JP7198946B2 - Optical laminate, polarizing plate, image display device, resistive touch panel and capacitive touch panel - Google Patents

Description

TECHNICAL FIELD The present invention relates to an optical laminate, a polarizing plate, an image display device, a resistive touch panel, and a capacitive touch panel.

Conventionally, glasses such as chemically strengthened glass have been mainly used for applications requiring high durability such as front-side polarizing plates of image display devices, particularly front-side polarizing plates of touch panels. On the other hand, plastic has advantages over glass in that it is lightweight, hard to crack, and can be made thin. Therefore, in recent years, attention has been paid to the usefulness of plastics as a substitute for glass in applications where glass was mainly used. In particular, the use of a hard coat film having a cured layer on a support as a substitute for glass has been studied.
Here, regarding the hard coat film used for the surface of the touch panel, the pencil hardness of the surface is regarded as important.

For example, Patent Document 1 discloses a scattering-prevention pressure-sensitive adhesive sheet in which a hard coat layer of a hard coat film having a pencil hardness of 2H or more, a base film, and a pressure-sensitive adhesive layer are laminated in this order. The coating layer has a thickness of 8 to 20 μm, the adhesive layer has a thickness of 1 to 13 μm, and the storage elastic modulus of the adhesive layer at 0° C. is 1.0×10 ⁶ to 1.0×10 ⁸ Pa. A scattering-preventive pressure-sensitive adhesive sheet characterized by Patent Document 1 describes that this scattering-preventive pressure-sensitive adhesive sheet maintains a pencil hardness of H or higher and has good punching processability and cutting processability, and uses a polyethylene terephthalate film as a base film. Examples are given.
Further, Patent Document 2 discloses a hard coat film comprising a substrate and a hard coat layer laminated on at least one surface of the substrate, wherein the hard coat film has an in-plane retardation of 6000 nm. 40000 nm or less, and at least one surface has a pencil hardness of 5H or more, and the first hard coat layer, which is the nearest hard coat layer on the surface having a pencil hardness of 5H or more in the hard coat film, is 30 A hard coat film is described which contains a filler in a content of vol % or more and 70 vol % or less and has a thickness of 20 μm or more and 100 μm or less. Patent Document 2 describes that the hard coat film can suppress the occurrence of color unevenness caused by providing the hard coat layer, and describes an example using a polyethylene terephthalate film as the substrate.
Furthermore, Patent Document 3 discloses a laminate having at least a resin film and an adhesive layer arranged on one side of the resin film, and in the laminated state of the laminate, the resin film is different from the surface having the adhesive layer. On the opposite side, the surface roughness Sa at a measurement field of view of 4 mm × 5 mm is 30 nm or less, the adhesive layer has a thickness of 100 μm or less, and the maximum value of the loss tangent at a frequency of 1 Hz is 0 ° C to -40 ° C. and has a maximum value of 1.3 or more. According to the laminate described in Patent Document 3, it is described that excellent glass quality can be exhibited even when laminated on another member.

JP 2011-168652 A JP 2016-164641 A WO2017/204228

As a result of studies by the present inventors, the film using a polyethylene terephthalate film as a base film as described in Patent Documents 1 and 2 has a low pencil hardness as a hard coat film, It has been found that the hardness is insufficient for faceplate applications. In addition, although Patent Document 3 describes a laminate exhibiting high pencil hardness, as a result of investigations by the present inventors, it was found that a hard coat film exhibiting high pencil hardness was attached to an adherend such as a polarizing plate. It has been found that there is room for improvement in that the pencil hardness may be greatly reduced due to lamination via an adhesive layer or the like.
The present invention provides an optical laminate that has excellent pencil hardness as a hard coat film and is excellent in suppressing a decrease in pencil hardness caused by lamination via an adhesive layer, a polarizing plate, and an image display device comprising the same. , to provide a resistive touch panel and a capacitive touch panel.

As a result of intensive studies conducted by the present inventors in order to solve the above problems, the inventors have found that the above problems can be solved by the following means.
<1>
An optical laminate having at least an adhesive layer, a support provided on one side of the adhesive layer, and a hard coat layer provided on the support,
The storage elastic modulus A and thickness B of the adhesive layer satisfy the following formula (1),
A×30−B≧0 Formula (1)
The support has a tensile modulus of 4.5 GPa or more, a product of the indentation modulus and recovery rate of 3.75 or more, and a thickness of 80 μm or more,
The hard coat layer has an indentation modulus of elasticity of 7 GPa or more and a thickness of 10 μm or more,
An optical layered body, wherein a difference between a pencil hardness of a hard coat film comprising the support and the hard coat layer and a pencil hardness of the optical layered body is 1H or less.
However, in the above formula (1), the unit of storage elastic modulus A is MPa, and the unit of thickness B is μm.
<2>
2. The optical laminate according to claim 1, wherein the support contains a triacetylcellulose resin.
<3>
3. The optical laminate according to claim 1, wherein the support has a thickness of 100 [mu]m or more.
<4>
The hard coat layer has a polymerizable compound 1 having a (meth)acrylic group, and a polymerizable compound 2 having an epoxy group and a (meth)acrylic group in the same molecule and different from the polymerizable compound 1. Formed from a curable composition for forming a hard coat layer containing
4. The optical laminate according to any one of claims 1 to 3, wherein the polymerizable compound 2 accounts for 51% by mass or more of the polymerizable compounds contained in the curable composition for forming a hard coat layer.
<5>
Having a scratch-resistant layer on the surface of the hard coat layer opposite to the support,
The scratch-resistant layer is formed from a scratch-resistant layer-forming curable composition containing a polymerizable compound having at least three (meth)acrylic groups in the same molecule and a fluorine-containing compound having a (meth)acrylic group. The optical laminate according to any one of claims 1 to 4, wherein
<6>
The curable composition for forming a hard coat layer contains inorganic particles modified with a (meth)acrylic group or an epoxy group, and the content of the inorganic particles in the solid content of the curable composition for forming a hard coat layer The optical laminate according to any one of claims 1 to 5, wherein the is 20% by mass or more.
<7>
The optical laminate according to any one of claims 1 to 6, wherein the storage elastic modulus A and thickness B of the adhesive layer satisfy the following formula (2).
A×30−B≧6 Formula (2)
However, in the above formula (2), the unit of storage elastic modulus A is MPa, and the unit of thickness B is μm.
<8>
A polarizing plate comprising the optical layered body according to any one of claims 1 to 7 and a polarizer disposed on the adhesive layer side of the optical layered body.
<9>
9. The polarizing plate according to claim 8, comprising a polarizer protective film made of polyethylene terephthalate between the polarizer and the adhesive layer constituting the optical laminate.
<10>
The polarizing plate of <8> or <9>, wherein the difference between the pencil hardness of the hard coat film comprising the support and the hard coat layer and the pencil hardness of the polarizing plate is 1H or less.
<11>
An image display device comprising the polarizing plate according to any one of <8> to <10> and an image display element.
<12>
The image display device according to <11>, wherein the image display element is a liquid crystal display element.
<13>
The image display device according to <11> or <12>, wherein the image display element is an organic electroluminescence display element.
<14>
The image display device according to any one of <11> to <13>, wherein the image display element is an in-cell touch panel display element.
<15>
The image display device according to any one of <11> to <13>, wherein the image display element is an on-cell touch panel display element.
<16>
A resistive touch panel comprising the polarizing plate according to any one of <8> to <10>.
<17>
A capacitive touch panel comprising the polarizing plate according to any one of <8> to <10>.

In the present invention, when there are multiple substituents or connecting groups (hereinafter referred to as substituents, etc.) indicated by a specific symbol or formula, or when multiple substituents, etc. are defined at the same time, there is no particular notice. As long as the respective substituents and the like may be the same or different. This also applies to the number of substituents and the like. In addition, when a plurality of substituents and the like are close to each other (especially when they are adjacent), they may be linked together to form a ring unless otherwise specified. In addition, unless otherwise specified, rings such as alicyclic rings, aromatic rings, and heterocyclic rings may be condensed to form condensed rings.
In this specification, unless otherwise specified, the double bond may be either E-type or Z-type in the molecule, or a mixture thereof.
In the present invention, the expression of a compound (including a complex) is meant to include those whose structures are partially changed within a range that does not impair the effects of the present invention. Furthermore, compounds that are not specified as substituted or unsubstituted are meant to have optional substituents within a range that does not impair the effects of the present invention. This also applies to substituents and linking groups.
Further, in the present invention, a numerical range represented by "-" means a range including the numerical values described before and after "-" as lower and upper limits.
In the present invention, a composition means a mixture having a constant component concentration (each component is uniformly dispersed), and a mixture having a variable component concentration within a range that does not impair the intended color conversion function. encompasses
In the present invention, the term "(meth)acrylate" is used to include both acrylate and methacrylate. The same applies to "(meth)acrylic acid", "(meth)acrylamide", "(meth)acryl group", "(meth)acryloyl group" and "(meth)acryloyloxy group". In the present invention, the term "(meth)acrylic group" is used to include both "(meth)acryloyl group" and "(meth)acryloyloxy group".
In the present invention, each component may be used alone or in combination of two or more.
In the present invention, the solid content of the composition means the components excluding the solvent from the total composition of the composition.
In the present invention, the term "cured layer" refers to a layer formed from a composition containing at least a curable compound and having a surface pencil hardness of 2H or more. Examples of the cured layer that the optical laminate of the present invention has or may have include a hard coat layer and an abrasion-resistant layer. is formed from a curable composition for forming an abrasion resistant layer.

The optical laminate of the present invention has excellent pencil hardness as a hard coat film, and is also excellent in the effect of suppressing a decrease in pencil hardness caused by lamination via an adhesive layer. Therefore, the polarizing plate, the image display device, the resistive touch panel, and the capacitive touch panel of the present invention, which contain this optical laminate as a constituent member, maintain the excellent pencil hardness of the hard coat film at an excellent level. be able to.

(Optical laminate)
The optical laminate of the present invention has at least an adhesive layer, a support arranged on one side of the adhesive layer, and a hard coat layer arranged on the support, and the storage elastic modulus A of the adhesive layer and thickness B satisfy the following formula (1). However, in the following formula (1), the unit of storage elastic modulus A is MPa, and the unit of thickness B is μm.
A×30−B≧0 is satisfied. Formula (1)
Further, the support in the optical laminate of the present invention has a tensile modulus of 4.5 GPa or more, a product of the indentation modulus and recovery rate of 3.75 or more, and a thickness of 80 μm or more. is the body,
The hard coat layer has an indentation modulus of elasticity of 7 GPa or more and a thickness of 10 μm or more,
The difference between the pencil hardness of the hard coat film comprising the support and the hard coat layer and the pencil hardness of the optical layered body is within 1H.
The optical laminate of the present invention achieves a hard coat film having a high pencil hardness as a hard coat film comprising a support and a hard coat layer by increasing the elastic modulus and thickness of the hard coat layer to a specific value or higher. can do. On the other hand, when a hard coat film exhibiting a high pencil hardness is laminated to an adherend such as a polarizing plate via an adhesive layer, the pencil hardness is lowered due to the lamination. As a result of intensive studies, a specific adhesive layer that satisfies the above formula (1) is provided as an adhesive layer, the thickness and tensile elastic modulus of the support are increased to a specific value or more, and the indentation elastic modulus and recovery rate of the support are By increasing the product of to a specific value or more, the optical laminate of the present invention has a high pencil hardness as a hard coat film, and furthermore, even after lamination to an adherend such as a polarizing plate via an adhesive layer, , the decrease in pencil hardness can be suppressed to within 1H, and good pencil hardness can be maintained.

Each layer constituting the optical laminate of the present invention will be described in detail below.

[1] Adhesive layer The adhesive layer in the optical layered body of the present invention may be the pressure-sensitive adhesive layer (a) or the adhesive layer (b) as long as the above formula (1) is satisfied. The pressure-sensitive adhesive layer (a) and the adhesive layer (b) used as the adhesive layer in the optical laminate of the present invention will be described in detail.

[Adhesive layer (a)]
The pressure-sensitive adhesive layer means a layer composed of a pressure-sensitive adhesive, that is, a viscoelastic body that develops adhesiveness only by applying force after bonding. The pressure-sensitive adhesive layer (a) used in the present invention is a pressure-sensitive adhesive layer that is usually used for bonding retardation films or display elements, and is particularly limited as long as it is a pressure-sensitive adhesive layer that satisfies the above formula (1). can be used without
The pressure-sensitive adhesive in the present invention does not include the below-described adhesive that develops adhesiveness due to drying or reaction after bonding.

Examples of adhesives used in the adhesive layer (a) include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinylpyrrolidone adhesives, polyacrylamide adhesives, and cellulose adhesives. agents and the like.
Among these, acrylic adhesives (pressure-sensitive adhesives) are preferable from the viewpoint of transparency, weather resistance, heat resistance, and the like.

The pressure-sensitive adhesive layer (a) can be formed, for example, by applying a pressure-sensitive adhesive solution onto a release sheet, drying it, and then transferring it to the surface of the transparent resin layer; It can be formed by a method of coating and drying;
The adhesive solution is prepared as a solution of about 10 to 40% by mass by dissolving or dispersing the adhesive in a solvent such as toluene or ethyl acetate.
As the coating method, a roll coating method such as reverse coating or gravure coating, a spin coating method, a screen coating method, a fountain coating method, a dipping method, a spray method, or the like can be employed.

Materials constituting the release sheet include, for example, synthetic resin films such as polyethylene, polypropylene, and polyethylene terephthalate; rubber sheets; paper; cloth; mentioned.

[Adhesive layer (b)]
The adhesive layer means a layer composed of an adhesive, that is, an agent that develops adhesiveness by drying, reaction, or the like after lamination. As the adhesive layer (b) used in the present invention, any adhesive layer that satisfies the above formula (1) can be used without particular limitation.
For example, a polyvinyl alcohol adhesive (PVA adhesive) exhibits adhesiveness when dried, and can bond materials together.
Specific examples of curable adhesives that exhibit adhesiveness through reaction include active energy ray curable adhesives such as (meth)acrylate adhesives and cationic polymerization curable adhesives such as epoxy adhesives. Examples of the curable component in the (meth)acrylate adhesive include a compound having a (meth)acrylic group and a compound having a vinyl group.
As the cationic polymerization-curable adhesive, a compound having at least one of an epoxy group and an oxetanyl group, which is a cationic polymerizable group, can also be used. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various commonly known curable epoxy compounds can be used. Preferred epoxy compounds include compounds having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compounds), and compounds having at least two epoxy groups in the molecule, at least one of which Examples include compounds (alicyclic epoxy compounds) formed between two adjacent carbon atoms constituting an alicyclic ring.

The adhesive layer in the optical laminate of the present invention is either an acrylic pressure-sensitive adhesive, an active energy ray-curable adhesive such as a (meth)acrylate adhesive, or a cationic polymerization-curable adhesive such as an epoxy adhesive. It is preferably composed of an acrylic adhesive, a (meth)acrylate adhesive, or an epoxy adhesive, more preferably composed of an acrylic adhesive or a (meth)acrylate adhesive. is more preferred.
These pressure-sensitive adhesives and adhesives are not particularly limited as long as they satisfy the above formula (1). Adhesives, acrylic adhesives described in JP-A-2011-128439, acrylic adhesives described in JP-A-2010-44211, etc. can be appropriately adjusted and used.

The storage elastic modulus of the adhesive layer in the optical laminate of the present invention is preferably 0.04 MPa or more, more preferably 0.1 MPa or more, still more preferably 0.3 to 5 MPa, particularly preferably 0.5 to 5 MPa, and 0.5 MPa. 7-2.5 MPa is most preferred. When the storage elastic modulus of the adhesive layer is at least the preferred lower limit, the adhesive layer is difficult to stretch and has good handleability.
<Method for measuring storage modulus>
In the present invention, the storage elastic modulus is a value measured at a frequency of 1 Hz and 25° C. using a dynamic viscoelasticity measuring device (trade name: DVA-200) manufactured by IT Keisoku Co., Ltd.

The thickness of the adhesive layer in the optical laminate of the present invention is preferably 1 to 30 μm, more preferably 3 to 15 μm, still more preferably 5 to 10 μm. When the thickness of the adhesive layer is equal to or less than the above preferable upper limit, it is possible to suppress a decrease in pencil hardness that occurs when the hard coat film is attached to an adherend via the adhesive layer. Moreover, when the thickness of the adhesive layer is at least the above preferable lower limit value, the handleability is good without causing breakage or the like.
<Method for measuring thickness>
In the present invention, the thickness of the adhesive layer is obtained by cutting the optical layered body or the layer constituting the optical layered body with a microtome to expose a cross section, observing with a SEM (Scanning Electron Microscope) at a magnification of 1000 to 3000 times, and measuring the thickness by 5. Point measurement is performed, and the average of these measurements is taken as the thickness. The thickness of the support and the thickness of the hard coat layer are values measured and calculated in the same manner as the thickness of the adhesive layer.

The storage elastic modulus A and thickness B of the adhesive layer in the optical laminate of the present invention satisfy the following formula (1), preferably the following formula (2), and the following formula (3). more preferred. However, in the following formulas (1) to (3), the unit of storage elastic modulus A is MPa, and the unit of thickness B is μm, which are values measured by the above-described method.
A×30−B≧0 Formula (1)
A×30−B≧6 Formula (2)
A×30−B≧16 Formula (3)

From the viewpoint of further improving the pencil hardness of the hard coat film, the adhesive layer in the optical laminate of the present invention satisfies the above formula (2), has a thickness of 3 to 15 μm, and a storage elastic modulus of 0.3. It is preferably ~5 MPa, from the viewpoint of further improving the pencil hardness of the hard coat film and further suppressing the decrease in pencil hardness when the hard coat film is bonded to the adherend via the adhesive layer, the above formula More preferably, it satisfies (3), has a thickness of 5 to 10 μm, and has a storage elastic modulus of 0.7 to 2.5 MPa.
The adhesive layer may have a one-layer structure, or may have a laminated structure of two or more layers. In the case of a laminated structure of two or more layers, the relationship of the above formulas (1) to (3) may be satisfied by the adhesive layer as a whole.

[2] Support The support in the optical laminate of the present invention has a tensile modulus of 4.5 GPa or more, a product of the indentation modulus and recovery rate of 3.75 or more, and a thickness of 80 μm or more. As long as it is a certain support, the film used in the front plate of the image display device can be used without any particular limitation. A resin film is preferable as the support.
Examples of resin films include acrylic resin films, polycarbonate (PC) resin films, triacetylcellulose (TAC) resin films, polyolefin resin films, polyester resin films, and acrylonitrile-butadiene-styrene copolymer films. Films, triacetyl cellulose resin films or polycarbonate resin films are preferred.
Incidentally, the acrylic resin film refers to a polymer or copolymer resin film whose constituent component is one or more compounds selected from acrylic acid esters and methacrylic acid esters. Examples of acrylic resin films include polymethyl methacrylate (PMMA) films.
The support preferably contains triacetyl cellulose, more preferably a triacetyl cellulose resin film.

The structure of the triacetylcellulose resin film is not particularly limited, and it may be a single-layer film or a laminated film composed of two or more layers. The number of laminated layers of the laminated film is preferably 2 to 10 layers, more preferably 2 to 5 layers, and still more preferably 2 or 3 layers. In the case of three or more layers, the outer layer and the layers other than the outer layer (core layer, etc.) preferably have different compositions. Moreover, the outer layers are preferably films having the same composition.
Specifically, it is a film having a laminated structure of TAC-a/TAC-b/TAC-a, and films Tac-a with the same reference numeral a indicate films with the same composition.
Moreover, it is preferable that the triacetyl cellulose resin film contains a sugar ester compound or a phthalate compound as a plasticizer. As the sugar ester compound or phthalate compound, for example, compounds described in JP-A-2012-215689 can be used.
The triacetylcellulose resin film can be produced, for example, according to the method for forming a resin film described in paragraphs 0021 to 0043 of International Publication No. 2017/204228.
The ratio of methylene chloride in the total solvent used for the surface layer dope represented by TAC-a is preferably 83 to 97% by mass, more preferably 83 to 92% by mass. Within this range, the adhesiveness when the hard coat layer is applied to the cellulose ester film is good, and the reworkability of the polarizing plate is good.
The stretching of the cellulose ester film in the transport direction or width direction is effective for adjusting the curl of the hard coat layer-attached film alone and the curl of the polarizing plate, and is preferably 3 to 20%, more preferably 5 to 15%. is.

When the support is a resin film, it may optionally contain one or more other components such as known additives in addition to the resin component.
Examples of the optional components include light stabilizers such as ultraviolet absorbers, and inorganic particles such as matting agents.
Examples of UV absorbers include benzotriazole compounds and triazine compounds. Here, the benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various benzotriazole-based ultraviolet absorbers described in paragraph 0033 of JP-A-2013-111835. . A triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in paragraph 0033 of JP-A-2013-111835.
The content of the ultraviolet absorber contained in the resin film is not particularly limited, but can be, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin contained in the film. Further, regarding the ultraviolet absorber, the description in paragraph 0032 of JP-A-2013-111835 can also be referred to. In the present invention, ultraviolet rays (UV) means light having an emission central wavelength in the wavelength band of 200 to 380 nm.

The tensile modulus of the support in the optical layered body of the present invention is 4.5 GPa or more, preferably 4.8 GPa or more. By setting the tensile modulus of elasticity of the support to 4.5 GPa or more, the pencil hardness of the optical layered body can be increased. On the other hand, although the upper limit of the tensile modulus is not particularly defined, it is preferably 20 GPa or less, more preferably 15 GPa or less, even more preferably 10 GPa or less, and particularly preferably 8 GPa or less.
In the present invention, the tensile modulus is a value measured and calculated by the method described in Examples below. It should be noted that the conveying direction (MD direction) of the support during film production described in Examples below can be determined by analyzing the support even when the process during production of the support is unknown. .

The product of the indentation elastic modulus and the recovery rate of the support in the optical layered body of the present invention is 3.75 or more, preferably 3.80 or more. By setting the product of the indentation elastic modulus and the recovery rate to 3.75 or more, the pencil hardness of the optical layered body can be increased. On the other hand, the upper limit of the product of the indentation modulus and recovery rate is not particularly defined, but is preferably 19.00 or less, more preferably 10.00 or less, and even more preferably 5.00 or less.
In the present invention, the product of the indentation modulus and recovery rate of the support is a value calculated by measuring the indentation modulus and recovery rate by the method described in Examples below.

The thickness (film thickness) of the support is 80 μm or more, preferably 100 μm or more. By setting the thickness to 80 μm or more, it is possible to suppress a decrease in pencil hardness during bonding to an adherend such as a polarizing plate. On the other hand, although the upper limit of the thickness (film thickness) is not particularly defined, it is preferably 500 μm or less, more preferably 400 μm or less, even more preferably 300 μm or less, particularly preferably 200 μm or less, and most preferably 150 μm or less.
When the support has a laminated structure of two or more layers, the support as a whole should satisfy the tensile modulus, the product of the indentation modulus and the recovery rate, and the thickness.

[3] Hard coat layer The hard coat layer in the optical laminate of the present invention is not particularly limited as long as it has an indentation modulus of 7 GPa or more and a thickness of 10 µm or more. A hard coat layer used for the front plate of the device can be used.
The hard coat layer of the present invention is a cured layer, and is preferably formed from a curable composition for forming a hard coat layer.
The curable composition for forming a hard coat layer preferably contains a polymerizable compound 1 having a radically polymerizable group, and from the viewpoint of further improving the pencil hardness of the hard coat film, a polymerizable compound having a radically polymerizable group. 1 and a polymerizable compound 2 which has a cationic polymerizable group and a radically polymerizable group in the same molecule and is different from the polymerizable compound 1, and is contained in the curable composition for forming a hard coat layer. It is more preferable that the content of the polymerizable compound 2 in the polymerizable compound is 51% by mass or more, and the polymerizable compound 1 having a (meth)acryl group and an epoxy group and a (meth)acrylic group in the same molecule. and a polymerizable compound 2 different from the polymerizable compound 1 is contained, and the content of the polymerizable compound 2 in the polymerizable compounds contained in the curable composition for forming a hard coat layer is 51% by mass or more. is more preferred.
Each component contained in the hard coat layer-forming curable composition will be described below.

<<polymerizable compound 1>>
Polymerizable compound 1 used in the present invention has a radically polymerizable group. The polymerizable compound 1 used in the present invention is a different compound from the polymerizable compound 2. That is, the polymerizable compound 1 used in the present invention is a polymerizable compound other than compounds having a cationically polymerizable group and a radically polymerizable group in the same molecule among compounds having a radically polymerizable group.
The polymerizable compound 1 may be a high molecular weight compound (for example, a weight average molecular weight of 2000 or more) or a low molecular weight compound (for example, a molecular weight of less than 2000), but is preferably a low molecular weight compound. By using the low-molecular-weight polymerizable compound 1, the number of sites other than the radically polymerizable group is reduced, and the pencil hardness of the hard coat film can be increased more effectively. Specifically, the molecular weight of the polymerizable compound 1 is preferably 1500 or less, more preferably 1200 or less, even more preferably 1000 or less. Regarding the lower limit of the molecular weight, the molecular weight of the polymerizable compound 1 is preferably 100 or more, more preferably 120 or more. With such a range, volatilization of the polymerizable compound 1 can be more effectively suppressed during the formation of the hard coat layer.
In the present invention, the weight average molecular weight is a value measured by GPC (Gel Permeation Chromatography) unless otherwise specified.

The number of radically polymerizable groups possessed by the polymerizable compound 1 may be one, but preferably two or more in the same molecule, more preferably three or more, more preferably four or more, and six or more. is particularly preferred. By setting the number of radically polymerizable groups possessed by the polymerizable compound 1 to two or more in the same molecule, pencil hardness and adhesiveness can be more effectively improved. Although the upper limit of the number of radically polymerizable groups possessed by the polymerizable compound 1 is not particularly defined, even if the number is 10 or less in the same molecule, the effects of the present invention can be sufficiently exhibited. The radically polymerizable group possessed by the polymerizable compound 1 is preferably a styryl group and a (meth)acryl group, more preferably a (meth)acryl group, and still more preferably a (meth)acryloyloxy group. A (meth)acryl group is preferably a methacryl group.

As the polymerizable compound 1, a (meth)acrylate compound is preferably used. As the (meth)acrylate compound, a compound having a (meth)acrylic group and forming a hard cured product used in the technical field of the present invention can be widely employed.

(Meth)acrylate compounds include esters of polyhydric alcohols and (meth)acrylic acid.
Esters of polyhydric alcohols and (meth)acrylic acid include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, 1,4- Cyclohexane diacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide (EO) modified trimethylolpropane tri(meth)acrylate, propylene oxide (PO) modified Trimethylolpropane tri(meth)acrylate, EO-modified phosphoric acid tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta (Meth)acrylates, dipentaerythritol hexa(meth)acrylate, pentaerythritol hexa(meth)acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate and caprolactone-modified tris(acryloxyethyl) isocyanurate etc.

The (meth)acrylate compound is also preferably a compound (urethane (meth)acrylate) containing one or more urethane bonds in one molecule together with the (meth)acrylic group.
Commercially available products of the urethane (meth)acrylate are not particularly limited. 101I, UA-101T, AT-600, AH-600, AI-600, Shin-Nakamura Chemical Co., Ltd. U-4HA, U-6HA, U-6LPA, UA-32P, U-15HA, UA-1100H, Nippon Gosei Chemical Industry Co., Ltd. Shikou UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, Same UV-7640B, Same UV-6630B, Same UV-7000B, Same UV-7510B, Same UV-7461TE, Same UV-3000B, Same UV-3200B, Same UV-3210EA, Same UV-3310EA, Same UV-3310B, The same UV-3500BA, the same UV-3520TL, the same UV-3700B, the same UV-6100B, the same UV-6640B, the same UV-2000B, the same UV-2010B, and the same UV-2250EA can be mentioned. In addition, Shikou UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UL-503LN manufactured by Kyoeisha Chemical Co., Ltd., Unidic 17-806, 17-813, V-4030 and V-4030 manufactured by Dainippon Ink and Chemicals Co., Ltd. 4000BA, EB-1290K manufactured by Daicel Allnex, Hicope AU-2010 and AU-2020 manufactured by Tokushiki, and the like.

As specific examples of urethane (meth)acrylates, the following illustrative compounds A-1 to A-8 are also preferred.

When the polymerizable compound 1 is a (meth)acrylate compound having no urethane bond, the following compounds can also be exemplified. However, the present invention is not limited to the compounds exemplified below.
polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 300 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, triethylene glycol di(meth)acrylate, epichlorohydrin-modified ethylene glycol di(meth)acrylate (Meth)acrylates (commercially available products such as Denacol DA-811 manufactured by Nagase & Co., Ltd.), polypropylene glycol 200 di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, ethylene oxide (EO; Ethylene Oxide)/Propylene Oxide (PO; Propylene Oxide) block polyether di(meth)acrylate (commercially available, for example, BLEMMER PET series manufactured by NOF Corporation), dipropylene glycol di(meth)acrylate, bisphenol A EO addition type di (meth) acrylate (commercially available products, such as M-210 manufactured by Toagosei Co., Ltd., NK Ester A-BPE-20 manufactured by Shin Nakamura Chemical Co., Ltd.), hydrogenated bisphenol A EO addition type di ( meth) acrylate (NK ester A-HPE-4, etc. manufactured by Shin-Nakamura Chemical Co., Ltd.), bisphenol A PO addition type di(meth) acrylate (commercially available, for example, light acrylate BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.), Bisphenol A epichlorohydrin-added di(meth)acrylate (commercially available, for example Epicryl 150 manufactured by Daicel-Ornex), bisphenol A EO/PO-added di(meth)acrylate (commercially available, for example manufactured by Toho Chemical Industry Co., Ltd. BP-023-PE, etc.), bisphenol F EO addition type di(meth)acrylate (commercially available, such as Aronix M-208 manufactured by Toagosei Co., Ltd.), 1,6-hexanediol di(meth)acrylate, and Epichlorohydrin-modified products thereof, neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate hydroxypivalate, and caprolactone-modified products thereof, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, trimethylolpropane di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, pentaerythritol Di (meth) acrylate monostearate, trimethylolpropane acrylic acid / benzoic acid ester, isocyanuric acid EO-modified di (meth) acrylate (commercially available, for example, Toagosei Co., Ltd. Aronix M-215, etc.) bifunctional ( meth)acrylate compounds.

Trimethylolpropane tri(meth)acrylate and its EO, PO or epichlorohydrin modified products, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate and its EO, PO or epichlorohydrin modified products, isocyanuric acid EO modified tri( meth)acrylate (commercially available, such as Aronix M-315 manufactured by Toagosei Co., Ltd.), tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl) ) trifunctional (meth)acrylate compounds such as ethyl, glycerol tri(meth)acrylate and their EO, PO or epichlorohydrin modified products; pentaerythritol tetra(meth)acrylate and its EO, PO or epichlorohydrin modified products, ditrimethylolpropane Tetra(meth)acrylate and other tetrafunctional (meth)acrylate compounds; dipentaerythritol penta(meth)acrylate, and pentafunctional (meth)acrylate compounds such as EO, PO or epichlorohydrin, fatty acid and alkyl-modified products thereof; dipentaerythritol Hexa(meth)acrylate, its EO, PO or epichlorohydrin, fatty acid, alkyl-modified products, sorbitol hexa(meth)acrylate, and its EO, PO or epichlorohydrin, fatty acid, alkyl-modified products and other hexafunctional (meth)acrylate compounds.

As the (meth)acrylate compound that is the polymerizable compound 1, a polyester (meth)acrylate or an epoxy (meth)acrylate having a weight average molecular weight of 200 or more and less than 1000 is also preferable.
Commercially available polyester (meth)acrylates manufactured by Arakawa Chemical Industries, Ltd. under the trade name of Beamset 700 series, namely Beamset 700 (hexafunctional), Beamset 710 (tetrafunctional), Beamset 720 (trifunctional), etc. is mentioned.

Further, as a specific example of the (meth)acrylate compound that is the polymerizable compound 1, a (meth)acrylate compound having three or more (meth)acrylic groups other than the above is also mentioned as a preferred embodiment.
Examples of (meth)acrylate compounds having three or more (meth)acrylic groups include the following exemplary compounds A-9 to A-11.

Examples of (meth)acrylate compounds having three or more (meth)acrylic groups include the exemplary compounds shown in paragraph 0096 of JP-A-2007-256844.
Furthermore, specific compounds of (meth)acrylate compounds having three or more (meth)acrylic groups include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, and TPA- manufactured by Nippon Kayaku Co., Ltd. 320, TPA-330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, manufactured by Osaka Organic Chemical Industry Co., Ltd. and esters of polyol and (meth)acrylic acid, such as V#400 and V#36095D. Also, the same UV-1400B, the same UV-1700B, the same UV-6300B, the same UV-7550B, the same UV-7600B, the same UV-7605B, the same UV-7610B, the same UV-7620EA, the same UV-7630B, the same UV-7640B , UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA , the same UV-3520TL, the same UV-3700B, the same UV-6100B, the same UV-6640B, the same UV-2000B, the same UV-2010B, the same UV-2250EA, the same UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), UNIDIC 17-806, 17-813, V-4030, V-4000BA (manufactured by Dainippon Ink and Chemicals Co., Ltd.), EB-1290K, EB- 220, EB-5129, EB-1830, EB-4358 (manufactured by Daicel Allnex Co., Ltd.), Hicope AU-2010, AU-2020 (manufactured by Tokushiki Co., Ltd.), Aronix M-1960 (Toagosei Co., Ltd.) ), Artresin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T and other trifunctional or higher urethane acrylate compounds, Aronix M-8100, M-8030, M-9050 (Toagosei ( Co., Ltd.) and KBM-8307 (manufactured by Daicel Cytec Co., Ltd.) trifunctional or higher polyester compounds can also be suitably used.

Furthermore, in the present invention, the polymerizable compound 1 is preferably at least one selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate and diethylene glycol di(meth)acrylate. Examples of these commercially available products include those described in Examples below.
The polymerizable compound 1 may be of one type or two or more types, and as a blend form of two or more types, a combination of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is exemplified.

The proportion of the polymerizable compound 1 in the polymerizable compounds contained in the hard coat layer-forming curable composition is preferably 49% by mass or less, more preferably 45% by mass or less, and even more preferably 35% by mass or less. The lower limit of the proportion of the polymerizable compound 1 is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 8% by mass or more, particularly more preferably 10% by mass or more, and particularly 20% by mass or more. preferable. Adhesion and pencil hardness can be improved more effectively by setting the amount to 5% by mass or more.
Only one kind of the polymerizable compound 1 may be contained in the hard coat layer-forming curable composition, or two or more kinds thereof may be contained. When two or more kinds are contained, the total amount is preferably within the above range.

<<polymerizable compound 2>>
Polymerizable compound 2 used in the present invention is a polymerizable compound that has a cationic polymerizable group and a radically polymerizable group in the same molecule and is different from polymerizable compound 1 . By using a polymerizable compound having a cationically polymerizable group and a radically polymerizable group, it is possible to further improve the effect of suppressing a decrease in pencil hardness when the hard coat film is attached to the adherend via the adhesive layer. .
The polymerizable compound 2 preferably has a low molecular weight, and specifically preferably has a molecular weight of less than 10,000. By using the low-molecular-weight polymerizable compound 2, sites other than the cationic polymerizable group and the radically polymerizable group are reduced, and the effect of suppressing the decrease in pencil hardness can be more effectively enhanced. Specifically, the molecular weight of the polymerizable compound 2 is preferably 400 or less, more preferably 300 or less, even more preferably 250 or less. The lower limit of the molecular weight of the polymerizable compound 2 is preferably 100 or more, more preferably 120 or more. By setting it as such a range, volatilization of the polymerizable compound 2 can be suppressed more effectively at the time of hard-coat layer formation.

In the polymerizable compound 2, the number of cationic polymerizable groups in one molecule is preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, especially 1 preferable. The number of radically polymerizable groups in one molecule is preferably large, preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1. . In the polymerizable compound 2, the ratio of the number of radically polymerizable groups to the number of cationically polymerizable groups in one molecule (number of cationically polymerizable groups/number of radically polymerizable groups) is 0.5 to 2.0. is preferable, and 0.8 to 1.2 is more preferable.

The cationically polymerizable group possessed by the polymerizable compound 2 is preferably at least one of an oxetanyl group and an epoxy group, more preferably an epoxy group, and still more preferably an alicyclic epoxy group. The alicyclic structure contained in the alicyclic epoxy group includes, for example, a cyclo ring, a dicyclo ring, and a tricyclo ring structure, and specific examples thereof include a dicyclopentanyl ring, a cyclohexane ring, and the like. .
The radically polymerizable group possessed by the polymerizable compound 2 is preferably a styryl group and a (meth)acryl group, more preferably a (meth)acryl group, and still more preferably a (meth)acryloyloxy group. A (meth)acryl group is preferably a methacryl group.

The polymerizable compound 2 preferably has one alicyclic epoxy group and one radically polymerizable group in the same molecule.
Polymerizable compound 2 is more preferably a compound represented by the following general formula (1).

In general formula (1), R represents a monocyclic hydrocarbon or a bridged hydrocarbon, L represents a single bond or a divalent linking group, and Q represents a radically polymerizable group.

When R in the general formula (1) is a monocyclic hydrocarbon, it is preferably an alicyclic hydrocarbon, more preferably an alicyclic group having 4 to 10 carbon atoms, and an alicyclic group having 5 to 7 carbon atoms. group is more preferred, and an alicyclic group having 6 carbon atoms is particularly preferred. Specifically, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group are preferred, and a cyclohexyl group is particularly preferred.
When R in the general formula (1) is a bridged hydrocarbon, bicyclic bridged (bicyclo ring) and tricyclic bridged (tricyclo ring) are preferred, including bridged hydrocarbons having 5 to 20 carbon atoms, and a norbornyl group. , bornyl group, isobornyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, tricyclopentanyl group, adamantyl group and lower alkyl group-substituted adamantyl group.
When L represents a divalent linking group, a divalent aliphatic hydrocarbon group is preferred. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1-6, more preferably 1-3, and even more preferably 1. The divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group, and still more preferably a linear alkylene group.
The radically polymerizable group represented by Q is synonymous with the radically polymerizable group described above, and the preferred range is also the same.

Specific examples of the polymerizable compound 2 include an alicyclic epoxy group-containing (meth)acrylate described in paragraph 0015 of JP-A-10-17614, and the following general formula (1A) or (1B). can be mentioned. Among them, the compound represented by the following general formula (1A) or (1B) is more preferable, and the compound represented by the following general formula (1A) is even more preferable because of its lower molecular weight. The isomers of the compound represented by the following general formula (1A) are also preferred. In the general formula (1A) below, L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and 1 carbon atom (that is, polymerizable (Compound 2 is epoxycyclohexylmethyl (meth)acrylate) is more preferable from the viewpoint of further improving the effect of suppressing the decrease in pencil hardness when the hard coat film is attached to the adherend via the adhesive layer.

In general formula (1A), R ₁ represents a hydrogen atom or a methyl group, and L ₂ represents a C 1-6 divalent aliphatic hydrocarbon group.

In general formula (1B), R ₁ represents a hydrogen atom or a methyl group, and L ₂ represents a C 1-6 divalent aliphatic hydrocarbon group.

The divalent aliphatic hydrocarbon group for L ₂ in general formulas (1A) and (1B) has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and still more preferably 1 carbon atom. The divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group, and still more preferably a linear alkylene group.
In particular, in the present invention, polymerizable compound 2 is preferably at least one selected from glycidyl (meth)acrylate and epoxycyclohexylmethyl methacrylate.

Polymerizable compound 2 can be synthesized by a known method.
Moreover, the polymerizable compound 2 can also be obtained as a commercial item. Examples of the commercially available products include Cychromer M100 manufactured by Daicel Corporation, Light Ester G manufactured by Kyoeisha Chemical Co., Ltd., 4HBAGE manufactured by Nippon Kasei Chemical Co., Ltd., and SP series manufactured by Showa Polymer Co., Ltd., such as SP-1506, 500 and SP. -1507, 480, VR series such as VR-77, trade names EA-1010/ECA, EA-11020, EA-1025, EA-6310/ECA manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

The proportion of the polymerizable compound 2 in the polymerizable compounds contained in the hard coat layer-forming curable composition is 51% by mass or more, preferably 55% by mass or more, and more preferably 65% by mass or more. . With such a range, an excellent hard coat film can be obtained due to the effect of suppressing a decrease in pencil hardness when the hard coat film is adhered to an adherend via the adhesive layer. The upper limit of the proportion of the polymerizable compound 2 is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 92% by mass or less, particularly preferably 90% by mass or less, and 80% by mass or less. good too.
The curable composition for forming a hard coat layer may contain only one polymerizable compound 2, or may contain two or more of them. When two or more kinds are contained, the total amount is preferably within the above range.

<<Other polymerizable compounds>>
The curable composition for forming a hard coat layer may contain other polymerizable compounds different from polymerizable compound 1 and polymerizable compound 2 .
The other polymerizable compound is preferably a polymerizable compound having a cationic polymerizable group. The cationic polymerizable group is synonymous with the cationic polymerizable group described in Polymerizable Compound 2, and the preferred range is also the same. In particular, in the present invention, a nitrogen-containing heterocyclic ring-containing compound containing a cationic polymerizable group is preferable as another polymerizable compound. By using such a compound, the adhesion between the support and the hard coat layer can be more effectively improved. Nitrogen-containing heterocycles include isocyanurate rings (nitrogen-containing heterocycles contained in Exemplified Compounds B-1 to B-3 described later) and glycoluril rings (nitrogen-containing heterocycles contained in Exemplified Compound B-10 described later). Nitrogen-containing heterocycles selected from the group consisting of are exemplified, and isocyanurate rings are more preferred. The number of cationic groups possessed by the other polymerizable compound is preferably 1-10, more preferably 2-5. When a polymerizable compound having a cationic polymerizable group and a nitrogen-containing heterocyclic structure is used as another polymerizable compound, the support is preferably a support containing an acrylic resin film. Such a structure tends to further improve the adhesion between the support and the hard coat layer.
Exemplary compounds B-1 to B-10 are shown below as specific examples of other polymerizable compounds, but the present invention is not limited to the following specific examples.

A commercial item may be used as another polymerizable compound. For example, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate (for example, UVR6105 and UVR6110 manufactured by Union Carbide and commercially available products such as CELLOXIDE 2021P manufactured by Daicel), bis ( 3,4-epoxycyclohexylmethyl)adipate (for example, UVR6128 manufactured by Union Carbite), vinylcyclohexene monoepoxide (for example, Celloxide 2000 manufactured by Daicel), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl 3′, 4′-epoxycyclohexane carboxylate (for example, Celoxide 2081 manufactured by Daicel Corporation) and the like can be mentioned.

When the curable composition for forming a hard coat layer contains the other polymerizable compound (especially, a polymerizable compound having a cationic polymerizable group), the content of the curable composition for forming a hard coat layer is It is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, of the total polymerizable compounds contained. The lower limit of the content is preferably 1% by mass or more, more preferably 3% by mass or more.
The curable composition for forming a hard coat layer may contain only one type of the other polymerizable compound, or may contain two or more types thereof. When two or more kinds are contained, the total amount is preferably within the above range.
Further, in the present invention, the curable composition for forming a hard coat layer may be configured so as not to substantially contain the other polymerizable compound. The term "substantially free of" refers to, for example, less than 1% by mass of all polymerizable compounds contained in the hard coat layer-forming curable composition, preferably 0% by mass (hereinafter, "substantially free of" The same is true for ).

<<Inorganic particles>>
The curable composition for forming a hard coat layer also preferably contains inorganic particles. By including inorganic particles, the effect of improving the pencil hardness of the hard coat film is exhibited more effectively.
There are no particular restrictions on the inorganic particles that can be used in the curable composition for forming a hard coat layer. Examples include silica particles, zirconia particles and alumina particles, with silica particles being preferred. These inorganic particles may be surface-modified inorganic particles, and inorganic particles modified with (meth)acrylic groups or epoxy groups are preferred.
Commercially available inorganic particles may be used, such as MEK-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.).
When the curable composition for forming a hard coat layer contains inorganic particles, the content of the inorganic particles in the solid content of the curable composition for forming a hard coat layer is preferably 10% by mass or more, more preferably 20% by mass or more. , more preferably 40% by mass or more. Although the upper limit is not particularly limited, it is practically 80% by mass or less, preferably 60% by mass or less.

<<Polymerization initiator>>
The hard coat layer-forming curable composition preferably contains a polymerization initiator. The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
Polymerization initiators include radical polymerization initiators and cationic polymerization initiators. By adding a radical polymerization initiator, the polymerization reaction of the radically polymerizable group can be promoted, and by adding the cationic polymerization initiator, the polymerization reaction of the cationic polymerizable group can be promoted.
The hard coat layer-forming curable composition preferably contains at least one of a radical polymerization initiator and a cationic polymerization initiator, and more preferably contains both a radical polymerization initiator and a cationic polymerization initiator.
The polymerization initiator will be described below in order.

<<<radical polymerization initiator>>>
The radical polymerization initiator is preferably a radical photopolymerization initiator.
Any radical photopolymerization initiator may be used as long as it can generate radicals as active species upon irradiation with light, and known radical photopolymerization initiators can be used without any limitation. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone , 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy -2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)
-benzyl]phenyl}-2-methyl-propan-1-one and other acetophenones; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and other oxime esters; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoins such as isopropyl ether and benzoin isobutyl ether; -butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl) benzophenones such as trimethylammonium chloride; Thioxanthones such as 3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthon-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6- acylphosphine oxides such as dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; In addition, as auxiliary agents for radical photopolymerization initiators, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4- Ethyl dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone etc. may be used together.
The above radical photopolymerization initiators and auxiliaries can be synthesized by known methods and are available as commercial products.
Examples of commercially available radical photopolymerization initiators include IRGACURE (registered trademark) 184 (1-hydroxy-cyclohexyl-phenyl-ketone, α-hydroxyalkylphenone-based radical photopolymerization initiator, manufactured by BASF). .

The content of the radical polymerization initiator is not particularly limited and may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radically polymerizable compound proceeds satisfactorily. The above content is preferably 1 to 8% by mass, more preferably 1 to 5% by mass, and more preferably 3 to 5% by mass based on the solid content of the curable composition for forming a hard coat layer.
Moreover, the radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<<<Cationic polymerization initiator>>>
The cationic polymerization initiator is preferably a cationic photopolymerization initiator.
Any known cationic photopolymerization initiator may be used as long as it can generate cations as active species upon irradiation with light, and any known cationic photopolymerization initiator can be used without any limitation. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (eg, diaryliodonium salts), triarylsulfonium salts, diazonium salts, iminium salts and the like. More specifically, for example, cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, JP-A-8-283320 and those exemplified as cationic polymerization catalysts in paragraph 0020 of paragraph 0020, the contents of which are incorporated herein. Moreover, the cationic photopolymerization initiator can be synthesized by a known method and is also available as a commercial product. Commercially available products include, for example, CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855 and CI-2855 manufactured by Nippon Soda Co., Ltd. 5102, PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974 and UVI-6990 manufactured by Union Carbide, and CPI-10P manufactured by Sun-Apro.

As the cationic photopolymerization initiator, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoints of the photosensitivity of the photopolymerization initiator to light, the stability of the compound, and the like. In terms of weather resistance, iodonium salts are most preferred.

Specific commercial products of iodonium salt cationic photopolymerization initiators include, for example, B2380 manufactured by Tokyo Kasei Co., Ltd., BBI-102 manufactured by Midori Chemical Co., Ltd., WPI-113 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and Fujifilm. WPI-124 manufactured by Wako Pure Chemical Industries, Ltd., WPI-169 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., WPI-170 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., and DTBPI-PFBS manufactured by Toyo Gosei Chemical Co., Ltd. can.

Specific examples of iodonium salt compounds that can be used as cationic photopolymerization initiators include the following compounds PAG-1 and PAG-2.

The content of the cationic polymerization initiator used in the curable composition for forming a hard coat layer may be adjusted as appropriate within a range in which the polymerization reaction (cationic polymerization) of the cationic polymerizable compound proceeds favorably, and is particularly limited. is not. The content of the cationic polymerization initiator is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less in the solid content of the hard coat layer-forming curable composition. The lower limit of the content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more in the solid content of the curable composition for forming a hard coat layer. .
Moreover, the cationic polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<<Solvent>>
The hard coat layer-forming curable composition preferably contains a solvent. As the solvent, an organic solvent is preferable, and one or two or more organic solvents can be mixed in an arbitrary ratio and used. Specific examples of organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; toluene. , xylene and the like; glycol ethers such as propylene glycol monomethyl ether; acetic esters such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like. Among these, methyl ethyl ketone, methyl isobutyl ketone and methyl acetate are preferable, and it is more preferable to use a mixture of methyl ethyl ketone, methyl isobutyl ketone and methyl acetate in an arbitrary ratio. With such a structure, a hard coat film exhibiting better pencil hardness can be obtained.

The amount of solvent in the curable composition for forming a hard coat layer can be appropriately adjusted within a range in which the coating suitability of the composition can be ensured. For example, the solvent can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass, per 100 parts by mass of the total amount of the polymerizable compound and the photopolymerization initiator.
The solid content of the hard coat layer-forming curable composition is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, and particularly preferably 65 to 75% by mass. .

<<Other materials for the hard coat layer>>
In addition, the hard coat layer can optionally contain one or more known additives, if necessary. Examples of such additives include antifouling agents, surface conditioners, leveling agents, polymerization inhibitors, and the like. Details thereof can be referred to, for example, paragraphs 0032 to 0034 of JP-A-2012-229412, the contents of which are incorporated herein. In addition, various additives generally used in photopolymerizable compositions can be used. The amount of various additives to be added to the hard coat layer or the hard coat layer-forming curable composition may be appropriately adjusted, and is not particularly limited.

<<Leveling agent>>
A fluorine-containing polymer is preferably used as the leveling agent. For example, fluoroaliphatic group-containing polymers described in Japanese Patent No. 5,175,831 can be mentioned. In addition, a fluoroaliphatic group-containing polymer having a fluoroaliphatic group-containing monomer represented by the general formula (1) that constitutes the fluoroaliphatic group-containing polymer and having a content of 50% by mass or less of the total polymerization units is used as a leveling agent. can also

<<Antifouling agent>>
As for the details of the antifouling agent, the antifouling agents described later in the curable composition for forming an abrasion resistant layer can be employed, and the preferred range is also the same.
When the curable composition for forming a hard coat layer contains an antifouling agent, the content thereof is preferably 0.01 to 7% by mass of the solid content of the curable composition for forming a hard coat layer, and is preferably 0.05 to 0.05%. 5% by mass is more preferred, and 0.1 to 2% by mass is even more preferred.
The curable composition for forming a hard coat layer may contain only one type of antifouling agent, or may contain two or more types of antifouling agents. When two or more kinds are contained, the total amount is preferably within the above range.
Moreover, the curable composition for forming a hard coat layer may be configured so as not to substantially contain an antifouling agent.

The indentation modulus of the hard coat layer in the optical layered body of the present invention is preferably 5 to 30 GPa, more preferably 7 to 25 GPa, still more preferably 10 to 20 GPa, and particularly preferably 12 to 20 GPa. By setting the indentation modulus of the hard coat layer to a value within the above preferred range, cracks are less likely to occur and a high pencil hardness can be exhibited.
In the present invention, the indentation modulus is a value measured by the method described in Examples below.

<<Film thickness of hard coat layer>>
Although the film thickness of the hard coat layer is not particularly defined, it is preferably 10 μm or more, more preferably 15 μm or more. By making it more than the said preferable lower limit, it becomes possible to raise a pencil hardness more effectively. On the other hand, the upper limit of the thickness of the hard coat layer is preferably 60 μm or less, more preferably 50 μm or less, even more preferably 45 μm or less, still more preferably 30 μm or less, and even more preferably 25 μm or less.

[4] Abrasion Resistant Layer From the viewpoint of improving abrasion resistance, the optical laminate of the present invention preferably has an abrasion resistant layer on the surface of the hard coat layer opposite to the support.
The rub-resistant layer is formed from a curable composition for forming a rub-resistant layer.
The scratch-resistant layer-forming curable composition is a composition containing a polymerizable compound 3 having at least two radically polymerizable groups in the same molecule, and having at least three (meth)acrylic groups in the same molecule. A composition containing a polymerizable compound and a fluorine-containing compound having a (meth)acrylic group is preferred.

<<polymerizable compound 3>>
Polymerizable compound 3 has at least two radically polymerizable groups in the same molecule.
The number of radically polymerizable groups possessed by the polymerizable compound 3 is preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. By setting the number of radically polymerizable groups of the polymerizable compound 3 to two or more in the same molecule, the abrasion resistance and adhesion can be improved more effectively. Although the upper limit of the number of radically polymerizable groups possessed by the polymerizable compound 3 is not particularly defined, the effects of the present invention can be sufficiently achieved even if the number is 10 or less in the same molecule.
The radically polymerizable group of the polymerizable compound 3 is preferably a styryl group and a (meth)acryl group, more preferably a (meth)acryl group, and still more preferably a (meth)acryloyloxy group. A (meth)acryl group is preferably a methacryl group.
The polymerizable compound 3 may be a high molecular weight compound (for example, a weight average molecular weight of 2000 or more) or a low molecular weight compound (for example, a molecular weight of less than 2000), but is preferably a low molecular weight compound. By using a low-molecular-weight polymer, the number of sites other than radically polymerizable groups is reduced, and the pencil hardness of the hard coat film can be more effectively increased. Specifically, the molecular weight of the polymerizable compound 3 is preferably 1500 or less, more preferably 1200 or less, even more preferably 700 or less, and particularly preferably 250 or less. Regarding the lower limit of the molecular weight, the molecular weight of the polymerizable compound 3 is preferably 100 or more, more preferably 120 or more. By setting it to such a range, it is possible to more effectively suppress volatilization of the polymerizable compound 3 during the formation of the rub-resistant layer.
Specific examples of the polymerizable compound 3 include (meth)acrylate compounds, and the (meth)acrylate compounds exemplified for the polymerizable compound 1 are more preferable.
In the present invention, it is particularly preferred that the polymerizable compound 1 contained in the curable composition for forming a hard coat layer and the polymerizable compound 3 contained in the curable composition for forming an abrasion resistant layer are the same compound. By using the same compound, the compatibility at the interface between the hard coat layer and the abrasion-resistant layer is improved, and the adhesion between the hard coat layer and the abrasion-resistant layer can be improved more effectively.

The content of the polymerizable compound 3 is preferably 70% by mass or more, more preferably 75% by mass or more, particularly preferably 80% by mass or more, of the polymerizable compounds contained in the curable composition for forming an abrasion-resistant layer. It is preferably 90% by mass or more, and still more preferably 95% by mass or more. By setting it as such a range, abrasion resistance can be improved more. Moreover, the upper limit of the content is not particularly limited, and can be 100% by mass or less.
The scratch-resistant layer-forming curable composition may contain only one type of polymerizable compound 3, or may contain two or more types. When two or more kinds are contained, the total amount is preferably within the above range.

<<Other polymerizable compounds>>
The scratch-resistant layer-forming curable composition may contain polymerizable compounds other than the polymerizable compound 3. As other polymerizable compounds, the polymerizable compound 2 blended in the hard coat layer-forming curable composition, other polymerizable compounds that may be blended in the composition, and the like can be employed. Further, the other polymerizable compound is preferably a polymerizable compound having a cationic polymerizable group. As the polymerizable compound having a cationically polymerizable group, a polymerizable compound having a cationically polymerizable group which may be blended in the curable composition for forming a hard coat layer can be employed, and the preferred range is the same.

When the scratch-resistant layer-forming curable composition contains the other polymerizable compound (particularly, the polymerizable compound having a cationic polymerizable group), the content is included in the scratch-resistant layer-forming curable composition. It is preferably 20% by mass or less, more preferably 15% by mass or less, particularly preferably 10% by mass or less, and even more preferably 5% by mass or less, of the total polymerizable compound. When it is contained, the lower limit of the content is preferably 1% by mass or more, more preferably 3% by mass or more.
The scratch-resistant layer-forming curable composition may contain only one type of the other polymerizable compound, or may contain two or more types thereof. When two or more kinds are contained, the total amount is preferably within the above range.
Further, in the present invention, the curable composition for forming an abrasion-resistant layer may be configured so as not to substantially contain the other polymerizable compound.

<<Inorganic particles>>
The scratch-resistant layer-forming curable composition may contain inorganic particles. As the inorganic particles, inorganic particles that may be blended in the curable composition for forming a hard coat layer can be used, and the preferred range is also the same.
When the scratch-resistant layer-forming curable composition contains inorganic particles, the content thereof is preferably 20% by mass or less, more preferably 17% by mass or less, based on the solid content of the scratch-resistant layer-forming curable composition. The lower limit of the content is preferably 1% by mass or more, more preferably 7% by mass or more.
In particular, in the present invention, the curable composition for forming an abrasion resistant layer may be configured so as not to substantially contain inorganic particles.

<<polymerization initiator>>
The scratch-resistant layer-forming curable composition preferably contains a polymerization initiator, preferably a radical polymerization initiator. The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
As the radical polymerization initiator used in the scratch-resistant layer-forming curable composition, a radical polymerization initiator that may be used in the hard coat layer-forming curable composition can be employed, and the preferred range is the same. .
When the scratch-resistant layer-forming curable composition contains a cationic polymerizable compound as the polymerizable compound, it also preferably contains a cationic polymerization initiator.
Cationic polymerization initiators that may be used in the hard coat layer-forming curable composition can be employed as the cationic polymerization initiator used in the scratch-resistant layer-forming curable composition, and the preferred ranges are the same.

The content of the cationic polymerization initiator used in the scratch-resistant layer-forming curable composition may be adjusted as appropriate within a range in which the polymerization reaction (cationic polymerization) of the cationic polymerizable compound proceeds favorably, and is particularly limited. is not. The above content is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less in the solid content of the curable composition for forming an abrasion resistant layer. The lower limit of the above content is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the solid content of the scratch-resistant layer-forming curable composition.
Moreover, the cationic polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<<Antifouling agent>>
The scratch-resistant layer or the curable composition for forming the scratch-resistant layer preferably contains an antifouling agent. By including the antifouling agent, it is possible to reduce the adhesion of fingerprints and dirt, and to facilitate wiping off the adhered dirt. In addition, it is possible to further improve the abrasion resistance by improving the slipperiness of the surface.
The antifouling agent preferably contains a fluorine-containing compound. The fluorine-containing compound preferably has a perfluoropolyether group and a polymerizable group (preferably a radically polymerizable group), has a perfluoropolyether group and a polymerizable group, and has a polymerizable group in one molecule. It is more preferable to have a plurality of With such a configuration, the effect of improving the abrasion resistance can be exhibited more effectively.
As the radically polymerizable group that the fluorine-containing compound preferably has, the description of the radically polymerizable group possessed by the polymerizable compound 3 described above can be applied. For example, a fluorine-containing compound having a (meth)acryl group preferable.
In this specification, even if the antifouling agent has a polymerizable group, it is treated as not falling under the polymerizable compounds 1 to 3 and the other polymerizable compounds.
The fluorine-containing compound may be a monomer, an oligomer or a polymer, but is preferably an oligomer (fluorine-containing oligomer).

As for the antifouling agent that can be used in the present invention, in addition to the above, materials described in paragraphs 0012 to 0101 of JP-A-2012-088699 can be used, and the contents of this publication are incorporated herein. .
As the antifouling agent described above, one synthesized by a known method may be used, or a commercially available product may be used. As commercially available products, RS-90 and RS-78 manufactured by DIC can be preferably used.

When the curable composition for forming an abrasion resistant layer contains an antifouling agent, the content thereof is preferably 0.01 to 7% by mass, more preferably 0.05 to 0.05, based on the solid content of the curable composition for forming an abrasion resistant layer. 5% by mass is more preferred, and 0.1 to 2% by mass is even more preferred.
The scratch-resistant layer-forming curable composition may contain only one antifouling agent, or may contain two or more antifouling agents. When two or more kinds are contained, the total amount is preferably within the above range.
Moreover, the curable composition for forming an abrasion-resistant layer may be configured so as not to substantially contain an antifouling agent.

<<Solvent>>
The curable composition for forming an abrasion resistant layer preferably contains a solvent. Solvents used in the curable composition for forming a scratch-resistant layer can be those used in the curable composition for forming a hard coat layer, and the preferred ranges are the same.
The amount of the solvent in the scratch-resistant layer-forming curable composition can be appropriately adjusted within a range in which the coating suitability of the composition can be ensured. For example, the solvent is preferably contained in an amount of 50 to 500 parts by mass, more preferably 80 to 200 parts by mass, based on 100 parts by mass of the total amount of the polymerizable compound and the photopolymerization initiator.
The solid content of the curable composition for forming an abrasion resistant layer is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, and particularly preferably 65 to 75% by mass. .

<<Other Materials for the Abrasion Resistant Layer>>
In addition, the scratch-resistant layer or the curable composition for forming the scratch-resistant layer can optionally contain one or more known additives. Examples of such additives include surface conditioners, leveling agents, polymerization inhibitors, and the like. For details thereof, for example, paragraphs 0032 to 0034 of JP-A-2012-229412 can be referred to. However, the additives are not limited to these, and various additives generally used in polymerizable compositions can be used. Moreover, the amount of various additives to be added to the curable composition for forming an abrasion resistant layer may be appropriately adjusted, and is not particularly limited.

<<Film thickness of scratch-resistant layer>>
The thickness of the abrasion-resistant layer is not particularly defined, but is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.1 μm or more, particularly preferably 1 μm or more, and even if it is 3 μm or more. good. By making it 0.05 μm or more, it becomes possible to more effectively improve pencil hardness and abrasion resistance. On the other hand, the upper limit of the thickness of the scratch-resistant layer is preferably 40 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, particularly preferably 15 μm or less, and may be 8 μm or less.

[5] Other Layers The optical layered body of the present invention optionally has one or more other layers in addition to the adhesive layer, the support, the hard coat layer, and the abrasion resistant layer described above. You may Examples of other layers include, but are not limited to, hardened layers other than the hard coat layer and the abrasion resistant layer, antireflection layers, easy adhesion layers, decorative layers, and 1/4 layers described later. It may have an optically anisotropic layer used for a wavelength retardation plate. Details of other layers can be referred to, for example, paragraphs 0069 to 0091 of Japanese Patent No. 5048304, the contents of which are incorporated herein.

<<Antireflection layer>>
When the hard coat film in the optical laminate of the present invention is used as an antireflection film, one or more Lamination of the antireflection layer of is also a preferred embodiment. Here, in this specification, the high refractive index layer, the medium refractive index layer and the low refractive index layer may be collectively referred to as an antireflection layer. Preferred embodiments in which the optical layered body of the present invention has an antireflection layer are shown below.

A: Adhesive layer/support/hard coat layer/scratch resistant layer/low refractive index layer B: Adhesive layer/support/hard coat layer/scratch resistant layer/high refractive index layer/low refractive index layer C: adhesive layer/ Support/Hard Coat Layer/Abrasion Resistant Layer/Medium Refractive Index Layer/High Refractive Index Layer/Low Refractive Index Layer

The hard coat film in the optical laminate of the present invention preferably has a low refractive index layer directly or via another layer on the cured layer.
Preferred embodiments of the low refractive index layer are described in paragraphs 0077 to 0102 of JP-A-2009-204725, and the contents of this publication are incorporated herein.
In the hard coat film in the optical laminate of the present invention, a layer with a high refractive index (a high refractive index layer, a medium refractive index layer) is provided between the low refractive index layer and the cured layer to improve antireflection properties. . The terms "high", "medium", and "low" of the high refractive index layer, the medium refractive index layer, and the low refractive index layer represent relative magnitude relationships between the layers. In terms of the relationship with the support, the refractive index preferably satisfies the following relationship: support>low refractive index layer, high refractive index layer>support.
Preferred embodiments of the high refractive index layer are described in paragraphs 0103 to 0112 of JP-A-2009-204725, the contents of which are incorporated herein.

- Low refractive index layer -
As the material constituting the low refractive index layer, a material having a lower refractive index than the material constituting the high refractive index layer, such as aluminum oxide (Al ₂ O ₃ ), silicon dioxide (SiO ₂ ), non-stoichiometric oxide Silicon (SiO _2-X , 0≦X<1), magnesium fluoride (MgF ₂ ), mixtures thereof, and the like, among which silicon oxide is preferred.

The refractive index of the low refractive index layer is preferably 1.35 or more and 1.5 or less. The lower limit of the refractive index of the low refractive index layer is more preferably 1.38 or more, and further preferably 1.47 or less. Further, the optical thickness of the low refractive index layer is preferably 0.44λ0 or less, more preferably 0.35λ0 or less, and 0.14λ0 or less when the design wavelength λ0 is 500 nm. is more preferred.

―High refractive index layer―
As the material constituting the high refractive index layer, a material having a higher refractive index than the material constituting the low refractive index layer, such as tantalum pentoxide (Ta ₂ O ₅ ), niobium pentoxide (Nb ₂ O ₅ ), titanium Lanthanum oxide ( _LaTiO3 ), hafnium oxide (HfO2), titanium oxide ( _TiO2 ), chromium oxide _{( Cr2O3} ) _, zirconium oxide (ZrO), zinc sulfide (ZnS), tin-doped indium oxide (ITO), antimony Doped tin oxide (ATO), and mixtures thereof, and the like.

The refractive index of the high refractive index layer is preferably 1.7 or more and 2.5 or less, more preferably 1.8 or more and 2.2 or less. The optical thickness of the high refractive index layer is preferably 0.036λ0 or more and 0.54λ0 or less, more preferably 0.072λ0 or more and 0.43λ0 or less, when the design wavelength λ0 is 500 nm. .

The method for forming the low refractive index layer and the high refractive index layer is not particularly limited, and examples include a wet coating method and a dry coating method. Dry coating methods such as vacuum deposition, CVD (chemical vapor deposition), sputtering, and electron beam deposition are preferable, and sputtering and electron beam deposition are more preferable, because the film thickness of the thin film can be easily adjusted.

<Formation of hard coat layer>
The hard coat layer in the optical layered body of the present invention comprises the polymerizable compound 1 having a radically polymerizable group and the polymerizable compound 1 having a cationically polymerizable group and a radically polymerizable group in the same molecule. It is preferably formed using a curable composition for forming a hard coat layer containing a polymerizable compound 2 different from the above.

<<Preparation>>
The hard coat layer-forming curable composition can be prepared by mixing various components constituting the hard coat layer-forming curable composition simultaneously or sequentially in any order. The preparation method is not particularly limited, and a known stirrer or the like can be used for preparation.

<<Lamination>>
By laminating the curable composition for forming a hard coat layer prepared as described above on the surface of a support or via other layers such as an adhesive layer, a pressure-sensitive adhesive layer and an easy-adhesion layer, A hard coat layer can be formed. In the present invention, it is preferable to directly form a hard coat layer on the surface of the support.
The lamination method is not particularly limited and any known method can be employed, but coating is preferred. Coating can be performed by known coating methods such as dip coating, air knife coating, curtain coating, roller coating, die coating, wire bar coating, gravure coating and the like. The coating amount may be adjusted so as to form a hard coat layer having a desired thickness. There is no limit to the conveying speed during coating, but it can be, for example, 10 to 50 m/min.
The hard coat layer is formed as a cured layer having a laminated structure of two or more layers (for example, about two to five layers) by laminating two or more hard coat layer-forming compositions having different compositions simultaneously or sequentially. You can also Also, the hard coat layer and the abrasion resistant layer may be laminated at the same time.

<< Curing >>
The hard coat layer is preferably formed by curing a curable composition for forming a hard coat layer. The curing method is not particularly limited, and includes a method of performing photopolymerization treatment or thermal polymerization treatment, but photopolymerization treatment is preferred in the present invention. When performing photopolymerization treatment, the following aspects are preferable.
By subjecting the curable composition for forming the hard coat layer to photopolymerization treatment (light irradiation), the polymerization reaction of the radically polymerizable group and the cationic polymerizable group is initiated by a radical photopolymerization initiator and a cationic photopolymerization initiator, respectively. starts and progresses under the influence of The wavelength of the light to be irradiated may be determined according to the types of polymerizable compound and polymerization initiator used. Light sources for light irradiation include high pressure mercury lamps, ultra high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, light emitting diodes (LEDs), etc., which emit light in the wavelength band of 150 to 450 nm. can be mentioned. Also, the light irradiation amount is usually in the range of 10 to 3000 mJ/cm ² , preferably in the range of 20 to 1500 mJ/cm ² . As long as the amount of light irradiation can be within this range, there are no particular restrictions on the lamp output or illuminance. Further, the light irradiation is preferably performed under a nitrogen purge, more preferably at an oxygen concentration of 0.1% by volume or less.
In addition, when the hard coat layer further has an abrasion resistant layer, the abrasion resistant layer is formed in a state in which a part of the polymerizable compound having a radically polymerizable group in the hard coat layer-forming curable composition is unreacted. Preferably, a curable forming composition is provided. Such a structure tends to improve the adhesion between the hard coat layer and the abrasion resistant layer, which is preferable.
Furthermore, the hard coat layer-forming curable composition and the abrasion resistant layer-forming curable composition may be cured at the same time. That is, the curable composition for forming a hard coat layer and the curable composition for forming an abrasion resistant layer may be applied simultaneously or sequentially and then cured at once.

<<Dry>>
Before and/or after curing, the curable composition for forming a hard coat layer or the hard coat layer may be subjected to a drying treatment, if necessary. The drying treatment can be performed by blowing hot air, placing in a heating furnace, conveying in a heating furnace, or the like. The heating temperature is not particularly limited, and may be set to a temperature at which the solvent can be removed by drying. For example, it can be dried at 40-80° C. for 100-200 seconds. Here, the heating temperature refers to the temperature of hot air or the temperature of the atmosphere in the heating furnace.

<Formation of scratch-resistant layer>
When the optical layered body of the present invention further has an abrasion-resistant layer on the hard coat layer, it contains a polymerizable compound 3 having at least two radically polymerizable groups in the same molecule on the hard coat layer. It is preferable to form a scratch-resistant layer using a curable composition for forming a scratch-resistant layer. The scratch-resistant layer is formed in the order of the support, the hard coat layer, and the scratch-resistant layer. The abrasion resistant layer may be formed on the surface of the hard coat layer, or may be formed via another layer. A preferable mode is to form it on the surface of the hard coat layer.
In addition, preferred aspects of the formation of the scratch-resistant layer are the same as those of the hard coat layer.

-Pencil hardness-
In the optical layered body of the present invention, the difference between the pencil hardness of the hard coat film comprising the support and the hard coat layer and the pencil hardness of the optical layered body is within 1H, preferably within 0H. .
In the present invention, the pencil hardness is a value measured by the method described in Examples below, and measures the hardness of the hard coat layer side, and when the abrasion resistant layer is provided, the hardness of the abrasion resistant layer side.
The above-mentioned "pencil hardness of a hard coat film comprising a support and a hard coat layer" refers to the adhesive layer, the support, and the hard coat layer constituting the optical laminate of the present invention, except for the adhesive layer. It means the pencil hardness of a laminate (hard coat film) comprising a hard coat layer as a measurement sample.
When the optical layered body of the present invention has other layers (for example, an abrasion-resistant layer) in addition to the adhesive layer, the support, and the hard coat layer, the pencil hardness of the hard coat film and the optical layered body Pencil hardness is measured with these and other layers.

<Preparation of optical laminate>
The method for producing the optical laminate of the present invention is not particularly limited, but can be produced, for example, by bonding the adhesive layer produced as described above to the support side of the hard coat film.
The method for forming the adhesive layer is as described above.

<Processing of optical laminate>
The optical layered body of the present invention is processed and used for various purposes.
Processing includes, for example, winding the manufactured optical layered body into a roll-shaped optical layered body.
Further, the optical layered body of the present invention may be punched (also referred to as punching) using a punching blade into a desired shape. Desired shapes include, for example, shapes such as polarizing plates, liquid crystal display devices, and touch panels. Punching is preferably a method of inserting a punching blade from the hard coat layer side of the optical laminate of the present invention and passing through the support and the adhesive layer in that order. By inserting the punching blade from the hard coat layer side and punching, the optical layered body can be punched out satisfactorily.
The direction in which the punching blade is inserted is preferably a direction of 90° ± 10°, more preferably a direction of 90° ± 3°, and a direction of 90° ± 1° with respect to the surface of the abrasion resistant layer. is more preferable.
The punching machine used for punching is not particularly limited, but a manual press machine Torque Pack Press TP series manufactured by Amada Co., Ltd. can be preferably used. Punching is preferably performed at 10 to 40° C. and 30 to 80% relative humidity, more preferably 20 to 30° C. and 50 to 70% relative humidity.

-Article including optical laminate-
Examples of articles containing the optical laminate of the present invention include various articles that require improved abrasion resistance in various industrial fields such as the home appliance industry, the electrical and electronic industry, the automobile industry, and the housing industry. . Specific examples include a touch sensor, a touch panel, an image display device such as a liquid crystal display device, an automobile window glass, a residential window glass, and the like. By providing these articles with the optical laminate of the present invention, preferably as a surface protective film, it is possible to provide articles having excellent pencil hardness. The optical laminate of the present invention is preferably used as a hard coat film used for the front side polarizing plate of an image display device, and more preferably as a hard coat film used for the front side polarizing plate of the image display element of a touch panel. .
The touch panel in which the optical laminate of the present invention can be used is not particularly limited and can be appropriately selected depending on the purpose. A touch panel etc. are mentioned. Details will be described later.
Note that the touch panel includes a so-called touch sensor. The layer structure of the touch panel sensor electrode part in the touch panel is any of the lamination method in which two transparent electrodes are laminated together, the method in which transparent electrodes are provided on both sides of a single substrate, the single-sided jumper or through-hole method, or the single-sided layer method. It's okay.

<Image display device>
The image display device of the present invention is an image display device having a polarizing plate containing the optical layered body of the present invention and a polarizer, and an image display element. Preferably, the optical layered body of the present invention and a polarizer are used. polarizer as a front-side polarizer.
As the image display device, it can be used for an image display device such as a liquid crystal display (LCD), a plasma display panel, an electroluminescence display, a cathode tube display and a touch panel.
Liquid crystal display devices include TN (Twisted Nematic) type, STN (Super-Twisted Nematic) type, TSTN (Triple Super Twisted Nematic) type, multi-domain type, VA (Vertical Alignment) type, IPS (In Plane Switching) type, An OCB (Optically Compensated Bend) type and the like are included.
It is preferable that the image display device is improved in brittleness, excellent in handling property, does not impair display quality due to surface smoothness or wrinkles, and can reduce light leakage during a wet heat test.
That is, in the image display device of the present invention, the image display element is preferably a liquid crystal display element. As an image display device having a liquid crystal display element, Xperia P (trade name) manufactured by Sony Ericsson can be cited.

In the image display device of the present invention, it is also preferable that the image display element is an organic electroluminescence (EL) display element.
A known technique can be applied to the organic electroluminescence display element without any limitation. As an image display device having an organic electroluminescence display element, GALAXY SII (trade name) manufactured by SAMSUNG can be mentioned.

In the image display device of the present invention, it is also preferable that the image display element is an in-cell touch panel display element. An in-cell touch panel display element has a touch panel function built in an image display element cell.
For the in-cell touch panel display element, for example, known techniques such as Japanese Patent Application Laid-Open No. 2011-76602 and Japanese Patent Application Laid-Open No. 2011-222009 can be applied without any limitation. An example of an image display device having an in-cell touch panel display element is Xperia P (trade name) manufactured by Sony Ericsson.

Further, in the image display device of the present invention, it is also preferable that the image display element is an on-cell touch panel display element. An on-cell touch panel display element has a touch panel function arranged outside the image display element cell.
For the on-cell touch panel display element, for example, a known technique such as Japanese Patent Application Laid-Open No. 2012-88683 can be applied without any limitation. As an image display device having an on-cell touch panel display element, GALAXY SII (trade name) manufactured by SAMSUNG can be mentioned.

<<Touch Panel>>
The optical layered body of the present invention is produced by bonding a touch sensor film to the surface of the optical layered body of the present invention on the adhesive layer side (the side opposite to the side on which the hard coat layer is arranged with respect to the support) to form a touch sensor. It can be used as a touch panel including.
Although the touch sensor film is not particularly limited, it is preferably a conductive film having a conductive layer formed thereon.
The conductive film is preferably a conductive film in which a conductive layer is formed on any support.

<<Resistive touch panel>>
The resistive touch panel of the present invention is a resistive touch panel having a polarizing plate containing the optical layered body of the present invention and a polarizer, preferably a polarizing plate containing the optical layered body of the present invention and a polarizer. It has a polarizing plate on the front side.
A resistive touch panel has a basic configuration in which a pair of upper and lower substrates having conductive films are arranged so that the conductive films face each other with spacers interposed therebetween. The structure of the resistive touch panel is known, and the known technology can be applied to the present invention without any limitation.

<< capacitive touch panel >>
The capacitive touch panel of the present invention is a capacitive touch panel having a polarizing plate containing the optical layered body of the present invention and a polarizer, preferably a polarizing plate containing the optical layered body of the present invention and a polarizer. plate as front polarizer.
As a system of the capacitive touch panel, a surface capacitive type, a projected capacitive type, and the like can be mentioned. A projected capacitive touch panel has a basic configuration in which an X-axis electrode and a Y-axis electrode perpendicular to the X-axis electrode are arranged with an insulator interposed therebetween. Specific modes include a mode in which the X electrodes and the Y electrodes are formed on separate surfaces of a single substrate, and a mode in which the X electrodes, the insulator layer, and the Y electrodes are formed in the above order on a single substrate. , an embodiment in which the X electrodes are formed on one substrate and the Y electrodes are formed on another substrate (in this embodiment, the structure in which the two substrates are bonded together is the basic structure). The structure of the capacitive touch panel is known, and the known technology can be applied to the present invention without any limitation.

<Polarizing plate>
The polarizing plate of the present invention (hereinafter also referred to as an optical layered body with a polarizing plate) includes at least the optical layered body of the present invention and a polarizer. The optical layered body of the present invention can be used as a polarizing plate having a polarizer on the surface of the optical layered body of the present invention on the adhesive layer side (the side opposite to the side on which the hard coat layer is arranged with respect to the support). can.
More specifically, in the polarizing plate of the present invention, the polarizer protective film of the polarizing plate comprising a polarizer and polarizer protective films disposed on both sides of the polarizer is in contact with the adhesive layer in the optical laminate of the present invention. It can be used as an optical laminated body with a polarizing plate, which is laminated in the following manner. That is, this optical layered body with a polarizing plate includes a polarizer protective film between the polarizer and the adhesive layer in the optical layered body of the present invention.
In this case, a commonly used polarizer protective film can be used as the polarizer protective film, and examples thereof include cellulose acetate film and polyethylene terephthalate film. As the cellulose acetate film, a cellulose acetate film produced by a solution casting method and stretched in the width direction in the form of a roll film at a stretch ratio of 10 to 100% may be used.

Further, the support in the optical layered body of the present invention may be used as an optical layered body with a polarizing plate, which is laminated so as to correspond to one or both of the polarizer protective films.
For example, one polarizer protective film may have the support of the optical laminate of the present invention, and the other polarizer protective film may be a commonly used polarizer protective film such as a cellulose acetate film. In this case, the polarizer protective film which is not composed of the support in the optical layered body of the present invention is produced by a solution film forming method and stretched in the width direction in the form of a roll film at a draw ratio of 10 to 100%. It is preferred to use a cellulose acetate film.

It is also a preferred embodiment that the film other than the optical laminate of the present invention is an optical compensation film having an optical compensation layer containing an optically anisotropic layer. An optical compensation film (retardation film) can improve the viewing angle characteristics of a liquid crystal display screen. As the optical compensation film, known ones can be used, but the optical compensation film described in JP-A-2001-100042 is preferable from the viewpoint of widening the viewing angle.

Examples of polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based polarizers and dye-based polarizers are generally manufactured using polyvinyl alcohol films.
As the polarizer, a known polarizer may be used, or a polarizer cut from a long polarizer whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizer whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, a continuously supplied polymer film such as a polyvinyl alcohol film is stretched by applying tension while holding both ends thereof by a holding means, and stretching at least 1.1 to 20.0 times in the film width direction. After that, the difference in the speed of movement in the longitudinal direction of the holding device at both ends of the film is within 3%, and the angle formed by the film transport direction and the actual stretching direction of the film at the exit of the step of holding both ends of the film is inclined by 20 to 70°. , the film can be produced by a stretching method in which both ends of the film are held and bent in the transport direction. In particular, a stretching method in which the angle formed by the film transport direction at the exit of the step of holding both ends of the film and the actual stretching direction of the film is inclined by 45° is preferably used from the viewpoint of productivity.

A method for stretching a polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554, which can be referred to.

-Pencil hardness-
In the polarizing plate of the present invention comprising the optical laminate of the present invention and a polarizer, the difference between the pencil hardness of the hard coat film comprising the support and the hard coat layer and the pencil hardness of the polarizing plate of the present invention is within 1H. and this difference is preferably within 0H.
In the present invention, pencil hardness is a value measured by the method described in Examples below.
The above-mentioned "pencil hardness of a hard coat film comprising a support and a hard coat layer" refers to the adhesive layer, the support, and the hard coat layer constituting the optical laminate of the present invention, except for the adhesive layer. It means the pencil hardness of a laminate (hard coat film) comprising a hard coat layer as a measurement sample.
When the optical layered body of the present invention has other layers (for example, an abrasion-resistant layer) in addition to the adhesive layer, the support, and the hard coat layer, the above pencil hardness of the hard coat film and the optical layered body Pencil hardness is measured with these and other layers.

<Phase plate>
The optical layered body of the present invention is an optical layered body formed from a hard coat film and a composition containing a liquid crystalline compound on one of the supports, as described in Japanese Patent No. 5703187, for example. It may be used as a retardation plate having an anisotropic layer. The surface of the support on which the optically anisotropic layer is laminated is not particularly limited, but it is preferably laminated on the side opposite to the side on which the cured layer is laminated. An alignment film for controlling the alignment of the liquid crystal compound may be provided between the support and the optically anisotropic layer containing the liquid crystal compound. The optical properties of the hard coat film laminated with the optically anisotropic layer are not particularly specified, but the in-plane retardation Re at 550 nm is preferably 5 to 300 nm, more preferably 10 to 250 nm, and 80 to 200 nm. is more preferred. In addition, the Nz value defined below is preferably 0 to 2.0, more preferably 0.1 to 1.6, and particularly preferably 0.1 to 0.9 (here (Nz value=0.5+Rth/Re, where Rth is retardation in the thickness direction. Methods for measuring these optical characteristics will be described later). Especially when a quarter-wave retardation plate is assumed, Re is preferably 80 to 200 nm and Nz value is 0.1 to 0.9, and Re is 100 to 150 nm and Nz value is 0.1 to 0.9. is more preferred.

<Quarter Wave Retardation Plate>
The optical layered body of the present invention may be used for a quarter-wave retardation plate. Since the quarter-wave retardation plate can convert the linearly polarized light emitted from the polarizer into circularly polarized light, for example, visibility when the viewer is wearing polarized sunglasses can be improved. . The 1/4 wavelength retardation plate may be produced by a known method, may be obtained by using a commercially available resin film having a 1/4 wavelength retardation function as it is, or may be obtained by stretching a commercially available resin film. A device having a /4 wavelength phase difference function may be used. The optically anisotropic layer may be provided on the hard coat film by laminating the support surface of the hard coat film and the film having the optically anisotropic layer laminated thereon with an adhesive, and peeling off only the film portion. . Further, the quarter-wave retardation plate may be prepared by coating a curable composition containing a liquid crystalline compound on any support, for example, as described in Japanese Patent No. 4866638. . The quarter-wave retardation plate may be provided on the surface of the support of the hard coat film on which the hard coat layer and the abrasion resistant layer are not formed, or may be provided on the surface of the abrasion resistant layer.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the invention is not limited to the specific examples shown below. A mixing ratio means a mass ratio unless otherwise specified. Also, the steps described below were performed at room temperature unless otherwise specified. Here, the room temperature is 25°C.

<1. Production of support>
(1-1. Support A)

(Preparation of cellulose ester solution)
The following composition was charged into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose ester solution.
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Composition of cellulose ester solution－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
・Cellulose ester (acetyl substitution degree 2.86, viscosity average polymerization degree 310)
100 parts by mass · Sugar ester compound 1 having the following structure (sugar ester 1 described in [Chemical 5] of JP-A-2012-215689, average degree of substitution 5.5) 4.0 parts by mass · Methylene chloride 375 parts by mass · Methanol 82 parts by mass, butanol 5 parts by mass

(Preparation of Matting Agent Dispersion M-2)
The following composition was put into a disperser and stirred to prepare a matting agent dispersion liquid M-2.
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Composition of Matting Agent Dispersion M-2----------------
・ Silica particle dispersion (average particle size 16 nm, trade name: AEROSIL R97
2, Japan Aerosil Co., Ltd.) 10.0 parts by mass Methylene chloride 62.5 parts by mass Methanol 14.1 parts by mass Butanol 0.8 parts by mass Cellulose ester solution 10.3 parts by mass ---- －－－－－－－－－－－－－－－－－－－－－－－－－－－－－－

(Preparation of UV absorber solution U-2)
The following composition was placed in another mixing tank and stirred while heating to dissolve each component to prepare UV absorber solution U-2.
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Composition of UV absorber solution U-2---------------------------
・Ultraviolet absorber (UV-1) with the following structure: 10.0 parts by mass ・Ultraviolet absorber with the following structure (UV-2): 10.0 parts by mass ・Methylene chloride: 54.3 parts by mass ・Methanol: 12.0 parts by mass ・0.7 parts by mass of butanol and 12.9 parts by mass of the above cellulose ester solution

(Preparation of dope for core layer)
To the above cellulose ester solution, 8.0 parts by mass of sugar ester compound 1 was added per 100 parts by mass of cellulose ester, and an ultraviolet absorber (UV-1) and an ultraviolet absorber (UV-2) were added per 100 parts by weight of cellulose ester. The UV absorber solution U-2 was added so that each of the components was 1.2 parts by mass, and the mixture was sufficiently stirred while heating to dissolve each component, thereby preparing a dope for the core layer.

(Preparation of dope 1 for surface layer)
To the cellulose ester solution, the ultraviolet absorbent solution U-2 is added so that the ultraviolet absorbent (UV-1) and the ultraviolet absorbent (UV-2) are each 1.2 parts by weight per 100 parts by weight of the cellulose ester. In addition, the above-described matting agent dispersion M-2 was added so that the amount of silica particles was 0.026 parts by mass per 100 parts by mass of cellulose ester, and methylene chloride was added so as to be 85% by weight of the dope solvent, followed by heating. The mixture was sufficiently stirred to dissolve each component, and a surface layer dope 1 was prepared.

(Preparation of dope 2 for surface layer)
To the cellulose ester solution, the ultraviolet absorbent solution U-2 is added so that the ultraviolet absorbent (UV-1) and the ultraviolet absorbent (UV-2) are each 1.2 parts by weight per 100 parts by weight of the cellulose ester. In addition, the above-described matting agent dispersion M-2 was added so that the amount of silica particles was 0.078 parts by mass per 100 parts by mass of cellulose ester, and methylene chloride was added so as to be 85% by weight of the dope solvent, followed by heating. The contents were sufficiently stirred to dissolve each component, and a surface layer dope 2 was prepared.

-Preparation of support A-
The obtained dope was heated to 30° C. and co-cast in a three-layer structure from a die onto a specular stainless steel support, which was a drum with a diameter of 3 m, through a casting Giesser. The first layer in contact with the support is the surface layer dope 1 so that the dry film thickness is 6 μm, the second layer is the core layer dope so that the dry film thickness is 69 μm, and the third layer is the above dope. A surface layer dope 2 was prepared so as to form a surface layer having a film thickness of 5 μm. The surface temperature of the support was set at 4° C., and the casting width was 1470 mm. The spatial temperature of the entire casting section was set at 15°C. Then, 50 cm before the end point of the casting part, the cast and rotated cellulose ester film was peeled off from the drum with a residual solvent amount of 240%, and then both ends were clipped with a pin tenter. At the time of peeling, the film was stretched by 6% in the transport direction. After that, while holding both ends of the film in the width direction (direction perpendicular to the casting direction) with a pin tenter (the pin tenter described in FIG. 3 of JP-A-4-1009), the film is stretched 5% in the width direction. did As a result, a support A comprising a cellulose ester film having a total thickness of 80 μm and having the first to third layers having the above film thicknesses was produced.

(1-2. Support B)

In the preparation of the support A, the dry film thickness of the surface layer dopes 1 and 2 remained unchanged, and the dry film thickness of the core layer dope was changed to 89 μm, thereby changing the total thickness of the cellulose ester film to 100 μm. A support B was prepared in the same manner as the support A except for the above.

(1-3. Support C)
A support C comprising a three-layer cellulose acylate laminated film of outer layer/core layer/outer layer was prepared by the following method.

(1) Preparation of Core Layer Cellulose Acylate Dope The following composition was put into a mixing tank and stirred to prepare a core layer cellulose acylate dope.
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Core layer cellulose acylate dope－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
・100 parts by mass of cellulose acetate having a degree of acetyl substitution of 2.88 and a weight average molecular weight of 260,000 ・10 parts by mass of phthalate ester oligomer A having the following structure ・4 parts by mass of compound (A-1) represented by the following formula I ・4 parts by mass of the following formula UV absorber represented by II (manufactured by BASF) 2.7 parts by mass Light stabilizer (manufactured by BASF, trade name: TINUVIN123)
0.18 parts by mass N-alkenylpropylenediamine triacetic acid (Takeran DO manufactured by Nagase ChemteX) 0.02 parts by mass Methylene chloride (first solvent) 430 parts by mass Methanol (second solvent) 64 parts by mass -- －－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－

The compounds used are shown below.
Phthalic acid ester oligomer A (weight average molecular weight: 750)

Compound (A-1) represented by the following formula I
Formula I:

UV absorber Formula II represented by Formula II:

(2) Preparation of Outer Layer Cellulose Acylate Dope To 90 parts by mass of the above core layer cellulose acylate dope, 10 parts by mass of the following inorganic particle-containing composition was added to prepare an outer layer cellulose acylate dope solution.
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Composition containing inorganic particles－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
2 parts by mass of silica particles with an average primary particle size of 20 nm (manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL R972)
Methylene chloride (first solvent) 76 parts by mass Methanol (second solvent) 11 parts by mass Core layer cellulose acylate dope 1 part by mass －－－－－－－－－－－－－

(3) Preparation of Support C (TAC) The outer layer cellulose acylate dope, the core layer cellulose acylate dope, and the outer layer cellulose acylate dope were prepared so that the outer layer cellulose acylate dope was arranged on both sides of the core layer cellulose acylate dope. Three types of dope were simultaneously cast onto a drum having a surface temperature of 20°C from a casting port. After the amount of residual solvent in the resulting casting film was adjusted to about 20% by mass, the casting film was stripped off from the drum. Then, both ends of the obtained film in the width direction were fixed with tenter clips, and the film with a residual solvent amount of 3 to 15% by mass was stretched 1.18 times in the transverse direction and dried. Thereafter, the film was further dried by transporting it between rolls of a heat treatment apparatus, and a laminated film having a thickness of 100 µm (outer layer/core layer/outer layer = 3 µm/94 µm/3 µm) was produced as support C.

(1-4. Support D)
In the preparation of the support A, the dry film thickness of the surface layer dopes 1 and 2 was unchanged, the dry film thickness of the core layer dope was changed to 49 μm, and the total thickness of the cellulose ester film was changed to 60 μm. A support D was prepared in the same manner as for the support A.

(1-5. Support E)
Support A was prepared in the same manner as Support A, except that the surface layer dopes 1 and 2 were not used, only the core layer dope was used, and the total thickness of the cellulose ester film was changed to 60 μm. , a support E was produced.

(1-6. Support F)
Support A was prepared in the same manner as Support A, except that the surface layer dopes 1 and 2 were not used, only the core layer dope was used, and the total thickness of the cellulose ester film was changed to 80 μm. , a support F was produced.

<2. Preparation of hard coat layer-forming curable composition and scratch-resistant layer-forming curable composition>
After mixing each component shown in Table 1 below in the formulation shown in Table 1, it was filtered through a polypropylene filter with a pore size of 10 μm, and the curable compositions HC1 to HC4 for forming a hard coat layer and a group curing for forming an abrasion resistant layer were obtained. Synthetic product T1 was prepared.

(Note to table)
"-" in the column of the table means that the component is not contained.
In addition, in RS-90, 8SS-723 and MEK-AC-2140Z in the table, the % notation on the right side means the amount of active ingredient (% by mass). For these components, the compounding amount described in the table means the total amount.
<Polymerizable compound>
DPHA: a mixture of dipentaerythritol pentaacrylate (5 radically polymerizable groups, no cationically polymerizable group) and dipentaerythritol hexaacrylate (6 radically polymerizable groups), DPCA manufactured by Nippon Kayaku Co., Ltd. -60: KAYARAD DPCA-60 (trade name), manufactured by Shin-Nakamura Chemical Co., Ltd., 6 acrylate groups in the compound, no cationic polymerizable group.
Cychromer: 3,4-epoxycyclohexylmethyl methacrylate, manufactured by Daicel Corporation, Cychromer M100 (trade name), the number of radically polymerizable groups in the compound is one, and the number of cationic polymerizable groups is one.

<Inorganic particles>
MEK-AC-2140Z: trade name, manufactured by Nissan Chemical Industries, Ltd., organosilica sol, particle size 10 to 15 nm

<Polymerization initiator>
Radical photopolymerization initiator Irg184: IRGACURE184 (trade name), manufactured by BASF, 1-hydroxy-cyclohexyl-phenyl-ketone, α-hydroxyalkylphenone-based radical photopolymerization initiator Cationic photopolymerization initiator PAG-1: shown below A cationic photoinitiator that is an iodonium salt compound shown

<Antifouling agents, leveling agents>
RS-90: antifouling agent, trade name, manufactured by DIC, fluorine-containing oligomer having a radically polymerizable group 8SS-723: antifouling agent, trade name, manufactured by Taisei Fine Chemical Co., Ltd., silicone acrylic polymer P-112: leveling agent, Compound P-112 described in paragraph [0053] of Japanese Patent No. 5175831

<3. Preparation of adhesive layer>

<Production of adhesive layers N1 to N4 and N11>
An acrylate polymer was synthesized according to the following procedure.
95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were polymerized by a solution polymerization method in a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirring device to obtain a mass average molecular weight of 2,000,000 and a molecular weight distribution of 2,000,000. An acrylate polymer A1 having a (Mw/Mn) of 3.0 was obtained.

Acrylic adhesives N1 to N4 and N11 having the compositions shown in Table 2 below were prepared, and the prepared adhesives were applied using a die coater to a separate film surface-treated with a silicone-based release agent, and placed in an environment of 90 ° C. It was dried for 1 minute and irradiated with ultraviolet rays (UV) under the following conditions to prepare adhesive layers N1 to N4 and N11, respectively.
The composition of the acrylic pressure-sensitive adhesive and the film thickness and storage elastic modulus of the resulting adhesive layer are summarized in Table 2 below. The unit of the compounding amount of each component in the table is parts by mass. The methods for measuring the film thickness and storage modulus are as described below.
<UV irradiation conditions>
・Fusion's electrodeless lamp H bulb ・Illuminance 600mW/cm ² , light intensity 150mJ/cm ²
- The UV illuminance and the amount of light were measured using UVPF-36 (trade name) manufactured by Eye Graphics.

(Note to table)
Acrylate polymer A1: Acrylate polymer A1 prepared above
(A) Polyfunctional acrylate monomer: tris(acryloyloxyethyl) isocyanurate, molecular weight = 423, trifunctional type (manufactured by Toagosei Co., Ltd., trade name “Aronix M-315”)
(B) Photopolymerization initiator: a mixture of benzophenone and 1-hydroxycyclohexylphenyl ketone at a mass ratio of 1:1, manufactured by Ciba Specialty Chemicals, trade name "Irgacure 500"
(C) Isocyanate cross-linking agent: trimethylolpropane-modified tolylene diisocyanate, manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L"
(D) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”

<Preparation of adhesive layer N5>
Adhesive layer N5 was prepared by preparing adhesive composition N5 based on Synthesis Example 2 in the preparation of the adhesive sheet described in International Publication No. 2017/204228 pamphlet. Specifically, it is as follows.
96 parts of butyl acrylate (BA), 4 parts of acrylic acid (AA), 0.08 parts of t-dodecanethiol (chain transfer agent), polyoxy An emulsion of 2 parts of sodium ethylene lauryl sulfate (emulsifier) and 153 parts of ion-exchanged water (that is, an emulsion of raw materials for monomers) was charged and stirred at room temperature (25° C.) for 1 hour while nitrogen gas was introduced.
Thereafter, the temperature was raised to 60° C., and 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (polymerization initiator) prepared as a 10% aqueous solution (trade name: VA) was -057, manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 0.1 part in terms of solid content, and the mixture was stirred at 60° C. for 3 hours to polymerize. 10% aqueous ammonium solution was added to this reaction solution to adjust the pH to 7.5 to obtain a water-dispersible (meth)acrylic polymer (A).
70 parts of the above water-dispersible (meth)acrylic polymer (A) in terms of solid content and 30 parts in terms of solid content of synthetic polyisoprene latex (trade name: Seporex IR-100K, manufactured by Sumitomo Seika Co., Ltd.) were blended. . Next, as a tackifier, 25 parts of an aromatic modified terpene resin emulsion (trade name: Nanolet R-1050, manufactured by Yasuhara Chemical Co., Ltd., softening point: 100° C.) is blended in terms of solid content, and an epoxy cross-linking agent (trade name: TETRAD-C) is added. , manufactured by Mitsubishi Gas Chemical Co., Ltd.) was blended to prepare a water-dispersed pressure-sensitive adhesive composition N5.
The water-dispersible pressure-sensitive adhesive composition N5 prepared above was applied to the release-treated surface of a release sheet (manufactured by Lintec, trade name: SP-PET3811) obtained by releasing one side of a polyethylene terephthalate film with a silicone-based release agent. was applied to a thickness of 15 μm and heated at an atmospheric temperature of 100° C. for 1 minute to prepare an adhesive layer N5.

<Preparation of adhesive layer N6>
Adhesive layer N6 was prepared by preparing adhesive solution N6 in the same manner as described in Example 1 of JP-A-2005-298641, except that the amount of coronate was changed to 4 parts by weight. Specifically, it is as follows.
An acrylic copolymer was synthesized by polymerizing 70 parts by weight of 2-ethylhexyl acrylate, 20 parts by weight of ethyl acrylate, 6 parts by weight of hydroxyethyl methacrylate and 4 parts by weight of acrylic acid by a solution polymerization method. The synthesized acrylic copolymer had a weight average molecular weight of 300,000 and a glass transition point of -35°C.
To 100 parts by weight of this acrylic copolymer, 4 parts by weight of a polyfunctional isocyanate cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate L) was blended and diluted with toluene to a concentration of 30% by weight. The obtained pressure-sensitive adhesive solution N6 was poured onto a polyethylene terephthalate (PET) film having a thickness of 50 μm and was dried at 90° C. for 2 minutes. An adhesive sheet was produced.

<Production of adhesive layer N9>
In the preparation of the adhesive layer N6, bonding was performed in the same manner as in the preparation of the adhesive layer N6, except that the amount of the coronate L was changed from 4 parts by mass to 8 parts by mass and the thickness of the adhesive layer was adjusted to 15 μm. Layer N9 was made.

<Preparation of adhesive layer N10>
An adhesive layer N10 was produced in the same manner as the adhesive layer N9, except that the thickness of the adhesive layer N9 was adjusted to 3 μm.

<Production of adhesive layer N12>
In the preparation of the adhesive layer N6, bonding was performed in the same manner as in the preparation of the adhesive layer N6, except that the amount of the coronate L was changed from 4 parts by mass to 5 parts by mass and the thickness of the adhesive layer was adjusted to 10 μm. Layer N12 was produced.

<Preparation of adhesive layer N13>
An adhesive layer N13 was produced in the same manner as the adhesive layer N2, except that the thickness of the adhesive layer N12 was adjusted to 5 μm.

<Production of adhesive layers N7 and N8>
Adhesive layers N7 and N8 were prepared using the adhesive compositions of Comparative Examples 2 and 5 described in JP-A-2011-128439, respectively. Specifically, it is as follows.
(Preparation of copolymer solutions 6 and 9)
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet pipe to replace the air in the reactor with nitrogen gas. After that, 0.1 part by mass of azobisisobutyronitrile and 120 parts by mass of ethyl acetate were added to the reactor, as shown in Table 3 below. The mixture was reacted at 60° C. for 8 hours in a nitrogen gas stream while being stirred to obtain a solution of an acrylic copolymer having a weight-average molecular weight shown in Table 3 below. Further, by diluting with ethyl acetate, copolymer solutions 6 and 9 having a solid content of 15% were prepared.
In Table 3 below, the unit for the blending amount of each monomer component is parts by mass, and the unit for the weight average molecular weight is 10,000.

A pressure-sensitive adhesive composition N7 having the following composition was applied onto a silicone resin-coated PET film, and dried at 90° C. to remove the solvent to prepare an adhesive layer N7 having a thickness of 1 μm.
An adhesive layer N8 having a thickness of 3 μm was produced in the same manner as the adhesive layer N7, except that an adhesive composition N8 having the following composition was used instead of the adhesive composition N7.
In the description of the composition below, 100 parts by mass of each copolymer solution means that the solid content is 100 parts by mass.

－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Adhesive composition N7
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Copolymer solution 6 100 parts by mass Coronate L 5 parts by mass (trade name, polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.)
Titanium chelate 0.1 part by mass (manufactured by Matsumoto Fine Chemicals Co., Ltd., titanium acetylacetonate)
JERYX4000 2 parts by mass (trade name, manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin)
(Epoxy equivalent 186 g / eq, Mw 354)
KBM-403 0.2 parts by mass (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltriethoxysilane)
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－

－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Adhesive composition N8
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－
Copolymer solution 9 100 parts by mass Takenate D-120N 5 parts by mass (trade name, manufactured by Mitsui Chemicals, hydrogenated xylene diisocyanate compound)
JER806: 2 parts by mass (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin)
(Epoxy equivalent 165 g / eq, Mw 350)
KBM-403 0.2 parts by mass (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltriethoxysilane)
－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－－

<4-1. Preparation of optical laminate: no abrasion-resistant layer>
[Example 1]
(1) Formation of Hard Coat Layer A curable composition HC1 for forming a hard coat layer was applied to the side of the support A that was in contact with the casting band, and cured to form a hard coat layer having a thickness of 10 μm.
Specifically, the coating and curing methods were as follows. By the die coating method using the slot die described in Example 1 of JP-A-2006-122889, the curable composition HC1 for forming the HC layer was applied at a conveying speed of 30 m/min, and the temperature was adjusted to 150°C at an ambient temperature of 60°C. Dried for seconds. Thereafter, a nitrogen purge is further performed, and an air-cooled metal halide lamp (manufactured by igraphics) of 160 W/cm is used under the condition of an oxygen concentration of about 0.1% by volume, with an illuminance of 300 mW/cm ² and an irradiation dose of 600 mJ/cm ² . After curing the applied hard coat layer forming curable composition HC1 to form a hard coat layer, it was wound up to obtain a hard coat film.

(2) Preparation of Optical Laminate After bonding the adhesive layer N2 to the surface of the support A opposite to the surface on which the hard coat layer is formed, the separate film was peeled off, and the optical laminate of Example 1 was obtained. Obtained.

[Examples 2, 3 and 13 to 23, Comparative Examples 1 to 10]
Examples 2, 3 and 13 were prepared in the same manner as in Example 1, except that the structures of the support, the hard coat layer and the adhesive layer were changed as shown in Table 4 in the preparation of the optical layered body of Example 1. 23 and Comparative Examples 1 to 10 were produced.

<4-2. Production of Optical Laminate: With Abrasion Resistant Layer>
[Example 4]
(1) Formation of hard coat layer In the formation of the hard coat layer in Example 1, except that the UV irradiation conditions for curing the hard coat layer were changed to illuminance of 20 mW/cm ² and irradiation of UV rays of 30 mJ/cm ² . After forming a hard coat layer in the same manner, the film was wound up.

(2) Formation of abrasion-resistant layer A curable composition T1 for forming an abrasion-resistant layer is applied to the surface of the hard coat layer opposite to the surface having the support A, and cured to form an abrasion-resistant layer having a thickness of 4 μm. formed.
Specifically, the coating and curing methods were as follows. By a die coating method using a slot die described in Example 1 of JP-A-2006-122889, the curable composition for forming an abrasion resistant layer is applied at a conveying speed of 30 m / min, and the temperature is 150 at an atmospheric temperature of 60 ° C. Dried for seconds. Thereafter, a nitrogen purge is further performed, and an air-cooled metal halide lamp (manufactured by igraphics) of 160 W/cm is used under the condition of an oxygen concentration of about 0.1% by volume, with an illuminance of 300 mW/cm ² and an irradiation dose of 600 mJ/cm ² . was irradiated with ultraviolet rays to effect the applied curable composition T1 for forming an abrasion resistant layer to form an abrasion resistant layer, followed by winding to prepare a hard coat film with an abrasion resistant layer.

(3) Formation of adhesive layer After bonding the adhesive layer N2 to the surface of the support A opposite to the surface on which the hard coat layer and the abrasion resistant layer are formed, the separate film is peeled off, and the optical adhesive layer of Example 4 is formed. A laminate was obtained.

[Examples 5 to 8, Comparative Example 11]
In the preparation of the optical layered body of Example 4, the configurations of the support, the hard coat layer and the adhesive layer were changed as shown in Table 4 in the same manner as in Example 4, Examples 5 to 8, Comparative An optical laminate of Example 11 was produced.

〔evaluation〕
For each optical laminate prepared above, the indentation modulus and thickness of the hard coat layer, the tensile modulus of elasticity, indentation modulus, recovery rate and thickness of the support, the storage modulus and thickness of the adhesive layer, The pencil hardness of each of the hard coat film and the optical laminate was measured and evaluated. Moreover, the abrasion resistance of the optical layered body was evaluated by the following method. These results are summarized in Table 4.

<Measurement of indentation modulus of hard coat layer>
An indentation test was performed on the surface of the hard coat layer of the hard coat film using an HM2000 type hardness tester (trade name, manufactured by Fisher Instruments Co., Ltd., diamond Knoop indenter) under the conditions of a maximum load of 50 mN, an indentation speed of 10 seconds, and a creep of 5 seconds. was performed to obtain the indentation modulus.

<Measurement of tensile modulus of support>
A sample of 200 mm (measurement direction) × 10 mm was cut out with the longitudinal direction being the transport direction (MD direction) during film production of the support. C. and a relative humidity of 60% for 24 hours, the stress at 0.1% elongation and 0.5% elongation was measured at a tensile speed of 10%/min, and the tensile modulus was determined from the slope.

<Measurement of indentation elastic modulus and recovery rate of support>
Using an HM2000 type hardness tester (trade name, Fisher Instruments Co., Ltd., diamond Knoop indenter), an indentation test was performed on the support surface under the conditions of a maximum load of 50 mN, an indentation speed of 10 seconds, and a creep of 5 seconds. rate and recovery rate were determined.
The product of the indentation modulus and the recovery rate is a value calculated by the formula: indentation modulus x recovery rate x 0.01, where the unit of the indentation modulus is GPa and the unit of the recovery rate is %. In the table below, the values calculated by this calculation are shown without units.

<Measurement of storage modulus of adhesive layer>
For each adhesive layer prepared above, the storage elastic modulus is measured using a dynamic viscoelasticity measuring device (trade name: DVA-200) manufactured by IT Keisoku Co., Ltd. under the conditions of a frequency of 1 Hz and 25 ° C. did.

<Measurement of Thickness of Hard Coat Layer, Support and Adhesive Layer>
The thickness of each layer constituting the optical laminate of the present invention was obtained by cutting a cross section using a microtome, observing the thickness with an SEM at a magnification of 1,000 to 3,000 times, measuring the thickness at five points, and taking the average of these values as the thickness. .

<Measurement of pencil hardness of hard coat film>
The hard coat film was placed on glass so that the surface on the support side was in contact with the glass, and the pencil hardness was measured according to JIS K 5600-5-4 (1999). A load of 500 g was applied. Tests were conducted using 5 pencils for each hardness scale, and the case where scratches or other defects did not occur for 3 or more pencils was passed, and the hardness of the hardest pencil that passed was called the pencil hardness. bottom. In the table, 3/5 means that 3 out of 5 failed and no traces or other defects occurred, and 5/5 means that 5 out of 5 failed and traces or other defects occurred. means it didn't.
As for the hard coat film with an abrasion resistant layer, a hard coat film having an abrasion resistant layer (hard coat film with an abrasion resistant layer) was used as a measurement sample.

<Measurement of Pencil Hardness of Optical Laminate>
The optical laminate was placed on the glass so that the adhesive layer side surface was in contact with the glass, and the pencil hardness was measured according to JIS K 5600-5-4 (1999). A load of 500 g was applied. Tests were conducted using 5 pencils for each hardness scale, and the case where scratches or other defects did not occur for 3 or more pencils was passed, and the hardness of the hardest pencil that passed was called the pencil hardness. did. In the table, 3/5 means that 3 out of 5 failed and no traces or other defects occurred, and 5/5 means that 5 out of 5 failed and traces or other defects occurred. means it didn't.

<Abrasion resistance of optical laminate>
For a hard coat film without an abrasion resistant layer, the surface of the hard coat layer, for a hard coat film with an abrasion resistant layer, the surface of the abrasion resistant layer, respectively, with a rubbing tester (manufactured by Tester Sangyo Co., Ltd., trade name: AB-301 COLOR FASTNESS RUBBING TESTER) was used to conduct a rubbing test under the following conditions.
(Measurement condition)
Evaluation environment conditions: 25°C, relative humidity 60%
Rubbing material: steel wool (manufactured by Japan Steel Wool Co., Ltd., grade No. 0000)
Wrap around the rubbing tip (1 cm x 1 cm) of the tester that comes into contact with the sample and fix the band Moving distance (one way): 13 cm,
Rubbing speed: 13 cm/sec,
Load: 1000g/ ^cm2
Tip contact area: 1 cm x 1 cm,
Number of times of rubbing: 100 reciprocations, 10000 reciprocations

Oil-based black ink was applied to the entire surface of the hard coat film on the support side (the back side of the sample) after the rubbing test. The reflected light of this hard coat film was visually observed from the side opposite to the support to evaluate scratches on the rubbed portion. The abrasion resistance is so excellent that no scratches are visible, and in the present invention, an evaluation of "B" or higher is acceptable.
- Evaluation criteria -
A: No scratches are visible even when viewed very carefully.
B: A weak scratch is visible when viewed carefully, but it is not a problem.
C: Scratches that can be recognized at first glance are very conspicuous.

(Note to table)
<Abrasion resistant layer>
"Yes" means having a scratch-resistant layer produced using the scratch-resistant layer-forming curable composition T1 prepared above.
<Hard coat layer>
HC1 to HC4: means hard coat layers prepared using the hard coat layer-forming curable compositions HC1 to HC4 prepared above.
<Support>
Supports A to F: Supports A to F prepared above
FUJITAC TD80UL: Product name, cellulose triacetate film, manufactured by FUJIFILM Corporation FUJITAC TG60UL: Product name, cellulose triacetate film, manufactured by FUJIFILM Corporation PET: Polyethylene terephthalate film, manufactured by Toyobo Co., Ltd., Cosmo Shine A4100 (product name)
For FUJITAC TD80UL, FUJITAC TG60UL and PET, the hard coat layer-forming curable composition was applied to the outer surface of FUJITAC and to the easily adhesive layer surface of PET in the hard coat layer forming step.
Indentation modulus x Recovery rate:
<Adhesive layer>
N1 to N13: Adhesive layers N1 to N13 prepared above
A×30−B: means a value calculated by A×30−thickness B of the adhesive layer storage elastic modulus of the adhesive layer. However, the unit of storage elastic modulus A is MPa, and the unit of thickness B is μm.
(evaluation)
PH _H -PH _O : difference between the pencil hardness of the hard coat film and the pencil hardness of the optical laminate

The results in Table 4 show the following.
The optical layered body of Comparative Example 1 has a support with a tensile modulus of 4.2 GPa, which is not equal to or higher than the 4.5 GPa specified in the present invention. The optical layered bodies of Comparative Examples 2 and 9 to 11 all have a support thickness of 60 μm, which is not the optical layered body of the present invention in that the thickness is not 80 μm or more as defined in the present invention. The optical layered bodies of Comparative Examples 3, 4 and 7 are not optical layered bodies of the present invention in that the storage elastic modulus and thickness of the adhesive layer do not satisfy the relationship of formula (1) defined in the present invention. The optical laminates of Comparative Examples 1 to 4, 7 and 9 to 11 had a large difference of 2H or 3H between the pencil hardness of the hard coat film and the pencil hardness of the optical laminate. It was inferior because it was not possible to suppress the decrease in pencil hardness due to lamination to the adherend through an intervening layer.
Further, the optical layered body of Comparative Example 5 has an indentation modulus of elasticity of 4 GPa of the hard coat layer, which is not equal to or higher than 7 GPa specified in the present invention, and is not the optical layered body of the present invention. The optical layered body of Comparative Example 6 has a hard coat layer with a thickness of 5 μm, which is not the optical layered body of the present invention in that it is not 10 μm or more as specified in the present invention. The optical layered body of Comparative Example 8 has a product of the indentation modulus of the support and the recovery rate of 3.71, which is not the optical layered body of the present invention in that it does not satisfy the requirement of 3.75 or more defined in the present invention. The optical laminates of Comparative Examples 5, 6 and 8 were inferior in that the pencil hardness of the hard coat film was as low as H or 2H.
On the other hand, in the optical laminates of Examples 1 to 23, which are the optical laminates of the present invention, the pencil hardness of the hard coat film is as high as 4H or more. The difference from the hardness is as small as 0H or 1H, and the effect of suppressing the pencil hardness by bonding the hard coat film to the adherend via the adhesive layer is excellent, and as a result, the optical laminate has excellent pencil hardness. I found out that

<4-3. Preparation of Optical Laminate with Polarizing Plate>
[Example 9]
(1) Fabrication of Polarizer According to Example 1 of JP-A-2001-141926, a stretched polyvinyl alcohol film was adsorbed with iodine to fabricate a polarizer having a thickness of 26 μm.

(2) Saponification Treatment Fujitac ZRD40SL (trade name, cellulose acylate film manufactured by Fujifilm Corporation) was immersed in a 1.5 mol/L NaOH aqueous solution (saponification solution) maintained at 55°C for 2 minutes, and then the film was washed with water. After that, the film was immersed in a 0.05 mol/L aqueous solution of sulfuric acid at 25° C. for 30 seconds and then washed with running water for 30 seconds to neutralize the film. Then, water was removed by an air knife three times, and after the water was removed, it was dried by staying in a drying zone at 70° C. for 15 seconds to prepare saponified FUJITAC ZRD40SL.

(3) Fabrication of optical laminate with polarizing plate Using a polyvinyl alcohol adhesive, the above saponified Fujitac ZRD40SL was attached to both sides of the polarizer that was prepared by the method described above and had nothing attached to both sides. , to produce a polarizing plate.
The optical layered body of Example 7 and the polarizing plate were placed so that one of the two FUJITAC ZRD40SLs in the polarizing plate was in contact with the adhesive layer side of the optical layered body produced in Example 7. By bonding, an optical laminate with a polarizing plate of Example 9 was produced.

[Example 10]
(1) Fabrication of Polarizer According to Example 1 of JP-A-2001-141926, a stretched polyvinyl alcohol film was adsorbed with iodine to fabricate a polarizer having a thickness of 26 μm.

(2) Saponification Treatment Fujitac ZRD40SL (trade name, cellulose acylate film manufactured by Fujifilm Corporation) was immersed in a 1.5 mol/L NaOH aqueous solution (saponification solution) maintained at 55°C for 2 minutes, and then the film was washed with water. After that, the film was immersed in a 0.05 mol/L aqueous solution of sulfuric acid at 25° C. for 30 seconds and then washed with running water for 30 seconds to neutralize the film. Then, water was removed by an air knife three times, and after the water was removed, it was dried by staying in a drying zone at 70° C. for 15 seconds to prepare saponified FUJITAC ZRD40SL.
<Corona treatment>
One side of COSMOSHINE SRF80 (trade name, manufactured by Toyobo Co., Ltd., polyethylene terephthalate film) was subjected to corona treatment at a discharge amount of 125 W·min/m ² .

(3) Preparation of polarizing plate The saponified FUJITAC ZRD40SL was attached to one side of the polarizer, which was prepared by the method described above and had nothing attached to both sides, using a polyvinyl alcohol adhesive. Further, the corona-treated side of the COSMOSHINE SRF80 was attached to the surface of the polarizer opposite to the surface to which the FUJITAC ZRD40SL was attached using a polyvinyl alcohol adhesive. The obtained laminate was dried at 70° C. for 10 minutes or more to prepare a polarizing plate.

(4) Preparation of Optical Laminate with Polarizing Plate The optical laminate of Example 7 and the polarizing plate were assembled so that the adhesive layer side of the optical laminate prepared in Example 7 was in contact with the COSMOSHINE SRF80 side of the polarizing plate. were bonded to prepare an optical laminate with a polarizing plate of Example 10.

[Examples 11 and 12]
The polarizing plate of Example 11 was prepared in the same manner as in Example 10, except that the optical layered body of Example 5 was used in place of the optical layered body of Example 7. An optical layered product was produced.
Further, in the production of the optical layered body with a polarizing plate of Example 10, the optical layered body of Example 12 was prepared in the same manner as in Example 10 except that the optical layered body of Example 6 was used instead of the optical layered body of Example 7. An optical laminate with a polarizing plate was produced.

〔evaluation〕
For each of the optical laminates with polarizing plates produced above, the pencil hardness of the optical laminate with polarizing plates was measured and evaluated by the following method. These results are summarized in Table 5.
<Measurement of Pencil Hardness of Optical Laminate with Polarizing Plate>
The optical laminate with a polarizing plate was placed on glass so that the surface on the polarizing plate side was in contact with the glass, and the pencil hardness was measured according to JIS K 5600-5-4 (1999). A load of 500 g was applied. Tests were conducted using 5 pencils for each hardness scale, and the case where scratches or other defects did not occur for 3 or more pencils was passed, and the hardness of the hardest pencil that passed was called the pencil hardness. did.

(Note to table)
PH _H -PH _O : difference between the pencil hardness of the hard coat film and the pencil hardness of the optical laminate PH _H -PH _P : difference between the pencil hardness of the hard coat film and the pencil hardness of the optical laminate with a polarizing plate

As can be seen from the results in Table 5 above, all of the polarizing plates obtained by laminating the optical layered bodies of Examples 5 to 7, which are the optical layered bodies of the present invention, had a hard coat film with a high pencil hardness of 7H or more. Moreover, the difference between the pencil hardness of the hard coat film and the pencil hardness of the optical laminate with a polarizing plate is as small as 0H or 1H. As a result, it was found that the optical laminate had an excellent pencil hardness in a state in which it was attached to the polarizing plate.

<5-1. Fabrication of image display device having in-cell touch panel display element>
A liquid crystal display element, which is an in-cell touch panel display element incorporated in a commercially available liquid crystal display device (manufactured by Sony Ericsson, trade name: Xperia P), was prepared. The optical laminate with a polarizing plate produced in Example 10 was adhered onto this in-cell touch panel display element via an adhesive layer having a thickness of 20 μm to produce an image display device having an in-cell touch panel display element.

<5-2. Production of image display device having on-cell touch panel display element>
An organic electroluminescence display element, which is an on-cell touch panel display element incorporated in a commercially available organic EL display device (manufactured by SAMSUNG, trade name: GALAXY SII), was prepared. The optical laminate with a polarizing plate prepared in Example 10 was attached to the on-cell touch panel display element via an adhesive layer having a thickness of 20 μm to prepare an image display device having an on-cell touch panel display element. .

In both the image display device having the in-cell touch panel display element produced above and the image display device having the on-cell touch panel display element, the adhesive layer is interposed in the same manner as in the optical laminate and the optical laminate with a polarizing plate described above. The effect of suppressing a decrease in pencil hardness by bonding the hard coat film to the image display element was excellent, and as a result, the optical laminate with a polarizing plate had excellent pencil hardness when bonded to the image display element.

While we have described our invention in conjunction with embodiments thereof, we do not intend to limit our invention in any detail to the description unless specified otherwise, which is contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted broadly.

This application claims priority based on Japanese Patent Application No. 2019-220723 filed in Japan on December 5, 2019 and Japanese Patent Application No. 2020-202322 filed in Japan on December 4, 2020. , the contents of which are hereby incorporated by reference as part of the present description.

Claims (17)

An optical laminate comprising at least an adhesive layer, a support provided on one side of the adhesive layer, and a hard coat layer provided on the support,
The storage elastic modulus A and thickness B of the adhesive layer satisfy the following formula (1),
A×30−B≧0 Formula (1)
The support has a tensile modulus of 4.5 GPa or more, a product of the indentation modulus and recovery rate of 3.75 or more, and a thickness of 80 µm or more,
The hard coat layer has an indentation modulus of elasticity of 7 GPa or more and a thickness of 10 μm or more,
The optical layered body, wherein the difference between the pencil hardness of the hard coat film comprising the support and the hard coat layer and the pencil hardness of the optical layered body is 1H or less.
However, in the above formula (1), the unit of storage elastic modulus A is MPa, and the unit of thickness B is μm. The optical layered body according to claim 1, wherein the support contains a triacetylcellulose resin. 3. The optical laminate according to claim 1, wherein the support has a thickness of 100 [mu]m or more. The hard coat layer comprises a polymerizable compound 1 having a (meth)acrylic group, and a polymerizable compound 2 having an epoxy group and a (meth)acrylic group in the same molecule and different from the polymerizable compound 1. Formed from a curable composition for forming a hard coat layer containing
4. The optical laminate according to claim 1, wherein the polymerizable compound 2 accounts for 51% by mass or more of the polymerizable compounds contained in the hard coat layer-forming curable composition. A scratch-resistant layer is provided on the surface of the hard coat layer opposite to the support,
The scratch-resistant layer is formed from a scratch-resistant layer-forming curable composition containing a polymerizable compound having at least three (meth)acrylic groups in the same molecule and a fluorine-containing compound having a (meth)acrylic group. The optical laminate according to any one of claims 1 to 4, wherein The curable composition for forming a hard coat layer contains inorganic particles modified with a (meth)acrylic group or an epoxy group, and the content of the inorganic particles in the solid content of the curable composition for forming a hard coat layer The optical laminate according to any one of claims 1 to 5, wherein the is 20% by mass or more. The optical laminate according to any one of claims 1 to 6, wherein the storage elastic modulus A and thickness B of the adhesive layer satisfy the following formula (2).
A×30−B≧6 Formula (2)
However, in the above formula (2), the unit of storage elastic modulus A is MPa, and the unit of thickness B is μm. A polarizing plate comprising the optical layered body according to any one of claims 1 to 7 and a polarizer disposed on the adhesive layer side of the optical layered body. 9. The polarizing plate according to claim 8, comprising a polarizer protective film made of polyethylene terephthalate between the polarizer and the adhesive layer constituting the optical laminate. 10. The polarizing plate according to claim 8, wherein a difference between a pencil hardness of a hard coat film comprising said support and said hard coat layer and a pencil hardness of said polarizing plate is within 1H. An image display device comprising the polarizing plate according to any one of claims 8 to 10 and an image display element. 12. The image display device according to claim 11, wherein said image display element is a liquid crystal display element. 13. The image display device according to claim 11, wherein said image display element is an organic electroluminescence display element. The image display device according to any one of claims 11 to 13, wherein said image display element is an in-cell touch panel display element. The image display device according to any one of claims 11 to 13, wherein said image display element is an on-cell touch panel display element. A resistive touch panel comprising the polarizing plate according to any one of claims 8 to 10. A capacitive touch panel comprising the polarizing plate according to any one of claims 8 to 10.