one of items (3) to (3).

  (9) An optical film comprising the resin composition according to any one of items (1) to (8).

  (10) The optical film as described in (9) above, which is a film obtained by a melt extrusion method.

  (11) The optical film as described in (9) or (10) above, which is a stretched film.

  (12) The optical film as described in (11) above, wherein the in-plane retardation is 10 nm or less and the thickness direction retardation is 20 nm or less.

  (13) A polarizer protective film comprising the film described in (11) or (12) above.

  The resin composition of the present invention is useful as a resin composition for optical molded articles having excellent optical homogeneity, particularly for films, and has an extremely high ultraviolet absorption efficiency. Blocks efficiently.

  An embodiment of the present invention will be described as follows. Note that the present invention is not limited to this.

  The resin composition of the present invention includes (A) a unit represented by the following general formula (1), a unit represented by the following general formula (2) and / or a unit represented by the following general formula (3). And (B) a triazine ultraviolet absorber, a benzotriazole ultraviolet absorber, and one or more ultraviolet absorbers selected from the group consisting of benzophenone ultraviolet absorbers, A resin composition characterized in that the film molded product has a haze of 1.0% or less, a total light transmittance of 85% or more, and a light transmittance of 380 nm of 10% or less.

(However, R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(However, R 4 and R 5 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 6 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(However, R 7 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 8 represents an aryl group having 6 to 10 carbon atoms.)
The first structural unit constituting the imide resin of the present invention is represented by the following general formula (1), and is generally called a glutarimide unit (hereinafter referred to as general formula (1)). Sometimes abbreviated as glutarimide unit.)

(However, R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, R 3 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or an aryl group having 6 to 10 carbon atoms.)
As a preferable glutarimide unit, R 1 and R 2 are hydrogen or a methyl group, and R 3 is hydrogen, a methyl group, a butyl group, or a cyclohexyl group. The case where R 1 is a methyl group, R 2 is hydrogen, and R 3 is a methyl group is particularly preferred.

The glutarimide unit may be a single type or may include a plurality of types in which R 1 , R 2 , and R 3 are different.

  The glutarimide unit can be formed by imidizing the second structural unit described below. In addition, acid anhydrides such as maleic anhydride or half esters of these and linear or branched alcohols having 1 to 20 carbon atoms; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Α, β-ethylenically unsaturated carboxylic acids such as crotonic acid, fumaric acid, and citraconic acid can also be imidized and can be used to form glutarimide units.

  The second structural unit constituting the imide resin of the present invention is represented by the following general formula (2), and is generally called a (meth) acrylate unit (here, (Meth) acrylic acid ester refers to acrylic acid ester and methacrylic acid ester.Hereinafter, general formula (2) may be abbreviated as (meth) acrylic acid ester unit).

(However, R 4 and R 5 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 6 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or an aryl group having 6 to 10 carbon atoms.)
When the imide resin of the present invention is produced, first, a (meth) acrylic acid ester-aromatic vinyl copolymer or a (meth) acrylic acid ester polymer is polymerized and formed by post-imidization, The raw material that gives the (meth) acrylic acid ester unit as a residue is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ( Examples include isobutyl acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Of these, methyl methacrylate is particularly preferred.

These second structural units may be of a single type, or may include a plurality of types in which R 4 , R 5 and R 6 are different. Similarly, a plurality of types of raw materials that give the (meth) acrylic acid ester unit as a residue may be used.

  The third structural unit contained in the imide resin of the present invention as needed is represented by the following general formula (3), and is generally called an aromatic vinyl unit (hereinafter, generally referred to as general vinyl). (Formula (3) may be abbreviated as an aromatic vinyl unit.)

(However, R 7 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 8 represents an aryl group having 6 to 10 carbon atoms.)
Preferred aromatic vinyl structural units include styrene, α-methylstyrene, and the like. Of these, styrene is particularly preferred.

These third structural units may be of a single type, or may include a plurality of types in which R 7 and R 8 are different.

The content of the glutarimide unit represented by the general formula (1) in the imide resin of the present invention depends on, for example, the structure of R 3 , but is preferably 20% by weight or more of the imide resin. The preferable content of the glutarimide unit is 20% to 95% by weight, more preferably 40 to 90% by weight, and still more preferably 50 to 80% by weight. When the ratio of the glutarimide unit is smaller than this range, the resulting imide resin may have insufficient heat resistance or the transparency may be impaired. On the other hand, if it exceeds this range, the heat resistance and melt viscosity are unnecessarily increased, the moldability becomes worse, the mechanical strength of the resulting film becomes extremely brittle, and the transparency may be impaired.

  The content of the aromatic vinyl unit represented by the general formula (3) in the thermoplastic resin is preferably 10% by weight or more based on the total repeating unit of the imide resin. The preferred content of the aromatic vinyl unit is 10 to 40% by weight, more preferably 15 to 30% by weight, and still more preferably 15 to 25% by weight. When the aromatic vinyl unit is larger than this range, the resulting imide resin has insufficient heat resistance. If it is smaller than this range, the mechanical strength of the resulting film may be lowered.

  By adjusting the ratios of the general formulas (1), (2), and (3), it is possible to adjust various required physical properties. For example, when the imide resin of the present invention is formed by first polymerizing a (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer and then imidizing, for example, (meth) acrylic The ratio of the general formula (3) is determined by adjusting the polymerization ratio of the acid ester and the aromatic vinyl (the ratio of the general formula (3) may be set to 0), and further, the primary amine is added during the post-imidation By adjusting the ratio, the ratios of the general formulas (1) and (2) can be further adjusted.

  If necessary, the imide resin of the present invention may further be copolymerized with a fourth structural unit. A constitution obtained by copolymerizing a nitrile monomer such as acrylonitrile or methacrylonitrile, or a maleimide monomer such as maleimide, N-methylmaleimide, N-phenylmaleimide or N-cyclohexylmaleimide as the fourth structural unit Units can be used. These may be directly copolymerized in a thermoplastic resin or may be graft copolymerized.

  In producing the imide resin of the present invention, first, a (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer or a (meth) acrylic acid ester such as methyl methacrylate polymer is used. When a polymer is polymerized and converted into an imide resin, the (meth) acrylate-aromatic vinyl copolymer and (meth) acrylate polymer that can be used in the present invention can undergo an imidization reaction. As long as it is a linear polymer, it may be a block polymer, a core-shell polymer, a branched polymer, a ladder polymer, or a crosslinked polymer. The block polymer may be an A-B type, an A-B-C type, an A-B-A type, or any other type of block polymer. The core-shell polymer may be composed of only one core and only one shell, or each may be a multilayer.

The imide resin preferably has a weight average molecular weight of 1 × 10 4 to 5 × 10 5 . When the weight average molecular weight is less than 1 × 10 4 , the mechanical strength in the case of a film is insufficient, and when it exceeds 5 × 10 5 , the viscosity at the time of melt extrusion is high and the molding processability is lowered. , Productivity of molded products may decrease.

  The glass transition temperature of the imide resin is preferably 110 ° C. or higher, and more preferably 120 ° C. or higher. When the glass transition temperature is lower than the above value, the application range is limited in applications where heat resistance is required.

  In the imide resin of the present invention, the type containing the general formula (3) is optical by adjusting the content of each constituent unit and glutarimide unit in the methyl (meth) acrylate-styrene copolymer. It is also possible to reduce the anisotropy. The small optical anisotropy referred to here requires not only the optical anisotropy in the in-plane direction (length direction and width direction) of the film but also the optical anisotropy in the thickness direction. There is. That is, the direction in which the in-plane refractive index is maximum is the X-axis, the direction perpendicular to the X-axis is the Y-axis, the thickness direction of the film is the Z-axis, and the refractive index in each axial direction is nx, ny, nz, film In-plane retardation Re = (nx−ny) × d and thickness direction retardation Rth = | (nx + ny) / 2−nz | × d (where || represents an absolute value). (In an ideal film, which is completely optically isotropic in the three-dimensional direction, both the in-plane retardation Re and the thickness direction retardation Rth are zero).

  The optical film of the present invention preferably has an in-plane retardation of the film of 10 nm or less and a thickness direction retardation of 20 nm or less. The in-plane retardation of the film is more preferably 5 nm or less. The thickness direction retardation is more preferably 10 nm or less. When a polarizer protective film having an in-plane retardation of the film exceeding 10 nm or a retardation in the thickness direction exceeding 20 nm is used as a polarizing plate, a problem such as a decrease in contrast may occur in a liquid crystal display device. . In this specification, unless otherwise specified, it means birefringence that develops when stretched 100% at a temperature 5 ° C. higher than the glass transition temperature of the imide resin. Here, the orientation birefringence (Δn) is defined by Δn = nx−ny = Re / d using the above-described nx and ny, and is measured by a phase difference meter.

The orientation birefringence value is preferably 0 or more and 0.1 × 10 −3 or less, and more preferably 0 or more and 0.01 × 10 −3 or less. When the orientation birefringence is out of the above range, the birefringence is likely to occur during the molding process with respect to environmental changes, and it becomes difficult to obtain stable optical characteristics.

  In order to obtain an imide resin having substantially no orientation birefringence, the amount of each structural unit in the (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer is adjusted, Furthermore, it is necessary to prepare the degree of imidization, and the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (3) are 2.0: 1.0 to 4.0 by weight ratio. Is preferably in the range of 1.0, more preferably in the range of 2.5: 1.0 to 4.0: 1.0, and in the range of 3.0: 1.0 to 3.5: 1.0. Is more preferable.

  The imide resin of the present invention is imidized into a (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer or a (meth) acrylic acid ester polymer such as methyl methacrylate polymer. If it is a method of processing an agent, it can manufacture by various methods, an extruder etc. may be used and a batch type reaction tank (pressure vessel) etc. may be used.

  When the method for producing an imide resin of the present invention is carried out with an extruder, various extruders can be used. For example, a single screw extruder, a twin screw extruder, a multi screw extruder, or the like can be used. In particular, a twin screw extruder is preferable as an extruder that can promote mixing of an imidizing agent or a ring closure accelerator with respect to the raw polymer. There are non-mesh type co-rotating type, meshing type co-rotating type, non-meshing type bi-directional rotating type, meshing type bi-directional rotating type, etc. The meshing type co-rotating type is preferable because it can rotate at a high speed and can promote mixing of an imidizing agent or a ring-closing accelerator to be used if necessary. These extruders may be used alone or connected in series.

  The extruder is preferably equipped with a vent port that can be depressurized below atmospheric pressure in order to remove unreacted imidizing agent or by-products such as methanol and monomers.

  For example, instead of an extruder, imide resin can be produced by using a high-viscosity reactor such as a horizontal biaxial reactor such as Violac manufactured by Sumitomo Heavy Industries, Ltd. or a vertical biaxial agitation tank such as Super Blend. It can be used suitably.

  When the production method of the imide resin of the present invention is carried out in a batch type reaction vessel (pressure vessel), it is particularly limited as long as the raw material polymer can be melted by heating and stirred, and an imidizing agent or a ring closure accelerator can be added. However, the viscosity of the polymer may increase with the progress of the reaction, and those with good stirring efficiency are preferred. For example, Sumitomo Heavy Industries, Ltd. agitation tank Max blend etc. can be illustrated.

  The resin composition of the present invention is one or more selected from the group consisting of (B) a triazine-based UV absorber, a benzotriazole-based UV absorber, and a benzophenone-based UV absorber in addition to the above-described (A) imide resin. The film molded body has a haze of 1.0% or less, a total light transmittance of 85% or more, and a light transmittance at 380 nm of 10% or less. It is the resin composition characterized.

  The in-plane retardation of the film does not deteriorate even when an ultraviolet absorber is added to the above.

  For example, in a preferred embodiment, the film in-plane retardation can be controlled to 10 nm or less, and in a more preferred embodiment, it can be controlled to 6 nm or less. Further, for example, the retardation in the film thickness direction can be controlled to 20 nm or less, and in a more preferred embodiment, it can be controlled to 10 nm or less. In addition, when the haze exceeds 1% or the total light transmittance is less than 85%, there is a problem that the transparency is deteriorated in optical applications requiring transparency. Further, when the light transmittance at 380 nm exceeds 10%, there is a fear that the ultraviolet blocking property is insufficient in an optical application that requires ultraviolet blocking property.

The photoelastic coefficient is preferably 20 × 10 −12 m 2 / N or less, more preferably 10 × 10 −12 m 2 / N or less, and 5 × 10 −12 m 2 / N or less. More preferably. When the absolute value of the photoelastic coefficient is larger than 20 × 10 −12 m 2 / N, the liquid crystal display device is likely to cause phase difference unevenness, lower the contrast of the peripheral portion, and light leakage easily. The tendency becomes remarkable in a high humidity environment.

  The photoelastic coefficient means that when an external force is applied to an isotropic solid to cause stress (ΔF), it temporarily exhibits optical anisotropy and exhibits birefringence (Δn). The ratio of stress to birefringence is called the photoelastic coefficient (c) and is represented by c = Δn / ΔF.

  In the present invention, the photoelastic coefficient is a value measured at 23 ° C. and 50% RH at a wavelength of 515 nm by the Senarmon method.

2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol is a preferred compound of the preferred triazine-based UV absorber used in the present invention. Yes, this exhibits good compatibility with the imide resin (A). Further, since this has a low vapor pressure at 25 ° C. of 9 × 10 −10 , gas volatilization from a vent and a die is less preferred in melt extrusion. The gas volatility of the ultraviolet absorber can also be expressed by a temperature at which the weight is reduced by 10%. In the present invention, the ultraviolet absorber is preferably 300 ° C. or higher, more preferably 350 ° C. or higher, more preferably 380 ° C. or higher. Is used.

  A preferred benzotriazole-based UV absorber used in the present invention is, for example, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl]. ) Phenol], 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H -Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2- [5- Chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6- -Tert-butylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4- Methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate / The reaction product of polyethylene glycol 300, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, and the like.

A particularly preferred benzotriazole-based UV absorber is 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, which is good for the imide resin (A). Show good compatibility. The ultraviolet absorber is particularly preferable because the vapor pressure at 25 ° C. is as low as 10 −5 Pa or less and the 10% weight loss temperature is as high as 304 ° C., so that gas volatilization is small. Another particularly preferred benzotriazole UV absorber is 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]. The 10% weight loss temperature is 389 ° C., which is even higher, and therefore gas volatilization is small.

Preferred compounds of the preferred benzophenone ultraviolet absorber used in the present invention include 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, bis (5-benzoyl-4 -Hydroxy-2-methoxyphenyl) methane, 1,4-bis (4-benzoyl-3-hydroxyphenone) -butane and the like, which show good compatibility with the imide resin (A). Moreover, since the vapor pressure of 25 degreeC is as low as 10 < -5 > Pa or less, it is preferable.

  It is preferable that the addition amount of the ultraviolet absorber (B) in this invention is 0.1 to 5 weight% with respect to 100 weight% of imide resin (A). More preferably, it is 0.2 to 3% by weight. When the added amount of the UV absorber is less than 0.1% by weight, the UV transmittance at 380 nm is increased, and the UV blocking effect may be insufficient, and when it is more than 5% by weight, the coloring becomes intense. There is a fear. Moreover, when there is more addition amount of a ultraviolet absorber than 5 weight%, there exists a possibility that the haze of a film molded body may become high and transparency may deteriorate.

  These ultraviolet absorbers (B) may be used singly or in combination. For example, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and 2- [5-chloro (2H) -benzotriazol-2-yl]- Examples thereof include a combination of 4-methyl-6- (tert-butyl) phenol.

  By appropriately selecting the preferred composition, an unstretched film and a stretched film having low haze and light transmittance at 380 nm and high total light transmittance can be obtained simultaneously with the birefringence performance described above. Specifically, for example, in a preferred embodiment, a film having a haze of 1% or less is easily obtained, and in a more preferred embodiment, a film having a haze of 0.7% or less is obtained. In a more preferred embodiment, a film having a haze of 0.5% or less is obtained. In a preferred embodiment, a film having a total light transmittance of 85% or more can be easily obtained, and in a more preferred embodiment, a film having a total light transmittance of 88% or more can be obtained. Furthermore, in a preferred embodiment, a film having a light transmittance at 380 nm of 10% or less is easily obtained, and in a more preferred embodiment, a film of 7% or less is obtained. Any film having a haze of 1.0% or less and a total light transmittance of 85% or more and a light transmittance of 380 nm of 10% or less can be used as a high-performance film for various optical applications.

  Furthermore, the light transmittance at 420 nm is preferably 90%. When the light transmittance at 420 nm is 90%, the transmittance in the visible light region is high, which is particularly suitable for use in optical applications.

  The total light transmittance is ideally 100%, but in reality, even if it is 98% or less, it does not become a big problem in the optical film application. Also, haze is ideally 0%, but in reality, even if it is 0.1% or more, it does not pose a major problem in optical film applications.

  As a method for obtaining the resin composition used in the present invention, any known method can be used as long as the imide resin (A) and the ultraviolet absorber (B) can be mixed and put into a film forming machine. Can be employed. For example, a method of obtaining a resin composition by simply mixing an imide resin (A) and an ultraviolet absorber (B), or a resin composition obtained by hot-melt kneading an imide resin (A) and an ultraviolet absorber (B) The method of obtaining etc. are mentioned.

  The resin composition of the present invention may contain known additives such as lubricants, plasticizers, stabilizers, fillers, and other resins as necessary. In the present specification, such components other than the imide resin (A) and the ultraviolet absorber (B) are also referred to as “third component”.

  In order to improve the mechanical properties of the film, a plasticizer or a flexible polymer may be added to the resin composition. However, when these materials are used, the glass transition temperature may be lowered and heat resistance may be impaired, or transparency may be impaired. For this reason, when these plasticizers or flexible polymers are used, the amount added should not interfere with the performance of the film. Preferably, it is 20% by weight or less in the resin composition. More preferably, it is 10 weight% or less, More preferably, it is 5 weight% or less. When the imide content of the imide resin (A) is high, the resulting film tends to be hard and brittle, so adding a small amount of plasticizer is effective because it can prevent stress whitening and tearing of the film. As such a plasticizer, conventionally known plasticizers can be used. For example, aliphatic dibasic acid plasticizers such as di-n-decyl adipate and phosphate ester plasticizers such as tributyl phosphate can be exemplified.

  When a resin is used as the third component, it may be a thermoplastic resin or a thermosetting resin. A thermoplastic resin is preferable. In this case, the third component may be a single resin or a blend of a plurality of types of resins. When the resin is used as the third component, the amount used is preferably 30% by weight or less in the resin composition, more preferably 20% by weight or less, and still more preferably 10% by weight or less. Moreover, it is preferable that it is 1 weight% or more of a resin composition, More preferably, it is 2 weight% or more, More preferably, it is 3 weight% or more. When there are too many 3rd components, the performance of an imide resin (A) and a ultraviolet absorber (B) is not fully exhibited. Moreover, when the 3rd component with low compatibility with an imide resin (A) and a ultraviolet absorber (B) is used, the optical performance of the film obtained will fall easily. When the third component is too small, it is difficult to obtain the effect of adding the third component.

  If necessary, the film of the present invention may contain a filler for the purpose of improving the slipperiness of the film or for other purposes. As the filler, any conventionally known filler used for a film can be used. The filler may be inorganic fine particles or organic fine particles. Examples of inorganic fine particles include metal oxide fine particles such as silicon dioxide, titanium dioxide, aluminum oxide and zirconium oxide, silicate fine particles such as calcined calcium silicate, hydrated calcium silicate, aluminum silicate and magnesium silicate, And calcium carbonate, talc, clay, calcined kaolin and calcium phosphate. Examples of the organic fine particles include resin fine particles such as silicon resin, fluorine resin, acrylic resin, and cross-linked styrene resin.

  A filler is added in the range which does not impair the optical characteristic of a film remarkably. Preferably, it is 10 weight% or less in a resin composition.

  Even when the third component is used, the mixing ratio of the imide resin (A) and the ultraviolet absorber (B) is the same as described above, as in the case where the third component is not used. Is preferred.

  As a method for molding a molded body comprising the resin composition of the present invention, any conventionally known method can be used. Examples thereof include injection molding, melt extrusion film molding, inflation molding, blow molding, compression molding, and spinning molding. Further, a solution casting method or a spin coating method in which the resin composition of the present invention is dissolved in a soluble solvent and then molded is also possible. Any of them can be employed, but a melt extrusion method that does not use a solvent is more likely to show the effects of the present invention, and is preferable from the viewpoint of production cost and the influence of the solvent on the global environment and working environment. .

  In this specification, in order to distinguish the film shape | molded by the said melt extrusion method from the film shape | molded by other methods, such as a solution casting method, it expresses as a melt extrusion film.

  In a preferred embodiment, the thermoplastic resin to be used is pre-dried before film formation. The preliminary drying is performed by, for example, a hot air dryer or the like in the form of pellets or the like. Pre-drying is very useful because it can prevent foaming of the extruded resin. Next, the thermoplastic resin is supplied to an extruder. The thermoplastic resin heated and melted in the extruder is supplied to the T die through a gear pump and a filter. The use of the gear pump is very useful because it has a high effect of improving the uniformity of the extrusion amount of the resin and reducing thickness unevenness. The use of the filter is useful for removing a foreign substance in the resin and obtaining a film having an excellent appearance without defects. In a more preferred embodiment, a sheet-like molten resin extruded from a T die is sandwiched between two cooling rolls and cooled to form an optical film. It is particularly preferable that one of the two cooling rolls is a rigid metal roll having a smooth surface, and the other is a flexible roll having an elastically deformable metal elastic outer cylinder having a smooth surface. . With a rigid roll and a flexible roll, the sheet-shaped molten resin extruded from the T-die is sandwiched and cooled to form a film, thereby correcting minute irregularities on the surface and die lines, etc., and smoothing the surface. Since a film having a thickness unevenness of 5 μm or less can be obtained, it is particularly useful.

  The cooling roll is sometimes called a “touch roll” or a “cooling roll”, but the term “cooling roll” in this specification includes these rolls. When the sheet-like molten resin extruded from the T-die is cooled while being sandwiched between a rigid roll and a flexible roll to form a film, even if one roll can be elastically deformed, any roll surface Since it is a metal, when forming a thin film, the roll surfaces come into contact with each other and the roll outer surface is easily damaged, or the roll itself is easily damaged. Therefore, the thickness of the film to be molded is preferably 10 μm or more, more preferably 50 μm or more, still more preferably 80 μm or more, and particularly preferably 100 μm or more. In addition, when a film is formed by cooling a sheet-like molten resin extruded from a T-die while being sandwiched between a rigid roll and a flexible roll, if the film is thick, the cooling of the film tends to be uneven, and optical Characteristic tends to be non-uniform. Accordingly, the thickness of the film is preferably 200 μm or less, and more preferably 170 μm or less. In addition, as an embodiment in the case of producing a thinner film, after obtaining a relatively thick raw material film by such sandwich molding, a film having a predetermined thickness is produced by uniaxial stretching or biaxial stretching. Things are preferable. If an example of an embodiment is given, after manufacturing a raw material film with a thickness of 150 μm by such sandwich molding, an optical film with a thickness of 40 μm can be manufactured by vertical and horizontal biaxial stretching.

  The stretched film according to the present invention can be obtained by forming the above-described resin composition of the present invention into an unstretched raw material film and further performing uniaxial stretching or biaxial stretching.

  In the present specification, for convenience of explanation, a film after the resin composition is formed into a film and before being stretched is referred to as “raw film” or “unstretched film”.

  The film of this invention can be made into a final product in the state of a raw material film, that is, in the state of an unstretched film. Moreover, it can be set as a final product in the state of a uniaxially stretched film. Furthermore, it is good also as a biaxially stretched film by carrying out combining a extending process.

  By performing the stretching, the mechanical properties are improved. In conventional films, it has been difficult to avoid the occurrence of retardation when a stretching process is performed. However, a film formed using the particularly preferable resin composition of the present invention has an advantage that a phase difference does not substantially occur even when subjected to a stretching treatment. The film may be stretched continuously immediately after forming the raw material film.

  Here, the state of the “raw material film” may exist only momentarily. In the case where it exists only momentarily, that momentary state after the film is formed and then stretched is referred to as a raw material film. In addition, the raw material film only needs to be in a film shape sufficient to be stretched thereafter, and does not have to be in a complete film state. Of course, it does not have performance as a completed film. Also good. If necessary, after forming the raw material film, the film may be temporarily stored or moved, and then the film may be stretched.

  As a method of stretching the raw material film, any conventionally known stretching method can be adopted. Specifically, for example, there are transverse stretching using a tenter, longitudinal stretching using a roll, and sequential biaxial stretching in which these are sequentially combined. A simultaneous biaxial stretching method in which the longitudinal and lateral directions are simultaneously stretched can also be employed. You may employ | adopt the method of performing horizontal extending | stretching by a tenter after performing roll longitudinal stretching.

  In the present invention, when the film is stretched, the film is preferably preheated to a temperature 0.5 to 5 ° C. higher than the stretching temperature, and then cooled to the stretching temperature and stretched. More preferably, it is preferably preheated to a temperature 1 to 3 ° C. higher than the stretching temperature, and then cooled to the stretching temperature and stretched. If the preheating temperature is too high, such a problem that the film sticks to the roll or loosens by its own weight is not preferable. Further, if the preheating temperature is not much different from the stretching temperature, it is difficult to maintain the thickness accuracy of the film before stretching, or the thickness unevenness tends to increase, and the thickness accuracy tends to decrease. In the case of a crystalline thermoplastic resin, a necking phenomenon can be used in stretching, and in this case, the thickness accuracy is improved by stretching. On the other hand, in the case of the resin composition of the present invention, it is difficult to use the necking phenomenon at the time of stretching. Therefore, such temperature control is particularly important in order to maintain or improve the thickness accuracy.

  The stretching temperature and stretching ratio of the film can be appropriately adjusted using the mechanical strength, surface properties, and thickness accuracy of the obtained film as indices. The range of the stretching temperature is preferably in the range of (Tg-30 ° C) to (Tg + 30 ° C), where Tg is the glass transition temperature of the film obtained by the DSC method. More preferably, it is the range of (Tg-20 degreeC-Tg + 20 degreeC). More preferably, it is in the range of (Tg ° C.) to (Tg + 20 ° C.). When the stretching temperature is too high, the thickness unevenness of the obtained film tends to increase, and the improvement of mechanical properties such as elongation, tear propagation strength, and fatigue resistance tends to be insufficient. Moreover, the trouble that the film adheres to the roll is likely to occur. On the other hand, when the stretching temperature is too low, the haze of the stretched film tends to increase, and in the extreme case, problems such as tearing and cracking of the film tend to occur. The preferred draw ratio depends on the drawing temperature, but is selected in the range of 1.1 to 3 times. More preferably, it is 1.3 times to 2.5 times. More preferably, it is 1.5 times to 2.3 times. By adjusting the imide resin (A) and the ultraviolet absorber (B) to the above-mentioned preferable mixing range and selecting appropriate stretching conditions, the birefringence is not caused substantially, and the haze is increased. It is possible to easily obtain a film having a small thickness unevenness without substantially accompanying the above. Preferably, by stretching 1.3 times or more, more preferably 1.5 times or more, mechanical properties such as film elongation, tear propagation strength, and fatigue resistance are greatly improved. A film having a thickness of 5 μm or less, a birefringence of substantially zero, and a haze of 1% or less can be obtained.

  The stretched film thickness of the present invention is preferably 10 μm to 200 μm, more preferably 20 μm to 150 μm, and still more preferably 30 μm to 100 μm. When forming a film that is too thick, for example, when forming a film exceeding 200 μm as an unstretched film, the cooling of the film is likely to be non-uniform, and the optical homogeneity and the like are likely to decrease. In the case of forming a film that is too thin, the draw ratio becomes excessive and haze is likely to deteriorate.

  A molded body comprising the resin composition of the present invention, particularly an optical film, can be subjected to a surface treatment if necessary. Examples of the surface treatment method include corona treatment, plasma treatment, ultraviolet irradiation, and alkali treatment. In particular, when surface treatment such as coating is applied to the film surface, or when another film is laminated with an adhesive, surface treatment of the film should be performed as a means for improving mutual adhesion. Is preferred. Corona treatment is a particularly preferred method. A preferable degree of surface treatment is 50 dyn / cm or more. Although the upper limit is not particularly defined, it is more preferably 80 dyn / cm or less from the viewpoint of equipment for surface treatment.

  In addition, a coating layer such as a hard coat layer can be formed on the surface of the molded article comprising the resin composition of the present invention, particularly the optical film, if necessary. In addition, a molded body made of the resin composition of the present invention, particularly an optical film, may be formed with an indium tin oxide-based transparent conductive layer by sputtering or the like with or without a coating layer. It can also be used as an electrode substrate of a plastic liquid crystal display device or an electrode substrate of a touch panel.

  The molded body made of the resin composition of the present invention, particularly an optical film, can be used as it is for various applications as a final product. Alternatively, it can be used for various purposes by performing various processes. For example, imaging fields such as cameras, VTRs, projector lenses, viewfinders, filters, prisms, and Fresnel lenses, lens fields such as optical pickup lenses for CD players, DVD players, MD players, CD players, DVD players, Optical recording fields for optical discs such as MD players, liquid crystal light guide plates, liquid crystal display films such as polarizer protective films and retardation films, information equipment fields such as surface protective films, optical fibers, optical switches, optical connectors, etc. Optical communication field, automotive headlights, tail lamp lenses, inner lenses, instrument covers, sunroofs and other vehicle fields, eyeglasses, contact lenses, internal vision lenses, medical equipment fields such as medical supplies that require sterilization, road light transmission Board Glass lens, lighting windows and car port, illumination lens and lighting cover, construction and building materials sectors such as building materials for sizing, and a microwave cooking container (tableware), and the like. In particular, the molded body and film of the present invention use the optical homogeneity, transparency, low birefringence, etc. of the optical isotropic film, polarizer protective film, transparent conductive film and the like around the liquid crystal display device. It can use suitably for well-known optical uses, such as. In particular, it is suitable for known optical applications such as optical isotropic films, polarizer protective films, transparent conductive films, and the like around liquid crystal display devices by utilizing excellent optical homogeneity, transparency, low birefringence, etc. Can be used.

  The optical film of the present invention can be used by being bonded to a polarizer. That is, it can be used as a polarizer protective film. Here, any conventionally known polarizer can be used as the polarizer. Specifically, for example, iodine can be contained in stretched polyvinyl alcohol to obtain a polarizer. Such a polarizer can be used as a polarizing plate by bonding the film of the present invention as a polarizer protective film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this Example.

  Each physical property value of the film was measured as follows.

(1) Haze The haze was measured by using a turbidimeter NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd. according to the method described in 6.4 of JIS K7105-1981.

(2) Total light transmittance Measured by using a turbidimeter NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd., according to the method described in 5.5 of JIS K7105-1981.

(3) Light transmittance at 380 nm Measured with a double monochrome spectrophotometer U-3300 manufactured by Hitachi, Ltd.

(4) In-plane retardation Re and thickness direction retardation Rth
A 40 mm × 40 mm test piece was cut out from the film. Using an automatic birefringence meter (KOBRA-WR manufactured by Oji Scientific Co., Ltd.), the in-plane retardation Re was measured at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% at a wavelength of 590 nm and an incident angle of 0 °. It was measured. The thickness d of the test piece measured using a digimatic indicator (manufactured by Mitutoyo Corporation), the refractive index n measured by an Abbe refractometer (manufactured by Atago Co., Ltd. 3T), the wavelength 590 nm measured by an automatic birefringence meter, and the surface The three-dimensional refractive index nx, ny, nz is obtained from the internal phase difference Re and the phase difference value in the 40 ° tilt direction, and the thickness direction phase difference Rth = | (nx + ny) / 2−nz | × d (|| is the absolute value) Represents).

(5) 10% weight reduction temperature of ultraviolet absorber Measured with a heat loss measuring device TGA-50 manufactured by Shimadzu Corporation under the condition of a temperature rising rate of 10 ° C./min.

(6) Ratio of general formula (1) in imide resin The pellet of the product was used as it was, and IR spectrum was measured at room temperature using TravelIR manufactured by SensIR Technologies. From the obtained spectrum, the absorption intensity (Abs Ester) attributed to the ester carbonyl group of 1720 cm -1, the imidization ratio from the ratio of the absorption intensity assignable to an imide carbonyl group of 1660cm -1 (Abs imide) (Im % (IR)). Here, the imidation rate refers to the proportion of the imide carbonyl group in all carbonyl groups.

(Resin production example 1)
Polymethyl methacrylate (PMMA) resin (Sumitomo Chemical's Sumipex MH), which is an acrylic ester resin, is imidized with monomethylamine (Mitsubishi Gas Chemical Co., Ltd.), which is an imidizing agent, to produce an imidized PMMA resin. . The extruder used was a meshing type co-rotating twin screw extruder having a diameter of 15 mm. The set temperature of each temperature control zone of the extruder was 230 ° C., the screw rotation speed was 150 rpm, the methacrylic resin was supplied at 1.0 kg / hr, and the supply amount of monomethylamine was 3 parts by weight with respect to the methacrylic resin. A methacrylic resin was introduced from a hopper, and the resin was melted and filled with a kneading block, and then monomethylamine was injected from a nozzle. A seal ring was placed at the end of the reaction zone to fill the resin. By-products after the reaction and excess methylamine were devolatilized by reducing the pressure at the vent port to -0.08 MPa. The resin that came out as a strand from a die provided at the exit of the extruder was cooled in a water tank and then pelletized with a pelletizer. This imidized PMMA resin corresponds to an imide resin obtained by copolymerization of the unit represented by the general formula (1) and the unit represented by the general formula (2) described in the embodiment. Was 20 mol%.

(Resin production example 2)
A polymethyl methacrylate-styrene copolymer (MS) resin (the composition of the general formula (2) and the general formula (3) is 80 mol%: 20 mol%) is supplied at 2.0 kg / hr, and an imidizing agent is used. 40 parts of a certain monomethylamine (Mitsubishi Gas Chemical Co., Ltd.) was used to imidize in the same manner as in Production Example 1 to produce an imidized MS resin. This imidized MS resin is an imide obtained by copolymerizing the unit represented by the general formula (1), the unit represented by the general formula (2), and the unit represented by the general formula (3) described in the embodiment. Corresponding to the resin, the general formula (1) was 69 mol%.

(Resin production example 3)
(1) A methacrylic resin composition (core-shell polymer) was synthesized by the following method.

The following substances were charged into an 8 L polymerization apparatus equipped with a stirrer.
Deionized water 200 parts Sodium dioctylsulfosuccinate 0.25 parts Sodium formaldehyde sulfoxylate 0.15 parts Ethylenediaminetetraacetic acid-2-sodium 0.005 parts Ferrous sulfate 0.0015 parts The inside of the polymerization apparatus is nitrogen gas After sufficiently substituting and substantially free of oxygen, the internal temperature is set to 60 ° C., and 70% butyl acrylate (BA) and methyl methacrylate (MMA) 30 are used as raw materials for the acrylate ester-based crosslinked elastic particles. % Monomer mixture consisting of 2 parts of allyl methacrylate (AlMA) and 0.5 part of cumene hydroxide (CHP)> 20 parts at a rate of 10 parts / hour The addition was continuously carried out, and after completion of the addition, the polymerization was further continued for 0.5 hours to obtain acrylic ester-based crosslinked elastic particles. The polymerization conversion was 99.5% and the average particle size was 800 mm. Thereafter, 0.3 part of sodium dioctylsulfosuccinate was charged, the internal temperature was set to 60 ° C., and a monomer mixture 100 consisting of 10% styrene (St) and 90% MMA as raw materials for the methacrylate polymer. 80 parts of a monomer mixture consisting of 0.8 part of tert-dodecyl mercaptan (tDM) and 0.5 part of CHP is continuously added at a rate of 10 parts / hour, and polymerization is continued for another hour. A methacrylic resin composition (core-shell polymer) was obtained. The polymerization conversion rate was 99.0%. The obtained latex was salted out and coagulated with calcium chloride, washed with water and dried to obtain a resin powder (1) of a methacrylic resin composition (C). Furthermore, using a single screw extruder with a 40 mmφ vent, the cylinder temperature was set to 230 ° C., and melt kneading was performed to pelletize.

  (2) The methacrylic resin composition (core-shell polymer) obtained in (1) above is supplied at 2.0 kg / hr, and 10 parts of monomethylamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as an imidizing agent is used. Imidized in the same manner as in Production Example 1 to produce an imidized MS resin (core-shell polymer). General formula (1) was 51 mol%.

Example 1
100% by weight of the imide resin obtained in Production Example 1 and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol as an ultraviolet absorber A pellet made of 1.0% by weight with an extruder is dried at 100 ° C. for 5 hours, and then extruded at 240 ° C. using a 40 mmφ single-screw extruder and a 400 mm wide T-die to obtain a sheet-like molten resin. A film having a width of 300 mm and a thickness of 150 μm was obtained by cooling with a cooling roll. The haze of this film was 0.31%, and the total light transmittance was 92.5%. The light transmittance at 380 nm was 3.1%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 350 degreeC.

(Example 2)
The same procedure as in Example 1 was performed except that 1.0% by weight of 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole was used as the ultraviolet absorber. The haze of the obtained film was 0.35%, and the total light transmittance was 92.7%. The light transmittance at 380 nm was 3.0%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 304 degreeC.

(Example 3)
The same procedure as in Example 1 was performed except that 1.0% by weight of 2,2′-dihydroxy-4,4′-dimethoxybenzophenone was used as the ultraviolet absorber. The haze of the obtained film was 0.37%, and the total light transmittance was 91.5%. The light transmittance at 380 nm was 3.4%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 308 degreeC.

Example 4
The same procedure as in Example 1 was performed except that 1.0% by weight of 2-hydroxy-4-n-octyloxybenzophenone was used as the ultraviolet absorber. The haze of the obtained film was 0.32%, and the total light transmittance was 92.2%. The light transmittance at 380 nm was 4.6%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 4 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 293 degreeC.

(Example 5)
As a UV absorber, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] 2.0% by weight was used. Except for this, the same procedure as in Example 1 was performed. The obtained film had a haze of 0.2% and a total light transmittance of 92.5%. The light transmittance at 380 nm was 6.7%, the light transmittance at 420 nm was 90.5%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 389 degreeC.

(Example 6)
100% by weight of the imide resin obtained in Production Example 2 and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol as an ultraviolet absorber A pellet made of 1.0% by weight with an extruder is dried at 100 ° C. for 5 hours, and then extruded at 240 ° C. using a 40 mmφ single-screw extruder and a 400 mm wide T-die to obtain a sheet-like molten resin. A film having a width of 300 mm and a thickness of 150 μm was obtained by cooling with a cooling roll. The haze of this film was 0.37% and the total light transmittance was 91.3%. The light transmittance at 380 nm was 2.7%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 350 degreeC.

(Example 7)
The same procedure as in Example 6 was performed except that 1.0% by weight of 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole was used as the ultraviolet absorber. The haze of the obtained film was 0.42%, and the total light transmittance was 91.5%. The light transmittance at 380 nm was 2.6%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 304 degreeC.

(Example 8)
The same procedure as in Example 6 was performed except that 1.0% by weight of 2,2′-dihydroxy-4,4′-dimethoxybenzophenone was used as the ultraviolet absorber. The haze of the obtained film was 0.44%, and the total light transmittance was 90.3%. The light transmittance at 380 nm was 3.0%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 308 degreeC.

Example 9
The same procedure as in Example 6 was performed except that 1.0% by weight of 2-hydroxy-4-n-octyloxybenzophenone was used as the ultraviolet absorber. The haze of the obtained film was 0.40%, and the total light transmittance was 91.0%. The light transmittance at 380 nm was 4.2%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 4 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 293 degreeC.

(Example 10)
As a UV absorber, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] 2.0% by weight was used. Except for this, the same procedure as in Example 6 was performed. The obtained film had a haze of 0.3% and a total light transmittance of 91.3%. The light transmittance at 380 nm was 6.6%, the light transmittance at 420 nm was 89.6%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 389 degreeC.

(Example 11)
The film prepared in Example 1 was preheated to 130 ° C. with a preheating roll of a longitudinal stretching machine, then once cooled to 128 ° C., and stretched 1.8 times with a stretching roll. Subsequently, after preheating to 132 degreeC in the preheating zone of a horizontal extending | stretching machine, it extended | stretched 1.8 times in the extending | stretching zone of 130 degreeC, and obtained the biaxially stretched film sequentially. This film had a thickness of 45 μm, a haze of 0.12%, and a total light transmittance of 92.4%. The light transmittance at 380 nm was 2.8%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm.

(Example 12)
The film prepared in Example 5 was preheated to 130 ° C. with a preheating roll of a longitudinal stretching machine, then cooled to 128 ° C., and stretched 1.8 times with a stretching roll. Subsequently, after preheating to 132 degreeC in the preheating zone of a horizontal extending | stretching machine, it extended | stretched 1.8 time in the 130 degreeC extending | stretching zone, and obtained the biaxially stretched film sequentially. The film had a thickness of 40 μm, a haze of 0.12%, and a total light transmittance of 92.4%. The light transmittance at 380 nm was 6.2%, the in-plane retardation was 2 nm, and the retardation in the thickness direction was 3 nm.

(Example 13)
The film prepared in Example 6 was preheated to 158 ° C. with a preheating roll of a longitudinal stretching machine, then cooled to 156 ° C., and stretched 1.8 times with a stretching roll. Subsequently, after preheating to 158 degreeC in the preheating zone of a horizontal extending | stretching machine, it extended | stretched 1.8 time in the extending zone of 156 degreeC, and obtained the biaxially stretched film sequentially. The film had a thickness of 45 μm, a haze of 0.15%, and a total light transmittance of 91.0%. The light transmittance at 380 nm was 2.4%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm.

(Example 14)
The film prepared in Example 10 was preheated to 158 ° C. with a preheating roll of a longitudinal stretching machine, then cooled to 156 ° C. and stretched 1.8 times with a stretching roll. Subsequently, after preheating to 158 degreeC in the preheating zone of a horizontal extending | stretching machine, it extended | stretched 1.8 time in the extending zone of 156 degreeC, and obtained the biaxially stretched film sequentially. This film had a thickness of 40 μm, a haze of 0.15%, and a total light transmittance of 91.0%. The light transmittance at 380 nm was 6.5%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm.

(Example 15)
As an ultraviolet absorber, 1.6% by weight of 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and 2- [5-chloro (2H)- The same procedure as in Example 1 except that 0.2% by weight of benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol was used. The haze of the obtained film was 0.41%, and the total light transmittance was 91.8%. The light transmittance at 380 nm was 6.0%, the light transmittance at 420 nm was 90.2%, the in-plane retardation was 4 nm, and the retardation in the thickness direction was 6 nm. In addition, the 10% weight reduction temperature of the ultraviolet absorber used was 310 ° C.

(Example 16)
100% by weight of the imide resin obtained in Production Example 3, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol as an ultraviolet absorber A pellet made of 1.0% by weight with an extruder is dried at 100 ° C. for 5 hours, and then extruded at 240 ° C. using a 40 mmφ single-screw extruder and a 400 mm wide T-die to obtain a sheet-like molten resin. A film having a width of 300 mm and a thickness of 150 μm was obtained by cooling with a cooling roll. The haze of this film was 0.44%, and the total light transmittance was 92.0%. The light transmittance at 380 nm was 3.8%, the in-plane retardation was 4 nm, and the retardation in the thickness direction was 5 nm. Moreover, the 10% weight reduction | decrease temperature of the used ultraviolet absorber was 350 degreeC.

(Comparative Example 1)
It implemented like Example 1 except not having used a ultraviolet absorber. The haze of the obtained film was 0.25%, and the total light transmittance was 92.7%. The light transmittance at 380 nm was 92.3%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm.

(Comparative Example 2)
The same operation as in Example 6 was carried out except that no ultraviolet absorber was used. The haze of the obtained film was 0.32%, and the total light transmittance was 91.5%. The light transmittance at 380 nm was 91.0%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm.

(Comparative Example 3)
Example 1 with the exception that 6.0% by weight of 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol was used as the UV absorber. It carried out similarly. The haze of the obtained film was 1.61%, and the total light transmittance was 91.7%. The light transmittance at 380 nm was 1.7%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm.

(Comparative Example 4)
Example 6 with the exception that 6.0% by weight of 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol was used as the UV absorber. It carried out similarly. The haze of the obtained film was 1.68%, and the total light transmittance was 90.6%. The light transmittance at 380 nm was 1.3%, the in-plane retardation was 3 nm, and the retardation in the thickness direction was 3 nm.

Claims (13)

  1. It is formed by containing the following components (A) and (B), the haze of the film molded product is 1.0% or less, the total light transmittance is 85% or more, and the light transmittance at 380 nm is 10% or less. The resin composition characterized by the above-mentioned.
    (A) An imide resin having a unit represented by the following general formula (1) and a unit represented by the following general formula (2) and / or a unit represented by the following general formula (3)
    (However, R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)
    (However, R 4 and R 5 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 6 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)
    (However, R 7 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 8 represents an aryl group having 6 to 10 carbon atoms.)
    (B) One or more UV absorbers selected from the group consisting of triazine-based UV absorbers, benzotriazole-based UV absorbers, and benzophenone-based UV absorbers
  2.   The resin composition according to claim 1, wherein the content of the ultraviolet absorber (B) in the imide resin (A) is 0.1 to 5% by weight.
  3.   The resin composition according to claim 1 or 2, comprising an ultraviolet absorber having a 10% weight loss temperature of 300 ° C or higher as the ultraviolet absorber (B).
  4.   The resin composition according to any one of claims 1 to 3, wherein the ultraviolet absorber (B) contains a benzotriazole-based ultraviolet absorber.
  5.   Contains 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] as the ultraviolet absorber of (B) The resin composition according to claim 4.
  6.   The resin composition according to claim 4, comprising 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole as the ultraviolet absorber (B).
  7.   The ultraviolet absorber (B) contains 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol. Item 4. The resin composition according to any one of Items 3.
  8.   4. The ultraviolet absorber (B) contains at least one of 2,2′-dihydroxy-4,4′-dimethoxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone. The resin composition according to any one of the above.
  9.   An optical film comprising the resin composition according to any one of claims 1 to 8.
  10.   The optical film according to claim 9, which is a film obtained by a melt extrusion method.
  11.   The optical film according to claim 9 or 10, which is a stretched film.
  12.   The optical film according to claim 11, wherein the in-plane retardation is 10 nm or less and the thickness direction retardation is 20 nm or less.
  13.   The polarizer protective film which uses the film described in Claim 11 or Claim 12.
JP2005159341A 2005-04-28 2005-05-31 Resin composition, optical film and polarizer protection film using the same Pending JP2006328334A (en)

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JP2008158295A (en) * 2006-12-25 2008-07-10 Nitto Denko Corp Method of manufacturing optical film, optical film, polarizing plate, and image display device
JP2008242426A (en) * 2006-12-22 2008-10-09 Nippon Shokubai Co Ltd Manufacturing method of retardation film
JP2008299096A (en) * 2007-05-31 2008-12-11 Nippon Shokubai Co Ltd Polarizer protective film, polarizing plate, and liquid crystal display device
JP2009161744A (en) * 2007-12-11 2009-07-23 Kaneka Corp Thermoplastic resin composition, optical film and polarizer protection film
WO2009145150A1 (en) 2008-05-27 2009-12-03 日東電工株式会社 Adhesive polarization plate, image display device and methods for manufacturing adhesive polarization plate and image display device
JP2009298965A (en) * 2008-06-16 2009-12-24 Denki Kagaku Kogyo Kk Resin composition or molding thereof
JP2010270162A (en) * 2009-04-22 2010-12-02 Kaneka Corp Optical film
JP2012093725A (en) * 2010-09-30 2012-05-17 Jiroo Corporate Plan:Kk Protective sheet and polarizing plate
WO2013011828A1 (en) 2011-07-20 2013-01-24 株式会社日本触媒 Molding material
JP2015034286A (en) * 2013-07-10 2015-02-19 リケンテクノス株式会社 Poly (meth) acryl imide film, easily-adhesive film thereof, and hard coat laminated film thereof
JP2015143842A (en) * 2013-12-27 2015-08-06 住友化学株式会社 Protective film for polarizing plate and polarizing plate using the same
US9557463B2 (en) 2013-03-08 2017-01-31 Fujifilm Corporation Optical film, polarizing plate and liquid crystal display device
JP2017191334A (en) * 2013-03-08 2017-10-19 富士フイルム株式会社 Liquid crystal display device
US10112369B2 (en) 2013-09-20 2018-10-30 Riken Technos Corporation Transparent multilayer film containing poly(meth)acrylimide-based resin layer, and method for producing said transparent multilayer film
US10173392B2 (en) 2014-03-24 2019-01-08 Riken Technos Corporation Process for producing article from layered hardcoat object, and article formed from layered hardcoat object including poly(meth)acrylimide-based resin layer
KR20190025933A (en) 2016-07-06 2019-03-12 덴카 주식회사 Resin composition for polarizer protective film, Polarizer protective film
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004045893A (en) * 2002-07-12 2004-02-12 Kanegafuchi Chem Ind Co Ltd Transparent film, polarizer protection film, and polarizing plate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004045893A (en) * 2002-07-12 2004-02-12 Kanegafuchi Chem Ind Co Ltd Transparent film, polarizer protection film, and polarizing plate

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JP2008158295A (en) * 2006-12-25 2008-07-10 Nitto Denko Corp Method of manufacturing optical film, optical film, polarizing plate, and image display device
JP2008299096A (en) * 2007-05-31 2008-12-11 Nippon Shokubai Co Ltd Polarizer protective film, polarizing plate, and liquid crystal display device
JP2009161744A (en) * 2007-12-11 2009-07-23 Kaneka Corp Thermoplastic resin composition, optical film and polarizer protection film
EP2535748A1 (en) 2008-05-27 2012-12-19 Nitto Denko Corporation Adhesive polarization plate, image display device and methods for manufacturing adhesive polarization plate and image display device
WO2009145150A1 (en) 2008-05-27 2009-12-03 日東電工株式会社 Adhesive polarization plate, image display device and methods for manufacturing adhesive polarization plate and image display device
JP2009298965A (en) * 2008-06-16 2009-12-24 Denki Kagaku Kogyo Kk Resin composition or molding thereof
JP2010270162A (en) * 2009-04-22 2010-12-02 Kaneka Corp Optical film
JP2014095926A (en) * 2009-04-22 2014-05-22 Kaneka Corp Optical film
JP2012093725A (en) * 2010-09-30 2012-05-17 Jiroo Corporate Plan:Kk Protective sheet and polarizing plate
WO2013011828A1 (en) 2011-07-20 2013-01-24 株式会社日本触媒 Molding material
US9557463B2 (en) 2013-03-08 2017-01-31 Fujifilm Corporation Optical film, polarizing plate and liquid crystal display device
JP2017191334A (en) * 2013-03-08 2017-10-19 富士フイルム株式会社 Liquid crystal display device
US9885907B2 (en) 2013-03-08 2018-02-06 Fujifilm Corporation Optical film, polarizing plate and liquid crystal display device
JP2015034286A (en) * 2013-07-10 2015-02-19 リケンテクノス株式会社 Poly (meth) acryl imide film, easily-adhesive film thereof, and hard coat laminated film thereof
US10450431B2 (en) 2013-07-10 2019-10-22 Riken Technos Corporation Poly(meth)acrylimide film, easy-adhesion film using same, and method for manufacturing such films
US10112369B2 (en) 2013-09-20 2018-10-30 Riken Technos Corporation Transparent multilayer film containing poly(meth)acrylimide-based resin layer, and method for producing said transparent multilayer film
JP2015143842A (en) * 2013-12-27 2015-08-06 住友化学株式会社 Protective film for polarizing plate and polarizing plate using the same
US9650481B2 (en) 2013-12-27 2017-05-16 Sumitomo Chemical Company, Limited Protective film for polarizing plate and polarizing plate using the same
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