CN104936778A - Transparent face plate with an adhesive layer, laminate, display device, and production methods thereof - Google Patents

Transparent face plate with an adhesive layer, laminate, display device, and production methods thereof Download PDF

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Publication number
CN104936778A
CN104936778A CN201380067251.5A CN201380067251A CN104936778A CN 104936778 A CN104936778 A CN 104936778A CN 201380067251 A CN201380067251 A CN 201380067251A CN 104936778 A CN104936778 A CN 104936778A
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CN
China
Prior art keywords
adhesive layer
weir
transparent facestock
shape portion
oligomer
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.)
Pending
Application number
CN201380067251.5A
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Chinese (zh)
Inventor
网野阳介
铃木豊一
川上玲美
德永谦治
新山聪
青木直子
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AGC Inc
Original Assignee
Asahi Glass 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 Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of CN104936778A publication Critical patent/CN104936778A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • B32B2307/412—Transparent
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/40—Compositions for pressure-sensitive adhesives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The present invention provides a transparent face plate (1) with an adhesive layer, and a display device. The transparent face plate (1) with the adhesive layer is characterized by comprising a transparent face plate (10) and an adhesive layer (14) that is formed on the surface of the transparent face plate (10) and has a layer-like portion (18) and a weir-like portion (20), and which is also characterized in that the difference between the content (W1) of a non-curable oligomer (II) in the layer-like portion (18), said content (W1) being expressed in mass%, and the content (W2) of a non-curable oligomer (II') in the weir-like portion (20), said content (W2) being expressed in mass%, namely (W2)-(W1) is set to be 40 or less. A display device which comprises a display panel and a transparent face plate (1) with an adhesive layer, said transparent face plate (1) being bonded to the display panel so that the adhesive layer is in contact with the display panel.

Description

Transparent facestock with adhesive layer, duplexer, display unit and their manufacture method
Technical field
The present invention relates to the transparent facestock of band adhesive layer, duplexer, display unit and their manufacture method.
Background technology
Such as the display unit protecting display floater (by laminating plane materiel) with baffle (transparent facestock), the display unit that known display floater and baffle are fitted across adhesive layer.As clipping the adhesive layer used in the duplexer of adhesive layer as this display unit between a facestock, propose a kind of adhesive layer, this adhesive layer have along the extended surface of plane materiel superimposed portions and surround the shape portion, weir of periphery in layered portion, layered portion is made up of (with reference to patent document 1,2) the solidfied material of the hardening resin composition comprising curability compound and non-curable oligomer.
As the manufacture method of the such duplexer of above-mentioned display unit, such as, there are following method (i) and (ii).
After in i region that () surrounds to the uncured shape portion, weir by the circumference being formed at transparent facestock surface, supply forms the hardening resin composition of superimposed portions; under reduced atmosphere, superposition is pasted with the supporting plane materiel of diaphragm; under returning to atmospheric pressure atmosphere; make uncured shape portion, weir and superimposed portions solidification, obtain the duplexer being formed with adhesive layer in transparent facestock, the protected film of this adhesive layer covers.Then, in the desired time, the diaphragm of this duplexer is peeled off, under reduced atmosphere, this duplexer is superposed laminating, under being returned to atmospheric pressure atmosphere with adhesive layer with the mode contacted by plane materiel of fitting with by laminating plane materiel.
(ii) to by after being formed at and being supplied form the resin combination of superimposed portions by the region that the uncured shape portion, weir of the circumference of laminating facestock surface surrounds, transparent facestock is superposed under reduced atmosphere, under returning to atmospheric pressure atmosphere, make uncured shape portion, weir and superimposed portions solidification.
In method (i), by when being formed with the transparent facestock of the band adhesive layer of adhesive layer and being fitted under reduced atmosphere by laminating plane materiel in transparent facestock, the interface of display floater and adhesive layer produces space.But when returning under atmospheric pressure atmosphere after laminating, due to the pressure (keep decompression) in this space and the pressure differential of pressure (atmospheric pressure) putting on adhesive layer, the volume in this space reduces, space disappearance.Too, even if create space when superposing transparent facestock under reduced atmosphere, this space also can disappear when returning under atmospheric pressure atmosphere method (ii).
If formed containing the non-curable oligomer not participating in curing reaction in the hardening resin composition of superimposed portions, then, compared with not containing the situation of non-curable oligomer, the mobility of the superimposed portions of formation is high.Therefore, superimposed portions is easily towards interstitial flow, and the space that the interface of adhesive layer and plane materiel produces disappears at short notice.
In addition, by containing non-curable oligomer, the elasticity of superimposed portions reduces.Therefore, the stress putting on the display floater contacted with above-mentioned adhesive layer is little, and the display inequality of display unit is inhibited.
Prior art document
Patent document
Patent document 1: No. 2011/158839th, International Publication
Patent document 2: No. 2012/077726th, International Publication
Summary of the invention
Invent technical problem to be solved
But, in the transparent facestock of above-mentioned band adhesive layer, after certain hour, non-curable oligomer spreads from the superimposed portions of adhesive layer to shape portion, weir, at the near interface of shape portion, weir and superimposed portions, cause due to the impact of the diffusion of non-curable oligomer the thickness of shape portion, weir and superimposed portions to produce difference, therefore when fitting, having and producing space or the bad possibility of laminating occurs between by binding face.In addition, if the plane materiel of band adhesive layer and by the duplexer of laminating plane materiel laminating through certain hour, then non-curable oligomer is to the diffusion of shape portion, weir, and the volume in shape portion, weir increases, may produce engage bad and by the space of binding face.
Even if the invention provides a kind of transparent facestock of the band adhesive layer that superimposed portions and shape portion, weir also not easily have problems after certain hour, display unit and duplexer.In addition, even if the invention provides a kind of transparent facestock of band adhesive layer that superimposed portions and shape portion, weir also not easily have problems after certain hour and the manufacture method of display unit.
The technical scheme that technical solution problem adopts
The feature of the transparent facestock of band adhesive layer of the present invention is, comprise transparent facestock and be formed at the adhesive layer on surface of at least one party of described transparent facestock, described adhesive layer have along the extended surface of described transparent facestock superimposed portions and surround the shape portion, weir of periphery in layered portion, shape portion, described weir is formed by the shape portion, weir comprising following curability compound (I ') and following non-curable oligomer (II ') and forms with the solidfied material of hardening resin composition, layered portion is formed by the superimposed portions comprising following curability compound (I) and following non-curable oligomer (II) and forms with the solidfied material of hardening resin composition, the difference (W1-W2) of the content W2 represented with quality % of described non-curable oligomer in the content W1 represented with quality % of the described non-curable oligomer (II) in layered portion and shape portion, described weir (II ') is below 40,
Curability compound (I '): the molecular weight comprising urethane acrylate oligomer (A ') and there is more than 1 curability functional group lower than 600 monomer (B ');
Non-curable oligomer (II '): that be not cured reaction with described curability compound (I ') during any one solidification in layered portion's formation hardening resin composition and weir shape portion formation hardening resin composition, that there is hydroxyl oligomer;
Curability compound (I): the molecular weight comprising urethane acrylate oligomer (A) and there is more than 1 curability functional group lower than 600 monomer (B);
Non-curable oligomer (II): be not cured reaction with described curability compound (I) during any one solidification in layered portion's formation hardening resin composition and weir shape portion formation hardening resin composition, the oligomer with hydroxyl.
Described urethane acrylate oligomer (A) and (A ') are preferably with the urethane acrylate oligomer that polyoxyalkylene polyol and polyisocyanates are Material synthesis.
Described non-curable oligomer (II) and (II ') preferably polyoxyalkylene polyol.
The number-average molecular weight that every 1 hydroxyl of described non-curable oligomer (II) and (II ') is corresponding is preferably 400 ~ 8000.
The number-average molecular weight of described urethane acrylate oligomer (A) is preferably 1000 ~ 100000.
Layered portion's formation hardening resin composition preferably comprises Photoepolymerizationinitiater initiater (C1), and described weir shape portion formation hardening resin composition preferably comprises Photoepolymerizationinitiater initiater (C2).
In the transparent facestock of band adhesive layer of the present invention, more than the storage shear modulus of the storage shear modulus at 35 DEG C of shape portion, described weir preferably at 35 DEG C of layered portion and below 15 times.
Storage shear modulus at 35 DEG C of shape portion, described weir is preferably 1 ~ 150kPa.
Storage shear modulus at 35 DEG C of layered portion is preferably 1 ~ 100kPa.
Described transparent facestock in the transparent facestock of band adhesive layer of the present invention preferably has the shading Printing Department of the circumference being formed at its surface, and superimposed portions and shape portion, weir direction are positioned at than described shading Printing Department position more in the inner part at least partially in the face on the surface of described transparent facestock.
The shape quality award from the ministry choosing of described weir also comprises the solidfied material be made up of the oligomer of number-average molecular weight 30000 ~ 100000.The shape quality award from the ministry choosing of described weir comprises the solidfied material be made up of the monomer not containing acidic group of molecular weight 125 ~ 600.Viscosity during shape portion, described weir uncured is preferably 40Pas ~ 100Pas.
The transparent facestock of band adhesive layer of the present invention can also have diaphragm that cover the surface at least partially of described adhesive layer, that can peel off.
The manufacture method with the transparent facestock of the band adhesive layer of the present invention of described diaphragm is the method comprising following operation (a) ~ (e).
A () is coated with aqueous described weir shape portion formation hardening resin composition in the circumference on the surface of transparent facestock, form the operation in uncured shape portion, weir;
B () supplies aqueous layered portion and forms operation with hardening resin composition in the region surrounded by uncured shape portion, weir on transparent facestock surface;
C () is under reduced atmosphere, on superimposed portions formation hardening resin composition, superpose in the mode making diaphragm contact with superimposed portions formation hardening resin composition the supporting plane materiel being pasted with diaphragm, obtain the operation being formed the precursor duplexer that the uncured superimposed portions that forms with hardening resin composition is sealed by transparent facestock, diaphragm and uncured shape portion, weir by superimposed portions;
D (), under the state being placed under the pressure atmosphere higher than described operation (c) by described precursor duplexer, makes uncured superimposed portions and the solidification of shape portion, weir, forms the operation with the adhesive layer in superimposed portions and shape portion, weir;
E operation that supporting plane materiel is peeled off from diaphragm by ().
Display unit of the present invention comprises the transparent facestock of display floater and band adhesive layer of the present invention, and the mode that the transparent facestock of band adhesive layer of the present invention contacts with display floater with adhesive layer fits in display floater.
The manufacture method of display unit of the present invention is under the reduced atmosphere of below 10kPa, display floater and the transparent facestock of band adhesive layer is superposed the method for laminating in the mode that adhesive layer contacts with display floater.
Duplexer of the present invention is by the transparent facestock of band adhesive layer of the present invention with by the duplexer of laminating plane materiel laminating.
The effect of invention
If use the transparent facestock of band adhesive layer of the present invention, though then after certain hour superimposed portions and shape portion, weir also not easily have problems.
By the manufacture method of the transparent facestock of band adhesive layer of the present invention, even if the transparent facestock of the band adhesive layer that superimposed portions and shape portion, weir also not easily have problems after certain hour can be obtained.
Even if display unit of the present invention superimposed portions and shape portion, weir after certain hour also not easily have problems.
By the manufacture method of display unit of the present invention, even if the display unit that superimposed portions and shape portion, weir also not easily have problems after certain hour can be obtained.
Even if duplexer of the present invention superimposed portions and shape portion, weir after certain hour also not easily have problems.
Accompanying drawing explanation
Fig. 1 is the sectional view of an example of the transparent facestock representing band adhesive layer of the present invention.
Fig. 2 is the top view of an example of the form representing operation (a).
Fig. 3 is the sectional view of an example of the form representing operation (a).
Fig. 4 is the top view of an example of the concrete form representing operation (a).
Fig. 5 is the sectional view of an example of the concrete form representing operation (a).
Fig. 6 is the top view of another example of the concrete form representing operation (a).
Fig. 7 is the sectional view of another example of the concrete form representing operation (a).
Fig. 8 is the stereogram of the main points representing the operation shown in Fig. 6 and Fig. 7.
Fig. 9 is the top view of an example of the form representing operation (b).
Figure 10 is the sectional view of an example of the form representing operation (b).
Figure 11 is the sectional view of an example of the form representing operation (c).
Figure 12 is the sectional view of the example representing display unit of the present invention.
Figure 13 is the stereogram of the form in the space represented on the interface of display floater in display unit of the present invention and adhesive layer.
Detailed description of the invention
In this description, " transparent " refer to by the display surface of plane materiel and display floater across adhesive layer tight fit after, the image that shows all or in part of display floater can observe through plane materiel and not be subject to the form of warp.Therefore, even if the part being incident to the light of plane materiel from display floater is absorbed by plane materiel or reflects, or due to optical phase change etc. and cause the transmission of visible light of plane materiel low, as long as can the display image of display floater be observed through plane materiel and not have warp, just can be called " transparent ".Such as, transparent facestock also comprises the plane materiel with polarizer.
In addition, " curability functional group " refers to the functional group with free-radical polymerised unsaturated bond.In addition, " (methyl) acrylate " refers to acrylate or methacrylate.
" average thickness " in this description is the mean value of the thickness measuring 10 places and obtain.
" transparent facestock of band adhesive layer "
Fig. 1 is the sectional view of an example of the transparent facestock representing band adhesive layer of the present invention.
The transparent facestock 1 with the band adhesive layer of diaphragm 16 comprises transparent facestock 10, is formed at the shading Printing Department 12 of the circumference on the surface of transparent facestock 10, is formed at the adhesive layer 14 on the surface of the transparent facestock 10 of the side being formed with shading Printing Department 12, cover the surface of adhesive layer 14, the diaphragm 16 that can peel off.
The transparent facestock 1 of the band adhesive layer shown in Fig. 1 diaphragm 16 can be peeled off afterwards and display floater is fitted, thus manufactures display unit.
For adhesive layer 14 is formed at the situation of the one side of transparent facestock 10 shown in Fig. 1, but adhesive layer 14 also can be formed at the two sides of transparent facestock 10, and now, each surface of adhesive layer 14 is also all covered by the diaphragm 16 that can peel off.
< transparent facestock >
Transparent facestock 10 is preferably arranged at the image display side of following display floater, the baffle for the protection of display floater.
As transparent facestock 10, glass plate or transparent resin plate can be exemplified.As transparent facestock 10, except to from except the emergent light of display floater or the transparency height of reverberation, from have light resistance, low birefringence, high plane precision, resistance to surface damage, high mechanical properties angle consider, also preferably glass plate.In addition, from make Photocurable resin composition solidification light fully through angle consider, transparent facestock 10 is preferred glass plate also.
As the material of glass plate, the glass materials such as soda-lime glass can be exemplified.As glass plate, lower, the blue less high transmission glass (ultrawhite plate glass) of preferred ferrous components.As glass plate, in order to improve security, also tempered glass can be used.When using glass plate thin especially, preferably use and implemented chemical enhanced glass plate.
As the material of transparent resin plate, the resin material (Merlon, polymethyl methacrylate etc.) that the transparency is high can be exemplified.
For transparent facestock 10, in order to improve the interface binding force with adhesive layer 14, also surface treatment can be implemented.As surface-treated method, the method on the surface by silane coupler process transparent facestock 10 can be exemplified, utilize the oxidizing flame produced by flame burner to form the method etc. of silicon oxide film.
For transparent facestock 10, in order to improve the contrast of display image, also anti-reflection layer can be set on the surface of the opposition side being formed with adhesive layer 14 side.As the method arranging anti-reflection layer, the method directly forming inorganic thin film on the surface of transparent facestock 10 can be exemplified, the transparent resin film being provided with anti-reflection layer be fitted in the method etc. of baffle 10.In addition, also can carry out painted to a part for transparent facestock 10 or entirety according to object, or the part on the surface of transparent facestock 10 or entirety are made ground glass shape and make light scattering, or a part on the surface of transparent facestock 10 or overall formed trickle concavo-convex etc. and make transmitted light that refraction or reflection occur.In addition, also coloring film, light-diffusing films, light refracting films, optical reflection film etc. can be pasted on a part or the entirety on the surface of transparent facestock 10.
In order to the profile of matched display device, the shape of transparent facestock 10 is generally rectangle.According to the profile of display unit, the baffle of shape that cover the whole display surface of display floater, that comprise curve in outer shape also can be used.
The size of transparent facestock 10 suitably can set matchingly with the profile of display unit.Such as, when display unit is television receiver, size it is suitable that 0.5m × more than the 0.4m of transparent facestock 10, particularly preferably 0.7m × more than 0.4m.The upper limit of the size of transparent facestock 10 depends on the size of display floater mostly.In addition, oversize display unit not easily carries out the operations such as installation.Due to these restrictions, the upper limit of the size of baffle 10 is generally about 2.5m × 1.5m.
Consider from the angle of mechanical strength, the transparency, during for glass plate, the thickness of transparent facestock 10 is preferably 0.5 ~ 25mm.In the purposes such as television receiver, PC display of indoor use, considering from the light-weighted angle of display unit, be preferably 1 ~ 6mm, being arranged in outdoor public display purposes, being preferably 3 ~ 20mm.When using chemically reinforced glass, consider from the angle of intensity, the thickness of glass is preferably about 0.5 ~ 1.5mm.When for transparent resin plate, the thickness of transparent resin plate is preferably 2 ~ 10mm.
< shading Printing Department >
The Wiring member etc. be connected with display floater is sheltered by shading Printing Department 12, thus the part beyond the image display area making cannot to observe following display floater from transparent facestock 10 side.Shading Printing Department 12 can be formed in and be formed with the side of adhesive layer 14 or the surface of its opposition side.Considering from the angle of the parallax reducing shading Printing Department 12 and image display area, is better form shading Printing Department 12 on the surface of the side being formed with adhesive layer 14.When transparent facestock 10 is glass plate, if adopt the ceramic printing comprising black pigment to shading Printing Department 12, then light-proofness is good, therefore preferably.When shading Printing Department is formed at the opposition side of the side being formed with adhesive layer, also can by the hyaline membrane being previously provided with shading Printing Department be fitted in baffle to be formed.Also the film circumference of hyaline membrane in the one side fitting in baffle can be provided with shading Printing Department, the most surface at its back side, i.e. display unit being provided with anti-reflection layer fits in baffle.The Wiring members of display floater etc. are sheltering from other components such as the frameworks of observing structure or the shown device side of display floater cannot observed, or when the transparent facestock 1 of plane materiel with band adhesive layer of being fitted beyond display floater being fitted, sometimes in transparent facestock 10, do not form shading Printing Department 12.
< adhesive layer >
Adhesive layer 14 comprises along the superimposed portions 18 of the extended surface of transparent facestock 10, is connected and the shape portion, weir 20 superimposed portions 18 surrounded with the periphery of superimposed portions 18.
Superimposed portions 18 is by making superimposed portions form the part formed with the solidfied material (transparent resin) that hardening resin composition (being sometimes also denoted as below " the first composition ") is solidified to form.
Shape portion, weir 20 forms by coating shape portion, weir the part formed with hardening resin composition (being sometimes also denoted as below " the second composition "), the solidfied material (transparent resin) that makes it be solidified to form.
The feature of the transparent facestock 1 with adhesive layer is, the difference (W1-W2) of the content W2 represented with quality % of non-curable oligomer in the content W1 represented with quality % of the non-curable oligomer (II) in following superimposed portions 18 and shape portion, weir 20 (II ') is below 40.
If described difference (W1-W2) is below 40, the difference of the content of non-curable oligomer in the content of the non-curable oligomer (II) then in superimposed portions and shape portion, weir (II ') is little, can suppress non-curable oligomer (II) from superimposed portions to the diffusion in shape portion, weir.Therefore, even if become the duplexer that superimposed portions and shape portion, weir also not easily have problems after certain hour.
Described difference (W1-W2) below 40, preferably less than 30, more preferably less than 10, particularly preferably less than 5.In addition, (W1-W2) is preferably greater than 0 (i.e. W1>W2).
When solidfied material for hardening resin composition, carry out in the region being determined at more than the outermost perimembranous 2cm apart from nearest shape portion, weir in superimposed portions of the content W1 of the non-curable oligomer (II) in superimposed portions.In addition, carry out in the region that the distance be determined at apart from the outermost perimembranous in shape portion, weir of the content W2 of non-curable oligomer in weir shape portion (II ') is equivalent to the half of the height in this shape portion, weir.
By the measurement site in superimposed portions is decided to be above-mentioned zone, the impact of the diffusion of the non-curable oligomer (II) of the near interface in superimposed portions and shape portion, weir can be got rid of.In addition, by the measurement site in shape portion, weir is decided to be above-mentioned zone, even if the outermost perimembranous in shape portion, weir contacts with ambient atmos and solidifies deficiency, its impact can also be got rid of.
In addition, can using the content W1 of the content of the non-curable oligomer (II) in the first composition as the non-curable oligomer (II) in superimposed portions.Similarly, can using the content W2 of the content of the non-curable oligomer (II ') in the second composition as the non-curable oligomer (II ') in shape portion, weir.
[superimposed portions]
The first composition forming superimposed portions 18 both can be Photocurable resin composition, also can be hot curing resin composition.As superimposed portions 18, from can low-temperature setting and the fast angle of curing rate consider, preferably comprise the solidfied material of the Photocurable resin composition of curability compound and Photoepolymerizationinitiater initiater (C1).In addition, if the first composition is Photocurable resin composition, then because solidification does not need high temperature, the possibility of the damage of the display floater therefore caused by high temperature, touch-screen etc. is also less.
First composition of photo-curable preferred in the present invention is described.First composition of photo-curable is the composition comprising curability compound (I), non-curable oligomer (II) and Photoepolymerizationinitiater initiater (C1).In addition, the first composition can contain additive as required.
The viscosity of the first composition preferably at 25 DEG C is at more than 0.05Pas, and the viscosity at 40 DEG C is at below 50Pas, and the viscosity more preferably at 25 DEG C is at more than 0.2Pas, and the viscosity at 40 DEG C is at below 10Pas.If the viscosity at 25 of the first composition DEG C is more than lower limit, when then obtaining superimposed portions by following decompression laminating method, until the coating shape becoming the first composition of superimposed portions before stacked is kept, independently space is easily become when returning under atmospheric pressure atmosphere after stacked, due to the pressure (keep decompression) in space and the pressure differential of pressure (atmospheric pressure) putting on adhesive layer, the volume in space reduces, space evanescence, therefore can obtain the cured film that bubble-free is residual.If the viscosity at 40 of the first composition DEG C is below higher limit, then the mobility of the first composition is high, therefore not easily residual clearance in superimposed portions.The viscosity E type viscosimeter of the first composition measures.
The viscosity of the first composition is by the molecular weight of non-curable oligomer (II) and regulate containing proportional.In addition, also by regulating the molecular weight of oligomer (A) and regulating containing proportional.
(curability compound (I))
The molecular weight that curability compound (I) in first composition comprises urethane acrylate oligomer (A) (noting work " oligomer (A) " below by abridging) and has more than a 1 curability functional group lower than 600 monomer (B).Curability compound (I) is preferably made up of oligomer (A) and monomer (B).
Monomer (B) preferably comprises the monomer (B1) with hydroxyl.In the superimposed portions be made up of the solidfied material of the first composition comprising monomer (B1), there is this hydroxyl remaining.The stabilisation having the non-curable oligomer (II) helped in superimposed portions of this hydroxyl.
Oligomer (A):
The number-average molecular weight of oligomer (A) is preferably 1000 ~ 100000, is more preferably 10000 ~ 70000, is particularly preferably 10000 ~ 40000.If the number-average molecular weight of oligomer (A) is within the scope of this, then the easy viscosity by the first composition is adjusted to above-mentioned scope.
The number-average molecular weight of oligomer (A) is the number-average molecular weight being measured the polystyrene conversion obtained by gel permeation chromatography (GPC).In addition, this peak value when there is the peak value of unreacted low molecular weight compositions (monomer etc.), forecloses and obtains number-average molecular weight in measuring by GPC.
Oligomer (A) has acryloxy.
Consider from the angle of the mechanical property of the curability of the first composition, superimposed portions, the average of the acryloxy that every 1 molecule of oligomer (A) is corresponding is preferably 1.8 ~ 4.
Oligomer (A) can be a kind, also can be two or more.
As oligomer (A), preferred following urethane acrylate oligomer (A1) (being denoted as below " oligomer (A1) ").
Oligomer (A1): polyalcohol and polyisocyanates are reacted, obtains after end has the prepolymer of NCO, making the urethane acrylate oligomer that the NCO of this prepolymer and following monomer (a1) react and obtain.
Monomer (a1): molecular weight is 125 ~ 600, there is the acryloxy of more than 1 and have 1 with the monomer of the group of isocyanates radical reaction.
As monomer (a1), the monomer of group (hydroxyl, amino etc.) and the acryloxy had containing reactive hydrogen can be exemplified.
As the concrete example of monomer (a1), the acrylic acid hydroxy alkyl ester (2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, acrylic acid-2-hydroxybutyl, acrylic acid-4-hydroxybutyl etc.) etc. of the hydroxyalkyl with carbon number 2 ~ 6 can be exemplified.
As the monomer (a1) reacted with described prepolymer, preferably there is the acrylic acid hydroxy alkyl ester of the hydroxyalkyl of carbon number 2 ~ 4.
As polyalcohol and polyisocyanates, known compound can be used, the raw material as carbamate quasi-oligomer (a) and the polyalcohol (i), vulcabond (ii) etc. recorded recorded in such as No. 2009/016943rd, International Publication can be exemplified.
As the concrete example of polyalcohol, polyoxyalkylene polyol (polyoxyethylene glycol, polyoxypropylene polyol etc.), PEPA, polycarbonate polyol etc. can be exemplified.Wherein, as polyalcohol, preferred polyoxyalkylene polyol, more preferably polyoxypropylene polyol.In addition, if a part for the oxypropylene group of polyoxypropylene polyol is substituted by oxyethylene group, then the intermiscibility with other composition of the first composition can be improved, therefore more preferably.
Polyalcohol can be used alone a kind, also can two or more also use.
As polyisocyanates, be preferably selected from aliphatic diisocyanate, alicyclic diisocyanate and at least one vulcabond without xanthochromia aromatic diisocyanate.
As aliphatic polyisocyante, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanates, 2,4,4-trimethyl hexamethylene diisocyanates etc. can be exemplified.
As alicyclic polyisocyanates, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (another name: IPDI), di-2-ethylhexylphosphine oxide (4-cyclohexyl isocyanate) etc. can be exemplified.
As without xanthochromia aromatic diisocyanate, XDI etc. can be exemplified.
Polyisocyanates can be used alone a kind, also can two or more also use.
In the synthesis of oligomer (A1), following monomer (a2) can be used as diluent.Diluent remains in the oligomer (A1) of gained, becomes a part of monomer (B) in curability compound (I).
Monomer (a2): molecular weight is 125 ~ 600, has the curability functional group of more than 1 and do not have the monomer with the group of isocyanates radical reaction.
As monomer (a2), preferred following monomer (B21).
Monomer (B):
The molecular weight of monomer (B) is less than 600, is preferably more than 125 and be less than 600, and more preferably 140 ~ 400.The molecular weight of monomer (B) is less, then the adaptation of transparent facestock and superimposed portions is better.If the molecular weight of monomer (B) is more than lower limit, then can suppress the volatilization by the monomer (B) during following decompression laminating method manufacture display unit.
Monomer (B) can be a kind, also can be two or more.
The quantity of the curability functional group that every 1 molecule of monomer (B) is corresponding is more than 1, from the curability of the first resin combination 26, the first resin combination 26 is solidified and the angle of the mechanical property of superimposed portions 18 that obtains is considered, is preferably 1 ~ 3.In curability compound (I), be more preferably that monomer (B) and the curability functional group of 1 is the monomer (B) of more than 2 and uses by curability functional group.
As the curability functional group of monomer (B), the combination etc. of the unsaturated group (acryloyl group, methacryl, acryloxy, methacryloxy etc.) of addition polymerization, unsaturated group and sulfydryl can be exemplified.As the curability functional group of monomer (B), the angle fast from curing rate is considered with the angle obtaining transparent high superimposed portions, be preferably selected from the group of acryloxy and methacryloxy, the angle of little from reactive difference of the curability functional group of oligomer (A) and monomer (B), to obtain homogeneous superimposed portions is considered, particularly preferably methacryloxy.
Monomer (B1) contributes to the stabilisation of non-curable oligomer (II).In addition, by containing monomer (B1), the good adaptation of transparent facestock and superimposed portions can be obtained.
The hydroxyl value that monomer (B1) has is preferably 1 or 2.
As the monomer (B1) with 1 hydroxyl, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-2-hydroxybutyl, (methyl) acrylic acid-4-hydroxybutyl, the own ester of methacrylic acid-6-hydroxyl etc. can be exemplified.
As the monomer (B1) with 2 hydroxyls, glycerin monomethyl acrylic ester, acrylic acid-2,3-dihydroxy propyl ester etc. can be exemplified.
As monomer (B1), preferably there is the hydroxyl-metacrylate (methacrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxybutyl, methacrylic acid-4-hydroxybutyl etc.) of hydroxyalkyl of hydroxyl value 1 ~ 2, carbon number 3 ~ 8, particularly preferably methacrylic acid-2-hydroxybutyl.
Monomer (B1) can be a kind, also can be two or more.
In addition, as monomer (B), following monomer (B2) can be comprised.
Monomer (B2): there is the curability functional group of more than 1, molecular weight is less than 600, do not have the monomer of hydroxyl.
Monomer (B2) contributes to the flexibility of giving superimposed portions.
As monomer (B2), preferred following monomer (B21).If the content of monomer (B21) is more than the content of monomer (B1) by quality ratio, after then the plane materiel of being fitted such as duplexer and display floater being formed with adhesive layer in transparent facestock being fitted under reduced atmosphere, when being returned under atmospheric pressure atmosphere, there is the tendency of the time shorten needed for the disappearance of space produced in adhesive layer.On the other hand, if containing monomer (B21), then have the tendency that the time needed for the solidification of the first composition is elongated.
Monomer (B21): not there is hydroxyl, there is the alkyl of carbon number 8 ~ 22 or the methacrylate of cyclic alkyl.
As monomer (B21), can exemplified by methyl acrylic acid dodecyl ester, methacrylic acid n-octadecane base ester, methacrylic acid n-docosane base ester, isobornyl methacrylate, adamantylmethacrylate etc.As monomer (B21), preferable methyl acrylic acid dodecyl ester, methacrylic acid n-octadecane base ester.
Monomer (B2) can be a kind, also can be two or more.
Relative to the total amount (100 quality %) of the oligomer (A) in the first composition and monomer (B), the ratio of oligomer (A) is preferably 20 ~ 90 quality %, is more preferably 30 ~ 80 quality %.If the ratio of this oligomer (A) is more than lower limit, then the heat resistance of superimposed portions is good.If the ratio of this oligomer (A) is below higher limit, then the curability of the first composition and the adaptation of transparent facestock and superimposed portions good.
Relative to the total amount (100 quality %) of the oligomer (A) in the first composition and monomer (B), the ratio of monomer (B) is preferably 10 ~ 80 quality %, is more preferably 20 ~ 70 quality %.
Relative to the total amount (100 quality %) of the oligomer (A) in the first composition and monomer (B), the ratio of monomer (B1) is preferably 10 ~ 60 quality %, is more preferably 20 ~ 50 quality %.If the ratio of described monomer (B1) is more than lower limit, then the stability of the first composition and the adaptation of transparent facestock and superimposed portions good.
Relative to the total amount (100 quality %) of the oligomer (A) in the first composition and monomer (B), the ratio of monomer (B2) is preferably 5 ~ 50 quality %, is more preferably 15 ~ 40 quality %.If the ratio of described monomer (B2) is more than lower limit, then easily fully obtain the additive effect of monomer (B2).
In addition, in the synthesis of oligomer (A1), exist with the monomer (a1) of the isocyanates radical reaction of the prepolymer part as oligomer (A), be not therefore included in the ratio of the monomer (B) in the first composition.On the other hand, in the synthesis of oligomer (A1), the monomer (monomer do not reacted with prepolymer) added as diluent when the synthesis of oligomer (A1) or after synthesis is equivalent to monomer (B), this monomer is also contained in the ratio of the monomer (B) in the first composition.
(non-curable oligomer (II))
Non-curable oligomer (II) is not cured reaction with curability compound (I), has the oligomer of hydroxyl when the first composition solidification.But also be that be not also cured reaction with curability compound (I) when following the second composition (i.e. weir shape portion formation hardening resin composition) solidifies, that there is hydroxyl oligomer.
The average hydroxyl number that every 1 molecule of non-curable oligomer (II) is corresponding is preferably 0.8 ~ 3, is more preferably 1.8 ~ 2.3.
The number-average molecular weight (Mn) that every 1 hydroxyl of non-curable oligomer (II) is corresponding is preferably 400 ~ 8000.If the number-average molecular weight that every 1 hydroxyl is corresponding is more than 400, then the polarity of non-curable oligomer (II) can not be too high, easily obtains the good intermiscibility with the curability compound (I) in the first composition.If the number-average molecular weight that every 1 hydroxyl is corresponding is less than 8000, then owing to being derived from the interaction between the hydroxyl of curability compound (I) and the hydroxyl of non-curable oligomer (II), easily obtain the effect making non-curable oligomer (II) stabilisation in superimposed portions after hardening.Can infer in this interaction has hydrogen bond to participate in.In addition, if number-average molecular weight corresponding to every 1 hydroxyl is less than 8000, then by making it be included in the first composition, the viscosity of the first composition can be reduced.
Non-curable oligomer (II) can be used alone a kind, also can two or more also use.
As non-curable oligomer (II), the polyalcohol etc. of HMW can be exemplified.As non-curable oligomer (II), preferred polyoxyalkylene polyol, PEPA, polycarbonate polyol.
As polyoxyalkylene polyol, the polyoxyalkylene diols such as polyoxyethylene glycol, polyoxypropylene diols, polyoxypropylene triol, polyoxytetramethylene glycol can be exemplified.
The number-average molecular weight (Mn) that every 1 hydroxyl of polyoxyalkylene polyol is corresponding is preferably 400 ~ 8000, is more preferably 600 ~ 5000.
As PEPA, the aliphatic category polyester diol etc. of the residue of residue and the aliphatic dicarboxylic acid (glutaric acid, adipic acid, decanedioic acid etc.) with aliphatic dihydroxy alcohol (ethylene glycol, propane diols, BDO etc.) can be exemplified.
The number-average molecular weight (Mn) that every 1 hydroxyl of PEPA is corresponding is preferably 400 ~ 8000, is more preferably 800 ~ 6000.
As polycarbonate polyol, the aliphatic polycarbonate diol etc. such as the aliphatic polycarbonate diol of residue, the ring-opening polymerization polymer of aliphatic cyclic carbonic ester with dihydroxylic alcohols (1,6-hexylene glycol etc.) can be exemplified.
The number-average molecular weight (Mn) that every 1 hydroxyl of polycarbonate polyol is corresponding is preferably 400 ~ 8000, is more preferably 800 ~ 6000.
The number-average molecular weight of the non-curable oligomer (II) in this description is according to average hydroxyl number Q corresponding to every 1 molecule of the hydroxyl value P (mgKOH/g) measured for benchmark with JIS K1557-1 (version in 2007) and non-curable oligomer (II), the value that calculated by following formula (1).
Molecular weight=56.1 × Q × the 1000/P of non-curable oligomer (II) ... (1)
The angle more easily reduced from the elastic modelling quantity of the superimposed portions after solidification is considered, as non-curable oligomer (II), preferred use polyoxyalkylene polyol, preferred use has polyoxyethylene polyoxypropylene polyalcohol or the polyoxypropylene polyol of oxypropylene group and oxyethylene group, the angle low from viscosity is considered, particularly preferably polyoxypropylene polyol.
In addition, in the present invention, from making the angle that is stable, that suppress non-curable oligomer (II) to be separated from the superimposed portions after solidification of the superimposed portions before solidification consider, oligomer (A) and non-curable oligomer (II) are better have identical structure or the strand of similar.
Specifically, as the raw material of the oligomer (A) in the first composition, preferred use has the compound (being denoted as below " hydroxy-containing compounds ") of hydroxyl, and uses identical hydroxy-containing compounds as non-curable oligomer (II).
In first composition, consider from the angle of intermiscibility, particularly preferably oligomer (A) is the urethane acrylate oligomer using polyoxyalkylene polyol and polyisocyanates to synthesize as raw material, and non-curable oligomer (II) is polyoxyalkylene polyol.
When the hydroxy-containing compounds used as the raw material of oligomer (A) is different from the hydroxy-containing compounds used as non-curable oligomer (II), these hydroxy-containing compounds are also better that strand each other has common repetitive etc., part has common structure, and polarity degree is identical.As long as oligomer (A) and non-curable oligomer (II) some there is identical molecular structure, then the intermiscibility of the non-curable oligomer (II) in composition is higher.
As the method for adjustment of the polarity of hydroxy-containing compounds, the method such as introducing polar group, the method making the hydroxy-containing compounds with oxypropylene group and oxyethylene group can be exemplified.If introducing polar group, then the polarity of hydroxy-containing compounds improves.In addition, if make the hydroxy-containing compounds with oxypropylene group and oxyethylene group, then the polarity of hydroxy-containing compounds improves.These methods also can combinationally use.
The preferred compositions when hydroxy-containing compounds used as the raw material of oligomer (A) is different from the hydroxy-containing compounds used as non-curable oligomer (II) can exemplify following combination.
The combination of oligomer (A) and non-curable oligomer (II): this oligomer (A) is the urethane acrylate oligomer using the polyoxyethylene polyoxypropylene polyalcohol with oxypropylene group and oxyethylene group and polyisocyanates to synthesize as raw material, this non-curable oligomer (II) does not have oxyethylene group and the little polyoxypropylene polyol of the polyalcohol that uses as oligomer (A) of molecular weight ratio corresponding to every 1 hydroxyl.
As the combination of the curability compound (I) comprised in the first composition with non-curable oligomer (II), most preferably comprise the curability compound (I-1) of following oligomer (A12) and monomer (B1) and the combination of following non-curable oligomer (II-1).
Oligomer (A12): the polyoxyethylene polyoxypropylene glycol and the polyisocyanates that make to have oxypropylene group and oxyethylene group react, obtain after end has the prepolymer of NCO, reacting with described monomer (a1) and the urethane acrylate oligomer obtained.
Non-curable oligomer (II-1): identical with the raw material of oligomer (A12), that there is oxypropylene group and oxyethylene group polyoxyethylene polyoxypropylene glycol.
In addition, as the combination of the curability compound (I) comprised in the first composition with non-curable oligomer (II), also preferably comprise the curability compound (I-1) of following oligomer (A12) and monomer (B1) and the combination of following non-curable oligomer (II-2).
Non-curable oligomer (II-2): not there is oxyethylene group and the polyoxypropylene diols less than the molecular weight of the raw material polyoxyethylene polyoxypropylene glycol of oligomer (A12).
Non-curable oligomer (II) in first composition contribute under reduced atmosphere by the duplexer being formed with adhesive layer in transparent facestock with fitted by plane materiel of fitting after return under atmospheric pressure atmosphere time, to be disappeared by the space that the interface of fit plane materiel and adhesive layer produces needed for the shortening of time.
The content of the non-curable oligomer (II) in the first composition (100 quality %) is preferably 10 ~ 70 quality %, is more preferably 26 ~ 60 quality %.If the content of non-curable oligomer (II) is more than lower limit, then not easily remaining space in adhesive layer.If the content of non-curable oligomer (II) is below higher limit, then the superimposed portions of adhesive layer is easily fully solidified.If superimposed portions is fully solidified, then easy by diaphragm from solidification after adhesive layer peel off.
In addition, chain-transferring agent also contribute to being disappeared by space that the interface of fit plane materiel and adhesive layer produces needed for the shortening of time.
In addition, if comprise monomer (B2) or chain-transferring agent in the first composition, then have the tendency that curing rate slows down, therefore the consumption of monomer (B2) and chain-transferring agent is more few better.Monomer (B2) in first composition is less than 0.6 relative to the mass ratio of monomer (B1), and when not containing chain-transferring agent, the content of the non-curable oligomer (II) in the first composition (100 quality %) is preferably 40 ~ 70 quality %, is more preferably 50 ~ 70 quality %.
First composition containing chain-transferring agent, be 0.6 ~ 2.5 containing monomer (B1) and monomer (B2), monomer (B2) relative to the mass ratio of monomer (B1) when, the content of the non-curable oligomer (II) in the first composition (100 quality %) is more preferably 30 ~ 70 quality %, more preferably 40 ~ 70 quality %.
First composition contain relative to the curability compound (I) of 100 mass parts be the chain-transferring agent of below 1 mass parts, the content of monomer (B2) be less than monomer (B1) when, the content of the non-curable oligomer (II) in the first composition (100 quality %) is preferably 40 ~ 70 quality %, is more preferably 50 ~ 70 quality %.
First composition contain monomer (B1) and monomer (B2), monomer (B2) relative to the mass ratio of monomer (B1) be 1 ~ 3, containing when being the chain-transferring agent of below 1 mass parts relative to the curability compound (I) of 100 mass parts, the content of the non-curable oligomer (II) in the first composition (100 quality %) is more preferably 5 ~ 55 quality %, more preferably 10 ~ 50 quality %, are particularly preferably 35 ~ 50 quality %.
In addition, forming when being made up of oligomer (A), monomer (B) and non-curable oligomer (II) as the first composition, in oligomer (A): monomer (B): the ratio containing proportional (quality %) of non-curable oligomer (II) is preferably 6 ~ 80:3 ~ 70:10 ~ 70.
If within the scope of this, then the first composition can have suitable viscosity.
(Photoepolymerizationinitiater initiater (C1))
As Photoepolymerizationinitiater initiater (C1), the Photoepolymerizationinitiater initiater such as acetophenone class, ketal class, benzoin or benzoin ethers, phosphinoxides, Benzophenones, thioxanthene ketone, quinones can be exemplified.As Photoepolymerizationinitiater initiater (C1), the Photoepolymerizationinitiater initiater of preferential oxidation phosphine class, thioxanthene ketone, from the viewpoint of suppressing painted after photopolymerization reaction, particularly preferably phosphinoxides.
The content of the Photoepolymerizationinitiater initiater (C1) in the first composition of photo-curable is preferably 0.01 ~ 10 mass parts relative to total amount 100 mass parts of oligomer (A) and monomer (B), is more preferably 0.1 ~ 5 mass parts.
(additive)
As additive, polymerization inhibitor, photocuring promoter, chain-transferring agent, light stabilizer (ultra-violet absorber, scavenger of free radicals etc.), antioxidant, fire retardant, cementability improving agent (silane coupler etc.), pigment, dyestuff etc. can be exemplified.As the additive added in the first composition, preferred polymerization inhibitor, light stabilizer.Particularly by containing polymerization inhibitor with the amount being less than polymerization initiator, the stability of the first composition can be improved, the molecular weight of the superimposed portions after solidification can also be adjusted.
As polymerization inhibitor, the polymerization inhibitors such as hydroquinones (2,5-di-tert-butyl hydroquinone etc.), pyrocatechol (p-tert-butyl catechol etc.), Anthraquinones, phenothiazines, hydroxy-methylbenzene class can be exemplified.
As light stabilizer, ultra-violet absorber (benzotriazole, Benzophenones, salicylate class etc.), scavenger of free radicals (hindered amines) etc. can be exemplified.
As antioxidant, compound etc. that is Phosphorus, sulphur class can be exemplified.
The content of the additive in the first composition is preferably below 10 mass parts relative to total amount 100 mass parts of oligomer (A) and monomer (B), is more preferably below 5 mass parts.
If containing chain-transferring agent in the first composition, then have with transparent facestock on be formed with being fitted by plane materiel of fitting of adhesive layer time the space that produces disappear needed for the tendency of time shorten.Therefore, if usage chain transfer agent, then can reduce in order to obtain this space is disappeared well effect needed for the addition of non-curable oligomer (II).If the addition of non-curable oligomer (II) is few, then the difference of the cure shrinkage of weir shape portion and superimposed portions easily reduces.On the other hand, considering from the angle obtaining good curing rate, is better not containing chain-transferring agent, or only containing a small amount of chain-transferring agent.
Be preferably below 1 mass parts containing addition during chain-transferring agent relative to total amount 100 mass parts of oligomer (A) and monomer (B), be more preferably below 0.5 mass parts.
The thickness of superimposed portions 18 is preferably 0.03 ~ 2mm, is more preferably 0.1 ~ 0.8mm.If the thickness of superimposed portions 18 is more than lower limit, then the impact etc. that the external force that superimposed portions 18 can cushion origin self-induced transparency plane materiel 10 side effectively causes, can protect display floater.In addition, even if be mixed into the foreign matter of the thickness being no more than superimposed portions 18 when being fitted with the transparent facestock 1 of band adhesive layer by laminating plane materiel by display floater etc. between which, also can not there is larger change in the thickness of superimposed portions 18, thus little on the impact of optical transmittance property.If the thickness of superimposed portions 18 is below higher limit, then not easily residual clearance in superimposed portions 18, and when making display unit, the thickness of entirety can be thickening necessarily.
Storage shear modulus at 35 DEG C of superimposed portions 18 is preferably 1.0 ~ 100kPa.The higher limit of the above-mentioned storage shear modulus of superimposed portions 18 is more preferably 25kPa, is more preferably 12kPa further.If storage shear modulus is at more than 1.0kPa, then easily maintain the shape of superimposed portions 18.In addition, even if when the thickness of superimposed portions 18 is thicker, whole superimposed portions 18 also can maintain thickness equably, by the transparent facestock 1 of band adhesive layer with when being fitted by fitting body, is not easily being produced space, therefore preferably by the interface of fitting body and adhesive layer 14.On the other hand, if storage shear modulus is at below 100kPa, then under reduced atmosphere by the transparent facestock 1 of band adhesive layer with fit by fitting body afterwards, returned under atmospheric pressure atmosphere time, disappeared at short notice by the space that the interface of fitting body and adhesive layer 14 produces, not easily remaining, therefore preferably.
[shape portion, weir]
The second composition forming shape portion, weir 20 both can be Photocurable resin composition, also can be hot curing resin composition.As shape portion, weir 20, from can low-temperature setting and the fast angle of curing rate consider, preferably comprise the solidfied material of the Photocurable resin composition of curability compound and Photoepolymerizationinitiater initiater (C2).In addition, if the second composition is Photocurable resin composition, then because solidification does not need high temperature, the display floater therefore caused by high temperature, touch-screen etc. are also less by the possibility of the damage of laminating plane materiel.
In addition, also can coat with the second composition of the first composition same composition of using in the formation of superimposed portions the circumference on the surface of transparent facestock and make its semi-solid preparation, as the uncured shape portion, weir before solidification in following operation (d).
Second composition of photo-curable preferred in the present invention is described.Second composition of photo-curable is the composition comprising curability compound (I '), non-curable oligomer (II ') and Photoepolymerizationinitiater initiater (C2).
In addition, the second composition can contain additive as required.
Viscosity at 25 DEG C of second composition is preferably 10 ~ 3000Pas, is more preferably 300 ~ 3000Pas, is more preferably 500 ~ 2800Pas, more preferably 800 ~ 2500Pas, is particularly preferably 1000 ~ 2000Pas.If the viscosity at 25 of the second composition DEG C is more than lower limit, then easily the long period maintains the shape in uncured shape portion, weir, easily fully maintains the height in uncured shape portion, weir.If the viscosity of the second composition is below higher limit, then form uncured shape portion, weir by coating.
In addition, even if the viscosity when the coating of the second composition forming uncured shape portion, weir is less than 300Pas, if the second composition is Photocurable composition, as long as then by irradiating light immediately after coating, make the viscosity in the postradiation uncured shape portion, weir of light reach above-mentioned preferable range.Consider from the complexity of coating, the viscosity during coating of the second composition is preferably below 300Pas, is more preferably below 200Pas.The viscosity of the second composition does not now have special lower limit, is preferably more than 0.01Pas.
The viscosity of the second composition measures with E type viscosimeter at 25 DEG C.
(curability compound (I '))
The molecular weight that curability compound (I ') comprises urethane acrylate oligomer (A ') (noting work " oligomer (A ') " below by abridging) and has more than a 1 curability functional group lower than 600 monomer (B ').Curability compound (I ') is preferably made up of oligomer (A ') and monomer (B ').
As oligomer (A '), monomer (B '), oligomer, the monomer enumerated in such as oligomer (A), monomer (B) can be exemplified.
In addition, as oligomer (A '), from the curability of the second composition, make the second composition solidification and the angle consideration of the mechanical property in shape portion, weir 20 that obtain, preferably every 1 molecule on average has the oligomer of 1.8 ~ 4 curability groups.
Monomer (B ') preferably comprise the monomer (B ' 1) with hydroxyl.In the shape portion, weir be made up of the solidfied material of the second composition comprising monomer (B ' 1), there is this hydroxyl remaining.The having of this hydroxyl helps the stabilisation of non-curable oligomer in shape portion, weir (II ').In addition, as the curability functional group of monomer (B ' 1), preferred acryloxy.
In addition, monomer (B ') can comprise the monomer (B ' 2) beyond monomer (B ' 1).As monomer (B ' 2), the compound identical with monomer (B2) can be exemplified, but with monomer (B2) unlike, methacrylate is also same with acrylate can be enumerated as preferred compound.In addition, the diluent that monomer (B ' 2) is same with monomer (B2) when can synthesize as oligomer (A ') uses.
As monomer (B2 '), (methyl) acryloxy, the molecular weight preferably with more than 1 are less than 600, do not have the monomer of hydroxyl.Specifically, (methyl) acrylate ((methyl) acrylic acid dodecyl ester, (methyl) acrylic acid n-octadecane base ester, (methyl) acrylic acid n-docosane base ester, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters etc.) of the alkyl such as with carbon number 8 ~ 22 or cyclic alkyl can be exemplified.
The curability compound that uses in second composition (I ') be better identical with the curability compound (I) used in the first composition, but also can be different.
The angle controlled in above-mentioned scope from the easy viscosity by uncured shape portion, weir is considered, the number-average molecular weight of oligomer (A ') is preferably 30000 ~ 100000, be more preferably 40000 ~ 80000, more preferably 50000 ~ 70000, be more preferably 50000 ~ 65000 further.
Number-average molecular weight be the oligomer (A ') of 30000 ~ 100000 because viscosity is high, be therefore difficult to conventional method synthesis, and namely allow to synthesis and be also difficult to mix with monomer (B ').Therefore, when the synthesis of oligomer (A '), better dilute with monomer (B ' 2), under the state that viscosity reduces after synthesis, the product of direct use gained, or the product of gained is diluted with following monomer (B ' 1) further, uses as curability compound (I ').
As the monomer (B ' 1) with hydroxyl, preferably there is hydroxyl value 1 ~ 2, the hydroxy acrylate (2-hydroxypropyl acrylate, acrylic acid-2-hydroxybutyl, acrylic acid-4-hydroxybutyl, the own ester of acrylic acid-6-hydroxyl etc.) of hydroxyalkyl of carbon number 3 ~ 8 or hydroxyl-metacrylate (methacrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxybutyl, metering system-sour 4-hydroxybutyl, own ester of methacrylic acid-6-hydroxyl etc.), particularly preferably acrylic acid-4-hydroxybutyl or methacrylic acid-2-hydroxybutyl.Monomer (B) can use a kind, also can use two or more.
Non-curable oligomer (II ') is not cured reaction with curability compound (I '), has the oligomer of hydroxyl when the second composition solidification.But also be not also cured reaction with curability compound (I), there is the oligomer of hydroxyl when described first composition solidification.
In addition, non-curable oligomer (II ') preferably with non-curable oligomer (II) same or similar oligomer, most preferably identical oligomer.Such as, when be repetitive being the polyoxyalkylene polyol of oxyalkylene group, identical oligomer refers to the oligomer that the kind of repetitive is identical with quantity.When oligomer is made up of the repetitive of variety classes and quantity, oligomer like preferred class.Similar oligomer refers to the oligomer that predominant repeat unit is identical, its quantity is different.As similar oligomer, preferably to comprise be better more than 30 quality %, be more preferably the oligomer of the same repetitive of more than 50 quality %.If use polyoxyalkylene polyol as non-curable oligomer (II), then the elastic modelling quantity in the shape portion, weir 20 after solidification more easily reduces.
Relative to the total amount (100 quality %) of the oligomer (A ') in the second composition and monomer (B '), the ratio of oligomer (A ') is preferably 20 ~ 90 quality %, is more preferably 30 ~ 80 quality %.If the ratio of this oligomer (A ') is more than lower limit, then the heat resistance in weir shape portion is good.If the ratio of this oligomer (A ') is below higher limit, then the curability of the second composition and the adaptation of transparent facestock and superimposed portions good.
When non-curable oligomer (II) in first composition is polyalcohol congener with the polyol phase that uses in oligomer (A '), the ratio of oligomer in the second composition (A ') is fewer, more can suppress non-curable oligomer (II) from superimposed portions to the diffusion in shape portion, weir.
Relative to the total amount (100 quality %) of the oligomer (A ') in the second composition and monomer (B '), the ratio of monomer (B ') is preferably 15 ~ 70 quality %, be more preferably 15 ~ 50 quality %, be more preferably 20 ~ 45 quality %, more preferably 25 ~ 40 quality %.
The content of non-curable oligomer in the second composition (II ') sets with the content of the non-curable oligomer (II) in the first composition, accordingly to make described difference (W1-W2) below the difference of afore mentioned rules.The content of non-curable oligomer in the second composition (II ') is preferably more than 1 quality %, is more preferably more than 2 quality %, is particularly preferably more than 5 quality %.By comprising non-curable oligomer (II ') in the shape portion, weir formed by the second composition, non-curable oligomer (II) can be suppressed from the diffusion of superimposed portions.The content of non-curable oligomer in the second composition (II ') decides according to the content of the non-curable oligomer (II) in the first composition, less than 40 are reached to make described difference (W1-W2), consider from the angle of the adaptation with plane materiel, be preferably below 65 quality %.
In addition, if comprise non-curable oligomer (II ') in the second composition, then, in the adhesive layer formed, the refractive index of shape portion, weir and superimposed portions is close, and the border of shape portion, weir and superimposed portions therefore can be made invisible.
(Photoepolymerizationinitiater initiater (C2))
As the Photoepolymerizationinitiater initiater (C2) comprised in the second composition of photo-curable, the Photoepolymerizationinitiater initiater such as acetophenone class, ketal class, benzoin or benzoin ethers, phosphinoxides, Benzophenones, thioxanthene ketone, quinones can be exemplified.Wherein, as Photoepolymerizationinitiater initiater (C2), the Photoepolymerizationinitiater initiater of preferred acetophenone class, ketal class, benzoin ethers.When using the visible ray of short wavelength to be cured, consider from the angle of absorbing wavelength scope, the more preferably Photoepolymerizationinitiater initiater of phosphinoxides.By also with the Photoepolymerizationinitiater initiater of more than two kinds (C2) that absorbing wavelength scope is different, hardening time can be accelerated further, improve the surface cure in shape portion, weir.
The content of the Photoepolymerizationinitiater initiater (C2) in the second composition of photo-curable is preferably 0.01 ~ 10 mass parts relative to total amount 100 mass parts of oligomer (A ') and monomer (B '), is more preferably 0.1 ~ 5 mass parts.
(additive)
As the additive added in the second composition, can exemplify and the identical additive enumerated in the first composition.As the additive added in the second composition, preferred polymerization inhibitor, light stabilizer.Particularly by containing polymerization inhibitor with the amount being less than polymerization initiator, the stability of the second composition can be improved, the molecular weight in the shape portion, weir after solidification can also be adjusted.
The total amount of these additives is preferably below 10 mass parts relative to total amount 100 mass parts of oligomer (A ') and monomer (B '), is more preferably below 5 mass parts.
Because the exterior lateral area of the image display area of display floater is narrower, therefore in this purposes, preferably the width in shape portion, weir 20 is obtained narrowly.Now, the width in shape portion, weir 20 is preferably 0.5 ~ 2mm, is more preferably 0.8 ~ 1.6mm.
Consider from the angle not easily producing externally open space when being fitted by the transparent facestock 1 of laminating plane materiel and band adhesive layer, the thickness in shape portion, weir 20 is better larger than the thickness of superimposed portions 18.
If the thickness of the Thickness Ratio superimposed portions 18 in shape portion, weir 20 is thick, then as shown in figure 13, when display floater 50 and duplexer 1 are fitted, in the circumference of adhesive layer 14, have space 110 even if remaining on the interface of display floater 50 and adhesive layer 14, this space 110 is also covered by shape portion, weir 20, by this, space 110 can not externally opening, becomes independently space 110.Therefore, by display floater 50 with after being with the transparent facestock 1 of adhesive layer to fit under reduced atmosphere, when being returned under atmospheric pressure atmosphere, due to the pressure (keep decompression) in space 110 and the pressure differential of pressure (atmospheric pressure) putting on adhesive layer 14, the volume in space 110 reduces, and space 110 disappears.
Consider from the angle of the generation suppressing the space caused by the jump of shape portion, weir 20 and superimposed portions 18, the difference of the thickness in shape portion, weir 20 and the thickness of superimposed portions 18 is preferably below 0.05mm, is more preferably below 0.03mm.
The difference of the thickness in shape portion, weir 20 and the thickness of superimposed portions 18 measures the gross thickness in transparent facestock 10 and superimposed portions 18 formed thereon or shape portion, weir 20, tried to achieve by its difference.In addition, the thickness of superimposed portions 18 is the thickness of the circumference of the superimposed portions 18 contacted with shape portion, weir 20.
Storage shear modulus at 35 DEG C of shape portion, weir 20 is better the modulus of shearing that can erect voluntarily with shape portion, weir 20 is lower limit, with 15 times of the storage shear modulus at 35 of superimposed portions 18 DEG C for the upper limit, be specifically preferably 1 ~ 150kPa.By the storage shear modulus at make shape portion, weir 20 35 DEG C at more than 1kPa, shape portion, weir 20 can be made to erect voluntarily.
In addition, the storage shear modulus at 35 DEG C of weir shape portion 20 is better larger than the storage shear modulus at 35 DEG C of superimposed portions 18.If the storage shear modulus in shape portion, weir 20 is larger than the storage shear modulus of superimposed portions 18, then by display floater with when being with the transparent facestock 1 of adhesive layer to fit, in the circumference of adhesive layer 14, space is had even if remaining on the interface of display floater and adhesive layer 14, space is not easily externally opening also, easily becomes independently space.Therefore, by display floater with after being with the transparent facestock 1 of adhesive layer to fit under reduced atmosphere, when being returned under atmospheric pressure atmosphere, due to the pressure (keep decompression) in space and the pressure differential of pressure (atmospheric pressure) putting on adhesive layer 14, the volume in space reduces, space evanescence.
In addition, by less than 15 times of the storage shear modulus of storage shear modulus at 35 DEG C of superimposed portions 18 at make shape portion, weir 20 35 DEG C, by the transparent facestock 1 of band adhesive layer with when being fitted by fitting body, the display inequality caused with the difference of the storage shear modulus of superimposed portions 18 by shape portion, weir 20 can be suppressed.
In addition, the storage shear modulus at 35 DEG C of the shape portion, weir formed by the solidfied material of the resin combination of photo-curable is the value measured by the following method.In addition, the storage shear modulus at 35 DEG C of superimposed portions is also the same value measured.
Storage shear modulus at 35 DEG C of shape portion, weir 20 after solidification uses flow graph (Anton Paar company (Anton paar) system, modularization flow graph Physica MCR-301), make mensuration rotor identical with the thickness in shape portion, weir 20 with the gap of light transmission fixed head, configure the second uncured resin combination in the gap, light needed for solidification is irradiated to the second uncured resin combination, and the storage shear modulus of Simultaneously test solidification process, using the storage shear modulus of the measured value under condition of cure when forming shape portion 20, weir as shape portion, weir 20.
< diaphragm >
For diaphragm 16, require not closely sealed securely with adhesive layer 14, and supporting plane materiel can be pasted in following manufacture method of the present invention.Therefore, as diaphragm 16, be better the tack diaphragm using the one side of the lower base material film of the adaptations such as polyethylene, polypropylene, fluorine-type resin as adhesive surface.
For the test body that the 50mm in 180 degree of disbonded tests under peeling rate 300mm/ minute that carries out acrylic resin board is wide, the bonding force of the adhesive surface of diaphragm 16 is preferably 0.01N ~ 0.1N, is more preferably 0.02N ~ 0.06N.If described bonding force is more than lower limit, then can be pasted on supporting plane materiel.If described bonding force is below higher limit, then easy by diaphragm 16 from supporting plane materiel peel off.
The thickness of diaphragm 16 is different with used resin, when the film using polyethylene, polypropylene etc. more soft, is preferably 0.04 ~ 0.2mm, is more preferably 0.06 ~ 0.1mm.If the thickness of diaphragm 16 is more than lower limit, then, when being peeled off from adhesive layer 14 by diaphragm 16, the distortion of diaphragm 16 can be suppressed.If the thickness of diaphragm 16 is below higher limit, then when peeling off, diaphragm 16 easily bends, and is easily peeled off from adhesive layer 14 by diaphragm 16.
In addition, back layer is set by the back side of the opposition side of the adhesive surface at diaphragm 16, the stripping of auto-adhesive layer 14 can also be made easier.Layer also preferably uses the film that the adaptations such as polyethylene, polypropylene, fluorine-type resin are lower overleaf.In order to make the stripping of diaphragm 16 be more prone to, also the releasing agents such as siloxanes can be coated with not causing in dysgenic scope adhesive layer 14 on diaphragm 16.In addition, be more preferably and barrier layer is set in a part for diaphragm, be mixed in adhesive layer 14 through diaphragm 16 to prevent the gas (oxygen, nitrogen, steam etc.) from outside.
< action effect >
In the transparent facestock of band adhesive layer of the present invention, the difference (W1-W2) of the content W2 (quality %) of (II ') is below 40 because the non-curable oligomer comprised in the content W1 (quality %) of the non-curable oligomer (II) comprised in superimposed portions and shape portion, weir, so after fitting with plane materiel of being fitted, even if through certain hour, superimposed portions and shape portion, weir also not easily have problems, and can improve the reliability of product.
Other form > of <
In addition; the example of the transparent facestock 1 of the band adhesive layer of illustrated example to be transparent facestock the be baffle of display unit; but the transparent facestock of band adhesive layer of the present invention is not limited to illustrated example, as long as be formed with the transparent facestock of the band adhesive layer of specific adhesive layer on the surface of at least one party of transparent facestock.
Such as, the transparent facestock of band adhesive layer of the present invention can be the transparent facestock of the band adhesive layer being all formed with specific adhesive layer on the two sides of transparent facestock.
In addition; in the transparent facestock of band adhesive layer of the present invention, polarization unit (membranaceous absorption-type polarizer, wire grid polarizers etc.), light-modulating cell (1/4 wavelength plate equiphase difference film, pattern are processed into the phase retardation film etc. of strip) etc. can be set between transparent facestock (baffle) and specific adhesive layer.
" manufacture method of the transparent facestock of band adhesive layer "
The manufacture method with the transparent facestock of the band adhesive layer of the present invention of diaphragm is the method comprising following operation (a) ~ (e).
A () is coated with the second aqueous composition in the circumference on the surface of transparent facestock, form the operation in uncured shape portion, weir.
B () supplies the operation of the first aqueous composition in the region surrounded by uncured shape portion, weir on transparent facestock surface.
C () is under reduced atmosphere; on the first composition; superpose the supporting plane materiel being pasted with diaphragm in the mode making diaphragm contact with the first composition, obtain the operation of the precursor duplexer that the uncured superimposed portions that is made up of the first composition is sealed by transparent facestock, diaphragm and the uncured shape portion, weir that is made up of the second composition.
D precursor duplexer is being placed under the state under the pressure atmosphere higher than described operation (c) by (), make uncured superimposed portions and the solidification of shape portion, weir, form the operation with the adhesive layer in superimposed portions and shape portion, weir.
E operation that supporting plane materiel is peeled off from diaphragm by ().
Manufacture method of the present invention is following method: under reduced atmosphere, encloses the first composition between transparent facestock and the diaphragm being pasted on supporting plane materiel, under the inferior high pressure atmosphere of atmospheric pressure atmosphere, makes the first composition solidification of inclosure, forms superimposed portions.As the method for under reduced pressure enclosing the first composition; be not to transparent facestock and be pasted on supporting plane materiel diaphragm gap flat space in inject the method for the first composition; but adopt almost whole surface supply the first composition to transparent facestock; then superposition is pasted on the diaphragm of supporting plane materiel, to the method for enclosing the first composition between transparent facestock and the diaphragm being pasted on supporting plane materiel.
The example utilizing the solidification of the hardening resin composition under the inclosure of the hardening resin composition under decompression and atmospheric pressure atmosphere to manufacture the method for Sparent laminate is known.Such as, the hardening resin composition used in the manufacture method of Sparent laminate and this manufacture method is described in No. 2008/81838th, International Publication, No. 2009/16943rd, International Publication.The manufacture method recorded in these documents can be adopted in the manufacture of the transparent facestock of band adhesive layer of the present invention.
Below, for the manufacture method with the transparent facestock 1 of the band adhesive layer of diaphragm 16 of Fig. 1, accompanying drawing is utilized to be specifically described.
< operation (a) >
As shown in Figures 2 and 3, along the shading Printing Department 12 second aqueous composition of photo-curable such as coating such as distributor 30 grade of the circumference of transparent facestock 10, uncured shape portion, weir 20A is formed.
The coating of the second composition is undertaken by using printing machine, distributor etc.
Operation (a) is such as shown in Fig. 4 and Fig. 5; the device of structure distributor 30 being moved horizontally in the almost gamut on the surface of baffle 10 by horizontal mobile mechanism 3 can be used to implement, and this horizontal mobile mechanism 3 is made up of a pair feed screw 32 and the feed screw 34 orthogonal with a pair feed screw 32.
Uncured shape portion, weir 20A can be the uncured state not being cured reaction completely, also can be the state of partially cured semi-solid preparation.When second composition is Photocurable resin composition, partially cured being penetrated by illumination of uncured shape portion, weir 20A is carried out.Such as, irradiate the visible ray of ultraviolet from light source (uviol lamp, high-pressure sodium lamp, UV-LED etc.) or short wavelength, make Photocurable resin composition partially cured.
When making uncured shape portion, weir 20A partially cured; such as shown in Fig. 6 ~ Fig. 8; multiple UV-LED light source 31 can be configured and surround distributor 30 to make it; thus immediately the second resin combination 21 be coated in transparent facestock (baffle) 10 is exposed equably after coating, make it solidify.
In addition, in order to keep the interval of transparent facestock 10 and display floater, also the sept particle with regulation particle diameter can be mixed in the second composition.
After being coated with the second composition, if make the light of the second composition solidification make the partially cured or viscosity of the second composition increase by short irradiation, then can maintain the shape of uncured shape portion, weir 20A better, therefore preferably.
< operation (b) >
Then, as shown in Figure 9 and Figure 10, in the rectangular area 24 surrounded by uncured shape portion, weir 20A in transparent facestock 10, the first aqueous composition 26 is supplied.
The supply of the first composition 26 is implemented by the following method: as shown in Figure 9 and Figure 10, transparent facestock 10 is lain on lower platform 28, supplies the first composition 26 by the distributor 30 of movement in the horizontal direction with wire, band shape or point-like.The distributor 30 of this example can be moved horizontally in the gamut in region 24 by the known horizontal mobile mechanism be made up of a pair feed screw 32 and the feed screw 34 orthogonal with feed screw 32.
The quantity delivered of the first composition 26 is redefined for by being full of the space that formed by uncured shape portion, weir 20A, transparent facestock 10 and diaphragm 16 with the first composition 26 thus making to have between transparent facestock 10 and diaphragm 16 amount at the interval (that is, making superimposed portions 18 have the thickness of regulation) of regulation.Now, be better that the volume considering in advance to cause because of the cure shrinkage of the first composition 26 reduces.Therefore, the quantity delivered of the first composition 26 be better compared with the specific thickness of the superimposed portions 18 after solidification, solidify before the thickness of superimposed portions 18 will be thicker amount.
Owing to having uncured shape portion, weir 20A, thus the circumference of the first composition 26 is expanded outward, the phenomenon of circumference thin-walled property is suppressed, and the thickness of the first composition 26 entirety can be made to keep evenly.By making the thickness of superimposed portions 18 entirety even, when fitting with thing of being fitted, easily suppress the phenomenon of residual clearance on its interface, thus preferably.
< operation (c) >
Then, as shown in figure 11, transparent facestock 10 and the supporting plane materiel 36 being pasted with diaphragm 16 are moved in decompressor 38.Supporting plane materiel 36 is undertaken by the diaphragm 16 supplied with the winding article form of roll rubber rollers etc. is fitted in the method supporting plane materiel 36 with the stickup of diaphragm 16.Now, for making not produce space between the adhesive surface of supporting plane materiel 36 and diaphragm 16, rubber rollers can be pressed on supporting plane materiel 36, or fitting in pressure reduction space.In order to easily hold on the end of diaphragm 16 when adhesive layer 14 is peeled off, it is better the diaphragm 16 using a circle larger than supporting plane materiel 36.
Top in decompressor 38 is configured with the upper mounting plate 42 with multiple absorption layer 40, is provided with lower platform 44 in bottom.Upper mounting plate 42 can be moved along the vertical direction by cylinder 46.
Make to be pasted with facing down and being arranged on absorption layer 40 by supporting plane materiel 36 of diaphragm 16.Supply is made to have facing up and transparent facestock 10 being fixed on lower platform 44 of the first composition 26.So, to make the first composition 26 in transparent facestock 10 place in opposite directions with the discontiguous mode of diaphragm 16 on the surface of supporting plane materiel 36.
Supporting plane materiel 36 is the transparent facestock such as glass plate, resin plate.Thickness as the glass plate of supporting plane materiel 36 use is preferably 0.5 ~ 10mm, is particularly preferably 1.0 ~ 5.0mm.If the thickness of this glass plate is more than lower limit, then supports plane materiel 36 and not easily warpage or flexure occur.If the thickness of this glass plate is below higher limit, then the quality supporting plane materiel 36 can increase necessarily, and when the precursor duplexer before adhesive layer 14 is solidified moves, supporting plane materiel 36 not easily misplaces.
After transparent facestock 10 and supporting plane materiel 36 are configured in assigned position, attract the air in decompressor 38 with vavuum pump 48, make the inner pressure relief of decompressor 38, become the reduced atmosphere of regulation.
Described reduced atmosphere is preferably below 1kPa, is more preferably 10 ~ 100Pa, more preferably 15 ~ 40Pa.If reduced atmosphere is more than lower limit, then each composition (curability compound, Photoepolymerizationinitiater initiater, polymerization inhibitor, chain-transferring agent, light stabilizer etc.) comprised in the first composition not easily gasifies.In addition, in order to reach the time shorten that reduced atmosphere needs.
After atmosphere pressures in decompressor 38 reaches the reduced atmosphere of such as 15 ~ 40Pa, under the state that the absorption layer 40 by upper mounting plate 42 keeps absorption supporting plane materiel 36, start cylinder 46 and decline towards transparent facestock 10 standby below.Then; transparent facestock 10 is overlapping across uncured shape portion, weir 20A with the supporting plane materiel 36 being pasted with diaphragm 16; the precursor duplexer that the uncured superimposed portions that formation is made up of the first composition 26 is sealed by transparent facestock 10, diaphragm 16 and uncured shape portion, weir 20A, keeps the stipulated time by this precursor duplexer under reduced atmosphere.
In this precursor duplexer, by the supporting deadweight of plane materiel 36, the pressing etc. from mobile supporting device, the first composition 26 is pressed and expands, and is full of the first composition 26, forms uncured superimposed portions in described space.
Be not particularly limited for from by the time the moment of transparent facestock 10 and supporting plane materiel 36 overlap to releasing reduced atmosphere, after sealing first composition 26, reduced atmosphere can be removed immediately, also after sealing first composition 26, decompression state can be maintained with the stipulated time.By maintaining decompression state with the stipulated time, the first composition flows in confined space, and the interval between transparent facestock 10 and the diaphragm 16 being pasted on supporting plane materiel 36 becomes even, even if improve atmosphere pressures also easily maintain sealing state.
The time maintaining decompression state can be the long-time of a few hours more than, but considers from the angle of production efficiency, is better within 1 hour, within being more preferably 10 minutes.
In manufacture method of the present invention, the second composition that application viscosity is high and when forming uncured shape portion, weir 20A, the thickness of the first composition 26 in the precursor duplexer obtained in operation (c) can be thicker, reaches 0.03 ~ 2mm.
< operation (d) >
Remove the reduced atmosphere in operation (c), under precursor duplexer is placed in the pressure atmosphere higher than operation (c).Such as, after the inside of decompressor 38 becomes such as atmospheric pressure atmosphere, precursor duplexer is taken out from decompressor 38.
If under precursor duplexer is placed in the pressure atmosphere higher than operation (c), then under the effect of the pressure raised, transparent facestock 10 and supporting plane materiel 36 are pressed on closely sealed direction.Therefore, even if the closely sealed space in precursor duplexer exists space, uncured superimposed portions also can flow in space, and whole confined space is full of uncured superimposed portions equably.
Pressure atmosphere in operation (d) can be atmospheric pressure atmosphere, also can be the pressure higher than it.Pressure atmosphere in operation (d) is preferably 80 ~ 120kPa.In addition, the angle never needing special equipment also can carry out the operations such as the solidification of superimposed portions 18 is considered, the preferably atmospheric pressure atmosphere of the pressure atmosphere in operation (d).
Time (following, to be designated as " high pressure retention time ") from the moment be placed in by precursor duplexer under the pressure atmosphere higher than operation (c) to uncured superimposed portions starts to solidify is not particularly limited.Precursor duplexer is moved to solidification equipment after decompressor takes out, until when the operation starting to solidify is carried out under atmospheric pressure atmosphere, the time needed for this operation is the high pressure retention time.Thus, when being placed in the time point under atmospheric pressure atmosphere and not had space to be present in the confined space of precursor duplexer, or space disappears in this process, uncured superimposed portions solidification can be made immediately.When needing some times to space disappears, under precursor duplexer being remained on the pressure atmosphere higher than operation (c) till space disappears.In addition, even if usually also can not obstruction be produced, so also can extend the high pressure retention time as required outside operation owing to extending the high pressure retention time.The high pressure retention time can be more than 1 day long-time, but considers from the angle of production efficiency, is better within 6 hours, within being more preferably 1 hour, considers, particularly preferably within 10 minutes from the angle of enhancing productivity further.
Then, make uncured weir shape portion 20A and the superimposed portions solidification of precursor duplexer inside, form the adhesive layer 14 with superimposed portions 18 and shape portion, weir 20.
The solidification of uncured shape portion, weir 20A can be carried out with the solidification of uncured superimposed portions simultaneously, also can before making uncured superimposed portions solidification, uncured shape portion, weir 20A be solidified.
When uncured superimposed portions and uncured shape portion, weir 20A are made up of Photocurable resin composition, from supporting plane materiel 36 side, light (visible ray of ultraviolet or short wavelength) is irradiated to uncured weir shape portion 20A and uncured superimposed portions, make it solidify.Such as, irradiate the visible ray of ultraviolet from light source (uviol lamp, high-pressure sodium lamp, UV-LED etc.) or short wavelength, superimposed portions 18 and shape portion, weir 20 are solidified.
As light, it is better the visible ray of ultraviolet or below 450nm.
When the circumference of transparent facestock is formed with shading Printing Department, or when being provided with anti-reflection layer in transparent facestock, irradiate light from supporting plane materiel side.
If superimposed portions 18 is made up of the first composition of photo-curable and makes its abundant photocuring, when cannot obtain suitable modulus of shearing, illumination can be interrupted in solidification midway to penetrate, after fitting with plane materiel (display floater etc.) of being fitted, penetrate by again carrying out illumination to superimposed portions 18 or heat the solidification promoting superimposed portions 18.When promoting to solidify by heating, the thermal polymerization of trace in the first composition of photo-curable, can be comprised.In addition, even if when also not using thermal polymerization, by keeping heating after incomplete photocuring, also can by the solid state stabilisation of superimposed portions 18, therefore preferably.
If the first composition and the second composition are photo-curable, then the transparent facestock 1 of fabricated ribbon adhesive layer under the low temperature that can be able to tolerate at film is therefore favourable in the protection of diaphragm.
< operation (e) >
Then, supporting plane materiel 36 is peeled off from diaphragm 16.Obtain the transparent facestock 1 of the band adhesive layer with diaphragm 16 by this.
In order to make diaphragm easily peel off, can cool adhesive layer.By cooling adhesive layer, the distortion of adhesive layer when peeling off diaphragm can be suppressed, improving the homogeneity of the thickness of the adhesive layer after peeling off diaphragm, also can suppress the generation in space when fitting with display floater.
The temperature cooled adhesive layer is different according to the vitrification point of the resin used as adhesive layer, when vitrification point being decided to be the temperature of the maximum of the loss modulus demonstrated in modulus of shearing mensuration, be better below the temperature of high 40 DEG C than vitrification point.The temperature of lower limit is not particularly limited, but according to the difference of diaphragm resin used, may become fragile, causing film cracking when peeling off, being therefore better more than-30 DEG C when low temperature.Cool time is better 5 minutes, can adjust according to the complexity peeled off.
The transparent facestock 1 of the band adhesive layer of present embodiment can be manufactured by the manufacture method identical with embodiment 1 without any problems.
[other]
In present embodiment, in the superimposed portions 18 forming adhesive layer 14 and shape portion, weir 21, as long as at least one party wherein comprises above-mentioned uncured composition, also can both comprise.
In addition, the difference of the uncured composition (W2) comprised in the uncured composition (W1) comprised in superimposed portions 18 and shape portion, weir 21 is below 40.
" duplexer "
Duplexer of the present invention is by the transparent facestock (not having diaphragm) of band adhesive layer of the present invention with by the duplexer of laminating plane materiel laminating.In duplexer of the present invention, transparent facestock and the plane materiel of being fitted of band adhesive layer are fitted, and contact with plane materiel of being fitted to make the adhesive layer of the transparent facestock of band adhesive layer.
In duplexer of the present invention, because at least one party clamped in a facestock of adhesive layer is transparent facestock, so Photocurable resin composition can be made to solidify from this transparent facestock side.Can be transparent by laminating plane materiel, also can be opaque.
As duplexer of the present invention, preferred display unit.
< display unit >
Figure 12 is the sectional view of the example representing display unit.
Display unit 2 comprises: as fitted in by the display floater 50 of laminating plane materiel, the mode that contacts with display floater 50 with adhesive layer 14 the band adhesive layer of display floater 50 transparent facestock 1 (not there is diaphragm), be equipped with and be connected and the flexible printing patch panel 60 (FPC) of the drive IC that display floater 50 is worked with display floater 50.So, display unit 2 comprises transparent facestock 10, display floater 50, is clipped in adhesive layer 14 between transparent facestock 10 and display floater 50.
Illustrated example are display floaters by laminating plane materiel 50, be that of the liquid crystal panel of the structure of the transparency carrier 52 being provided with colored filter and the transparency carrier 54 that is provided with TFT (thin film transistor (TFT)) being fitted across liquid crystal layer 56, use a pair polarizer 58 to clamp is routine.
In the display unit of this example, being display floater by laminating plane materiel, but being not limited to display floater by laminating plane materiel, such as, also can be touch-screen.
The manufacture method > of < display unit
As an example of the manufacture method of duplexer of the present invention, the manufacture method of display unit is described.The manufacture method of display unit of the present invention is under the reduced atmosphere of below 10kPa, display floater and the transparent facestock (not having diaphragm) of band adhesive layer is superposed the method for laminating in the mode that adhesive layer contacts with display floater.
When the surface of adhesive layer being covered with diaphragm as the transparent facestock 1 of the band adhesive layer shown in Fig. 1, after diaphragm is peeled off, the transparent facestock of display floater and band adhesive layer is fitted.
Reduced atmosphere by display floater and when being with the transparent facestock of adhesive layer to fit is below 10kPa, is preferably 1 ~ 100Pa, is more preferably 5 ~ 50Pa.
Duplexer of the present invention can be manufactured by the method beyond said method.Such as, if for described display unit 2, then can be manufactured by the method comprising following operation (f) ~ (i).
F () is coated with the second aqueous composition in the circumference on the surface of display floater 50, form the operation in uncured shape portion, weir.
G () supplies the operation of the first aqueous composition in the region surrounded by uncured shape portion, weir on the surface of display floater 50.
H (), under reduced atmosphere, the first composition superposes transparent facestock 10, the uncured superimposed portions obtaining being made up of the first composition is shown the operation of the precursor duplexer that panel 50, transparent facestock 10 and uncured shape portion, weir seal.
I precursor duplexer is being placed under the state under the pressure atmosphere higher than described operation (h) by (), make uncured superimposed portions and the solidification of uncured shape portion, weir, form the operation with the adhesive layer 14 in superimposed portions 18 and shape portion, weir 20.
[operation (f)]
In operation (f), replace, except the transparent facestock 10 (baffle) in described operation (a), to carry out in the same manner as described operation (a) except using display floater 50.
[operation (g)]
Operation (g) can be carried out in the same manner as described operation (b).
[operation (h)]
In operation (h), replace, except the supporting plane materiel 36 being fitted with diaphragm 16 in described operation (c), to carry out in the same manner as described operation (c) except using transparent facestock 10 (baffle).
[operation (i)]
Operation (i) can be carried out in the same manner as described operation (d).
The connection of flexible printing patch panel 60 (FPC) can be carried out before operation (a), also can carry out after operation (a).
Embodiment
The present invention is described in detail by the following examples, but the present invention is not by the restriction of following record.
[embodiment 1 ~ 6, comparative example 1]
[transparent facestock]
In the circumference of a side surface of the soda-lime glass of long 100mm, wide 100mm, thick 1.3mm, by using containing the ceramic printing of black pigment, form shading Printing Department with picture frame shape, such that the length of transmittance section is 68mm, width is 68mm, make transparent facestock-i.
[supporting plane materiel]
In the one side of the transparent panel be made up of soda-lime glass of long 100mm, wide 100mm, thick 3mm; with rubber rollers paste long 130mm, wide 130mm in the mode of the adhesive surface of diaphragm and glass contact, the diaphragm ((East セ ロ society of Tung Sai Lu Co., Ltd) of thick 0.75mm makes; PURETECT VLH-9), make the supporting plane materiel-ii being pasted with diaphragm.
[by laminating plane materiel]
As by laminating plane materiel, be used in long 100mm, wide 100mm, thick 1.7mm soda-lime glass a face on the polarizer (Bora Co., Ltd. (Port ラ テ Network ノ society) make, KN-18240T) of adhesive band adhesive layer replace display panels by laminating plane materiel-iii.
[the first composition]
4000) and 3-isocyanatomethyl-3 by the molecular end ethylene-oxide-modified dual functional polypropylene glycol (number-average molecular weight according to hydroxyl value calculates:, 5,5-trimethylcyclohexylisocyanate mixes with mol ratio 4:5, under the existence of tin catalyst, at 70 DEG C, make it react, obtain prepolymer.In the prepolymer of gained, add 2-Hydroxy ethyl acrylate with mol ratio 1:2, at 70 DEG C, make it react, obtain urethane acrylate oligomer (A-1) (being denoted as below " oligomer (A-1) ").The curability functional group number of oligomer (A-1) is 2, and number-average molecular weight is about 24000, and the viscosity at 25 DEG C is about 830Pas.
By the oligomer (A-1) of 40 mass parts, methacrylic acid-2-hydroxybutyl (Kyoeisha Chemical Co., Ltd. (the altogether Sakae society chemistry society) system of 30 mass parts, Light Ester HOB), the methacrylic acid dodecyl ester Homogeneous phase mixing of 30 mass parts, two (2 of 0.3 mass parts are dissolved equably in this mixture of 100 mass parts, 4, 6-trimethylbenzoyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals (チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ society) makes, IRGACURE 819), 2 of 0.04 mass parts, 5-di-tert-butyl hydroquinone (polymerization inhibitor, Tokyo changes into Co., Ltd. (East capital and changes into society) system), ultra-violet absorber (Ciba Specialty Chemicals's system of 0.3 mass parts, TINUVIN 109), with the n-dodecyl mercaptan (chain-transferring agent of 0.3 mass parts, Kao Corp (Hua Wangshe) makes, THIOKALCOL 20), obtain base composition-iv.
By the oligomer (A-1) of 40 mass parts, methacrylic acid-2-hydroxybutyl (Kyoeisha Chemical Co., Ltd.'s system of 40 mass parts, Light Ester HOB), the methacrylic acid dodecyl ester Homogeneous phase mixing of 20 mass parts, two (2 of 0.3 mass parts are dissolved equably in this mixture of 100 mass parts, 4, 6-trimethylbenzoyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals's system, IRGACURE 819), 2 of 0.04 mass parts, 5-di-tert-butyl hydroquinone (polymerization inhibitor, Tokyo changes into Co., Ltd.'s system), with ultra-violet absorber (Ciba Specialty Chemicals's system of 0.3 mass parts, TINUVIN 109), obtain base composition-v.
Then, base composition-iv or base composition-v, non-curable oligomer (II-i) are dissolved with the ratio uniform shown in table 1, directly after adding in container be arranged in decompressor with open state, about 20Pa will be decompressed in decompressor, keep 10 minutes, thus carry out deaeration process, obtain the first composition-1 and the first composition-2.
As non-curable oligomer (II-i), identical, the molecular end ethylene-oxide-modified dual functional polypropylene glycol (number-average molecular weight according to hydroxyl value calculates: 4000) used when using synthesis with oligomer (A-1).
[the second composition]
By molecular end with ethylene-oxide-modified dual functional polypropylene glycol (number-average molecular weight according to hydroxyl value calculates: 4000) and hexamethylene diisocyanate mix with mol ratio 6:7, then (Osaka Organic Chemical Industry Co., Ltd. (Osaka You Machine chemical industry society) makes to use isobornyl acrylate, IBXA) after dilution, under the existence of tin catalyst, at 70 DEG C, make it react, obtain prepolymer.2-Hydroxy ethyl acrylate is added with mol ratio 1:2 in the prepolymer of gained, at 70 DEG C, make it react, obtain the urethane acrylate oligomer (A '-2) (being denoted as below " oligomer (A '-2) ") diluted with the isobornyl acrylate of 30 quality %.The curability functional group number of oligomer (A '-2) is 2, and number-average molecular weight is the viscosity at 55000,60 DEG C is 580Pas.
By methacrylic acid-2-hydroxybutyl (Kyoeisha Chemical Co., Ltd.'s system, the Light Ester HOB) Homogeneous phase mixing of the oligomer (A '-2) of 90 mass parts and 10 mass parts, obtain mixture.By this mixture of 100 mass parts, 1-hydroxycyclohexylphenylketone (the Photoepolymerizationinitiater initiater of 0.9 mass parts, Ciba Specialty Chemicals's system, IRGACURE 184), two (2 of 0.1 mass parts, 4, 6-trimethylbenzoyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals's system, IRGACURE 819), 2 of 0.04 mass parts, 5-di-tert-butyl hydroquinone (polymerization inhibitor, Tokyo changes into Co., Ltd.'s system), with ultra-violet absorber (Ciba Specialty Chemicals's system of 0.3 mass parts, TINUVIN 109) Homogeneous phase mixing, obtain base composition-vi.
By methacrylic acid-2-hydroxybutyl (Kyoeisha Chemical Co., Ltd.'s system, the Light Ester HOB) Homogeneous phase mixing of the oligomer (A '-2) of 70 mass parts and 30 mass parts, obtain mixture.By this mixture of 100 mass parts, 1-hydroxycyclohexylphenylketone (the Photoepolymerizationinitiater initiater of 0.9 mass parts, Ciba Specialty Chemicals's system, IRGACURE 184), two (2 of 0.1 mass parts, 4, 6-trimethylbenzoyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals's system, IRGACURE 819), 2 of 0.04 mass parts, 5-di-tert-butyl hydroquinone (polymerization inhibitor, Tokyo changes into Co., Ltd.'s system), with ultra-violet absorber (Ciba Specialty Chemicals's system of 0.3 mass parts, TINUVIN 109) Homogeneous phase mixing, obtain base composition-vii.
Directly after base composition-vi or base composition-vii being added in container be arranged in decompressor with open state, about 20Pa will be decompressed in decompressor, keep 10 minutes, thus carry out deaeration process, obtain the second composition-1.
In addition, make base composition-v or base composition-vii, non-curable oligomer (II '-i) dissolves with the ratio uniform shown in table 1, directly after adding in container be arranged in decompressor with open state, about 20Pa will be decompressed in decompressor, keep 10 minutes, thus carry out deaeration process, obtain the second composition-2 ~ the second composition-7.
As non-curable oligomer (II '-i), use the non-curable oligomer identical with non-curable oligomer (II-i).
[table 1]
[embodiment 1]
(operation (a))
Be about the complete cycle of the position of 7mm in the genesis in shading Printing Department of transparent facestock-i, be coated with the second composition-1 with distributor to make the condition that width reaches about 1mm, coating thickness reaches about 0.6mm, form uncured shape portion, weir.
Then, the uncured shape portion, weir be formed on transparent facestock-i is irradiated equably be derived from chemical lamp (Nippon Electric Company, Ltd.'s system, FL15BL, peak wavelength: 365nm, exposure intensity: 2mW/cm 30 seconds 2) ultraviolet and the visible ray of below 450nm.By this, the viscosity in uncured shape portion, weir increases.(operation (b))
The inside region in the uncured shape portion, weir that transparent facestock-i is formed, the condition using distributor to reach 2.5g according to gross mass supplies the first composition-1 to many places.
In the process of supply first composition-1, the damaged part such as do not burst, and maintains the shape in uncured shape portion, weir.
(operation (c))
Make facing up of the first composition-1, transparent facestock-i is lain on the lower platform in the decompressor of the lowering or hoisting gear being provided with a pair platform.
To be 10mm with the distance of transparent facestock-i in vertical direction, mode remains on below the upper mounting plate of the lowering or hoisting gear in decompressor by the supporting plane materiel-ii being pasted with diaphragm to use electrostatic chuck.
Be exhausted after making decompressor be in sealing state until the pressure in decompressor reaches about 40Pa.Utilize the lowering or hoisting gear in decompressor to make lower platform close, with the pressure of 2kPa by transparent facestock-i and be pasted with the supporting plane materiel-ii of diaphragm across the first composition-1 pressing, kept for 10 seconds.By electrostatic chuck except electricity is to make supporting plane materiel-ii leave from upper mounting plate; make decompressor inherence return to atmospheric pressure atmosphere in about 15 seconds, obtain the uncured superimposed portions that is made up of the first composition-1 by the precursor duplexer-1 of transparent facestock-i, diaphragm and the sealing of uncured shape portion, weir.
The shape in shape portion, weir uncured in precursor duplexer-1 almost maintains initial state in good condition.
(operation (d))
From supporting plane materiel-ii side, the uncured shape portion, weir of precursor duplexer-1 and superimposed portions are irradiated equably and within 10 minutes, be derived from chemical lamp (Nippon Electric Company, Ltd.'s system, FL15BL, peak wavelength: 365nm, exposure intensity: 2mW/cm 2) ultraviolet and the visible ray of below 450nm, make uncured shape portion, weir and superimposed portions solidification, thus form adhesive layer.
Exposure intensity illumination photometer (oxtail Electric Co., Ltd (ウ シ オ Electricity Machine society) makes, ultraviolet ray intensity meter Uni Meter UIT-101) measures.
The thickness of the superimposed portions after solidification is 0.4mm and roughly even.
(operation (e))
Under the state that adhesive layer is cooled to about-20 DEG C, supporting plane materiel-ii is peeled off from diaphragm, thus obtain the transparent facestock-1 of the band adhesive layer being pasted with diaphragm.
[embodiment 2 ~ 6, comparative example 1]
Except the kind of change first composition as shown in table 2 and the second composition, obtain the transparent facestock-7 of transparent facestock-2 ~ band adhesive layer being with adhesive layer similarly to Example 1.
[jump evaluation]
(1) accelerated test
Diaphragm is peeled off by the transparent facestock of the band adhesive layer obtained from each example, preserves 5 days in the thermostat of 80 DEG C.
(2) shape evaluation of adhesive layer
In the shape evaluation of adhesive layer, use Keyemce company (キ ー エ Application ス society) make digital microscope VHX-1000, utilize the depth of focus to measure shape.Measurement site is the part that the peripheral end in the shape portion, weir of the middle body on one side of adhesive layer on self-induced transparency plane materiel-i plays till the distance of the about 5mm of the adhesive surface across superimposed portions.In mensuration, in order to improve mensuration sensitivity, be coated with thin silver-colored thickener on the surface of adhesive layer.The front and back being determined at (1) accelerated test are implemented.As change in shape, the shape portion, weir before and after evaluation accelerated test and the jump of superimposed portions.
The difference of height of the highs and lows in measurement site calculates as jump in evaluating by jump.
[evaluation that space produces]
Transparent facestock-1 after (1) accelerated test evaluated by described jump, that peel off the band adhesive layer after diaphragm lies on the lower platform in the decompressor of the lowering or hoisting gear being provided with a pair platform, and makes facing up of adhesive layer.
Electrostatic chuck is used to be held in by laminating plane materiel-iii below the upper mounting plate of the lowering or hoisting gear in decompressor in the mode that the distance of the transparent facestock-1 with band adhesive layer is 10mm.
Be exhausted after making decompressor be in sealing state until the pressure in decompressor reaches about 30Pa.Utilize the lowering or hoisting gear in decompressor to make lower platform close, with the pressure of 2kPa by by the transparent facestock-1 of laminating plane materiel-iii and band adhesive layer across adhesive layer pressing, kept for 10 seconds.Electrostatic chuck is left from upper mounting plate with the plane materiel-iii that makes to be fitted except electricity, makes decompressor inherence return to atmospheric pressure in about 20 seconds, obtain by transparent facestock-i and the duplexer-1 adhesive layer clamped by laminating plane materiel-iii.
Observe duplexer-1 immediately after stacked, result is in plane materiel-iii and the visible space (bubble) fine in a large number on the interface of the adhesive layer of the transparent facestock-1 of band adhesive layer of being fitted.Place duplexer-1, measure the time (space extinction time) needed for the disappearance of space.Use the transparent facestock-2 ~-7 of band adhesive layer, similarly obtain duplexer-2 ~-7, measure space extinction time.
Result is shown in table 1.Space extinction time is the average of the result of 2 samples.
The evaluation result of each example is shown in table 2.In addition, " W1-W2 " in table 2 refers to the difference (W1-W2) of the content W2 (quality %) of non-curable oligomer in the content W1 (quality %) of the non-curable oligomer (II-i) in the first composition and the second composition (II '-i).
[table 2]
As shown in table 2, in the comparative example 1 of W1-W2 more than 40, even if space is also still remaining through 2 hours, then space does not disappear yet.On the other hand, in the embodiment 1 ~ 6 of W1-W2 below 40, space disappeared within 90 minutes, and productivity is very good.In addition, particularly W1-W2 is in the embodiment 1 ~ 5 of 30 ~ 0, and space all disappeared at 0 minute, and productivity is very good.
[embodiment 7]
[transparent facestock]
Using the soda-lime glass of long 250mm, wide 190mm, thick 1.3mm as transparent facestock.In the present embodiment, in order to easily confirm to show uneven impact, will the glass substrate of shading Printing Department do not formed as transparent facestock.
[supporting plane materiel]
In the one side of the transparent panel be made up of soda-lime glass of long 100mm, wide 100mm, thick 3mm; paste diaphragm (Tung Sai Lu Co., Ltd's system of long 130mm, wide 130mm, thick 0.75mm in the mode of the adhesive surface of diaphragm and glass contact by rubber rollers; PURETECT VLH-9), make the supporting plane materiel being pasted with diaphragm.
[the first resin combination (superimposed portions resin combination)]
Amount except n-dodecyl mercaptan is except 0.5 mass parts, manufactures the base composition-i identical with described base composition-iv.
Then, with base composition-i be 100 mass parts, described non-curable oligomer (II-i) is that the ratio of 100 mass parts makes their uniform dissolution, directly after adding in container be arranged in decompressor with open state, about 20Pa will be decompressed in decompressor, keep 10 minutes, thus carry out deaeration process, obtain the first resin combination (in face (superimposed portions) resin combination).
[the second resin combination (shape portion, weir resin combination)]
By the described oligomer (A '-2) of 55 mass parts and acrylic acid-4-hydroxybutyl (Osaka Organic Chemical Industry Co., Ltd.'s system, the 4HBA) Homogeneous phase mixing of 45 mass parts, obtain mixture.By this mixture of 100 mass parts, 1-hydroxycyclohexylphenylketone (the Photoepolymerizationinitiater initiater of 3.0 mass parts, Ciba Specialty Chemicals's system, IRGACURE 184), two (2 of 0.5 mass parts, 4, 6-trimethylbenzoyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals's system, IRGACURE 819), 2 of 0.04 mass parts, 5-di-tert-butyl hydroquinone (polymerization inhibitor, Tokyo changes into Co., Ltd.'s system), with ultra-violet absorber (Ciba Specialty Chemicals's system of 0.3 mass parts, TINUVIN 109) Homogeneous phase mixing, obtain base composition-ii.
Then, with base composition-ii be 75 mass parts, described non-curable oligomer (II-i) is that the ratio of 25 mass parts makes their uniform dissolution, obtains the second resin combination.
[the 3rd resin combination (shape portion, weir resin combination)]
As the 3rd resin combination, use described base composition vi.
Then, use flow graph (Anton Paar Inc., Physica MCR301), uncured resin bed formation Photocurable resin composition is clamped in base and mensuration rotor (the Anton Paar Inc. of soda-lime glass, D-PP20/AL/S07) between, the 2mW/cm that the black light lamp (Nippon Electric Company, Ltd.'s system, FL15BL) being arranged at base bottom irradiates 10 minutes is utilized under nitrogen atmosphere at 35 DEG C 2light, and apply the dynamic shearing strain of 1% simultaneously, resin bed formation Photocurable resin composition solidified, measure and make the first ~ three resin composition and the storage shear modulus of resin bed that obtains.The storage shear modulus of the resin bed obtained by each resin combination is shown in following table 3.
[table 3]
Elastic modelling quantity (35 DEG C) [KPa]
First resin combination 10
Second resin combination 70
3rd resin combination 600
[embodiment 7]
First, the complete cycle of the position of 25mm is about in self-induced transparency plane materiel periphery genesis, the second resin combination is coated with to make the condition that width reaches about 1mm, coating thickness reaches about 0.6mm with distributor, the LED light source subsidiary from distributor irradiates UV light, the shape portion, weir (with reference to Fig. 4 ~ 5) of forming section solidification.
The condition using distributor to reach 2.5g to multiple positions of the inside region in shape portion, weir with gross mass supplies the first resin combination.In the process of supply first resin combination, the damaged part such as do not burst, and maintains the shape in uncured shape portion, weir.
Then, make to be coated with facing up of the first resin combination, transparent facestock is lain on the lower platform in the decompressor (with reference to Fig. 6) of the lowering or hoisting gear being provided with a pair platform, be exhausted until the pressure in decompressor reaches about 40Pa.After decompression, utilize the lowering or hoisting gear in decompressor to make lower platform close, with the pressure of 2kPa by transparent facestock and be pasted with the supporting plane materiel of diaphragm across the first resin combination pressing, kept make it fit 10 seconds.After laminating, return to atmospheric pressure atmosphere by decompressor, obtain the precursor duplexer sealed by the first resin combination by transparent facestock, diaphragm and shape portion, weir.
From supporting plane materiel side, precursor duplexer is irradiated equably and within 10 minutes, be derived from chemical lamp (Nippon Electric Company, Ltd.'s system, FL15BL, peak wavelength: 365nm, exposure intensity: 2mW/cm 2) ultraviolet and the visible ray of below 450nm, make shape portion, weir (the second resin combination) and the first resin composition, thus form adhesive layer.
Exposure intensity illumination photometer (oxtail Electric Co., Ltd (ウ シ オ Electricity Machine society) makes, ultraviolet ray intensity meter Uni Meter UIT-101) measures.
The thickness of the superimposed portions after solidification is 0.4mm and roughly even.
Then, under the state that adhesive layer is cooled to about-20 DEG C, supporting plane materiel is peeled off from diaphragm, thus make the transparent facestock being pasted with the band adhesive layer of diaphragm.
[table 4]
As shown in table 4, in the embodiment 7 that the ratio of the elastic modelling quantity in superimposed portions and shape portion, weir is minimum, fail to observe display uneven.Can confirm, be suppressed in low-level by the ratio of the elastic modelling quantity by superimposed portions and shape portion, weir, good visuognosis degree can be maintained.
Above, preferred embodiments of the present invention have been disclosed for illustrative, but the present invention is not limited to these embodiments.In the scope not departing from technological thought of the present invention, the increase can carrying out forming, omission, displacement and other change.The present invention by the restriction of above-mentioned explanation, is not only limited by the scope of subsidiary claims.
Here the announcement of full content as description of the present invention of the description of No. 2012-288004, the Japanese patent application of filing an application on December 28th, 2012 and No. 2013-037505, the Japanese patent application of filing an application on February 27th, 2013, claims, accompanying drawing and summary is quoted.
The explanation of symbol
The transparent facestock of 1 band adhesive layer
2 display unit
10 transparent facestock
14 adhesive layers
16 diaphragms
18 superimposed portions
20 shape portion, weirs
24 regions
26 first compositions
36 supporting plane materiels
50 display floaters

Claims (15)

1. the transparent facestock with adhesive layer, is characterized in that, comprises transparent facestock and is formed at the adhesive layer on surface of at least one party of described transparent facestock,
Described adhesive layer have along the extended surface of described transparent facestock superimposed portions and surround the shape portion, weir of periphery in layered portion,
Shape portion, described weir is formed by the shape portion, weir comprising following curability compound (I ') and following non-curable oligomer (II ') and forms with the solidfied material of hardening resin composition,
Layered portion is formed by the superimposed portions comprising following curability compound (I) and following non-curable oligomer (II) and forms with the solidfied material of hardening resin composition,
The difference (W1-W2) of the content W2 represented with quality % of described non-curable oligomer in the content W1 represented with quality % of the described non-curable oligomer (II) in layered portion and shape portion, described weir (II ') is below 40;
Curability compound (I '): the molecular weight comprising urethane acrylate oligomer (A ') and there is more than 1 curability functional group lower than 600 monomer (B ');
Non-curable oligomer (II '): that be not cured reaction with described curability compound (I ') during any one solidification in layered portion's formation hardening resin composition and weir shape portion formation hardening resin composition, that there is hydroxyl oligomer;
Curability compound (I): the molecular weight comprising urethane acrylate oligomer (A) and there is more than 1 curability functional group lower than 600 monomer (B);
Non-curable oligomer (II): be not cured reaction with described curability compound (I) during any one solidification in layered portion's formation hardening resin composition and weir shape portion formation hardening resin composition, the oligomer with hydroxyl.
2. the transparent facestock of band adhesive layer as claimed in claim 1, it is characterized in that, the urethane acrylate oligomer that described urethane acrylate oligomer (A) and (A ') are is Material synthesis with polyoxyalkylene polyol and polyisocyanates.
3. the transparent facestock of band adhesive layer as claimed in claim 1 or 2, is characterized in that, described non-curable oligomer (II) and (II ') are polyoxyalkylene polyols.
4. the transparent facestock of the band adhesive layer according to any one of claims 1 to 3, is characterized in that, the number-average molecular weight that every 1 hydroxyl of described non-curable oligomer (II) and (II ') is corresponding is 400 ~ 8000.
5. the transparent facestock of the band adhesive layer according to any one of Claims 1 to 4, is characterized in that, the number-average molecular weight of described urethane acrylate oligomer (A) is 1000 ~ 100000.
6. the transparent facestock of the band adhesive layer according to any one of Claims 1 to 5, it is characterized in that, layered portion's formation hardening resin composition comprises Photoepolymerizationinitiater initiater (C1), and described weir shape portion formation hardening resin composition comprises Photoepolymerizationinitiater initiater (C2).
7. the transparent facestock of the band adhesive layer according to any one of claim 1 ~ 6, is characterized in that, more than the storage shear modulus of the storage shear modulus at 35 DEG C of shape portion, described weir at 35 DEG C of layered portion and below 15 times.
8. the transparent facestock of the band adhesive layer according to any one of claim 1 ~ 7, is characterized in that, the storage shear modulus at 35 DEG C of shape portion, described weir is 1 ~ 150kPa.
9. the transparent facestock of the band adhesive layer according to any one of claim 1 ~ 8, is characterized in that, the storage shear modulus at 35 DEG C of layered portion is 1 ~ 100kPa.
10. the transparent facestock of the band adhesive layer according to any one of claim 1 ~ 9, is characterized in that,
Described transparent facestock has the shading Printing Department of the circumference being formed at its surface,
Superimposed portions and shape portion, weir direction are positioned at than described shading Printing Department position more in the inner part at least partially in the face on the surface of described transparent facestock.
The transparent facestock of 11. band adhesive layers according to any one of claim 1 ~ 10, is characterized in that, also has diaphragm that cover the surface at least partially of described adhesive layer, that can peel off.
The manufacture method of 12. 1 kinds of transparent facestock with adhesive layer, it is the method for the transparent facestock of the band adhesive layer described in manufacturing claims 11, it is characterized in that, comprises following operation (a) ~ (e):
A () is coated with aqueous described weir shape portion formation hardening resin composition in the circumference on the surface of transparent facestock, form the operation in uncured shape portion, weir;
B () supplies aqueous layered portion and forms operation with hardening resin composition in the region surrounded by uncured shape portion, weir on transparent facestock surface;
C () is under reduced atmosphere, on superimposed portions formation hardening resin composition, superpose in the mode making diaphragm contact with superimposed portions formation hardening resin composition the supporting plane materiel being pasted with diaphragm, obtain the operation being formed the precursor duplexer that the uncured superimposed portions that forms with hardening resin composition is sealed by transparent facestock, diaphragm and uncured shape portion, weir by superimposed portions;
D (), under the state being placed under the pressure atmosphere higher than described operation (c) by described precursor duplexer, makes uncured superimposed portions and the solidification of shape portion, weir, forms the operation with the adhesive layer in superimposed portions and shape portion, weir;
E operation that supporting plane materiel is peeled off from diaphragm by ().
13. 1 kinds of display unit, is characterized in that, comprising:
Display floater,
The mode contacted with display floater with adhesive layer fits in the transparent facestock of the band adhesive layer according to any one of claim 1 ~ 10 of display floater.
The manufacture method of 14. 1 kinds of display unit, it is the method for the display unit described in manufacturing claims 13, it is characterized in that,
Under the reduced atmosphere of below 10kPa, the mode that display floater and the transparent facestock of band adhesive layer contact with display floater with adhesive layer is superposed laminating.
15. 1 kinds of duplexers, is characterized in that, transparent facestock and the plane materiel laminating of being fitted of the band adhesive layer according to any one of claim 1 ~ 10 form.
CN201380067251.5A 2012-12-28 2013-12-26 Transparent face plate with an adhesive layer, laminate, display device, and production methods thereof Pending CN104936778A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2012-288004 2012-12-28
JP2012288004 2012-12-28
JP2013-037505 2013-02-27
JP2013037505 2013-02-27
PCT/JP2013/084968 WO2014104231A1 (en) 2012-12-28 2013-12-26 Transparent face plate with adhesive layer, laminate, display device, and production methods thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111669969A (en) * 2018-02-01 2020-09-15 Ａｇｃ株式会社 Base material and copolymer
CN114390952A (en) * 2019-09-17 2022-04-22 迪睿合株式会社 Method for forming bank and method for manufacturing laminate

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6413405B2 (en) * 2014-07-07 2018-10-31 Ａｇｃ株式会社 Double-sided adhesive film, transparent surface material with adhesive layer, and laminate
JP6492925B2 (en) * 2015-04-21 2019-04-03 Ａｇｃ株式会社 Method for producing double-sided pressure-sensitive adhesive sheet, method for producing transparent surface material with double-sided pressure-sensitive adhesive sheet, method for producing display device
KR102062225B1 (en) * 2015-11-26 2020-01-03 반도 카가쿠 가부시키가이샤 Display apparatus which has an optically transparent adhesive sheet, a manufacturing method of an optically transparent adhesive sheet, a laminated body, and a touch panel
JP6665508B2 (en) * 2015-12-10 2020-03-13 日立化成株式会社 Adhesive and adhesive sheet
EP4130859A1 (en) * 2017-08-25 2023-02-08 Panasonic Intellectual Property Management Co., Ltd. Display device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110070433A1 (en) * 2009-09-24 2011-03-24 Lintec Corporation Sheet and Adhesive Sheet
WO2011158839A1 (en) * 2010-06-16 2011-12-22 旭硝子株式会社 Curable resin composition, laminate comprising same, and process for production of the laminate
TW201210812A (en) * 2010-06-16 2012-03-16 Asahi Glass Co Ltd Curable resin composition, laminate comprising same, and process for production of the laminate
CN102597155A (en) * 2009-10-30 2012-07-18 旭硝子株式会社 Curable resin composition for sealing portion formation, laminate, and production method therefor
TW201231610A (en) * 2010-12-08 2012-08-01 Asahi Glass Co Ltd Adhesive-layer-equipped transparent surface material, display device, and methods for producing same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5596262B2 (en) * 2007-08-22 2014-09-24 三菱樹脂株式会社 Adhesive sheet
JP2009091434A (en) * 2007-10-05 2009-04-30 Sekisui Chem Co Ltd Polymerizable composition for interlayer, interlayer and transparent laminate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110070433A1 (en) * 2009-09-24 2011-03-24 Lintec Corporation Sheet and Adhesive Sheet
CN102597155A (en) * 2009-10-30 2012-07-18 旭硝子株式会社 Curable resin composition for sealing portion formation, laminate, and production method therefor
WO2011158839A1 (en) * 2010-06-16 2011-12-22 旭硝子株式会社 Curable resin composition, laminate comprising same, and process for production of the laminate
TW201210812A (en) * 2010-06-16 2012-03-16 Asahi Glass Co Ltd Curable resin composition, laminate comprising same, and process for production of the laminate
TW201231610A (en) * 2010-12-08 2012-08-01 Asahi Glass Co Ltd Adhesive-layer-equipped transparent surface material, display device, and methods for producing same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111669969A (en) * 2018-02-01 2020-09-15 Ａｇｃ株式会社 Base material and copolymer
CN114390952A (en) * 2019-09-17 2022-04-22 迪睿合株式会社 Method for forming bank and method for manufacturing laminate
EP4032622A4 (en) * 2019-09-17 2023-10-04 Dexerials Corporation Dam formation method and layered body manufacturing method

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