CN104530331B - 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

Info

Publication number
CN104530331B
CN104530331B CN201410753543.0A CN201410753543A CN104530331B CN 104530331 B CN104530331 B CN 104530331B CN 201410753543 A CN201410753543 A CN 201410753543A CN 104530331 B CN104530331 B CN 104530331B
Authority
CN
China
Prior art keywords
layer
antistatic
antistatic layer
thin film
base material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410753543.0A
Other languages
Chinese (zh)
Other versions
CN104530331A (en
Inventor
山本佳奈
堀尾智之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
Original Assignee
Dai Nippon Printing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Publication of CN104530331A publication Critical patent/CN104530331A/en
Application granted granted Critical
Publication of CN104530331B publication Critical patent/CN104530331B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (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 hardening resin composition, optical thin film, polaroid and display Panel
The application is filing date July 12, Application No. 2011800314732, invention entitled antistatic in 2011 The divisional application of the application of layer hardening resin composition, optical thin film, polaroid and display floater.
Technical field
The present invention relates to that one is arranged at liquid crystal display (LCD, Liquid Crystal Display), cathode tube shows The display such as equipment (CRT, Cathode-ray Tube) or plasma scope (PDP, Plasma Display Panel) The optical thin film with antistatic layer before (image display) and the compositions of this antistatic layer, and use should The polaroid of optical thin film and display floater.
Background technology
In above-mentioned display, generally it is provided with to comprise in outmost surface there is anti-reflective, hard painting property or antistatic The optical thin film of the layer of the various functions such as property.It addition, in this manual, sometimes it is referred to simply as " HC " by being firmly coated with.
One of functional layer as this kind of optical thin film, it is known to for giving the antistatic layer of antistatic behaviour.This resists quiet Electric layer by add the stannum oxide (ATO, Antimony Tin Oxide) doped with antimony or the Indium sesquioxide. doped with stannum (ITO, Indium Tin Oxide) etc. the electric conductivity ultra micron of burning system, polymer electrolyte conductive composition or quaternary ammonium salt system The antistatic additive such as conductive material and form (such as patent documentation 1).In the case of using these antistatic additive, in order to hold concurrently simultaneously Antistatic behaviour needed for tool and optical characteristics (low haze value or high full light transmittance), be by being formed containing antistatic additive Thin layer about 0.1～1 μm gives required function.
It addition, in above-mentioned display, it is desirable to give hardness to the picture display face of display, so that it is when processing Injury-free.To this, disclosed in patent documentation 1, there is the composition of following optical thin film: (below, have at triacetyl cellulose Time be only called the antistatic backing that thin film is set on " TAC (Triacetyl Cellulose) " base material, and set on this antistatic layer Put HC layer.
But, owing to antistatic layer is thin film, therefore there is following problem: tetramethylolmethane three propylene included in layer Acid esters (following, sometimes referred to simply as " PETA (Pentaerythritol triacrylate) " or dipentaerythritol six acrylic acid Ester (following, sometimes referred to simply as " DPHA (Di-Pentaerythritol hexaacrylate) " etc adhesive ingredients and The amount of antistatic additive is limited, and then the adhesion easily causing and being adjacent to the HC layer of this antistatic layer is not enough.
It is being in the optical thin film substantially constituted with base material/antistatic layer/HC layer, is having the boundary between antistatic layer and HC layer Interface between face and antistatic layer and base material, and the problem that there is adhesion at each interface.
Interface between antistatic layer and HC layer, each reactive base of antistatic layer and HC layer carry out crosslinking be bonded and Contiguity, but require that antistatic layer plays antistatic property simultaneously.In the case of antistatic additive is metal-oxide, in order to make to resist Electrostatic layer plays antistatic property, and the microgranule of antistatic additive must touch each other, therefore to add substantial amounts of antistatic additive, but deposit In the situation that haze value increases or full light transmittance deteriorates.But, if paying attention to optical characteristics and reducing the amount of metal-oxide, Then it is difficult to play antistatic property.If it addition, increase the amount of antistatic additive, then it is present in the antistatic layer interface with adjoining course The amount of adhesive ingredients is not enough, thus the probability that the adhesion of antistatic layer and adjoining course is deteriorated.But, if paying attention to adhesion And reduce the amount of metal-oxide, then it is difficult to play antistatic property.
In the case of antistatic additive is quaternary ammonium salt, in order to make antistatic layer play antistatic property, must exist in layer Content quaternary ammonium salt more more than binding agent.Or, quaternary ammonium salt must concentrate the interface adjacent with HC layer being present in antistatic layer Near.But, in this case, there is following probability: be present in the quaternary ammonium salt of near interface hinder antistatic layer with The contiguity of HC layer, the adhesive ingredients being present in the interface of antistatic layer and adjacent HC layer (has the crosslinking improved with HC layer The composition of the reactive base of density) amount not enough, thus the adhesion of antistatic layer and adjacent HC layer is deteriorated.But, if weight Reduce the amount of quaternary ammonium salt depending on adhesion, then antistatic property can deteriorate.
In order to realize antistatic behaviour and adhesion simultaneously, it is contemplated that merely increase PETA (pentaerythritol triacrylate) Or the method for the amount of the adhesive ingredients of DPHA (dipentaerythritol acrylate) etc, if but increasing this kind of adhesive ingredients Amount, then the thickness of antistatic layer thickens, and is accompanied by this, and there is the problem that the curling (warpage) of antistatic layer becomes big, Yi Jifen The usage amount dissipating the expensive antistatic additive in antistatic layer also increases, and causes the problem that cost increases.It addition, in order to carry High density of access, it is contemplated that the method for the composition with reactive base in increase binding agent, but as it has been described above, anti-quiet in order to manifest Electrical property and the amount of antistatic additive that is necessary, the amount of binding agent is restricted, therefore, it is difficult to use the method.
It addition, as it has been described above, because of the adhesive ingredients included in the layer as the antistatic layer of thin film and antistatic additive Total amount limited, therefore to by reduce antistatic additive usage amount, and respective amount ground increase adhesive ingredients usage amount come Improve the adhesion of antistatic layer and HC layer, then the usage amount that there is antistatic additive reduces and causes what antistatic property reduced to ask Topic.
On the other hand, on the interface between antistatic layer and base material, in order to make antistatic layer be close contact in base material, need to make The adhesive ingredients of the compositions of antistatic layer infiltrates in base material, and on the base material interface with antistatic layer, infiltrates into base Adhesive ingredients in material and the adhesive ingredients solidification forming antistatic layer combine.
In the case of antistatic additive is quaternary ammonium salt, it is known that prior art uses to improve durability or antistatic behaviour The quaternary ammonium salt that molecular weight is bigger.But, if the molecular weight of quaternary ammonium salt is relatively big, then the adhesive ingredients of the compositions of antistatic layer is difficult To infiltrate in base material, therefore to obtain the adhesion of antistatic layer and base material, it is necessary to use substantial amounts of penetrating solvents or Use the binding agent of the molecular weight being permeable in base material.But, in this case, there is the boundary of antistatic layer and HC layer The problem that the adhesion in face is deteriorated.
It addition, be currently known by using penetrating solvents can prevent interference fringe and outward appearance can be made to become good Technology, if but use penetrating solvents, in base material, the most sometimes also can form new interface, except above-mentioned adhesion deteriorate with Outward, also there are generation interference fringe and the problem of degraded appearance.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2009-086660 publication
Summary of the invention
(inventing problem to be solved)
The present invention is the invention completed to solve the problems referred to above, and its first purpose is to provide a kind of antistatic layer to use Hardening resin composition, this antistatic layer hardening resin composition can form optical characteristics and outward appearance is good, antistatic Property fully and the antistatic layer excellent with the adhesion of adjacent HC layer and TAC base material.
It addition, the second object of the present invention is to provide a kind of optical thin film, it has use above-mentioned composition and is formed Antistatic layer, and preventing property of dust attachment is excellent.
It addition, the third object of the present invention is to provide a kind of polaroid, it has above-mentioned optical thin film.
It addition, the fourth object of the present invention is to provide a kind of display floater, it has above-mentioned optical thin film.
(solving the means of problem)
The present inventor etc. have carried out making great efforts research, and result is learnt, if gluing included in the compositions as antistatic layer Mixture composition and for improving the molecular weight of the crosslink density with adjacent HC layer PETA or DPHA obtaining adhesion etc It is the smaller adhesive ingredients of molecular weight of less than 900, when the most all infiltrating in TAC base material, or according to bonding Agent composition from the surface belonging to interface with HC layer of TAC base material to TAC base material not for the depth direction at the back side of HC layer The difference of penetration degree, the adhesive ingredients included in antistatic layer when adhesive ingredients is stored in base material partially, on base material Reducing, carry out the composition that reacts at the interface of HC layer Yu antistatic layer not enough, the most sometimes cannot fully obtain antistatic layer and The adhesion of HC layer.It addition, also learn: not permeate with gradient profile if infiltrating into the part within TAC base material, but infiltration Material the most equally infiltrate into the same depth in TAC base material, then in TAC base material, form binding agent permeable formation, and Produce new interface in base material, and produce interference fringe etc. and cause deteriorated appearance.
Therefore, present inventor et al. finds: by by the antistatic additive included in compositions, belong to and be difficult to infiltrate into The urethane acrylate of the specified molecular weight of TAC base material or the impermeable adhesive ingredients to TAC base material and infiltrate into TAC The adhesive ingredients (polyfunctional monomer) of base material is set as specific ratio, can be formed and have sufficient antistatic behaviour, and with The antistatic layer that the adhesion of HC layer and TAC base material is excellent, overall as optical thin film, the dust attachment that can obtain excellence prevents Performance, thus complete the present invention.
That is, the antistatic layer hardening resin composition of the present invention solving the problems referred to above is characterised by comprising:
(A) antistatic additive,
(B) photo-curable base and the molecular weight in 1 molecule with more than 2 are the polyfunctional monomer of less than 900, And
(C) there is in 1 molecule the acryloyl group of more than 6 and/or methylacryloyl and weight average molecular weight is The urethane acrylate of 1000～11000,
Described (A) ratio relative to this (A), the total amount of (B) and (C) is 1～30 mass %, and
Described (C) ratio relative to this (B) and the total amount of (C) is 1～40 mass %.
By the ratio of antistatic additive (A) is set to above-mentioned scope, the thickness using above-mentioned composition to be formed is 1～5 μ The antistatic layer of m has sufficient antistatic behaviour, even if thereon stacking HC layer and in the case of forming optical thin film, it is possible to Guarantee that sufficient dust adheres to preventing property.
In prior art, the thickness of antistatic layer is in view of optical property and the transparency, thin by about 0.1～1 μm Film is arranged, if but this kind of thin layer, in order to give antistatic behaviour, it is necessary to the major part of the compositions in layer is set to anti-quiet Electric material, therefore cannot add q.s have in order to manifest with the adhesion of base material or the layer above it necessary to anti- Some binding agent of Ying Xingji.Therefore, in this application, make thickness thickening to a certain degree, and guarantee that antistatic layer is with adjacent The adhesion of layer, thus the fully interpolation of the adhesive ingredients with reactive base beyond antistatic behaviour material can be made to become can Energy.
It addition, by by urethane acrylate (C) relative to polyfunctional monomer (B) and urethane acrylate (C) The ratio of total amount is set to above-mentioned scope, is i.e. easy on TAC base material sequentially form antistatic layer and HC layer from TAC substrate side, also Owing to urethane acrylate (C) is impermeable to being less susceptible to infiltrate into TAC base in TAC base material or compared to polyfunctional monomer (B) In material, therefore may utilize urethane acrylate (C) and obtain the sufficient adhesion between antistatic layer and HC layer, and due to many Functional monomer (B) infiltrates in TAC base material, the most also can obtain the adhesion of antistatic layer and TAC base material.
In the antistatic layer hardening resin composition of the present invention, may refrain from the antistatic additive infiltration towards TAC base material And for coating excellence, preferably antistatic additive (A) be weight average molecular weight be the quaternary ammonium salt of 1000～50000.
In the antistatic layer hardening resin composition of the present invention, just improve polyfunctional monomer (B) and polyurethane third For the viewpoint of the effect of olefin(e) acid ester (C), the most also include (D) penetrating solvents and (E) impermeability solvent.
In the antistatic layer hardening resin composition of the present invention, it is possible to by above-mentioned antistatic layer curable resin The thickness of compositions is that the surface resistivity of the solidfied material of 1～5 μm is set to less than 1 × 1012Ω/□.By antistatic layer is used The solidfied material (namely antistatic layer) of hardening resin composition is set to this kind of antistatic property, on antistatic layer stacking 5～ The optical thin film of the hard conating of 15 μm can play dust preventing property of attachment.
Furthermore, surface resistivity refers to following value: form above-mentioned antistatic layer curable resin group on TAC base material The thickness of compound is the solidfied material (antistatic layer) of 1～5 μm, then utilizes (Mitsubishi Chemical's Analytech (the strain of high resistivity meter Formula commercial firm) manufacture, trade name: Hiresta IP MCP-HT260), adjust in applying voltage 1000V, temperature 25 DEG C, humidity 40% Under conditions of wet 24 hours, this solidfied material surface is measured the value of gained.
The optical thin film of the present invention is in the side of triacetyl cellulose base material, opens from described triacetyl cellulose substrate side Begin the antistatic layer and the optical thin film of hard conating that thickness is 1～5 μm is set adjacently, it is characterised in that this antistatic layer by The solidfied material of above-mentioned antistatic layer hardening resin composition is formed, and above-mentioned polyfunctional monomer (B) infiltrates into described triacetyl The region of the near interface of the antistatic layer side of cellulosic substrates also solidifies.
In the side of TAC base material, start setting up, from TAC substrate side, the antistatic layer and the basis of HC layer that thickness is 1～5 μm The optical thin film of invention, because antistatic layer comprises the solidfied material of above-mentioned antistatic layer hardening resin composition, and has and fills Dust the preventing property of attachment divided.And then, HC layer becomes excellent with the adhesion of antistatic layer.It addition, by polyfunctional monomer (B) Infiltrate into the region of the interface side of the antistatic layer side of TAC base material and solidify, it is possible to obtaining the contiguity of antistatic layer and TAC base material Property.Overall as optical thin film, the dust attachment that can obtain excellence prevents performance.
The present invention optical thin film preferred embodiment in, it is possible to by above-mentioned hard conating, above-mentioned antistatic layer and The contiguity rate of the grid adhesion test between above-mentioned triacetyl cellulose base material is set as 90～100%, and will temperature 30 DEG C, Humidity 40% time, with 500W/m per hour2The light quantity irradiation ultraviolet radiation described contiguity rate after 192 hours be set as 80～ 100%.
Furthermore, the contiguity rate of so-called grid adhesion test (Cross Cut Adhesion Test), refer to in temperature Spend 25 DEG C, optical thin film after 40% time damping of humidity 24 hours, according to grid test (the Cross Cut of JIS K5400 Test) method, makes 100 grids, by Nichiban in 11 gaps of incision the most respectively with 1mm interval on hard conating face After the Cellotape (registered trade mark) that (Co., Ltd.) manufactures is attached on grid, rapidly it is stretched in the direction of 90 ° and make It is peeled off, and the ratio of the grid remained according to not peeling off of being calculated of following benchmark.
Contiguity rate (%)=(unpeeled number of squares/total number of squares 100) × 100
The present invention optical thin film preferred embodiment in, it is possible at hard conating with antistatic layer opposition side Face arranges low-index layer further.
The present invention optical thin film preferred embodiment in, hard conating may be used without containing ionizing radiation solidify The solidfied material of the compositions of property resin.
The polaroid of the present invention is characterised by, the triacetyl cellulose substrate side at optical thin film is provided with polarization unit Part.
The display floater of the present invention is characterised by, the triacetyl cellulose substrate side at optical thin film is configured with display Device.
(invention effect)
Antistatic additive (A), polyfunctional monomer (B) and urethane acrylate is contained by making with above-mentioned specific ratio (C) compositions is solidified to form the antistatic layer into thickness 1～5 μm, even if on TAC base material from TAC substrate side tool The layer having antistatic layer and HC layer is constituted, and can obtain and have sufficient dust preventing property of attachment, and antistatic layer and TAC base material and The optical thin film that the adhesion of HC layer is good.It addition, contain this antistatic additive (A), polyfunctional monomer with above-mentioned specific ratio (B) and the compositions of urethane acrylate (C), it is suitable for being formed have used in the optical thin film of this kind of characteristic anti- In electrostatic layer.
Accompanying drawing explanation
Fig. 1 represents the schematic diagram of an example of the layer composition of the optical thin film of the present invention.
Fig. 2 represents the schematic diagram of another example of the layer composition of the optical thin film of the present invention.
Fig. 3 represents the schematic diagram of an example of the layer composition of the polaroid of the present invention.
Detailed description of the invention
Hereinafter, the antistatic layer of the present invention (below, is sometimes referred to simply as " antistatic layer with hardening resin composition By compositions "), optical thin film and use the polaroid of this optical thin film and display floater to be illustrated.
In the present invention, (methyl) acryloyl group represents acryloyl group and/or methylacryloyl, (methyl) acrylate Represent acrylate and/or methacrylate.
The light of the present invention not only includes the electromagnetic wave of the wavelength in visible ray and the non-visible region such as ultraviolet and X-ray, Also include such as the particle beam of electron beam etc and be referred to as lonizing radiation or the ionizing radiation of electromagnetic wave and particle beam.
In the present invention, so-called " hard conating ", refer to the pencil hardness test of regulation in JIS K5600-5-4 (1999) (4.9N load) shows the hardness person more than " H ".
Furthermore, about thin film and sheet material, according to the definition in JIS-K6900, sheet material refers to relatively thin and usual its thickness ratio Length and the little flat article of width, thin film refers to that thickness minimum and maximum gauge compared with length and width is arbitrarily limited Relatively thin flat article, its generally with volume form supply.Therefore, in sheet material, the extremely thin person of thickness can be described as thin film, but by In sheet material and the border of thin film unclear, it is difficult to be distinguish between clearly, the most in the present invention, including thickness relatively thick one and The implication of relatively thin both persons, is all defined as " thin film ".
In the present invention, resin, in addition to the concept of monomer or oligomer, also comprises the concept of polymer, and it refers to solid The composition of the substrate of other functional layers such as antistatic layer or HC layer is become after change.
In the present invention, so-called molecular weight, in the case of there is molecular weight distribution, refer to as at THF By gel permeation chromatography (GPC, Gel Permeation in (Tetrahydrofuran, oxolane) solvent The weight average molecular weight of the polystyrene conversion value Chromatograph) measured, in the case of not there is molecular weight distribution, Refer to the molecular weight of compound itself.
In the present invention, the mean diameter of so-called microgranule, in the case of microgranule in the composition, refer to use day machine dress The value that the Microtrac grain size analysis meter that (Co., Ltd.) manufactures is measured, in the case of the microgranule in cured film, refers to lead to Cross cured film observed by transmission electron microscope (TEM, Transmission electron microscopy) photo The meansigma methods of 10 particles of section.
In the present invention, so-called infiltration, is to instigate TAC base material to dissolve or swelling.
In the present invention, so-called solid state component, refer to remove the composition of solvent.
(antistatic layer hardening resin composition)
The antistatic layer hardening resin composition of the present invention is characterised by comprising:
(A) antistatic additive,
(B) photo-curable base and the molecular weight in 1 molecule with more than 2 are the polyfunctional monomer of less than 900, And
(C) (methyl) acryloyl group and the weight average molecular weight in 1 molecule with more than 6 are 1000～11000 Urethane acrylate,
Described (A) ratio relative to this (A), the total amount of (B) and (C) is 1～30 mass %, and
Described (C) ratio relative to this (B) and the total amount of (C) is 1～40 mass %.
By the ratio of antistatic additive (A) is set to above-mentioned scope, antistatic layer can give antistatic behaviour, even and if Thickness is to be formed in the case of HC layer on the antistatic layer of 1～5 μm, it is possible to guarantee that sufficient dust adheres to preventing property.
It addition, by by urethane acrylate (C) relative to polyfunctional monomer (B) and urethane acrylate (C) The ratio of total amount is set to above-mentioned scope, if sequentially forming antistatic layer, HC layer on TAC base material from TAC substrate side, then because of poly- Urethane acrylate (C) will not infiltrate in TAC base material, or is less susceptible to infiltrate into TAC base material compared to polyfunctional monomer (B) In, therefore urethane acrylate (C) is there is also at the interface of antistatic layer Yu HC layer, urethane acrylate (C) is had (methyl) acryloyl group combines with the reactive base solidification in HC layer, thus can obtain the sufficient contiguity of antistatic layer and HC layer Property.
And then, in polyfunctional monomer (B) appropriateness infiltrates into TAC base material (the most equally infiltrate into same depth, but with Gradient profile permeate), the reactive base (photo-curable base) of the polyfunctional monomer (B) permeated in the presence of TAC base material with The reactive base of the polyfunctional monomer (B) in the presence of antistatic layer and the reactive base ((methyl) of urethane acrylate (C) Acryloyl group) solidification combination, the most also can obtain the adhesion of antistatic layer and TAC base material.
Hereinafter, for the above-mentioned antistatic additive (A) of required composition of the antistatic layer compositions as the present invention, many officials Can monomer (B) and urethane acrylate (C) and other compositions that can optionally and suitably contain be illustrated.
(A: antistatic additive)
Antistatic additive (A) is that the antistatic layer to the cured film as antistatic layer compositions or optical thin film give and leading Electrically prevent charged, and have imparting prevent dust or dust attachment, or prevent because of charged and in-process produce bad The composition of the effect of character (namely antistatic behaviour).
As antistatic additive (A), previously known antistatic additive can be used, be not particularly limited.
Include, for example the aniones such as cationic compound, sulphonate-base such as quaternary ammonium salt described in patent documentation 1 Nonionic compound, organo-metallic compound and the metal of amphoteric compound such as property compound, aminoacid system etc., amino alcohol system etc. Complex compound and the compound that these compound macromolecules are quantified, polymerizable compound, average 1 particle diameter It is the electric conductivity ultra micron such as tin indium oxide (ITO) of 1～100nm and the polymer electrolyte such as polyacetylene of aliphatic conjugated system is led Conductive composition.
In the antistatic layer hardening resin composition of the present invention, may refrain from antistatic additive (A) oozing towards TAC base material Thoroughly and for coating excellence, preferably antistatic additive (A) be weight average molecular weight be the quaternary ammonium salt of 1000～50000.If exceeding State the upper limit, then the coating of compositions deteriorates, if less than above-mentioned lower limit, then antistatic additive easily ooze out into antistatic layer and HC On the interface of layer, and there is the probability of antistatic layer and the adhesion deterioration of HC layer.
Previously, the thickness of antistatic layer, it is contemplated that optical property and the transparency, is arranged with the thin film about 0.1～1 μm, If but this kind of thin layer, then in order to give antistatic behaviour, it is necessary to the major part of the compositions in layer is set to antistatic behaviour material Material, therefore, it is difficult to add q.s have in order to manifest with the adhesion of base material or the layer above it necessary to reactive base Resin combination.Therefore, in the present invention, thickness is set to 1～5 μm, relatively previously thicker, and guarantee that antistatic layer is with adjacent The adhesion of layer, the fully interpolation of the resin combination with reactive base beyond antistatic behaviour material therefore can be made to become can Energy.Because thickness increases, therefore the antistatic additive preferably added selects the material that the transparency is higher.In this aspect, preferably The organic material of inorganic material it is higher than for the transparency, and then, in organic material, colour few quaternary ammonium salt most suitable.Work as use During quaternary ammonium salt, in the case of in the transparency, base material is TAC, the full light transmittance that optical thin film can be made overall become 90% with On, with regard to this put for it is also preferred that.Additionally, it is possible to make haze value become less than 0.5%.Full light transmittance can be according to JIS K7361 (1997), the HM150 etc. manufactured by color technical research institute in village is measured, and haze value can be logical according to JIS K7136 (2000) Cross the HM150 etc. that in village, color technical research institute manufactures to measure.
And then, the adhesion aspect of antistatic layer and HC layer is just improved by the cross-linking reaction of HC layer Yu adhesive ingredients For, preferably this quaternary ammonium salt has photo-curable base.Photo-curable base is preferably polymerism unsaturated group, more preferably ionization and puts Ray-curable unsaturated group.As its concrete example, (methyl) acryloyl group, (methyl) acryloxy, vinyl can be enumerated And pi-allyl etc. has base and the epoxy radicals etc. of ethylene unsaturated bond.
As the commercially available product of the quaternary ammonium salt that this kind of weight average molecular weight is 1000～50000, include, for example Mitsubishi Chemical's (strain Formula commercial firm) trade name H6100 that manufactures, and the trade name Uniresin AS-that Xin Zhong village chemical industry (Co., Ltd.) manufactures 10/M, Uniresin AS-12/M, Uniresin AS-15/M and Uniresin ASH26 etc..
In antistatic layer compositions, relative to antistatic additive (A) and polyfunctional monomer described later (B) and polyurethane third The total amount of olefin(e) acid ester (C), the antistatic additive (A) containing 1～30 mass %.
If the ratio of antistatic additive (A), less than 1 mass % then cannot obtain sufficiently relative to above-mentioned total amount (A+B+C) Antistatic property.If it addition, the ratio of antistatic additive (A) relative to above-mentioned total amount (A+B+C) more than 30 mass %, then antistatic Polyfunctional monomer (B) and the ratio of urethane acrylate (C) in layer compositions reduce, it is impossible to obtain antistatic layer with adjacent It is connected to the TAC base material of this layer or the sufficient adhesion of HC layer.
The ratio of antistatic additive (A) is 1～30 mass % relative to above-mentioned total amount (A+B+C), but preferably 5～20 matter Amount %.
(B: polyfunctional monomer)
Polyfunctional monomer (B) be become after solidification antistatic layer substrate adhesive ingredients one by one, and be in 1 molecule There is the monomer that molecular weight is less than 900 of the photo-curable base of more than 2.Its molecular weight and be multifunctional, thus have Help to improve in antistatic layer or with the crosslink density of the HC layer being adjacent to antistatic layer, contribute to promoting the composition of adhesion. It addition, polyfunctional monomer infiltrates in TAC base material at least partially by it and solidifies, and also contribute to promote antistatic layer with The adhesion of TAC base material.
If the molecular weight of polyfunctional monomer (B) is more than 900, then towards TAC base material permeability decline, and have cannot obtain anti- The probability of the abundant adhesion of electrostatic layer and TAC base material.
Polyfunctional monomer (B) if molecular weight be less than 900, but just make polyfunctional monomer (B) moderately towards TAC Base material permeates, and make the adhesion of antistatic layer and HC layer and antistatic behaviour (surface resistivity) highly and the viewpoint deposited and Speech, the molecular weight of polyfunctional monomer (B) is preferably more than 230, and more preferably more than 290.If molecular weight is less than 230, the most officials Can monomer (B) towards the infiltration of TAC base material immoderation, have and all infiltrate into the same degree of depth and produce the feelings at new interface Condition, and have the light reflected at its interface and the light reflected at the interface of antistatic layer Yu HC layer or anti-in HC layer surface institute Produce the interference of light between the light penetrated, and produce interference fringe and cause the probability of deteriorated appearance.
As polyfunctional monomer (B), can be used one or more.
The photo-curable base of polyfunctional monomer (B), is more than 2 to form cross-linked structure, it is however preferred to have 3 with On, more preferably there are more than 5.If more than 3, being then readily available the closeest of antistatic layer and HC layer and TAC base material Connecing property.As photo-curable base, can enumerate and the identical person of photo-curable base cited in antistatic additive.
As polyfunctional monomer (B), include, for example tetramethylolmethane three (methyl) acrylate, dipentaerythritol six (first Base) acrylate, dipentaerythritol five (methyl) acrylate, trimethylolpropane tris (methyl) acrylate and trihydroxy methyl Propane six (methyl) acrylate and these modified body.
Furthermore, as modified body, EO (Ethylene oxide, oxirane) modified body, PO (Propylene can be enumerated Oxide, expoxy propane) modified body, CL (Caprolactone, caprolactone) modified body and fulminuric acid modification body etc..
In above-mentioned polyfunctional monomer, for the viewpoint of solidification reactivity, compared with methacryl, photo-curable base For acryloyl group more preferably.
As polyfunctional monomer (B), the most preferably use Dipentaerythritol Pentaacrylate (DPPA, Di- Pentaerythritol pentaacrylate), dipentaerythritol acrylate (DPHA).
In the antistatic layer compositions of the present invention, polyfunctional monomer (B) meets the content ratio of above-mentioned antistatic additive, And be 60～99 mass % relative to the total amount of polyfunctional monomer (B) Yu urethane acrylate described later (C).If less than 60 matter Amount %, then cannot obtain antistatic layer and HC layer and the sufficient adhesion of TAC base material.If it addition, more than 99 mass %, then gathering The ratio of urethane acrylate (C) is less, it is impossible to obtain the sufficient adhesion of antistatic layer and HC layer.
(C: urethane acrylate)
Urethane acrylate (C) is one of adhesive ingredients becoming antistatic layer substrate after solidification, in its 1 molecule There is (methyl) acryloyl group of more than 6, and weight average molecular weight is 1000～11000, preferably 1000～10000, more excellent Elect 1000～5000 as.
Be 1000～11000 by weight average molecular weight, then coating is good, impermeable to TAC base material, or compared to many Functional monomer (B) is less susceptible to infiltrate in TAC base material, is easily controlled infiltration, and is positively present in whole antistatic layer.
In the case of antistatic additive (A) is quaternary ammonium salt, as the character of this compound, with the compatibility of hydrophilic compounds Property is good.Therefore, if the binding agent in antistatic layer is compound (PETA, PETTA (tetramethylolmethane tetrapropylene acid with OH base Ester), DPPA (Dipentaerythritol Pentaacrylate) etc.), then during antistatic additive is excessively scattered in whole layer, and cannot obtain anti-quiet Electrically.Known DPHA does not contains OH base on structural formula, but is generally difficult to be formed 6 officials' energy of 100% in synthesis, the most actually For with 5 officials can or the mixing cpd of 4 functional moieties, owing to generally the most commercially available resin is the compound remaining OH base, therefore And preferred antistatic behaviour cannot be obtained.
Can control this dispersibility person is the urethane acrylate (C) belonging to hydrophobic resin.By making polyurethane propylene Acid esters (C) is present in whole layer, in the case of antistatic additive (A) is quaternary ammonium salt system, can positively control antistatic additive and exist Situation about excessively disperseing in layer or ooze out in the direction, interface with HC.The reason easily oozed out in direction, HC interface is, as above Described, because hydrophilic liked by quaternary ammonium salt, therefore by antistatic layer stacking and when solidifying, there is air on its surface, and in this air Moisture react and ooze out.
And, there is (methyl) acryloyl group of more than 6, be favorably improved in antistatic layer or be adjacent to antistatic The crosslink density of the reactive base in the HC layer of layer, and promote the adhesion of antistatic layer and HC layer.Ooze further, since improve Polyurethane propylene in the presence of the reactive base of the polyfunctional monomer (B) of the saturating antistatic layer to TAC base material and antistatic layer (methyl) acryloyl group of acid esters (C) or the crosslink density of the reactive base of polyfunctional monomer, so urethane acrylate (C) Also contribute to the adhesion promoting antistatic layer with TAC base material.In the case of from the point of view of in terms of adhesion, without polyurethane Acrylate (C), as long as being the polyfunctional monomer (B) with a large amount of reactive base in addition to antistatic additive (A), but In order to as above control the antistatic additive (A) variation in antistatic layer, if only polyfunctional monomer (B), then it is difficult to control to, In order to antistatic additive (A) does not disperses, need hydrophobicity and there is the urethane acrylate (C) of a large amount of reactive base.
It addition, it is the most effective for the generation of suppression curling (warpage) containing urethane acrylate (C).
If less than 1000, then there is following probability in the weight average molecular weight of urethane acrylate (C): polyurethane propylene Acid esters (C) is readily permeable to TAC base material, in excessive permeation to TAC base material, causes the propylene of antistatic layer and the interface of HC layer Acyl group reduces, it is difficult to obtain the adhesion of antistatic layer and HC layer.
If the weight average molecular weight of urethane acrylate (C) is more than 11000, then there is the probability that coating deteriorates.
As long as urethane acrylate (C) has (methyl) acryloyl group of more than 6, ionizing radiation the most also can be contained Other the functional group of crosslinking reactivity such as curable unsaturated group.(methyl) has more than 6 as long as acryloyl group adds up to Acryloyl group and methylacryloyl, can only have acryloyl group, it is possible to only have methylacryloyl.
As the urethane acrylate (C) of the present invention, as long as there is urethane bonds (-NH-CO-O-), there are more than 6 (methyl) acryloyl group and be above-mentioned weight average molecular weight, then be not particularly limited.As urethane acrylate (C), preferably For making the C of the light transmission that the film time can pass through, it is possible to as requested performance etc. and suitably use and belong to by with ultraviolet Ionizing radiation representated by line or electron beam and the ionizing radiation curable urethane acrylate of the resin that solidifies, other Known urethane acrylate etc..
As the commercially available product of above-mentioned urethane acrylate, include, for example Japan's synthesis described in patent documentation 1 Trade name UN3320HS that on trade name UV1700B that chemical industry (Co., Ltd.) manufactures, root, industry (Co., Ltd.) manufactures, Trade name BS577 that waste river chemical industry (Co., Ltd.) manufactures and the commodity that Xin Zhong village chemical industry (Co., Ltd.) manufactures Name U15HA, U15H, U9HA, U9H, U6HA and U6H etc..
In the antistatic layer compositions of the present invention, urethane acrylate (C) meets containing of above-mentioned antistatic additive Ratio, and be 1～40 mass % relative to the total amount of above-mentioned polyfunctional monomer (B) Yu urethane acrylate (C).If less than 1 Quality %, then cannot obtain the abundant adhesion of antistatic layer and HC layer.If it addition, more than 40 mass %, then polyfunctional monomer (B) ratio is less, it is impossible to obtain the abundant adhesion of antistatic layer and TAC base material.
The ratio of urethane acrylate (C) is 1～40 mass % relative to above-mentioned total amount (B+C), but preferably 5～30 Quality %.
So, the ratio by the polyfunctional monomer (B) in binding agent, urethane acrylate (C) is suitable, antistatic additive (A) both will not excessively disperse in antistatic layer, also will not ooze out, can be so that the degree concentration of antistatic behaviour can be played in layer Exist.Just because of it is this composition, the surface resistivity of antistatic layer can be less than 1 × 1012Ω/□。
In antistatic layer compositions, in addition to above-mentioned (A), (B) and (C) composition, the most also can be containing suitable Solvent and polymerization initiator.Hereinafter, these other compositions are illustrated.
(solvent)
As solvent, can use the ester series solvents such as ketone series solvent, methyl acetate such as acetone described in patent documentation 1, The halogenated hydrocaron solvent such as ether series solvent, dichloromethane such as glycol series solvent, THF such as the nitrogenous series solvent such as acetonitrile, Propylene Glycol and The penetrating solvents such as glycol ethers series solvent such as methyl cellosolve.
As penetrating solvents, it is preferably selected from methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl tert-butyl At least one in base ketone (MIBK, Methyl Isobutyl Ketone) and Ketohexamethylene.
It addition, be used as propylene glycol monomethyl ether (PGME, Propylene Glycol Monomethyl Ether), The impermeability solvents such as normal propyl alcohol, isopropanol, n-butyl alcohol, sec-butyl alcohol, isobutanol and the tert-butyl alcohol.
Above-mentioned solvent can be used alone one, it is possible to two or more mixing is used.
In the antistatic layer compositions of the present invention, just speculate by using penetrating solvents, above-mentioned many officials can be promoted Can monomer (B) towards TAC base material infiltration, promote the adhesion of antistatic layer and TAC base material for, permeability is preferably used molten Agent.
It addition, in the antistatic layer compositions of the present invention, just speculate by using impermeability solvent, can suppress on State urethane acrylate (C) towards TAC base material infiltration, promote the adhesion of antistatic layer and HC layer for, be preferably used non- Penetrating solvents.
Therefore, in the antistatic layer compositions of the present invention, in the case of solvent is one, infiltration is preferably used molten Agent, but in the case of two or more solvents, most preferably penetrating solvents is applied in combination with impermeability solvent.Its reason exists In, although even if a kind of solvent (only penetrating solvent), it is possible to control to ooze by the molecular weight of urethane acrylate (C) Thoroughly, but penetrating solvents and impermeability solvent are applied in combination and can more easily control infiltration, and obtain and use compositions The stable performance of antistatic layer.
In the case of penetrating solvents and impermeability solvent being applied in combination, being preferably its mass ratio is that permeability is molten Agent: impermeability solvent=100: 0～, preferably 90: 10～50: 50, and relative to total solid-state of antistatic layer compositions Composition 100 mass parts is preferably 30～500 mass parts.
(polymerization initiator)
Polymerization initiator is initiation or the composition of the cross-linking reaction promoting above-mentioned adhesive ingredients (B), optionally can be suitable Ground selects to use previously known free radical and cationic polymerization initiators etc..As radical polymerization initiator, such as can be excellent Selection of land uses trade name Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-one) that Ciba Japan (Co., Ltd.) manufactures. Using in the case of polymerization initiator, its content relative to the total quality of total solid state component of antistatic layer compositions, It is preferably 0.4～2.0 mass %.By as above the amount of the polymerization initiator used in antistatic layer compositions being set For the 1/10～1/2 of the amount of the polymerization initiator used in HC layer, the reactive base of antistatic layer can be made to remain in a large number.By This, reaction is difficult to, therefore is also prevented from the generation of curling.
(preparation of antistatic layer hardening resin composition)
Above-mentioned antistatic layer hardening resin composition can be scattered in by making above-mentioned (A), the mixing of (B) and (C) composition Solvent obtains.Even if it addition, solvent-free, in the case of above-mentioned (A), (B) or (C) composition still have sufficient mobility, Also can be solvent-free.Mixing dispersion can use the known method such as coating vibrating machine or ball mill.
In the antistatic layer hardening resin composition of the present invention, by antistatic additive (A) is set to above-mentioned scope, Also can make the surface resistivity of the solidfied material that thickness is 1～5 μm of above-mentioned antistatic layer hardening resin composition less than 1 × 1012Ω/□.By making antistatic layer be this kind of antistatic property, even if the HC layer that stacked film thickness rate is thicker, it is possible at whole light The dust attachment playing excellence in thin film prevents performance.
If the thickness of antistatic layer is less than 1 μm, then must increase as antistatic to maintain identical sheet resistance The amount of the quaternary ammonium salt of agent, but in this case, the reactive base that there is antistatic additive reduces, and the contiguity of antistatic layer and HC layer is disliked The probability changed.
If the thickness of antistatic layer is more than 5 μm, then sheet resistance easily shows, but exists and produce curling, cost rising, place The probability that rationality deteriorates.
And then, in antistatic layer compositions, by making antistatic additive (A) relative to antistatic additive (A), multifunctional list The total amount of body (B) and urethane acrylate (C) is 5～20 mass %, and makes urethane acrylate (C) relative to multifunctional The total amount of monomer (B) and urethane acrylate (C) is 5～30 mass %, then in addition to can obtaining sufficient antistatic behaviour, Also the adhesion excellent durability relative to ultraviolet (UV) of optical thin film can be obtained.
(optical thin film)
The optical thin film of the present invention is in the side of triacetyl cellulose base material, from the beginning of this triacetyl cellulose substrate side Antistatic layer and hard conating and winner that thickness is 1～5 μm are set adjacently, it is characterised in that this antistatic layer comprises above-mentioned The solidfied material of antistatic layer hardening resin composition, and above-mentioned polyfunctional monomer (B) infiltrates into triacetyl cellulose base material The region of interface side of antistatic layer side and solidify.
The optically thin of antistatic layer that thickness is 1～5 μm and HC layer is set from TAC substrate side in the side of TAC base material Film, is formed by the solidfied material of above-mentioned antistatic layer hardening resin composition by antistatic layer, can have sufficient dust Preventing property of attachment, and HC layer is excellent with the adhesion of antistatic layer.It addition, by making polyfunctional monomer (B) infiltrate into TAC base The region of the interface side of the antistatic layer side of material also solidifies, it is possible to obtain the adhesion of antistatic layer and TAC base material.As optics Thin film is overall, and the dust attachment that can obtain excellence prevents performance.
The present invention optical thin film preferred embodiment in, by making antistatic layer by above-mentioned antistatic layer group The solidfied material of compound is formed, it is possible to make the above-mentioned hard conating of optical thin film, above-mentioned antistatic layer and above-mentioned triacetyl cellulose base The contiguity rate of the grid adhesion test between material is 90～100%, and makes in temperature 30 DEG C, humidity 40% time with per hour 500W/m2Light quantity irradiate after 192 hours ultraviolet that (following, sometimes referred to simply as " UV resistant (UV, Ultraviolet) tries After testing ") this contiguity rate be 80～100%.
This contiguity rate represents the contiguity of HC layer, antistatic layer and the contiguity of TAC base material, i.e. antistatic layer and HC interlayer and resists Adhesion between electrostatic layer and TAC base material.
Have without urethane acrylate (C) existing, mainly contain only polyfunctional monomer (B) as binding agent Compositions, even if or not containing antistatic additive (A), polyfunctional monomer with specific ratio containing urethane acrylate (C) (B) and in the optical thin film of antistatic layer that constituted of the solidfied material of compositions of urethane acrylate (C), antistatic layer with Though the contiguity between TAC base material is good, but antistatic layer and the contiguity of HC interlayer insufficient.So, at antistatic layer and HC layer Between adhesion sufficiently in the case of, if carrying out adhesion test, though then not producing stripping between antistatic layer and TAC base material From, but can be peeling and peel off between antistatic layer and HC layer.Contiguity between antistatic layer and TAC base material is the most sufficient In the case of, can be peeling and peel off between antistatic layer and TAC base material.Accordingly, as optical thin film, in order to obtain the close of excellence Connecing property, needs the contiguity between antistatic layer and the contiguity of HC interlayer and antistatic layer and TAC base material.
By making above-mentioned antistatic layer compositions be solidified to form antistatic layer, thickness be 1～5 μm antistatic layer with Contiguity between the contiguity of HC interlayer and antistatic layer and TAC base material is excellent, as the adhesion that optical thin film whole show is excellent. Especially, this adhesion is more significant after resistance to UV tests.The optical thin film of the present invention also manifests the contiguity of excellence after resistance to UV tests Property.
Fig. 1 is the schematic diagram of an example of the layer composition of the optical thin film representing the present invention.At triacetyl cellulose base material 10 Side, be provided with antistatic layer 20 and hard conating 30 the most adjacently.Fig. 2 is that the layer of the optical thin film representing the present invention is constituted The schematic diagram of another example.The hard conating of the optical thin film identical with Fig. 1 is further provided with low-index layer 40.
Hereinafter, the triacetyl cellulose base material of required element, the antistatic layer to the optical thin film as the present invention And hard conating, and can the optionally high refractive index layer being appropriately arranged with, middle index layer, low-index layer, antiglare layer and anti- Other layers such as pollution layer are illustrated.
(triacetyl cellulose base material)
Triacetyl cellulose base material used in the present invention is the triacetylcellulose film that light transmission is higher, as long as and For meeting the physical property person of the Mght-transmitting base material that can be used as optical thin film, then it is not particularly limited, use can be properly selected at present Known hard-coated film or the TAC base material of optical thin film.
The average transmittance of the TAC base material in visible region 380～780nm is preferably more than 80%, is particularly preferably More than 90%.Furthermore, the mensuration of light transmittance uses and uses UV, visible light light splitting luminance meter (such as Shimadzu Seisakusho Ltd. (Co., Ltd.) Trade name UV-3100PC manufactured), the value measured in room temperature, air.
TAC base material can be implemented saponification process or arrange the surface process such as priming coat.Add it addition, antistatic additive etc. can be added Add agent.
The thickness of TAC base material is not particularly limited, usually 30～200 μm, preferably 40～200 μm.
(antistatic layer)
The antistatic layer of the present invention is formed by the solidfied material of above-mentioned antistatic layer hardening resin composition, and thickness is 1 ～5 μm.If thickness is thinner than 1 μm, then cannot obtain sufficient antistatic property, it is impossible to add fully and be used for guaranteeing and other layers Adhesion and required binding agent.If being thicker than 5 μm, then can not be to be the most closely present in layer due to antistatic additive And performance cannot be played, so the curling of antistatic layer becomes big, therefore processability deteriorates, if thickness is the most thickening, is then wrapped The amount of the antistatic additive etc. contained increases, and cost increases.
As the performance of antistatic layer, sheet resistance is preferably less than 1 × 1012Ω/, more preferably 1 × 1011Ω/□ Below and then be 1 × 1010Ω/below.As long as the sheet resistance of antistatic layer is good, it is laminated with the optical thin film of HC layer Dust preventing property of attachment can be better.
(hard conating)
Hard conating is in JIS K5600-5-4 (1999) in the pencil hardness test (4.9N load) of regulation, shows " H " The layer of above hardness, and give hardness to the optical thin film of the present invention.
HC layer comprises the solidfied material of composition for hard coat, can use previously known hard conating, it is possible to only contain for comprising The solidfied material person of the composition for hard coat of adhesive ingredients, additionally, it is possible to contain above-mentioned antistatic layer group in the composition Polymerization initiator etc. cited in compound.In order to improve the hardness etc. of HC layer, it is possible to containing previously known imparting hardness Described in composition, such as Japanese Patent Laid-Open 2008-165040 publication, there is crosslinking reactivity with adhesive ingredients Reactive silicon dioxide microgranule.
As concrete example, can be by being coated with as the resin combination of transparent resin containing ionizing radiation curable resin Cloth over the transparent substrate, and makes the monomer included in this resin combination, oligomer and prepolymer crosslinking and/or is polymerized and shape Become HC layer.
As transparent resin, preferably ionizing radiation curable resin, as the sense of monomer, oligomer and prepolymer Base, the preferably functional group of ionizing radiation polymerism, wherein preferred optical polymerism functional group.By this functional group and antistatic layer Solidify with the reactive base of the urethane acrylate (C) in resin combination and combine, filling of antistatic layer and HC layer can be obtained The adhesion divided.
As optical polymerism functional group, the insatiable hungers such as (methyl) acryloyl group, vinyl, styryl, pi-allyl can be enumerated With polymerizable functional groups etc..
It addition, as prepolymer and oligomer, polyurethane (methyl) acrylate, polyester (methyl) acrylic acid can be enumerated Acrylate, unsaturated polyester (UP), the epoxy resin etc. such as ester, epoxy (methyl) acrylate.
As monomer, the styrenic monomers such as styrene, α-methyl styrene can be enumerated, (methyl) acrylic acid methyl ester., (first Base) acrylic acid-2-ethyl caproite, tetramethylolmethane (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane Four (methyl) acrylate, tetramethylolmethane ethyoxyl four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two Tetramethylolmethane five (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ethyoxyl three (first Base) acrylate, glycerol propoxylate, two-trimethylolpropane tetra-acrylate, Polyethylene Glycol two (methyl) third Olefin(e) acid ester, EO modification two (methyl) acrylate of Bisphenol F, EO modification two (methyl) acrylate of bisphenol-A, fulminuric acid EO modification two (methyl) acrylate, fulminuric acid EO modification three (methyl) acrylate, polypropylene glycol two (methyl) propylene Acid esters, trimethylolpropane PO modification three (methyl) acrylate, trimethylolpropane EO modification three (methyl) acrylate, The acrylic monomers such as two-trimethylolpropane four (methyl) acrylate, trimethylolpropane tris thioglycolic acid esters, three hydroxyls Methylpropane trithio propylate, tetramethylolmethane four thioglycol equimolecular have the polyol of the mercapto of more than 2 Thing, it addition, have polyurethane (methyl) acrylate or polyester (methyl) acrylate etc. of the unsaturated bond of more than 2.
Especially, for improving the viewpoint of crosslink density, acquisition damage-resistant, preferably polyfunctional acrylate monomer, its In, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol six (methyl) acrylic acid Ester, dipentaerythritol five (methyl) acrylate are because of, pencil hardness good with the contiguity of antistatic layer the most well and more preferably.Separately Outward, these monomers mix the oligomer compositions such as polyurethane polyfunctional acrylic ester hardness also can be made to become good, and make Polymerization shrinkage reduces, and can be formed well and prevent curling or the performance of slight crack, therefore preferably.
In this kind of resin combination, it is possible to contain the inorganic particles etc. such as silicon dioxide to promote hardness.It addition, be Make the compatibility with resin combination become good, the process of organic surface can be carried out, it is possible to there is reactive base.
It addition, as binding agent, it is possible to polymer is added and uses to above-mentioned resin combination.As polymer, Include, for example polymethyl methacrylate (PMMA, Polymethyl Methacrylate), cellulose acetate-propionate (CAP, Cellulose Acetate Propionate) etc..By adding polymer, the viscosity of adjustable masking liquid, thus make coating Become easy advantage.
It addition, in above-mentioned resin combination, optical free radical polymerization initiator optionally can be added.Preferably addition phase Total quality for total solid state component of above-mentioned resin combination is 0.8～8.0 mass %.Cause as optical free radical polymerization Agent, can use acetophenones, benzoin class, benzophenone, phosphinoxides, ketal class, Anthraquinones, 9-thioxanthene ketone, azo Compound etc..
As acetophenones, 2 can be enumerated, 2-dimethoxy-acetophenone, 2,2-diethoxy acetophenone, to dimethyl benzene second Ketone, 1-hydroxy-dimethyl phenyl ketone, 1-hydroxy-dimethyl-p-isopropyl phenyl ketone, 1-hydroxycyclohexylphenylketone, 2-first Base-4-methyl mercapto-2-raorpholino propiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 4-phenoxy group Dichloroacetophenone, the 4-tert-butyl group-dichloroacetophenones etc., as benzoin class, can enumerate benzoin, benzoin methylether, benzoin Ether, benzoin iso-propylether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin tosylate, benzoin methylether, Benzoin ethyl ether etc..
It addition, as benzophenone, benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 '-methyl two can be used Phenyl sulfide, 2,4-dichloro benzophenone, 4,4-dichloro benzophenone and p-dichlorobenzene ketone, 4,4 '-dimethylamino two Benzophenone (meter Qi Le ketone), 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone etc..
Additionally, it is possible to be used in mixed way photosensitizer, as its concrete example, n-butylamine, triethylamine, poly-normal-butyl can be enumerated Phosphine etc..
As long as the thickness of HC layer suitably regulates, such as, as long as being 1～20 μm.It is preferably 5～15 μm.If it is super Crossing 15 μm then to obtain the dust attachment of excellence and prevent performance, if less than 5 μm, then hardness becomes not enough and adhesion and also becomes Weak.
Generally, if the HC layer being laminated on antistatic layer is thickening, then dust attachment prevents degradation, if but the application Composition and compositions, then can obtain excellence dust attachment prevent performance.
In the preferred embodiment of the optical thin film of the present invention, even if with antistatic layer be 1～5 μm, HC layer be 5～ The mode of 15 μm is laminated with thicker HC layer on antistatic layer, and optical thin film also can obtain sufficient dust preventing property of attachment Energy and sufficiently antistatic layer and the adhesion of HC layer.
(other layers)
In the optical thin film of the present invention, without departing from the spirit and scope of the invention, quiet with anti-at above-mentioned HC layer On the face of electric layer opposition side, it is possible to high refraction is set for anti-reflective, anti-glare and the soil resistance etc. of improving optical thin film Other layers such as rate layer, middle index layer, low-index layer, antiglare layer and stain-proofing layer.
(high refractive index layer and middle index layer)
High refractive index layer and middle index layer are the reflectance of the optical thin film in order to adjust the present invention and the layer that arranges.? In the case of high refractive index layer is set, although not shown, but often abut against the TAC substrate side of low-index layer and arrange.It addition, In arranging in the case of index layer, although not shown, middle index layer, high folding but are generally sequentially set from TAC substrate side Penetrate rate layer and low-index layer.
High refractive index layer and middle index layer comprise and mainly contain adhesive ingredients and the combination of refractive index adjustment particle The solidfied material of thing.As adhesive ingredients, polyfunctional monomer etc. cited in antistatic layer compositions can be used.As folding Penetrating rate adjustment particle, include, for example particle diameter is 100nm particles below.As this kind of microgranule, can enumerate selected from zinc oxide (refractive index: 1.90), titanium dioxide (refractive index: 2.3～2.7), ceria (refractive index: 1.95), tin-doped indium oxide (refraction Rate: 1.95), antimony doped tin oxide (refractive index: 1.80), yittrium oxide (refractive index: 1.87), in zirconium oxide (refractive index: 2.0) one More than Zhong.
Specifically, the refractive index of high refractive index layer is preferably 1.50～2.80.The refractive index of middle index layer is less than height The refractive index of index layer, preferably 1.50～2.00.
As long as the thickness of high refractive index layer and middle index layer suitably regulates, preferably 50～300nm.
(low-index layer)
Low-index layer comprises the group of the composition relatively low containing the refractive index such as silicon dioxide or Afluon (Asta) and adhesive ingredients Compound or the solidfied material of the low-index layer compositions containing fluorine resins such as vinylidene fluoride copolymers, can be formed existing There is known low-index layer.
In the compositions for forming low-index layer, in order to reduce the refractive index of low-index layer, it is possible in containing Empty particle.Hollow-particle refers to the particle that inside is Porous tissue or hole having outer shell and being surrounded by outer shell. Containing air (refractive index: 1) in this Porous tissue or hole, it is 1.20～1.45 by making low-index layer contain refractive index Hollow-particle, it is possible to decrease the refractive index of low-index layer.The mean diameter of hollow-particle is preferably 1～100nm.Hollow-particle The particle used in previously known low-index layer can be used, such as, can enumerate Japanese Patent Laid-Open 2008-165040 The microgranule with space described in publication.
When the number average primary particle diameter of above-mentioned fatty acid metal salt particle is less than above-mentioned lower limit, there are following feelings Shape: easily produce the cohesion each other of fatty acid metal salt particle or fatty acid metal salt particle is covered for pigmentary resin particle The unfavorable condition such as bury, the lettering performance of carbon dust is had undesirable effect.
On the other hand, when the number average primary particle diameter of above-mentioned fatty acid metal salt particle exceedes the above-mentioned upper limit, exist Following situation: fatty acid metal salt particle is prone to free (disengaging) from pigmentary resin particle, it is impossible to by required additive Function (carbon dust gives the function of charging stability and mobility etc.) gives fully to carbon powder particles, the lettering to carbon dust Performance has undesirable effect.
(antiglare layer)
Antiglare layer comprises containing adhesive ingredients and the solidfied material of the antiglare layer compositions of anti-dazzle dose, and adhesive ingredients can Use polyfunctional monomer etc. cited in above-mentioned antistatic layer compositions.
As anti-dazzle dose, microgranule can be enumerated, include, for example styrene pellets (refractive index is 1.59), melamine particles (refractive index is 1.57) and acrylic particles (refractive index is 1.49) etc..The mean diameter of the microgranule that this kind gives anti-glare is preferred It is 100～500nm.Give the content of microgranule of anti-glare relative to the adhesive ingredients included in antiglare layer compositions Gross mass, preferably 2～30 mass %.
(stain-proofing layer)
According to a preferred embodiment of the invention, in order to prevent the spot of optical thin film most surface, can be at optical thin film The most surface with TAC base material opposition side stain-proofing layer is set.By stain-proofing layer, optical thin film can be sought soil resistance and scratch resistance Property further improvement.Stain-proofing layer comprises the solidfied material of the stain-proofing layer compositions containing anti-fouling agent and adhesive ingredients.
The adhesive ingredients of stain-proofing layer compositions can use previously known person, such as, can use above-mentioned antistatic layer group The polyfunctional monomer enumerated in compound.
Anti-fouling agent included in stain-proofing layer compositions can suitably select one from the anti-fouling agents such as known levelling agent Or two or more use.The content of anti-fouling agent is relative to total matter of the adhesive ingredients included in stain-proofing layer compositions Amount, preferably 0.1～5 mass %.
(manufacture method of optical thin film)
As the manufacture method of the optical thin film of the present invention, if the method that the layer that can obtain above-mentioned optical thin film is constituted, Then it is not particularly limited, previously known method can be used.
As one example, comprise the steps: that (i) prepares triacetyl cellulose base material；(ii) above-mentioned antistatic layer is prepared With compositions and composition for hard coat；(iii) side at this TAC base material is coated with this antistatic layer compositions to make painting Film；(iv) film of this antistatic layer compositions is carried out light irradiation so that it is be solidified to form antistatic layer；V () is anti-quiet This composition for hard coat it is coated with to make film in electric layer；(vi) film of this HC layer compositions is carried out light irradiation, make It is solidified to form HC layer.
In addition, it is possible to do not make the film of antistatic layer compositions be fully cured (full in above-mentioned (iv) step Cure), and make its semi-solid preparation (half cure), and coating HC layer compositions make film on the film of this semi-solid preparation, Make the film of this semi-solid preparation carry out light irradiation after merging with the film of HC layer compositions, then make it be fully cured and obtain light Learn thin film.Semi-solid preparation method is used, the advantage having antistatic layer and the adhesion raising of HC layer by manner described above.
As long as coating process uses previously known method, it is not particularly limited, gravure coating process, spin coating can be used Method, infusion process, nebulization, ramp type rubbing method, stick coating method, rolling method, meniscus rubbing method, quick-drying print process, screen painting The various methods such as method and drop rubbing method (bead coater).
Light irradiates and mainly uses ultraviolet, visible ray, electron beam or ionizing radiation etc..Situation in ultraviolet curing Under, use the light from extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, low pressure mercury lamp, carbon arc lamp, xenon arc lamp, metal halide lamp etc. The ultraviolet etc. that line sends.The irradiation dose in energy-ray source with the accumulated exposure amount under ultraviolet wavelength 365nm be calculated as 50～ 500mJ/cm2.Irradiation dose in the case of semi-solid preparation is 5～50mJ/cm2.Situation about heating also is carried out on the basis of light irradiates Under, generally process at a temperature of 40 DEG C～120 DEG C.
Coating antistatic layer compositions after and carry out light pre-irradiation, it is possible to be dried.As drying means, example As drying under reduced pressure or heat drying can be enumerated and then these are dried the method etc. being combined.It addition, doing with normal pressure In the case of dry, it be preferably and be dried at 30～110 DEG C.Such as, using methyl ethyl ketone as antistatic layer group In the case of the solvent of compound, can room temperature～80 DEG C, be preferably 40 DEG C～70 DEG C in the range of at a temperature of, carry out 20 seconds～ 3 minutes, preferably 30 seconds～the drying steps of 1 minute.
As long as the compositions of HC layer or low-index layer etc. is prepared with the method identical with above-mentioned antistatic layer.Separately Outward, in the case of low-index layer etc. is set on HC layer, coating process or the curing of above-mentioned antistatic layer can be used.
(polaroid)
The polaroid of the present invention is characterised by: the triacetyl cellulose substrate side at above-mentioned optical thin film is provided with polarization Element.Fig. 3 is the schematic diagram of an example of the layer composition of the polaroid representing the present invention.Polaroid 80 shown in Fig. 3 has light Learn thin film 1 and be laminated with the polarizer 70 of protective film 50 and polarization layer 60, and polarizer 70 is arranged at optical thin film 1 Triacetyl cellulose base material 10 side.
Furthermore, the so-called triacetyl cellulose substrate side at optical thin film is configured with polarizer, not only includes independently Form optical thin film and the situation of polarizer, also include that the component of composition optical thin film doubles as constituting the component of polarizer Situation.
It addition, in the case of the polaroid of the present invention is used for display floater, generally in the configuration display of polarizer side Panel.
Furthermore, about optical thin film, as long as owing to using above-mentioned optical thin film, so omitting explanation herein.With Under, other compositions in the polaroid of the present invention are illustrated.
(polarizer)
As the polarizer used in the present invention, as long as possessing the polarization characteristic of regulation, it is not particularly limited, Commonly used polarizer in liquid crystal display can be used.
About the form of polarizer, as long as the form of the polarization characteristic for regulation can be kept for a long time, there is no It is particularly limited to, such as, can be only made up of polarization layer, it is possible to protective film is formed with polarization layer laminating.By protective film with partially In the case of the laminating that shakes closes, only can form protective film on the one side of polarization layer, it is possible to formed on the two sides of polarization layer and protect Protect thin film.
As polarization layer, generally use by making iodine be infiltrated in the thin film comprising polyvinyl alcohol, and by its uniaxial tension And define the polarization layer of polyvinyl alcohol and the complex of iodine.
It addition, as protective film, as long as above-mentioned polarization layer can be protected and there is required light transmission, then there is no especially Limit.As the light transmission of protective film, the absorbance in visible region is preferably more than 80%, more preferably 90% with On.Furthermore, the absorbance of above-mentioned protective film can pass through the JIS K7361-1 (test of the all-optical transmittance of plastics-transparent material Method) it is measured.
As the resin of composition protective film, include, for example cellulose derivative, cyclic olefine resin, polymethyl Acid methyl ester, polyvinyl alcohol, polyimides, polyarylate, polyethylene terephthalate etc..Wherein, it is preferable to use cellulose Derivant or cyclic olefine resin.
Protective film can be made up of single layer, it is possible to the multiple layer of stacking and constitute.It addition, at protective film for being laminated with In the case of multiple layers, multiple layers of same composition can be laminated with, additionally, it is possible to be laminated with multiple layers with different compositions.
It addition, about the thickness of protective film, if the pliability of the polaroid of the present invention can be made to be in required scope In and by with polarization layer fit and the change in size of polarizer can be made to be in the scope in the range of regulation, there is no It is particularly limited to, but in the range of preferably 5～200 μm, is particularly preferably in the range of 15～150 μm, more preferably 30～100 μm In the range of.If above-mentioned thickness is thinner than 5 μm, then the change in size of the polaroid that there is the present invention becomes big probability.If it addition, Above-mentioned thickness is thicker than 200 μm, the most such as, add man-hour the polaroid of the present invention is carried out cutting, and there are processing bits increases or cut out The probability that the abrasion of shears accelerates.
Protective film can have phase contrast.Be there is by use the protective film of phase contrast, exist and can make the present invention The polaroid advantage that becomes the viewing angle compensation function person with display floater.
There is the embodiment of phase contrast as protective film, as long as being the embodiment party that can manifest required phase contrast Formula, then be not particularly limited.As this kind of embodiment, include, for example: protective film is made up of simple layer, and contain Manifest the optical characteristics visualization reagent of phase contrast, thus there is the embodiment of phase contrast；And by having on comprising State the composition being laminated with the phase difference layer comprising the compound with refractive anisotrop on the protective film of resin, and have The embodiment of phase contrast.In the present invention, these any embodiment the most preferably uses.
(display floater)
The display floater of the present invention is characterised by, the triacetyl cellulose substrate side at above-mentioned optical thin film is configured with aobvious Show device.
As display, (Electroluminescent Display, electroluminescence shows can to enumerate LCD, PDP, ELD Device) (organic EL, inorganic EL), CRT, contact panel, Electronic Paper, tablet PC (Tablet Personal Computer) Deng.
The display floater of the present invention can also be used for contact panel, Electronic Paper, flat board PC etc..
As the LCD of the typical example of aforementioned display device, for infiltration type, and for possessing permeability display body and from back side illuminaton Its light supply apparatus.In the case of aforementioned display device is LCD, it configures the present invention's on the surface of this permeability display body Optical thin film or possess the above-mentioned polaroid of this optical thin film and form.
As the PDP of another example of aforementioned display device, possess Watch glass substrate and Watch glass substrate is opposed joins with this The back glass substrate putting and being filled with between the two discharge gas forms.In the case of aforementioned display device is PDP, it is on surface Above-mentioned optical thin film is possessed on the surface of glass substrate or its front panel (glass substrate or film substrate).
If aforementioned display device is alternatively applies voltage, the luminous body such as luminous zinc sulfide, Diamines material is deposited with in glass On substrate, and control to put on the ELD device that the voltage of substrate carries out showing, or electric signal is converted to light, produce people The display such as the CRT of the visible picture of eye.In the case, it is on ELD device or the outmost surface of CRT or the surface of its front panel On possess above-mentioned optical thin film.
[embodiment]
Hereinafter, enumerate embodiment and further illustrate the present invention.The present invention is not limited by these records.
Preparation has antistatic layer the compositions 1 and HC layer compositions 1 of following composition.
(antistatic layer compositions 1)
Antistatic additive (A): (weight average molecular weight is trade name UV-ASHC-01 that Japan's chemical conversion (Co., Ltd.) manufactures 20000, 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 name: KAYARAD DPHA, Japan's chemical medicine (Co., Ltd.) manufactures, 6 officials' energy, and molecular weight is 578): 64 mass parts
Urethane acrylate (C): trade name BS577 (6 officials' energy, the weight average that waste river chemical industry (Co., Ltd.) manufactures Molecular weight is 1000): 35 mass parts
Polymerization initiator: trade name Irgacure 184 that Ciba Specialty Chemicals (Co., Ltd.) manufactures (1-hydroxycyclohexylphenylketone): 1 mass parts
Methyl ethyl ketone: 100 mass parts
(HC layer compositions 1)
(trade name: KAYARAD DPHA, Japan's chemical medicine (Co., Ltd.) manufactures dipentaerythritol acrylate, 6 officials Can, molecular weight is 578): 98 mass parts
Polymerization initiator: trade name Irgacure 184 that Ciba Specialty Chemicals (Co., Ltd.) manufactures (1-hydroxycyclohexylphenylketone): 4 mass parts
Methyl ethyl ketone: 100 mass parts
(embodiment 1)
Prepare the TAC base material (trade name TF80UL that Fuji Film (Co., Ltd.) manufactures) that thickness is 80 μm, at TAC Above-mentioned antistatic layer compositions 1 prepared by the single spreading of base material, and be dried 60 seconds in the oven heat that temperature is 70 DEG C Clock and make the solvent in film evaporate, then in the way of making accumulative light quantity reach 50mJ irradiation ultraviolet radiation and make curing of coating, Thickness when being consequently formed dry is the antistatic layer of 2.5 μm.
Then, the antistatic layer obtained is coated with prepared above-mentioned composition for hard coat 1, same with antistatic layer Be dried sample, then in the way of making accumulative light quantity reach 150mJ irradiation ultraviolet radiation and make curing of coating, formed when being dried The hard conating that thickness is 12 μm, be thus made in the side of TAC base material and sequentially there is from TAC substrate side antistatic layer and hard The optical thin film of coating.
It addition, for the surface resistivity measuring antistatic layer, at TAC base material in the same manner as above-mentioned optical thin film (TF80UL), till the enterprising step walking to formation antistatic layer, the side being formed in TAC base material only has the layer of antistatic layer Stack.
(embodiment 2～7)
In embodiment 1, by antistatic layer antistatic additive (A) included in compositions 1, polyfunctional monomer (B) and The amount of urethane acrylate (C) or kind respectively as shown in table 1 as replaced, in addition, with same as in Example 1 Mode makes optical thin film and duplexer.Furthermore, the urethane acrylate (C) used in embodiment 7 is trade name UV- 7610B (Japan is synthetically produced).
(comparative example 1,2)
In embodiment 1, by antistatic layer antistatic additive (A) included in compositions 1, polyfunctional monomer (B) and The amount of urethane acrylate (C) respectively as shown in table 1 as replaced, in addition, make in the same manner as example 1 Make optical thin film and duplexer.
(comparative example 3)
In embodiment 1, as antistatic layer polyfunctional monomer (B) included in compositions 1, use Japan's chemical medicine The R128H (simple function, molecular weight is 222) that (Co., Ltd.) manufactures replaces DPHA, and by antistatic additive (A), multifunctional list The amount of body (B) and urethane acrylate (C) respectively as shown in table 1 as replaced, in addition, with same as in Example 1 Mode make optical thin film and duplexer.
(comparative example 4)
In embodiment 1, as antistatic layer polyfunctional monomer (B) included in compositions 1, use Japan's chemical medicine The DPCA60 (6 officials' energy, molecular weight is 1263) that (Co., Ltd.) manufactures replaces DPHA, and by antistatic additive (A), multifunctional list The amount of body (B) and urethane acrylate (C) respectively as shown in table 1 as replaced, in addition, with same as in Example 1 Mode make optical thin film and duplexer.
(comparative example 5)
In embodiment 1, as antistatic layer urethane acrylate (C) included in compositions 1, use The EBECRYL270 (2 officials' energy, molecular weight is 1500) that Daicel-Cytec (Co., Ltd.) manufactures replaces BS577, and will be anti- The amount of electrostatic agent (A), polyfunctional monomer (B) and urethane acrylate (C) respectively as shown in table 1 as replaced, except this with Outward, optical thin film and duplexer are made in the same manner as example 1.
(comparative example 6)
In embodiment 1, as antistatic layer urethane acrylate (C) included in compositions 1, use The EBECRYL5129 (6 officials' energy, molecular weight is 800) that Daicel-Cytec (Co., Ltd.) manufactures replaces BS577, and will be anti- The amount of electrostatic agent (A), polyfunctional monomer (B) and urethane acrylate (C) respectively as shown in table 1 as replaced, except this with Outward, optical thin film and duplexer are made in the same manner as example 1.
(comparative example 7)
In embodiment 1, as antistatic layer urethane acrylate (C) included in compositions 1, use waste river The BS371MLV (50 officials' energy, molecular weight is 20000) that chemical industry (Co., Ltd.) manufactures replaces BS577, and by antistatic The amount of agent (A), polyfunctional monomer (B) and urethane acrylate (C) respectively as shown in table 1 as replaced, in addition, with Mode same as in Example 1 makes optical thin film and duplexer.
(comparative example 8～11)
In embodiment 1, by antistatic layer antistatic additive (A) included in compositions 1, polyfunctional monomer (B) and The amount of urethane acrylate (C) respectively as shown in table 1 as replaced, in addition, make in the same manner as example 1 Make optical thin film and duplexer.
(reference example 1)
In embodiment 6, the solvent included in antistatic layer compositions 1 is replaced with only impermeable solvent, removes Beyond this, make optical thin film and duplexer in the same manner as in example 6.
(comparative example 12)
In embodiment 3, the urethane acrylate (C) included in antistatic layer compositions 1 is replaced with in oneself Ester modified dipentaerythritol acrylate (trade name: KAYARAD DPCA-60, Japan's chemical medicine (Co., Ltd.) manufactures), removes Beyond this, in the way of same as in Example 3, make optical thin film and duplexer.This compound is because of the reason identical with DPHA There is hydrophilic tendency.
(reference example 2)
In embodiment 3, the antistatic additive (A) included in antistatic layer compositions 1 is replaced with antistatic additive (B) (metal particle: ATO, trade name: ELCOM V3560 are waved catalyst chemical conversion day and manufactured), in addition, with same as in Example 3 Mode makes optical thin film and duplexer.
(reference example 3)
In reference example 2, by antistatic layer with the amount of the antistatic additive (B) included in compositions 1 as shown in table 1 as increase Many, in addition, in the way of identical with reference example 2, make optical thin film and duplexer.
(evaluation of the surface resistivity of antistatic layer)
The stacking of antistatic layer it is laminated with on base material for embodiment 1～7, comparative example 1～12 and reference example 1～3 Body, utilizes high resistivity meter (trade name Hiresta that Mitsubishi Chemical Analytech (Co., Ltd.) manufactures IP MCP-HT260) to apply voltage 1000V mensuration surface resistivity.The results are shown in table 1.Furthermore, described in this case The unit Ω/ of surface resistivity refer to Ω/sq. (resistance of per unit area).
(evaluation of dust the preventing property of attachment of optical thin film)
Utilize mylar by the optical layers comprising base material/antistatic layer/hard conating made in embodiment and comparative example The HC aspect of stack comes and goes wiping 20 times, then make this wiping surface close to tobacco ash and with following benchmark evaluation dust attachment preventProperty。
Zero: ash non-cohesive, have dust attachment preventing effectiveness and good.
×: a large amount of attachment of ash, free from dust attachment preventing effectiveness.
(evaluation of the adhesion of optical thin film)
For embodiment 1～7, comparative example 1～12 and the optical thin film of reference example 1～3, in temperature 25 DEG C, humidity 40% After lower damping 24 hours, according to the method for the grid test of JIS K5400, hard conating face is cut the most respectively with 1mm interval Entering 11 gaps and make 100 grids, the Cellotape (registered trade mark) manufactured by Nichiban (Co., Ltd.) is attached at After on grid, rapidly it is pulled up in the side of 90 ° and makes it peel off, and calculate contiguity rate according to following benchmark.
Contiguity rate (%)=(unpeeled number of squares/total number of squares 100) × 100
It addition, for embodiment 1～7, comparative example 1～12 and the optical thin film of reference example 1～3, also obtain in temperature 25 DEG C, after 40% time damping of humidity 24 hours, in temperature 30 DEG C, humidity 40% time with 500W/m per hour2Light quantity irradiate ultraviolet Line contiguity rate after 192 hours.The measurement result of the contiguity rate of the optical thin film before and after being tested by resistance to UV is shown in Table 1 in the lump.
(summary of result)
According to table 1, embodiment 1～7 all obtains the surface resistivity of good duplexer (antistatic layer), and optically thin The adhesion of film is the best.It addition, optical characteristics and outward appearance are the best.
But, in comparative example 1,2, owing to antistatic layer compositions not comprising polyfunctional monomer (B) or polyurethane Acrylate (C), although therefore contiguity rate before resistance to UV test is good, but the contiguity rate after resistance to UV test is poor.
In comparative example 3, owing to polyfunctional monomer (B) is simple function, so not obtaining sufficient contiguity rate.
In comparative example 4, the molecular weight of polyfunctional monomer (B) is more than 1000, and contiguity rate is relatively low, after the most resistance to UV test Contiguity rate relatively low.It is believed that its reason is: polyfunctional monomer (B) is insufficient towards the infiltration of TAC base material, TAC base material is with anti- The adhesion of electrostatic layer becomes insufficient.
In comparative example 5, the sense radix of urethane acrylate (C) is 2 and less, and contiguity rate is relatively low, the most resistance to Contiguity rate after UV test is relatively low.It is believed that its reason is: less by the crosslinking caused by urethane acrylate (C), anti- Electrostatic layer becomes insufficient with the adhesion of HC layer.
In comparative example 6, the molecular weight of urethane acrylate (C) is less than 1000, the contiguity rate after the most resistance to UV test Relatively low.It is believed that its reason is: due in urethane acrylate (C) excessive permeation to TAC base material, so antistatic layer with The adhesion of HC layer becomes insufficient.
In comparative example 7, the molecular weight of urethane acrylate (C) is more than 10000, and contiguity rate is relatively low, the most resistance to UV Contiguity rate after test is relatively low.Surface resistivity is the highest, it is believed that its reason is: urethane acrylate (C) is the most complete Infiltrating in TAC base material, the relative quantity of the antistatic additive (A) in antistatic layer tails off.
In comparative example 8, the content ratio of antistatic additive (A) is less, and surface resistivity uprises.
In comparative example 9, the content ratio of antistatic additive (A) is more, and antistatic behaviour is good, but owing to becoming binding agent The quantitative change of polyfunctional monomer (B) and urethane acrylate (C) is few, so contiguity rate is relatively low before and after resistance to UV tests.
In comparative example 10, owing to the content ratio of polyfunctional monomer (B) is more, urethane acrylate (C's) contains Ratio is less, so contiguity rate is relatively low, the contiguity rate after the most resistance to UV test is relatively low.
In comparative example 11, owing to the content ratio of urethane acrylate (C) is more, polyfunctional monomer (B's) contains Ratio is less, so contiguity rate is good before resistance to UV test, but the contiguity rate after resistance to UV test is relatively low.
In reference example 1, contiguity rate is relatively low, and surface resistivity is higher.It is believed that its reason is: due to by antistatic layer Only it is set to be saturated solvent with the solvent in compositions, so urethane acrylate (C) the most fully infiltrates in TAC base material, The relative quantity of the antistatic additive (A) in antistatic layer tails off.
In comparative example 12, owing to not using the urethane acrylate (C) as hydrophobic resin, so quaternary ammonium salt mistake Degree dispersion, surface resistivity is higher.Therefore, dust preventing property of attachment is not obtained yet.
In reference example 2, use metal particle as antistatic additive.Identical with the situation of quaternary ammonium salt owing to being set to obtain The addition (the fewest) of water degree of full light transmittance, so surface resistivity is poor.
In reference example 3, obtaining required antistatic behaviour to not consider full light transmittance, allotment has compares reference example 2 more as the metal particle of antistatic additive, and therefore adhesion is poor.There is coloring because addition is more, full light is saturating Rate of penetrating uprises less than the situation (88%) of quaternary ammonium salt, haze value (0.8%).
The result being evaluated the preventing property of dust attachment of the optical thin film of embodiment, comparative example and reference example, at layer The surface resistivity of stack is less than 1 × 1012In the case of Ω/ all good, but in the case of in addition, ash is the most attached ?.That is, if having the antistatic layer of preferred surface resistivity, even if being laminated with HC layer the most thereon, it is possible to optically thin Film gives dust preventing property of attachment.
Symbol description
1,2 optical thin film
10 triacetyl cellulose base materials
20 antistatic layers
30 hard conatings
40 low-index layers
50 protective films
60 polarization layers
70 polarizers
80 polaroids

Claims (5)

1. an optical thin film, it is characterised in that be the side at triacetyl cellulose base material, from described triacetyl cellulose base Material side starts to be provided with adjacently the optically thin of the antistatic layer that thickness is 2.5～5 μm and the hard conating that thickness is 1～20 μm Film,
Described antistatic layer is formed by the solidfied material of following antistatic layer hardening resin composition, and described antistatic layer is with solid The property changed resin combination comprises:
A: antistatic additive, it is the quaternary ammonium salt of weight average molecular weight 1000～50000；
B: there is in 1 molecule the photo-curable base of more than 2, and molecular weight is the polyfunctional monomer of less than 900；And
C: there is in 1 molecule acryloyl group and/or the methylacryloyl of more than 6, and weight average molecular weight be 1000～ The urethane acrylate of 11000,
The ratio of the described A total amount relative to described A, B and C is 1～30 mass %,
And the ratio of the total amount that described C is relative to described B and C is 1～40 mass %,
Described polyfunctional monomer B infiltrates into the region of the near interface of the antistatic layer side of described triacetyl cellulose base material and consolidates Change,
The haze value of described optical thin film is less than 0.5%, and full light transmittance is more than 90%.
2. optical thin film as claimed in claim 1, wherein,
Described antistatic layer hardening resin composition also includes:
D: penetrating solvents；And
E: impermeability solvent.
3. optical thin film as claimed in claim 1, wherein,
The contiguity rate of the grid adhesion test between described hard conating, 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 hour2Light quantity irradiation ultraviolet radiation after 192 hours Described contiguity rate is 80～100%.
4. a polaroid, it is characterised in that
Triacetyl cellulose substrate side at the optical thin film described in described claim 1 is provided with polarizer.
5. a display floater, it is characterised in that
Triacetyl cellulose substrate side at the optical thin film described in described claim 1 is configured with display.
CN201410753543.0A 2010-07-12 2011-07-12 Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel Active CN104530331B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010157808 2010-07-12
JP2010-157808 2010-07-12
CN201180031473.2A CN102958963B (en) 2010-07-12 2011-07-12 Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201180031473.2A Division CN102958963B (en) 2010-07-12 2011-07-12 Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel

Publications (2)

Publication Number Publication Date
CN104530331A CN104530331A (en) 2015-04-22
CN104530331B true CN104530331B (en) 2017-01-11

Family

ID=45469442

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201410753543.0A Active CN104530331B (en) 2010-07-12 2011-07-12 Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel
CN201180031473.2A Active CN102958963B (en) 2010-07-12 2011-07-12 Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201180031473.2A Active CN102958963B (en) 2010-07-12 2011-07-12 Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel

Country Status (5)

Country Link
JP (1) JP5811090B2 (en)
KR (1) KR101466520B1 (en)
CN (2) CN104530331B (en)
TW (1) TWI482705B (en)
WO (1) WO2012008444A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6235287B2 (en) * 2013-09-30 2017-11-22 日東電工株式会社 Optical laminate
CN107791632A (en) * 2017-11-24 2018-03-13 惠州市摩码菱丽光电材料有限公司 A kind of antiradar reflectivity of TAC base materials is without rainbow line hardening diaphragm and preparation method thereof
CN111566129B (en) * 2017-12-18 2022-06-14 Dic株式会社 Active energy ray-curable composition and film using same
CN108802885A (en) * 2018-04-23 2018-11-13 深圳市运宝莱光电科技有限公司 A kind of electromagnetic shielding polaroid and preparation method
WO2024101232A1 (en) * 2022-11-07 2024-05-16 Ａｇｃ株式会社 Film and method for producing semiconductor package

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101676310A (en) * 2008-09-16 2010-03-24 日本油漆株式会社 Fingerprint resistance photo-curing combination and coating article having a fingerprint resistance coating layer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006306008A (en) 2005-03-31 2006-11-09 Jsr Corp Antistatic layered product
WO2007116831A1 (en) * 2006-03-31 2007-10-18 Dai Nippon Printing Co., Ltd. Optical laminated body
JP4670745B2 (en) * 2006-06-12 2011-04-13 日本化成株式会社 Antistatic composition, antistatic layer and antistatic film
US20090075074A1 (en) * 2007-09-12 2009-03-19 Dai Nippon Printing Co., Ltd. Optical layered body, method of producing the same, polarizer, and image display device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101676310A (en) * 2008-09-16 2010-03-24 日本油漆株式会社 Fingerprint resistance photo-curing combination and coating article having a fingerprint resistance coating layer

Also Published As

Publication number Publication date
TW201223758A (en) 2012-06-16
KR20130054314A (en) 2013-05-24
KR101466520B1 (en) 2014-11-27
JPWO2012008444A1 (en) 2013-09-09
CN104530331A (en) 2015-04-22
TWI482705B (en) 2015-05-01
CN102958963B (en) 2014-11-05
JP5811090B2 (en) 2015-11-11
CN102958963A (en) 2013-03-06
WO2012008444A1 (en) 2012-01-19

Similar Documents

Publication Publication Date Title
CN102667535B (en) Method for producing optical film, optical film, polarizing plate and display device
KR101226229B1 (en) Anti-reflective coating film
EP2209860B1 (en) Coating composition for antireflection and antireflection film prepared by using the same
CN103080778B (en) Optical laminate, polaroid and image display device
CN103492913B (en) Optical laminate
US10908322B2 (en) Antistatic hardcoat film, process for producing same, polarizer, and image display device
CN104530331B (en) Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel
JP5935802B2 (en) Method for producing antiglare film
TWI359834B (en) Hard-coated antiglare film, method of manufacturin
KR20130057413A (en) Hard coat film, polarizing film, image display device, and hard coat film manufacturing method
TW201323916A (en) Optical film, polarizing plate and image display device
TWI479179B (en) Optical film, method of producting optical film, polarizer, display panel, and display
CN102443343B (en) For the formation of the preparation method of the composition of antistatic hard coating, blooming, blooming, polaroid and image display device
JP2012133079A (en) Hard coat film, production method of the same, antireflection film, polarizing plate and image display device
JP2011046193A (en) Laminate, anti-reflection film, polarizing plate, and image displaying apparatus
KR20130122964A (en) Anti-glare film, method for producing anti-glare film, anti-glare anti-reflection film, polarizing plate, and image display device
CN107641348A (en) Hard coat film and the Flexible Displays window including touch sensor using the hard coat film
KR101205477B1 (en) Composition for anti-reflective coating and anti-reflective coating film using the same
CN103105631B (en) The manufacture method of optical thin film, image display device and image display device
JP2012128064A (en) Antireflection film, polarizer and image display device
JP2006156249A (en) Transparent conductor
WO2015126178A1 (en) Electronic board

Legal Events

Date Code Title Description
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant