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CN104530331A - Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel - Google Patents

Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel Download PDF

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Publication number
CN104530331A
CN104530331A CN201410753543.0A CN201410753543A CN104530331A CN 104530331 A CN104530331 A CN 104530331A CN 201410753543 A CN201410753543 A CN 201410753543A CN 104530331 A CN104530331 A CN 104530331A
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Prior art keywords
antistatic layer
layer
thin film
optical thin
antistatic
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Granted
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CN201410753543.0A
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CN104530331B (en
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山本佳奈
堀尾智之
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/121—Antistatic or EM shielding layer

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Liquid Crystal (AREA)

Abstract

Disclosed is a curable resin composition for antistatic layers that can form antistatic layers with sufficient antistatic properties and excellent adhesion with adjacent HC layers. Also disclosed is an optical film with said antistatic layer. Specifically disclosed is a curable resin composition for antistatic layers that is characterized by containing: (A) an antistatic agent; (B) a polyfunctional monomer with two or more photocuring groups per molecule and a molecular weight of 900 max.; and (C) a urethane acrylate with six or more (meth) acryloyl groups per molecule and a weight average molecular weight of 1,000 - 11,000; and wherein the ratio of (A) to the total amount of (A), (B), and (C) is 1 - 30 mass% and the ratio of (C) to the total amount of (B) and (C) is 1 - 40 mass%. Also specifically disclosed is an optical film provided with an antistatic layer with a film thickness of 1 - 5 [mu]m formed by a cured product from the curable resin composition for antistatic layers, and a hard coat layer, which are provided on one surface side of a TAC substrate, from the TAC substrate side.

Description

Antistatic layer curable resin composition, optical thin film, polaroid and display panel
The divisional application that the application is the applying date is on July 12nd, 2011, application number is 2011800314732, denomination of invention is the application of antistatic layer curable resin composition, optical thin film, polaroid and display panel.
Technical field
The present invention relates to one and be arranged at liquid-crystal display (LCD, Liquid CrystalDisplay), cathode tube display equipment (CRT, Cathode-ray Tube) or plasma display (PDP, Plasma Display Panel) etc. there is the optical thin film of antistatic layer and the composition of this antistatic layer before indicating meter (image display), and use polaroid and the display panel of this optical thin film.
Background technology
In above-mentioned indicating meter, be usually provided with the optical thin film comprising the layer with various functions such as anti-reflective, hard painting property or static resistances in outmost surface.In addition, in this manual, be sometimes simply called being firmly coated with " HC ".
As one of the functional layer of this kind of optical thin film, there will be a known the antistatic layer for giving static resistance.This antistatic layer is by adding the stannic oxide (ATO doped with antimony, AntimonyTin Oxide) or doped with the electroconductibility ultra micron of the burning system such as Indium sesquioxide (ITO, Indium Tin Oxide) of tin, the static inhibitor such as polymer conductive composition or quaternary ammonium salt system electro-conductive material and being formed (such as patent documentation 1).When using these static inhibitor, in order to have required static resistance and optical characteristics (low haze value or high full light transmittance) concurrently simultaneously, required function to be given by the thin film layer of about 0.1 ~ 1 μm formed containing static inhibitor.
In addition, in above-mentioned indicating meter, require to give hardness to the picture display face of indicating meter, to make it injury-free when processing.To this, the formation of following optical thin film is disclosed: (following at triacetyl cellulose in patent documentation 1, sometimes be only called the antistatic backing " TAC (Triacetyl Cellulose) " base material being arranged film, and HC layer is set on this antistatic layer.
But, because antistatic layer is film, therefore there is following problem: the pentaerythritol triacrylate comprised in layer is (following, sometimes be simply called that " PETA (Pentaerythritol triacrylate) " or dipentaerythritol acrylate are (following, sometimes be simply called that the amount of the binder constituents of " DPHA (Di-Pentaerythritol hexaacrylate) " and so on and static inhibitor is limited, and then easily cause with the adhesion of the HC layer being adjacent to this antistatic layer not enough.
Being in the optical thin film of basic comprising with base material/antistatic layer/HC layer, there being the interface between antistatic layer and HC layer and the interface between antistatic layer and base material, and there is the problem of adhesion at each interface.
Interface between antistatic layer and HC layer, each reactive base of antistatic layer and HC layer carries out crosslinked bonding and touches, but requires that antistatic layer plays antistatic property simultaneously.When static inhibitor is metal oxide, in order to make antistatic layer play antistatic property, the particulate of static inhibitor must touch each other, therefore will add a large amount of static inhibitor, but there is the situation that haze value increases or full light transmittance worsens.But, if pay attention to optical characteristics and reduce the amount of metal oxide, be then difficult to play antistatic property.In addition, if increase the amount of static inhibitor, be then present in the quantity not sufficient of the binder constituents at the interface of antistatic layer and adjoining course, thus the possibility that the adhesion of antistatic layer and adjoining course is deteriorated.But, if pay attention to adhesion and reduce the amount of metal oxide, be then difficult to play antistatic property.
When static inhibitor is quaternary ammonium salt, in order to make antistatic layer play antistatic property, the more quaternary ammonium salt of content specific viscosity mixture in layer, must be there is.Or quaternary ammonium salt must concentrate the near interface adjacent with HC layer being present in antistatic layer.But, in such cases, there is following possibility: the quaternary ammonium salt being present near interface hinders the contiguity of antistatic layer and HC layer, be present in the quantity not sufficient of the binder constituents (there is the composition improved with the reactive base of the cross-linking density of HC layer) at the interface of antistatic layer and adjacent HC layer, thus antistatic layer is deteriorated with the adhesion of adjacent HC layer.But if pay attention to adhesion and reduce the amount of quaternary ammonium salt, then antistatic property can worsen.
In order to realize static resistance and adhesion simultaneously, the method of the amount of the binder constituents merely increasing PETA (pentaerythritol triacrylate) or DPHA (dipentaerythritol acrylate) and so on can be considered, if but increase the amount of this kind of binder constituents, then the thickness of antistatic layer thickens, be accompanied by this, curling (warpage) that there is antistatic layer becomes large problem, and the usage quantity of the static inhibitor being scattered in the costliness in antistatic layer also increases, and the problem causing cost to increase.In addition, in order to improve adhesion, can consider to increase the method with the composition of reactive base in tackiness agent, but as mentioned above, in order to manifest the amount of the static inhibitor that antistatic property is necessary, the amount of tackiness agent is restricted, is therefore difficult to adopt the method.
In addition, as mentioned above, the binder constituents comprised in layer because of the antistatic layer as film and the total amount of static inhibitor limited, therefore to the usage quantity by reducing static inhibitor, and respective amount ground increases the adhesion that the usage quantity of binder constituents improves antistatic layer and HC layer, then there is the usage quantity minimizing of static inhibitor and the problem that causes antistatic property to reduce.
On the other hand, on interface between antistatic layer and base material, base material is close contact in order to make antistatic layer, need to make the binder constituents of the composition of antistatic layer infiltrate in base material, and on the interface of base material and antistatic layer, the binder constituents infiltrated in base material solidifies with the binder constituents forming antistatic layer and combines.
When static inhibitor is quaternary ammonium salt, known prior art is in order to improve weather resistance or static resistance and the quaternary ammonium salt using molecular weight larger.But, if the molecular weight of quaternary ammonium salt is larger, then the binder constituents of the composition of antistatic layer is difficult to infiltrate in base material, therefore in order to obtain the adhesion of antistatic layer and base material, a large amount of penetrating solvents or use must be used to be permeable to the tackiness agent of the molecular weight in base material.But, in this case, the problem that the adhesion that there is the interface of antistatic layer and HC layer is deteriorated.
In addition, there will be a known at present by using penetrating solvents and can interference stripes be prevented and the technology that outward appearance becomes good can be made, if but use penetrating solvents, then sometimes in base material, also can form new interface, except above-mentioned adhesion worsens, also have and produce interference stripes and the problem of degraded appearance.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2009-086660 publication
In prior art, the thickness of antistatic layer is for considering optical property and the transparency, arrange by the film of about 0.1 ~ 1 μm, if but this kind of thin film layer, in order to give static resistance, the major part of the composition in layer must be set to static resistance material, that therefore cannot add q.s has to manifest some tackiness agent with the necessary reactive base of adhesion of base material or the layer above it.Therefore, in this application, make thickness thickening extremely to a certain degree, and guarantee the adhesion of antistatic layer and adjoining course, therefore the abundant interpolation with the binder constituents of reactive base beyond static resistance material can be made to become possibility.
In addition, by urethane acrylate (C) is set to above-mentioned scope relative to polyfunctional monomer (B) and the ratio of the total amount of urethane acrylate (C), namely be convenient to TAC base material sequentially forms antistatic layer and HC layer from TAC substrate side, also because urethane acrylate (C) is impermeable to TAC base material or more not easily infiltrate in TAC base material compared to polyfunctional monomer (B), therefore urethane acrylate (C) can be utilized to obtain sufficient adhesion between antistatic layer and HC layer, and infiltrate in TAC base material due to polyfunctional monomer (B), therefore the adhesion of antistatic layer and TAC base material can also be obtained.
In antistatic layer curable resin composition of the present invention, with regard to suppress static inhibitor towards the infiltration of TAC base material and coating excellent with regard to, preferred static inhibitor (A) to be weight-average molecular weight be 1000 ~ 50000 quaternary ammonium salt.
In antistatic layer curable resin composition of the present invention, with regard to improving the viewpoint of the effect of polyfunctional monomer (B) and urethane acrylate (C), preferably also comprise (D) penetrating solvents and (E) impermeability solvent.
In antistatic layer curable resin composition of the present invention, the surface resistivity that can be also the cured article of 1 ~ 5 μm by the thickness of above-mentioned antistatic layer curable resin composition is set to and is less than 1 × 10 12Ω/.By the cured article of antistatic layer curable resin composition (also i.e. antistatic layer) is set to this kind of antistatic property, on antistatic layer, the optical thin film of hard coat of stacked 5 ~ 15 μm can play dust attachment preventive.
Moreover, surface resistivity refers to following value: the thickness forming above-mentioned antistatic layer curable resin composition on TAC base material is the cured article (antistatic layer) of 1 ~ 5 μm, then (Mitsubishi Chemical Analytech (Co., Ltd.) manufactures to utilize high resistivity meter, trade(brand)name: Hiresta IP MCP-HT260), under applying voltage 1000V, temperature 25 DEG C, the humidity 40% damping condition of 24 hours, the value measuring gained is carried out to this cured article surface.
Optical thin film of the present invention is in the side of triacetyl cellulose base material, from described triacetyl cellulose substrate side, arrange thickness is adjacently the antistatic layer of 1 ~ 5 μm and the optical thin film of hard coat, it is characterized in that, this antistatic layer is formed by the cured article of above-mentioned antistatic layer curable resin composition, and above-mentioned polyfunctional monomer (B) infiltrates into the region of the near interface of the antistatic layer side of described triacetyl cellulose base material and solidifies.
In the side of TAC base material, from TAC substrate side, be provided with thickness is the antistatic layer of 1 ~ 5 μm and the optical thin film of the present invention of HC layer, because antistatic layer comprises the cured article of above-mentioned antistatic layer curable resin composition, and there is sufficient dust attachment preventive.And then the adhesion of HC layer and antistatic layer becomes excellent.In addition, infiltrated into the region of the interface side of the antistatic layer side of TAC base material by polyfunctional monomer (B) and solidify, also can obtain the adhesion of antistatic layer and TAC base material.Overall as optical thin film, excellent dust attachment can be obtained and prevent performance.
Optical thin film of the present invention preferred embodiment in, also the contiguity rate of the grid adhesion test between above-mentioned hard coat, above-mentioned antistatic layer and above-mentioned triacetyl cellulose base material can be set as 90 ~ 100%, and will in temperature 30 DEG C, humidity 40% time, with 500W/m per hour 2the described contiguity rate of light quantity irradiation ultraviolet radiation after 192 hours be set as 80 ~ 100%.
Moreover, the contiguity rate of so-called grid adhesion test (Cross Cut Adhesion Test), refer to for temperature 25 DEG C, the optical thin film of humidity 40% time damping after 24 hours, according to grid test (Cross Cut Test) method of JIS K5400, 11 gaps are cut anyhow respectively with 1mm interval in hard coat face and makes 100 grids, the Cellotape (registered trademark) manufactured by Nichiban (Co., Ltd.) is attached at after on grid, rapidly it stretched in the direction of 90 ° and make it peel off, and the ratio of the grid residual according to not peeling off of calculating of following benchmark.
Contiguity rate (%)=(unpeeled number of squares/total number of squares 100) × 100
Optical thin film of the present invention preferred embodiment in, also with the face of antistatic layer opposition side, low-index layer can be set further at hard coat.
Optical thin film of the present invention preferred embodiment in, hard coat also can adopt the cured article of the composition containing ionizing radiation curable resin.
The feature of polaroid of the present invention is, the triacetyl cellulose substrate side of optical thin film is provided with polarizer.
The feature of display panel of the present invention is, is configured with indicating meter in the triacetyl cellulose substrate side of optical thin film.
(invention effect)
Antistatic layer into thickness 1 ~ 5 μm is solidified to form by making the composition containing static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C) with above-mentioned specific ratio, even if for the layer from TAC substrate side on TAC base material with antistatic layer and HC layer is formed, can obtain and there is sufficient dust attachment preventive, and the optical thin film that the adhesion of antistatic layer and TAC base material and HC layer is good.In addition, contain the composition of this static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C) with above-mentioned specific ratio, be suitable for being formed in the antistatic layer having and use in the optical thin film of this kind of characteristic.
Summary of the invention
(inventing problem to be solved)
The present invention is the invention completed to solve the problem, its first object is to provide a kind of antistatic layer curable resin composition, and this antistatic layer curable resin composition can form optical characteristics and outward appearance is good, the antistatic layer of the adhesion excellence of static resistance fully and with adjacent HC layer and TAC base material.
In addition, the second object of the present invention is to provide a kind of optical thin film, and it has the antistatic layer using above-mentioned composition to be formed, and dust attachment preventive is excellent.
In addition, the third object of the present invention is to provide a kind of polaroid, and it has above-mentioned optical thin film.
In addition, the fourth object of the present invention is to provide a kind of display panel, and it has above-mentioned optical thin film.
(means of dealing with problems)
The present inventor etc. have carried out making great efforts research, result is learnt, if as the binder constituents comprised in the composition of antistatic layer, and for improve with the adjacent cross-linking density of HC layer and the molecular weight of PETA or DPHA obtaining adhesion and so on be less than 900 the smaller binder constituents of molecular weight, when all infiltrating in TAC base material substantially, or be not penetration degree different of the depth direction at the back side of HC layer from belonging to of TAC base material from the surface at the interface of HC layer to TAC base material according to binder constituents, when binder constituents is stored in base material partially, the binder constituents comprised in antistatic layer on base material reduces, the composition carrying out reacting at the interface of HC layer and antistatic layer is not enough, therefore the adhesion of antistatic layer and HC layer cannot sometimes fully be obtained.In addition, also learn: if the part infiltrating into TAC base material inside is not permeated with gradient profile, but the material of infiltration all equally infiltrates into the same depth in TAC base material, then in TAC base material, form adhesive permeation layer, and in base material, produce new interface, and produce interference stripes etc. and cause deteriorated appearance.
Therefore, the people such as present inventor finds: by by the static inhibitor comprised in composition, belong to the urethane acrylate being difficult to the specified molecular weight infiltrating into TAC base material or the impermeable binder constituents to TAC base material and the binder constituents (polyfunctional monomer) infiltrating into TAC base material is set as specific ratio, can be formed and there is sufficient static resistance, and the antistatic layer of the adhesion excellence with HC layer and TAC base material, overall as optical thin film, excellent dust attachment can be obtained and prevent performance, thus complete the present invention.
That is, the feature of the antistatic layer curable resin composition of the present invention solved the problem is to comprise:
(A) static inhibitor,
(B) there is the light solidified base of more than 2 in 1 molecule and molecular weight is the polyfunctional monomer of less than 900, and
(C) there is in 1 molecule the acryl of more than 6 and/or methacryloyl and weight-average molecular weight is the urethane acrylate of 1000 ~ 11000,
Described (A) is 1 ~ 30 quality % relative to the ratio of the total amount of this (A), (B) and (C), and
Described (C) is 1 ~ 40 quality % relative to the ratio of the total amount of this (B) and (C).
By the ratio of static inhibitor (A) is set to above-mentioned scope, the thickness using above-mentioned composition to be formed is that the antistatic layer of 1 ~ 5 μm has sufficient static resistance, even if thereon stacked HC layer and form optical thin film when, also can guarantee sufficient dust attachment preventive.
Accompanying drawing explanation
Fig. 1 represents the schematic diagram of the example that the layer of optical thin film of the present invention is formed.
Fig. 2 represents the schematic diagram of another example that the layer of optical thin film of the present invention is formed.
Fig. 3 represents the schematic diagram of the example that the layer of polaroid of the present invention is formed.
Embodiment
Below, to antistatic layer curable resin composition of the present invention (following, be sometimes simply called " antistatic layer composition "), optical thin film and use the polaroid of this optical thin film and display panel to be illustrated.
In the present invention, (methyl) acryl represents acryl and/or methacryloyl, and (methyl) acrylate represents acrylate and/or methacrylic ester.
Light of the present invention not only comprises the hertzian wave of the wavelength in visible ray and the non-visible region such as ultraviolet and X-ray, also comprise as electron beam and so on particle beam and be referred to as radioactive rays or the ionizing radiation of hertzian wave and particle beam.
In the present invention, so-called " hard coat ", refers to hardness person more than display " H " in the pencil hardness test (4.9N load) of regulation in JIS K5600-5-4 (1999).
Moreover, about film and sheet material, according to the definition in JIS-K6900, sheet material refers to thinner and its Thickness Ratio length and the little flat article of width usually, film refers to thickness, and minimum and maximum ga(u)ge is by the thinner flat article limited arbitrarily compared with length and width, and it is usually with the supply of the form of volume.Therefore, in sheet material, the thin especially person of thickness can be described as film, but unclear due to the border of sheet material and film, is difficult to be distinguished clearly, therefore in the present invention, comprises the implication of thickness compared with thick one and thinner both persons, is all defined as " film ".
In the present invention, resin is except the concept of monomer or oligomer, and also comprise the concept of polymkeric substance, it becomes the composition of the matrix of other functional layers such as antistatic layer or HC layer after referring to solidification.
In the present invention, so-called molecular weight, when having molecular weight distribution, refer to as at THF (Tetrahydrofuran, tetrahydrofuran (THF)) in solvent by gel permeation chromatography (GPC, Gel Permeation Chromatograph) weight-average molecular weight of polystyrene conversion value that measures, when not having molecular weight distribution, refer to the molecular weight of compound itself.
In the present invention, the median size of so-called particulate, when particulate in the composition, refer to the value that the Microtrac sreen analysis meter using day machine dress (Co., Ltd.) to manufacture measures, when particulate in cured film, refer to the mean value of 10 particles of the section by the cured film observed by transmission electron microscope (TEM, Transmission electron microscopy) photo.
In the present invention, TAC base material dissolves or swelling is instigated in so-called infiltration.
In the present invention, so-called solid state component, refers to the composition removing solvent.
(antistatic layer curable resin composition)
The feature of antistatic layer curable resin composition of the present invention is to comprise:
(A) static inhibitor,
(B) there is the light solidified base of more than 2 in 1 molecule and molecular weight is the polyfunctional monomer of less than 900, and
(C) there is (methyl) acryl of more than 6 in 1 molecule and weight-average molecular weight is the urethane acrylate of 1000 ~ 11000,
Described (A) is 1 ~ 30 quality % relative to the ratio of the total amount of this (A), (B) and (C), and
Described (C) is 1 ~ 40 quality % relative to the ratio of the total amount of this (B) and (C).
By the ratio of static inhibitor (A) is set to above-mentioned scope, antistatic layer can give static resistance, even and if when forming HC layer on the antistatic layer that thickness is 1 ~ 5 μm, also can guarantee sufficient dust attachment preventive.
In addition, by urethane acrylate (C) is set to above-mentioned scope relative to the ratio of the total amount of polyfunctional monomer (B) and urethane acrylate (C), if sequentially form antistatic layer on TAC base material from TAC substrate side, HC layer, then because urethane acrylate (C) can not infiltrate in TAC base material, or more not easily infiltrate in TAC base material compared to polyfunctional monomer (B), therefore also there is urethane acrylate (C) at the interface of antistatic layer and HC layer, reactive base in (methyl) acryl that urethane acrylate (C) has and HC layer solidifies and combines, the sufficient adhesion of antistatic layer and HC layer can be obtained thus.
And then; polyfunctional monomer (B) appropriateness infiltrates in TAC base material and (not equally infiltrates into same depth; but with gradient profile infiltration); the reactive base of polyfunctional monomer (B) existing in the reactive base (light solidified base) of the polyfunctional monomer (B) permeated existing in TAC base material and antistatic layer and the reactive base ((methyl) acryl) of urethane acrylate (C) solidify and combine, and therefore also can obtain the adhesion of antistatic layer and TAC base material.
Below, be illustrated for the above-mentioned static inhibitor (A) of the required composition as antistatic layer composition of the present invention, polyfunctional monomer (B) and urethane acrylate (C) and other compositions that can optionally and suitably contain.
(A: static inhibitor)
Static inhibitor (A) is give electroconductibility to the antistatic layer of the cured film as antistatic layer composition or optical thin film to prevent charged, and there is imparting prevent dust or dust attachment, or prevent the composition producing the effect of bad character (also i.e. static resistance) because of charged at in-process.
As static inhibitor (A), previous known static inhibitor can be used, be not particularly limited.
Include, for example the cationic compounds such as quaternary ammonium salt described in patent documentation 1, the anionic property compounds such as sulphonate-base, the amphoteric substances such as amino acid system, the nonionic compound of amino alcohol system etc., organometallic compound and meal chelate compounds, and by the compound of these compound polymers quantification, polymerizable compound, average 1 particle diameter is the electroconductibility ultra microns such as the tin indium oxide (ITO) of 1 ~ 100nm, and the polymer conductive composition such as the polyacetylene of aliphatics conjugated system.
In antistatic layer curable resin composition of the present invention, with regard to suppress static inhibitor (A) towards the infiltration of TAC base material and coating excellent with regard to, preferred static inhibitor (A) to be weight-average molecular weight be 1000 ~ 50000 quaternary ammonium salt.If exceed the above-mentioned upper limit, then the coating of composition worsens, if lower than above-mentioned lower limit, then static inhibitor easily ooze out into antistatic layer with on the interface of HC layer, and have the possibility that the adhesion of antistatic layer and HC layer worsens.
Previously, the thickness of antistatic layer, consider optical property and the transparency, arrange with the film of about 0.1 ~ 1 μm, if but this kind of thin film layer, then in order to give static resistance, the major part of the composition in layer must be set to static resistance material, what be therefore difficult to add q.s has to manifest the resin combination with the necessary reactive base of adhesion of base material or the layer above it.Therefore, in the present invention, thickness is set to 1 ~ 5 μm, comparatively previously thicker, and guarantee the adhesion of antistatic layer and adjoining course, the abundant interpolation with the resin combination of reactive base beyond static resistance material therefore can be made to become possibility.Because thickness increases, therefore the comparatively ideal material being added static inhibitor and selecting that the transparency is higher.In this, be preferably the organic materials of the transparency higher than inorganic materials, and then in organic materials, painted few quaternary ammonium salt is most suitable.When using quaternary ammonium salt, when transparent base material is TAC, the full light transmittance of optical thin film entirety can be made to become more than 90%, put also preferred at this point.In addition, haze value also can be made to become less than 0.5%.Full light transmittance can according to JIS K7361 (1997), the HM150 etc. manufactured by color technical institute in village is measured, haze value can according to JIS K7136 (2000), and the HM150 etc. manufactured by color technical institute in village is measured.
And then with regard to improved the adhesion aspect of antistatic layer and HC layer by the crosslinking reaction of HC layer and binder constituents with regard to, preferably this quaternary ammonium salt has light solidified base.Light solidified base is preferably polymerizability unsaturated group, is more preferably ionizing radiation solidified nature unsaturated group.As its concrete example, base and epoxy group(ing) etc. that (methyl) acryl, (methyl) acryloxy, vinyl and allyl group etc. have ethene unsaturated link(age) can be enumerated.
It is the commercially available product of the quaternary ammonium salt of 1000 ~ 50000 as this kind of weight-average molecular weight, include, for example the trade(brand)name H6100 that Mitsubishi Chemical (Co., Ltd.) manufactures, and trade(brand)name Uniresin AS-10/M, UniresinAS-12/M, Uniresin AS-15/M and Uniresin ASH26 etc. that Xin Zhong village chemical industry (Co., Ltd.) manufactures.
In antistatic layer composition, relative to the total amount of static inhibitor (A) and polyfunctional monomer described later (B) and urethane acrylate (C), the static inhibitor (A) containing 1 ~ 30 quality %.
If the ratio of static inhibitor (A) is less than 1 quality % relative to above-mentioned total amount (A+B+C), then cannot obtain sufficient antistatic property.In addition, if the ratio of static inhibitor (A) relative to above-mentioned total amount (A+B+C) more than 30 quality %, the ratio of the polyfunctional monomer (B) then in antistatic layer composition and urethane acrylate (C) reduces, and cannot obtain antistatic layer and be adjacent to the TAC base material of this layer or the sufficient adhesion of HC layer.
The ratio of static inhibitor (A) is 1 ~ 30 quality % relative to above-mentioned total amount (A+B+C), but is preferably 5 ~ 20 quality %.
(B: polyfunctional monomer)
Polyfunctional monomer (B) for become after solidification the binder constituents of antistatic layer matrix one by one, and be the molecular weight of the light solidified base in 1 molecule with more than 2 be the monomer of less than 900.Its molecular weight and be multifunctional, thus to contribute to improving in antistatic layer or with the cross-linking density of HC layer being adjacent to antistatic layer, contribute to the composition promoting adhesion.In addition, polyfunctional monomer to be infiltrated at least partially in TAC base material by it and solidifies, and also contributes to the adhesion promoting antistatic layer and TAC base material.
If the molecular weight of polyfunctional monomer (B) is more than 900, then the perviousness towards TAC base material declines, and has the possibility of the abundant adhesion that cannot obtain antistatic layer and TAC base material.
Polyfunctional monomer (B) if molecular weight be less than 900, but just make polyfunctional monomer (B) moderately permeate towards TAC base material, and make the adhesion of antistatic layer and HC layer and static resistance (surface resistivity) to heavens and the viewpoint of depositing, the molecular weight of polyfunctional monomer (B) is preferably more than 230, is more preferably more than 290.If molecular weight is less than 230, then polyfunctional monomer (B) is towards the infiltration of TAC base material and immoderation, have and all infiltrate into the same degree of depth and the situation that produces new interface, and have the light that reflects at its interface and produce the interference of light between the light that reflects at the interface of antistatic layer and HC layer or the light reflected on HC layer surface, and produce interference fringe and cause the possibility of deteriorated appearance.
As polyfunctional monomer (B), one or more can be used.
The light solidified base of polyfunctional monomer (B) is more than 2 to form crosslinking structure, preferably has more than 3, is more preferably and has more than 5.If more than 3, then easily obtain the abundant adhesion of antistatic layer and HC layer and TAC base material.As light solidified base, can enumerate and the identical person of light solidified base cited in static inhibitor.
As polyfunctional monomer (B), include, for example tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, trimethylolpropane tris (methyl) acrylate and TriMethylolPropane(TMP) six (methyl) acrylate and these modification body.
Moreover, as modification body, EO (Ethylene oxide, oxyethane) modification body, PO (Propylene oxide can be enumerated, propylene oxide) modification body, CL (Caprolactone, caprolactone) modification body and isocyanuric acid modification body etc.
In above-mentioned polyfunctional monomer, with regard to the viewpoint of solidification reactivity, compared with methacryloyl, light solidified base be acryl more preferably.
As polyfunctional monomer (B), Dipentaerythritol Pentaacrylate (DPPA, Di-Pentaerythritol pentaacrylate), dipentaerythritol acrylate (DPHA) especially preferably can be used.
In antistatic layer composition of the present invention, it is proportional that polyfunctional monomer (B) meets containing of above-mentioned static inhibitor, and be 60 ~ 99 quality % relative to polyfunctional monomer (B) and the total amount of urethane acrylate described later (C).If less than 60 quality %, then cannot obtain the sufficient adhesion of antistatic layer and HC layer and TAC base material.In addition, if more than 99 quality %, then the ratio of urethane acrylate (C) is less, cannot obtain the sufficient adhesion of antistatic layer and HC layer.
(C: urethane acrylate)
Urethane acrylate (C) is for becoming one of binder constituents of antistatic layer matrix after solidification; there is in its 1 molecule (methyl) acryl of more than 6; and weight-average molecular weight is 1000 ~ 11000, is preferably 1000 ~ 10000, is more preferably 1000 ~ 5000.
Be 1000 ~ 11000 by weight-average molecular weight, then coating is good, impermeable in TAC base material, or more not easily infiltrates in TAC base material compared to polyfunctional monomer (B), easily controls infiltration, and is positively present in whole antistatic layer.
When static inhibitor (A) is for quaternary ammonium salt, as the character of this compound, good with the compatibility of hydrophilic compounds.Therefore, if the tackiness agent in antistatic layer is the compound (PETA, PETTA (tetramethylol methane tetraacrylate), DPPA (Dipentaerythritol Pentaacrylate) etc.) with OH base, then static inhibitor is excessively scattered in whole layer, and cannot obtain static resistance.Known DPHA does not contain OH base on structural formula, but 6 officials being usually difficult to formation 100% in synthesis can, therefore be actually with 5 officials can or the mixing cpd of 4 functional moieties, because usual commercially available resin is the compound remaining OH base, so preferred static resistance cannot be obtained.
Can control this dispersed person is the urethane acrylate (C) belonging to hydrophobic resin.By making urethane acrylate (C) be present in whole layer, when static inhibitor (A) is for quaternary ammonium salt system, positively can control the situation that static inhibitor excessively disperses or oozes out in the direction, interface with HC in layer.The reason of easily oozing out in direction, HC interface is, as mentioned above, because wetting ability liked by quaternary ammonium salt, thus antistatic layer is stacked and when solidifying, there is air on its surface, react with the moisture in this air and ooze out.
And, there is (methyl) acryl of more than 6, to contribute to improving in antistatic layer or with the cross-linking density of the reactive base be adjacent in the HC layer of antistatic layer, and promote the adhesion of antistatic layer and HC layer.In addition; owing to improve the reactive base of the polyfunctional monomer (B) of the antistatic layer infiltrating into TAC base material, the cross-linking density with existing (methyl) acryl of urethane acrylate (C) in antistatic layer or the reactive base of polyfunctional monomer, so urethane acrylate (C) also contributes to the adhesion promoting antistatic layer and TAC base material.When from the viewpoint of adhesion, do not add urethane acrylate (C), as long as be the polyfunctional monomer (B) with a large amount of reactive base except static inhibitor (A), but in order to as above control static inhibitor (A) variation in antistatic layer, if be only polyfunctional monomer (B), then be difficult to control, in order to static inhibitor (A) does not disperse, need hydrophobicity and there is the urethane acrylate (C) of a large amount of reactive base.
In addition, also effective for suppressing the generation of curling (warpage) containing urethane acrylate (C).
If the weight-average molecular weight of urethane acrylate (C) is less than 1000; then there is following possibility: urethane acrylate (C) easily infiltrates in TAC base material; excessive permeation is in TAC base material; cause the acryl at the interface of antistatic layer and HC layer to reduce, be difficult to the adhesion obtaining antistatic layer and HC layer.
If the weight-average molecular weight of urethane acrylate (C) is more than 11000, then there is the possibility that coating worsens.
As long as urethane acrylate (C) has (methyl) acryl of more than 6, then also can containing other the functional group of crosslinking reaction such as ionizing radiation solidified nature unsaturated group.(methyl), as long as acryl adds up to acryl and the methacryloyl with more than 6, only can have acryl, also only can have methacryloyl.
As urethane acrylate of the present invention (C), as long as there is urethane bonds (-NH-CO-O-), there is (methyl) acryl of more than 6 and for above-mentioned weight-average molecular weight, be then not particularly limited.As urethane acrylate (C), preferably make the film time can through the C of light transmission, also can performance etc. and suitably adopt the ionizing radiation solidified nature urethane acrylate, other known urethane acrylates etc. of the resin belonged to by solidifying with the ionizing radiation representated by ultraviolet or electron beam as requested.
As the commercially available product of above-mentioned urethane acrylate, the trade(brand)name BS577 that the trade(brand)name UN3320HS that on the trade(brand)name UV1700B that the Japanese synthetic chemical industry (Co., Ltd.) described in include, for example in patent documentation 1 manufactures, root, industry (Co., Ltd.) manufactures, waste river chemical industry (Co., Ltd.) manufacture and the trade(brand)name U15HA that Xin Zhong village chemical industry (Co., Ltd.) manufactures, U15H, U9HA, U9H, U6HA and U6H etc.
In antistatic layer composition of the present invention, it is proportional that urethane acrylate (C) meets containing of above-mentioned static inhibitor, and be 1 ~ 40 quality % relative to above-mentioned polyfunctional monomer (B) and the total amount of urethane acrylate (C).If be less than 1 quality %, then cannot obtain the abundant adhesion of antistatic layer and HC layer.In addition, if more than 40 quality %, then the ratio of polyfunctional monomer (B) is less, cannot obtain the abundant adhesion of antistatic layer and TAC base material.
The ratio of urethane acrylate (C) is 1 ~ 40 quality % relative to above-mentioned total amount (B+C), but is preferably 5 ~ 30 quality %.
So, suitable by the ratio of the polyfunctional monomer (B) in tackiness agent, urethane acrylate (C), static inhibitor (A) both excessively can not disperse in antistatic layer, also can not ooze out, can concentrate with the degree that can play static resistance in layer and exist.Just because of it is this composition, the surface resistivity of antistatic layer can be less than 1 × 10 12Ω/.
In antistatic layer composition, except above-mentioned (A), (B) and (C) composition, optionally also suitable solvent and polymerization starter can be contained.Below, these other compositions are illustrated.
(solvent)
As solvent, the penetrating solvents such as the glycol ethers such as halogenated hydrocaron solvent and methylcyclohexane series solvent such as ether series solvent, the methylene dichloride such as glycol series solvent, the THF such as the nitrogenous series solvent such as ester series solvent, acetonitrile, methyl glycol such as ketone series solvent, methyl acetate such as acetone described in patent documentation 1 can be used.
As penetrating solvents, be preferably selected from least one in methyl acetate, ethyl acetate, butylacetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) (MIBK, Methyl Isobutyl Ketone) and pimelinketone.
In addition, the impermeability solvent such as propylene glycol monomethyl ether (PGME, Propylene GlycolMonomethyl Ether), n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol and the trimethyl carbinol can also be used.
Above-mentioned solvent can use one individually, also two or more mixing can be used.
In antistatic layer composition of the present invention, just infer by using penetrating solvents, can promote above-mentioned polyfunctional monomer (B) towards TAC base material infiltration, promote the adhesion of antistatic layer and TAC base material, preferably use penetrating solvents.
In addition, in antistatic layer composition of the present invention, just infer by using impermeability solvent, can suppress above-mentioned urethane acrylate (C) towards TAC base material infiltration, promote the adhesion of antistatic layer and HC layer, preferably use impermeability solvent.
Therefore, in antistatic layer composition of the present invention, when solvent is a kind of, preferably use penetrating solvent, but when two or more solvent, most preferably penetrating solvents and impermeability solvent are combinationally used.Its reason is, even if although a kind of solvent (only penetrating solvent), also the molecular weight by urethane acrylate (C) controls infiltration, but penetrating solvents and impermeability solvent are combinationally used and can more easily control to permeate, and obtain the stable performance of the antistatic layer using composition.
When penetrating solvents and impermeability solvent are combinationally used, being preferably its mass ratio is penetrating solvents: impermeability solvent=100: 0 ~, be preferably 90: 10 ~ 50: 50, and be preferably 30 ~ 500 mass parts relative to total solid state component 100 mass parts of antistatic layer composition.
(polymerization starter)
Polymerization starter, optionally can the suitably previous known free radical of choice for use and cationic polymerization initiators etc. for causing or promote the composition of crosslinking reaction of above-mentioned binder constituents (B).As radical polymerization initiator, the trade(brand)name Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-one) that such as can preferably use Ciba Japan (Co., Ltd.) to manufacture.When using polymerization starter, its content, relative to the total quality of total solid state component of antistatic layer composition, is preferably 0.4 ~ 2.0 quality %.By as above the amount of the polymerization starter used in antistatic layer composition being set to 1/10 ~ 1/2 of the amount of the polymerization starter used in HC layer, the reactive base of antistatic layer can be made to remain in a large number.Thus, reaction is difficult to carry out, therefore also prevents curling generation.
(preparation of antistatic layer curable resin composition)
Above-mentioned antistatic layer curable resin composition by making above-mentioned (A), (B) and (C) composition blending dispersion obtains in solvent.In addition, even if solvent-free, when above-mentioned (A), (B) or (C) composition still have sufficient mobility, also can be solvent-free.Blending dispersion can use the known methods such as coating vibrating machine or ball mill.
In antistatic layer curable resin composition of the present invention, by static inhibitor (A) is set to above-mentioned scope, the thickness of above-mentioned antistatic layer curable resin composition also can be made to be that the surface resistivity of the cured article of 1 ~ 5 μm is less than 1 × 10 12Ω/.By making antistatic layer be this kind of antistatic property, even if the HC layer that stacked film thickness rate is thicker, also can play excellent dust attachment and preventing performance in whole optical thin film.
If the thickness of antistatic layer is less than 1 μm, then must increase the amount of the quaternary ammonium salt as static inhibitor to maintain identical surface resistivity, but in this case, the reactive base that there is static inhibitor reduces, the possibility that the contiguity of antistatic layer and HC layer worsens.
If the thickness of antistatic layer is more than 5 μm, then surface resistivity easily shows, but there is the possibility that generation is curling, cost raises, treatability worsens.
And then, in antistatic layer composition, be 5 ~ 20 quality % by making static inhibitor (A) relative to the total amount of static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C), and make urethane acrylate (C) be 5 ~ 30 quality % relative to the total amount of polyfunctional monomer (B) and urethane acrylate (C), then except can obtaining sufficient static resistance, also can obtain the weather resistance of adhesion relative to the excellence of ultraviolet (UV) of optical thin film.
(optical thin film)
Optical thin film of the present invention is the side in triacetyl cellulose base material, antistatic layer and the hard coat person of forming that thickness is 1 ~ 5 μm are set adjacently from this triacetyl cellulose substrate side, it is characterized in that, this antistatic layer comprises the cured article of above-mentioned antistatic layer curable resin composition, and above-mentioned polyfunctional monomer (B) infiltrates into the region of the interface side of the antistatic layer side of triacetyl cellulose base material and solidifies.
From TAC substrate side, arrange thickness in the side of TAC base material be the antistatic layer of 1 ~ 5 μm and the optical thin film of HC layer, formed by the cured article of antistatic layer by above-mentioned antistatic layer curable resin composition, can have sufficient dust attachment preventive, and the adhesion of HC layer and antistatic layer is excellent.In addition, by making polyfunctional monomer (B) infiltrate into the region of the interface side of the antistatic layer side of TAC base material and solidify, the adhesion of antistatic layer and TAC base material can also be obtained.Overall as optical thin film, excellent dust attachment can be obtained and prevent performance.
Optical thin film of the present invention preferred embodiment in, formed by the cured article of above-mentioned antistatic layer composition by making antistatic layer, the contiguity rate that the grid adhesion between the above-mentioned hard coat of optical thin film, above-mentioned antistatic layer and above-mentioned triacetyl cellulose base material also can be made to test is 90 ~ 100%, and makes in temperature 30 DEG C, humidity 40% time with 500W/m per hour 2light quantity irradiate 192 hours ultraviolets after this contiguity rate of (following, to be sometimes simply called " after UV resistant (UV, Ultraviolet) test ") be 80 ~ 100%.
This contiguity rate represents the contiguity of HC layer, antistatic layer and TAC base material, i.e. the contiguity of antistatic layer and HC interlayer and the adhesion between antistatic layer and TAC base material.
Have not containing urethane acrylate (C) existing, main only containing the composition of polyfunctional monomer (B) as tackiness agent, even if or in the optical thin film of antistatic layer that formed of the cured article also not containing the composition of static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C) with specific ratio containing urethane acrylate (C), though the contiguity between antistatic layer and TAC base material is good, the contiguity of antistatic layer and HC interlayer is also insufficient.So, fully in situation in the adhesion of antistatic layer and HC interlayer, if carry out adhesion test, though be not then peeling between antistatic layer and TAC base material, can be peeling and peel off between antistatic layer and HC layer.In the not sufficient situation of contiguity between antistatic layer and TAC base material, can be peeling and peel off between antistatic layer and TAC base material.Therefore, as optical thin film, in order to obtain excellent adhesion, need the contiguity of antistatic layer and HC interlayer and the contiguity between antistatic layer and TAC base material.
By making above-mentioned antistatic layer composition be solidified to form antistatic layer, thickness is that the antistatic layer of 1 ~ 5 μm and the contiguity of HC interlayer and the contiguity between antistatic layer and TAC base material are excellent, as the adhesion of optical thin film whole show excellence.Especially, this adhesion is more remarkable after resistance to UV test.Optical thin film of the present invention also manifests excellent adhesion after resistance to UV test.
Fig. 1 is the schematic diagram representing the example that the layer of optical thin film of the present invention is formed.In the side of triacetyl cellulose base material 10, be sequentially provided with antistatic layer 20 and hard coat 30 adjacently.Fig. 2 is the schematic diagram representing another example that the layer of optical thin film of the present invention is formed.The hard coat of the optical thin film identical with Fig. 1 is provided with low-index layer 40 further.
Below, to the triacetyl cellulose base material of the required integrant as optical thin film of the present invention, antistatic layer and hard coat, and other layers such as the high refractive index layer that can optionally and suitably arrange, middle index layer, low-index layer, antiglare layer and stain-proofing layer are illustrated.
(triacetyl cellulose base material)
The triacetyl cellulose base material used in the present invention is the higher triacetylcellulose film of light transmission, as long as and can be used as the physical property person of the Mght-transmitting base material of optical thin film for meeting, then be not particularly limited, can the TAC base material of the suitably current known hard-coated film of choice for use or optical thin film.
The average transmittance of the TAC base material in the 380 ~ 780nm of visible region is preferably more than 80%, is particularly preferably more than 90%.Moreover the mensuration of transmittance adopts and uses UV, visible light to divide luminometer (the trade(brand)name UV-3100PC that such as Shimadzu Seisakusho Ltd. (Co., Ltd.) manufactures), the value measured in room temperature, air.
Can saponification process be implemented to TAC base material or the surface treatments such as undercoat are set.In addition, the additives such as static inhibitor can be added.
The thickness of TAC base material is not particularly limited, and is generally 30 ~ 200 μm, is preferably 40 ~ 200 μm.
(antistatic layer)
Antistatic layer of the present invention is formed by the cured article of above-mentioned antistatic layer curable resin composition, and thickness is 1 ~ 5 μm.If thickness is thinner than 1 μm, then cannot obtaining sufficient antistatic property, cannot adding fully for guaranteeing with the adhesion of other layers and required tackiness agent.If be thicker than 5 μm, then because static inhibitor can not to be closely present in layer and cannot to play performance to a certain degree, so the curling change of antistatic layer is large, therefore processibility worsens, if thickness is thickening further, then the amount of comprised static inhibitor etc. increases, and cost increases.
As the performance of antistatic layer, surface resistivity is preferably less than 1 × 10 12Ω/, is more preferably 1 × 10 11Ω/below and then be 1 × 10 10Ω/below.As long as the surface resistivity of antistatic layer is good, the dust attachment preventive being laminated with the optical thin film of HC layer can be better.
(hard coat)
Hard coat is in the pencil hardness test (4.9N load) of regulation in JIS K5600-5-4 (1999), the layer of hardness more than display " H ", and gives hardness to optical thin film of the present invention.
HC layer comprises the cured article of composition for hard coat, previous known hard coat can be used, also can be and comprise only containing the cured article person of the composition for hard coat of binder constituents, in addition, also can in the composition containing polymerization starter etc. cited in above-mentioned antistatic layer composition.In order to improve the hardness etc. of HC layer, also can contain the composition of previous known imparting hardness, that such as, records in Japanese Patent Laid-Open 2008-165040 publication has the reactive silicon dioxide particulate with the crosslinking reaction of binder constituents.
As concrete example, by being coated with containing the resin combination of ionizing radiation curable resin as transparent resin over the transparent substrate, and monomer, oligomer and the prepolymer comprised in this resin combination is made to be cross-linked and/or to be polymerized and to form HC layer.
As transparent resin, preferred ionizing radiation curable resin, as the functional group of monomer, oligomer and prepolymer, the functional group of preferred ionizing radiation polymerizability, wherein preferred light polymerizable functional groups.Solidified by the reactive base of the urethane acrylate (C) in this functional group and antistatic layer resin combination and combine, the sufficient adhesion of antistatic layer and HC layer can be obtained.
As optical polymerism functional group, the unsaturated polymerizable functional groups etc. such as (methyl) acryl, vinyl, styryl, allyl group can be enumerated.
In addition, as prepolymer and oligomer, acrylate, unsaturated polyester, the epoxy resin etc. such as urethane (methyl) acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate can be enumerated.
As monomer, vinylbenzene can be enumerated, the styrenic monomers such as alpha-methyl styrene, (methyl) methyl acrylate, (methyl) ethyl acrylate, tetramethylolmethane (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane oxyethyl group four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, TriMethylolPropane(TMP) oxyethyl group three (methyl) acrylate, glycerine propoxylate, two-trimethylolpropane tetra-acrylate, polyoxyethylene glycol two (methyl) acrylate, EO modification two (methyl) acrylate of Bisphenol F, EO modification two (methyl) acrylate of dihydroxyphenyl propane, isocyanuric acid EO modification two (methyl) acrylate, isocyanuric acid EO modification three (methyl) acrylate, polypropylene glycol two (methyl) acrylate, TriMethylolPropane(TMP) PO modification three (methyl) acrylate, TriMethylolPropane(TMP) EO modification three (methyl) acrylate, the acrylic monomers such as two-TriMethylolPropane(TMP) four (methyl) acrylate, trimethylolpropane tris thioglycolic acid esters, trimethylolpropane tris sulfo-propylate, there is in tetramethylolmethane four thioglycol equimolecular the polyol compound of the thiol group of more than 2, in addition, there is urethane (methyl) acrylate or polyester (methyl) acrylate etc. of the unsaturated link(age) of more than 2.
Especially, with regard to improving cross-linking density, obtaining the viewpoint of damage-resistant, preferred polyfunctional acrylate monomer, wherein, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate because of, pencil hardness good with the contiguity of antistatic layer also well and more preferably.In addition, in these monomers, mix the oligomer compositions such as urethane polyfunctional acrylic ester hardness also can be made to become good, and polymerization shrinkage is reduced, the performance preventing curling or slight crack can be formed well, therefore preferably.
In this kind of resin combination, also can in order to promote hardness containing inorganic particles etc. such as silicon-dioxide.In addition, in order to make to become good with the compatibility of resin combination, can organic surface treatment be carried out, also can have reactive base.
In addition, as tackiness agent, also polymkeric substance can be added in above-mentioned resin combination and use.As polymkeric substance, include, for example polymethylmethacrylate (PMMA, Polymethyl Methacrylate), cellulose acetate-propionate (CAP, Cellulose AcetatePropionate) etc.By adding polymkeric substance, the viscosity of adjustable masking liquid, makes coating become easy advantage thus.
In addition, in above-mentioned resin combination, optionally can add optical free radical polymerization starter.Preferred addition is 0.8 ~ 8.0 quality % relative to the total quality of total solid state component of above-mentioned resin combination.As optical free radical polymerization starter, acetophenones, bitter almond oil camphor class, benzophenone, phosphinoxides, ketal class, Anthraquinones, 9-thioxanthene ketone, azo-compound etc. can be used.
As acetophenones, can 2 be enumerated, 2-dimethoxy-acetophenone, 2, 2-diethoxy acetophenone, to dimethyl acetophenone, 1-hydroxy-dimethyl phenyl ketone, 1-hydroxy-dimethyl-p-isopropyl phenyl ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio group-2-raorpholino propiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 4-phenoxydichloroacetophenone, the 4-tertiary butyl-dichloroacetophenone etc., as bitter almond oil camphor class, bitter almond oil camphor can be enumerated, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, benzyl dimethyl ketal, bitter almond oil camphor benzene sulfonate, benzoin tosylate, benzoin methylether, ethoxybenzoin etc.
In addition; as benzophenone; benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 '-methyldiphenyl sulfide, 2 can be used; 4-dichloro benzophenone, 4; 4-dichloro benzophenone and p-dichlorobenzene ketone, 4,4 '-dimethylamino benzophenone (meter Qi Le ketone), 3,3 '; 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone etc.
In addition, also can photosensitizers used in combination, as its concrete example, n-butylamine, triethylamine, poly-normal-butyl phosphine etc. can be enumerated.
Such as, as long as the thickness of HC layer suitably regulates, as long as be 1 ~ 20 μm.Be preferably 5 ~ 15 μm.If more than 15 μm, cannot obtain excellent dust attachment and prevent performance, if be less than 5 μm, then hardness becomes not enough and adhesion also dies down.
Usually, if the HC layer be laminated on antistatic layer is thickening, then dust attachment prevents degradation, if but the formation of the application and composition, then can obtain excellent dust attachment and prevent performance.
In the preferred example of optical thin film of the present invention, even if with antistatic layer be 1 ~ 5 μm, HC layer is that the mode of 5 ~ 15 μm is laminated with thicker HC layer on antistatic layer, optical thin film also can obtain the adhesion that the attachment of sufficient dust prevents performance and antistatic layer and HC layer fully.
(other layers)
In optical thin film of the present invention, without departing from the spirit and scope of the invention, at above-mentioned HC layer with on the face of antistatic layer opposition side, also can other layers such as high refractive index layer, middle index layer, low-index layer, antiglare layer and stain-proofing layer be set in order to the anti-reflective of improving optical film, anti-glare and didirtresistance etc.
(high refractive index layer and middle index layer)
High refractive index layer and middle index layer are reflectivity in order to adjust optical thin film of the present invention and the layer arranged.When arranging high refractive index layer, although not shown, but be usually adjacent to the TAC substrate side of low-index layer and arrange.In addition, when in arranging when index layer, although not shown, but usually middle index layer, high refractive index layer and low-index layer are sequentially set from TAC substrate side.
High refractive index layer and middle index layer comprise the main cured article containing the composition of binder constituents and specific refractory power adjustment particle.As binder constituents, polyfunctional monomer etc. cited in antistatic layer composition can be used.As specific refractory power adjustment particle, include, for example the particulate that particle diameter is below 100nm.1.90), titanium dioxide (specific refractory power: 2.3 ~ 2.7), cerium dioxide (specific refractory power: 1.95), tin-doped indium oxide (specific refractory power: 1.95), antimony doped tin oxide (specific refractory power: 1.80), yttrium oxide (specific refractory power: 1.87), zirconium white (specific refractory power: more than one 2.0) as this kind of particulate, can enumerate and be selected from zinc oxide (specific refractory power:.
Specifically, the specific refractory power of high refractive index layer is preferably 1.50 ~ 2.80.The specific refractory power of middle index layer, lower than the specific refractory power of high refractive index layer, is preferably 1.50 ~ 2.00.
As long as the thickness of high refractive index layer and middle index layer suitably regulates, be preferably 50 ~ 300nm.
(low-index layer)
Low-index layer comprises the cured article containing the lower composition of the specific refractory power such as silicon-dioxide or magnesium fluoride and the composition of binder constituents or the low-index layer composition containing fluorine resins such as vinylidene fluoride copolymers, can form existing known low-index layer.
For the formation of in the composition of low-index layer, in order to reduce the specific refractory power of low-index layer, also hollow-particle can be contained.Hollow-particle refer to there is outer shell and the inside that surrounds by outer shell be the particle in Porous tissue or hole.In this Porous tissue or hole, containing air, (specific refractory power: 1) containing by making low-index layer the hollow-particle that specific refractory power is 1.20 ~ 1.45, can reduce the specific refractory power of low-index layer.The median size of hollow-particle is preferably 1 ~ 100nm.Hollow-particle can use the particle used in previous known low-index layer, such as, can exemplify the particulate with space described in Japanese Patent Laid-Open 2008-165040 publication.
When the number average primary particle diameter of above-mentioned fatty acid metal salt particle is less than above-mentioned in limited time lower, there is following situation: easily produce the cohesion each other of fatty acid metal salt particle or the fatty acid metal salt particle unfavorable condition such as to bury for pigmentary resin particle, detrimentally affect is caused to the lettering performance of carbon dust.
On the other hand, when the number average primary particle diameter of above-mentioned fatty acid metal salt particle exceedes above-mentioned in limited time upper, there is following situation: fatty acid metal salt particle is easy to from pigmentary resin particle free (disengaging), the function of required additive (carbon dust being given to the function of charging stability and mobility etc.) cannot be imparted to carbon powder particles fully, detrimentally affect is caused to the lettering performance of carbon dust.
(antiglare layer)
Antiglare layer comprises the cured article of the antiglare layer composition containing binder constituents and anti-dazzle dose, and binder constituents can use polyfunctional monomer etc. cited in above-mentioned antistatic layer composition.
As anti-dazzle dose, can particulate be enumerated, include, for example styrene pellets (specific refractory power is 1.59), melamine particles (specific refractory power is 1.57) and acrylic particles (specific refractory power is 1.49) etc.The median size that this kind gives the particulate of anti-glare is preferably 100 ~ 500nm.Give the total mass of content relative to the binder constituents comprised in antiglare layer composition of the particulate of anti-glare, be preferably 2 ~ 30 quality %.
(stain-proofing layer)
According to a preferred embodiment of the invention, in order to prevent the spot of optical thin film most surface, at optical thin film, stain-proofing layer can be set with the most surface of TAC base material opposition side.By stain-proofing layer, the further improvement of didirtresistance and scuff resistance can be sought to optical thin film.Stain-proofing layer comprises the cured article of the stain-proofing layer composition containing stain control agent and binder constituents.
The binder constituents of stain-proofing layer composition can use previous known person, such as, can use the polyfunctional monomer enumerated in above-mentioned antistatic layer composition.
The stain control agent comprised in stain-proofing layer composition can suitably be selected one or more to use from the stain control agents such as known levelling agent.The content of stain control agent, relative to the total mass of the binder constituents comprised in stain-proofing layer composition, is preferably 0.1 ~ 5 quality %.
(manufacture method of optical thin film)
As the manufacture method of optical thin film of the present invention, if the method that the layer that can obtain above-mentioned optical thin film is formed, be then not particularly limited, previous known method can be used.
As one example, comprise the steps: that (i) prepares triacetyl cellulose base material; (ii) above-mentioned antistatic layer composition and composition for hard coat is prepared; (iii) this antistatic layer composition is coated with in the side of this TAC base material to make film; (iv) rayed is carried out to the film of this antistatic layer composition, make it be solidified to form antistatic layer; V () is coated with this composition for hard coat to make film on antistatic layer; (vi) rayed is carried out to the film of this HC layer composition, make it be solidified to form HC layer.
In addition, can the film of antistatic layer composition not be made to solidify completely (full cure) in above-mentioned (iv) step yet, and make its semicure (half cure), and on the film of this semicure, be coated with HC layer composition to make film, carry out rayed after the film of the film of this semicure and HC layer composition is merged, then make it solidify completely and obtain optical thin film.By using semicure method in above-mentioned mode, there is the advantage that the adhesion of antistatic layer and HC layer improves.
As long as coating process uses previous known method, be not particularly limited, the various methods such as gravure coating process, spin-coating method, pickling process, spray method, ramp type coating method, stick coating method, rolling method, meniscus coating method, quick-drying print process, screen painting method and drop coating method (bead coater) can be used.
Rayed mainly uses ultraviolet, visible ray, electron beam or ionizing radiation etc.When ultraviolet curing, use the ultraviolet etc. sent from the light of extra-high-pressure mercury vapour lamp, high pressure mercury vapour lamp, Cooper-Hewitt lamp, carbon arc lamp, xenon arc lamp, metal halide lamp etc.The irradiation dose in energy-ray source with the accumulated exposure gauge under ultraviolet wavelength 365nm for 50 ~ 500mJ/cm 2.Irradiation dose when semicure is 5 ~ 50mJ/cm 2.Light-struck basis is also heated, usually process at the temperature of 40 DEG C ~ 120 DEG C.
Before carrying out rayed, also drying can be carried out after the coating antistatic layer composition.As drying means, the method etc. that include, for example drying under reduced pressure or heat drying and then these dryings are combined.In addition, when carrying out drying with normal pressure, preferably at 30 ~ 110 DEG C, carry out drying.Such as, when using the solvent of methyl ethyl ketone as antistatic layer composition, can room temperature ~ 80 DEG C, be preferably in the scope of 40 DEG C ~ 70 DEG C temperature under, carry out 20 seconds ~ 3 minutes, be preferably the drying step of 30 seconds ~ 1 minute.
As long as the composition of HC layer or low-index layer etc. is prepared with the method identical with above-mentioned antistatic layer.In addition, when arranging low-index layer etc. on HC layer, coating process or the curing of above-mentioned antistatic layer can be used.
(polaroid)
The feature of polaroid of the present invention is: the triacetyl cellulose substrate side of above-mentioned optical thin film is provided with polarizer.Fig. 3 is the schematic diagram representing the example that the layer of polaroid of the present invention is formed.Polaroid 80 shown in Fig. 3 has optical thin film 1 and is laminated with the polarizer 70 of protective film 50 and polarization layer 60, and polarizer 70 is arranged at triacetyl cellulose base material 10 side of optical thin film 1.
Moreover what is called is configured with polarizer in the triacetyl cellulose substrate side of optical thin film, not only comprise the situation forming optical thin film and polarizer independently, also comprise the situation that the component forming optical thin film doubles as the component forming polarizer.
In addition, when polaroid of the present invention is used for display panel, usually at polarizer side configuration display panel.
Moreover, about optical thin film, as long as owing to using above-mentioned optical thin film, so omit explanation herein.Below, other formations in polaroid of the present invention are illustrated.
(polarizer)
As the polarizer used in the present invention, as long as possess the polarization characteristic of regulation, be not particularly limited, usual used polarizer in liquid crystal display can be used.
About the form of polarizer, as long as keeping the form of the polarization characteristic specified for a long time, be not particularly limited, such as, can be only made up of polarization layer, also protective film and polarization layer can be fitted forms.When protective film and polarization layer being fitted, only protective film can be formed on the one side of polarization layer, also protective film can be formed on the two sides of polarization layer.
As polarization layer, usually use and comprise in the film of polyvinyl alcohol by making iodine be infiltrated in, and its uniaxial extension is defined the polarization layer of the complex compound of polyvinyl alcohol and iodine.
In addition, as protective film, as long as above-mentioned polarization layer can be protected and there is required light transmission, be then not particularly limited.As the light transmission of protective film, the transmissivity in visible region is preferably more than 80%, is more preferably more than 90%.Moreover the transmissivity of above-mentioned protective film measures by JIS K7361-1 (test method of the all-optical transmittance of plastics-transparent material).
As the resin forming protective film, include, for example derivatived cellulose, cyclic olefine resin, polymethylmethacrylate, polyvinyl alcohol, polyimide, polyarylester, polyethylene terephthalate etc.Wherein, use derivatived cellulose or cyclic olefine resin is preferably.
Protective film can be made up of single layer, also can stacked multiple layer and forming.In addition, when protective film is for being laminated with multiple layers, multiple layers of same composition can be laminated with, in addition, also can be laminated with multiple layers with different compositions.
In addition; about the thickness of protective film; if the pliability of polaroid of the present invention can be made to be in required scope and the dimensional change of polarizer can be made by fitting with polarization layer to be in scope in the scope of regulation; be not particularly limited; but be preferably in the scope of 5 ~ 200 μm; be particularly preferably, in the scope of 15 ~ 150 μm, be more preferably in the scope of 30 ~ 100 μm.If above-mentioned thickness is thinner than 5 μm, then the dimensional change that there is polaroid of the present invention becomes large possibility.In addition, if above-mentioned thickness is thicker than 200 μm, then such as add man-hour carrying out cutting to polaroid of the present invention, there is the possibility that processing bits increase or the wearing and tearing of shearing knife accelerate.
Protective film can have phase differential.By using, there is the protective film of phase differential, there is the advantage that polaroid of the present invention can be made to become have the viewing angle compensation merit able one of display panel.
There is as protective film the embodiment of phase differential, as long as the embodiment for required phase differential can be manifested, be then not particularly limited.As this kind of embodiment, include, for example: protective film is made up of simple layer, and containing manifesting the optical characteristics visualization reagent of phase differential, there is the embodiment of phase differential thus; And by having the formation being laminated with the phasic difference layer comprising the compound with refractive anisotrop on the protective film comprising above-mentioned resin, and there is the embodiment of phase differential.In the present invention, these arbitrary embodiment all can preferably use.
(display panel)
The feature of display panel of the present invention is, is configured with indicating meter in the triacetyl cellulose substrate side of above-mentioned optical thin film.
As indicating meter, LCD, PDP, ELD (ElectroluminescentDisplay, electroluminescent display) (organic EL, inorganic EL), CRT, contact panel, Electronic Paper, tablet PC (Tablet Personal Computer) etc. can be enumerated.
Display panel of the present invention also can be used for contact panel, Electronic Paper, dull and stereotyped PC etc.
As the LCD of the typical example of aforementioned display device, be infiltration type, and for possessing perviousness display body and from its light supply apparatus of back side illuminaton.When aforementioned display device is LCD, its above-mentioned polaroid configuring optical thin film of the present invention or possess this optical thin film on the surface of this perviousness display body forms.
As the PDP of another example of aforementioned display device, possesses Watch glass substrate and the arranged opposite and back glass substrate being filled with discharge gas between the two forms with this Watch glass substrate.When aforementioned display device is PDP, its surface at Watch glass substrate or its front panel (glass substrate or film substrate) possesses above-mentioned optical thin film.
If aforementioned display device also can be apply voltage, the luminous twinkler evaporation such as zinc sulphide, Diamines material is on glass substrate, and the voltage controlling to put on substrate carries out the ELD device that shows, or electric signal is converted to light, produces the indicating meters such as the CRT of human eye visible picture.In the case, it possesses above-mentioned optical thin film on ELD device or the outmost surface of CRT or the surface of its front panel.
[embodiment]
Below, enumerate embodiment and further illustrate the present invention.The present invention does not record restriction by these.
Preparation has antistatic layer composition 1 and the HC layer composition 1 of following composition.
(antistatic layer composition 1)
Static inhibitor (A): (weight-average molecular weight is 20000 to the trade(brand)name UV-ASHC-01 that Japan changes into (Co., Ltd.) manufactures, solid state component is 70%, and in solid state component, quaternary ammonium salt composition is 15%): solid state component converts 1 mass parts
Polyfunctional monomer (B): dipentaerythritol acrylate (DPHA) (trade(brand)name: KAYARAD DPHA, Japanese chemical drug (Co., Ltd.) manufactures, 6 officials' energy, and molecular weight is 578): 64 mass parts
Urethane acrylate (C): the trade(brand)name BS577 (6 officials' energy, weight-average molecular weight is 1000) that waste river chemical industry (Co., Ltd.) manufactures: 35 mass parts
Polymerization starter: the trade(brand)name Irgacure 184 (1-hydroxycyclohexylphenylketone) that Ciba Specialty Chemicals (Co., Ltd.) manufactures: 1 mass parts
Methyl ethyl ketone: 100 mass parts
(HC layer composition 1)
Dipentaerythritol acrylate (trade(brand)name: KAYARAD DPHA, Japanese chemical drug (Co., Ltd.) manufactures, 6 officials' energy, and molecular weight is 578): 98 mass parts
Polymerization starter: the trade(brand)name Irgacure 184 (1-hydroxycyclohexylphenylketone) that Ciba Specialty Chemicals (Co., Ltd.) manufactures: 4 mass parts
Methyl ethyl ketone: 100 mass parts
(embodiment 1)
Prepare the TAC base material (the trade(brand)name TF80UL that Fuji Film (Co., Ltd.) manufactures) that thickness is 80 μm, above-mentioned antistatic layer composition 1 prepared by the single spreading of TAC base material, and in temperature be in the oven heat of 70 DEG C dry 60 seconds the solvent in film is evaporated, then make curing of coating to make accumulative light quantity reach the mode irradiation ultraviolet radiation of 50mJ, thickness when being formed dry is thus the antistatic layer of 2.5 μm.
Then, obtained antistatic layer is coated with prepared above-mentioned composition for hard coat 1, drying is carried out in the same manner as antistatic layer, then curing of coating is made to make accumulative light quantity reach the mode irradiation ultraviolet radiation of 150mJ, thickness when being formed dry is the hard coat of 12 μm, and the side being made in TAC base material thus sequentially has the optical thin film of antistatic layer and hard coat from TAC substrate side.
In addition, in order to measure the surface resistivity of antistatic layer, proceed to the step forming antistatic layer on TAC base material (TF80UL) in the same manner as above-mentioned optical thin film till, the side being formed in TAC base material only has the duplexer of antistatic layer.
(embodiment 2 ~ 7)
In embodiment 1, replaced as the amount of the static inhibitor comprised in antistatic layer composition 1 (A), polyfunctional monomer (B) and urethane acrylate (C) or kind is as shown in table 1 respectively, in addition, optical thin film and duplexer is made in the same manner as example 1.Moreover the urethane acrylate (C) used in embodiment 7 is trade(brand)name UV-7610B (Japan's synthesis manufactures).
(comparative example 1,2)
In embodiment 1, replaced as the amount of the static inhibitor comprised in antistatic layer composition 1 (A), polyfunctional monomer (B) and urethane acrylate (C) is as shown in table 1 respectively, in addition, optical thin film and duplexer is made in the same manner as example 1.
(comparative example 3)
In embodiment 1, as the polyfunctional monomer comprised in antistatic layer composition 1 (B), use the R128H (simple function that Japanese chemical drug (Co., Ltd.) manufactures, molecular weight is 222) replace DPHA, and the amount of static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C) is as shown in table 1 respectively as replaced, in addition, optical thin film and duplexer is made in the same manner as example 1.
(comparative example 4)
In embodiment 1, as the polyfunctional monomer comprised in antistatic layer composition 1 (B), (6 officials can for the DPCA60 using Japanese chemical drug (Co., Ltd.) to manufacture, molecular weight is 1263) replace DPHA, and the amount of static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C) is as shown in table 1 respectively as replaced, in addition, optical thin film and duplexer is made in the same manner as example 1.
(comparative example 5)
In embodiment 1, as the urethane acrylate comprised in antistatic layer composition 1 (C), (2 officials can for the EBECRYL270 using Daicel-Cytec (Co., Ltd.) to manufacture, molecular weight is 1500) replace BS577, and the amount of static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C) is as shown in table 1 respectively as replaced, in addition, optical thin film and duplexer is made in the same manner as example 1.
(comparative example 6)
In embodiment 1, as the urethane acrylate comprised in antistatic layer composition 1 (C), (6 officials can for the EBECRYL5129 using Daicel-Cytec (Co., Ltd.) to manufacture, molecular weight is 800) replace BS577, and the amount of static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C) is as shown in table 1 respectively as replaced, in addition, optical thin film and duplexer is made in the same manner as example 1.
(comparative example 7)
In embodiment 1, as the urethane acrylate comprised in antistatic layer composition 1 (C), (50 officials can for the BS371MLV using waste river chemical industry (Co., Ltd.) to manufacture, molecular weight is 20000) replace BS577, and the amount of static inhibitor (A), polyfunctional monomer (B) and urethane acrylate (C) is as shown in table 1 respectively as replaced, in addition, optical thin film and duplexer is made in the same manner as example 1.
(comparative example 8 ~ 11)
In embodiment 1, replaced as the amount of the static inhibitor comprised in antistatic layer composition 1 (A), polyfunctional monomer (B) and urethane acrylate (C) is as shown in table 1 respectively, in addition, optical thin film and duplexer is made in the same manner as example 1.
(reference example 1)
In embodiment 6, by the solvent replacing comprised in antistatic layer composition 1 for being only impermeable solvent, in addition, optical thin film and duplexer is made in the same manner as in example 6.
(comparative example 12)
In embodiment 3, the urethane acrylate comprised in antistatic layer composition 1 (C) is replaced with caprolactone modification dipentaerythritol acrylate (trade(brand)name: KAYARAD DPCA-60, Japan's chemical drug (Co., Ltd.) manufactures), in addition, optical thin film and duplexer is made in the mode identical with embodiment 3.Wetting ability tendency is there is in this compound because of the reason identical with DPHA.
(reference example 2)
In embodiment 3, the static inhibitor comprised in antistatic layer composition 1 (A) is replaced with static inhibitor (B) (metal particle: ATO, trade(brand)name: ELCOM V3560, day waves catalyst and changes into manufacture), in addition, optical thin film and duplexer is made in the mode identical with embodiment 3.
(reference example 3)
In reference example 2, increase as shown in table 1 for the amount of the static inhibitor comprised in antistatic layer composition 1 (B), in addition, make optical thin film and duplexer in the mode identical with reference example 2.
(evaluation of the surface resistivity of antistatic layer)
Layers on substrates for embodiment 1 ~ 7, comparative example 1 ~ 12 and reference example 1 ~ 3 folds the duplexer of antistatic layer, utilizes high resistivity meter (the trade(brand)name Hiresta IP MCP-HT260 that Mitsubishi ChemicalAnalytech (Co., Ltd.) manufactures) to apply voltage 1000V chart surface resistivity.The results are shown in table 1.Moreover the unit Ω/ of surface resistivity described in this case refers to Ω/sq. (resistance of per unit area).
(evaluation of the dust attachment preventive of optical thin film)
Utilize mylar that the HC aspect comprising the optical laminate of base material/antistatic layer/hard coat made in embodiment and comparative example is come and gone wiping 20 times, then make this wiping surface close to cigarette ash and prevent with following benchmark evaluation dust attachment property.
Zero: ash is non-cohesive, there is dust attachment preventing effectiveness and good.
×: ash adheres in a large number, free from dust attachment preventing effectiveness.
(evaluation of the adhesion of optical thin film)
For the optical thin film of embodiment 1 ~ 7, comparative example 1 ~ 12 and reference example 1 ~ 3, in temperature 25 DEG C, humidity 40% time damping after 24 hours, according to the method for the grid test of JIS K5400,11 gaps are cut anyhow respectively with 1mm interval in hard coat face and makes 100 grids, the Cellotape (registered trademark) manufactured by Nichiban (Co., Ltd.) is attached at after on grid, it stretched on the direction of 90 ° and makes it peel off rapidly, and calculating contiguity rate according to following benchmark.
Contiguity rate (%)=(unpeeled number of squares/total number of squares 100) × 100
In addition, for the optical thin film of embodiment 1 ~ 7, comparative example 1 ~ 12 and reference example 1 ~ 3, also obtain in temperature 25 DEG C, humidity 40% time damping after 24 hours, in temperature 30 DEG C, humidity 40% time with 500W/m per hour 2the contiguity rate of light quantity irradiation ultraviolet radiation after 192 hours.The measurement result of the contiguity rate of the optical thin film before and after resistance to UV test is shown in Table 1 in the lump.
(summary of result)
According to table 1, all obtain the surface resistivity of good duplexer (antistatic layer) in embodiment 1 ~ 7, and the adhesion of optical thin film is also good.In addition, optical characteristics and outward appearance are also good.
But, in comparative example 1,2, owing to not comprising polyfunctional monomer (B) or urethane acrylate (C) in antistatic layer composition, although therefore resistance to UV test before contiguity rate good, the contiguity rate after resistance to UV test is poor.
In comparative example 3, because polyfunctional monomer (B) is simple function, so do not obtain sufficient contiguity rate.
In comparative example 4, the molecular weight of polyfunctional monomer (B) is more than 1000, and contiguity rate is lower, and the contiguity rate after especially resistance to UV test is lower.Can think that its reason is: polyfunctional monomer (B) is insufficient towards the infiltration of TAC base material, the adhesion of TAC base material and antistatic layer becomes insufficient.
In comparative example 5, the sense radix of urethane acrylate (C) is 2 and less, and contiguity rate is lower, and the contiguity rate after especially resistance to UV test is lower.Can think that its reason is: crosslinked less caused by urethane acrylate (C), the adhesion of antistatic layer and HC layer becomes insufficient.
In comparative example 6, the molecular weight of urethane acrylate (C) is less than 1000, and the contiguity rate after especially resistance to UV test is lower.Can think that its reason is: because urethane acrylate (C) excessive permeation is in TAC base material, so the adhesion of antistatic layer and HC layer becomes insufficient.
In comparative example 7, the molecular weight of urethane acrylate (C) is more than 10000, and contiguity rate is lower, and the contiguity rate after especially resistance to UV test is lower.Surface resistivity is also higher, can think that its reason is: urethane acrylate (C) does not infiltrate in TAC base material completely, and the relative quantity of the static inhibitor (A) in antistatic layer tails off.
In comparative example 8, containing of static inhibitor (A) is proportional less, and surface resistivity uprises.
In comparative example 9, containing of static inhibitor (A) is proportional more, static resistance is good, but due to the quantitative change of the polyfunctional monomer (B) that becomes tackiness agent and urethane acrylate (C) few, so contiguity rate is lower before and after resistance to UV test.
In comparative example 10, because containing of polyfunctional monomer (B) is proportional more, containing of urethane acrylate (C) is proportional less, so contiguity rate is lower, the contiguity rate after especially resistance to UV test is lower.
In comparative example 11, due to urethane acrylate (C) containing proportional more, polyfunctional monomer (B) containing proportional less, so resistance to UV test before contiguity rate good, but resistance to UV test after contiguity rate lower.
In reference example 1, contiguity rate is lower, and surface resistivity is higher.Can think that its reason is: owing to being only set to the solvent in antistatic layer composition by penetrating solvent, so urethane acrylate (C) does not fully infiltrate in TAC base material, the relative quantity of the static inhibitor (A) in antistatic layer tails off.
In comparative example 12, owing to not being used as the urethane acrylate (C) of hydrophobic resin, so quaternary ammonium salt excessively disperses, surface resistivity is higher.Therefore, dust attachment preventive is not obtained yet.
In reference example 2, use metal particle as static inhibitor.Owing to being set to the addition (quite few) of the water degree that can obtain the full light transmittance identical with the situation of quaternary ammonium salt, so surface resistivity is poor.
In reference example 3, in order to not consider that full light transmittance obtains required static resistance, allotment has than reference example 2 more as the metal particle of static inhibitor, and therefore adhesion is poor.Exist painted because addition is more, full light transmittance uprises lower than the situation (88%) of quaternary ammonium salt, haze value (0.8%).
To the result that the dust attachment preventive of the optical thin film of embodiment, comparative example and reference example is evaluated, be less than 1 × 10 in the surface resistivity of duplexer 12all good when Ω/, but when in addition, ash adheres in a large number.That is, if having the antistatic layer of preferred surface resistivity, even if be then laminated with HC layer thereon, also dust attachment preventive can be given to optical thin film.
nomenclature
1,2 optical thin films
10 triacetyl cellulose base materials
20 antistatic layers
30 hard coats
40 low-index layers
50 protective films
60 polarization layers
70 polarizers
80 polaroids

Claims (12)

1. an antistatic layer curable resin composition, is characterized in that,
Comprise
A: static inhibitor;
B: the light solidified base in 1 molecule with more than 2, and molecular weight is the polyfunctional monomer of less than 900; And
C: acryl and/or the methacryloyl in 1 molecule with more than 6, and weight-average molecular weight is the urethane acrylate of 1000 ~ 11000,
Described A is 1 ~ 30 quality % relative to the ratio of the total amount of described A, B and C,
And described C is 1 ~ 40 quality % relative to the ratio of the total amount of described B and C.
2. antistatic layer curable resin composition as claimed in claim 1, wherein,
Described A to be weight-average molecular weight be 1000 ~ 50000 quaternary ammonium salt.
3. antistatic layer curable resin composition as claimed in claim 1, wherein,
Also comprise
D: penetrating solvents; And
E: impermeability solvent.
4. antistatic layer curable resin composition as claimed in claim 1, wherein,
The thickness of described antistatic layer curable resin composition is that the surface resistivity of the cured article of 1 ~ 5 μm is less than 1 × 10 12Ω/mouth.
5. antistatic layer curable resin composition as claimed in claim 1, wherein, the light solidified radix in 1 molecule of described B is more than 6, and/or described C is 1 ~ 35 quality % relative to the ratio of the total amount of described B and described C.
6. an optical thin film, is characterized in that, is the side at triacetyl cellulose base material, and from described triacetyl cellulose substrate side, be provided with thickness is adjacently the antistatic layer of 1 ~ 5 μm and the optical thin film of hard coat,
The cured article of the antistatic layer curable resin composition of described antistatic layer according to any one of Claims 1 to 5 is formed,
Described polyfunctional monomer B infiltrates into the region of the near interface of the antistatic layer side of described triacetyl cellulose base material and solidifies.
7. optical thin film as claimed in claim 6, it has dust attachment preventive.
8. optical thin film as claimed in claim 6, wherein,
The contiguity rate of the grid adhesion test between described hard coat, described antistatic layer and described triacetyl cellulose base material is 90 ~ 100%, and in temperature 30 DEG C, humidity 40% time, with 500W/m per hour 2the described contiguity rate of light quantity irradiation ultraviolet radiation after 192 hours be 80 ~ 100%.
9. optical thin film as claimed in claim 6, wherein,
Described hard coat with the face of antistatic layer opposition side, be also provided with low-index layer.
10. optical thin film as claimed in claim 6, wherein,
Described hard coat is the cured article of the composition containing ionizing radiation curable resin.
11. 1 kinds of polaroids, is characterized in that,
The triacetyl cellulose substrate side of described optical thin film according to claim 6 is provided with polarizer.
12. 1 kinds of display panels, is characterized in that,
Indicating meter is configured with in the triacetyl cellulose substrate side of described optical thin film according to claim 6.
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