JP2014013367A - Optical laminate and picture display unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical laminate with extremely high stability of an antistatic performance, with a stable surface resistance value even after a durability test, capable of restraining generation of rainbow-like irregularities and a color taste change when viewed by a viewer wearing sunglasses having a polarization property.SOLUTION: An optical laminate has an antistatic layer on one surface of a light transmissive substrate having in-plane birefringence. The antistatic layer is formed using a composition for an antistatic layer including conductive fine particles, a resin component and a solvent. The resin component has no reactive functional group within molecules thereof, and also has solubility to the solvent and compatibility to the conductive fine particles. Retardation of the light transmissive substrate is 5,000 nm or larger.

Description

The present invention relates to an optical laminate and an image display device.

On the outermost surface of image display devices such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), electroluminescence display (ELD), field emission display (FED), touch panel, An optical laminate comprising functional layers having various functions such as hardware and transparency is provided.
As the base material for these functional layers, an acrylic resin having excellent transparency and hardness is used. However, the base material of such a functional layer is easily charged due to its high insulating properties, and dirt due to adhesion of dust or the like is generated, and there are obstacles due to charging in the display manufacturing process as well as in use. There was a problem that occurred.

In order to prevent such charging, an antistatic layer containing a conductive antistatic agent has been conventionally provided on a part of the optical laminate (see, for example, Patent Documents 1 and 2).
There are two types of anti-static agents added to the anti-static layer that exhibit the anti-static function: an electron conduction type in which electrons move through carriers such as solitons and polarons, and an ion conduction type in which ions move within the system. It is classified into two types.
As the electron conduction type antistatic agent, for example, various metal oxides and conductive polymers are known. On the other hand, as the ion conduction type antistatic agent, for example, a quaternary ammonium salt or a lithium salt is used. Etc. are known.
Among these, as the antistatic agent added to the antistatic layer, a quaternary ammonium salt that is a cationic surfactant is preferably used.

However, an optical laminate provided with an antistatic layer using a quaternary ammonium salt as an antistatic agent has a problem that the surface resistance value is not stable depending on the coating environment when the antistatic layer is formed. In recent years, optical laminates have been required to have extremely high durability performance (light resistance performance and heat resistance performance), but the stability of the surface resistance when forming an antistatic layer is charged Since the optical layered body having an antistatic layer using a quaternary ammonium salt is linked with the stability of the surface resistance value of the optical layered body having the anti-reflection layer, the surface resistance value of the optical layered body before and after the durability test is There was a problem that the value was not stable. Specifically, when an optical laminate with an antistatic layer is used for a capacitive touch panel, if the surface resistance of the optical laminate after the durability test becomes too low, the touch sensor can sufficiently detect it. If the surface resistance value of the optical laminate after the durability test becomes too high after the endurance test, the electric charge temporarily concentrates on the touch part and affects the liquid crystal molecules, resulting in white turbidity on the display screen. was there.
In addition, it is conventionally known to use a conductive polymer or conductive fine particles as an antistatic agent to be added to the antistatic layer. However, an optical laminate provided with an antistatic layer using such an antistatic agent. The body also had a problem that the surface resistance value was deteriorated by the durability test.

Conventionally, an antistatic layer or the like is laminated on a light-transmitting substrate to constitute an optical laminate, and as this light-transmitting substrate, a film made of cellulose ester typified by triacetyl cellulose is used. It was used. This is because cellulose ester is excellent in transparency and optical isotropy, and has almost no phase difference in the plane (almost no birefringence in the plane), so that the vibration direction of incident linearly polarized light can be changed. Since there is little influence on the display quality of the liquid crystal display device and it has moderate water permeability, the moisture remaining in the polarizer when the polarizing plate using the optical laminate is produced is removed from the optical laminate. It is based on the advantage that it can be dried through the body.
However, the cellulose ester film is a disadvantageous material in terms of cost, and has insufficient moisture resistance and heat resistance. If the optical laminate is used as a polarizing plate protective film in a hot and humid environment, the polarizing function and hue There is a disadvantage that the polarizing plate function is lowered.

From the problems of such cellulose ester film, it is excellent in transparency, heat resistance and mechanical strength, and is cheaper than cellulose ester film and easily available in the market, or can be produced by a simple method. It is desired to use a versatile film as a light-transmitting substrate of an optical laminate. For example, attempts have been made to use a polyester film such as polyethylene terephthalate as a cellulose ester substitute film (for example, Patent Document 3). reference).

However, the polyester film has an aromatic ring with a high polarizability in the molecular chain, so the intrinsic birefringence is extremely large, and the molecular chain is oriented by stretching to give excellent transparency, heat resistance, and mechanical strength. Along with this, birefringence is easily developed.
When an optical laminate using a light-transmitting substrate having a birefringence index in the plane of such a polyester film is installed on the surface of the image display device, the display screen of the image display device has polarization characteristics. When viewed with sunglasses, there is a problem that unevenness of different colors (hereinafter also referred to as “Nijimura”) occurs.
In addition, when an image display device in which an optical laminate using a light-transmitting base material having a birefringence index in such a plane is installed, such as a smartphone or a tablet terminal, a state in which sunglasses having polarization characteristics are put on When the image display device is rotated in the outer peripheral direction of the display screen while visually recognizing, there is also a problem that a change in color occurs in the display image.

JP 2006-126808 A JP 200531282 A JP 2004-205773 A

In view of the above situation, the present invention has a very high antistatic performance, and there is little change in the surface resistance value before and after the durability test, even when it is viewed with sunglasses having polarization characteristics. An object of the present invention is to provide an optical layered product in which the occurrence of azimuth and color change are suppressed, and an image display device using the optical layered product.

That is, the present invention provides an optical laminate having an antistatic layer on one surface of a light-transmitting substrate having a birefringence index in the plane, the antistatic layer comprising conductive fine particles, a resin component, and the like. The resin component is formed using a composition for an antistatic layer containing a solvent, and the resin component does not have a reactive functional group in the molecule, and has solubility in the solvent and the conductive fine particles. And the optically transparent substrate is characterized in that the retardation is 5000 nm or more.

In the optical layered body of the present invention, the conductive fine particles are preferably chain-like or needle-like.
In addition, the optical laminate of the present invention has a change rate of the surface resistance value {(test) before and after the durability test (1) for 500 hours in an 80 ° C. environment and the durability test (2) for 300 hours irradiation with xenon arc. (Surface resistance value) / (Surface resistance value before test)} is preferably 0.5 to 2.0.
The resin component preferably has a weight average molecular weight of 20,000 to 200,000 and a glass transition temperature of 80 to 120 ° C.
The resin component is at least one selected from the group consisting of acrylic resins, cellulose resins, urethane resins, vinyl chloride resins, polyester resins, polyolefin resins, polycarbonate, nylon, polystyrene, and ABS resins. It is preferable that
The conductive fine particles are preferably antimony tin oxide (ATO), the resin component is polymethyl methacrylate, and the solvent is preferably propylene glycol monomethyl ether.

Moreover, it is preferable that the optical laminated body of this invention has a hard-coat layer on the surface on the opposite side to the light transmissive base material side of the said antistatic layer.
Moreover, it is preferable that the said hard-coat layer contains the same resin component as the resin component contained in an antistatic layer.
The hard coat layer preferably contains conductive fine particles.
Moreover, it is preferable that the said hard-coat layer contains a ultraviolet absorber.
Moreover, it is preferable that content of the said ultraviolet absorber is 3-15 mass%.

Moreover, this invention is also an image display apparatus provided with the optical laminated body of this invention.
Hereinafter, the present invention will be described in detail.

As a result of earnestly examining the fact that the conventional optical laminate is not stable in surface resistance after performing a durability test (light resistance test and heat resistance test), the conventional optical laminate is It has been found that the antistatic agent contained in the antistatic layer moves and changes its position before and after the durability test. And in order to solve such a problem, as a result of further examination, by configuring the antistatic layer with a combination of specific materials, the surface resistance value was measured before and after the durability test (light resistance test and heat resistance test). We found that the change was small. Furthermore, as a light-transmitting substrate having an in-plane birefringence index, it has a predetermined retardation value, so that it is possible to generate nitrile and color change even when viewed through sunglasses having polarization characteristics. The inventors have found that this can be prevented and have completed the present invention.

The present invention is an optical laminate having an antistatic layer on one surface of a light-transmitting substrate.
In the optical layered body of the present invention, the antistatic layer is formed using an antistatic layer composition containing conductive fine particles, a resin component, and a solvent. That is, in the optical layered body of the present invention, the antistatic layer does not contain a monomer component in the layer.
Here, the monomer component reacts when a durability test of the optical laminate, for example, a high temperature test at 80 ° C., a carbon arc fade meter, a durability test using a xenon weather meter using a xenon lamp is performed. And a component that causes curing shrinkage in the antistatic layer.
Since the optical layered body of the present invention does not contain such a monomer component in the antistatic layer, curing shrinkage does not occur in the antistatic layer after the durability test, and the surface resistance value does not change before and after the durability test. It will be a thing.
Specifically, the optical layered body of the present invention has a rate of change in surface resistance before and after a durability test (1) for 500 hours in an 80 ° C. environment and a durability test (2) for 300 hours irradiation with a xenon arc. {(Surface resistance value after test) / (Surface resistance value before test)} is preferably 0.5 to 2.0.
When it is less than 0.5, the surface resistance value of the optical laminate of the present invention after the durability test is low and the conductivity is high, so the optical laminate of the present invention is used for a capacitive touch panel The surface charge when touched with a finger diffuses and the sensor cannot be detected and the touch sensor may not operate. On the other hand, if it exceeds 2.0, the surface resistance value of the optical laminate of the present invention after the durability test is high and the conductivity decreases, so the optical laminate of the present invention was used for a capacitive touch panel. In this case, the charge on the surface when touched with a finger cannot be sufficiently diffused, and the high charge is temporarily concentrated. As a result, the liquid crystal molecules may be affected and the display screen may become cloudy. is there.
In the optical layered body of the present invention, the antistatic layer does not contain a monomer component. In addition to the case where the antistatic layer contains no monomer component, there is a difference in surface resistance after a durability test. It also includes the case where it is included within the above range.
Furthermore, the antistatic layer preferably does not contain a resin that is decomposed by ultraviolet rays. Examples of the resin that is decomposed by ultraviolet rays include, for example, a resin having a highly polarized functional group, a resin having an unsaturated bond in the main chain, and the like.

The conductive fine particles are a material that ensures the antistatic performance of the optical laminate of the present invention.
Such conductive fine particles are not particularly limited, and conventionally known materials such as metal fine particles, metal oxide fine particles, carbon nanotubes, and coating fine particles can be used. Among these, metal oxide fine particles are preferably used because of good light resistance, heat resistance, and environmental dependency.

The metal constituting the metal fine particles is not particularly limited, and examples thereof include Au, Ag, Cu, Al, Fe, Ni, Pd, and Pt.
Further, no particular limitation is imposed on the metal oxide constituting the metal oxide fine particles, for example, tin oxide _(SnO 2), antimony oxide _{(Sb 2 O} 5), antimony tin oxide (ATO), indium tin oxide (ITO), aluminum zinc oxide (AZO), fluorinated tin oxide (FTO), ZnO and the like.
Here, the “metal oxide” in the present invention is a concept including a metal oxide doped with a different metal.

Moreover, it does not specifically limit as said coating fine particle, For example, the conventionally well-known fine particle of the structure by which the electroconductive coating layer was formed on the surface of core fine particle is mentioned.
The core fine particles are not particularly limited, and examples thereof include inorganic fine particles such as silica fine particles and glass fine particles; polymer fine particles such as fluororesin fine particles, acrylic resin particles, and silicone resin particles; and fine particles such as organic inorganic composite particles. Moreover, it does not specifically limit as a material which comprises the said electroconductive coating layer, For example, the metal mentioned above or these alloys, the metal oxide mentioned above, etc. are mentioned.

The conductive fine particles preferably have an average primary average particle diameter of 6 to 40 nm. If it is less than 6 nm, it is necessary to increase the amount of addition in order to impart sufficient antistatic performance to the optical laminate of the present invention, which may be inferior in transparency and adhesion between other layers, Moreover, since the resistance of the conductive fine particles increases rapidly, the conductive performance of the antistatic layer may deteriorate. If it exceeds 40 nm, the resistance of the conductive fine particles themselves is low, but the conductive fine particles are scattered in the antistatic layer, and there is a possibility that good resistance cannot be obtained. The more preferable lower limit of the average primary particle diameter of the conductive fine particles is 7 nm, and the more preferable upper limit is 20 nm.
The average particle size of the conductive fine particles means a value measured using a MICROTRAC particle size analyzer manufactured by Nikkiso Co., Ltd. in the antistatic layer composition for forming the antistatic layer, In the above antistatic increase, it means an average value of 10 particle diameters of conductive fine particles observed by a transmission electron microscope (TEM) photograph and a scanning transmission electron microscope (STEM) photograph of the cross section of the antistatic layer.

In the optical layered body of the present invention, the conductive fine particles are preferably chain-like or needle-like. The conductive fine particles having such a shape are difficult to move in the antistatic layer, and even when some shrinkage of the antistatic layer is caused during the durability test, the surface resistance value of the optical laminate is hardly increased. It can be contained in the antistatic layer stably without being changed.
Further, in the antistatic layer, adjacent chain or needle-like conductive fine particles are easily contacted, and an antistatic layer having sufficient conductive performance can be obtained with a small addition amount.
Here, if the conductive fine particles in the antistatic layer are in the form of single particles, it is difficult to make contact between adjacent conductive fine particles in the antistatic layer. Need to be more. As a result, there may be a problem that the adhesion between the antistatic layer and another layer is lowered and the probability of being affected by the change in conductivity with time is increased.
The chain or needle shape means a form in which two or more conductive fine particles are connected in a linear or branched manner.
Hereinafter, the chain or needle-like conductive fine particles will be referred to as “chain conductive fine particles”.

The chain conductive fine particles are different from those in which the primary particles of the conductive fine particles are simply aggregated by the attractive force between the particles, and it is preferable that the conductive fine particles are bonded to each other. It may be linear, broken, or curved.

The chain conductive fine particles are not particularly limited as long as the conductive fine particles have a connected form of two or more, but the conductive fine particles are connected in a straight chain with 2 to 50 conductive fine particles. Is preferred.
If the number of connected conductive fine particles is less than 2, the surface resistance value may not be reduced effectively. If the number of connected conductive fine particles exceeds 50, the light transmission of the antistatic layer may be reduced. The rate may decrease and haze may increase.
The more preferable lower limit of the number of connected conductive fine particles constituting the chain conductive fine particles is 3, and the more preferable upper limit is 30.

The average length of the chain conductive fine particles is preferably 12 to 500 nm. If the thickness is less than 12 nm, the contact resistance increases, and the surface resistance value of the antistatic layer may not be effectively reduced. If the thickness exceeds 500 nm, the antistatic layer may not be transparent. Because there is. A more preferable lower limit of the average length of the chain conductive fine particles is 20 nm, and a more preferable upper limit is 300 nm.
The “average length of the chain conductive fine particles” means 10 chain conductive fine particles observed by a transmission electron microscope (TEM) photograph or a scanning transmission electron microscope (STEM) photograph of the cross section of the antistatic layer. Means the average length of
Specifically, for example, transmission through the cross section of the antistatic layer taken at a magnification (for example, 200,000 times or more) at which one size of the chain-like conductive fine particles in which two or more conductive fine particles are connected can be confirmed. In a scanning electron microscope (TEM) photograph or the like, an antistatic layer is selected by selecting 10 chain conductive fine particles, measuring the length of the longest portion of the selected chain conductive fine particles, and determining the average value thereof. The average length of the chain-like conductive fine particles can be obtained.
The chain conductive fine particles exist in various shapes such as a curved shape. In measuring the length, the length between the two most distant points is measured.

The chain conductive fine particles can be obtained, for example, by the following method.
First, an alcohol solution containing metal salt or metal alkoxide at a concentration of 0.1 to 5% by mass is heated to hydrolyze the metal salt or metal alkoxide, and conductive fine particles having an average primary particle diameter of 1 to 100 nm. A gel dispersion is prepared.
At this time, you may add warm water and an alkali as needed.
Next, the obtained gel dispersion is filtered, washed, and fired in air at a temperature of 200 to 800 ° C. to prepare conductive fine particles (metal oxide fine particles).
Next, the fired conductive fine particle powder is dispersed in at least one of acidic or alkaline water and an alcohol solvent to obtain a dispersion having a concentration of 10 to 50% by mass, and if necessary, in the presence of an organic stabilizer. Then, this dispersion is mechanically dispersed.
Specific examples of the organic stabilizer include gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and citric acid. And polyvalent carboxylic acids and salts thereof, heterocyclic compounds or mixtures thereof.
By this mechanical dispersion treatment, a sol in which the generated gel is peptized and the chain conductive fine particles are dispersed is obtained.
Examples of the mechanical dispersion treatment include a sand mill method and an impact dispersion method. In particular, the impact dispersion method is preferably used.
The chain conductive fine particles obtained in this manner are usually taken out from the produced dispersion by a method such as centrifugation, and washed with an acid or the like as necessary.
Further, the obtained dispersion liquid containing chain conductive fine particles can be used as it is for the formation of the antistatic layer.

Examples of commercially available dispersions containing the chain conductive fine particles include ELCOM-V3560, DP1197, DP1203, DP1204, DP1207, and DP1208 manufactured by JGC Catalysts & Chemicals.

The content of the conductive fine particles in the antistatic layer is appropriately adjusted according to the type, shape, size, and the like of the conductive fine particles to be used. For example, the content is 100 with respect to 100 parts by mass of the resin component described later. It is preferable that it is -300 mass parts. If it is less than 100 parts by mass, the antistatic performance of the optical layered body of the present invention may be insufficient, and if it exceeds 300 parts by mass, the adhesion to other layers of the antistatic layer is poor. In addition, there is a possibility that the probability of being affected by the change in conductivity with time increases. The minimum with more preferable content of the said electroconductive fine particles is 150 mass parts, and a more preferable upper limit is 250 mass parts. By being in this range, it is possible to ensure adhesion to the light-transmitting substrate while obtaining a stable resistance value.

The resin component is a polymer and a material that plays a role as a binder component of the antistatic layer, does not have a reactive functional group in the molecule, and has a solubility in a solvent described later and the conductivity. It has compatibility with fine particles.
When the antistatic layer contains a resin component that is a polymer as a binder component, the optical laminate of the present invention is stable in that the antistatic layer does not undergo curing shrinkage and the surface resistance value does not change after the durability test. Will be.
For this reason, the resin component has no reactive functional group in the molecule. Since the resin component does not have a reactive functional group in the molecule, there is no secondary reaction of the resin component, and the performance of the antistatic layer formed after applying and drying the antistatic layer composition Can be maintained. When the resin component has a reactive group in the molecule, the resin component gradually proceeds by a dark reaction in the antistatic layer formed after coating and drying the antistatic layer composition. When the reaction of the resin component proceeds gradually over a long period of time, the resin component may be bound by the reaction, and the physical distance formed by the resin component may shrink. As a result, the physical distance of the conductive fine particles in the antistatic layer is also shortened, resulting in a problem that the conductive path is increased, the conductivity of the antistatic layer is improved, and the resistance value is lowered.
Further, when the resin component has a reactive functional group in the molecule, the reactive functional group reacts by a durability test, causing curing shrinkage in the antistatic layer, and the surface resistance value changes.
The reactive functional group means a functional group that may react in the durability test, for example, a functional group having an unsaturated double bond such as an acryloyl group or a vinyl group, an epoxy ring, an oxetane ring, or the like. A cyclic ether group, a ring-opening polymerization group such as a lactone ring, an isocyanate group that forms urethane, and the like.
These reactive functional groups are preferably not contained in the resin component at all, but may be contained as long as they do not cause curing shrinkage in the antistatic layer after the durability test.
The level that does not cause curing shrinkage in the antistatic layer means that the rate of change in surface resistivity after the durability test is in the above-described range.

The resin component has solubility in a solvent described later and compatibility with the conductive fine particles.
The antistatic layer using the antistatic layer composition containing such a resin component is excellent in the dispersibility of the conductive fine particles and in the stability of the surface resistance value over time.
In the present specification, “having solubility” means that a gel component is not generated in a resin solution obtained by dissolving the resin component in a solvent described later, and the solvent ratio in the resin solution is increased. It means having a characteristic that the viscosity decreases accordingly.
In addition, “compatible” means that in the antistatic layer composition obtained by mixing the resin solution and the conductive fine particles, the conductive fine particles are at least 100 to 300 masses with respect to 100 parts by mass of the resin component. Even if they are mixed at an arbitrary ratio in the range of the part, they are uniformly dispersed without forming a gelled product, and the above antistatic layer composition can be applied evenly to form a coating film. It means that appearance deterioration such as an increase in haze does not occur in the antistatic layer obtained by drying the film.

Moreover, it is preferable that the said resin component is what has a side chain.
The resin component having the above side chain is difficult to move in the antistatic layer due to the steric hindrance of the side chain, and the optical laminate of the present invention is more preferably excellent in stability of the surface resistance value. Can do.

The resin component preferably has a weight average molecular weight of 20,000 to 200,000. If it is less than 20,000, sufficient hardness cannot be obtained for the antistatic layer, and the surface resistance value may become unstable before and after the durability test. On the other hand, when it exceeds 200,000, the viscosity of the composition for an antistatic layer described later may become too high to be applied. The minimum with said more preferable weight average molecular weight is 50,000, and a more preferable upper limit is 100,000.
In addition, the said weight average molecular weight can be calculated | required by polystyrene conversion by gel permeation chromatography (GPC). Tetrahydrofuran or chloroform can be used as the solvent for the GPC mobile phase. The measurement column may be used in combination with a commercially available column such as a column for tetrahydrofuran or a column for chloroform. Examples of the commercial product column include Shodex GPC KF-801, GPC KF-802, GPC KF-803, GPC KF-804, GPC KF-805, GPC KF-800D (all trade names, manufactured by Showa Denko KK). And the like. As the detector, an RI (differential refractive index) detector and a UV detector may be used. Using such a solvent, column, and detector, the weight average molecular weight can be appropriately measured by a GPC system such as Shodex GPC-101 (manufactured by Showa Denko).

The resin component preferably has a glass transition temperature of 80 to 120 ° C. When the temperature is lower than 80 ° C., the resin component becomes soft and the resistance value may become unstable. On the other hand, when the temperature exceeds 120 ° C., the resin component becomes hard and the adhesion to the light-transmitting substrate decreases. There is a fear. A more preferable lower limit of the glass transition temperature is 90 ° C., and a more preferable upper limit is 110 ° C. By being in this range, it is possible to ensure adhesion to the light-transmitting substrate while obtaining a stable resistance value.

The resin component is at least one selected from the group consisting of acrylic resin, cellulose resin, urethane resin, vinyl chloride resin, polyester resin, polyolefin resin, polycarbonate, nylon, polystyrene, and ABS resin. Preferably there is.
Examples of the acrylic resin include polymethyl methacrylate.
Examples of the cellulose resin include diacetyl cellulose, cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB).
Moreover, as said urethane type resin, a urethane resin etc. are mentioned, for example.
Examples of the vinyl chloride resin include polyvinyl chloride and vinyl chloride-vinyl acetate copolymers.
Moreover, as said polyester-type resin, a polyethylene terephthalate etc. are mentioned, for example.
Moreover, as said polyolefin resin, polyethylene, a polypropylene, etc. are mentioned, for example.
The resin component in the optical layered body of the present invention is preferably a thermoplastic resin. Among them, polymethyl methacrylate is preferred because it easily prevents bleeding out of the conductive fine particles and is excellent in compatibility. Used.

The antistatic layer preferably has a thickness of 0.1 to 1.0 μm. If the thickness is less than 0.1 μm, a sufficient resistance value may not be obtained. If the thickness exceeds 1.0 μm, the adhesiveness to the light-transmitting substrate is inferior. The rate may decrease. A more preferable lower limit of the thickness of the antistatic layer is 0.2 μm, and a more preferable upper limit is 0.5 μm.
The thickness of the antistatic layer is a value measured by observing a cross section of the antistatic layer using an electron microscope (for example, SEM, TEM, STEM, etc.).

As the solvent, an organic solvent in which the resin component exhibits the above-described solubility is preferably used. For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), fat Aromatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, acetic acid) Ethyl, butyl acetate, etc.), alcohols (ethanol, isopropanol, butanol, cyclohexanol, propylene glycol monomethyl ether, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfo) Sid), amides (dimethylformamide, dimethylacetamide, etc.) and the like, may be a mixed solvent.

Here, when the conductive fine particles are the chain conductive fine particles described above, the chain conductive fine particles are prepared using water or alcohol as described above. For this reason, when using the said chain | strand-shaped electroconductive fine particles, alcohol is the most preferable as a solvent of the said composition for antistatic layers. In the case of using a solvent having a small polar group, particularly a solvent having no hydroxyl group, it is necessary to add a dispersant for dispersing the chain conductive fine particles. This is because the inter-particle distance of the chain conductive fine particles increases in the direction, and the resulting surface resistance value of the antistatic layer increases.
On the other hand, when the resin component is polymethyl methacrylate, the polymethyl methacrylate is generally insoluble or hardly soluble in alcohol, tends to be easily dissolved in a solvent having no hydroxyl group and few polar groups. Specifically, the polymethyl methacrylate tends to be easily dissolved in ketones, aliphatics, hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and esters. Therefore, by selecting these solvents, a polymethyl methacrylate solution can be prepared, and the use of the solution can facilitate the preparation of the antistatic layer composition.
In the antistatic layer composition, the conductive fine particles (chain conductive fine particles) and the resin component (polymethyl methacrylate) need to be stably present. That is, if too much solvent having a small number of polar groups is added as the solvent, the chain conductive fine particles cannot be present stably, and problems such as aggregation, gelation, and sedimentation occur. On the other hand, if too much solvent having high polarity such as alcohol is added too much, polymethyl methacrylate which is a resin component cannot be stably present, and problems such as precipitation and gelation occur. As a result, the composition cannot be used as the antistatic layer composition, and the object of the present invention cannot be achieved.
For this reason, when the composition for an antistatic layer uses polymethyl methacrylate as the resin component, for example, when methyl isobutyl ketone is used as the solvent and mixed with an alcohol dispersion containing the chain conductive fine particles. In addition, in order to make the polymethyl methacrylate and chain conductive fine particles more stable, glycol esters having an intermediate property between methyl isobutyl ketone and alcohol and a slow evaporation rate are additionally mixed as a solvent. It is preferable to make it. Of these, it is more preferable to additionally mix propylene glycol monomethyl ether. As a result, propylene glycol monomethyl ether having a low evaporation rate remains at the end even during the drying of the antistatic layer composition, and adverse effects during drying such as gelation of polymethyl methacrylate and aggregation of chain conductive fine particles The antistatic layer obtained can stably achieve the intended durability performance.

The antistatic layer composition containing such a material preferably does not contain the above-described monomer component. However, as described above, the antistatic layer to be formed does not cause curing shrinkage after the durability test. If present, it may contain a monomer component.

The method for preparing the antistatic layer composition is not particularly limited as long as each component can be uniformly mixed. For example, the composition can be performed using a known apparatus such as a paint shaker, a bead mill, a kneader, or a mixer.

The antistatic layer can be formed by applying the antistatic layer composition onto a light-transmitting substrate to form a coating film and then drying the coating film.
The coating method is not particularly limited. For example, spin coating method, dip method, spray method, die coating method, bar coating method, roll coater method, meniscus coater method, flexographic printing method, screen printing method, pea coater method, etc. Can be mentioned.

The optical layered body of the present invention has a light-transmitting substrate having a birefringence in the plane.
The light-transmitting substrate having a birefringence in the plane is not particularly limited, and examples thereof include substrates made of polycarbonate, cycloolefin polymer, acrylic, polyester, etc. Among them, cost and mechanical strength are mentioned. It is preferred that the polyester base is advantageous. In the following description, a light-transmitting substrate having a birefringence in the plane will be described as a polyester substrate.

The polyester base material has a retardation of 5000 nm or more. When it is less than 5000 nm, when the display image of the above-described image display device is viewed through sunglasses having polarization characteristics, it becomes impossible to suppress the occurrence of nitrile and color change. Further, such a low retardation polyester substrate may be inferior in transparency, heat resistance and mechanical strength. On the other hand, the upper limit of the retardation of the polyester base material is not particularly limited, but is preferably about 30,000 nm. If it exceeds 30,000 nm, the film thickness becomes considerably large, which is not preferable.
It is preferable that the retardation of the said polyester base material is 6500-25000 nm from a viewpoint of thin film formation. A more preferable range is 9000 to 20,000 nm.

The retardation is the refractive index (nx) in the direction having the highest refractive index (slow axis direction) in the plane of the polyester substrate, and the refraction in the direction orthogonal to the slow axis direction (fast axis direction). It is represented by the following formula by the rate (ny) and the thickness (d) of the polyester base material.
Retardation (Re) = (nx−ny) × d
The retardation can be measured, for example, by KOBRA-WR manufactured by Oji Scientific Instruments (measurement angle 0 °, measurement wavelength 589.3 nm).
In addition, using two polarizing plates, the orientation axis direction (main axis direction) of the film is obtained, and the refractive indexes (nx, ny) of two axes orthogonal to the orientation axis direction are measured with an Abbe refractometer ( It is determined by Atago Co., Ltd. NAR-4T. Here, an axis showing a larger refractive index is defined as a slow axis. The film thickness d (nm) is measured using an electric micrometer (manufactured by Anritsu), and the unit is converted to nm. The retardation can also be calculated from the product of the refractive index difference (nx−ny) and the film thickness d (nm).
In addition, a refractive index can also be measured using an Abbe refractometer and an ellipsometer, or using a spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation), an average reflectance (R of 380 to 780 nm) ) And the value of the refractive index (n) may be obtained from the obtained average reflectance (R) using the following formula.
The average reflectance (R) of the optical functional layer including the antistatic layer is such that each raw material composition is applied on 50 μm PET without easy adhesion treatment to form a cured film having a thickness of 1 to 3 μm, and PET is not applied. In order to prevent back surface reflection, a black vinyl tape (for example, Yamato vinyl tape NO200-38-21 38 mm width) larger than the measurement spot area is pasted on the back surface (back surface) and then the average reflectance of each cured film Was measured. The refractive index of the polyester base material was measured after black vinyl tape was similarly applied to the surface opposite to the measurement surface.
R (%) = (1-n) ² / (1 + n) ²
Further, as a method for measuring the refractive index of the optical functional layer after becoming an optical layered product, a cured film of each layer is scraped off with a cutter or the like to prepare a powder sample, and JIS K7142 (2008) B method (powder) Alternatively, the Becke method according to (for granular transparent materials) can be used. In the Becke method, a Cargill reagent having a known refractive index is used, the powder sample is placed on a glass slide, the reagent is dropped on the sample, and the sample is immersed in the reagent. This is observed by using a microscope, and this is a method in which the refractive index of the sample is the refractive index of the reagent in which the bright line generated in the sample outline due to the difference in refractive index between the sample and the reagent;
In the case of a polyester base material, since the refractive index varies depending on the direction, the average reflectance can be measured and determined by applying the black vinyl tape on the treated surface of the optical functional layer instead of the Becke method.

In the present invention, the nx-ny (hereinafter also referred to as Δn) is preferably 0.05 or more. If Δn is less than 0.05, the film thickness necessary to obtain the retardation value described above is increased, which is not preferable. On the other hand, the Δn is preferably 0.25 or less. When it exceeds 0.25, the polyester base material tends to be torn and torn, and the practicality as an industrial material may be significantly reduced.
A more preferable lower limit of Δn is 0.07, and a more preferable upper limit is 0.20. This is because if Δn is smaller than 0.07, it is difficult to obtain the sufficient effect of suppressing the above-mentioned azimuth and color change. In addition, when said (DELTA) n exceeds 0.20, the durability of the polyester base material in a heat-and-moisture resistance test may be inferior. Since the durability in the heat and humidity resistance test is excellent, a more preferable upper limit of Δn is 0.15.
In addition, as said (nx), it is preferable that it is 1.66-1.78, a more preferable minimum is 1.68, and a more preferable upper limit is 1.73. Moreover, as said (ny), it is preferable that it is 1.55-1.65, a more preferable minimum is 1.57 and a more preferable upper limit is 1.62.
When the above nx and ny are in the above range and satisfy the above-described relationship of Δn, a suitable azimuth and color change suppression effect can be obtained.

In addition, when the said polyester base material is a PEN base material which uses the polyethylene naphthalate (PEN) mentioned later as a raw material, as a range of said (DELTA) n, a preferable minimum is 0.05 or more and a preferable upper limit is 0.30. is there. If Δn is less than 0.05, the film thickness necessary to obtain the retardation value described above is increased, which is not preferable. On the other hand, if the above Δn exceeds 0.30, the PEN substrate tends to be torn and torn, and the practicality as an industrial material may be significantly reduced. The more preferable lower limit of Δn in the case of the PEN substrate is 0.07, and the more preferable upper limit is 0.27. This is because if Δn is smaller than 0.07, it is difficult to obtain the sufficient effect of suppressing the above-mentioned azimuth and color change. In addition, when said (DELTA) n exceeds 0.27, durability of the polyester base material in a moist heat resistance test may be inferior. Moreover, since the durability in a heat-and-moisture resistance test is excellent, a more preferable upper limit of Δn in the case of the PEN substrate is 0.25.
In addition, as (nx) in the case of the said PEN base material, it is preferable that it is 1.70-1.90, a more preferable minimum is 1.72 and a more preferable upper limit is 1.88. Moreover, as (ny) in the case of the said PEN base material, it is preferable that it is 1.55-1.75, a more preferable minimum is 1.57 and a more preferable upper limit is 1.73.
When the above nx and ny are in the above range and satisfy the above-described relationship of Δn, a suitable effect of suppressing nitrile and color change can be obtained using the PEN base material.

Here, in the case of suppressing only the occurrence of the above-mentioned nitrite, the retardation of the light-transmitting substrate may be about 3000 nm or more. However, in the light-transmitting substrate having such a retardation, color change is suppressed. I can't. However, in the optical layered body of the present invention, the retardation of the light-transmitting substrate is 5000 nm or more, and thus it is possible to suitably suppress the occurrence of nitrite and the color change.
When the optical laminate of the present invention is installed in an image display device, the color change is suppressed even when the display screen is observed through polarized sunglasses. Specifically, the color difference measured by the following method is used. Δu′v ′ is preferably 0.03 or less, and a more preferable upper limit is 0.01.
That is, first, the optical laminate of the present invention is installed so that the slow axis of the light-transmitting substrate is 45 ° with respect to the absorption axis of the polarizing plate of an image display device such as a liquid crystal display device.
Next, the front color when the angle between the absorption axis of polarized sunglasses and the absorption axis of the polarizing plate is 0 ° (parallel Nicol) and 90 ° (cross Nicol) is measured with a luminance meter. Then, the color difference Δu′v ′ is calculated.

The material constituting the polyester base material is not particularly limited as long as it satisfies the retardation described above, but is synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Examples include linear saturated polyester. Specific examples of such polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene naphthalate (polyethylene-2,6-naphthalate, polyethylene-1,4-naphthalate). , Polyethylene-1,5-naphthalate, polyethylene-2,7-naphthalate, polyethylene-2,3-naphthalate).
The polyester used for the polyester substrate may be a copolymer of these polyesters. The polyester is mainly used (for example, a component of 80 mol% or more), and a small proportion (for example, 20 mol% or less). It may be blended with these types of resins. Polyethylene terephthalate or polyethylene naphthalate is particularly preferable as the polyester because of good balance between mechanical properties and optical properties. In particular, it is preferably made of polyethylene terephthalate (PET). This is because polyethylene terephthalate is highly versatile and easily available. In the present invention, an optical laminate that can produce a liquid crystal display device with high display quality can be obtained even with a highly versatile film such as PET. Furthermore, PET is excellent in transparency, heat or mechanical properties, can control the retardation by stretching, has a large intrinsic birefringence, and can obtain a large retardation relatively easily even when the film thickness is small.
Moreover, in this invention, polyethylene naphthalate (PEN) is also used suitably as polyester used for the said polyester base material. This is because PEN is a material having a large Δn compared to the above PET, so that the polyester base material using PEN as a raw material can be about half as thick as the polyester base material using PET. It is possible to suitably prevent the occurrence of nitrile. For this reason, the optical layered body of the present invention having a PEN base material and an antistatic layer is suitable for mobile applications where the film thickness has been reduced in recent years, particularly as a protective film for a polarizer.

The method for obtaining the polyester base material is not particularly limited as long as the above-described retardation is satisfied. For example, the polyester, such as PET, as a material is melted and extruded into a sheet to form glass. The method of heat-processing after transverse stretching using a tenter etc. at the temperature more than transition temperature is mentioned.
The transverse stretching temperature is preferably 80 to 130 ° C, more preferably 90 to 120 ° C. Further, the transverse draw ratio is preferably 2.5 to 6.0 times, more preferably 3.0 to 5.5 times. When the transverse draw ratio exceeds 6.0 times, the transparency of the resulting polyester base material tends to be lowered, and when the transverse draw ratio is less than 2.5 times, the draw tension becomes small. In some cases, the birefringence of the substrate becomes small, and the retardation cannot be increased to 5000 nm or more.
In the present invention, the unstretched polyester is subjected to transverse stretching under the above conditions using a biaxial stretching test apparatus, and then stretched in the flow direction with respect to the transverse stretching (hereinafter also referred to as longitudinal stretching). Also good. In this case, the longitudinal stretching preferably has a stretching ratio of 2 times or less. When the draw ratio of the above-mentioned longitudinal stretching exceeds twice, the value of Δn may not be within the preferred range described above.
The treatment temperature during the heat treatment is preferably 100 to 250 ° C, more preferably 180 to 245 ° C.

Examples of the method for controlling the retardation of the polyester substrate produced by the above-described method to 5000 nm or more include a method of appropriately setting the draw ratio, the drawing temperature, and the film thickness of the produced polyester substrate. Specifically, for example, the higher the stretching ratio, the lower the stretching temperature, and the thicker the film, the easier it is to obtain high retardation. The lower the stretching ratio, the higher the stretching temperature, and the film thickness. The thinner, the easier it is to obtain low retardation.

The thickness of the polyester substrate is preferably in the range of 40 to 500 μm. If the thickness is less than 40 μm, the retardation of the polyester base material cannot be increased to 5000 nm or more, the anisotropy of mechanical properties becomes remarkable, and tearing, tearing, and the like are likely to occur, and the practicality as an industrial material is significantly reduced. Sometimes. On the other hand, if it exceeds 500 μm, the polyester base material is very rigid, the flexibility specific to the polymer film is lowered, and the practicality as an industrial material is also lowered, which is not preferable. The minimum with more preferable thickness of the said polyester base material is 50 micrometers, a more preferable upper limit is 400 micrometers, and a still more preferable upper limit is 300 micrometers.
However, when the said polyester base material is a polyethylene naphthalate (PEN) base material, it is preferable that it is in the range of 10-400 micrometers as the thickness. When the thickness is less than 10 μm, the retardation of the PEN base material cannot be increased to 5000 nm or more, the anisotropy of mechanical properties becomes remarkable, and tearing, tearing, etc. easily occur, and the practicality as an industrial material is remarkably reduced. Sometimes. On the other hand, if it exceeds 400 μm, the PEN substrate is very rigid, the flexibility specific to the polymer film is lowered, and the practicality as an industrial material is also lowered, which is not preferable. The minimum with more preferable thickness of the said PEN base material is 15 micrometers, a more preferable upper limit is 250 micrometers, and a still more preferable upper limit is 150 micrometers. From the viewpoint of thinning the optical layered body of the present invention, a more preferable range of the thickness of the PEN substrate is 20 to 50 μm.

The polyester base material preferably has a transmittance in the visible light region of 80% or more, more preferably 84% or more. In addition, the said transmittance | permeability can be measured by JISK7361-1 (The test method of the total light transmittance of a plastic-transparent material).

In the present invention, the polyester substrate may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, and flame treatment without departing from the spirit of the present invention. Good.

The optical layered body of the present invention may have a primer layer between the polyester substrate and the antistatic layer.
The primer layer is a layer provided for the first purpose to improve the adhesion between the polyester base material and the antistatic layer. For other purposes, the refractive index can be adjusted to reduce interference fringes.
The material for the primer layer is not particularly limited. For example, conventionally known materials may be appropriately selected and used. Specifically, thermosetting or thermoplastic polyester resins, urethane resins, acrylic resins, and These modified products are exemplified. Moreover, in order to adjust the refractive index of the said primer layer, high refractive index microparticles | fine-particles, a chelate compound, etc. can be added.

As said polyester resin, the polyester obtained from the following polybasic acid component and a diol component can be used, for example.
Examples of the polyvalent base component include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyro Examples include merit acid, dimer acid, and 5-sodium sulfoisophthalic acid.

Examples of the diol component include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycol, and dimethylolpropane. Examples thereof include poly (ethylene oxide) glycol and poly (tetramethylene oxide) glycol.

Moreover, as said acrylic resin, what is obtained by copolymerizing the monomer illustrated below is mentioned, for example.
Examples of the monomer include alkyl acrylate and alkyl methacrylate (the alkyl group includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, Cyclohexyl groups, etc.); hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether; Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt) ) Monomers having a carboxy group or a salt thereof; acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl acrylamide, N, N-dialkyl methacrylate (the alkyl group includes a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), N-alkoxyacrylamide, N-alkoxymethacrylamide, N, N-di Alkoxyacrylamide, N, N-dialkoxymethacrylamide (alkoxy groups include methoxy, ethoxy, butoxy, isobutoxy, etc.), acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide, -Monomers having amide groups such as phenylacrylamide and N-phenylmethacrylamide; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride; 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2- Such as oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, etc. Oxazoline group-containing monomer: methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, vinyl isocyanate, allyl isocyanate, styrene, α-methyl styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkylmer Ynoic acid monoesters, alkyl fumaric acid monoesters, alkyl itaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, butadiene.

Moreover, as said urethane resin, what is comprised with a polyol, polyisocyanate, a chain extension agent, a crosslinking agent etc. is mentioned, for example.
Examples of the polyol include a dehydration reaction between a dicarboxylic acid and a glycol containing a polyether such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyethylene adipate, polyethylene-butylene adipate, polycaprolactone, and the like. Examples include polyesters to be produced, polycarbonates having carbonate bonds, acrylic polyols, and castor oil.

Examples of the polyisocyanate include tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

Examples of the chain extender or crosslinking agent include ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, hydrazine, ethylenediamine, diethylenetriamine, triethylenetetramine, 4,4′-diaminodiphenylmethane, and 4,4′-diamino. Examples include dicyclohexylmethane and water.

As the high refractive index fine particles, for example, metal oxide fine particles having a refractive index of 1.60 to 2.80 are preferably used.
Specific examples of the metal oxide fine particles include titanium oxide (TiO ₂ , refractive index: 2.71), zirconium oxide (ZrO ₂ , refractive index: 2.10), cerium oxide (CeO ₂ , refraction). rate: 2.20), tin oxide (SnO _2, refractive index: 2.00), antimony tin oxide (ATO, refractive index: 1.75 to 1.95), indium tin oxide (ITO, the refractive index: 1.95 to 2.00), phosphorus tin compound (PTO, refractive index: 1.75 to 1.85), antimony oxide (Sb ₂ O ₅ , refractive index: 2.04), aluminum zinc oxide (AZO, Refractive index: 1.90 to 2.00), gallium zinc oxide (GZO, refractive index: 1.90 to 2.00) and zinc antimonate (ZnSb ₂ O ₆ , refractive index: 1.90 to 2.00) ) And the like.
The high refractive index fine particles preferably have an average primary particle diameter of 5 to 100 nm. When the average primary particle diameter exceeds 100 nm, optical scattering occurs in the primer layer, and the transparency may be deteriorated. When the average primary particle diameter is less than 5 nm, aggregation of fine particles increases, and the secondary particle diameter increases. Optical scattering may occur, and the transparency of the primer layer may deteriorate.
The refractive index of these high refractive index fine particles is, for example, mixed with a thermoplastic resin whose refractive index is known and a metal oxide whose mass is measured, and then molded into a transparent pellet having an appropriate thickness, The refractive index of the pellet can be measured, and the refractive index of the high refractive index fine particles can be calculated from the blending ratio with the resin having the known refractive index. The refractive index measurement can be obtained by, for example, an Abbe refractometer by the Becke method according to JIS K7142 (2008) A method, and for example, DR-M4 manufactured by Atago Co., Ltd. can be used. The wavelength for measuring the refractive index is 589 nm.
The average primary particle diameter can be determined as an average value of the particle diameters of 20 particles by image analysis by observation with a transmission electron microscope such as TEM or STEM.

Examples of the chelate compound include a water-soluble titanium chelate compound, a water-soluble titanium acylate compound, and a water-soluble zirconium compound.
Examples of the water-soluble titanium chelate compound include diisopropoxybis (acetylacetonato) titanium, isopropoxy (2-ethyl-1,3-hexanediolato) titanium, diisopropoxybis (triethanolaminato). Examples thereof include titanium, di-n-butoxybis (triethanolaminato) titanium, hydroxybis (lactato) titanium, ammonium salt of hydroxybis (lactato) titanium, ammonium beloxocitrate ammonium salt, and the like.
Examples of the water-soluble titanium acylate compound include oxotitanium bis (monoammonium oxalate).
Examples of the water-soluble zirconium compound include zirconium tetraacetylacetonate and zirconium acetate.

The thickness of the primer layer may be appropriately adjusted according to the required performance, and is not particularly limited, but may be, for example, 10 to 1000 nm. The maximum thickness of the primer layer is preferably 500 nm or less because the pencil hardness (according to JIS K5600-5-4) of the optical laminate of the present invention can be improved, and particularly 300 nm or less, for example, a thickness of 800 nm. Since the pencil hardness is clearly improved, such as sometimes H becomes 2H, it is more preferable.
In addition, the thickness of the said primer layer is the average value (nm) obtained by measuring arbitrary 10 points | pieces, for example by observing the cross section of the said primer layer with an electron microscope (SEM, TEM, STEM). is there. In the case of a very thin thickness, a high-magnification observation is recorded as a photograph and further magnified for measurement. When enlarged, a layer interface line that is very thin enough to be clearly recognized as a boundary line becomes a thick line. In that case, the center portion obtained by dividing the thick line width into two is measured as a boundary line.

The primer layer can be formed using a primer layer composition prepared by mixing and dispersing the above-described materials and, if necessary, a photopolymerization initiator and other components in a solvent.
The mixing and dispersing may be performed using a known apparatus such as a paint shaker, a bead mill, a kneader.

As the solvent, water is preferably used, and is preferably used in the form of an aqueous coating liquid such as an aqueous solution, an aqueous dispersion, or an emulsion. Further, some organic solvent may be included.
Examples of the organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketones (eg, acetone, methyl ethyl ketone, methyl). Isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone), aliphatic hydrocarbon (eg, hexane, cyclohexane), halogenated hydrocarbon (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic carbonization Hydrogen (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran) ), Ether alcohols (e.g., 1-methoxy-2-propanol), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate) and the like.

The other components are not particularly limited. For example, a leveling agent, organic or inorganic fine particles, a photopolymerization initiator, a thermal polymerization initiator, a crosslinking agent, a curing agent, a polymerization accelerator, a viscosity modifier, an antistatic agent, an oxidation agent. Examples thereof include an inhibitor, an antifouling agent, a slip agent, a refractive index adjuster, and a dispersant.

The primer layer composition preferably has a total solid content of 3 to 20%. If it is less than 3%, residual solvent may remain or whitening may occur. If it exceeds 20%, the viscosity of the composition for the primer layer is increased, the coatability is lowered, unevenness and streaks appear on the surface, and the desired film thickness may not be obtained. The solid content is more preferably 4 to 10%.

Application of the primer layer composition to the polyester substrate can be carried out at any stage, but it is preferably carried out during the production process of the polyester substrate, and further before the orientation crystallization is completed. It is preferable to apply to a polyester substrate.
Here, the polyester base material before the crystal orientation is completed is an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and further in the longitudinal direction and the transverse direction. In the direction (low-stretch orientation orientation (biaxially stretched film before reorientation in the machine direction or transverse direction to complete orientation crystallization)). Especially, it is preferable to apply | coat the aqueous coating liquid of the said composition for primer layers to an unstretched film or the uniaxially stretched film orientated to one direction, and to perform longitudinal stretch and / or lateral stretch and heat setting as it is.
When the primer layer composition is applied to a polyester substrate, physical treatment such as corona surface treatment, flame treatment, plasma treatment or the like is performed on the polyester substrate surface as a pretreatment for improving the coating property, or It is preferred to use a chemically inert surfactant together with the primer layer composition.

As a method for applying the primer layer composition, any known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method and the like can be used alone or in combination. In addition, a coating film may be formed only in the single side | surface of a polyester base material as needed, and may be formed in both surfaces.

The optical layered body of the present invention preferably has a hard coat layer on the surface of the antistatic layer opposite to the light transmissive substrate side.
The antistatic layer is present between the hard coat layer and the light transmissive substrate, and the optical laminate of the present invention can be excellent in hard coat performance, and further, a durability test. Later surface resistance can be made more stable.

The hard coat layer is formed by using a hard coat layer forming composition containing conductive fine particles, a monomer component, a resin component, and an ultraviolet absorber, and the resin component includes the antistatic layer described above. The resin component contained in the hard coat layer composition is preferably the same as the resin component contained in the antistatic layer. By containing the same kind of resin component as the antistatic layer, the adhesion between the antistatic layer and the hard coat layer is excellent.
In addition, the said composition for hard-coat layers may contain the same kind of resin component contained in the said antistatic layer as a resin component, and a different kind of resin component. However, in this case, the main component of the resin component in the hard coat layer composition (that is, 50% by mass or more of all resin components) is the same type of resin component as the resin component contained in the antistatic layer. Is preferred.

Examples of the monomer component include compounds having one or more unsaturated bonds, such as compounds having an acrylate functional group. Examples of the compound having one unsaturated bond include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like. Examples of the compound having two or more unsaturated bonds include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri ( Polyfunctional compounds such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, or the above polyfunctional compound and (meth) acrylate And the like (for example, poly (meth) acrylate esters of polyhydric alcohols).
In the present specification, the monomer component includes a precursor of a curable resin, and includes a so-called oligomer.

In addition to the above compounds, the hard coat layer composition is a relatively low molecular weight polyester resin having an unsaturated double bond, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, a spiroacetal resin, Polybutadiene resin, polythiol polyene resin, and the like can also be used as the resin component.

The conductive fine particles are fine particles for ensuring the antistatic performance of the optical layered body of the present invention, and play a role of establishing conduction between the surface of the hard coat layer and the antistatic layer.
Such conductive fine particles are not particularly limited, and for example, coated fine particles in which a conductive coating layer is formed on the surface of the core fine particles are preferably used.
Examples of the material constituting the coating fine particles include the same materials as those described for the conductive fine particles in the antistatic layer described above.

The average particle diameter of the conductive fine particles is preferably 3 to 10 μm. If it is less than 3 μm, the thickness of the hard coat layer to be formed becomes too thin and the hard coat performance may be insufficient. On the other hand, if it exceeds 10 μm, the hard coat layer becomes too thick and the transparency is poor. Or the conductive fine particles may fall off. The more preferable lower limit of the average particle diameter of the conductive fine particles is 4 μm, and the more preferable upper limit is 7 μm.
The conductive fine particles preferably have a size equal to or exceeding the thickness of the hard coat layer. That is, the conductive fine particles are preferably present near the surface of the hard coat layer or protrude from the surface. When the conductive fine particles are too small with respect to the thickness of the hard coat layer, the surface resistance value of the optical layered body of the present invention is increased, and the antistatic performance may be deteriorated. Specifically, the average particle diameter of the conductive fine particles is preferably 0.8 to 1.5 times the thickness of the hard coat layer. If it is less than 0.8 times, the antistatic performance of the optical layered body of the present invention may be insufficient, and if it exceeds 1.5 times, the conductive fine particles may fall off the hard coat layer.

The content of the conductive fine particles is preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the resin component in the hard coat layer. If it is less than 0.5 parts by mass, the antistatic performance of the optical laminate of the present invention may be insufficient. If it exceeds 2.0 parts by mass, the hard coat layer to be formed becomes hazy (turbidity is low). May cause problems such as inferior optical properties, and the viscosity of the hard coat layer composition may be increased, resulting in reduced coatability and unevenness and streaks on the surface. The hard coat performance of the hard coat layer may be inferior. A more preferable upper limit of the content of the conductive fine particles is 1.5 parts by mass.

The said ultraviolet absorber is a material which plays the role which ensures the light resistance of the optical laminated body of this invention. That is, by containing the ultraviolet absorber, the optical layered body of the present invention can suppress a change in the surface resistance value even after the durability test.
That is, the ultraviolet absorber in the hard coat layer absorbs the ultraviolet rays irradiated during the durability test, thereby suppressing degradation reactions such as decomposition of the resin components constituting the antistatic layer by ultraviolet rays, and charging The distance between the conductive fine particles contained in the prevention layer can be maintained, and as a result, the durability of the optical laminate of the present invention is improved.
In order to achieve such an effect, the ultraviolet absorber is contained at a position where the antistatic layer of the hard coat layer can be protected.

The ultraviolet absorber is not particularly limited, and an organic or inorganic ultraviolet absorber can be used. Among these, an organic ultraviolet absorber having excellent transparency is preferably used.
Examples of such an ultraviolet absorber include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-). tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-amyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 ′ 2 'such as -hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole -Hydroxyphenyl-5-chlorobenzotriazole UV absorbers, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazol Benzotriazole-based UV absorbers such as 2'-hydroxyphenylbenzotriazole-based UV absorbers such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2,2'-dihydroxy-4- 2,2′-dihydroxybenzophenone-based ultraviolet absorbers such as methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-tetrahydroxybenzophenone, 2- Benzophenone UV absorbers such as 2-hydroxybenzophenone UV absorbers such as hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, salicylic acid esters such as phenyl salicylate and 4-t-butyl-phenyl-salicylate An ultraviolet absorber is mentioned. Of these, hydroxyphenyltriazine-based ultraviolet absorbers are preferred.
In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into the benzotriazole skeleton is also used. Or when high transparency is not requested | required, an inorganic type ultraviolet absorber can also be added. As the inorganic ultraviolet absorber, titanium oxide, cerium oxide, iron oxide or the like having a particle size of 0.2 μm or less is used.

The ultraviolet absorber preferably has an ultraviolet transmittance of 2 to 40% at a transmittance of 380 nm. If it is less than 2%, the curability of the hard coat layer may be insufficient and the hard coat performance may be inferior. If it exceeds 40%, the temporal change in light resistance of the optical laminate of the present invention may increase. In addition, the adhesion of each layer in the optical laminate of the present invention may be inferior. The ultraviolet transmittance is measured by measuring the transmittance of ultraviolet light having a wavelength of 380 nm with a spectroscope using the optical laminate of the present invention including a light-transmitting substrate, an antistatic layer and a hard coat layer. Value.

The content of the ultraviolet absorber is appropriately determined so as to fall within the range of the ultraviolet transmittance depending on the ultraviolet absorbing ability of the ultraviolet absorber to be used. For example, when hydroxyphenyltriazine is used as the ultraviolet absorber. Preferably, it is 3 to 15% by mass in the hard coat layer.

The hard coat layer composition may contain a thermosetting resin as the resin component. Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin. And polysiloxane resin.

The hard coat layer composition preferably further contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it is a known one. For example, acetophenones (for example, trade name Irgacure 184, 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by BASF, trade name Irgacure 907, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one), benzophenones, thioxanthones, benzoin, benzoin methyl ether, aromatic diazonium salt, aromatic sulfonium manufactured by BASF Examples thereof include salts, aromatic iodonium salts, metathelon compounds, and benzoin sulfonic acid esters. Of these, acetophenones are preferable.

It is preferable that content of the said photoinitiator is 1-7 mass parts with respect to 100 mass parts of monomer components in the composition for hard-coat layers. If the amount is less than 1 part by mass, the amount of the photopolymerization initiator may be insufficient, resulting in insufficient curing. When the amount exceeds 7 parts by mass, the photopolymerization initiator becomes excessive, and a difference in the photopolymerization reaction due to the excess is caused.
As for content of the said photoinitiator, it is more preferable that it is 2-5 mass parts with respect to 100 mass parts of said monomer components.

The composition for hard coat layers may further contain other components as necessary in addition to the components described above.
Examples of the other components include a thermal polymerization initiator, a light stabilizer, a crosslinking agent, a curing agent, a polymerization accelerator, a viscosity modifier, an antioxidant, an antifouling agent, a slip agent, a refractive index modifier, a dispersant, A diffusing agent, a shaping agent, an antiglare agent, etc. can be mentioned. These can use a well-known thing.

The hard coat layer composition preferably has a total solid content of 20 to 45%. If it is lower than 20%, residual solvent may remain or whitening may occur. If it exceeds 45%, the viscosity of the composition for hard coat layer becomes high, and the coating property is lowered, and there is a possibility that unevenness and streaks appear on the surface. The solid content is more preferably 20 to 30%.

The hard coat layer composition can be prepared by mixing and dispersing the above-described conductive fine particles, monomer component, resin component and ultraviolet absorber, and other components such as a photopolymerization initiator in a solvent.
The mixing and dispersing may be performed using a known apparatus such as a paint shaker, a bead mill, a kneader.

Examples of the solvent include water, alcohol (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl). Ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone), aliphatic hydrocarbon (eg, hexane, cyclohexane), halogenated hydrocarbon (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbon (Eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether Ether alcohols (e.g., 1-methoxy-2-propanol) and the like. Of these, methyl isobutyl ketone is preferred because it has little influence on the antistatic layer and has high solubility in monomers and thermoplastic resins. Further, although the reason is unknown, it is preferable to contain isopropanol because coating defects such as unevenness are difficult to occur on the surface of the hard coat layer.

The hard coat layer composition can be applied on the antistatic layer to form a coating film, dried as necessary, and then cured to form a hard coat layer. .

Examples of a method for forming the coating film by applying the hard coat layer composition include, for example, a slit reverse method, a spin coating method, a dip method, a spray method, a die coating method, a bar coating method, a roll coater method, and a meniscus coater method. And various known methods such as flexographic printing, screen printing, and bead coater.

The coating amount is preferably ³ to 15 g / m ² . If it is less than 3 g / m ² , a hard coat layer having a desired hardness may not be obtained. If it exceeds 15 g / m ² , curling and damage may be insufficiently prevented. The coating amount is more preferably 4 to 10 g / m ² .

Although it does not specifically limit as said drying method, Generally, it is good to carry out at drying temperature 30-100 degreeC, and drying time 3 to 120 second. When the drying temperature is less than 30 ° C., it takes a long time to produce the optical laminate of the present invention, and the production cost may increase. On the other hand, when the said drying temperature exceeds 100 degreeC, there exists a problem which the planarity of a light-transmitting base material and the uniformity of the hard-coat layer surface deteriorate. A more preferable upper limit of the drying temperature is 70 ° C.
If the drying time is less than 3 seconds, the adhesion between the hard coat layer to be formed and the antistatic layer may be inferior. On the other hand, when the drying time exceeds 120 seconds, it takes a long time to dry the coating film, which may increase the production cost.

As a method for curing the coating film, a known method may be appropriately selected according to the content of the composition for the hard coat layer and the like. For example, a method of curing the coating film by irradiating with ultraviolet rays may be used. Can be mentioned.
When irradiating the ultraviolet light is preferably ultraviolet irradiation amount is 30 mJ / cm ² or more, more preferably 50 mJ / cm ² or more, more preferably 80 mJ / cm ² or more.

The hard coat layer preferably has a layer thickness of 3 to 15 μm.
If the film thickness is less than 3 μm, the hardness of the hard coat layer may be insufficient. On the other hand, if the film thickness exceeds 15 μm, residual solvent may remain in the hard coat layer, adhesion of the coating film may be lowered, and curling and damage prevention properties may be insufficient. The lower limit of the thickness of the hard coat layer is more preferably 3 to 10 μm.
The layer thickness is a value obtained by measuring the cross section of the hard coat layer with an electron microscope (SEM, TEM, STEM).

The hard coat layer preferably has a hardness of 2B or more, more preferably B or more, in a pencil hardness test (load 4.9N) according to JIS K5600-5-4 (1999).

The optical layered body of the present invention preferably has a total light transmittance of 85% or more. If it is less than 85%, color reproducibility and visibility may be impaired when mounted on the display surface, and a desired contrast may not be obtained. The total light transmittance is more preferably 88% or more.
The total light transmittance can be measured by a method based on JIS K7361 using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150).

The optical layered body of the present invention preferably has a haze of 2% or less. If it exceeds 2%, desired optical characteristics cannot be obtained, and the visibility when the optical laminate of the present invention is placed on the image display surface is lowered.
The haze can be measured by a method based on JIS K7136 using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150).
The optical layered body of the present invention can also have other layers (antiglare layer, other antistatic layer, low refractive index layer, antifouling layer, adhesive layer) as necessary within the range where the effects of the present invention are not impaired One layer or two or more layers of an agent layer, other hard coat layers, etc.) can be appropriately formed. Among these, it is preferable to have at least one of an antiglare layer, an antistatic layer, a low refractive index layer, and an antifouling layer. These layers may be the same as those of a known antireflection laminate.

The optical laminate of the present invention can be used in an image display device, and an image display device using such an optical laminate of the present invention is also one aspect of the present invention.
Examples of the image display device include LCD, PDP, FED, ELD (organic EL, inorganic EL), CRT, touch panel, electronic paper, tablet PC, and the like.

The LCD has at least a backlight light source, a liquid crystal cell, and a polarizing plate disposed on the viewing side of the liquid crystal cell. When the image display device of the present invention is an LCD, the optical laminate of the present invention is formed on the viewing side of the polarizing plate.
Although it does not specifically limit as said backlight light source, It is preferable that it is a white light emitting diode (white LED).
The white LED is an element that emits white by combining a phosphor with a phosphor system, that is, a light emitting diode that emits blue light or ultraviolet light using a compound semiconductor. In particular, white light-emitting diodes, which consist of light-emitting elements that combine blue light-emitting diodes using compound semiconductors with yttrium, aluminum, and garnet yellow phosphors, have a continuous and broad emission spectrum, so they have anti-reflection performance. In addition, it is effective for improving the bright room contrast and is excellent in luminous efficiency, and is therefore suitable as the backlight light source in the present invention. Further, since white LEDs with low power consumption can be widely used, it is possible to achieve an energy saving effect.

In the case where the present invention is an LCD having the optical laminate, the light source of the light source device is irradiated from the lower side (base material side) of the optical laminate. Note that a phase difference plate may be inserted between a liquid crystal display element and a polarizing plate in a TN mode, VA mode, or IPS mode liquid crystal display device. An adhesive layer may be provided between the layers of the liquid crystal display device as necessary.

The PDP includes a front glass substrate and a rear glass substrate disposed with a discharge gas sealed between the front glass substrate and the front glass substrate. In the case where the image display device of the present invention is a PDP, the surface of the surface glass substrate or the front plate (glass substrate or film substrate) is provided with the optical laminate described above.

Other image display devices are ELD devices that emit light when zinc is applied, such as zinc sulfide or diamine substances, deposited on a glass substrate, and display the voltage by controlling the voltage applied to the substrate. It may be an image display device such as a CRT that generates an image visible to the human eye. In this case, the optical laminated body described above is provided on the outermost surface of each display device as described above or the surface of the front plate.

In any case, the optical laminate of the present invention can be used for display display of a television, a computer or the like. In particular, it can be suitably used for the surface of a high-definition image display such as a liquid crystal panel, PDP, ELD, touch panel, and electronic paper.

In the optical layered body of the present invention, the antistatic layer is formed by using an antistatic layer composition containing conductive fine particles, a resin component, and a solvent. For this reason, the stability of the surface resistance value after the durability test is excellent. In addition, the optical laminate of the present invention has a hard coat layer made of a composition containing conductive fine particles, a monomer component, the same resin component as the antistatic layer, and an ultraviolet absorber on the antistatic layer. Hard coat performance can be imparted, adhesion between the constituent layers is excellent, and the change in surface resistance before and after the durability test is small.
Therefore, the optical laminate of the present invention includes a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, electronic paper, It can be suitably used for a tablet PC or the like.

It is a graph which shows the emission spectrum of the backlight light source of the liquid crystal monitor used in the Example etc.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.
In the text, “part” or “%” is based on mass unless otherwise specified.

Example 1
(Formation of antistatic layer)
The polyethylene terephthalate material was melted at 290 ° C., extruded through a film-forming die, into a sheet form, closely adhered onto a water-cooled and cooled rotating quenching drum, and cooled to produce an unstretched film.
This unstretched film was preheated at 120 ° C. for 1 minute using a biaxial stretching test apparatus, and then stretched at 120 ° C. to a stretch ratio of 4.5 times. Then, an aqueous dispersion of a polyester resin was solidified on one side. The primer layer resin composition consisting of 28.0 parts by mass and 72.0 parts by mass of water was uniformly applied using a roll coater.
Next, this coated film was dried at 95 ° C., and stretched at a stretch ratio of 1.5 times in the direction of 90 ° with respect to the previous stretching direction. Retardation = 10000 nm, film thickness = 100 μm, Δn = 0.10 A light transmissive substrate was produced.
Next, HRAG acrylic (25) MIBK (thermoplastic resin, polymethyl methacrylate resin, solid content 25%, MIBK solution, weight average molecular weight 70,000, glass transition temperature 100 ° C .: manufactured by DNP Fine Chemical Co., Ltd.) in propylene glycol monomethyl ether Dissolve and add V3560 (ATO dispersion: average particle size 8 nm, manufactured by JGC Catalysts & Chemicals Co., Ltd.) and stir to give a final solid content of 8% and a thermoplastic resin: ATO ratio of 100: 200 (mass ratio). Thus, an antistatic layer composition was obtained.
On one surface of the light-transmitting substrate from which the composition for antistatic layer was produced, a coating film was formed by slit reverse coating so that the dry coating thickness was 0.3 μm. The obtained coating film was dried at 70 ° C. for 1 minute to form an antistatic layer.

(Formation of hard coat layer)
4 parts by mass of Irgacure 184 (photopolymerization initiator, manufactured by BASF Japan) was added to a mixed solvent of methyl isobutyl ketone (MIBK) / isopropanol (IPA) and dissolved by stirring to obtain a final solid content of 25% by mass. A solution of was prepared. To this solution, pentaerythritol triacrylate (PETA) and HRAG acrylic (25) MIBK (thermoplastic resin: manufactured by DNP Fine Chemical Co., Ltd.) are added as resin components so that the mass ratio of the resin components is 70:30, and a leveling agent is added. 10-301 (TL) (manufactured by Dainichi Seika Kogyo Co., Ltd.) was added and stirred so as to be 0.2 parts by mass with respect to 100 parts by mass of the resin component. To this solution, 100 g of bright dispersion (conductive fine particle dispersion, manufactured by DNP Fine Chemical Co., Ltd., average particle diameter 4.6 μm, solid content 25%) was added to 12 kg of the hard coat layer composition as the final composition. Stirring is performed, and finally an ultraviolet absorber (TINUVI477: manufactured by BASF Japan Ltd.) is added to 6 parts by mass with respect to 100 parts by mass of the resin and stirred to obtain a composition for a hard coat layer having a total solid content of 25%. Obtained.
This hard coat layer composition was applied on the antistatic layer previously formed by slit reverse coating to form a dry coating amount of 6 g / m ² to form a coating film. After drying the obtained coating film at 70 ° C. for 1 minute, the coating film was cured by irradiating ultraviolet rays at an ultraviolet irradiation amount of 80 mJ / cm ² to form a 5 μm thick hard coat layer to obtain an optical laminate. .

(Example 2)
An optical laminate was obtained in the same manner as in Example 1 except that the blending amount of the ultraviolet absorber in the hard coat layer composition was 3 parts by mass.

(Example 3)
An optical laminate was obtained in the same manner as in Example 1 except that the blending amount of the ultraviolet absorber in the hard coat layer composition was 10 parts by mass.

Example 4
An optical laminate was obtained in the same manner as in Example 1 except that the blending amount of the ultraviolet absorber in the hard coat layer composition was 15 parts by mass.

(Example 5)
Instead of HRAG acrylic (25) MIBK (thermoplastic resin, weight average molecular weight 70,000, glass transition temperature 100 ° C .: manufactured by DNP Fine Chemical Co.), a thermoplastic resin having a weight average molecular weight 50,000 and glass transition temperature 100 ° C. was used. An antistatic layer was formed in the same manner as in Example 1 except for the above. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Example 6)
Instead of HRAG acrylic (25) MIBK (thermoplastic resin, weight average molecular weight 70,000, glass transition temperature 100 ° C .: manufactured by DNP Fine Chemical), a thermoplastic resin having a weight average molecular weight 100,000 and glass transition temperature 100 ° C. was used. An antistatic layer was formed in the same manner as in Example 1 except for the above. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Example 7)
Instead of HRAG acrylic (25) MIBK (thermoplastic resin, weight average molecular weight 70,000, glass transition temperature 100 ° C .: manufactured by DNP Fine Chemical), a thermoplastic resin having a weight average molecular weight 70,000 and glass transition temperature 80 ° C. was used. An antistatic layer was formed in the same manner as in Example 1 except for the above. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Example 8)
Instead of HRAG acrylic (25) MIBK (thermoplastic resin, weight average molecular weight 70,000, glass transition temperature 100 ° C .: manufactured by DNP Fine Chemical Co.), a thermoplastic resin having a weight average molecular weight 70,000 and glass transition temperature 110 ° C. was used. An antistatic layer was formed in the same manner as in Example 1 except for the above. Thereafter, a hard coat layer was formed in the same manner as in Example 1 except that the total solid content was 26% to obtain an optical laminate.

Example 9
An antistatic layer was formed in the same manner as in Example 1 except that the ratio of thermoplastic resin: ATO was adjusted to 100: 150 (mass ratio). Thereafter, a hard coat layer was formed in the same manner as in Example 1 except that the total solid content was 26% to obtain an optical laminate.

(Example 10)
An antistatic layer was formed in the same manner as in Example 1 except that the ratio of thermoplastic resin: ATO was adjusted to 100: 250 (mass ratio). Thereafter, a hard coat layer was formed in the same manner as in Example 1 except that the total solid content was 26% to obtain an optical laminate.

(Example 11)
An antistatic layer was formed in the same manner as in Example 1 except that the thickness was 0.2 μm, and then a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Example 12)
An antistatic layer was formed in the same manner as in Example 1 except that the thickness was 0.5 μm, and then a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Example 13)
An antistatic layer was formed in the same manner as in Example 1, and then a hard coat layer was formed in the same manner as in Example 1 except that the thickness was changed to 4 μm to obtain an optical laminate.

(Example 14)
An antistatic layer was formed in the same manner as in Example 1, and thereafter a hard coat layer was formed in the same manner as in Example 1 except that the thickness was changed to 7 μm to obtain an optical laminate.

(Example 15)
The stretch ratio of the unstretched film obtained in the same manner as in Example 1 was adjusted to obtain a light-transmitting substrate having retardation = 7200 nm, film thickness = 80 μm, and Δn = 0.09. An optical laminate was obtained in the same manner as in Example 1 except that the obtained light-transmitting substrate was used.

(Example 16)
The stretch ratio of the unstretched film obtained in the same manner as in Example 1 was adjusted to obtain a light-transmitting substrate having retardation = 5400 nm, film thickness = 60 μm, and Δn = 0.09. An optical laminate was obtained in the same manner as in Example 1 except that the obtained light-transmitting substrate was used.

(Example 17)
An unstretched film was produced in the same manner as in Example 1 except that a polyethylene naphthalate material was used as the material for the light transmissive substrate. The draw ratio of the obtained unstretched film was adjusted to obtain a light-transmitting substrate having retardation = 10100 nm, film thickness = 48 μm, and Δn = 0.21. An optical laminate was obtained in the same manner as in Example 1 except that the obtained light-transmitting substrate was used.

(Example 18)
An unstretched film was produced in the same manner as in Example 1 except that a polyethylene naphthalate material was used as the material for the light transmissive substrate. The stretch ratio of the obtained unstretched film was adjusted to obtain a light-transmitting substrate having retardation = 5500 nm, film thickness = 26 μm, and Δn = 0.21. An optical laminate was obtained in the same manner as in Example 1 except that the obtained light-transmitting substrate was used.

(Comparative Example 1)
4 parts by mass of Irgacure 184 (photopolymerization initiator, manufactured by BASF Japan) was added to propylene glycol monomethyl ether (PGME) and dissolved by stirring to prepare a solution having a final solid content of 25% by mass. To this solution, pentaerythritol triacrylate (PETA) was added as a resin component and stirred. ATO was added to this solution and stirred so that the PETA: ATO after curing was 100: 200, and an antistatic layer composition having a total solid content of 25% was obtained.
This antistatic layer composition was applied to a light transmissive substrate produced in the same manner as in Example 1 by slit reverse coating so that the dry coating thickness was 0.3 μm. The obtained coating film was dried at 70 ° C. for 1 minute and then irradiated with ultraviolet rays at an ultraviolet irradiation amount of 80 mJ / cm ² to cure the coating film to form an antistatic layer.
Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Comparative Example 2)
An antistatic layer was formed in the same manner as in Comparative Example 1 except that dipentaerythritol hexaacrylate (DPHA) was used instead of PETA. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Comparative Example 3)
An antistatic layer was formed in the same manner as in Comparative Example 1 except that 1,6-hexanediol (HDDA) was used instead of PETA. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Comparative Example 4)
Example 1 except that urethane acrylate (BS577, manufactured by Arakawa Chemical Co., Ltd.) was used instead of HRAG acrylic (25) MIBK (thermoplastic resin, weight average molecular weight 70,000, glass transition temperature 100 ° C .: manufactured by DNP Fine Chemical Co., Ltd.) In the same manner, an antistatic layer was formed. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Comparative Example 5)
Instead of PETA, an antistatic layer was formed in the same manner as in Comparative Example 1 except that a resin in which HRAG acrylic (25) MIBK and PETA were mixed at a resin ratio of 1: 1 (mass ratio) was used. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Comparative Example 6)
The stretch ratio of the unstretched film obtained in the same manner as in Example 1 was adjusted to obtain a light-transmitting substrate having retardation = 4000 nm, film thickness = 40 μm, and Δn = 0.10. An optical laminate was prepared in the same manner as in Example 1 except that the obtained light-transmitting substrate was used.

(Comparative Example 7)
The stretch ratio of the unstretched film obtained in the same manner as in Example 1 was adjusted to obtain a light-transmitting substrate having retardation = 2700 nm, film thickness = 30 μm, and Δn = 0.09. An optical laminate was prepared in the same manner as in Example 1 except that the obtained light-transmitting substrate was used.

(Reference Example 1)
An antistatic layer was formed in the same manner as in Example 1. Thereafter, a hard coat layer was formed in the same manner as in Example 1 except that no ultraviolet absorber was added, thereby obtaining an optical laminate.

(Reference Example 2)
An antistatic layer was formed in the same manner as in Example 1. Thereafter, a hard coat layer was formed in the same manner as in Example 1 except that the blending amount of the ultraviolet absorber was 16 parts by mass to obtain an optical laminate.

(Reference Example 3)
Instead of HRAG acrylic (25) MIBK (thermoplastic resin, weight average molecular weight 70,000, glass transition temperature 100 ° C .: manufactured by DNP Fine Chemical), a thermoplastic resin having a weight average molecular weight 10,000 and glass transition temperature 110 ° C. was used. An antistatic layer was formed in the same manner as in Example 1 except for the above. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Reference Example 4)
Instead of HRAG acrylic (25) MIBK (thermoplastic resin, weight average molecular weight 70,000, glass transition temperature 100 ° C .: manufactured by DNP Fine Chemical Co.), a thermoplastic resin having a weight average molecular weight 70,000 and glass transition temperature 70 ° C. was used. An antistatic layer was formed in the same manner as in Example 1 except for the above. Thereafter, a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Reference Example 5)
An antistatic layer was formed in the same manner as in Example 1 except that the ratio of thermoplastic resin: ATO was adjusted to 100: 50 (mass ratio). Thereafter, a hard coat layer was formed in the same manner as in Example 1 except that the total solid content was 26% to obtain an optical laminate.

(Reference Example 6)
An antistatic layer was formed in the same manner as in Example 1 except that the ratio of thermoplastic resin: ATO was adjusted to 100: 350 (mass ratio). Thereafter, a hard coat layer was formed in the same manner as in Example 1 except that the total solid content was 26% to obtain an optical laminate.

(Reference Example 7)
An antistatic layer was formed in the same manner as in Example 1 except that the thickness was changed to 0.09 μm, and then a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Reference Example 8)
An antistatic layer was formed in the same manner as in Example 1 except that the thickness was 1.2 μm, and then a hard coat layer was formed in the same manner as in Example 1 to obtain an optical laminate.

(Reference Example 9)
An antistatic layer was formed in the same manner as in Example 1, and then a hard coat layer was formed in the same manner as in Example 1 except that the thickness was changed to 2 μm to obtain an optical laminate.

(Reference Example 10)
An antistatic layer was formed in the same manner as in Example 1, and then a hard coat layer was formed in the same manner as in Example 1 except that the thickness was changed to 12 μm to obtain an optical laminate.

The following evaluation was performed about the optical laminated body obtained by the Example, the comparative example, and the reference example.
Each evaluation is performed immediately after manufacturing the optical laminate (initial performance), after the durability test (1) (held at 80 ° C. for 500 hours), and after the durability test (2) (300 hours of xenon arc irradiation). It was. In addition, about the resistance value of the optical laminated body after a durability test (1) and (2), change rate (surface resistance value after a test) / (surface resistance value before a test) with respect to immediately after manufacture (initial performance). Calculated. The results according to the examples are shown in Table 1, and the results according to the comparative example and the reference example are shown in Table 2.

(Total light transmittance, haze)
A method in accordance with JIS K7361 (total light transmittance) using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150) for the transmittance (total light transmittance) and haze of each optical laminate. It was measured by.

(Resistance value)
The surface resistance value of each optical laminate was measured using Hiresta UP MCP-HT450 (Mitsubishi Chemical Corporation: R probe, applied voltage 500 V) (unit: Ω / □).

(Adhesion)
A cross cut cross cut test was performed on each optical laminate, and the ratio of the number of cut parts remaining on the substrate after peeling the tape with respect to the original number of cut parts (100) was evaluated according to the following criteria.
○: 90/100 to 100/100
Δ: 50/100 to 89/100
X: 0/100 to 49/100

(Pencil hardness)
Each optical laminate was conditioned for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 60%, and then using JIS K5600-5-4 (1999) using a test pencil (hardness 2B to 3H) specified in JIS S6006. The pencil hardness of the surface on which the hard coat layer was formed was measured under a load of 4.9 N according to the pencil hardness evaluation method specified in (1).

Moreover, the following evaluation was performed about the optical laminated body obtained by the Example, the comparative example, and the reference example.
(Nijimura evaluation)
Each optical layered body was disposed on the polarizing plate on the viewer side of a liquid crystal monitor (FLATRON IPS 226V (manufactured by LG Electronics Japan)) to prepare a liquid crystal display device. In addition, it arrange | positioned so that the angle which the slow axis of a polyester base material and the absorption axis of the polarizing plate by the side of the observer of a liquid crystal monitor may make would be 45 degrees.
In the dark and bright places (illuminance around the LCD monitor 400 lux), the display image is observed visually and through polarized sunglasses from the front and diagonal directions (about 50 degrees), and the presence or absence of nidimra is evaluated according to the following criteria. did. Observation through polarized sunglasses is a much stricter evaluation method than visual observation. The observation is performed by 10 people, and the largest number of evaluations are the observation results.
FIG. 1 shows the emission spectrum of the backlight source of the liquid crystal monitor used.
◎: Nizimura is not observed ○: Nizimura is observed, but there is no problem in practical use ×: Nizimura is observed strongly

(Evaluation of color change)
Each optical laminated body was arrange | positioned through the adhesion | attachment on the polarizing plate by the side of the observer of the liquid crystal monitor (FLATRON IPS226V (made by LG Electronics Japan)), and the liquid crystal display device was produced. In addition, it arrange | positioned so that the angle which the slow axis of a polyester base material and the absorption axis of the polarizing plate by the side of the observer of a liquid crystal monitor may make would be 45 degrees.
In a dark place, the liquid crystal monitor is displayed in white, and when the angle between the polarizing sunglasses absorption axis and the absorption axis of the polarizing plate on the observer side of the liquid crystal monitor is 0 degree (parallel Nicol), 90 degrees ( The front color at the time of “cross nicols” was measured with a luminance meter BM-5 (manufactured by Topcon Corporation), and the color difference Δu′v ′ was calculated. At the same time, observation was carried out by 10 people and evaluated according to the following criteria. The most numerous evaluations are the observation results.
A: There is no color difference between parallel and crossed Nicols.
Color difference Δu′v ′ <0.01
○: There is a slight color difference between parallel Nicol and cross Nicol, but there is no problem in actual use.
0.01 ≦ color difference Δu′v ′ ≦ 0.03
X: There is a color difference between parallel Nicol and cross Nicol.
Color difference Δu′v ′> 0.03

As shown in Table 1, the optical laminate according to the example had a small rate of change in surface resistance value before and after the durability test, and extremely high antistatic performance. Moreover, it was excellent also in each evaluation of haze, a total light transmittance, adhesiveness, and pencil hardness. Furthermore, it was excellent in the evaluation of Nijimura and color change.
On the other hand, as shown in Table 2, the optical laminate according to the comparative example has a large rate of change of the surface resistance value before and after the durability test (2), and is inferior in stability of the antistatic performance. It was. Moreover, the optical laminated body which concerns on the comparative examples 6 and 7 was inferior to the evaluation of a nidimra and a tint change.
Further, the optical laminate according to Reference Example 5 in which the blending amount of the conductive fine particles in the antistatic layer was small, the optical laminate according to Reference Example 7 in which the thickness of the antistatic layer was too thin, and the thickness of the hard coat layer were The optical laminate according to Reference Example 10, which was too thick, had a surface resistance value that was too high and was insufficient in antistatic properties. In addition, the optical laminate according to another reference example has a small change rate of the surface resistance value before and after the durability test and an extremely high antistatic performance, but the haze, the total light transmittance, the adhesion, and the pencil. None of the hardness evaluations were excellent.

The optical laminate of the present invention includes a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, electronic paper, a tablet PC, and the like. Can be suitably used.

Claims (12)

An optical laminate having an antistatic layer on one surface of a light-transmitting substrate having a birefringence in the plane,
The antistatic layer is formed using a composition for an antistatic layer containing conductive fine particles, a resin component, and a solvent,
The resin component does not have a reactive functional group in the molecule, and has solubility in the solvent and compatibility with the conductive fine particles,
The optically transparent substrate is characterized in that the light transmissive substrate has a retardation of 5000 nm or more. The optical laminate according to claim 1, wherein the conductive fine particles are chain-like or needle-like. Change rate of surface resistance value before and after durability test (1) for 500 hours in 80 ° C. environment and durability test (2) for 300 hours irradiation with xenon arc {(surface resistance value after test) / (before test) The surface laminate value)} is 0.5 to 2.0 in any case. 3. The optical laminate according to claim 1 or 2. The optical laminate according to claim 1, 2 or 3, wherein the resin component has a weight average molecular weight of 20,000 to 200,000 and a glass transition temperature of 80 to 120 ° C. The resin component is at least one selected from the group consisting of acrylic resins, cellulose resins, urethane resins, vinyl chloride resins, polyester resins, polyolefin resins, polycarbonate, nylon, polystyrene, and ABS resins. Item 5. The optical laminate according to Item 1, 2, 3 or 4. The optical laminate according to claim 1, 2, 3, 4, or 5, wherein the conductive fine particles are antimony tin oxide (ATO), the resin component is polymethyl methacrylate, and the solvent is propylene glycol monomethyl ether. . The optical laminated body according to claim 1, 2, 3, 4, 5 or 6, further comprising a hard coat layer on the surface of the antistatic layer opposite to the light transmissive substrate side. The optical laminate according to claim 7, wherein the hard coat layer contains the same resin component as the resin component contained in the antistatic layer. The optical laminate according to claim 7 or 8, wherein the hard coat layer contains conductive fine particles. The optical layered body according to claim 7, wherein the hard coat layer contains an ultraviolet absorber. The optical laminate according to claim 10, wherein the content of the ultraviolet absorber is 3 to 15% by mass. An image display device comprising the optical laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11.

Images