JP2009175380A - Antiglare laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare film that achieves excellent antiglare property, prevention of scintillation and improvement in image sharpness, as well as has high weatherability and surface hardness, and is improved in workability and safety during manufacturing the antiglare film. <P>SOLUTION: The antiglare film comprises a lactone ring-containing resin film used as a base film, and an antiglare layer provided on the base film, wherein an internal haze Hi by internal diffusion of the antiglare layer is controlled to satisfy 1<Hi<15 and a surface haze Hs by a surface ruggedness feature of the antiglare layer is controlled to satisfy 7<Hs<30. The obtained antiglare layer achieves excellent antiglare property, prevention of scintillation and improvement in image sharpness, has high weatherability and high surface hardness, and is improved in workability/safety when manufacturing/processing the film. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an antiglare laminate provided on the surface of a high-definition display device such as a CRT, PDP (plasma display), LCD (liquid crystal display) panel or the like.

In recent years, with the progress of high-definition image displays such as CRT, PDP (plasma display), LCD (liquid crystal display) panels, infrared sensors, optical waveguides, etc., optically transparent polymer materials, especially planar (film or sheet) There is an increasing demand for optically transparent polymer materials, that is, optical films.

In particular, optical films used in the display field have low optical elastic modulus, heat resistance, and high mechanical strength in addition to high transparency and high optical isotropy.
In the display as described above, an anti-glare film for diffusing the light emitted from the inside to some extent is mainly dazzling when viewing the display surface when the light emitted from the inside goes straight without diffusing on the display surface. It is provided on the display surface.
For example, as disclosed in Patent Documents 1 and 2, the antiglare film is formed by applying a resin containing a filler such as silicon dioxide (silica) to the surface of a transparent substrate film.
These antiglare films are a type in which an irregular shape is formed on the surface of the antiglare layer by agglomeration of particles such as cohesive silica, and an organic filler having a particle size larger than the film thickness of the coating film is added to the resin. There is a type in which a concavo-convex shape is formed on the surface, or a type in which a concavo-convex shape is transferred by laminating a film having a concavo-convex shape on the layer surface.
When used outdoors, high weather resistance is required.
Further, when used on the display surface, high surface hardness is required.
In Patent Document 3, the anti-glare film is studied for controlling the internal haze and surface haze of the anti-glare film in order to suppress the scintillation (glare of the surface), to prevent white blur and to improve the image clarity. ing.
In patent document 4, the lactone ring containing resin is used for a base film, and the weather resistance and surface hardness of an anti-glare film are improved. However, the antiglare property was insufficient.
Furthermore, in consideration of the workability and safety of film handling, the surface potential of the film itself may be kept small and difficult to be charged in order to make it difficult to generate static electricity during the production and processing of the antiglare film. Required.
However, none of the conventional antiglare films satisfy the above-mentioned characteristics sufficiently.

JP-A-6-18706 JP 10-20103 A JP 11-305010 A JP2007-293272

The conventional anti-glare film as described above is designed to obtain light diffusing and anti-glare action by the action of the surface shape of the anti-glare layer in any type. However, when the unevenness becomes large, there is a problem that the haze value of the coating film increases, and the sharpness of the image decreases accordingly.
Similar to the above, a light diffusing film in which fine particles are dispersed in a layer to obtain a light dispersion effect is used, for example, as a reflection type liquid crystal display device, Journal of the Illuminating Society of Japan MD-96-48 (1996). Pp. 277-282.
In addition, when an anti-glare film with a light diffusing effect such as a light diffusing film on the display surface is used for anti-glare, the surface is almost flat so that external light is reflected on the display surface. There is also a problem that cannot be prevented.
In order to obtain a sufficient light diffusion effect due to the internal scattering effect used here, the particle size of the fine particles used must be increased. There is a problem that it is small.
Furthermore, the conventional type of antiglare film has a problem in that the surface of the film has a sparkle called scintillation (glare of the surface) and the visibility of the display screen is lowered.
One of the evaluation criteria for such an antiglare film is the haze value, but if the haze value on the surface is lowered, the scintillation becomes stronger.If the haze value is increased to eliminate this, the whole becomes whitish and the black density is increased. There is a problem that the contrast is lowered. On the other hand, if the haze value is lowered in order to remove the whitishness, there is a problem that so-called reflection and a feeling of glare increase.
Furthermore, when an existing film is used as a base film, there is a problem that weather resistance, surface hardness, workability during film production / processing, and safety cannot be sufficiently secured.
The present invention has been made in view of the above-mentioned conventional problems, and when attached to a display surface, suppresses a decrease in contrast, prevents scintillation, reflection, and whitening, and further provides high weather resistance and surface An object of the present invention is to provide a display device using an antiglare film that has hardness and simultaneously satisfies workability and safety during the production and processing of the antiglare film.

  According to the present invention, an antiglare layer comprising a binder containing fine particles having different refractive indexes is laminated on at least one surface of a lactone ring-containing resin film, which is a transparent substrate film. The above object is achieved by setting the surface haze value Hs of the surface irregularities of the layer to 7 <Hs <30 and the internal haze value Hi by internal diffusion of the antiglare layer to 1 <Hi <15.

  Further, a low refractive index layer having a refractive index lower than that of the antiglare layer may be further laminated on the antiglare layer.

  Furthermore, the low refractive index layer may be formed from a silicon-containing vinylidene fluoride copolymer.

  The silicon-containing vinylidene fluoride copolymer is a copolymer of vinylidene fluoride and hexafluoropropylene, and a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, and ethylenically unsaturated It is good also as a polymer with the polymeric compound which has group.

  Furthermore, the low refractive index layer is formed by applying or heating an active energy ray after applying a coating film composed of at least the fluorine-containing copolymer and the polymerizable compound having an ethylenically unsaturated group. It is good also as what was done.

  The low refractive index layer may be formed from a silicon oxide film, and an antifouling layer may be further formed thereon.

  You may make it the sum of the haze value Hs in the surface unevenness | corrugation of the anti-glare layer in the said anti-glare film, and the internal haze value Hi by the internal diffusion of the said anti-glare layer be 30 or less.

  Further, the refractive index difference Δn between the binder and the fine particles in the antiglare layer may be 0.01 ≦ Δn ≦ 0.5, and the average particle diameter d of the fine particles may be 0.1 μm ≦ d ≦ 5 μm. .

  The binder in the antiglare film may be at least one of a thermosetting resin and an ionizing radiation curable resin, and the fine particles may be organic fine particles.

  The organic fine particles may be styrene beads.

  Further, a transparent conductive layer may be provided between the transparent base film and the antiglare layer, and a conductive material may be contained in the antiglare layer.

  The display device according to the present invention as described in claim 12 has a plurality of pixels, and each pixel transmits light or reflects light to form an image, and a display surface side of the display panel The above object is achieved by a display device comprising any one of the above antiglare films provided on the screen.

  In the present invention, when an antiglare layer is formed by laminating an antiglare layer comprising binders containing fine particles having different refractive indexes, the surface haze value Hs of the surface irregularities of the antiglare layer is 7 <Hs <30, When the internal haze value Hi due to internal diffusion of the glare layer is 1 <Hi <15, the particle size of the fine particles can be reduced and the display quality in, for example, a liquid crystal display can be improved or better. .

  Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention.

  In the antiglare film of the embodiment of the present invention, an antiglare layer comprising a binder containing fine particles having different refractive indexes is laminated on one surface of a lactone ring-containing resin film which is a transparent substrate film, and further on the outer side. The surface haze value Hs in the surface unevenness of the antiglare layer is 7 <Hs <30, and the internal haze value Hi due to internal diffusion of the antiglare layer is 1 <Hi <15. It was made to become.

  Note that the low refractive index layer hardly affects the haze value of the surface of the antiglare layer as long as the material and film thickness are in a normal range that exhibits an antireflection effect.

  The lower the haze value of the surface of the antiglare layer, the smaller the blurring of the display and the clear display display can be obtained, but if the haze value is too low, reflection and surface glare will occur, and if it is too high, it will become whitish As shown below, the surface haze value Hs is preferably 7 <Hs <30, more preferably 7 ≦ Hs ≦ 20, and most preferably 7 ≦ Hs ≦ 15. Further, even if the surface haze value Hs is optimized, if the internal haze value Hi is low, surface glare is likely to occur. However, the internal haze value Hi of the antiglare layer is preferably 1 <Hi <15, more preferably 2 ≦ Hi. <15, most preferably 3 ≦ Hi ≦ 12, it was possible to reduce surface glare. Further, when the sum of the haze values of the surface and the inside of the antiglare layer was set to 30 or less, it was possible to prevent the black density (contrast) from being lowered.

  As described above, in the present invention, the surface diffusion in the antiglare layer and the internal diffusion are used together to obtain a predetermined effect. However, the surface haze value Hs and the internal haze value Hi as described above are obtained. By forming the antiglare layer so that the sum is a predetermined value, a greater effect can be obtained. Under the present circumstances, the moderate unevenness | corrugation can be normally provided in the resin layer surface with the microparticles | fine-particles contained in a glare-proof layer, and this is a preferable form.

  In addition, the transparent base film is coated with a binder mixed with fine particles, and from the top of this coating layer, a molded film in which fine irregularities having a surface roughness Ra of 1.2 μm or less are formed on the surface. Laminating so that the surface is in contact with the coating layer, and then, when the binder is an electron beam or an ultraviolet curable resin, the electron beam or ultraviolet ray is irradiated through a shaping film, and the solvent drying type In the case of a resin, it is possible to form irregularities by heating and curing, and then peeling the shaped film from the cured anti-glare layer.

  If it does in this way, the fine unevenness | corrugation whose surface roughness Ra previously formed in the shaping film will be 1.2 micrometers or less is shaped in the glare-proof layer.

  In order to achieve the above, in the example of the above-described embodiment, the difference Δn between the refractive index of the binder and the fine particles constituting the antiglare layer is set to 0.01 ≦ Δn ≦ 0.5, and the diffusing agent The average particle diameter d is set to 0.1 μm ≦ d ≦ 5 μm.

  As described above, the refractive index difference Δn is 0.01 or more, and if it is less than 0.01, a very large amount of diffusing agent is contained in the binder in order to exhibit light diffusibility in the antiglare layer. In this way, the adhesion and coating suitability of the antiglare layer to the transparent substrate film deteriorate, and when Δn is greater than 0.5, the content of fine particles in the binder is This is because an antiglare layer having a small amount and uniform unevenness cannot be obtained.

  When the average particle diameter d of the fine particles is less than 0.1 μm, it becomes difficult to disperse the fine particles in the binder, and aggregation cannot be formed to form a uniform and appropriate antiglare layer. When d> 5 μm, the diffusion effect inside the antiglare layer is reduced, so that the internal haze value is lowered and the surface is glaring. Furthermore, since the film thickness is increased, curing shrinkage in the production process of the binder is increased, and cracks and curls are generated.

  The reason why the haze value in the surface and the inside of the antiglare layer is as described above is based on knowledge obtained by experiments of the present inventors (see Examples and Tables described later). The haze value as described above is specifically obtained by adjusting a filler / binder ratio, which is a ratio of fine particles to a binder, a solvent, and the like.

≪Transparent substrate film≫
The lactone ring-containing resin film contains a lactone ring-containing polymer as a main component.

  The lactone ring-containing polymer preferably has a lactone ring structure represented by the following formula (1).

(In the formula, R ¹ , R ² and R ³ each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.)
The content ratio of the lactone ring structure represented by the general formula (1) in the lactone ring-containing polymer structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60% by mass. Especially preferably, it is 10-50 mass%. When the content of the lactone ring structure represented by the general formula (1) in the lactone ring-containing polymer structure is less than 5% by mass, the heat resistance, solvent resistance and surface hardness of the obtained polymer are lowered. Sometimes. On the other hand, when the content of the lactone ring structure exceeds 90% by mass, the moldability of the obtained polymer may be deteriorated.

  The lactone ring-containing polymer may have a structure other than the lactone ring structure represented by the general formula (1). The structure other than the lactone ring structure represented by the general formula (1) is not particularly limited. For example, a (meth) acrylic acid ester described later as a method for producing a lactone ring-containing polymer, Polymer structure formed by polymerizing at least one monomer selected from the group consisting of a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and a monomer represented by the following general formula (2) Units (repeating structural units) are preferred.

(Wherein R ⁴ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁵ group, or —CO It represents ^{-O-R 6} group, Ac represents an acetyl group, ^{R 5} and ^{R 6} represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
The content ratio of the structure other than the lactone ring structure represented by the general formula (1) in the lactone ring-containing polymer structure is a polymer structural unit (repeated structural unit) formed by polymerizing (meth) acrylic acid ester. In this case, it is preferably 10 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 40 to 90% by mass, particularly preferably 50 to 90% by mass, and the hydroxy group-containing monomer is polymerized. In the case of the polymer structural unit to be formed (repeating structural unit), it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 15% by mass, and particularly preferably 0 to 10% by mass. is there. In the case of a polymer structural unit (repeating structural unit) formed by polymerizing an unsaturated carboxylic acid, it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and still more preferably 0 to 15% by mass. Especially preferably, it is 0-10 mass%. Furthermore, in the case of a polymer structural unit (repeating structural unit) formed by polymerizing the monomer represented by the general formula (2), preferably 0 to 30% by mass, more preferably 0 to 20% by mass, More preferably, it is 0-15 mass%, Most preferably, it is 0-10 mass%.

  The method for producing the lactone ring-containing polymer is not particularly limited. For example, after the polymer (a) having a hydroxy group and an ester group in the molecular chain is obtained by a polymerization step, the obtained heavy polymer is obtained. It can be obtained by carrying out a lactone cyclization condensation step for introducing a lactone ring structure into the polymer by heat-treating the compound (a).

  In the polymerization step, a polymer having a hydroxy group and an ester group in the molecular chain is obtained by performing a polymerization reaction of a monomer component containing a monomer represented by the following general formula (3).

(Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
Examples of the monomer represented by the general formula (3) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, 2- ( Hydroxymethyl) n-butyl acrylate, t-butyl 2- (hydroxymethyl) acrylate, methallyl alcohol and the like. These monomers may be used alone or in combination of two or more.

  Of these monomers, methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are preferred, and methyl 2- (hydroxymethyl) acrylate is highly effective in improving heat resistance. Is particularly preferred.

  The content ratio of the monomer represented by the general formula (3) in the monomer component provided in the polymerization step is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60%. It is 10 mass%, Most preferably, it is 10-50 mass%. When the content ratio of the monomer represented by the general formula (3) is less than 5% by mass, the heat resistance, solvent resistance, and surface hardness of the obtained polymer may be lowered. On the other hand, when the content ratio of the monomer represented by the general formula (3) exceeds 90% by mass, gelation occurs in the polymerization step or the lactone cyclization condensation step, and the molding processability of the obtained polymer is low. May decrease.

  The monomer component used in the polymerization step may include a monomer other than the monomer represented by the general formula (3). Such a monomer is not particularly limited. For example, (meth) acrylic acid ester, hydroxy group-containing monomer, unsaturated carboxylic acid, and the following general formula (2) are used. And the like. These monomers may be used alone or in combination of two or more.

(Wherein R ⁴ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁵ group, or —CO It represents ^{-O-R 6} group, Ac represents an acetyl group, ^{R 5} and ^{R 6} represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
The (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylic acid ester other than the monomer represented by the general formula (3). For example, methyl acrylate, acrylic acid Acrylic esters such as ethyl, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacryl And methacrylic acid esters such as isobutyl acid, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. These (meth) acrylic acid esters may be used alone or in combination of two or more. Among these (meth) acrylic acid esters, methyl methacrylate is particularly preferable because the obtained polymer has excellent heat resistance and transparency.

  When using a (meth) acrylic acid ester other than the monomer represented by the general formula (3), the content ratio in the monomer component to be subjected to the polymerization step is sufficient to exert the effect of the present invention. The content is preferably 10 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass.

  The hydroxy group-containing monomer is not particularly limited as long as it is a hydroxy group-containing monomer other than the monomer represented by the general formula (3). For example, α-hydroxymethylstyrene, α-hydroxyethyl styrene, 2- (hydroxyalkyl) acrylic acid ester such as methyl 2- (hydroxyethyl) acrylate; 2- (hydroxyalkyl) acrylic acid such as 2- (hydroxyethyl) acrylic acid; . These hydroxy group-containing monomers may be used alone or in combination of two or more.

  When using a hydroxyl group-containing monomer other than the monomer represented by the general formula (3), the content ratio in the monomer component to be used in the polymerization step is sufficient to exert the effect of the present invention. The content is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, and particularly preferably 0 to 10% by mass.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, α-substituted methacrylic acid and the like. These unsaturated carboxylic acids may be used alone or in combination of two or more. Among these unsaturated carboxylic acids, acrylic acid and methacrylic acid are particularly preferable because the effects of the present invention are sufficiently exhibited.

  When using an unsaturated carboxylic acid, the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, in order to sufficiently exhibit the effects of the present invention. %, More preferably 0 to 15% by mass, particularly preferably 0 to 10% by mass.

  Examples of the monomer represented by the general formula (2) include styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. These monomers may be used alone or in combination of two or more. Of these monomers, styrene and α-methylstyrene are particularly preferable because the effects of the present invention are sufficiently exhibited.

  When using the monomer represented by the general formula (2), the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass in order to sufficiently exhibit the effects of the present invention. More preferably, it is 0-20 mass%, More preferably, it is 0-15 mass%, Most preferably, it is 0-10 mass%.

  As a form of the polymerization reaction for polymerizing the monomer component to obtain a polymer having a hydroxy group and an ester group in the molecular chain, a polymerization form using a solvent is preferable, and solution polymerization is particularly preferable. .

  Although the polymerization temperature and the polymerization time vary depending on the type and ratio of the monomer used, for example, the polymerization temperature is preferably 0 to 150 ° C., the polymerization time is 0.5 to 20 hours, and more preferably. Has a polymerization temperature of 80 to 140 ° C. and a polymerization time of 1 to 10 hours.

  In the case of polymerization using a solvent, the polymerization solvent is not particularly limited. For example, aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran And ether solvents such as These solvents may be used alone or in combination of two or more. Moreover, since the residual volatile matter of the lactone ring containing polymer finally obtained will increase when the boiling point of a solvent is too high, the solvent whose boiling point is 50-200 degreeC is preferable.

  During the polymerization reaction, a polymerization initiator may be added as necessary. The polymerization initiator is not particularly limited. For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl Organic peroxides such as carbonate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2 ′ -Azo compounds such as azobis (2,4-dimethylvaleronitrile); These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers and reaction conditions.

  When performing the polymerization, it is preferable to control the concentration of the produced polymer in the polymerization reaction mixture to be 50% by mass or less in order to suppress gelation of the reaction solution. Specifically, when the concentration of the produced polymer in the polymerization reaction mixture exceeds 50% by mass, it is preferable that the polymerization solvent is appropriately added to the polymerization reaction mixture and controlled to be 50% by mass or less. . The concentration of the produced polymer in the polymerization reaction mixture is more preferably 45% by mass or less, and further preferably 40% by mass or less. In addition, since productivity will fall when the density | concentration of the produced | generated polymer in a polymerization reaction mixture is too low, the density | concentration of the produced | generated polymer in a polymerization reaction mixture becomes like this. Preferably it is 10 mass% or more, More preferably, it is 20 mass%. That's it.

  The form in which the polymerization solvent is appropriately added to the polymerization reaction mixture is not particularly limited, and for example, the polymerization solvent may be added continuously or the polymerization solvent may be added intermittently. By controlling the concentration of the produced polymer in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, to increase the lactone ring content and improve the heat resistance. Even when the ratio between the hydroxy group and the ester group in the molecular chain is increased, gelation can be sufficiently suppressed. The polymerization solvent to be added may be, for example, the same type of solvent used during the initial charging of the polymerization reaction or a different type of solvent, but the solvent used during the initial charging of the polymerization reaction. It is preferable to use the same type of solvent. Moreover, the polymerization solvent to be added may be only one kind of single solvent or two or more kinds of mixed solvents.

  The polymerization reaction mixture obtained when the above polymerization step is completed usually contains a solvent in addition to the obtained polymer, but it is necessary to completely remove the solvent and take out the polymer in a solid state. Rather, it is preferably introduced into the subsequent lactone cyclization condensation step in a state containing a solvent. If necessary, after taking out in a solid state, a solvent suitable for the subsequent lactone cyclization condensation step may be added again.

  The polymer obtained in the polymerization step is a polymer (a) having a hydroxy group and an ester group in the molecular chain, and the weight average molecular weight of the polymer (a) is preferably 1,000 to 2,000. 5,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, and particularly preferably 50,000 to 500,000. The polymer (a) obtained in the polymerization step is subjected to heat treatment in the subsequent lactone cyclization condensation step, whereby a lactone ring structure is introduced into the polymer to become a lactone ring-containing polymer.

  The reaction for introducing a lactone ring structure into the polymer (a) is a reaction in which a hydroxy group and an ester group present in the molecular chain of the polymer (a) are cyclized and condensed to form a lactone ring structure by heating. The alcohol is by-produced by the cyclized condensation. By forming the lactone ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted. If the reaction rate of the cyclization condensation reaction leading to the lactone ring structure is insufficient, the heat resistance will not be improved sufficiently, or a condensation reaction will occur during the molding due to the heat treatment during molding, and the resulting alcohol will be contained in the molded product. May exist as bubbles or silver streaks.

  The lactone ring-containing polymer obtained in the lactone cyclization condensation step preferably has a lactone ring structure represented by the following general formula (1).

(In the formula, R ¹ , R ² and R ³ each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.)
The method for heat-treating the polymer (a) is not particularly limited, and a conventionally known method can be used. For example, you may heat-process the polymerization reaction mixture containing the solvent obtained by the superposition | polymerization process as it is. Or you may heat-process using a ring-closure catalyst as needed in presence of a solvent. Or heat processing can also be performed using the heating furnace and reaction apparatus provided with the vacuum apparatus or devolatilization apparatus for removing a volatile component, the extruder provided with the devolatilization apparatus, etc.

  In carrying out the cyclization condensation reaction, in addition to the polymer (a), another thermoplastic resin may coexist. When performing the cyclization condensation reaction, if necessary, an esterification catalyst or a transesterification catalyst such as p-toluenesulfonic acid generally used as a catalyst for the cyclization condensation reaction may be used. , Organic carboxylic acids such as propionic acid, benzoic acid, acrylic acid and methacrylic acid; an organic phosphorus compound may be used as a catalyst. Furthermore, as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 61-254608 and 61-261303, basic compounds, organic carboxylates, carbonates, and the like may be used.

  Among these cyclization condensation reaction catalysts, an organophosphorus compound is preferable because the cyclization condensation reaction rate can be improved and coloring of the resulting lactone ring-containing polymer can be greatly reduced. Furthermore, by using an organophosphorus compound as a catalyst for the cyclization condensation reaction, it is possible to suppress a decrease in molecular weight that can occur when a devolatilization step described later is used in combination, and to impart excellent mechanical strength.

  Examples of the organic phosphorus compound that can be used as a catalyst in the cyclocondensation reaction include alkyl (aryl) phosphonous acids such as methylphosphonous acid, ethylphosphonous acid, and phenylphosphonous acid (however, Tautomers (which may be alkyl (aryl) phosphinic acid) and monoesters or diesters thereof; dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid, etc. Dialkyl (aryl) phosphinic acids and esters thereof; alkyl (aryl) phosphonic acids such as methyl phosphonic acid, ethyl phosphonic acid, trifluoromethyl phosphonic acid, phenyl phosphonic acid, and monoesters or diesters thereof; methyl phosphite Acids, alkyl (aryl) phosphinic acids such as ethylphosphinic acid, phenylphosphinic acid and their esters; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, Phosphorous acid monoester, diester or triester such as diphenyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl phosphate , Isodecyl phosphate, lauryl phosphate, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, distearyl phosphate , Diisostearyl phosphate, diphenyl phosphate, triphosphate Phosphoric monoesters, diesters or triesters such as chill, triethyl phosphate, triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, Mono-, di- or tri-alkyl (aryl) phosphine such as dimethylphosphine, diethylphosphine, diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine; methyldichlorophosphine, ethyldichlorophosphine, phenyldichlorophosphine, dimethylchlorophosphine, Alkyl (aryl) halogen phosphines such as diethyl chlorophosphine and diphenylchlorophosphine; Mono-, di- or tri-alkyl (aryl) phosphines such as sphin, phenyl phosphine oxide, dimethyl phosphine oxide, diethyl phosphine oxide, diphenyl phosphine oxide, trimethyl phosphine oxide, triethyl phosphine oxide, triphenyl phosphine oxide; tetramethyl chloride And halogenated tetraalkyl (aryl) phosphonium such as phosphonium, tetraethylphosphonium chloride, and tetraphenylphosphonium chloride. These organic phosphorus compounds may be used alone or in combination of two or more. Among these organophosphorus compounds, since the catalytic activity is high and the colorability is low, alkyl (aryl) phosphonous acid, phosphorous acid monoester or diester, phosphoric acid monoester or diester, and alkyl (aryl) phosphonic acid Preferably, alkyl (aryl) phosphonous acid, phosphorous acid monoester or diester, phosphoric acid monoester or diester is more preferable, and alkyl (aryl) phosphonous acid, phosphoric acid monoester or diester is particularly preferable.

  Although the usage-amount of the catalyst used in the case of a cyclization condensation reaction is not specifically limited, For example, Preferably it is 0.001-5 mass% with respect to a polymer (a), More preferably, it is 0.01. -2.5 mass%, More preferably, it is 0.01-1 mass%, Most preferably, it is 0.05-0.5 mass%. When the amount of the catalyst used is less than 0.001% by mass, the reaction rate of the cyclization condensation reaction may not be sufficiently improved. On the other hand, when the amount of the catalyst used exceeds 5% by mass, the obtained polymer may be colored or the polymer may be cross-linked to make melt molding difficult.

  The addition timing of the catalyst is not particularly limited. For example, the catalyst may be added at the beginning of the reaction, may be added during the reaction, or may be added in both of them.

  It is preferable to carry out the cyclization condensation reaction in the presence of a solvent and to use a devolatilization step in combination with the cyclization condensation reaction. In this case, a mode in which the devolatilization step is used throughout the cyclization condensation reaction and a mode in which the devolatilization step is not used over the entire cyclization condensation reaction but only in a part of the process. In the method using the devolatilization step in combination, the alcohol produced as a by-product in the condensation cyclization reaction is forcibly devolatilized and removed, so that the equilibrium of the reaction is advantageous for the production side.

  The devolatilization step refers to a step of removing volatile components such as solvents and residual monomers and alcohol by-produced by a cyclization condensation reaction leading to a lactone ring structure under reduced pressure heating conditions as necessary. . If this removal treatment is insufficient, residual volatile components in the obtained polymer increase, and coloring may occur due to deterioration during molding, and molding defects such as bubbles and silver streaks may occur.

  In the case of using a devolatilization step throughout the cyclization condensation reaction, the apparatus to be used is not particularly limited. For example, in order to more effectively perform the present invention, a devolatilization step and devolatilization are performed. It is preferable to use a devolatilizer comprising a tank and an extruder with a vent, or a devolatilizer and an extruder arranged in series, and a devolatilizer comprising a heat exchanger and a devolatilizer or an extrusion with a vent It is more preferable to use a machine.

  The reaction treatment temperature in the case of using a devolatilizer comprising a heat exchanger and a devolatilizer is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. If the reaction treatment temperature is less than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase. On the other hand, when the reaction processing temperature exceeds 350 ° C., the obtained polymer may be colored or decomposed.

  The reaction treatment pressure when using a devolatilizer comprising a heat exchanger and a devolatilizer is preferably 931 to 1.33 hPa (700 to 1 mmHg), more preferably 798 to 66.5 hPa (600 to 50 mmHg). . When the reaction treatment pressure exceeds 931 hPa (700 mmHg), volatile components including alcohol may easily remain. On the other hand, when the reaction treatment pressure is less than 1.33 hPa (1 mmHg), industrial implementation may be difficult.

  When using the extruder with a vent, one or a plurality of vents may be used, but it is preferable to have a plurality of vents.

  The reaction processing temperature when using the extruder with a vent is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. If the reaction treatment temperature is less than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase. On the other hand, when the reaction processing temperature exceeds 350 ° C., the obtained polymer may be colored or decomposed.

  The reaction treatment pressure when using the extruder with a vent is preferably 931 to 1.33 hPa (700 to 1 mmHg), more preferably 798 to 13.3 hPa (600 to 10 mmHg). When the reaction treatment pressure exceeds 931 hPa (700 mmHg), volatile components including alcohol may easily remain. On the other hand, when the reaction treatment pressure is less than 1.33 hPa (1 mmHg), industrial implementation may be difficult.

  In the case of a form in which a devolatilization step is used throughout the cyclization condensation reaction, the physical properties of the lactone ring-containing polymer obtained may deteriorate under severe heat treatment conditions, as will be described later. It is preferable to carry out by using an extruder with a vent etc. on the conditions as mild as possible.

  In the case where the devolatilization step is used in combination throughout the cyclization condensation reaction, the polymer (a) obtained in the polymerization step is preferably introduced into the cyclization condensation reaction device together with a solvent. Depending on the situation, it may be passed once again through a cyclocondensation reaction apparatus such as a vented extruder.

  You may perform the form used together only in a part of process, without using a devolatilization process over the whole process of cyclization condensation reaction. For example, the apparatus for producing the polymer (a) is further heated, and if necessary, a part of the devolatilization step is used together to advance the cyclization condensation reaction to some extent in advance, followed by the devolatilization step. Is a form in which a cyclization condensation reaction is simultaneously used to complete the reaction.

  In the form of using the devolatilization step throughout the cyclization condensation reaction described above, for example, when the polymer (a) is heat-treated at a high temperature of about 250 ° C. or higher using a twin-screw extruder. Depending on the thermal history, partial decomposition or the like may occur before the cyclization condensation reaction occurs, and the physical properties of the obtained lactone ring-containing polymer may be lowered. Therefore, if the cyclization condensation reaction is allowed to proceed to some extent before the cyclization condensation reaction using the devolatilization process at the same time, the reaction conditions in the latter half can be relaxed and the physical properties of the resulting lactone ring-containing polymer are reduced. Is preferable. As a particularly preferred form, for example, a form in which the devolatilization step is started after a lapse of time from the start of the cyclization condensation reaction, that is, a hydroxy group present in the molecular chain of the polymer (a) obtained in the polymerization step A form in which an ester group is preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent and then a cyclization condensation reaction using a devolatilization step simultaneously is performed. Specifically, for example, a cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance using a kettle reactor, and then a reactor equipped with a devolatilizer, for example, heat exchange Preferred is a mode in which the cyclization condensation reaction is completed with a devolatilizer comprising a vessel and a devolatilization tank, an extruder with a vent, or the like. In particular, in the case of this form, it is more preferable that a catalyst for the cyclization condensation reaction is present.

  As described above, the hydroxy group and the ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent, The method of carrying out the cyclization condensation reaction using the devolatilization step at the same time is a preferred mode for obtaining a lactone ring-containing polymer in the present invention. With this form, a lactone ring-containing polymer having a higher glass transition temperature, a higher cyclization condensation reaction rate, and excellent heat resistance can be obtained. In this case, as a measure of the cyclization condensation reaction rate, for example, the mass reduction rate in the range of 150 to 300 ° C. in the dynamic TG measurement shown in the examples is preferably 2% or less, more preferably 1.5% or less. More preferably, it is 1% or less.

  The reactor that can be employed in the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization process at the same time is not particularly limited. For example, an autoclave, a kettle reactor, a heat exchanger And a devolatilizer comprising a devolatilization tank, and a vented extruder suitable for a cyclization condensation reaction using a devolatilization step at the same time can also be used. Of these reactors, an autoclave and a kettle reactor are particularly preferable. However, even when a reactor such as an extruder with a vent is used, the autoclave or kettle can be adjusted by adjusting the temperature conditions, barrel conditions, screw shape, screw operating conditions, etc. It is possible to carry out the cyclization condensation reaction in the same state as the reaction state in the type reactor.

  In the case of the cyclization condensation reaction carried out in advance before the cyclization condensation reaction using the devolatilization step at the same time, for example, a mixture containing the polymer (a) and the solvent obtained in the polymerization step is used as (i) a catalyst. And (ii) a method of performing a heat reaction without a catalyst, a method of performing the above (i) or (ii) under pressure, and the like.

  The “mixture containing the polymer (a) and the solvent” introduced into the cyclization condensation reaction in the lactone cyclization condensation step refers to the polymerization reaction mixture itself obtained in the polymerization step or the solvent once removed. It means a mixture obtained by re-adding a solvent suitable for the cyclization condensation reaction later.

  The solvent that can be re-added in the cyclization condensation reaction that is carried out in advance before the cyclization condensation reaction using the devolatilization step at the same time is not particularly limited. For example, aromatic carbonization such as toluene, xylene, ethylbenzene, etc. Hydrogens; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, dimethyl sulfoxide, tetrahydrofuran; and the like. These solvents may be used alone or in combination of two or more. Preferably, it is the same kind of solvent as the solvent used in the polymerization step.

  Examples of the catalyst added in the method (i) include commonly used esterification catalysts such as p-toluenesulfonic acid or transesterification catalysts, basic compounds, organic carboxylates, and carbonates. In the present invention, it is preferable to use the organophosphorus compound described above. The addition timing of the catalyst is not particularly limited. For example, the catalyst may be added at the beginning of the reaction, may be added during the reaction, or may be added in both of them. The addition amount of the catalyst is not particularly limited, but for example, is preferably 0.001 to 5% by mass, more preferably 0.01 to 2.5% by mass with respect to the mass of the polymer (a). More preferably, it is 0.01-1 mass%, Most preferably, it is 0.05-0.5 mass%. Although the heating temperature and heating time of method (i) are not particularly limited, for example, the heating temperature is preferably room temperature to 180 ° C., more preferably 50 to 150 ° C., and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If the heating temperature is less than room temperature or the heating time is less than 1 hour, the cyclization condensation reaction rate may be lowered. On the other hand, if the heating temperature exceeds 180 ° C. or the heating time exceeds 20 hours, the resin may be colored or decomposed.

  Examples of the method (ii) include a method of heating the polymerization reaction mixture obtained in the polymerization step as it is using a pressure-resistant kettle reactor or the like. Although the heating temperature and heating time of method (ii) are not particularly limited, for example, the heating temperature is preferably 100 to 180 ° C, more preferably 150 to 180 ° C, and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. When the heating temperature is less than 100 ° C. or the heating time is less than 1 hour, the cyclization condensation reaction rate may be lowered. Conversely, if the heating temperature exceeds 180 ° C. or the heating time exceeds 20 hours, the resin may be colored or decomposed.

  In any of the methods (i) and (ii), there is no problem even under pressure depending on conditions.

  In the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization step at the same time, there is no problem even if part of the solvent volatilizes spontaneously during the reaction.

  The mass reduction rate within the range of 150 to 300 ° C. in the dynamic TG measurement at the end of the cyclization condensation reaction performed in advance before the cyclization condensation reaction simultaneously used in combination with the devolatilization step, that is, immediately before the start of the devolatilization step is Preferably it is 2% or less, More preferably, it is 1.5% or less, More preferably, it is 1% or less. When the mass reduction rate exceeds 2%, the cyclization condensation reaction rate does not rise to a sufficiently high level even if the cyclization condensation reaction is performed simultaneously with the devolatilization step, and the physical properties of the resulting lactone ring-containing polymer. May decrease. In addition, when performing said cyclization condensation reaction, in addition to a polymer (a), you may coexist other thermoplastic resins.

  The hydroxy group and the ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent. In the case of a form in which a combined cyclization condensation reaction is carried out, a polymer obtained by a cyclization condensation reaction carried out in advance (a polymer in which at least a part of a hydroxy group and an ester group present in a molecular chain is subjected to a cyclization condensation reaction) And the solvent may be introduced into the cyclization condensation reaction using the devolatilization step at the same time, and if necessary, the polymer (at least a part of the hydroxy group and ester group present in the molecular chain is present). It may be introduced into a cyclization condensation reaction in which a devolatilization step is used at the same time after other treatments such as re-addition of a solvent after the cyclization condensation reaction polymer is isolated.

  The devolatilization step is not limited to being completed at the same time as the cyclization condensation reaction, and may be completed after a lapse of time from the completion of the cyclization condensation reaction.

  The weight average molecular weight of the lactone ring-containing polymer is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, particularly preferably. 50,000 to 500,000.

  The lactone ring-containing polymer preferably has a mass reduction rate in the range of 150 to 300 ° C. in dynamic TG measurement of 1% or less, more preferably 0.5% or less, and still more preferably 0.3% or less.

  Since the lactone ring-containing polymer has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage that bubbles and silver streaks enter the molded product after molding. Furthermore, since the lactone ring structure is sufficiently introduced into the polymer due to the high cyclization condensation reaction rate, the obtained lactone ring-containing polymer has sufficiently high heat resistance.

  The lactone ring-containing polymer has a coloring degree (YI) of preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1 or less when a chloroform solution having a concentration of 15% by mass is used. . If the degree of coloring (YI) exceeds 6, transparency may be impaired by coloring, and it may not be used for the intended purpose.

  The lactone ring-containing polymer has a 5% mass reduction temperature in thermal mass spectrometry (TG) of preferably 330 ° C. or higher, more preferably 350 ° C. or higher, and still more preferably 360 ° C. or higher. The 5% mass reduction temperature in thermal mass spectrometry (TG) is an index of thermal stability, and if it is less than 330 ° C., sufficient thermal stability may not be exhibited.

  The lactone ring-containing polymer has a glass transition temperature (Tg) of preferably 110 ° C. or higher, more preferably 115 ° C. or higher, and further preferably 120 ° C. or higher.

  The total amount of residual volatile components contained in the lactone ring-containing polymer is preferably 1,500 ppm or less, more preferably 1,000 ppm or less. If the total amount of residual volatile components exceeds 1,500 ppm, it may be colored due to alteration during molding, foaming, or molding defects such as silver streak.

  The lactone ring-containing polymer has a total light transmittance of 85% or more, more preferably 88% or more, and still more preferably measured by a method based on ASTM-D-1003 for a molded product obtained by injection molding. 90% or more. The total light transmittance is an index of transparency, and if it is less than 85%, the transparency is lowered and it may not be used for the intended purpose.

  The content ratio of the lactone ring-containing polymer contained in the lactone ring-containing resin film is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, and particularly preferably 80 to 100%. % By mass. When the content of the lactone ring-containing polymer contained in the lactone ring-containing resin film is less than 50% by mass, the effects of the present invention may not be sufficiently exhibited.

  The lactone ring-containing resin film may contain a polymer other than the lactone ring-containing polymer (hereinafter sometimes referred to as “other polymer”) as another component. Examples of other polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); halogens such as vinyl chloride, vinylidene chloride, and chlorinated vinyl resins. Acrylic polymers such as polymethyl methacrylate; Styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66 and nylon 610; polyacetals; polycarbonates; polyphenylene oxides; Polyether ether ketone; polysulfones; polyethersulfones; polyoxyethylene benzylidene alkylene; polyamideimide; polybutadiene rubber, rubber-like polymer such as ABS resin or ASA resin containing an acrylic rubber; and the like.

  The content of the other polymer in the lactone ring-containing resin film is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, further preferably 0 to 30% by mass, and particularly preferably 0 to 20% by mass. is there.

  The lactone ring-containing resin film may contain various additives. Examples of additives include hindered phenol-based, phosphorus-based and sulfur-based antioxidants; light-resistant stabilizers, weather-resistant stabilizers, heat stabilizers and other stabilizers; reinforcing materials such as glass fibers and carbon fibers; phenyls UV absorbers such as salicylate, (2,2′-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone; near infrared absorbers; tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide, etc. Flame retardants; Antistatic agents such as anionic, cationic and nonionic surfactants; Colorants such as inorganic pigments, organic pigments and dyes; Organic fillers and inorganic fillers; Resin modifiers; Organic fillers and inorganic fillers Agents, plasticizers, lubricants, antistatic agents, flame retardants, and the like.

  The structure of the ultraviolet absorber added to the lactone ring-containing resin film is not particularly limited, but an ultraviolet absorber having a hydroxyphenyltriazine skeleton as a chromophore is preferable, and among them, the glass transition temperature is 110 ° C. or higher. 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-alkyloxy-2) is highly compatible with other thermoplastic acrylic resins and has excellent absorption characteristics. -Hydroxypropyloxy) -5-α-cumylphenyl] -s-triazine skeleton (alkyloxy; long-chain alkyloxy groups such as octyloxy, nonyloxy, decyloxy, etc.) is more preferred, and is represented by the following formula (4): An ultraviolet absorber containing as a main component an ultraviolet absorber having the structure represented is particularly preferred.

  Examples of other ultraviolet absorbers include benzotriazole derivatives, benzophenone derivatives, benzoxazinone derivatives, triazine derivatives, and the like.

  Specific examples of the benzotriazole derivative include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, and 2- (2-hydroxy- 3,5-dicumylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1, 3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, -Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis [4-cumyl-6-benzotriazolephenyl], 2,2′-p-phenylenebis (1,3-benzoxazin-4-one), 2- [2-hydroxy-3- (3,4,5, 6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 3- [3-methyl- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate / polyethylene glycol 300 Reactive organism, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dode) Syl) -4-methylphenol and the like.

  Specific examples of the benzophenone derivative include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-hydroxy. -4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'- Tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy) -2-methoxyphenyl ) Methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-dihydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Specific examples of the benzoxazinone derivative include 2-p-methoxyphenyl (3,1-benzoxazin-4-one), 2-α-naphthyl (3,1-benzoxazin-4-one), 2 -Β-naphthyl (3,1-benzoxazin-4-one), 2-p-phthalimidophenyl (3,1-benzoxazin-4-one), 2,2'-bis (3,1-benzoxazine- 4-one), 2,2 ′-(1,4-diphenylene) bis (4H-3,1-benzoxazinon-4-one), 2,2 ′-(4,4′-diphenylene) bis (3 , 1-benzoxazin-4-one), 2,2 ′-(2,6 or 1,5-dinaphthalene) bis (3,1-benzoxazin-4-one), 1,3,5-tri ( 3,1-benzoxazin-4-one), among them 2,2 ′-(1,4-diphenylene) bis (4H-3,1-benzoxazinon-4-one) (manufactured by Nippon Cytec Industries, Ltd., products from the viewpoint of its high melting point and absorption characteristics Name: Siasorb UV-3638) is preferred.
As the triazine derivative, specifically, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-iso-octylphenyl) -s-triazine, and the like. Moreover, isooctyl substituted tris resorcinol triazine (for example, trade name “CGL777MPAD” manufactured by Ciba Specialty Chemicals), tert-butyl substituted tris resorcinol triazine, cumyl substituted tris resorcinol triazine and the like can be mentioned. These ultraviolet absorbers may be used alone or in combination of two or more.

  The content of the additive in the lactone ring-containing resin film is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and still more preferably 0 to 0.5% by mass.

  The method for producing the lactone ring-containing resin film is not particularly limited. For example, the lactone ring-containing polymer and other polymers and additives are sufficiently mixed by a conventionally known mixing method. Thus, a resin composition can be prepared and formed into a film. Moreover, it is good also as a stretched film by extending | stretching.

  First, in order to produce a thermoplastic resin composition, for example, the above film raw material is pre-blended with a conventionally known mixer such as an omni mixer, and then the obtained mixture is extrusion kneaded. In this case, the mixer used for extrusion kneading is not particularly limited. For example, a conventionally known mixer such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader can be used. .

  Examples of the film forming method include conventionally known film forming methods such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. Among these film forming methods, the solution casting method (solution casting method) and the melt extrusion method are preferable.

  Solvents used in the solution casting method (solution casting method) include, for example, aromatic hydrocarbons such as benzene, toluene, xylene; methanol, ethanol, isopropanol, butanol, isobutanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc. Alcohols such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; halogenation such as dichloromethane, chloroform and carbon tetrachloride Hydrocarbons; dimethylformamide; dimethyl sulfoxide; and the like. These solvents may be used alone or in combination of two or more.

  Examples of the apparatus for performing the solution casting method (solution casting method) include a drum casting machine, a band casting machine, and a spin coater.

  Examples of the melt extrusion method include a T-die method and an inflation method, and the molding temperature at that time is preferably 150 to 350 ° C., more preferably 200 to 300 ° C.

  When forming a film by the T-die method, a roll-shaped film can be obtained by attaching a T-die to the tip of a known single-screw extruder or twin-screw extruder and winding the film extruded into a film. it can. At this time, it is possible to perform uniaxial stretching by appropriately adjusting the temperature of the winding roll and adding stretching in the extrusion direction. Further, simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed by stretching the film in a direction perpendicular to the extrusion direction.

  The lactone ring-containing resin film may be either an unstretched film or a stretched film. In the case of a stretched film, either a uniaxially stretched film or a biaxially stretched film may be used. In the case of a biaxially stretched film, either a simultaneous biaxially stretched film or a sequential biaxially stretched film may be used. In the case of biaxial stretching, the mechanical strength is improved and the film performance is improved. The thermoplastic resin film containing a lactone ring-containing polymer as a main component can suppress an increase in retardation even when stretched by mixing other thermoplastic resins, and retains optical isotropy. be able to.

  Examples of the stretching method include conventionally known film stretching methods such as a uniaxial stretching method, a sequential biaxial stretching method, and a simultaneous biaxial stretching method.

  The stretching temperature is preferably in the vicinity of the glass transition temperature of a resin composition containing a lactone ring-containing polymer as a main component as a film raw material, specifically, preferably (glass transition temperature-30 ° C.) to (glass Transition temperature + 100 ° C.), more preferably in the range of (glass transition temperature−20 ° C.) to (glass transition temperature + 80 ° C.). If the stretching temperature is less than (glass transition temperature-30 ° C.), a sufficient stretching ratio may not be obtained. On the other hand, when the stretching temperature exceeds (glass transition temperature + 100 ° C.), the resin composition may flow, and stable stretching may not be performed.

  The draw ratio defined by the area ratio is preferably in the range of 1.1 to 25 times, more preferably 1.3 to 10 times. If the draw ratio is less than 1.1 times, the toughness accompanying the drawing may not be improved. On the other hand, when the draw ratio exceeds 25 times, the effect of increasing the draw ratio may not be recognized.

  The stretching speed is unidirectional, preferably 10 to 20,000% / min, more preferably 100 to 10,000% / min. When the stretching speed is less than 10% / min, it takes time to obtain a sufficient stretching ratio, and the production cost may increase. On the other hand, if the stretching speed exceeds 20,000% / min, the stretched film may break.

  In addition, the obtained film can be subjected to a heat treatment (annealing) or the like after the stretching treatment in order to stabilize its optical isotropy and mechanical properties. The conditions for the heat treatment may be appropriately selected similarly to the conditions for the heat treatment performed on a conventionally known stretched film, and are not particularly limited.

  The thickness of the lactone ring-containing resin film is preferably 5 μm to 250 μm, more preferably 10 to 150 μm. Outside this range, problems such as breakage due to changes in process tension or bending in the machining process are less likely to occur, and handling with a hand or machine in the state of each leaf sheet because it has an appropriate bending strength. Problems such as bending sometimes occur, which is not preferable.

  The lactone ring-containing resin film according to the present invention has high transparency, and the visible light transmittance is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.

  The tensile strength measured based on ASTM-D-882-61T of the lactone ring-containing resin film according to the present invention is preferably 10 MPa or more and less than 100 MPa, more preferably 30 MPa or more and less than 100 MPa. If the tensile strength is less than 10 MPa, sufficient mechanical strength may not be exhibited. On the other hand, if the tensile strength exceeds 100 MPa, the workability may decrease.

  The elongation rate measured based on ASTM-D-882-61T of the lactone ring-containing resin film according to the present invention is preferably 1% or more. Although an upper limit is not specifically limited, Usually, 100% or less is preferable. If the elongation is less than 1%, the toughness is insufficient, which is not preferable.

  The lactone ring-containing resin film according to the present invention has a tensile elastic modulus measured based on ASTM-D-882-61T, preferably 0.5 GPa or more, more preferably 1 GPa or more, and further preferably 2 GPa or more. Although an upper limit is not specifically limited, Usually, 20 GPa or less is preferable. If it is less than 0.5 GPa, sufficient mechanical strength may not be obtained.

The lactone ring-containing resin film has a surface wetting tension of preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more. When the surface wetting tension is at least 40 mN / m or more, the adhesion between the lactone ring-containing resin film and the antiglare layer is further improved. In order to adjust the surface wetting tension, for example, corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other conventionally known surface treatments can be performed.
≪Binder and its curing method≫
As the binder for forming the antiglare layer, a resin curable mainly by ultraviolet rays and electron beams, that is, an ionizing radiation curable resin, a mixture of an ionizing radiation curable resin and a thermoplastic resin and a solvent, a thermosetting resin Three types are used.

  The film forming component of the ionizing radiation curable resin composition is preferably one having an acrylate functional group, such as a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, Spiroacetal resin, polybutadiene resin, polythiol polyene resin, oligomers or prepolymers of polyfunctional compounds such as polyhydric alcohols such as (meth) arylate, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, Monofunctional monomers such as methylstyrene and N-vinylpyrrolidone as well as polyfunctional monomers such as polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate Diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. A large amount can be used.

  Furthermore, in order to make the ionizing radiation curable resin composition into an ultraviolet curable resin composition, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethyl Lam monosulfide, thioxanthones, and n-butylamine, triethylamine, poly-n-butylphosphine and the like can be used as a photosensitizer. In particular, in the present invention, it is preferable to mix urethane acrylate as an oligomer and dipentaerythritol hexa (meth) acrylate as a monomer.

  Further, as a binder for forming the antiglare layer, a solvent dry resin may be included in the ionizing radiation curable resin as described above. As the solvent-drying resin, a thermoplastic resin is mainly used. As the type of solvent-drying thermoplastic resin added to the ionizing radiation curable resin, those usually used can be used. Furthermore, there is an advantage of including a solvent dry resin in the ionizing radiation curable resin composition as follows.

  When an ionizing radiation curable resin composition is applied to a transparent substrate film with a roll coater having a metalling roll, the liquid residual resin film on the surface of the metalling roll flows and becomes streaks, unevenness, etc. over time. However, if the ionizing radiation curable resin composition contains a solvent-drying resin as described above, such coating defects on the coated surface will occur. Can be prevented.

  As a curing method for the ionizing radiation curable resin composition as described above, the curing method for the ionizing radiation curable resin composition can be cured by a normal curing method, that is, irradiation with an electron beam or ultraviolet rays.

  An electron beam or the like having KeV energy is used, and in the case of ultraviolet curing, ultraviolet rays emitted from light beams such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.

  The thermoplastic resin mixed with the ionizing radiation curable resin includes phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea. A co-condensation resin, a silicon resin, a polysiloxane resin, or the like is used, and a curing agent such as a crosslinking agent or a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, or the like is added to these resins as necessary.

≪Fine particles≫
As the fine particles to be contained in the antiglare layer, resin beads are preferable, and those having particularly high transparency and a difference in refractive index from the matrix resin (binder) are preferable.

  As resin beads, styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), polycarbonate beads, Polyethylene beads, polyvinyl chloride beads, etc. are used. As described above, the resin beads having a particle diameter of 0.1 to 5 μm are appropriately selected and used. Of the resin beads, styrene beads are particularly preferably used.

  When the fine particles as the organic filler as described above are added, the organic filler easily settles in the resin composition (binder). Therefore, an inorganic filler such as silica may be added to prevent sedimentation. The more inorganic filler is added, the more effective it is to prevent the organic filler from settling, but it adversely affects the transparency of the coating. Therefore, preferably, an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of less than 0.1% by weight so as not to impair the transparency of the coating film with respect to the binder.

  If an inorganic filler that is an anti-settling agent for preventing the settling of the organic filler is not added, the organic filler is precipitated at the bottom when applied to the transparent substrate film. Good.

  Here, in general, the ionizing radiation curable resin has a refractive index of about 1.5, which is about the same as that of glass, but when the refractive index of the resin used is low in comparison with the refractive index of the fine particles, Ti O2 (refractive index; 2.3 to 2.7), Y2 O3 (refractive index; 1.87), La2 O3 (refractive index; 1.95), ZrO2 (refractive), which are fine particles having a high refractive index, are used as a binder. The refractive index can be adjusted by increasing the refractive index in addition to the ratio of 2.05), Al2 O3 (refractive index; 1.63), etc., which can maintain the diffusibility of the coating film.

≪Low refractive index layer≫
The low refractive index layer used in the present invention is made of a silicon-containing vinylidene fluoride copolymer, and specifically, a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. It is a resin composition comprising 100 parts by weight of a fluorine-containing copolymer having a fluorine content ratio of 60 to 70% by weight and 80 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group. It is characterized by. Using this resin composition, a low refractive index layer having a refractive index of less than 1.60 (preferably 1.45 or less), which is a thin film having a thickness of 200 nm or less and is provided with scratch resistance, is formed.

  The fluorine-containing copolymer used for this low refractive index layer is a copolymer obtained by copolymerizing a monomer composition containing vinylidene fluoride and hexafluoropropylene, and each of the monomer compositions The proportion of the component is 30 to 90% by weight of vinylidene fluoride, preferably 40 to 80% by weight, particularly preferably 40 to 70% by weight, and 5 to 50% by weight of hexafluoropropylene, preferably 10 to 50%. % By weight, particularly preferably 15 to 45% by weight. This monomer composition may further contain 0 to 40% by weight, preferably 0 to 35% by weight, particularly preferably 10 to 30% by weight of tetrafluoroethylene.

  In addition, the monomer composition for obtaining this fluorine-containing copolymer has, as long as the object and effect of the present invention are not impaired, other copolymer components, for example, 20% by weight or less, preferably 10% by weight. It may be contained in the following range. Here, specific examples of the other copolymerization component include, for example, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 2-bromo-3,3,3-tri- Fluorine such as fluoroethylene, 3-bromo-3,3-difluoropropylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, α-trifluoromethacrylic acid A polymerizable monomer having an atom can be mentioned.

  The fluorine-containing copolymer obtained from such a monomer composition needs to have a fluorine content of 60 to 70% by weight, and a preferable fluorine content is 62 to 70% by weight, particularly preferably 64 to 70% by weight. 68% by weight.

  This fluorine-containing polymer has good solubility in a solvent described later, particularly when the fluorine content is in the specific range described above. Also, by containing such a fluorine-containing polymer as a component, it has excellent adhesion to various substrates, has high transparency and low refractive index, and has sufficiently excellent mechanical strength. Since the thin film is formed, mechanical properties such as scratch resistance on the surface of the substrate can be made sufficiently high, which is extremely suitable.

  The fluorine-containing copolymer preferably has a molecular weight of 5,000 to 200,000, particularly 10,000 to 100,000 in terms of polystyrene-equivalent number average molecular weight. By using a fluorine-containing copolymer having such a molecular weight, the viscosity of the resulting fluorine-based resin composition becomes a suitable size, and therefore surely has a suitable coating property. It can be.

  Further, the fluorine-containing copolymer preferably has a refractive index of 1.45 or less, particularly 1.42 or less, and further 1.40 or less. When a fluorine-containing copolymer having a refractive index exceeding 1.45 is used, a thin film formed from the obtained fluorine-based paint may have a small antireflection effect.

  The polymerizable compound used in the present invention undergoes addition polymerization by irradiation with an active energy ray in the presence or absence of a photopolymerization initiator, or by heating in the presence of a thermal polymerization initiator. The resulting compound has an ethylenically unsaturated group.

  As specific examples of such a polymerizable compound, for example, those described in JP-A-8-94806 described above can be used.

  Of these compounds, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate are particularly preferable.

  When the polymerizable compound to be used contains three or more ethylenically unsaturated groups in one molecule, the resulting fluororesin composition has particularly good adhesion to the substrate and the surface of the substrate. A thin film having extremely good mechanical properties such as scratch resistance is formed.

  The amount of the polymerizable compound used is 30 to 150 parts by weight, preferably 35 to 100 parts by weight, particularly preferably 40 to 70 parts by weight, based on 100 parts by weight of the fluorine-containing copolymer.

  If the use ratio of this polymerizable compound is too small, the thin film formed by the obtained paint has low adhesion to the substrate, while if the use ratio is excessive, the formed thin film has a refractive index. It becomes difficult to obtain a good antireflection effect.

  In the said fluorine-type resin composition, it is preferable that the fluorine content rate in the total amount of the polymer formation component containing a fluorine-containing copolymer and a polymeric compound is 30 to 55 weight%, especially 35 to 50 weight%. When such conditions are satisfied, a thin film that can more fully achieve the objects and effects of the present invention can be reliably formed. A thin film formed by a fluorine resin composition having an excessive fluorine content tends to have low adhesion to the substrate, and mechanical properties such as scratch resistance on the surface of the substrate are slightly reduced. On the other hand, a thin film formed from a fluorine-based resin composition having an excessive fluorine content ratio has a high refractive index and tends to have a reduced antireflection effect.

  The low refractive index layer of the present invention comprises a silicon-containing vinylidene fluoride polymer, and silicon and fluorine improve the antifouling property and scratch resistance of the surface, and the silicon has a low refractive index after saponification treatment described later. Deterioration of physical properties of the layer can be suppressed.

  In the antiglare film, the low refractive index layer has a fluorine content of 60 to 70 wt% obtained by copolymerization of a monomer composition containing 30 to 90 wt% vinylidene fluoride and 5 to 50 wt% hexafluoropropylene. % Fluorine-containing copolymer and a resin composition comprising 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group, in particular, the fluorine-containing copolymer. Since it contains a monomer component of 5 to 50% by weight of hexafluoropropylene in the low refractive index layer formed by application of this resin composition, a low refractive index of 1.45 or less can be realized, In particular, since the fluorine-containing copolymer contains a monomer component of 80 to 90% by weight of vinylidene fluoride, the resin composition obtained Agent solubility is increased, coating suitability is improved, it is possible to 200nm or less of a thin film suitable for the thickness to prevent reflection. Furthermore, since 30 to 150 parts by weight of the polymerizable compound having an ethylenically unsaturated group is contained in the applied resin composition, the resulting coating film has excellent scratch-resistant mechanical strength. Become. Moreover, since each resin component has high transparency, the low refractive index layer formed using the resin composition containing these components is excellent in transparency.

  In the antiglare film, an air layer (refractive index of 1.0), a low refractive index layer (refractive index of less than 1.60, preferably 1.45 or less), an antiglare layer (refractive) from the air in contact to the inside thereof. Ratio of 1.50 or more) and a transparent base film (lower or substantially the same refractive index as that of the antiglare layer), so that efficient antireflection can be performed. It is desirable that the refractive index of the antiglare layer is higher than the refractive index of the transparent base film, and in such a case, the effect of preventing reflection at the interface between the transparent base film and the antiglare layer Is further added.

  The solvent used for the low refractive index layer has a boiling point in the range of 50 to 200 ° C. under a pressure of 760 hectopascals from the viewpoint of the coating property of the fluororesin composition and the adhesion of the thin film formed to the substrate. The inside is preferable.

  Specific examples of such solvents include, for example, acetone, diethyl ketone, dipropyl ketone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, methyl acetate, Ethyl acetate, propyl acetate, isopropyl acetate. Solvents consisting of ketones or carboxylic acid esters such as butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, sec-amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate Can be mentioned. These solvents may be used singly or as a mixture of two or more components. Further, solvents other than those exemplified above may be added as long as the performance of the resin composition is not impaired.

  The amount of the solvent used is usually 200 to 10,000 parts by weight, preferably 1000 to 10,000 parts by weight, particularly preferably 1200 to 4000 parts by weight with respect to 100 parts by weight of the total amount of the fluorine-containing copolymer and the polymerizable compound. is there.

  By setting the amount of the solvent used within this range, the viscosity of the fluororesin composition can be adjusted to 0.5 to 5 cps (25 ° C.), particularly 0.7 to 3 cps at which preferable coating properties can be obtained as the resin composition. It is easy to make it within the range of (25 ° C.). As a result, the fluorine-based resin composition has a thickness of 100 to 200 nm which is practically suitable as an antireflection film for visible light and has no coating unevenness. A thin film can be easily formed, and a thin film with particularly excellent adhesion to a substrate can be formed.

  The fluorine-based resin composition used in the optical functional film of the present invention is cured by a polymerization reaction of the ethylenically unsaturated group of the contained polymerizable compound. Therefore, the resin composition is coated. Then, the coating film thus formed is subjected to a curing treatment in which the polymerizable compound is polymerized to form a solid thin film.

  As a means for such a curing treatment, a means for irradiating the coating film of the fluororesin composition with active energy rays or a means for heating the coating film is utilized. Since a thin film can be reliably and easily formed, it is extremely advantageous in practice, and is convenient in terms of thin film forming operations.

  When the fluororesin composition used in the optical functional film of the present invention is cured by irradiation with active energy rays, when an electron beam is used as the active energy rays, the fluororesin composition is particularly polymerized. The desired curing process can be performed without adding an initiator.

  In addition, when a light ray such as ultraviolet ray or visible ray is used as the active energy ray for the curing treatment, it is decomposed upon irradiation with the active energy ray to generate, for example, a radical, thereby generating a polymerizable compound. A photopolymerization initiator that initiates the polymerization reaction is added to the fluororesin composition.

  Specific examples of such a photopolymerization initiator are disclosed in the above-mentioned JP-A-8-94806, but 1-hydroxylcyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 Preferred are -morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylrotyl) -1-butanone, and the like.

  Furthermore, when a heating means is used for the curing treatment, a thermal polymerization initiator that generates, for example, radicals to start polymerization of the polymerizable compound by heating is added to the fluororesin composition.

  Specific examples of the thermal polymerization initiator include, for example, benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert- Examples include butyl peroxide, tert-butyl hydroperoxide, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and the like. Can do.

  The addition amount of the photopolymerization initiator or the thermal polymerization initiator in the fluororesin composition is usually 0.5 to 10 parts by weight, preferably 100 parts by weight in total for the fluorine-containing copolymer and the polymerizable compound. Is 1 to 8 parts by weight, particularly preferably 1 to 3 parts by weight. If the amount added exceeds 10 parts by weight, the handling of the resin composition and the mechanical strength of the thin film formed may be adversely affected. On the other hand, if the amount added is less than 0.5 parts by weight, the curing rate is low. It will be a thing.

  The fluororesin composition is made of various additives, for example, amine compounds such as triethanolamine, methyldiethanolamine, triethylamine, diethylamine, and the like as long as the purpose and effects of the present invention are not impaired. Sensitizer or polymerization accelerator; epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene styrene block copolymer, petroleum resin, xylene resin, ketone resin, silicone oligomer Polymers such as polysulfide oligomers or oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-tert-butyl-4-methylphenol; other leveling agents, leakage improvers, surfactants, plasticizers UV absorbers, silane coupling agents, inorganic fillers, may be incorporated resin particles, pigment, dyes and the like.

  In the above description, the antireflection effect of the low refractive index layer has been described. However, the low refractive index layer also has an effect of increasing the black density and increasing the contrast, and the preferred form is the same as described above.

  The method for forming the low refractive index layer may be other general thin film forming means, for example, appropriate means such as a vacuum deposition method, a sputtering method, a reactive sputtering method, an ion plating method, and an electroplating method. For example, it may be formed of a coating film of an antireflection paint other than the above, an ultrathin film such as MgF2 having a film thickness of about 0.1 μm, a metal vapor deposition film, or a vapor deposition film of SiOx or MgF2.

  As described above, when a refractive index binder satisfying the formula (1) is not obtained with respect to the refractive index of the material of the selected low refractive index layer, Adjust the refractive index by adding fine particles such as TiO2 having a high rate.

In addition, the anti-glare film of this invention is not limited to what provided the low refractive index layer, You may make it not provide a low refractive index layer.
≪Others≫
The antiglare film of the present invention may be provided with an adhesive layer and a separator.

  The adhesive layer provided on the side opposite to the antiglare layer of the transparent substrate film is used when the antiglare film is attached to, for example, a liquid crystal panel, and the exposed adhesive layer from which the separator is peeled is used as a liquid crystal panel or the like. An anti-glare film can be attached by pressing on the surface.

  Further, the antiglare film of the present invention comprises a transparent conductive layer between the transparent base film and the antiglare layer, and further comprises a conductive material in the antiglare layer. Antistatic performance can be imparted. This antistatic performance can be imparted to all the antiglare films in the embodiments of the present invention by providing a transparent conductive layer.

  The transparent conductive layer is obtained by dispersing conductive fine particles in a resin composition. Examples of the conductive fine particles include antimony-doped indium tin oxide (hereinafter referred to as ATO) and indium tin oxide (hereinafter referred to as ATO). (ITO), organic compound fine particles surface-treated with gold and / or nickel, etc., as a resin composition, (meth) acrylates of polyfunctional compounds such as alkyd resins and polyhydric alcohols (hereinafter referred to as acrylates and Those containing relatively large amounts of oligomers or prepolymers such as (meth) acrylate) and reactive diluents can be used.

  As the conductive material contained in the antiglare layer, particles that have been surface-treated with gold and / or nickel can be used. The particles before such surface treatment can be selected from the group consisting of silica, carbon black, metal particles and resin particles.

≪Display device≫
Next, an example of an embodiment in which the display device according to the present invention is applied to a liquid crystal display device will be described.

  The liquid crystal display device is a transmissive liquid crystal display device in which a polarizing element, a liquid crystal panel, and a polarizing plate are stacked in this order, and a backlight is disposed on the back side of the polarizing plate. As a polarizing plate, the polarizing plate used with a normal liquid crystal display device can be used.

  Moreover, it can replace with the backlight in the said liquid crystal display device, and can arrange | position a reflecting plate closely_contact | adhering to a polarizing plate.

  Liquid crystal modes used in the liquid crystal panel in the liquid crystal display device include twisted nematic type (TN), super twisted nematic type (STN), guest-host type (GH), phase transition type (PC), and polymer dispersion type. Any of (PDLC) etc. may be sufficient.

  The liquid crystal drive mode may be either a simple matrix type or an active matrix type. In the case of the active matrix type, a driving method such as TFT, MIM, etc. is adopted.

  Further, the liquid crystal panel may be either a color type or a monochrome type.

  Furthermore, the present invention is also applicable to display devices other than liquid crystal display devices, such as plasma display devices and CRT display devices.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.

≪Evaluation method≫
<Particle size of particles>
Measurement was performed using a Coulter Multisizer (manufactured by Beckman Coulter).

<Refractive index of particles>
After weighing 0.5 g of particles into a 100 cc flask and adding 40 g of carbon disulfide, the mixture was sufficiently stirred at room temperature with a magnetic stirrer to prepare a mixed solution. When ethanol is added dropwise to the mixed solution with a pipette, the initially cloudy liquid gradually becomes transparent. The point judged to be transparent by visual inspection is defined as the end point. A mixed solvent corresponding to the weight ratio of carbon disulfide and ethanol in the particle dispersion at the end point was separately prepared, and the refractive index of the mixed solvent was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.). Is the refractive index of the particles.

<Internal haze>
The internal haze is measured by applying silicone oil to both sides of the film and then sandwiching both sides of the film with a glass plate to eliminate the influence of the outside of the film (external haze), in accordance with JIS K7105. (Nippon Denshoku Industries Co., Ltd., NDH2000) was used for measurement.

<Surface haze>
As the surface haze, a value obtained by subtracting the internal haze value from the total haze value measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7105 was used.

<Reflectance>
The reflectance was measured with a spectral reflectance measuring machine MPC-3100 manufactured by Shimadzu Corporation, and an average reflectance at a wavelength of 380 to 780 nm was taken.

<Glare on the surface>
Surface glare is evaluated by installing a houndstooth color filter (pitch: 150 μm) on the backlight (light box 5700, Hakuba Photo Industry Co., Ltd.), and at a position 160 μm away from the color filter surface. The glare film-treated surface was attached facing upward, and the glare state of the surface was visually evaluated.

<Reflection>
An insulating vinyl tape (manufactured by Yamato, width 37.5 mm) was bonded to the back surface of the antiglare film, and an exposed fluorescent lamp (10000 cd / m ² ) was projected from a distance of 2 m, and evaluation was made based on the degree of blur of the reflected image.
Evaluation criteria ○: The outline of the fluorescent lamp is not known ×: The fluorescent lamp is hardly blurred and the outline looks very clear.

<Black density>
The black density was evaluated by applying a black insulating vinyl tape (manufactured by Yamato, width 37.5 mm) to the back of the antiglare film as a test piece, and observing the film surface under a fluorescent lamp. Furthermore, this test piece was measured with Macbeth RD914 made from Kollmorgen Instruments Corporation. Similarly, a lactone ring-containing resin film having a black insulating vinyl tape pasted on the back surface is measured, and this value is taken as a reference, that is, a black density of 100%, whereas a test piece having a measured value of 85% or more is considered good. did.

<Contact angle>
The contact angle was measured with pure water using a solid-liquid interface analysis system (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.).

<Abrasion resistance> (Steel wool resistance)
Using a Suga Test Instruments Co., Ltd., Gakushin Type Abrasion Resistance Tester, the degree of damage after visually reciprocating # 0000 steel wool 20 times with a load of 200 g / cm ₂ was evaluated visually.
Evaluation criteria ○: When no scratches are observed ×: When scratches are observed or when many particles fall off <Surface resistivity>
In accordance with JIS K6911, the measurement was performed using a digital insulation meter (DSM8104, manufactured by Toa DKK Corporation).

<Solvent resistance>
The antiglare film (70 mm × 70 mm) was immersed in methanol for 10 minutes, and then the film taken out was evaluated visually.
Evaluation criteria ○: Not dissolved at all ×: Completely or partially dissolved <Pencil hardness>
A pencil scratch test was performed in accordance with JIS K5600-5-4, and the scratch was evaluated.
<Film surface potential>
Under an environment of 23 ° C. and 50% RH, the anti-glare films were rubbed together 10 times and measured using a surface potentiometer (FMX-003, manufactured by SIMCO).
Evaluation criteria ○: Less than 3 kV Δ: 3 kV or more, 5 kV or less ×: More than 5 kV << Preparation of Lactone Ring-Containing Resin Film >>
Next, production examples of the lactone ring-containing resin film will be described.

  First, an evaluation method of a lactone ring-containing resin (hereinafter sometimes referred to as “lactone ring-containing polymer”) will be described.

<Polymerization reaction rate, polymer composition analysis>
For the reaction rate during the polymerization reaction and the content of the specific monomer unit in the polymer, the amount of unreacted monomer in the obtained polymerization reaction mixture was measured using a gas chromatograph (GC17A, manufactured by Shimadzu Corporation). It was obtained by measuring using.

<Dynamic TG>
The polymer (or polymer solution or pellet) is once dissolved or diluted in tetrahydrofuran, poured into excess hexane or methanol for reprecipitation, and the taken out precipitate is vacuum dried (1 mmHg (1.33 hPa), 80 ° C. Volatile components and the like were removed by conducting the reaction for 3 hours or more, and the obtained white solid resin was analyzed by the following method (dynamic TG method).
Measuring apparatus: differential type differential thermal balance (Thermo Plus2 TG-8120 Dynamic TG, manufactured by Rigaku Corporation)
Measurement conditions: Sample amount 5 to 10 mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 100 mL / min
Method: Step-like isothermal control method (controlled to a mass reduction rate of 0.005% / sec or less in the range from 60 ° C to 500 ° C)
<Containing ratio of lactone ring structure>
First, based on the amount of mass reduction that occurs when all hydroxyl groups are dealcoholated as methanol from the obtained polymer composition, 300 before the start of decomposition of the polymer from 150 ° C. before the mass reduction starts in dynamic TG measurement. The dealcoholization reaction rate was determined from the mass reduction due to the dealcoholization reaction up to ° C.

That is, in the dynamic TG measurement of the polymer having a lactone ring structure, the mass reduction rate between 150 ° C. and 300 ° C. is measured, and the obtained actual measurement value is defined as the actual mass reduction rate (X). On the other hand, from the composition of the polymer, the mass loss rate when assuming that all the hydroxyl groups contained in the polymer composition become alcohols and dealcoholized because they are involved in the formation of lactone rings (that is, 100% on the composition) The mass reduction rate calculated assuming that the dealcoholization reaction has occurred is defined as the theoretical mass reduction rate (Y). The theoretical mass reduction rate (Y) is more specifically the molar ratio of raw material monomers having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material single amount in the polymer composition. It can be calculated from the body content. These values are calculated for the dealcoholization:
1- (actual mass reduction rate (X) / theoretical mass reduction rate (Y))
Substituting for, the value is obtained and expressed in percentage (%), the dealcoholization reaction rate is obtained.

  As an example, the content ratio of the lactone ring structure is calculated in the pellet obtained in Production Example 1 described later. When the theoretical mass reduction rate (Y) of this polymer is obtained, the molecular weight of methanol is 32, the molecular weight of methyl 2- (hydroxymethyl) acrylate is 116, and 2- (hydroxymethyl) in the polymer is ) Since the content (mass ratio) of methyl acrylate is 20.0 mass% in terms of composition, (32/116) × 20.0≈5.52 mass%. On the other hand, the actual mass reduction rate (X) by dynamic TG measurement was 0.34% by mass. When these values are applied to the above-described dealcoholization calculation formula, 1− (0.34 / 5.52) ≈0.938 is obtained, and the dealcoholization reaction rate is 93.8%.

  And the content (mass ratio) in the said copolymer composition of the raw material monomer which has the structure (hydroxyl group) concerned in lactone cyclization as what the predetermined lactone cyclization was performed by this dealcoholization reaction rate The content rate of the lactone ring structure in the copolymer can be calculated by multiplying the reaction rate by the dealcoholization reaction rate and converting it to the content rate (mass ratio) of the lactone ring structure. In the case of the production example described later, 2- (hydroxymethyl) methyl acrylate has a content of 20.0% by mass in the copolymer, a calculated dealcoholization reaction rate of 93.8%, and a molecular weight of 116- ( Since the formula amount of the lactone ring structure produced when hydroxymethyl) methyl acrylate is condensed with methyl methacrylate is 170, the content of the lactone ring structure in the copolymer is 27.5 (20.0 × 0.938 × 170/116) mass%.

<Weight average molecular weight, number average molecular weight>
The weight average molecular weight and number average molecular weight of the polymer were determined in terms of polystyrene using a gel permeation chromatograph (GPC system, manufactured by Tosoh Corporation).

<Thermal analysis of polymer>
The thermal analysis of the polymer was performed using a differential scanning calorimeter (DSC-8230, manufactured by Rigaku Corporation) under the conditions of about 10 mg of sample, a heating rate of 10 ° C./min, and a nitrogen flow of 50 mL / min. In addition, the glass transition temperature (Tg) was calculated | required by the midpoint method based on ASTM-D-3418.

<< Production Example 1 >> (Production Example of Lactone Ring-Containing Resin Film (F-1))
First, in a reaction vessel having a capacity of 30 L equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen gas introduction pipe, 8 kg of methyl methacrylate, 2 kg of methyl 2- (hydroxymethyl) acrylate, 10 kg of methyl isobutyl ketone, n-dodecyl mercaptan 5 g was charged.

  While introducing nitrogen gas into the reaction vessel, the temperature was raised to 105 ° C. and refluxed. As a polymerization initiator, 5 g of t-butyl peroxyisopropyl carbonate (Kaya-Carbon BIC-75, manufactured by Kayaku Akzo Co., Ltd.) was added. At the same time as the addition, a solution prepared by dissolving 10 g of t-butylperoxyisopropyl carbonate (Kaya-Carbon BIC-75, manufactured by Kayaku Akzo Co., Ltd.) in 230 g of methyl isobutyl ketone was added dropwise over a period of 2 hours. Solution polymerization was performed at 120 ° C., and further aging was performed for 4 hours.

  To the obtained polymer solution, 30 g of stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added and cyclized at about 90 to 120 ° C. for 5 hours under reflux. A condensation reaction was performed. Subsequently, the obtained polymer solution was a vent type screw twin screw extruder having a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, and a forevent number of 4. (Φ = 29.75 mm, L / D = 30), introduced at a processing rate of 2.0 kg / h in terms of resin amount, and further subjected to cyclization condensation reaction and devolatilization in this extruder and extruded. A transparent pellet of the lactone ring-containing polymer was obtained.

  The obtained lactone ring-containing polymer was measured for dynamic TG, and a mass loss of 0.34% by mass was detected. The lactone ring-containing polymer had a weight average molecular weight of 144,000 and a glass transition temperature of 131 ° C.

The lactone ring-containing polymer pellets were melt-extruded from a coat hanger type T die having a width of 150 mm using a twin-screw extruder having a 20 mmφ screw to obtain a lactone ring-containing resin film (F-1) having a thickness of about 100 μm. ) Was prepared.
≪Production Example 2≫
(Production Example of Lactone Ring-Containing Resin Film (F-2) Provided with UV Absorption Capability)
1. In a 30 L reaction kettle equipped with a stirrer, temperature sensor, cooling pipe and nitrogen introduction pipe, 41.5 parts of methyl methacrylate (MMA), 6 parts of methyl 2- (hydroxymethyl) acrylate (MHMA), 5 parts 2- [2′-hydroxy-5′-methacryloyloxy] ethylphenyl] -2H-benzotriazole (Otsuka Chemical Co., Ltd., trade name: RUVA-93), 50 parts toluene, 0.025 part Adeka Stub 2112 (manufactured by Asahi Denka Kogyo Co., Ltd.), 0.025 part of n-dodecyl mercaptan was charged, and the temperature was raised to 105 ° C. while refluxing nitrogen. At the same time as t-amyl peroxy isononanoate (manufactured by Atofina Yoshitomi Corp., trade name: lupazole 570) was added, 0.10 parts of t-amyl peroxy Dropwise over 3 hours Sononanoeto perform solution polymerization under reflux (about devices 105 through 110 ° C.), the mixture was aged over an additional 4 hours.

  To the obtained polymer solution, 0.05 part of 2-ethylhexyl phosphate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: Phoslex A-8) was added and refluxed (about 90 to 110 ° C.) for 2 hours. A cyclization condensation reaction was performed. Subsequently, a heat treatment was carried out at 240 ° C. for 30 minutes by an autoclave to complete the cyclization condensation reaction.

  Subsequently, the polymer solution obtained by the cyclization condensation reaction was prepared by adding a barrel temperature of 240 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, and a forevent number of 4 (upstream). From the side, referred to as the first, second, third and fourth vents) vent type screw twin screw extruder (φ = 29.75 mm, L / D = 30) It was introduced at a treatment rate and devolatilized. At that time, separately prepared antioxidant / deactivator mixed solution was injected at a charging rate of 0.03 kg / hour using a high-pressure pump after the first vent. Moreover, it inject | poured with the injection | throwing-in speed | rate of 0.05 kg / hour of the ultraviolet absorber solution prepared separately after the 2nd vent. Further, after the third vent, ion exchange water was injected at a charging rate of 0.01 kg / hour using a high pressure pump. The antioxidant / deactivator mixed solution is 50 parts of Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.) and 35 parts of zinc octylate (3.6% Nikka octix zinc manufactured by Nippon Chemical Industry Co., Ltd.) in 200 parts of toluene. It is dissolved. The UV absorber solution is made by CGL777MPA (Ciba Specialty Chemicals Co., Ltd.) which has a hydroxyphenyl triazine skeleton with a UV absorber having a molecular weight of 954 as a main component (a mixture of UV absorbers having molecular weights of 771, 954 and 1138). Ingredient 80%) 19 parts dissolved in 31 parts toluene.

  By the devolatilization operation, a transparent thermoplastic resin composition pellet having a UV-absorbing monomer unit was obtained. The weight average molecular weight in terms of standard polystyrene of the resin part by GPC was 145000, and the glass transition temperature was 122 ° C.

  Using the above resin, extrusion was performed under the following conditions using a single screw extruder having a cylinder diameter of 20 mm at an extrusion temperature of 270 ° C. to obtain a lactone ring-containing resin film (F-2) having a thickness of 100 μm. (T-die: temperature 270 ° C., width 120 mm, film formation: two rolls with gloss, roll temperature 110 ° C., take-off speed: 2.5 m / min).

≪Synthesis of silica particles and resin particles≫
<Synthesis Example 1>
(Synthetic condenser tube of polymer seed particle (K-1), thermometer, and four-necked flask equipped with a dripping port were charged with 90 g of ion exchange water, 10 g of styrene, 0.5 g of n-decyl mercaptan, and 0.1 g of NaCl. Nitrogen gas was introduced for 1 hour to replace the nitrogen in the reaction vessel, and then the temperature of the reaction solution was raised to 70 ° C., and a solution obtained by dissolving 0.1 g of potassium persulfate in a small amount of ion-exchanged water was used as a syringe. And the reaction was carried out for 24 hours at 70 ° C. After completion of the reaction, the obtained emulsion was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and then with methanol to obtain a polymer seed. Particles (K-1) were obtained.
The obtained polymer seed particles (K-1) had a particle size of 0.7 μm and a coefficient of variation of 3.0%.

(Synthesis of acrylic resin particles (S-1))
Polymer seed particles (K-1) 0.5 g, ion-exchanged water 50 g, and sodium lauryl sulfate 0.05 g are added to a four-necked flask equipped with a condenser, a thermometer, and a dripping port, and uniformly dispersed. 20 g of a 3% by weight aqueous solution of alcohol was added to prepare a polymer seed particle dispersion. Next, a solution in which 0.25 g of styrene, 0.03 g of ethylene glycol dimethacrylate, and 0.01 g of benzoyl peroxide are added to a solution in which 0.1 g of sodium lauryl sulfate is dissolved in 50 g of ion-exchanged water as an emulsifier is added. An emulsion was prepared, and the obtained monomer emulsion was added to the polymer seed particle dispersion, followed by further stirring. Next, nitrogen gas was introduced into the reaction vessel, and the reaction solution was heated to 70 ° C. in a nitrogen atmosphere and held at 70 ° C. for 24 hours to perform radical polymerization of the monomer. After radical polymerization, the obtained emulsion was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and then with methanol, and further vacuum-dried at 80 ° C. for 12 hours to obtain acrylic resin particles (S-1). Got.
The acrylic resin particles (S-1) had a particle size of 1.3 μm, a coefficient of variation of 3.8%, and a refractive index of 1.60.
<Synthesis Example 2>
(Synthesis of silica particles (S-2))
A glass reactor with an internal volume of 10 liters equipped with a stirrer was charged with 1600 cc of methanol, 600 cc of aqueous ammonia (25% by weight), 10 cc of 5N-NaOH aqueous solution and 2 g of actinol F-3 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) as a surfactant. Mix well. Moreover, the raw material liquid which melt | dissolved the tetraethyl silicate (made by Colcoat Chemical Co., Ltd.) in the ratio of 208g with respect to 1 liter of methanol was prepared. Next, while keeping the temperature of the reaction medium at 20 ° C., the raw material liquid was dropped at a rate of 1.0 g / min, and after adding a total of 640 g of tetraethyl silicate raw material liquid, the reaction was stopped, The silica particles were allowed to settle and the supernatant liquid was separated. Further, redispersion-decantation treatment was performed in methanol, and methanol was removed by an evaporator to obtain silica particles (S-2). The obtained silica particles (S-2) had a particle size of 1.0 μm, a coefficient of variation of 2.1%, and a refractive index of 1.46.

≪Preparation of antiglare layer forming coating composition≫
<Preparation Example 1>
It consists of 3.64 g of pentaerythritol triacrylate, 0.4 g of resin particles (S-1), Irgacure 651 (manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 0.11 g, toluene, n-butyl acetate and isobutyl alcohol. 7.21 g of the mixed solvent was sufficiently mixed to obtain a coating composition for forming an antiglare layer (CH-1).

<Preparation Example 2>
Mixed solvent 4 consisting of 2.27 g of pentaerythritol triacrylate, 0.2 g of resin particles (S-1), Irgacure 651 (manufactured by Ciba Specialty Chemicals; photopolymerization initiator), 0.06 g of toluene and n-butyl acetate .38 g was sufficiently mixed to obtain a coating composition for forming an antiglare layer (CH-2).

<Preparation Example 3>
3.64 g of pentaerythritol triacrylate, 0.4 g of resin particles (S-1), 2.0 g of conductive fine particles (CX-S204IP; manufactured by Nissan Chemical Co., Ltd.), Irgacure 651 (manufactured by Ciba Specialty Chemicals); light Polymerization initiator) 0.11 g and 5.21 g of a mixed solvent composed of toluene, n-butyl acetate and isopropyl alcohol were sufficiently mixed to obtain a coating composition (CH-3) for forming an antiglare layer.

<Preparation Example 4>
Silicon-containing vinylidene fluoride 2 g, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 0.86 g, Irgacure 651 (Ciba Specialty Chemicals, Inc .; photopolymerization initiator) ) 0.01 g and methyl isobutyl ketone 140.14 g were mixed to obtain a coating composition (CL-1) for forming a low refractive index layer.

<Preparation Example 5>
2 g of silicon-containing vinylidene fluoride, 2 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), Irgacure 651 (manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 0 0.02 g and 196 g of methyl isobutyl ketone were mixed to obtain a coating composition for forming a low refractive index layer (CL-2).

<Comparison adjustment example 1>
Mixed solvent 4 consisting of 2.27 g of pentaerythritol triacrylate, 0.2 g of silica particles (S-2), Irgacure 651 (manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 0.06 g, toluene and n-butyl acetate .38 g was sufficiently mixed to obtain a coating composition for forming an antiglare layer (CHR-1).

<Comparison adjustment example 2>
It consists of 14.10 g of pentaerythritol triacrylate, 0.4 g of resin particles (S-1), Irgacure 651 (manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 0.399 g, toluene, n-butyl acetate and isobutyl alcohol. 36.8 g of the mixed solvent was sufficiently mixed to obtain a coating composition for forming an antiglare layer (CHR-2).

<Comparison adjustment example 3>
It consists of 10.6 g of pentaerythritol triacrylate, 0.4 g of resin particles (S-1), Irgacure 651 (manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 0.11 g, toluene, n-butyl acetate and isobutyl alcohol. 20 g of the mixed solvent was sufficiently mixed to obtain a coating composition for forming an antiglare layer (CHR-3).

<Comparison adjustment example 4>
3.64 g of pentaerythritol triacrylate, 0.4 g of resin particles (S-1), Irgacure 651 (manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 0.11 g, 7.21 g of a mixed solvent composed of ethyl acetate and cyclohexanone Were sufficiently mixed to obtain a coating composition for forming an antiglare layer (CHR-4).

<Comparison adjustment example 5>
3.64 g of pentaerythritol triacrylate, 0.4 g of resin particles (S-1), Irgacure 651 (manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 0.11 g, and 7.21 g of methyl isobutyl ketone are sufficiently mixed. A coating composition for forming an antiglare layer (CHR-5) was obtained.

<< Evaluation of anti-glare film >>
<Example 1>
On the lactone ring-containing resin film (F-1), the antiglare layer-forming coating composition (CH-1) was applied so that the film thickness after curing was 4 μm, and dried at 60 ° C. for 1 minute. Then, the lactone ring containing resin film which has a glare-proof layer was obtained by irradiating the ultraviolet-ray of 90 mJ / cm < ² > of integrated light quantity, and making it semi-harden.

Next, the coating composition for forming a low refractive index layer (CL-1) obtained in Preparation Example 4 is applied onto the obtained antiglare layer so that the film thickness after curing is 0.1 μm. Then, after drying at 80 ° C. for 1 minute, an antiglare film (A-1) is obtained by irradiating an ultraviolet ray with an accumulated light amount of 500 mJ / cm ² under a nitrogen purge and completely curing together with the antiglare layer. It was.

  About the obtained anti-glare film (A-3), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 2.

<Example 2>
On the lactone ring-containing resin film (F-2), the antiglare layer-forming coating composition (CH-2) was applied so that the film thickness after curing was 4 μm, and dried at 60 ° C. for 1 minute. Then, the lactone ring containing resin film which has a glare-proof layer was obtained by irradiating the ultraviolet-ray of 90 mJ / cm < ² > of integrated light quantity, and making it semi-harden.

Next, on the obtained anti-glare layer, the low refractive index layer-forming coating composition (CL-2) obtained in Preparation Example 5 was applied so that the film thickness after curing was 0.1 μm. Then, after drying at 80 ° C. for 1 minute, an antiglare film (A-2) is obtained by irradiating with an ultraviolet ray with an integrated light quantity of 500 mJ / cm ² under a nitrogen purge and completely curing together with the antiglare layer. It was.

  About the obtained anti-glare film (A-3), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 2.

<Example 3>
First, the lactone ring containing resin film in which the anti-glare layer was formed similarly to Example 1 was obtained.

Next, saponification treatment was performed on the obtained lactone ring-containing resin film on which the antiglare layer was formed, and then SiO ₂ was applied under conditions of a vacuum degree of 4 × 10 ⁻⁵ Torr, a voltage of 8 kV, and a current of 20 to 40 mA. A low refractive index layer made of a SiO ₂ film having a thickness of 0.1 μm was formed on the antiglare layer by vacuum deposition.

  Furthermore, a solution obtained by dissolving 0.07 g of KP-801M (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) in 9.93 g of a fluorine-based solvent PF5080 (trade name; manufactured by Sumitomo 3M Limited) on the low refractive index layer Was applied so that the film thickness after drying was about 5 nm, and dried at 80 ° C. for 1 minute to obtain an antiglare film (A-3) having an antifouling layer formed thereon.

  About the obtained anti-glare film (A-3), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 2.

<Example 4>
On the lactone ring-containing resin film (F-1), the antiglare layer-forming coating composition (CH-1) was applied so that the film thickness after curing was 4 μm, and dried at 60 ° C. for 1 minute. Then, the anti-glare film (A-4) was obtained by irradiating and hardening | curing the ultraviolet-ray of the integrated light quantity 500mJ / cm < ² > under nitrogen purge.

  About the obtained anti-glare film (A-4), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film A surface potential was performed. The results are shown in Table 2.

<Example 5>
An antiglare film (Example 4) was prepared in the same manner as in Example 4 except that the antiglare layer-forming coating composition (CH-1) was changed to an antiglare layer-forming coating composition (CH-2). A-5) was obtained.

  About the obtained anti-glare film (A-5), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film A surface potential was performed. The results are shown in Table 2.

<Example 6>
On the lactone ring-containing resin film (F-1), the antiglare layer-forming coating composition (CH-1) was applied so that the film thickness after curing was 4 μm, and dried at 60 ° C. for 1 minute. Thereafter, an antiglare layer was produced on the lactone ring-containing resin film by irradiating and curing ultraviolet rays with an integrated light amount of 500 mJ / cm ² under a nitrogen purge.

  Next, the lactone ring-containing resin film on which the obtained antiglare layer was formed was subjected to saponification treatment, and then 0.07 g of KP-801M (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a fluorinated solvent. A solution dissolved in 9.93 g of PF5080 (trade name; manufactured by Sumitomo 3M Limited) was applied so that the film thickness after drying was about 5 nm, and dried at 80 ° C. for 1 minute to form an antifouling layer. The formed anti-glare film (A-6) was obtained.

  About the obtained anti-glare film (A-5), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film A surface potential was performed. The results are shown in Table 2.

<Example 7>
On the lactone ring-containing resin film (F-1), as a material for forming a transparent conductive layer, ATO-containing conductive ink (DA-12, manufactured by Sumitomo Osaka Cement Co., Ltd.) was applied to a film thickness of 2 μm. After drying at ° C. for 1 minute, the film was semi-cured by irradiating with an ultraviolet ray with an integrated light amount of 50 mJ / m ² under a nitrogen purge to obtain a lactone ring-containing resin film having a transparent conductive layer.

Next, the coating composition for forming an antiglare layer (CH-3) was applied on the obtained transparent conductive layer so that the film thickness after curing was 4 μm, and dried at 60 ° C. for 1 minute. A lactone ring-containing resin film having a laminated film of a transparent conductive layer and an antiglare layer was obtained by irradiating and semi-curing ultraviolet rays with an integrated light quantity of 90 mJ / cm ² under nitrogen purge.

Furthermore, on the obtained anti-glare layer, the coating composition for forming a low refractive index layer (CL-1) was applied so that the film thickness after curing was 0.1 μm, and dried at 80 ° C. for 1 minute. Then, an anti-glare film (A-7) was obtained by irradiating ultraviolet rays with an integrated light amount of 500 mJ / cm ² under a nitrogen purge and completely curing together with the transparent conductive layer and the anti-glare layer.

  About the obtained anti-glare film (A-7), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film The surface potential was measured. The results are shown in Table 2.

<Comparative Example 1>
An antiglare film (RA) was prepared in the same manner as in Example 2 except that the antiglare layer-forming coating composition (CH-2) in Example 2 was changed to an antiglare layer-forming coating composition (CHR-1). -1) was obtained.

  About the obtained anti-glare film (RA-1), internal haze, surface haze, reflectance, surface glare, reflection, black density, measurement of contact angle, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 2.

<Comparative Example 2>
An antiglare film (RA) was prepared in the same manner as in Example 1, except that the antiglare layer-forming coating composition (CH-1) in Example 1 was changed to an antiglare layer-forming coating composition (CHR-2). -2) was obtained.

  About the obtained anti-glare film (RA-2), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 2.

<Comparative Example 3>
On the lactone ring-containing resin film (F-1), the antiglare layer-forming coating composition (CHR-3) was applied so that the film thickness after curing was 4 μm, and dried at 60 ° C. for 1 minute. Then, as a shaping film, Diafoil E-130 (Mitsubishi Chemical Polyester Film Co., Ltd .; thickness 26 μm) is laminated, and the antiglare layer is semi-cured by irradiating with an integrated light amount of 150 mJ / cm ^2. It was. Next, the lactone ring containing resin film which has the glare-proof layer which formed the fine unevenness | corrugation was obtained by peeling the said shaping | molding film.

  Next, the coating composition for forming a low refractive index layer (CL-1) obtained in Preparation Example 4 is applied onto the obtained antiglare layer so that the film thickness after curing is 0.1 μm. Then, after drying at 80 ° C. for 1 minute, an antiglare film (RA-3) was obtained by irradiating with an ultraviolet ray having an accumulated light amount of 500 mJ / cm 2 under a nitrogen purge and completely curing together with the antiglare layer. .

  About the obtained anti-glare film (RA-3), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 2.

<Comparative Examples 4-5>
The same procedure as in Example 1 was conducted except that the antiglare layer-forming coating composition (CH-1) in Example 1 was changed to the antiglare layer-forming coating compositions (CHR-4) to (CHR-5). The anti-glare films (RA-4) to (RA-5) were obtained.

  About the obtained anti-glare films (RA-4) to (RA-5), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance Evaluation was made by test, pencil hardness and film surface potential. The results are shown in Table 2.

<Comparative Examples 6 to 10>
The same procedure as in Example 4 was conducted except that the antiglare layer-forming coating composition (CH-1) in Example 4 was changed to antiglare layer-forming coating compositions (CHR-1) to (CHR-5). Antiglare films (RA-6) to (RA-10) were obtained.

  About the obtained anti-glare films (RA-6) to (RA-10), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance Tests, pencil hardness and film surface potential were performed. The results are shown in Table 2.

<Comparative Example 11>
First, the lactone ring containing resin film in which the anti-glare layer was formed similarly to Example 2 was obtained.

Next, on the obtained antiglare layer, a fluorine-based low refractive index polymer not containing silicon (TM005, manufactured by JSR Corporation) is applied so that the film thickness after curing is 0.1 μm, After drying at 80 ° C. for 1 minute, an antiglare film (RA-11) was obtained by irradiating with an ultraviolet ray having an accumulated light amount of 500 mJ / cm ² under a nitrogen purge and completely curing together with the antiglare layer.

About the obtained anti-glare film (RA-11), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 2.
<Comparative Example 12>
An antiglare film (RA-12) was prepared in the same manner as in Example 1 except that a triacetylcellulose film (TD-80U, manufactured by Fuji Film Co., Ltd.) was used instead of the lactone ring-containing resin film (F-1). Obtained.
About the obtained anti-glare film (RA-12), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 3.
<Comparative Example 13>
An antiglare film (RA-13) was obtained in the same manner as in Example 1 except that a cycloolefin polymer film (Zeonor ZF14, manufactured by Nippon Zeon Co., Ltd.) was used instead of the lactone ring-containing resin film (F-1). It was.
About the obtained anti-glare film (RA-13), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement, weather resistance test, solvent resistance test, pencil hardness and film Evaluation by surface potential was performed. The results are shown in Table 3.
<Comparative Example 14>
An antiglare film (RA-14) was obtained in the same manner as in Example 1 except that a PET film (HBPF8W, manufactured by Teijin DuPont) was used instead of the lactone ring-containing resin film (F-1).
About the obtained anti-glare film (RA-14), internal haze, surface haze, reflectance, surface glare, reflection, black density, contact angle measurement and scratch resistance test, saponification test, weather resistance test, Evaluation was made by a solvent resistance test, pencil hardness, and film surface potential. The results are shown in Table 3.

  The anti-glare film of the present invention has excellent anti-glare properties, scintillation prevention properties, image sharpness, weather resistance, surface hardness, workability and safety during film production and processing even when used in high-definition displays. All of them are higher than conventional ones and can fully exhibit the characteristics according to various optical applications. For example, flat panel displays such as liquid crystal display devices, plasma displays, and organic EL display devices have anti-glare properties and light diffusion. It is suitable for optical applications that impart properties.

Claims (12)

An anti-glare film comprising an anti-glare layer formed on a transparent substrate film, wherein the transparent substrate film has a lactone ring structure represented by the following general formula (1) A lactone ring-containing resin film, wherein the antiglare layer is composed of a binder containing fine particles having different refractive indexes, the surface haze value Hs of the surface irregularities of the antiglare layer is 7 <Hs <30, An anti-glare film characterized in that an internal haze value Hi due to internal diffusion is 1 <Hi <15.

[Wherein, R ¹ , R ² and R ³ independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms; the organic residue may contain an oxygen atom] 2. The antiglare film according to claim 1, wherein a low refractive index layer having a refractive index lower than that of the antiglare layer is further laminated on the antiglare layer. 3. The antiglare film according to claim 1, wherein the low refractive index layer is formed from a silicon-containing vinylidene fluoride copolymer. 4. The fluorine-containing copolymer according to claim 3, wherein the silicon-containing vinylidene fluoride copolymer is a copolymer of vinylidene fluoride and hexafluoropropylene, wherein the fluorine-containing ratio is 60 to 70% by weight, and ethylene An antiglare film, which is a polymer with a polymerizable compound having a polymerizable unsaturated group. In Claim 4, the said low-refractive-index layer irradiates or heats an active energy ray after apply | coating the coating film comprised from the polymeric compound which has the said fluorine-containing copolymer and the said ethylenically unsaturated group at least. An anti-glare film characterized by being formed. 6. The antiglare film according to claim 2, wherein the low refractive index layer is formed from a silicon oxide film, and an antifouling layer is further formed thereon. The sum of the haze value Hs in the surface irregularities of the antiglare layer and the internal haze value Hi due to internal diffusion of the antiglare layer is 30 or less according to any one of claims 1 to 5. Antiglare film. The refractive index difference Δn between the binder and the fine particles in the antiglare layer is 0.01 ≦ Δn ≦ 0.5, and the average particle size d of the fine particles is 0.00. 1. An antiglare film characterized in that 1 μm ≦ d ≦ 5 μm. The antiglare film according to any one of claims 1 to 7, wherein the binder is at least one of a thermosetting resin and an ionizing radiation curable resin, and the fine particles are organic fine particles. 10. The antiglare film according to claim 9, wherein the organic fine particles are styrene beads. 11. The antiglare according to claim 1, wherein the antiglare layer has a transparent conductive layer between the transparent base film and the antiglare layer, and a conductive material is contained in the antiglare layer. the film. 12. A display panel having a plurality of pixels, each of which transmits or reflects light and forms an image, and the prevention of any of claims 1 to 11 provided on the display surface side of the display panel. A dazzling film.