JP2009175387A - Antiglare laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare film that achieves excellent antiglare property, high definition, a high haze, and a low glossiness, as well as has high yield and 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. By controlling a surface structure of the antiglare layer and adjusting the amount of particles in a coating composition for the antiglare layer, the obtained antiglare film achieves excellent antiglare property, high definition, a high haze and a low glossiness, has a high yield, 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.
As the film used on the surface of the display, because it is located on the outermost surface of the display, it can be directly touched by hands, wiped with various chemicals including synthetic detergents, or exposed to sunlight, Specific coding is applied to the base film in order to impart scratch resistance, chemical resistance, weather resistance and the like. Furthermore, in order to make the screen displayed on the display easy to see, various processings and processes as described below are performed in order to satisfy other required performances including anti-glare properties. For example, as disclosed in Patent Document 1, it is known to provide an antiglare effect by forming an uneven shape on the surface or mixing a matting agent in a hard coat. In these methods, the 60 degree glossiness can be lowered by increasing the haze degree, but conversely, in this method, the total light transmittance and the screen resolution may be lowered.
Also, a method of adding a large amount of fine particles to an antiglare film has been proposed for the purpose of providing an antiglare effect with high definition, high haze, and low glossiness for use in LCD displays. However, when the amount of fine particles added is increased, the coating suitability is lowered, which causes a problem that streaks are generated on the coated surface and the yield is lowered.
When used outdoors, high weather resistance is required.
Further, when used on the display surface, high surface hardness is required.
In Patent Document 2, aiming at imparting high definition, high haze, and low glossiness to the antiglare property of the antiglare film, and adjusting the addition amount of fine particles, the coating suitability due to the generation of streaks on the coated surface is not reduced. A method is being considered.
In patent document 3, 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 59-151110 A International Publication Number WO95 / 31737 JP2007-293272

For the purpose of imparting an antiglare effect of high definition, high haze, and low gloss, a method of adding a large amount of fine powder particles to an antiglare film has been proposed. However, when the amount of fine particles added is increased, the coating suitability is lowered, which causes a problem that streaks are generated on the coated surface and the yield is lowered.
Furthermore, when an existing film is used as a base material, there are problems that weather resistance, surface hardness, workability and safety during film production / processing are insufficient.
The present invention has been made in view of the above-mentioned conventional problems, and does not reduce coating suitability and yield without giving a high-definition, high-haze, low-gloss antiglare effect, An object of the present invention is to provide an antiglare film having high weather resistance, surface hardness, improved workability and safety during film production and processing, and a transmissive display device using the antiglare film. .

  As a result of various studies, the present inventors have found that the antiglare film according to the present invention has a total light transmittance of 85% or more, haze provided on the lactone ring-containing resin film. The surface roughness is such that the optical properties are a degree of gloss of 3.0 to 35%, a gloss of 60 degrees and a gloss of 90% or less, a surface arithmetic average roughness Ra of 0.05 to 0.6 μm, and a pitch between surface irregularities of 5 to 200 μm. In addition to excellent anti-glare properties, it has image clarity, high contrast, high weather resistance and surface hardness, and also has excellent workability during film production and processing. And it discovered that the anti-glare film which improved safety | security was obtained, and completed this invention.

  The antiglare film according to the present invention is provided on a transparent film, a lactone ring-containing resin film, having a total light transmittance of 85% or more, a haze of 3.0 to 35%, and a gloss of 60 degrees. And an antiglare layer having an optical characteristic of 90% or less, an arithmetic average roughness Ra of 0.05 to 0.6 μm, and a surface roughness of a surface roughness of 5 to 200 μm. It is said.

  The higher the total light transmittance is, the better the display becomes brighter. However, in the present invention, it has been found that if it is 85% or more, it can be used practically without any problem.

  In order to obtain a good screen, the haze degree is in the range of 3.0 to 35%. When the haze degree exceeds the upper limit of the above range, the display screen looks whitish. Conversely, when the haze degree is less than the lower limit, the glossiness increases and the antiglare effect decreases.

  The 60-degree glossiness is a value defined by reflection of light incident on the screen from the outside. When this value exceeds 90%, the dazzle increases and does not meet the object of the present invention.

  The numerical ranges of the pitch between the surface irregularities and the surface roughness are necessary conditions in the present invention for obtaining appropriate physical properties of the total light transmittance, the haze degree, and the 60 degree glossiness.

  In the present invention, as an antiglare film particularly suitable for high-definition displays, it is preferable to control the arithmetic average roughness Ra in the range of 0.05 to 0.6 μm among the above surface characteristics. More preferably, it is the range of 0.05-0.25. Here, “high definition” means an increase in the number of pixels per unit area, for example, an increase in 640 × 480 pixels to 800 × 600 pixels in a diagonal 26 cm panel.

  The fine particles used in the production of a high haze antireflection film include 0. Silica fine particles and acrylic fine particles of 5 to 5 μm are mainly used. If it is a transparent resin that does not contain fine particles at all, it will not cause loss of coating properties in order to prevent the occurrence of light glare. It is desirable to mix fine particles to the extent. Further, when the fine particles are kneaded with the ionizing radiation curable resin, the fine particles are kneaded in an organic resin to coat the surface of the fine particles, thereby ensuring transparency and ensuring wettability.

≪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.

≪Curing resin≫
As a resin for forming a hard coat layer for an antiglare layer, an acrylic urethane-based ionizing radiation curable resin or the like is often used, and is a resin having a property of being cured by UV / EB. Therefore, a material that adheres to the lactone ring-containing resin film and is durable is selected.
In the present invention, the ionizing radiation curable resin to be used is not particularly limited as long as it is a resin that is cured by ionizing radiation so-called UV / EB. Examples of the ultraviolet curable resin used together with the photosensitizer include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, and an ultraviolet curable epoxy acrylate resin.

  For example, the ultraviolet curable acrylic urethane-based resin can be obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and reacting the resulting product with an acrylate or methacrylate-based monomer having a hydroxyl group. As the photopolymerization initiator, benzophenone derivatives, acetophenone derivatives, anthraquinone derivatives and the like can be used alone or in combination.

  In some cases, the ionizing radiation curable resin may be appropriately selected and mixed with a component for improving film formation, such as an acrylic resin. In addition, a viscosity modifier, a solvent, etc. are blended to form a coating solution.

  As the ionizing radiation curable resin for forming an uneven shape on the surface of the antiglare film, an ultraviolet curable resin or an electron beam curable resin is usually used.

  As ionizing radiation curable resin, (meth) acryloyl group, (meth) acryloyloxy group ((meth) acryloyl is used in the meaning of acryloyl or methacryloyl in the molecule, and the following (meth) has the same meaning. ) And the like, or a composition in which prepolymers, oligomers, and / or monomers having an epoxy group are appropriately mixed.

  Examples of these prepolymers and oligomers include acrylates such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate, silicon resins such as siloxane, unsaturated polyester, and epoxy.

  Examples of monomers include styrene monomers such as styrene and α-methylstyrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, and / or a polyol compound having two or more thiol groups in the molecule, for example, trimethylolpropane trithioglycolate , Trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like.

  The above compounds are used alone or in combination of two or more as required. In order to impart ordinary coating suitability to the resin composition, the prepolymer or oligomer is added in an amount of 5% by weight or more, and the monomer. And / or polythiol is preferably 9 5 wt% or less.

  When the flexibility of the cured product is required when selecting the monomer, the amount of the monomer is reduced within a range that does not hinder the suitability of coating, or a monofunctional or bifunctional acrylate monomer is added. Use a relatively low crosslink density structure.

In addition, when the cured product is required to have heat resistance, hardness, solvent resistance, etc., the amount of monomer is increased within a range that does not hinder coating suitability, or an acrylate monomer having three or more functions. It is preferable to use a high crosslink density structure.
A monofunctional monomer and a trifunctional or higher monomer can be mixed to adjust the coating suitability and the physical properties of the cured product. Examples of the monofunctional acrylate monomer as described above include 2-hydroxy acrylate, 2-hexyl acrylate, phenoxyethyl acrylate, and the like.
Examples of bifunctional acrylate monomers include ethylene glycol diacrylate and 1,6-hexanediol diacrylate. Examples of trifunctional acrylate monomers include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and pentaerythritol triacrylate. And dipentaerythritol hexaacrylate.
When the ionizing radiation curable resin is cured with ultraviolet rays, it is necessary to use a transparent resin. In addition, as a photopolymerization initiator in the ionizing radiation curable resin composition, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylmeurum monosulfide, thioxanthones, and / or photosensitization. As the agent, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used.
The film-forming component used in the ionizing radiation curable resin composition is preferably one having an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin. , Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, polyhydric alcohols and the like, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) Monofunctional monomers such as acrylate, styrene, methylstyrene, N-vinylpyrrolidone and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropyleneglycol 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 Those containing a relatively large amount can be used.

  Particularly preferably, a mixture of polyester acrylate and polyurethane acrylate is used. The reason is that polyester acrylate is very hard and suitable for obtaining a hard coat, but polyester acrylate alone has low impact and is brittle. In order to give the properties, polyurethane acrylate is used in combination.

  The blending ratio of polyurethane acrylate with respect to 10 0 parts by weight of polyester acrylate is 30 parts by weight or less. If this value is exceeded, the coating film is too soft and the hardness is lost. Furthermore, in order to make the ionizing radiation curable resin composition into an ultraviolet curable resin composition, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetra Methyl thiuram monosulfide, thioxanthones, and n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used as a photosensitizer. In particular, in the present invention, it is preferable to mix urethane acrylate as an oligomer and dipentaerythritol hexaacrylate as a monomer.

  The coating composition essentially consisting of such an ionizing radiation curable resin composition can be cured by an ordinary ionizing radiation curable resin composition curing method, that is, by irradiation with an electron beam or ultraviolet rays. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type, Preferably, an electron beam or the like having an energy of 100 to 300 KeV is used. 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. .

  As the binder for the antiglare layer, an ultraviolet curable resin that is easy to handle is selected as a binder from among ionizing radiation curable resins in consideration of adhesion to the sheet and scratch resistance.

  As the ionizing radiation curable resin, a composition in which a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule is appropriately mixed is used.

  These resin systems include urethane acrylates, unremethacrylates, polyester acrylates, polyester methacrylates, epoxy acrylates, epoxy methacrylates and other acrylates, silicone resins such as methacrylates and siloxanes, and polyester epoxies.

  The prepolymer and oligomer include unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol.

  Monomers include polyfunctional acrylate monomers such as pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol hexaacrylate, styrene, α-methylstyrene, methyl acrylate, methyl methacrylate, acrylamide, Examples include ethylene glycol diacrylate and trimethylolpropane trithioglycolate.

  In particular, when UV curing is performed, the ionizing radiation curable resin composition is added to a photopolymerization initiator, acetophenones, benzophenones, Michler benzoylbenzoate, thioxanthones, and / or triethylamine, tri-amine as a photosensitizer. A mixture of n-butylphosphine and the like can also be used.

≪Solvent drying resin≫
The coating composition for forming the anti-glare film used in the present invention may contain 10 parts by weight or more and 100 parts by weight or less of solvent-drying resin with respect to 100 parts by weight of the resin. As the solvent-drying resin, a thermoplastic resin is mainly used. In particular, when a mixture of polyester acrylate and polyurethane acrylate is used in the ionizing radiation curable resin composition, polymethacrylic acid methyl acrylate or polymethacrylic acid butyl acrylate is used as the solvent-drying resin. Since the affinity with the lactone ring-containing resin film, which is a material film, is good, the adhesiveness is improved, so that it is preferably used.

  The reason why the solvent-drying resin is included in the ionizing radiation curable resin composition in the present invention will be described below. When the coating material used in the present invention is applied to a transparent substrate with, for example, a roll coater having a metering roll, for example, a slit reverse coater, the solvent-drying resin is essentially made from the ionizing radiation curable resin composition as described above. This is because when it is included in the constituted coating composition, coating film defects do not occur during roll coating.

  In this slit reverse coating coating apparatus, the substrate is transferred to a backup roll, and the composition is coated on the substrate by the nozzle coating apparatus. The composition which became unnecessary by adjusting with a coating composition and a metalling roll is removed by a doctor.

≪Fine particles≫
Furthermore, it is also effective to limit the particle size to show good properties as the fine particles. Silica fine particles which have been subjected to organic coating treatment and have a particle size of 0.5 to 5 μm are excellent. Showed the effect. The fine particles subjected to the organic coating treatment are dispersed in the ionizing radiation curable resin, and the content thereof is preferably 10 parts by weight or less with respect to 120 parts of the ionizing radiation curable resin.

  The fine particles are appropriately selected from organic fine particles such as silica, calcium carbonate, precipitated barium sulfate, aluminum hydroxide powder, polyethylene particles, polymethyl methacrylate particles, and polycarbonate particles. In particular, silica powder has a high transmittance with respect to ultraviolet rays and is excellent without inhibiting the curing of the ultraviolet curable resin as a binder.

  The ionizing radiation curable resin composition is preferably mixed with resin fine particles having a refractive index of 1.40 to 1.60 in order to impart antiglare properties. The reason for limiting the refractive index of the resin fine particles to such a value is that the refractive index of the ionizing radiation curable resin is usually 1.40 to 1.50, so that the refractive index is as close as possible to the refractive index of the ionizing radiation curable resin. This is because, if resin fine particles having a ratio are selected, the transparency of the coating film is not impaired and the antiglare property can be increased. By the way, resin fine particles having a refractive index close to that of the ionizing radiation curable resin are shown below. The particle diameter of these resin fine particles is preferably 3 to 8 μm, and is 2 to 10 parts by weight, usually about 4 parts by weight, based on 100 parts by weight of the resin.

  When such resin fine particles are mixed in this coating composition, it is necessary to stir and disperse well the resin fine particles precipitated on the bottom of the container when using the coating. In order to eliminate such inconvenience, silica fine particles having a particle diameter of 0.5 μm or less, preferably 0.1 to 0.25 μm may be included in the coating composition as an anti-settling agent for resin fine particles. Note that the more silica fine particles are added, the more effective is the prevention of sedimentation of the organic filler, but the adverse effect on the transparency of the coating film. Therefore, it is preferable that the amount is less than 0.1 parts by weight, which is a range that can prevent sedimentation, without impairing the transparency of the coating film with respect to 100 parts by weight of the resin.

  Furthermore, an antistatic agent may be added to the coating composition for forming a hard coat coating film having an antiglare property used in the present invention for the purpose of preventing the coating film from being charged. As the antistatic agent, a metal filler, tin oxide, indium oxide, or the like can be used.

≪Other additives≫
A surfactant having an antistatic effect for the purpose of preventing dust from adhering to the antiglare film can be contained in the coating agent for the antiglare layer.

  The surfactant is appropriately selected from a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.

  For the purpose of improving the scratch resistance of the antiglare film, it can be appropriately selected from hydrocarbons, fatty acids, fatty acid esters, amides, amines, silicones and the like which are lubricants.

  The above compounds and additives are used alone or in combination of two or more as required. The resin varnish has a viscosity of 200 to 1500 centipoise suitable for a reverse roll coating method for smoothing the coated surface, and has a solid content of 60 to provide leveling properties after coating and cover fine protrusions. % Or more is good. And in order to satisfy said conditions, what adjusted the viscosity by adding a hardening | curing agent and a solvent to 100 parts of pentaerythritol triacrylates from the said monomer is preferable.

≪Coating and film forming process≫
As a coating means of ionizing radiation curable resin for forming a liquid composition mainly composed of ionizing radiation curable resin as described above on a base film, roll coating, reverse coating, gravure It can be carried out by a general coating method such as coating or slot orifice coating.

The coating amount is a coating amount after removing the solvent, and is 1 to 20 g / m ² , preferably 5 to 15 g / m ² .

  Next, the process of the present invention will be described. Applying the coating liquid mainly comprising an ionizing radiation curable resin to the transparent film, drying the solvent, and having flexibility, at least, a shaping film having fine irregularities on one side thereof, The dried coating surface is overlaid with an uneven surface, irradiated with ultraviolet rays through a transparent film or through a shaping film, and after curing the ionizing radiation curable resin, the shaping film is peeled off, Is transferred to the surface of the coat layer.

  When the thickness of the coating layer is 3 μm or less, it is impossible to cover the defects of the protrusions of the original fabric. When the thickness is 20 μm or more, curling becomes serious and mechanical suitability is deteriorated. 8 μm.

  The above coating liquid may be applied to the concavo-convex surface of the shaped film, and after drying the solvent of the coating liquid, the transparent film is overlaid, and thereafter the ultraviolet curing and peeling of the shaped film are performed as described above. Follow the same procedure.

  The obtained film is extremely useful in terms of performance as a scratch-resistant antiglare film.

  The coating method for forming the antiglare layer is determined by the properties of the coating solution and the coating amount, but in order to obtain surface smoothness, direct coating, reverse roll coating, bar coating, gravure coating, etc. Before curing, the coated surface is flowed to obtain a smooth uniform surface, and the viscosity is 200 to 1500 centipoise, which is a viscosity suitable for flowability.

≪Antireflection layer≫
In the present invention, the optical properties of the antiglare film can be further improved by further forming an antireflection layer made of a metal compound on the surface of the antiglare layer. As such an antireflection layer, for example, a vapor deposition layer of a metal compound such as Al ₂ O ₃ , ZnO ₂ and MgF ₂ can be used. For example, the antireflection layer can be provided by sequentially providing deposited layers of Al ₂ O _{3 of} about 1400 Å, ZnO _{2 of} about 2800 Å, and MgF ₂ 1400 Å.

≪Use of shaped film≫
Next, another embodiment for bringing the film surface into a desired state when obtaining the present invention will be described.

  That is, in this embodiment, the surface of the shaped film is formed into a desired concavo-convex shape by further coating the shaped film with a resin, whereby the haze and glossiness are low, and the antiglare effect is high in scratch resistance and resistance. An antiglare film having excellent chemical properties can be obtained.

  That is, in this method, a resin is applied to a matted film having a concavo-convex shape on the film surface to form a moldable film having the film surface improved to a desired concavo-convex shape. An irregular shape is formed on the ionizing radiation curable resin layer formed on the substrate, and the irregular shape is formed on the surface of the substrate film.

  In still another embodiment, a resin is applied to a matted film having a concavo-convex shape on the film surface to improve the film surface to a desired concavo-convex shape, and then the shaping film is applied with an ionizing radiation curable resin. Laminate on the ionizing radiation curable resin coating surface of the base film, and after irradiating ionizing radiation from the shaping sheet side or base side of the laminated film to cure the ionizing radiation curable resin, peel off the shaping film Thus, a predetermined antiglare film can be obtained.

  Next, in the above production method, the shaping film to which the resin is applied is a transparent resin or a particle size of 0. It is a shaping film formed by coating a resin to which 5 to 10 μm fine particles are added to form an uneven shape, and the ionizing radiation curable resin may be an ultraviolet curable resin, and the ionizing radiation may be ultraviolet rays.

  Furthermore, the surface roughness of the shaped film is an arithmetic average roughness Ra, and is preferably 0.1 to 10 μm.

  And in said manufacturing method, after peeling a shaping film, irradiating ionizing radiation again and hardening an ionizing radiation curable resin, It is set as the anti-glare film which improved abrasion resistance and chemical resistance. it can.

  According to the above method, the surface of the shaped film can be formed into a desired concavo-convex shape by further coating the matted shaped film base material with a resin, so that the haze and glossiness are low and anti-glare is achieved. It is possible to produce an antiglare film that is highly effective and has excellent scratch resistance and chemical resistance.

  Hereinafter, an example in the case of manufacturing the anti-glare film using the shaping film of this invention is shown.

  First, using a film having good dimensional stability such as a polyethylene terephthalate (hereinafter referred to as PET) film, an uneven shape is formed on the film by embossing, sandblasting or the like to make a matted shaped film substrate. Next, a thermosetting resin or ionizing radiation curable resin is coated on the uneven surface of the shaped film substrate to form a coating resin layer, and the roughness of the uneven surface is adjusted to a desired value. A shaped film having a surface roughness is obtained.

  When making an anti-glare film using the above-mentioned shaping film, an ionizing radiation curable resin is coated on this film substrate using a lactone ring-containing resin film as the substrate of the anti-glare film, and before curing. The ionizing radiation curable resin layer is formed. Next, the uneven shape surface of the shaping film is superimposed on the ionizing radiation curable resin layer before curing, and the uneven shape is formed on the ionizing radiation curable resin layer. The ionizing radiation curable resin layer is cured by irradiating ionizing radiation from the shaping film side of the laminate.

  After the ionizing radiation curable resin layer is sufficiently cured, an antiglare film having a concavo-convex shape on the surface of the base film is prepared by peeling the shaping film from the laminated sheet.

When the ionizing radiation curable resin is cured with ionizing radiation, it can be cured by irradiation with ionizing radiation from the opposite side of the shaping film.
Also, when using ultraviolet rays as ionizing radiation, after irradiating ultraviolet rays from the shaping film side and curing the ultraviolet curable resin, the shaping film is peeled off and irradiated again with ultraviolet rays to increase the crosslinking density, In some cases, the antiglare film has improved solvent resistance and scratch resistance.
In addition, when making a moldable film, a matted mold film base material is coated with a resin to which fine particles having a particle diameter of 0.5 to 10 μm are added to produce a moldable film, which is used for anti-glare. A film can be produced and an antiglare film having a high antiglare effect can be obtained.

  The base film used for the above-mentioned shaping film should just have dimensional stability and heat resistance, and can permeate ionizing radiation. Since ultraviolet rays such as a high-pressure mercury lamp are often used as ionizing radiation, a transparent PET film can be preferably used as the substrate film. A thickness of 10 to 200 [mu] m can be used, but the thickness is preferably about 25 [mu] m in consideration of the shapeable film production, reuse, cost, and the like. However, when an electron beam is used as the ionizing radiation, it may be a film that transmits the electron beam and does not necessarily need to be transparent.

  In general, thermosetting resin or ionizing radiation curable resin is used as the resin to be coated to adjust the roughness of the uneven shape of the shaping film, but it is applied to the surface of the antiglare film. The ionizing radiation curable resin can be used as long as it can form a predetermined uneven shape on the ionizing radiation curable resin layer without being softened or swollen, and is not particularly limited. Even thermoplastic resins can be used in combination with the type of ionizing radiation curable resin.

  The thermosetting resin that coats the moldable film is phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoargide resin, melamine-urea cocondensation There are resin, silicon resin, polysiloxane resin, cellulose acetate propionate, etc., and as necessary additives, curing agents such as crosslinking agents, polymerization initiators, polymerization accelerators, solvents, viscosity modifiers, extender pigments, etc. Added.

  As the curing agent, isocyanate is usually used for unsaturated polyester resins or polyurethane resins, and peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutyronitrile are often used for unsaturated polyesters. Furthermore, the isocyanate as a hardening | curing agent can use aliphatic or aromatic isocyanate more than bivalence.

  An ionizing radiation curable resin is also used as the coating resin. Since the ionizing radiation curable resin is also used for producing an antiglare film, it will be described in detail in the section of the antiglare film.

  When curing an ionizing radiation curable resin applied to a base film, ultraviolet rays such as a high-pressure mercury lamp are often used as ionizing radiation. Therefore, a film that transmits ultraviolet rays is usually used, but an ionizing radiation curable resin layer is used. In the case of curing by irradiating ultraviolet rays only from the shaping film side, it is not always necessary to transmit the ultraviolet rays.

  Overlay the shaping film on the resin layer formed on the base material to mold the uneven shape on the resin layer, and then completely cure the resin layer by irradiating with ionizing radiation such as ultraviolet rays and electron beams. .

  When ultraviolet rays are used as the ionizing radiation, if the curing is insufficient by a single irradiation from above the shaping film, the shaping layer is peeled off, and then the ultraviolet rays are irradiated again to completely cure the resin layer.

  As the ionizing radiation irradiation apparatus, an ultraviolet irradiation apparatus or an electron beam irradiation apparatus is usually used.

  For example, as an ultraviolet irradiation device, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light, or a metal halide lamp is used.

  As an electron beam source, various electron beam accelerators such as a Cochloftwald type, a bandegraph type, a resonant transformer type, an insulated core transformer type or a linear type, a dynamitron type, a high frequency type, etc. are used, and 100 to 1000 KeV, preferably 100 Irradiate electrons with energy of ˜300 KeV. The irradiation dose is usually about 0.5 to 30 KGy (kilo gray).

  A conventional transparent protective substrate having an antiglare property is provided with a coating film made of a resin composition containing amorphous silica on the surface. This amorphous silica is obtained by applying a coating with amorphous silica to the surface of the transparent substrate in order to impart antiglare properties to the surface of the transparent protective substrate. In order to impart antiglare properties, silica is blended in the order of about 2 parts by weight with respect to 100 parts by weight of the resin. However, if the coating film contains silica in such a blending ratio, the transparency is lowered.

  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≫
<Total light transmittance>
Based on JIS K7105, it measured using the haze meter (NDH2000, Nippon Denshoku Industries Co., Ltd. product).

<Haze>
Based on JIS K7105, it measured using the haze meter (NDH2000, Nippon Denshoku Industries Co., Ltd. product).

<Glossiness>
Based on JIS K7105, the glossiness at 60 degrees was measured using a gloss meter (VG2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

<Arithmetic mean roughness (Ra)>
Based on JIS B0601, it calculated | required using the surface roughness curve measured with the laser microscope (VK-9710, product made from Keyence Corporation).

<Average interval of unevenness (Sm)>
Based on JIS B0601, the average length of the obtained contour curve elements was determined as the average spacing of the irregularities using the contour curve of the surface measured with a laser microscope (VK-9710, manufactured by Keyence Corporation).

<Weather resistance>
The test was conducted using an ultra-accelerated weathering tester manufactured by Iwasaki Electric Co., Ltd., and evaluation was performed based on the amount of change from the initial value of Δb ^* value after 100 hours under the condition of 100 mW / cm 2.
Evaluation criteria ○: Change amount is less than 5.0% ×: Change amount is 5.0% or more <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 ×: Dissolved completely or partially <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 fine particles and resin fine particles≫
<Synthesis Example 1>
Synthesis of silica fine particles (S-1) In a glass reactor with an internal volume of 10 liters equipped with a stirrer, 1600 cc of methanol, 300 cc of aqueous ammonia (25 wt%), 8 cc of 5N NaOH aqueous solution and Actinol F-3 (Matsumoto as a surfactant) 2 g of Ogyu Seiyaku Co., Ltd. was charged and mixed 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 fine particles were allowed to settle and the supernatant liquid was separated. Furthermore, the redispersion-decantation process was performed in methanol, methanol was removed by the evaporator, and the produced silica fine particles (S-1) were taken out. The obtained silica fine particles (S-1) had a particle size of 3.0 μm.

<Synthesis Example 2>
(Synthesis of Silica Coupling Agent-treated Silica Fine Particles (S-2))
A glass reactor with an internal volume of 10 liters equipped with a stirrer was charged with 1600 cc of methanol, 400 cc of aqueous ammonia (25% by weight), 8 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 fine particles were allowed to settle and the supernatant liquid was separated. Further, redispersion-decantation treatment was performed in methanol, methanol was removed by an evaporator, and the generated silica fine particles were taken out.

  After adding 100 g of the obtained silica fine particles to a juice mixer and stirring, a solution obtained by dissolving 2 g of a silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) in 20 g of methanol was added and stirred for 30 minutes. It dried at 150 degreeC for 1 hour, and obtained the silica fine particle (S-2) by which the surface was coat | covered with the silane coupling agent. The average particle diameter of the obtained silane coupling agent-treated silica fine particles (S-2) was 3.0 μm.

<Synthesis Example 3>
(Synthesis of Silica Coupling Agent-treated Silica Fine Particles (S-3))
A glass reactor with an internal volume of 10 liters equipped with a stirrer was charged with 1600 cc of methanol, 500 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 fine particles were allowed to settle and the supernatant liquid was separated. Further, redispersion-decantation treatment was performed in methanol, methanol was removed by an evaporator, and the generated silica fine particles were taken out.

  100 g of the obtained silica fine particles were put into a juice mixer, and a solution prepared by dissolving 2.5 g of a silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) in 20 g of methanol was added and stirred for 30 minutes. Then, it dried at 150 degreeC for 1 hour, and obtained the silica fine particle (S-3) by which the surface was coat | covered with the silane coupling agent. The average particle diameter of the obtained silane coupling agent-treated silica fine particles (S-3) was 1.5 μm.

<Synthesis Example 4>
(Synthesis of Silane Coupling Agent-treated Silica Fine Particles (S-4))
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), 12 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 fine particles were allowed to settle and the supernatant liquid was separated. Further, redispersion-decantation treatment was performed in methanol, methanol was removed by an evaporator, and the generated silica fine particles were taken out.

  100 g of the obtained silica fine particles are put into a juice mixer, a solution prepared by dissolving 5 g of ethyltrimethoxysilane as a silane coupling agent in 20 g of methanol is added with stirring, and stirred for 30 minutes, and then dried at 150 ° C. for 1 hour. Thus, silica fine particles (S-4) whose surfaces were coated with a silane coupling agent were obtained. The average particle diameter of the obtained silane coupling agent-treated silica fine particles (S-4) was 1 μm.

<Synthesis Example 5>
(Synthesis of polymer seed particles (K-1))
In a four-necked flask equipped with a condenser, thermometer, and dripping port, 90 g of ion-exchanged water, 10 g of styrene, 0.5 g of n-decyl mercaptan and 0.1 g of NaCl are introduced, and nitrogen gas is introduced for 1 hour in the reaction vessel. Was replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 70 ° C., a solution prepared by dissolving 0.1 g of potassium persulfate in a small amount of ion-exchanged water was added using a syringe, and the reaction was performed at 70 ° C. for 24 hours. After completion of the reaction, the obtained emulsion was subjected to solid-liquid separation, and the obtained cake was washed with ion-exchanged water and then with methanol to obtain polymer seed particles (K-1). 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 fine particles (S-5))
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 0.1 g of sodium lauryl sulfate as an emulsifier was dissolved in 50 g of ion-exchanged water was added with a solution in which 14.31 g of methyl methacrylate, 1.59 g of ethylene glycol dimethacrylate and 0.80 g of benzoyl peroxide were added, and the mixture was homogenized. A monomer 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 fine particles (S-5). Got. The average particle diameter of the acrylic resin particles (S-5) was 5.1 μm.

<< Preparation Example of Coating Composition Forming Antiglare Layer >>
<Preparation Example 1>
Pentaerythritol triacrylate (KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd .; refractive index: 1.51) 98.8 g, polymethacrylic acid methyl acrylate (number average molecular weight 31800) 1.2 g, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc .; photopolymerization initiator) 4 g, benzophenone (photopolymerization initiator) 4 g, and toluene 95.8 g were sufficiently mixed to prepare a coating composition (C-1). .

<Preparation Example 2>
Pentaerythritol triacrylate (KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd .; refractive index: 1.51) 98.8 g, polymethacrylic acid methyl acrylate (number average molecular weight 31800) 1.2 g, 1-hydroxycyclohexylphenyl 4 g of ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd .; photopolymerization initiator), 4 g of benzophenone (photopolymerization initiator), 5 g of silica particles (S-1), and 100.2 g of toluene are sufficiently mixed for coating. A composition (C-2) was prepared.

<Preparation Example 3>
Pentaerythritol triacrylate (KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd .; refractive index: 1.51) 98.8 g, polymethacrylic acid methyl acrylate (number average molecular weight 31800) 1.2 g, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, Ciba Specialty Chemicals, Inc .; photopolymerization initiator) 2.7 g, benzophenone (photopolymerization initiator) 2.7 g, silane coupling agent-treated silica fine particles (S-2) 4.2 g, A coating composition (C-3) was prepared by sufficiently mixing 0.1 g of ether-modified silicone (X-22-4952, manufactured by Shin-Etsu Chemical Co., Ltd.), 84.8 g of toluene, and 5 g of ethyl acetate.

<Preparation Example 4>
In the same manner as in Preparation Example 3, except that 4.2 g of silica particles in Preparation Example 3 were changed to 2.8 g of acrylic resin fine particles (S-5) and 84.8 g of toluene were changed to 94.8 g, a coating composition (C— 4) was obtained.

<Preparation Example 5>
Except that 4.2 g of the silane coupling agent-treated silica fine particles (S-2) in Preparation Example 3 was changed to 3.8 g of the silane coupling agent-treated silica fine particles (S-3) and 84.8 g of toluene was changed to 104.4 g. In the same manner as in Preparation Example 3, a coating composition (C-5) was obtained.

<Preparation Example 6>
Except that 4.2 g of the silane coupling agent-treated silica fine particles (S-2) in Preparation Example 3 was changed to 5.6 g of the silane coupling agent-treated silica fine particles (S-3) and 84.8 g of toluene was changed to 106.4 g. In the same manner as in Preparation Example 3, a coating composition (C-6) was obtained.

<Preparation Example 7>
Pentaerythritol triacrylate (KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd .; refractive index: 1.51) 98.8 g, polymethacrylic acid methyl acrylate (number average molecular weight 31800) 1.2 g, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 3.3 g, benzophenone (photopolymerization initiator) 3.3 g, silane coupling agent-treated silica fine particles (S-4) 26.4 g, A coating composition (C-7) was prepared by sufficiently mixing 0.1 g of ether-modified silicone (X-22-4952, manufactured by Shin-Etsu Chemical Co., Ltd.), 128 g of toluene, and 5 g of ethyl acetate.

<Preparation Example 8>
Pentaerythritol triacrylate (KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd .; refractive index: 1.51) 98.8 g, polymethacrylic acid methyl acrylate (number average molecular weight 31800) 1.2 g, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals; photopolymerization initiator) 3 g, benzophenone (photopolymerization initiator) 3 g, ether-modified silicone (X-22-4952, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 g of toluene, 125 g of toluene, and 5 g of ethyl acetate were sufficiently mixed to prepare a coating composition (C-8).

≪Evaluation of antiglare film≫
A production example of an antiglare film obtained by forming an antiglare layer on a lactone ring-containing resin film will be described.

<Example 1>
On the lactone ring-containing resin film (F-1), the coating composition (C-1) was applied using a roll coating method so that the application amount was 8 g / m ² . After drying this coating film at 80 ° C. for 1 minute, a matte PET (Ra: 0.47, Sm: 47.5) is laminated as a shaping film, and a high-pressure mercury lamp with a lamp output of 160 W × 2 is used. Then, the coating layer was cured by irradiating from a distance of 15 cm and irradiating with ultraviolet rays at 10 m / min. Subsequently, the said shaping | molding film was peeled and the anti-glare film (A-1) was obtained.

  About the obtained anti-glare film, the total light transmittance, haze, glossiness, arithmetic average roughness (Ra), and average interval of unevenness (Sm) were measured. The results are shown in Table 1. No scintillation (glare on the surface) was observed in the obtained antiglare film.

<Example 2>
On the lactone ring-containing resin film (F-2), the coating composition (C-2) was applied using a roll coating method so that the application amount was 8 g / m ² . After the coating film was dried at 80 ° C. for 1 minute, matted PET (Ra: 0.46, Sm: 45.0) was laminated as a shaping film, and a high-pressure mercury lamp with a lamp output of 160 W × 2 lamps was used. Then, the coating layer was cured by irradiating from a distance of 15 cm and irradiating with ultraviolet rays at 10 m / min. Subsequently, the said shaping | molding film was peeled and the anti-glare film (A-2) was obtained.

  About the obtained anti-glare film, the total light transmittance, haze, glossiness, arithmetic average roughness (Ra), and average interval of unevenness (Sm) were measured. The results are shown in Table 1. No scintillation (glare on the surface) was observed in the obtained antiglare film.

<Comparative 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 80 ° C. for 1 minute. Then, the lactone ring containing resin film which has a glare-proof layer was obtained by irradiating and hardening | curing the ultraviolet-ray of integrated light quantity 250mJ / cm < ² >. About the obtained anti-glare film, the total light transmittance, haze, glossiness, arithmetic average roughness (Ra), and average interval of unevenness (Sm) were measured. The results are shown in Table 1. Scintillation (glare of the surface) was observed in the obtained antiglare film.

<Example 3>
On the lactone ring-containing resin film (F-1), the coating composition (C-3) was applied using a two-reverse method so that the coating amount was 5 g / m ² (Dry). After the coating film was dried at 70 ° C. for 1 minute, the coating layer was cured by irradiating with ultraviolet rays twice using a high-pressure mercury lamp with a lamp output of 160 W / cm at a line speed of 10 m / min. A conductive film (A-3) was obtained.

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 2.

<Example 4>
On the lactone ring-containing resin film (F-2), the coating composition (C-4) was applied using a two-reverse method so that the coating amount was 5 g / m ² (Dry). After drying this coating film at 80 ° C. for 1 minute, using a high pressure mercury lamp with a lamp output of 160 W / cm, the coating layer is cured by irradiating with ultraviolet rays twice under the condition of a line speed of 10 m / min, and anti-glare. The characteristic film (A-4) was obtained.

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 2.

<Example 5>
On the lactone ring-containing resin film (F-1), the coating composition (C-5) was applied using a two-reverse method so that the coating amount was 5 g / m ² (Dry). After drying this coating film at 40 ° C. for 1 minute, using a high pressure mercury lamp with a lamp output of 160 W / cm, the coating layer is cured by irradiating with ultraviolet rays twice under the condition of a line speed of 10 m / min. -Resistant film (A-5) was obtained.

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 2.

<Example 6>
In Example 5, the anti-glare film (A-6) was obtained like Example 5 except having made the coating composition (C-5) into the coating composition (C-6).

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 2.

<Example 7>
In Example 5, the anti-glare film (A-7) was obtained like Example 5 except having made the coating composition (C-5) into the coating composition (C-7).

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 2.

<Example 8>
On the lactone ring-containing resin film (F-1), the coating composition (C-8) was applied using a two-reverse method so that the coating amount was 8 g / m ² . After the coating film was dried at 40 ° C. for 1 minute, diamond foil E-130 (Mitsubishi Chemical Polyester Film Co., Ltd .; thickness 26 μm) was laminated as a shaping film, and a high-pressure mercury lamp with a lamp output of 160 W / cm was used. Used, the coating layer was cured by irradiating with ultraviolet rays twice at a line speed of 10 m / min. Subsequently, the said shaping | molding film was peeled and the anti-glare film (A-8) was obtained.

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 3.

<Example 9>
In Example 8, an antiglare film (A-9) was obtained in the same manner as in Example 8 except that the drying temperature of the coating film was set to 70 ° C.

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 3.

<Example 10>
In Example 8, except that Diafoil E-130 (Mitsubishi Chemical Polyester Film Co., Ltd .; thickness 26 μm) as a shaping film was Lumirror E-06 (Toray Industries, Inc., thickness 25 μm). In the same manner as in Example 8, an antiglare film (A-10) was obtained.

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 3.

<Example 11>
In Example 8, except that Diafoil E-130 (Mitsubishi Chemical Polyester Film Co., Ltd .; thickness: 26 μm) as a shaping film was changed to PTH-25 (Unitika Co., Ltd., thickness: 25 μm). In the same manner as in Example 8, an antiglare film (A-11) was obtained.

  About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 3.

<Example 12>
In Example 8, except that Diafoil E-130 (Mitsubishi Chemical Polyester Film Co., Ltd .; thickness 26 μm), which is a moldable film, was a moldable film (H-1) prepared by the method shown below. In the same manner as in Example 8, an antiglare film (A-12) was obtained.

  Below, the preparation method of a shaping film (H-1) is shown.

  100.0 g of polymethyl methacrylate, 1.5 g of silicone, 490.3 g of methyl ethyl ketone, 7.4 g of ethyl acetate, 414.1 g of toluene, and 416.8 g of cyclohexanone were sufficiently mixed to prepare a coating solution.

The obtained coating solution was applied onto Diafoil E-130 (Mitsubishi Chemical Polyester Film Co., Ltd .; thickness 26 μm) using a two-reverse system so that the coating amount was 3 g / m ² (Dry). did. This coating film was dried at 80 ° C. for 1 minute to obtain a shaped film (H-1).

<Comparative Example 2>
In Example 8, except for changing the shape film Diafoil E-130 (Mitsubishi Chemical Polyester Film Co., Ltd .; thickness 26 μm) to MT-HP (Toray Co., Ltd., thickness 25 μm). In the same manner as in Example 8, an antiglare film (A-11) was obtained.

About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 3.
<Comparative Example 3>
An antiglare film (A-12) was obtained in the same manner as in Example 3 except that a triacetyl cellulose film (TD-80U, manufactured by Fuji Film Co., Ltd.) was used instead of the lactone ring-containing resin film (F-1). Got. About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 3.

<Comparative Example 4>
An antiglare film (A-13) was prepared in the same manner as in Example 3 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). Obtained. About the obtained anti-glare film, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 3.

<Comparative Example 5>
An antiglare film (A-14) was obtained in the same manner as in Example 3 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, total light transmittance, haze, glossiness, arithmetic average roughness (Ra), average interval of unevenness (Sm), weather resistance, solvent resistance, pencil hardness, film surface potential are measured. did. The results are shown in Table 3.

  The antiglare film of the present invention has excellent antiglare properties, high definition, high haze, low glossiness, weather resistance, surface hardness, workability and safety during film production and processing even when used for high definition displays. Are higher than conventional ones, and can fully exhibit characteristics according to various optical applications. For example, anti-glare, light, etc. for flat panel displays such as liquid crystal display devices, plasma displays, and organic EL display devices. Suitable for optical applications that impart diffusibility

Claims (19)

A transparent base film, and optical properties of a total light transmittance of 85% or more, a haze of 3.0 to 35%, and a 60 degree gloss of 90% or less provided on the transparent base film; It consists of an antiglare layer having an arithmetic average roughness Ra of 0.05 to 0.6 μm and an average interval Sm of surface irregularities of 5 to 200 μm, and the transparent base film is represented by the following general formula (1) An antiglare film for display, which is a lactone ring-containing resin film having the lactone ring shown.

[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]   The antiglare film according to claim 1, wherein the arithmetic average roughness Ra of the surface is in the range of 0.05 to 0.4 μm.   The antiglare film according to claim 1, wherein the arithmetic average roughness Ra of the surface is in the range of 0.05 to 0.25 μm.   The antiglare film according to claim 1, wherein an antireflection layer made of a metal compound is further formed on the surface of the antiglare layer. The anti-glare film according to claim 4, wherein the antireflection layer comprises at least one of Al ₂ O ₃ , ZnO _2, and MgF ₂ .   The anti-glare film of Claim 1 obtained using the shaping | molding film base material formed into a mat by providing uneven | corrugated shape on the surface.   A shaping film having a desired concavo-convex shape is prepared by applying a resin to the concavo-convex surface of the shaping film base material formed into a mat by providing a concavo-convex shape on the surface, and this shaping film. The anti-glare film according to claim 1, which is obtained by forming an uneven shape on an ionizing radiation curable resin layer formed on a base film using the above.   In obtaining the antiglare film according to claim 1, a desired uneven shape is formed by applying a resin to the uneven surface of the shaped film substrate formed into a mat by providing an uneven shape on the surface. The shaped film obtained in this way and the one obtained by coating and forming the ionizing radiation curable resin on the base film are combined with the ionizing radiation curable resin coated surface. Is laminated so that the concavo-convex surface of the mold film is in contact, and further, the ionizing radiation curable resin is cured by irradiating with ionizing radiation from the shaping film side or the base film side of the laminate. A method for producing an antiglare film, comprising peeling a mold film.   The moldable film coated with the resin is a moldable film formed by forming a concavo-convex shape by coating a matted film with a transparent resin or a resin added with fine particles having a particle size of 0.5 to 10 μm, and an ionizing radiation curable resin. The method according to claim 7, wherein is an ultraviolet curable resin and the ionizing radiation is ultraviolet light.   The method according to claim 8, wherein the shaped film has an arithmetic average roughness Ra of 0.1 to 10 μm.   The method according to claim 7, further comprising the step of irradiating ionizing radiation again to cure the ionizing radiation curable resin after peeling the shaping film.   The antiglare film according to claim 1, wherein the ionizing radiation curable resin layer contains organic fine particles or inorganic fine particles.   The anti-glare film according to claim 1, wherein the electron radiation curable resin layer contains resin fine particles having a refractive index of 1.40 to 1.60.   A coating composition consisting essentially of organic fine particles or inorganic fine particles, preferably resin fine particles having a refractive index of 1.40 to 1.60, and an ionizing radiation curable resin composition is coated on a transparent substrate, The manufacturing method of the transparent protective substrate in which the anti-glare film of Claim 1 is formed by irradiating ionizing radiation on the uncured coating film of a thing, and hardening the coating film of the said coating composition.   The method according to claim 14, wherein the coating composition further comprises silica fine particles having a particle size of 0.5 µm or less as an anti-resin fine particle settling agent in an amount of less than 0.1 parts by mass relative to 100 parts by mass of the resin.   The method according to claim 14, wherein the coating composition contains 10 parts by mass or more and 100 parts by mass or less of the solvent-drying resin with respect to 100 parts by mass of the resin.   15. The method of claim 14, wherein the ionizing radiation curable resin composition consists essentially of polyester acrylate and polyurethane acrylate.   The coated surface formed by coating and forming an ionizing radiation curable resin composition containing organic or inorganic fine particles, preferably resin fine particles having a refractive index of 1.40 to 1.60 on a transparent substrate film, has an uneven shape on the surface. The anti-glare film of Claim 1 obtained by shaping | molding with the shaping | molding film formed by matting by providing.   An ionizing radiation curable type comprising a shaping film formed by matting by providing an uneven shape on the surface, and containing organic or inorganic fine particles, preferably resin fine particles having a refractive index of 1.40 to 1.60, on a substrate film A layered product is formed by overlapping the coated surface formed by coating and forming the resin composition so that the uneven surface of the shaped film is in contact with the ionizing radiation from the shaped film side or the base film side of the laminated material. Is applied to cure the ionizing radiation curable resin, and further peel the moldable film from the laminate.