CN102939312B - Curable resin composition, laminate comprising same, and process for production of the laminate - Google Patents

Curable resin composition, laminate comprising same, and process for production of the laminate Download PDF

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Publication number
CN102939312B
CN102939312B CN201180029238.1A CN201180029238A CN102939312B CN 102939312 B CN102939312 B CN 102939312B CN 201180029238 A CN201180029238 A CN 201180029238A CN 102939312 B CN102939312 B CN 102939312B
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CN
China
Prior art keywords
resin composition
resin layer
plane materiel
monomer
curable resin
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Expired - Fee Related
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CN201180029238.1A
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Chinese (zh)
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CN102939312A (en
Inventor
新山聪
青木直子
对马斉
铃木丰一
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AGC Inc
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Asahi Glass Co Ltd
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Publication date
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Publication of CN102939312A publication Critical patent/CN102939312A/en
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Publication of CN102939312B publication Critical patent/CN102939312B/en
Expired - Fee Related legal-status Critical Current
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • 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
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B32B37/1009—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using vacuum and fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)
  • Sealing Material Composition (AREA)

Abstract

Disclosed is a curable resin composition which can fix surface materials to each other satisfactorily in the lamination/ integration of the surface materials through a resin layer comprising a cured product of the curable resin composition, and which can reduce a stress caused by the shrinkage of the resin layer upon curing. Specifically disclosed is a curable resin composition characterized by comprising a curable compound (II) and a non-curable oligomer (D), wherein the content of the non-curable oligomer (D) is 10 to 90 mass%. The curable compound (II) comprises one or more curable compounds that can cause a curing reaction in the curing of the curable resin composition, and at least one of the curable compounds has a hydroxy group that cannot react in the curing of the curable resin composition. The non-curable oligomer (D) cannot cause a curing reaction with the curable compound (II) in the curing of the curable resin composition, and is an oligomer having 0.8 to 3 hydroxy groups per molecule.

Description

Curable resin composition and duplexer and the manufacture method thereof of using said composition
Technical field
The present invention relates to be suitable for curable resin composition that plane materiel engages, use the folded plane materiel of this cured resin composition layer and duplexer and the manufacture method of this duplexer.
Background technology
On display device, be situated between and be laminated with in the display unit of protecting sheet to engage resin layer, the stress producing because of the contraction of this joint resin layer when making to engage resin layer and solidifying may impact display device.If stress puts on display device, may produce following problem.
Demonstration in display device forms material (hereinafter referred to as display material) stress and is affected, and the homogeneity of demonstration may be impaired.For example, in the situation of liquid crystal display device, sometimes enclose display device liquid crystal arrangement because of external stress chaotic, as showing that inequality is observed.
In the situation that the substrate surface of the display surface side of display device is formed with the blooming that improves the display qualities such as visual angle, the optical characteristics stress of this blooming and localized variation occurs, the homogeneity of demonstration may be impaired.
In addition, engage the observation side that resin layer is located at display device, if curing joint resin layer exists bubble, may produce following problem.
Emergent light or reflected light from display device are mixed and disorderly because of bubble, show that the image quality of image may be significantly impaired.
When display device does not show image, the bubble that remains in joint resin layer easily sees through protecting sheet by identification out, therefore may significantly reduce the quality of goods.
The interface cohesive force of the interface cohesive force of resin layer and display device or resin layer and protecting sheet declines.
The method as manufacture with the display unit of the rhythmo structure that is laminated with transparent facestock on display device, known following method.
(1) liquid starting material is injected on resin protecting sheet and it is solidified to form and engage after resin; or after the joint resin of rolling sheet is pasted under degassing phase being arranged on resin protecting sheet, when pressing, one end makes that liquid crystal cell is closely sealed under degassing phase carrys out stacked method.Raw material as engaging resin, preferably adopts silica gel (patent documentation 1).
(2) display panel is located and is pre-fixed with stationary member after the prescribed position of glass protecting sheet processed, under decompression state to filling liquid resin material in formed space between protecting sheet and display panel and it is solidified, thereby stacked method.As liquid resin material, preferably adopt silicone resin (patent documentation 2).
Prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 7-209635 communique
Patent documentation 2: Japanese Patent Laid-Open 2006-58753 communique
The summary of invention
Invent technical problem to be solved
Known to waiting according to the inventor, by reducing to form polarity and the molecular weight of the resin that engages resin layer, can make the Young's modulus that engages resin layer reduce.If the Young's modulus of the joint resin layer between display device and transparent facestock reduces, the stress producing during cure shrinkage diminishes, and can suppress the impact on display quality.
Yet, only by reduction, engaging the Young's modulus of resin layer, the power of fixing display part and transparent facestock is not enough sometimes, and for example, while display unit vertically being arranged to use, display device may be from transparent facestock landing or disengaging through after a period of time.
In addition, also considered by adopting curing precursor compound that molecular weight is high as far as possible as the raw material etc. that engages resin layer, the quantity of the combining site of curing reaction to be reduced relatively, thereby reduce the method for the Young's modulus that engages resin layer, but the viscosity of composition when uncured is too high, may be difficult to inject and be coated with.In addition, if the cross-linking density of the resin layer after solidifying becomes too small because of the minimizing of combining site quantity, the power of fixing display part and transparent facestock is not enough, and for example, while display unit vertically being arranged to use, display device may be from transparent facestock landing or disengaging through after a period of time.
The present invention is the invention In view of the foregoing completing, its object is to provide the be situated between resin layer that forms with the cured article by curable resin composition that plane materiel is stacked when integrated, not only can fully plane materiel be interfixed, the curable resin composition of the stress that the contraction in the time of also can reducing resin layer and solidify produces and use the folded plane materiel of this cured resin composition layer and duplexer.
In addition, the present invention also aims to provide the be situated between resin layer that forms with the cured article by curable resin composition that plane materiel is stacked when integrated, can fully plane materiel be interfixed, the stress that contraction in the time of reducing resin layer and solidify produces, and can fully suppress the manufacture method of the duplexer of the generation of bubble in resin layer.
The technical scheme that technical solution problem adopts
Curable resin composition of the present invention is for by uncured curable resin composition being held between a facestock and making the curable resin composition of its duplexer being solidified to form, it is characterized in that, at least one party's plane materiel is transparent, comprise following solidified nature compound (II) and following uncured oligomers (D), the content of this uncured oligomers (D) is 10～90 quality %.
Solidified nature compound (II) comprises a kind of above solidified nature compound that curing reaction occurs when curable resin composition solidifies, and at least a kind in this solidified nature compound has the hydroxyl not reacting when described curable resin composition solidifies.
Uncured oligomers (D) is that curable resin composition with described solidified nature compound (II), curing reaction does not occur while solidifying, and average every 1 molecule has the oligopolymer of 0.8～3 hydroxyl.
Better that described solidified nature compound (II) comprises the monomer simultaneously with solidified nature group and hydroxyl.
Be better that described solidified nature compound (II) comprises and has the oligopolymer that solidified nature group and molecular weight are 1000～100000 (A ') and has solidified nature group and monomer that molecular weight is 125～600 (B '), this monomer (B ') comprises the monomer (B3) with hydroxyl.
Better that described uncured oligomers (D) is polyoxyalkylene polyol, and described oligopolymer (A ') for polyoxyalkylene polyol and polyisocyanates are used as to the synthetic oligourethane of raw material.
Be better that described oligopolymer (A ') has acryl, at least a portion of described monomer (B ') has methacryloyl.
Be better described monomer (B3) comprise there is hydroxyl value 1～2, the hydroxyl-metacrylate of the hydroxyalkyl of carbon number 3～8.
It is better the monomer (B4) that described monomer (B ') comprises the alkyl methacrylate that is selected from the alkyl with carbon number 8～22.
Better not containing chain-transfer agent, or comprise chain-transfer agent and its content with respect to 100 mass parts solidified nature compounds (II) below 1 mass parts.
The stacked integrated duplexer forming of resin layer that the facestock that to the invention provides at least one party be transparent facestock is situated between and forms with the cured article by curable resin composition of the present invention.
A side who is better a described facestock is transparent facestock, and the opposing party is display device.
The manufacture method of duplexer of the present invention be manufacture the first plane materiel that the either party comprise in the first plane materiel and the second plane materiel is transparent facestock and the second plane materiel, by the resin layer of this first plane materiel and the second plane materiel clamping, the method for surrounding the duplexer of resin layer sealing around, there is following operation (a)～(d):
(a) the surperficial circumference at the first plane materiel is coated with the aqueous sealing formation curable resin composition that comprises solidified nature compound (I) and polymerization starter, forms the operation of uncured sealing;
(b) region surrounding to the sealing by uncured is supplied with the resin layer being formed by curable resin composition of the present invention and is formed the operation with curable resin composition;
(c) under the reduced atmosphere below 100Pa, the second plane materiel is overlapped in to resin layer and forms with on curable resin composition, obtain resin layer and form with curable resin composition by the operation of the stacked precursor of the first plane materiel, the second plane materiel and uncured both seals;
(d), so that stacked precursor is placed in to the state under pressure atmosphere more than 50kPa, uncured sealing and resin layer are formed by the curing operation of curable resin composition.
A side who is better described the first plane materiel and the second plane materiel is transparent facestock, and the opposing party is display device.
The effect of invention
If adopt curable resin composition of the present invention, by making it be held between plane materiel and solidify, can a facestock is fully fixing, and can reduce the stress that the contraction while solidifying produces.
If adopt duplexer of the present invention, plane materiel and plane materiel are situated between fully fixingly with resin layer, and the stress that contraction during this resin layer curing produces is reduced.
If adopt the manufacture method of duplexer of the present invention, the resin layer that facestock Jie can be formed with the cured article by curable resin composition of the present invention is fully fixing, the stress that contraction while reducing this resin layer curing produces, and can be in fully suppressing resin layer manufacture duplexer in the generation of bubble.
Duplexer of the present invention is for example display unit; if adopt manufacture method of the present invention; the generation that can obtain bubble in the resin layer between display device and protecting sheet is fully suppressed; display device and protecting sheet are situated between fixing fully with this resin layer; and stress during cure shrinkage reduces, the display unit that the decline of the display quality that this stress causes is prevented.
The simple declaration of accompanying drawing
Fig. 1 means the sectional view of an example of the display unit that display device is protected by transparent facestock.
Fig. 2 is the vertical view of the display unit of Fig. 1.
Fig. 3 means the vertical view of an example of the situation of operation (a).
Fig. 4 means the sectional view of an example of the situation of operation (a).
Fig. 5 means the vertical view of an example of the situation of operation (b).
Fig. 6 means the sectional view of an example of the situation of operation (b).
Fig. 7 means the sectional view of an example of the situation of operation (c).
Fig. 8 means the sectional view of an example of the situation of operation (d).
The mode carrying out an invention
In the present invention, as give a definition.
In display unit, the transparent facestock of the protecting sheet as display unit is called to " front plane materiel ", display device is called " back side plane materiel ".
Front plane materiel and back side plane materiel are generically and collectively referred to as to " plane materiel ".
In this plane materiel, to in manufacture method of the present invention, at the plane materiel that circumference forms sealing and curable liquid resin composition is supplied with in the region that surrounds to sealed portion, be called " the first plane materiel ", the plane materiel being overlapped on this curable resin composition is called " the second plane materiel ".
The plane materiel with light transmission is called to " transparent facestock ".
The transparent facestock being formed by glass is called to " sheet glass ".
Below; as the preferred embodiment of the present invention, to the duplexer in the present invention, be that display unit, a facestock are that front plane materiel (becoming the transparent facestock of protecting sheet) and back side plane materiel (display device), sealing formation form and describe with the embodiment that curable resin composition is Photocurable resin composition with curable resin composition and resin layer.
< display unit >
Fig. 1 means the sectional view of an example of the display unit of present embodiment, and Fig. 2 is vertical view.
Display unit 1 has the transparent facestock 10 (the second plane materiel (or first plane materiel)) as front plane materiel, display device 50 (the first plane materiel (or second plane materiel)) as back side plane materiel, be sandwiched in the resin layer 40 between transparent facestock 10 and display device 50, surround resin layer sealing 42 around, be equipped with the flexible printing wiring board 54 (FPC) that is connected with display device 50 and makes the drive IC of display device 50 actions, be formed at the shading Printing Department 55 (light shielding part) of the circumference of transparent facestock 10.
In display unit 1, circumference in transparent facestock 10 is provided with shading Printing Department 55, the area of the resin layer 40 that the sealed portion 42 of Area Ratio of the transmittance section 56 being surrounded by shading Printing Department 55 surrounds is little, the area of the Area Ratio display device 50 of transparent facestock 10 is large, and the total area of resin layer 40 and sealing 42 is less than the area of transparent facestock 10 and display device 50 respectively.
[front plane materiel]
Front plane materiel is the transparent facestock (protecting sheet) of the demonstration image of transmissive display part.
As transparent facestock, can exemplify sheet glass or transparent resin plate, no matter be from the emergent light to from display device and the high angle of the catoptrical transparency, or from thering is the angle of photostabilization, low-birefringence, high plane precision, resistance to surface damage, high mechanical strength, sheet glass preferably all.Aspect the abundant transmission of curing light that is used in Photocurable resin composition, it is better also sheet glass.
As the material of sheet glass, can exemplify the glass materials such as soda-lime glass, be more preferably lower, the blue-colored few high transmission glass of ferrous components (ultrawhite sheet glass).In order to improve security, as front plane materiel, can use chilled glass.
As the material of transparent resin plate, can exemplify the high resin materials of the transparency such as polycarbonate, polymethylmethacrylate.
In order to make to improve with the interface cohesive force of resin layer, can implement surface treatment to transparent facestock.As surface-treated method, can exemplify the method the surface of transparent facestock processed with silane coupling agent, by adopting the oxidizing flame of flame burner to form the processing etc. of silicon oxide film.
Anti-reflection layer can be set at the back side on the junction surface with resin layer in transparent facestock and improve the contrast gradient that shows image.Anti-reflection layer can directly form the method for inorganic thin film by the front in transparent facestock, the method that the transparent resin film that is provided with anti-reflection layer is fitted in to transparent facestock arranges.
In addition, the object showing according to image, a part for transparent facestock or integral body is pigmentable also, or forms mat glass shape and make scattering of light, or refraction of light or reflection while making transmission by surperficial micro concavo-convex etc.Blooming that in addition, also blooming, polarizing coating of being form as above etc. can be carried out to optical modulation etc. fits in transparent facestock and forms one and is used as transparent facestock.
About the thickness of transparent facestock, from the angle of physical strength, the transparency, in the situation of employing sheet glass, be generally 0.5～25mm.At the television set of indoor use, PC, with in the purposes such as indicating meter, from the light-weighted angle of display unit, being better 0.7～6mm, being located in outdoor public demonstration purposes, is better 3～20mm.Transparent facestock can be used chilled glass, in the thin situation of transparent facestock, can use chemically reinforced glass.Adopting in the situation of transparent resin plate, is better 2～10mm.
[back side plane materiel]
Back side plane materiel is display device.
As the display device 50 of illustrated example, be bonding and use an example of the liquid crystal display device of the structure that a pair of polaroid 51 clamps by being provided with the transparent facestock 52 of color filter film and being provided with the transparent facestock 53 of TFT, the display device in present embodiment is not limited in the device of illustrated example.
Between the pair of electrodes that display device is is transparency electrode at least one party, clamping has optical states to pass through the device of the display material that outside electrical signal changes.According to the kind of display material, there are liquid crystal display device, EL display device, plasma display device, e-inks escope part etc.In addition, display device has that to make at least one party be the bonding structure of a facestock of transparent facestock, and the mode of joining with transparent facestock side and resin layer configures.At this moment, in the display device of a part, the outermost layer side in the transparent facestock of a side of joining with resin layer is provided with the bloomings such as polaroid, phase difference film sometimes.In this situation, resin layer is the blooming that engages on display device and the form of front plane materiel.
In order to make to improve with sealing interface cohesive force, can implement surface treatment to junction surface display device and resin layer.Surface treatment can only be carried out circumference, and carry out on whole surface that also can facestock.As surface-treated method, can exemplify the bonding method with processing such as base paints of use energy machining at low temperature etc.
About the thickness of display device, in the situation that make the liquid crystal display device of its action be generally 0.4～4mm by TFT, the in the situation that of EL display device, be generally 0.2～3mm.
[resin layer]
Resin layer is to make curable resin composition of the present invention (also claiming below resin layer formation Photocurable resin composition) solidify the layer forming.
Curable resin composition of the present invention (the resin layer formation Photocurable resin composition of present embodiment) can reduce the Young's modulus after solidifying, the stress producing while reducing to solidify.Therefore, can suppress the detrimentally affect that described stress produces the display performance of display device.In addition, viscosity during this curable resin composition uncured is low, therefore can carry out at short notice to the supply of the curable resin composition of facestock surface, is therefore easy to prevent front plane materiel and the residual bubble of back side facestock layer poststack.
The thickness of resin layer is better 0.03～2mm, is more preferably 0.1～0.8mm, particularly preferably 0.2～0.6mm.If the thickness of resin layer is more than 0.03mm, resin layer can cushion impact that the external force of origin self-induced transparency plane materiel side produces etc. effectively, thus protection display device.Particularly display device, in external force situation responsive and that easily display quality is impacted, is better the thickness adopting more than 0.2mm.In addition,, in the manufacture method of present embodiment, even if sneak into the foreign matter over resin layer thickness between transparent facestock and display device, the thickness of resin layer can significantly not change yet, few on the impact of light transmission.If the thickness of resin layer, below 2mm, be difficult for residual bubble in resin layer, and the thickness of display unit integral body can thicken necessarily.In the little situation of the Young's modulus of resin layer, be better to adopt the thickness below 0.6mm to suppress display device bonding station skew in time etc.
As the method for adjusting resin layer thickness, can exemplify and in the thickness that regulates sealing described later, regulate the aqueous resin layer that is supplied to the first plane materiel to form the method by the feed rate of Photocurable resin composition.
[sealing]
Sealing forms with Photocurable resin composition and is solidified to form by being coated with aqueous sealing described later.Because the region outside the image display area of display device is narrower, be better therefore that the width of sealing is less.The thickness of sealing is better 0.5～2mm, is more preferably 0.8～1.6mm.
[shading Printing Department]
Can be as required at the circumference of transparent facestock, shading Printing Department be set.Shading Printing Department makes the part beyond the image display area of display device can be not in sight from transparent facestock side, hides the Wiring member that is connected with display device etc.Shading Printing Department can be located at the Huo Qi back side, junction surface transparent facestock and resin layer, from reducing the angle of the parallax of shading Printing Department and image display area, is to be better located at transparent facestock and junction surface resin layer.Transparent facestock is in the situation of sheet glass, if shading Printing Department is used the ceramic printing containing black pigment, opacifying property is high, so preferably.Also can by by front or the back side transparent film that is provided with shading Printing Department be bonded in transparent facestock and form shading Printing Department.Can use the transparent facestock without shading Printing Department.
[shape]
The shape of display unit is generally rectangle.
The size of display unit is not particularly limited, the manufacture method of present embodiment is particularly suitable for the manufacture of larger area display unit, so in the situation of the PC watch-dog of use liquid crystal display device, better more than 0.3m * 0.18m, in the situation of television set, better more than 0.4m * 0.3m, particularly preferably more than 0.7m * 0.4m.The upper limit of the size of display unit is determined according to the size of display device mostly.In addition, excessive display unit is difficult to process aspect is set etc.Based on above-mentioned restriction, the upper limit of the size of display unit is generally 2.5m * 1.5m left and right.In the situation of miniscope, be better more than 0.14m * 0.08m.
Can be roughly the same as the transparent facestock of protecting sheet and the size of display device, but according to the relation with taking in other framework of display unit, transparent facestock is mostly than the large circle of display device.In addition, on the contrary, according to the structure of other framework, also can make transparent facestock slightly less than display device.
The manufacture method > of < display unit
The manufacture method of the display unit of present embodiment is the method that comprises following operation (a)～(d).
(a) the surperficial circumference at the first plane materiel (back side plane materiel (or front plane materiel)) is coated with the aqueous sealing formation Photocurable resin composition that comprises solidified nature compound (I) and Photoepolymerizationinitiater initiater (C1), forms the operation of uncured sealing; Wherein, in the situation that the first plane materiel is display device, the surface of the side showing at image forms sealing.
(b) region surrounding to the sealing by uncured is supplied with the aqueous resin layer that comprises solidified nature compound (II) and Photoepolymerizationinitiater initiater (C2) and is formed the operation with Photocurable resin composition;
(c) under the reduced atmosphere below 100Pa, the second plane materiel (front plane materiel (or back side plane materiel)) is overlapped in to resin layer and forms with on Photocurable resin composition, obtain resin layer and form with Photocurable resin composition by the operation of the stacked precursor of the first plane materiel, the second plane materiel and uncured both seals; Wherein, the surface of the second plane materiel is provided with in the situation of antireflection film, the mode of joining with Photocurable resin composition with surface and the resin layer formation of its rear side is overlapping, and in the situation that the second plane materiel is display device, it is overlapping that the side showing with image and resin layer form the mode of joining with Photocurable resin composition.
(d), so that stacked precursor is placed in to the state under pressure atmosphere more than 50kPa, uncured sealing and resin layer are formed with Photocurable resin composition irradiation light and make its curing operation.
Transparent facestock is not formed with in the situation of light shielding part, from the transparent facestock side of stacked precursor, through transmittance section, sealing and resin layer formation is irradiated to light with Photocurable resin composition.
The circumference of transparent facestock is formed with in the situation of light shielding part, the area of the resin layer that the sealed portion of Area Ratio of the transmittance section being surrounded by this light shielding part surrounds is little, above-mentioned resin layer forms with the contained Photoepolymerizationinitiater initiater of Photocurable resin composition (C2) to be had than above-mentioned sealing and forms the absorbing wavelength region (λ 2) with the more close long wavelength side in absorbing wavelength region (λ 1) of the contained Photoepolymerizationinitiater initiater (C1) of Photocurable resin composition, the light irradiating from the side of stacked precursor in above-mentioned operation (d) comprises the light of the wavelength in absorbing wavelength region (λ 1) and the light of the wavelength in absorbing wavelength region (λ 2).
The manufacture method of present embodiment is under reduced atmosphere, aqueous resin layer to be formed and enclosed between the first plane materiel and the second plane materiel with Photocurable resin composition, makes enclosed resin layer form the method (decompression laminating method) that is solidified to form resin layer with Photocurable resin composition under the inferior higher pressure atmosphere of normal atmosphere atmosphere.The lower resin layer of decompression forms inclosure with Photocurable resin composition and does not adopt resin layer is formed with light-cured resin and injects the method in the large area space of narrow gaps of the first plane materiel and the second plane materiel, but adopt to almost whole the supply resin layer formation of the first plane materiel, with overlapping the second plane materiel after Photocurable resin composition, resin layer formation is enclosed to the method between the first plane materiel and the second plane materiel with Photocurable resin composition.
Adopting the aqueous resin layer formation under decompression is known with inclosure and the formation of the resin layer under normal atmosphere of Photocurable resin composition with the example of the manufacture method of the curing Sparent laminate of Photocurable resin composition.For example, in No. 2008/81838 text of International Publication, No. 2009/16943 text of International Publication, record manufacture method and this manufacture method Photocurable resin composition used of Sparent laminate, be referenced in this specification sheets.
[operation (a)]
First, the periphery along a side surface of the first plane materiel forms uncured sealing.As the first plane materiel, use back side plane materiel or front plane materiel is arbitrarily.
The first plane materiel is in the situation as the transparent facestock of the protecting sheet of display device, and the face that forms uncured sealing is any in 2 surfaces.2 surperficial proterties under square one, are not selected a required side surface.For example, a side surface has been implemented to make, in surface-treated situation that the interface cohesive force with resin layer improves, on this surface, to form uncured sealing.In addition,, in the situation that a side surface is provided with anti-reflection layer, at its back side, form uncured sealing.
The first plane materiel is in the situation of display device, and the face that forms uncured sealing is the surface of a side of image demonstration.
For uncured sealing, importantly there is in operation described later (c) aqueous resin layer and form the interface cohesive force more than degree that can not spill from the interface of the interface of uncured sealing and the first plane materiel and uncured sealing and the second plane materiel with Photocurable resin composition and the hardness that can maintain the degree of shape.Therefore, uncured sealing is better that the high sealing of viscosity is formed and formed by coatings such as printing, distribution with Photocurable resin composition.
In addition, in order to keep the interval of the first plane materiel and the second plane materiel, can form with the spacer particle that mixes regulation particle diameter in Photocurable resin composition at sealing.
Also can form with after Photocurable resin composition at coating sealing, irradiation at once makes sealing part semicure for making the curing light of sealing, thereby makes the shape maintains longer time of sealing.
[sealing formation Photocurable resin composition]
It is the solidified nature compound (I) that comprises light solidified and the liquid composition of Photoepolymerizationinitiater initiater (C1) that sealing forms with Photocurable resin composition (also claiming below sealing material).
It is better 500～3000Pas by the viscosity of Photocurable resin composition that sealing forms, and is more preferably 800～2500Pas, is further more preferably 1000～2000Pas.If viscosity more than 500Pas, can maintain the shape of uncured sealing in a long time, can fully maintain the height of sealing.If viscosity, below 3000Pas, can form sealing by coating method.
Sealing forms by the viscosity of Photocurable resin composition and uses E type viscometer determining at 25 ℃.
(solidified nature compound (I))
From easily sealing being formed to the angle that is adjusted to above-mentioned scope by the viscosity of Photocurable resin composition, solidified nature compound (I) is better to comprise that a kind has above oligopolymer (A) that solidified nature group and number-average molecular weight are 30000～100000 and a kind and has above the monomer (B) that solidified nature group and molecular weight are 125～600.
Solidified nature group as oligopolymer (A) or monomer (B), can exemplify the combination etc. of unsaturated group (acryloxy, methacryloxy etc.), unsaturated group and the sulfydryl of addition polymerization, from the fast angle with obtaining transparent high sealing of curing speed, it is better the group that is selected from acryloxy and methacryloxy.
Solidified nature group in solidified nature group in oligopolymer (A) and monomer (B) can be identical, also can be different.The reactivity of the solidified nature group in the oligopolymer that molecular weight is higher (A) the easily solidified nature group in the monomer (B) lower than molecular weight is low, therefore solidifying of monomer (B) may first carry out and the viscosity of composition in its entirety sharply raises, and it is inhomogeneous that curing reaction becomes.Poor and obtain uniform sealing in order to reduce both reactivity of solidified nature group, the solidified nature group that is more preferably oligopolymer (A) adopts reactive higher acryloxy, and the solidified nature group of monomer (B) adopts reactive lower methacryloxy.
The number-average molecular weight of oligopolymer (A) is 30000～100000, is better 40000～80000, is more preferably 50000～65000.If the number-average molecular weight of oligopolymer (A), within the scope of this, easily forms sealing to be adjusted in described scope by the viscosity of Photocurable resin composition.
The number-average molecular weight of oligopolymer (A) is by GPC, to measure the number-average molecular weight of the polystyrene conversion obtaining.During GPC measures, occur, in the situation at peak of unreacted low molecular weight compositions (monomer etc.), removing this peak and obtaining number-average molecular weight.
The molecular weight of monomer (B) is 125～600, is better 140～400, is more preferably 150～350.If the molecular weight of monomer (B) is more than 125, the volatilization of the monomer (B) while making display unit by decompression laminating method described later is inhibited.If the molecular weight of monomer (B) below 600, can improve the solvability of monomer (B) to the oligopolymer of high molecular (A), can carry out well forming the viscosity adjustment with Photocurable resin composition as sealing.
(oligopolymer (A))
As oligopolymer (A), from sealing, form by the solidified nature of Photocurable resin composition, the angle of the mechanical characteristics of sealing is better that average every 1 molecule has 1.8～4 solidified nature groups.
As oligopolymer (A), can exemplify and there is the oligourethane of amino-formate bond, poly-(methyl) acrylate that gathers (methyl) acrylate, polyester polyol of polyoxyalkylene polyol etc.
From molecular designing that can be by carbamic acid ester chain etc. in a big way, adjust the resin solidifying mechanical characteristics, with the angle of the adaptation of plane materiel etc., be better that polyvalent alcohol and polyisocyanates are used as to the synthetic oligourethane of raw material, be more preferably oligourethane described later (A1).Polyvalent alcohol is more preferably polyoxyalkylene polyol.
(oligourethane (A1))
The viscosity of the oligourethane (A1) of number-average molecular weight in 30000～100000 scope is high, is therefore difficult to synthesize with usual method, allows to synthesize be also difficult to mix with monomer (B).
Therefore, better by using after the synthetic method synthesis of carbamates oligopolymer (A1) of monomer (B) (following monomer (B1) and monomer (B2)), the resultant of gained is directly used as to sealing formation Photocurable resin composition, or is used as sealing formation Photocurable resin composition after the resultant of gained is further used to monomer (B) (following monomer (B1), monomer (B3) etc.) dilution.
Monomer (B1): in monomer (B), there is solidified nature group and do not there is the monomer with the group of isocyanic ester radical reaction.
Monomer (B2): in monomer (B), there is solidified nature group and there is the monomer with the group of isocyanic ester radical reaction.
Monomer (B3): in monomer (B), there is solidified nature group and there is the monomer of hydroxyl.
The synthetic method of oligourethane (A1):
Under the existence of the monomer as thinner (B1), make polyvalent alcohol react with polyisocyanates and obtain after the prepolymer with isocyanate group, make the method for the isocyanic ester radical reaction of monomer (B2) and this prepolymer.
As polyvalent alcohol, polyisocyanates, can exemplify known compound, such as the polyvalent alcohol (I) of recording as the raw material of carbamate quasi-oligomer (a) in No. 2009/016943 text of International Publication, vulcabond (II) etc., is referenced in this specification sheets.
As polyvalent alcohol (I), can exemplify polyoxyalkylene polyol and polyester polyol, the polycarbonate polyols etc. such as polyoxyethylene glycol, polyoxypropylene diols.Wherein, be better polyoxyalkylene polyol, particularly preferably polyoxypropylene polyol.In addition,, if replace the partial oxygen propenyl of polyoxypropylene polyol with oxyethylene group, can improve resin layer and form the intermiscibility with Photocurable resin composition and other composition, more preferably.
Here, available oxyethylene group is replaced partial oxygen propenyl and is referred to that a part for the oxypropylene structure that forms polyoxypropylene polyol molecule replaces with the molecular structure of oxygen ethene structure.To same below record, also represent same implication.Oxygen ethene structure can form random or block exist in polyoxypropylene polyol.In addition, oxygen ethene structure can be present in the inside of polyoxypropylene polyol molecule, also terminal hydroxyl and then.Oxygen ethene structure, can be by obtaining ethyleneoxide addition and then in the situation of terminal hydroxyl in polyoxypropylene polyol.
As vulcabond (II), be to be better selected from aliphatic diisocyanate, alicyclic diisocyanate and without the vulcabond of xanthochromia aromatic diisocyanate.Wherein, as the example of aliphatic polyisocyante, can exemplify hexamethylene diisocyanate, 2,2,4-trimethylammonium-hexamethylene diisocyanate, 2,4,4-trimethylammonium-hexamethylene diisocyanate etc.As the example of ester ring type polyisocyanates, can exemplify isophorone diisocyanate, methylene bis(4-etc.As without xanthochromia aromatic diisocyanate, can exemplify xylylene diisocyanate etc.They can use separately a kind, also can two or more also use.
As monomer (B1), can exemplify (methyl) alkyl acrylate ((methyl) vinylformic acid dodecyl ester, (methyl) vinylformic acid Octadecane base ester, (methyl) vinylformic acid n-docosane base ester etc.) containing the alkyl of carbon number 8～22, containing (methyl) acrylate ((methyl) isobornyl acrylate, (methyl) vinylformic acid adamantane esters etc.) of alicyclic alkyl.
As monomer (B2), can exemplify the monomer containing active hydrogen (hydroxyl, amino etc.) and solidified nature group, specifically can exemplify (methyl) vinylformic acid hydroxyalkyl acrylate ((methyl) vinylformic acid-2-hydroxy methyl, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxyl butyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester etc.) containing the hydroxyalkyl of carbon number 2～6 etc., be better the vinylformic acid hydroxyalkyl acrylate containing the hydroxyalkyl of carbon number 2～4.
(monomer (B))
From sealing, form by the solidified nature of Photocurable resin composition, the angle of the mechanical characteristics of sealing, monomer (B) is better that average every 1 molecule has 1～3 solidified nature group.
Sealing forms with in Photocurable resin composition, can be included in the monomer (B1) that is used as thinner in the synthetic method of above-mentioned oligourethane (A1) as monomer (B).In addition, as monomer (B), can be included in the unreacted monomer (B2) using in the synthetic method of above-mentioned oligourethane (A1).
From the adaptation of plane materiel and sealing and the deliquescent angle of various additives described later, monomer (B) is better the monomer (B3) that comprises hydroxyl.
Monomer (B3) as hydroxyl, better the hydroxymethyl vinylformic acid (methacrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxyl butyl ester, methacrylic acid-4-hydroxyl butyl ester, the own ester of methacrylic acid-6-hydroxyl, glycerin monomethyl acrylic ester etc.) of the hydroxyalkyl of hydroxyl number 1～2, carbon number 3～8, particularly preferably methacrylic acid-2-hydroxyl butyl ester.
Sealing form with containing of the monomer in Photocurable resin composition (B) proportional at the whole 100 quality % of solidified nature compound (I), be to be better 15～50 quality % in the total 100 quality % of oligopolymer (A) and monomer (B), be more preferably 20～45 quality %, be further more preferably 25～40 quality %.If the ratio of monomer (B) is more than 15 quality %, sealing formation is good by the adaptation of solidified nature, plane materiel and the sealing of Photocurable resin composition.If the ratio of monomer (B) below 50 quality %, easily forms sealing more than viscosity with Photocurable resin composition is adjusted to 500Pas.
In oligourethane (A1) synthetic, with the isocyanic ester radical reaction of prepolymer monomer (B2) as the part of oligopolymer (A), exist, be therefore not included in sealing and form in the content with the monomer (B) in Photocurable resin composition.On the other hand, in oligourethane (A1) synthetic, the monomer (B) adding after the monomer (B1) using as thinner and synthesis of carbamates oligopolymer (A1) is included in sealing and forms in the content of using the monomer (B) in Photocurable resin composition.
(Photoepolymerizationinitiater initiater (C1))
As sealing, form with the contained Photoepolymerizationinitiater initiater (C1) of Photocurable resin composition, the Photoepolymerizationinitiater initiater that can exemplify phenyl methyl ketone class, ketal class, bitter almond oil camphor or benzoin ethers, phosphinoxides, Benzophenones, thioxanthene ketone, quinones etc. is better the Photoepolymerizationinitiater initiater of phenyl methyl ketone class, ketal class, benzoin ethers.In the situation that visible ray by short wavelength is cured, from absorbing wavelength region, be more preferably phosphinoxides Photoepolymerizationinitiater initiater.By also, with the different Photoepolymerizationinitiater initiater of more than two kinds (C1) in absorbing wavelength region, can further shorten set time, or improve the surface cure of sealing.In addition, transparent facestock is provided with shading Printing Department and forms with in the curing situation of Photocurable resin composition by uncured sealing and resin layer that the illumination from plane materiel side makes to be held on shading Printing Department, can form with in the curing scope of Photocurable resin composition and with Photoepolymerizationinitiater initiater described later (C2) not hindering resin layer with the part of uncured sealing adjacency.And the used time, from can be efficiently and the angle being effectively cured, the ratio of polymerization starter (C1) and polymerization starter (C2) be with (C1): it is 50:1～5:1 that mass ratio (C2) is haggled over.In order from the light of plane materiel side-irradiation, the resin layer formation that is held on shading Printing Department to be solidified with uncured sealing material by being situated between with Photocurable resin composition at short notice, be better that sealing is formed with Photocurable resin composition containing Photoepolymerizationinitiater initiater (C2).
It is better 0.01～10 mass parts with respect to total 100 mass parts of solidified nature compound (I) integral body, oligopolymer (A) and monomer (B) that sealing forms content with the Photoepolymerizationinitiater initiater in Photocurable resin composition (C1) (containing Photoepolymerizationinitiater initiater (C2) time be (C1) and total amount (C2)), is more preferably 0.1～5 mass parts.
(additive)
Sealing forms can comprise the various additives such as stopper, photocuring promotor, chain-transfer agent, photostabilizer (UV light absorber, radical scavenger etc.), antioxidant, difficult burning agent, cementability rising agent (silane coupling agent etc.), pigment, dyestuff as required with Photocurable resin composition, is better to comprise stopper, photostabilizer.Particularly by the amount with fewer than polymerization starter, comprise stopper, can improve sealing and form the stability with Photocurable resin composition, also can adjust the molecular weight of the resin layer after solidifying.By the light from plane materiel side-irradiation, make the curing situation of sealing material, be better not use as far as possible stopper or chain-transfer agent, photostabilizer, pigment or the dyestuff etc. with the effect that makes curing reaction delay, or reduce its content.
As stopper, can exemplify the stopper of hydroquinones (2,5 di tert butylhydroquinone etc.), pyrocatechol (p-tert-butyl catechol etc.), Anthraquinones, phenothiazines, hydroxytoluene class etc.
As photostabilizer, can exemplify UV light absorber (benzotriazole category, Benzophenones, salicylate class etc.), radical scavenger (hindered amines) etc.
As antioxidant, can exemplify compound Phosphorus, sulphur class.
The total amount of these additives is whole with respect to solidified nature compound (I), be that total 100 mass parts of oligopolymer (A) and monomer (B) are better below 10 mass parts, be more preferably below 5 mass parts.
[operation (b)]
After operation (a), aqueous resin layer formation Photocurable resin composition is supplied with in the region surrounding to the sealing by uncured.
Resin layer forms feed rate with Photocurable resin composition and is redefined for the space just being formed by sealing, the first plane materiel and the second plane materiel and is formed by the deal that between Photocurable resin composition filling and the first plane materiel and the second plane materiel is predetermined distance (that is, making resin layer is the thickness of stipulating) by resin layer.At this moment, be better to consider that in advance by resin layer, forming the volume that the cure shrinkage with Photocurable resin composition causes reduces.Therefore, this deal is better that resin layer forms the slightly thick amount of specific thickness with the Thickness Ratio resin layer of Photocurable resin composition.In the little situation of cure shrinkage, can make the specific thickness of resin layer form and substantially equate with the thickness of Photocurable resin composition with resin layer.
As supply method, can exemplify following method: the first plane materiel is kept flat, by feedwaies such as divider, mould painting machines, be point-like, wire or planar supply.
[resin layer formation Photocurable resin composition]
It is the liquid composition of the solidified nature compound (II), Photoepolymerizationinitiater initiater (C2) and the uncured oligomers (D) that comprise light solidified that resin layer forms with Photocurable resin composition.Uncured oligomers (D) be resin layer form while solidifying with Photocurable resin composition not with composition in solidified nature compound (II) there is curing reaction, and average every 1 molecule has the oligopolymer of 0.8～3 hydroxyl.
It is better 0.05～50Pas by the viscosity of Photocurable resin composition that resin layer forms, and is more preferably 1～20Pas.If viscosity more than 0.05Pas, can be controlled the ratio of monomer described later (B '), the physical property of resin layer declines and is inhibited.In addition, lower boiling composition reduces, and is therefore suitable for decompression laminating method described later.If viscosity, below 50Pas, is difficult for residual bubble in resin layer.
Resin layer forms by the viscosity of Photocurable resin composition and uses E type viscometer determining at 25 ℃.
(solidified nature compound (II))
Resin layer forms with the solidified nature compound (II) in Photocurable resin composition and comprises that a kind forms at this resin layer the solidified nature compound that curing reaction occurs while solidifying with Photocurable resin composition above, and in this solidified nature compound at least a kind is to have described resin layer to form the compound of the hydroxyl not reacting when curing with Photocurable resin composition (II a).
If solidified nature compound (II) comprises that (II a), makes solidified nature compound (II) be cured separately in the cured article that reacts and obtain and has hydroxyl described compound.Having of described hydroxyl is beneficial to the stabilization of the uncured oligomers in Photocurable resin composition for resin layer formation.
Therefore, (II is a) compound that has unreacted hydroxyl after curing reaction to have the compound of the described hydroxyl not reacting when curing, even if for example (II part of hydroxyl generation curing reaction a), there is not curing reaction and is residual with unreacted state in rest part to compound.
(II is a) when having the solidified nature group that participates in curing reaction, to have the compound of hydroxyl to the described compound with the hydroxyl not reacting when curing, can be monomer, can be also the oligopolymer with repeating unit.The angle of the viscosity of Photocurable composition when uncured from easy adjustment is better that as compound, (II a) by the monomer simultaneously with solidified nature group and hydroxyl.As have the monomer of hydroxyl compound (II object lesson a) can exemplify there is hydroxyl value 1～2, the hydroxyl of the hydroxyalkyl of carbon number 3～8 (methyl) acrylate ((methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxyl butyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, the own ester of (methyl) vinylformic acid-6-hydroxyl, glycerine list (methyl) acrylate etc.), particularly preferably methacrylic acid-2-hydroxyl butyl ester.
Solidified nature compound (II) is better to comprise that a kind has above the oligopolymer that solidified nature group and number-average molecular weight are 1000～100000 (A ') and a kind and has above the monomer that solidified nature group and molecular weight are 125～600 (B ').If use described solidified nature compound (II), easily resin layer is formed and is adjusted in above-mentioned preferable range by the viscosity of Photocurable resin composition.
In this situation, be better at least a portion as monomer (B '), use and there is the monomer (B3) that the molecular weight of solidified nature group and hydroxyl is 125～600 simultaneously.
Solidified nature group as oligopolymer (A ') or monomer (B '), can exemplify the combination etc. of unsaturated group (acryloxy, methacryloxy etc.), unsaturated group and the sulfydryl of addition polymerization, from the fast angle with obtaining transparent high resin layer of curing speed, it is better the group that is selected from acryloxy and methacryloxy.
Solidified nature group in solidified nature group in oligopolymer (A ') and monomer (B ') can be identical, also can be different.The reactivity of the solidified nature group in the oligopolymer that molecular weight is higher (A ') the easily solidified nature group in the monomer lower than molecular weight (B ') is low, therefore solidifying of monomer (B ') may first carry out and the viscosity of composition in its entirety sharply raises, and it is inhomogeneous that curing reaction becomes.Poor and obtain uniform resin layer in order to reduce both reactivity of solidified nature group, the solidified nature group that is more preferably oligopolymer (A ') adopts reactive higher acryloxy, and the solidified nature group of monomer (B ') adopts reactive lower methacryloxy.
(oligopolymer (A '))
Oligopolymer (A ') number-average molecular weight is better 1000～100000, is more preferably 10000～70000.If the number-average molecular weight of oligopolymer (A '), within the scope of this, easily becomes to be adjusted in described scope by the viscosity of Photocurable resin composition by resin layer.
The number-average molecular weight of oligopolymer (A ') is by GPC, to measure the number-average molecular weight of the polystyrene conversion obtaining.During GPC measures, occur, in the situation at peak of unreacted low molecular weight compositions (monomer etc.), removing this peak and obtaining number-average molecular weight.
As oligopolymer (A '), from resin layer, form by the solidified nature of Photocurable resin composition, the angle of the mechanical characteristics of resin layer is better that average every 1 molecule has 1.8～4 solidified nature groups.
As oligopolymer (A '), can exemplify and there is the oligourethane of amino-formate bond, many (methyl) acrylate of many (methyl) acrylate of polyoxyalkylene polyol, polyester polyol etc., due to the molecular designing etc. that oligourethane (A2) can be by carbamic acid ester chain significantly adjust the mechanical characteristics of the resin after solidifying, with the adaptation of plane materiel etc., therefore preferably.
Oligourethane (A2) is better by polyvalent alcohol is reacted obtain to make described monomer (B2) compound synthetic with the method for the isocyanic ester radical reaction of this prepolymer after the prepolymer with isocyanate group with polyisocyanates.
As polyvalent alcohol, polyisocyanates, can exemplify known compound, such as the polyvalent alcohol (I) of recording as the raw material of carbamate quasi-oligomer (a) in No. 2009/016943 text of International Publication, vulcabond (II) etc., is referenced in this specification sheets.
As oligourethane (A2), can use commercially available compound, can exemplify for example EB230 (Daicel match Tektronix Co., Ltd (ダ イ セ ルサ イテック society) system, functional group's number 2, confirm as the resultant of reaction of the own ester of polypropylene glycol/IPDI/ vinylformic acid-2-hydroxyethyl), U-200AX (Xin Zhong village chemical industry Co., Ltd. (Xin Zhong village chemistry society) system, functional group's number 2, confirms as the resultant of reaction of aliphatic polyester polyols/aliphatics or alicyclic polyisocyanates/vinylformic acid-own ester of 2-hydroxyethyl).
Oligopolymer (A ') containing proportional at the whole 100 quality % of solidified nature compound (II), be to be better 20～90 quality % in the total 100 quality % of oligopolymer (A ') and monomer (B '), be more preferably 30～80 quality %.If the ratio of this oligopolymer (A ') is more than 20 quality %, the thermotolerance of resin layer is good.If the ratio of this oligopolymer (A ') is below 90 quality %, resin layer forms by the adaptation of solidified nature, plane materiel and the resin layer of Photocurable resin composition good.
(monomer (B '))
The molecular weight of monomer (B ') is better 125～600, is more preferably 140～400.If the molecular weight of monomer (B ') is more than 125, the volatilization of the monomer while making display unit by decompression laminating method described later is inhibited.If the molecular weight of monomer (B ') is below 600, the adaptation of plane materiel and resin layer is good.
As monomer (B '), from resin layer, form by the solidified nature of Photocurable resin composition, the angle of the mechanical characteristics of resin layer is better that average every 1 molecule has 1～3 solidified nature group.
Monomer (B ') containing proportional at the whole 100 quality % of solidified nature compound (II), be to be better 10～80 quality % in the total 100 quality % of oligopolymer (A ') and monomer (B '), be more preferably 20～70 quality %.
Monomer (B ') be better to comprise the monomer (B3) simultaneously with solidified nature group and hydroxyl.Monomer (B3) is conducive to the stabilization of uncured oligomers (D).In addition,, if comprise monomer (B3), easily obtain the good adaptation of plane materiel and resin layer.Hydroxyl value in 1 molecule of monomer (B3) can select arbitrarily to make the stable quantity of uncured oligomers (D), from the angle that is easy to obtain, is better in 1 molecule 1～2.
As the monomer (B3) of hydroxyl, can exemplify with sealing and form with the same monomer of the monomer (B3) in Photocurable resin composition, particularly preferably methacrylic-2-hydroxyl butyl ester.
Monomer (B3) containing proportional at the whole 100 quality % of solidified nature compound (II), be to be better 10～60 quality % in the total 100 quality % of oligopolymer (A ') and monomer (B '), be more preferably 20～50 quality %.If containing of this monomer (B3) is proportional more than 10 quality %, easily fully obtains resin layer and form the effect of using the stability raising of Photocurable resin composition and the adaptation of plane materiel and resin layer to improve.If this monomer (B3) containing proportional below 60 quality %, by resin layer, forming the hardness of the cured article forming with Photocurable resin composition can be not too high, so preferred.
From the angle of the mechanical characteristics of resin layer, and monomer (B ') be better to comprise following monomer (B4).The second-order transition temperature (Tg) of the resin layer after monomer (B4) makes to solidify reduces, and is therefore conducive to the reduction of the Young's modulus of the resin layer after solidifying, and the flexibility of this resin layer is improved.
But, improve resin layer and form solidified nature with Photocurable resin composition and shorten in the situation of solidifying required time etc., be better the content of minimizing monomer (B4) or do not comprise monomer (B4).
Monomer (B4): be selected from the more than a kind of alkyl methacrylate containing the alkyl of carbon number 8～22.If carbon number more than 8, can make the second-order transition temperature of cured article decline, so preferably; If carbon number, below 22, can easily obtain raw alcohol by natural goods, so preferably.
As monomer (B4), can exemplified by methyl vinylformic acid dodecyl ester, methacrylic acid Octadecane base ester, methacrylic acid n-docosane base ester etc., be better methacrylic acid dodecyl ester or methacrylic acid Octadecane base ester.
Monomer (B4) containing proportional at the whole 100 quality % of solidified nature compound (II), be to be better 5～50 quality % in the total 100 quality % of oligopolymer (A ') and monomer (B '), be more preferably 15～40 quality %.If containing of this monomer (B4) is proportional more than 5 quality %, easily fully obtain the additive effect of monomer (B4).
(Photoepolymerizationinitiater initiater (C2))
As resin layer, form with the contained Photoepolymerizationinitiater initiater (C2) of Photocurable resin composition, can exemplify the Photoepolymerizationinitiater initiater of phenyl methyl ketone class, ketal class, bitter almond oil camphor or benzoin ethers, phosphinoxides, Benzophenones, thioxanthene ketone, quinones etc., it is better the Photoepolymerizationinitiater initiater of phosphinoxides or thioxanthene ketone, from photopolymerization reaction, suppress painted angle, particularly preferably phosphinoxides.
That resin layer forms is whole with respect to solidified nature compound (II) with the content of the Photoepolymerizationinitiater initiater in Photocurable resin composition (C2), be that total 100 mass parts of oligopolymer (A ') and monomer (B ') are better 0.01～10 mass parts, be more preferably 0.1～5 mass parts.
By the light irradiating from plane materiel side, make to form with the curing situation of a part for Photocurable resin composition with the resin layer of sealing material adjacency, Photoepolymerizationinitiater initiater (C2) is better the absorbing wavelength region (λ 2) having than the more close long wavelength side in the absorbing wavelength region of described Photoepolymerizationinitiater initiater (C1) (λ 1).Photoepolymerizationinitiater initiater (C2) can only have absorbing wavelength region (λ 2), also can have absorbing wavelength region (λ 1 ') and absorbing wavelength region (λ 2) of repeating with absorbing wavelength region (λ 1).
(uncured oligomers (D))
Uncured oligomers (D) forms with mixing well in Photocurable resin composition and not participating in solidifying at resin layer, so can reduce the stress of the contraction generation of resin layer when curing under not destroying the transparency and homogeneous situation.
Uncured oligomers (D) be resin layer form while solidifying with Photocurable resin composition not with composition in solidified nature compound (II) there is curing reaction, and average every 1 molecule has the oligopolymer of 0.8～3 hydroxyl.The hydroxyl of average every 1 molecule is more preferably 2～3.If the hydroxyl of average every 1 molecule is more than 0.8, can make by the interaction between the hydroxyl between uncured oligomers or between uncured oligomers and the cured article that obtained by solidified nature compound (II) uncured oligomers keep stable, so preferably; If the hydroxyl of average every 1 molecule is below 3, uncured oligomers can form with mixing well in Photocurable resin composition at resin layer, so preferably.
The number-average molecular weight (Mn) corresponding to average 1 hydroxyl of uncured oligomers (D) is better 400～8000.If number-average molecular weight corresponding to average 1 hydroxyl is more than 400, the polarity of uncured oligomers (D) can be not too high, can obtain and resin layer forms the good intermiscibility with the solidified nature compound (II) in Photocurable resin composition.If number-average molecular weight corresponding to average 1 hydroxyl is below 8000,, by deriving from the interaction between the hydroxyl of solidified nature compound (II) and the hydroxyl of uncured oligomers (D), easily obtain in the resin layer after solidifying and make the stable effect of uncured oligomers (D).Inferring in described interaction has hydrogen bond to participate in.
Uncured oligomers (D) can be used alone or two or more kinds may be used.
Example as the uncured oligomers (D) of hydroxyl, can exemplify the polyvalent alcohol of high molecular etc., is better polyoxyalkylene polyol, polyester polyol or polycarbonate polyol.
As polyoxyalkylene polyol, can exemplify polyoxyalkylene one alcohol, polyoxyalkylene diols or the polyoxyalkylene triols of the oxyalkylene repeat units with 2～4 of carbon numbers.Specifically, can exemplify polyoxypropylene one alcohol, polyoxyethylene glycol, polyoxypropylene diols (being also denoted as below polypropylene glycol), polyoxypropylene triol, polytetramethylene glycol etc.
The number-average molecular weight (Mn) corresponding to average 1 hydroxyl of polyoxyalkylene polyol is better 400～8000, is more preferably 600～5000.
As polyester polyol, can exemplify the aliphatic category polyester diol of the residue of the aliphatic dicarboxylic acids such as the residue of aliphatic dihydroxy alcohols such as thering is ethylene glycol, propylene glycol, BDO and pentanedioic acid, hexanodioic acid, sebacic acid.
As polycarbonate polyol, can exemplify there is 1,6-hexylene glycol etc. the aliphatic polycarbonate diol of residue of dihydric alcohol, the aliphatic polycarbonate diols such as ring-opening polymerization polymer of aliphatics cyclic carbonate.
The number-average molecular weight (Mn) corresponding to average 1 hydroxyl of polyester polyol or polycarbonate polyol is better 400～8000, is more preferably 800～6000.
The number-average molecular weight of the uncured oligomers (D) in this specification sheets is the value of being calculated by following formula (1) according to 1 intramolecular hydroxyl value B of the hydroxyl value A (KOH mg/g) measuring according to JISK1557-1 (version in 2007) and uncured oligomers (D).
Molecular weight=56.1 * B * the 1000/A of uncured oligomers (D) ... (1)
The angle that the Young's modulus of the resin layer from solidifying easily becomes lower, as uncured oligomers (D), is better to use polyoxyalkylene polyol, particularly preferably polyoxypropylene polyol.In addition, as described later, the partial oxygen propenyl of polyoxypropylene polyol can be replaced with to the polarity that oxyethylene group regulates uncured oligomers (D).The explanation of replacing partial oxygen propenyl about available oxyethylene group is identical with the explanation in above-mentioned polyvalent alcohol (I).
For example, and oligopolymer (A ') be that polyoxyalkylene polyol and polyisocyanates are used as to the synthetic oligourethane of raw material, when uncured oligomers (D) is polyoxyalkylene polyol, preferred from the angle of intermiscibility.
In the present invention, in order to make resin layer when uncured form with Photocurable resin composition stable, suppressing the resin layer of uncured oligomers (D) from solidifying separated, is better the molecular chain that oligopolymer (A ') and uncured oligomers (D) have same structure or similar structures.
Specifically, be better that the raw material of synthetic resin layer while forming with the oligopolymer in Photocurable resin composition (A ') used polyvalent alcohol etc. to have the compound (compound that also claims below hydroxyl) of hydroxyl, the compound of this same hydroxyl be used as to uncured oligomers (D) simultaneously.
For example, and oligopolymer (A ') be that polyoxyalkylene polyol and polyisocyanates are used as in the situation of the synthetic oligourethane of raw material, be better as uncured oligomers (D) by this polyoxyalkylene polyol.
Or, in the compound of the hydroxyl of the raw material of oligopolymer (the A ') situation different from the compound of hydroxyl as uncured oligomers (D), be better that both molecular chain possesses and has the common common structure of the parts such as repeating unit, the polarity that simultaneously makes both is equal extent.The inflation method of polarity can exemplify such as the method that improves polarity by introducing polar group, by replace partial oxygen propenyl with oxyethylene group, improve polarity method, by reducing average 1 molecular weight corresponding to hydroxyl, improve the method etc. of polarity.These methods are capable of being combined.
For example, oligopolymer (A ') is for replacing with oxyethylene group in the polyoxypropylene polyol that partial oxygen propenyl obtains (a ') and the situation of polyisocyanates as the synthetic oligourethane of raw material, is better to use and do not have polyvalent alcohol described in oxyethylene group and molecular weight ratio corresponding to average 1 hydroxyl polyoxypropylene polyol that (a ') is little as uncured oligomers (D).
As most preferred resin layer, form the example with Photocurable resin composition, can exemplify comprise make to using oxyethylene group replace partial oxygen propenyl and polyoxypropylene diols react with polyisocyanate compound and obtain it is reacted after the prepolymer with isocyanate group with described monomer (B2) and must oligourethane (A2) as oligopolymer (A '), comprise identical the usining of raw material with this oligourethane (A2) oxyethylene group replaced partial oxygen propenyl and polyoxypropylene diols as uncured oligomers (D), and comprise the monomer (B3) with hydroxyl as the composition of monomer (B ').
Can think if oligopolymer (A ') part has the molecular structure identical with uncured oligomers (D) like this, the intermiscibility of the uncured oligomers (D) in composition further improves, and monomer (B ') has hydroxyl, thereby the interaction of the hydroxyl in the hydroxyl in the molecular structure after solidifying by solidified nature compound (II) and the molecular structure of uncured oligomers (D), uncured oligomers (D) can stably be present in cured article.
In addition, as making comprising of another example to using oxyethylene group to replace partial oxygen propenyl polyoxypropylene diols react with polyisocyanate compound and obtain it is reacted after the prepolymer with isocyanate group with described monomer (B2) and must oligourethane (A2) as oligopolymer (A '), comprise do not using molecular weight ratio that oxyethylene group replaces as the little polyoxypropylene diols of the polyoxypropylene diols of the raw material of oligourethane (A2) as uncured oligomers (D), and comprise the monomer (B3) with hydroxyl as the composition of monomer (B '), also can obtain the good intermiscibility of the uncured oligomers (D) in composition, can make uncured oligomers (D) stably exist in cured article.
It is better 10～90 quality % with the content of the uncured oligomers (D) in Photocurable resin composition that resin layer forms, and is more preferably 30～80 quality %.If the content of uncured oligomers more than 10 quality %, easily fully obtains the effect that stress that the resin shrinkage owing to solidifying is produced reduces.If below 90 quality %, easily fully fixing between plane materiel, can prevent well the position skew in time after front plane materiel engages with back side plane materiel.
It is better 5 * 10 that resin layer forms by the storage shearing modulus of elasticity in the Measurement of Dynamic Viscoelasticity of the resin layer after Photocurable resin composition curing 2～1 * 10 5pa, is more preferably 8 * 10 2～5 * 10 4pa, is further more preferably 1 * 10 3～5 * 10 4pa.In addition, loss tangent (tan δ) is better below 1.4, is more preferably below 1.0.The lower value of loss tangent is not particularly limited, and can adopt and manufacture upper obtainable scope, in the situation of more soft resin layer, is generally more than 0.01.This measuring method that stores shearing modulus of elasticity and loss tangent as described later, by uncured resin layer being formed and irradiates light when applying dynamic shearing distortion with Photocurable resin composition the curing method of resin combination is carried out with Measurement of Dynamic Viscoelasticity device.
If the shearing modulus of elasticity after solidifying is 1 * 10 5below Pa, can fully reduce the stress that the resin shrinkage owing to solidifying produces, can suppress the impact on the display quality of display panel.If this shearing modulus of elasticity is 5 * 10 2more than Pa, can fix well a facestock (display device and transparent facestock).In addition, if loss tangent is below 1.4, during by the vertical setup and use of display unit, display device is also fixed on transparent facestock fully, because the deadweight of display device causes the situation of the position skew in time of resin layer distortion etc., display device, is prevented well.
By being formed, resin layer comprises uncured oligomers (D) with Photocurable resin composition, in the rising of the loss tangent (tan δ) of resin layer that can be after suppressing above-mentioned solidifying, reduce and store shearing modulus of elasticity, therefore can realize storage shearing modulus of elasticity in Measurement of Dynamic Viscoelasticity and loss tangent (tan δ) simultaneously respectively in preferable range.
(additive)
Resin layer forms can comprise the various additives such as stopper, photocuring promotor, chain-transfer agent, photostabilizer (UV light absorber, radical scavenger etc.), antioxidant, difficult burning agent, cementability rising agent (silane coupling agent etc.), pigment, dyestuff as required with Photocurable resin composition, is better to comprise stopper, photostabilizer.Particularly by the amount with fewer than polymerization starter, comprise stopper, can improve resin layer and form the stability with Photocurable resin composition, also can adjust the molecular weight of the resin layer after solidifying.
By containing on a small quantity chain-transfer agent, the molecular weight of the resin layer after capable of regulating solidifies, the storage elastic modulus of reduction resin layer, but in most cases curing speed can be slack-off.
The resin layer that comprises more uncured oligomers (D) of the present invention forms with in Photocurable resin composition, can adjust Young's modulus by the content of oligopolymer (D), is better therefore reduce the content of chain-transfer agent or do not contain.Specifically, whole with respect to solidified nature compound (II), be total 100 mass parts of oligopolymer (A ') and monomer (B '), the addition of chain-transfer agent is better below 1 mass parts, is more preferably below 0.5 mass parts.
[operation (c)]
After operation (b), by having supplied with resin layer formation, with the first plane materiel of Photocurable resin composition, put into reliever, with the first plane materiel being lain on the fixed support dish in reliever towards upper mode of curable resin composition.
Top in reliever is provided with the mobile supporting device that can move along the vertical direction, and the second plane materiel is installed on mobile supporting device.The second plane materiel is in the situation of display device, makes to show that the surface of a side of image is downward.The surface of the second plane materiel is provided with in the situation of anti-reflection layer, and the surface of a side that makes not form anti-reflection layer is downward.
The second plane materiel is placed in the top of the first plane materiel and does not form with resin layer the position contacting with Photocurable resin composition.That is, make the resin layer on the first plane materiel form with Photocurable resin composition relative in discontiguous mode with the second plane materiel.
The mobile supporting device that can move along the vertical direction can be located to the bottom in reliever, on mobile supporting device, place the first plane materiel of having supplied with curable resin composition.In this situation, the second plane materiel is arranged on the fixed support dish on the top of being located in reliever, makes the first plane materiel relative with the second plane materiel.
In addition, the first plane materiel and the second plane materiel all can be used to the upper and lower mobile supporting device supporting of being located in reliever.
The first plane materiel and the second plane materiel are disposed at behind the position of regulation, are reduced pressure and form the reduced atmosphere of regulation in the inside of reliever.If possible, in decompression operation or after the reduced atmosphere of formation regulation, in reliever, make the first plane materiel and the second plane materiel be positioned at the position of regulation.
The inside of reliever becomes after the reduced atmosphere of regulation, with the second plane materiel of mobile supporting device supporting, moves downwards, and the resin layer that the second plane materiel is overlapped on the first plane materiel forms with on Photocurable resin composition.
By overlapping, resin layer forms and to be sealed in by the surface (surface that shows a side in the situation of display device for image) of the first plane materiel, in the surface (surface that shows a side in the situation of display device for image) of the second plane materiel and space that uncured sealing surrounds with Photocurable resin composition.
When overlapping, deadweight by the second plane materiel, from extruding of mobile supporting device etc., resin layer forms and is extruded diffusion with Photocurable resin composition, resin layer forms and is full of in described space with Photocurable resin composition, while being then exposed to high pressure atmosphere in operation (d), forming the few or bubble-free resin layer of bubble and form the layer with Photocurable resin composition.
Reduced atmosphere when overlapping is better below 100Pa, more than 10Pa.If the hypotony of reduced atmosphere, may form with contained each composition (solidified nature compound, Photoepolymerizationinitiater initiater, stopper, photostabilizer etc.) of Photocurable resin composition and produce detrimentally affect resin layer.For example, if the hypotony of reduced atmosphere, each composition may gasify, and provides reduced atmosphere to need the time.The pressure of reduced atmosphere is more preferably 15～40Pa.
From overlapping the first plane materiel and the second plane materiel, the time till removing reduced atmosphere is not particularly limited, can form with removing immediately reduced atmosphere after the sealing of Photocurable resin composition at resin layer, also can after resin layer forms the sealing with Photocurable resin composition, maintain the decompression state specified time.By maintaining the decompression state specified time, resin layer forms with Photocurable resin composition and flows in enclosed space, and the interval between the first plane materiel and the second plane materiel becomes evenly, even if improve atmosphere pressures, also easily maintains sealed state.The time that maintains decompression state can be more than a few hours long-time, but from the angle of production efficiency, is better in 1 hour, is more preferably in 10 minutes.
In the manufacture method of present embodiment, the sealing that coating viscosity is high forms and forms in the situation of uncured sealing with Photocurable resin composition, the resin layer in the stacked precursor obtaining can be formed and is made as 10 thicker μ m～3mm with the thickness of Photocurable resin composition in operation (c).
[operation (d)]
In operation (c), remove after reduced atmosphere, stacked precursor is placed under the pressure atmosphere of atmosphere pressures more than 50kPa.
After stacked precursor is placed under pressure atmosphere more than 50kPa, the first plane materiel and the second plane materiel by the pressure extrusion after rising to closely sealed direction, if therefore there is bubble in the enclosed space in stacked precursor, resin layer forms and flows to bubble with Photocurable resin composition, and enclosed space integral body is formed and fills with Photocurable resin composition by resin layer equably.
Pressure atmosphere is generally 80kPa～120kPa.Pressure atmosphere can be normal atmosphere atmosphere, can be also than this higher pressure.From can carry out resin layer not needing specific installation, form the angle with the operation such as curing of Photocurable resin composition, preferably normal atmosphere atmosphere.
From stacked precursor being placed in pressure atmosphere more than 50kPa up to starting resin layer, forming and be not particularly limited with the time (being denoted as below the high pressure hold-time) till Photocurable resin composition curing.Stacked precursor is taken out and to move to solidification equipment from reliever, in the situation that proceed to the operation till starting to solidify under normal atmosphere atmosphere, the required time of this process is the high pressure hold-time.Therefore, be placed in the enclosed space of stacked precursor of lower time of normal atmosphere atmosphere and do not exist in the situation of bubble, or in the situation that in this process, bubble has disappeared, can make immediately resin layer form with Photocurable resin composition and solidify.Till bubble collapse, need in the situation of time, stacked precursor is remained on to more than 50kPa pressure atmosphere down to till bubble collapse.In addition, though the high pressure hold-time extend and also conventionally can not have problems, so can need to extend the high pressure hold-time according to other in operation.The high pressure hold-time can be 1 day above long period, but from the angle of production efficiency, is better in 6 hours, is more preferably in 1 hour, and the angle further improving from production efficiency, particularly preferably in 10 minutes.
Then, with the state stacked precursor being placed under pressure atmosphere more than 50kPa, resin layer formation is solidified with Photocurable resin composition, thereby form the resin layer that engages display device and protecting sheet, make display unit.
Resin layer forms with Photocurable resin composition and sealing and forms with Photocurable resin composition and solidify by irradiating light.For example, from light source (UV-lamp, high voltage mercury lamp, black lamp, chemical lamp, UV-LED etc.) irradiation ultraviolet radiation or short wavelength's visible ray, Photocurable resin composition is solidified.
In addition, at this moment, by sealing, forming the uncured sealing that forms with Photocurable resin composition can form in curing with Photocurable resin composition and solidify at resin layer, also can form before solidifying with Photocurable resin composition and solidify in advance at resin layer.In addition, in the situation that a part for transparent facestock is formed with shading Printing Department and is held on shading Printing Department and forms sealing, be difficult to, by sealing being solidified for resin layer formation with the light of the transmittance section of the curing transmission transparent facestock of Photocurable resin composition, therefore can after resin layer formation is solidified with Photocurable resin composition, make sealing curing.
For example, in first plane materiel and the second plane materiel of stacked precursor, from a side of tool light transmission, resin layer is formed and irradiates light with Photocurable resin composition, and from the side of stacked precursor, the uncured sealing and the resin layer formation that are sandwiched between light shielding part and display device are irradiated to light with Photocurable resin composition.
In the first plane materiel and the second plane materiel, display device is not had a light transmission under the state of being failure to actuate, and therefore from a side of the transparent facestock as protecting sheet, sees through transmittance section and irradiates light.
In addition, if the periphery in transparent facestock is provided with shading Printing Department, there is uncured sealing or resin layer formation Photocurable resin composition in the region of Bei shading Printing Department and display device clamping, only the light of the transmittance section by self-induced transparency plane materiel cannot be fully curing.Therefore, from the side of display device, irradiate light.
As light, be better ultraviolet ray or the visible ray below 450nm.Particularly transparent facestock is provided with anti-reflection layer and ultraviolet ray and cannot sees through anti-reflection layer or be formed with the transparent resin film of anti-reflection layer and be located in the situation of tack coat between this antireflection film and transparent facestock etc., need to be cured by visible ray.
As the light source of the illumination from side, can use the light source for the illumination of self-induced transparency plane materiel side, from the configuration space of light source be suitable for to the angle of the high-efficiency light irradiation of specific position, be better the LED that uses transmitting ultraviolet ray or the visible ray below 450nm.
Step as illumination, can after the illumination of self-induced transparency plane materiel side, from side, carry out illumination, also can be on the contrary or carry out illumination simultaneously, in order further to promote uncured sealing and the resin layer of shading Printing Department to form the photocuring with Photocurable resin composition, be better first from side, to carry out illumination or from transparent facestock side, carry out illumination with side simultaneously.In addition, after illumination, resin layer forms waits in time Photocurable resin composition with solidifying of Photocurable resin composition curing needs in the situation of time, also can form after substantially finishing with Photocurable resin composition curing and make sealing curing by the illumination from side at resin layer.
[concrete example]
In the manufacture method of present embodiment, as the first plane materiel, use back side plane materiel or front plane materiel is arbitrarily.Therefore, display unit can be manufactured by 2 kinds of following methods respectively according to the selection of the first plane materiel.
(α-1) first plane materiel adopts display device (back side plane materiel), and the second plane materiel adopts the method as the transparent facestock (front plane materiel) of protecting sheet.
(α-2) first plane materiel adopts the transparent facestock (front plane materiel) as protecting sheet, and the second plane materiel adopts the method for display device (back side plane materiel).
Below, the situation of method (α-1) of take is example, uses accompanying drawing to be specifically described the manufacture method of the display unit of Fig. 1.
(operation (a))
As shown in Figure 3 and Figure 4, the circumference along display device 50 (the first plane materiel) is formed and is formed uncured sealing 12 with Photocurable resin composition by coating sealings such as dividers (diagram is omitted).
Peripheral part at display device is provided with transmission sometimes for making the Wiring members such as FPC of the electrical signal of display device action.While keeping each plane materiel in the manufacture method of present embodiment, in order to make the configuration of Wiring member easy, preferably display device is configured in to downside as the first plane materiel.
(operation (b))
Then, as shown in Figure 5 and Figure 6, to the rectangular area being surrounded by uncured sealing 12 13 of display device 50, supply with resin layer and form with Photocurable resin composition 14.Resin layer forms feed rate with Photocurable resin composition 14 and is redefined for by uncured sealing 12, display device 50, space that transparent facestock 10 (with reference to Fig. 7) is airtight and just by resin layer, is formed the amount with Photocurable resin composition 14 fillings.
The supply of resin layer formation use Photocurable resin composition 14 as shown in Figure 5 and Figure 6, display device 50 is lain in to lower platform 18, and the divider 20 moving by along continuous straight runs is wire, band shape or the formation of point-like supply resin layer to be implemented with Photocurable resin composition 14.
Divider 20 can be by moving horizontally in the gamut in region 13 by a pair of feed screw 22 with the known horizontal mobile mechanism that the feed screw 24 of feed screw 22 quadratures forms.Can use mould painting machine to replace divider 20.
(operation (c))
Then, as shown in Figure 7, display device 50 and transparent facestock 10 (the second plane materiel) are moved in reliever 26.Top in reliever 26 disposes the upper mounting plate 30 with a plurality of absorption layers 32, is provided with lower platform 31 in bottom.Upper mounting plate 30 can move along the vertical direction by cylinder 34.
Transparent facestock 10 is installed on absorption layer 32.Display device 50 is fixed on lower platform 31 by the mode towards upper of Photocurable resin composition 14 to have supplied with resin layer formation.
Then, by the air in vacuum pump 28 suction relievers 26.Atmosphere pressures in reliever 26 reaches after the reduced atmosphere of 15～40Pa for example, under the state that absorption layer 32 absorption by upper mounting plate 30 keep by transparent facestock 10, towards below the display device 50 of standby, make cylinder 34 actions and decline.Then, display device 50 and transparent facestock 10 was situated between with the overlapping and constituting layer prestack body of uncured sealing 12, retaining layer prestack body specified time under reduced atmosphere.
For the installation site of display device 50 of lower platform 31, the number of absorption layer 32, for the installation site of the transparent facestock 10 of upper mounting plate 30 etc. suitably adjusting according to the size of display device 50 and transparent facestock 10, shape etc.At this moment, absorption layer adopts electrostatic chuck, by adopting the electrostatic chuck keeping method of recording in specification sheets (being referenced to this specification sheets) subsidiary in Japanese Patent Patent 2008-206124, glass substrate stably can be remained under reduced atmosphere.
(operation (d))
Then, the inside of reliever 26 is for example reached after normal atmosphere, stacked precursor is taken out from reliever 26.After stacked precursor is placed under normal atmosphere atmosphere, the surface of display device 50 sides and the surface of transparent facestock 10 of stacked precursor are pushed by normal atmosphere, and the resin layer in enclosed space forms with the shown device 50 of Photocurable resin composition 14 and transparent facestock 10 pressurizations.By this pressure, the resin layer in enclosed space forms with Photocurable resin composition 14 and flows, and enclosed space integral body is formed with Photocurable resin composition 14 and fills equably by resin layer.
Then, transparent facestock is provided with shading Printing Department and makes to be held in the uncured sealing of shading Printing Department and resin layer and form with Photocurable resin composition first in curing situation, as shown in Figure 8, from side Dui Bei shading Printing Department 55 and folded uncured sealing 12 and the resin layer of display device 50 of stacked precursor, form the complete cycle irradiation light (ultraviolet ray or the visible ray below 450nm) at display device with Photocurable resin composition 14, and from transparent facestock 10 sides, seeing through 56 pairs of transmittance sections resin layer forms with Photocurable resin composition 14 irradiation light (ultraviolet ray or the visible ray below 450nm), make uncured sealing 12 and the resin layer of stacked precursor inside form with Photocurable resin composition 14 curing, thereby make display unit 1.
Transparent facestock does not have in the situation of shading Printing Department, from transparent facestock 10 sides, whole of stacked precursor is irradiated to light, the uncured sealing 12 of stacked precursor inside and resin layer formation is solidified with Photocurable resin composition 14, thereby make display unit 1.
Above, the situation of method (α-1) of take illustrates the manufacture method of the display unit of present embodiment as example, but also can similarly manufacture display unit in the situation of other method (α-2).
[action effect: the manufacture method of display unit]
If adopt the manufacture method of the display unit of present embodiment described above, the in the situation that of can not producing bubble in making resin layer, manufacture the display unit that area is larger.Even if under reduced pressure the resin layer of sealing forms by entrapped air pockets in Photocurable resin composition, under high pressure atmosphere before solidifying, also hermetically sealed resin layer is formed and applies this pressure with Photocurable resin composition, the volume of its bubble reduces, bubble evanescence.For example, the resin layer of 100Pa lower seal forms and under 100kPa, is considered to reach 1/1000 with the gas volume in the bubble in Photocurable resin composition.Gas also can be dissolved in resin layer formation Photocurable resin composition, so the gas in the bubble of micro volume is promptly dissolved in resin layer formation, with Photocurable resin composition, disappears.
In addition, resin layer after sealing forms and bears normal atmosphere equipressure with Photocurable resin composition, it is the composition of tool mobility with Photocurable resin composition that aqueous resin layer forms, so this pressure the surface uniform of display device distribute, do not have a part that forms the display device surface join with Photocurable resin composition with resin layer and bear the situation of larger stress and occur, the impaired possibility of display device is little.
In addition, resin layer forms with the interface cohesive force curing and that the resin layer of generation and the interface cohesive force of display device and transparent facestock produce than thermal welding of Photocurable resin composition high.And, to the resin layer of tool mobility, form with Photocurable resin composition pressurization closely sealed with the surface of display device and transparent facestock, under this state, make it solidify, therefore can obtain higher interface cohesive force, for the surface of display device and transparent facestock, can obtain bondingly uniformly, the situation that interface cohesive force partly reduces is few simultaneously.
Therefore, rare the peeling off in the surface of resin layer, and seldom have moisture or the hypodynamic part of corrosive gases intrusion bonding interface.
In addition, form and compare by the method (injection method) of Photocurable resin composition with the resin layer that injects tool mobility to the narrow and large-area space between 2 plane materiels, the generation of bubble is few, and potting resin layer formation Photocurable resin composition at short notice.And resin layer forms with the restriction of the viscosity of Photocurable resin composition few, can easily fill full-bodied resin layer formation Photocurable resin composition.Therefore, can use and comprise the high viscosity resins layer formation Photocurable resin composition that can improve the solidified nature compound that the molecular weight of resin layer intensity is higher.
In addition, as resin layer, form the Photoepolymerizationinitiater initiater (C2) with Photocurable resin composition, use has than the Photoepolymerizationinitiater initiater (C2) in the absorbing wavelength region (λ 2) of the more close long wavelength side in the absorbing wavelength region of the Photoepolymerizationinitiater initiater of uncured sealing (C1) (λ 1), and the light irradiating as the side from stacked precursor, use the light of the wavelength in absorbing wavelength region (λ 1) and the light of the wavelength in absorbing wavelength region (λ 2) simultaneously, thereby the light of the wavelength in the absorbing wavelength region (λ 2) not absorbed by the Photoepolymerizationinitiater initiater of uncured sealing (C1) fully arrives the resin layer formation Photocurable resin composition being sandwiched between light shielding part and display device, by thering is the Photoepolymerizationinitiater initiater (C2) in absorbing wavelength region (λ 2), can fully carry out resin layer and form solidifying with Photocurable resin composition.
[action effect: curable resin composition]
In the engaging of display device and transparent facestock, the Young's modulus of the resin layer after the shrinking percentage while solidifying by reducing curable resin composition or reduction are solidified, can reduce the stress of display device generation effectively to prevent from showing the unequal destruction to display quality.
Yet, if the contraction in order to reduce to solidify and increase the average molecular weight that cure sites is corresponding of solidified nature compound, the viscosity of solidified nature compound increases, and may be difficult to curable resin composition to be supplied to equably plane materiel face, or curing reaction when curing is uneven.
In addition, if comprise in order to reduce the Young's modulus of the resin layer after solidifying the uncured property composition that does not participate in solidifying, intermiscibility when uncured in curable resin composition reduces, the transparency of the resin combination after likely solidifying is impaired, or the resin layer after solidifying and the reduction of the adaptation of plane materiel face, front plane materiel and back side plane materiel through time peel off.
For this point, curable resin composition of the present invention does not form with resin layer the uncured property composition that curing reaction occurs with the solidified nature compound (II) in Photocurable resin composition by the uncured oligomers that comprises especially average every 1 molecule of 10～90 quality % and have 0.8～3 hydroxyl when solidifying, in solidified nature compound (II), there is nonreactive hydroxyl while solidifying simultaneously, can make resin layer when uncured form having good stability with Photocurable resin composition, can reduce viscosity, having good uniformity of curing reaction while solidifying, contraction in the time of can reducing to solidify simultaneously, and the Young's modulus of the resin after reduce solidifying.
If the contraction while solidifying reduces, the Young's modulus of the resin after solidifying reduces, and the stress that cure shrinkage of resin layer produces reduces.If the formation of resin layer when uncured has good stability with Photocurable resin composition, having good uniformity of the curing reaction while solidifying, easily obtains the good resin layer of the transparency.If it is low that resin layer when uncured forms by the viscosity of Photocurable resin composition, the generation of bubble is easily fully suppressed, and is easy to obtain the good interface cohesive force of plane materiel and resin layer.
Particularly display device is liquid crystal display device, more specifically for IPS, (face is interior to be switched, In-PlaneSwitching) type or display surface are bonded with the TN (twisted nematic of the blooming that improves visual angle, TwistedNematic) in the situation of the liquid crystal display device of type, the stress that puts on display device easily causes detrimentally affect to display quality, and therefore engaging resin layer is better to have low elastic modulus.
Therefore, as the display device in the display unit of applicable curable resin composition of the present invention, be better liquid crystal display device, be more preferably the liquid crystal display device of IPS type or the liquid crystal display device of TN type.
Curable resin composition of the present invention is not limited in display unit, is also applicable to a facestock to be situated between with the stacked duplexer of resin layer, can obtain same effect.
In addition, curable resin composition of the present invention can be compositions of thermosetting resin, and in this situation, the solidified nature group of solidified nature compound adopts known thermoset group.In addition, make as required it comprise known thermal polymerization.In above-mentioned embodiment, it is in heat cured situation with curable resin composition that resin layer forms, and sealing forms and is also preferably thermoset with curable resin composition.
Photocurable resin composition does not need high temperature when curing, so the dysgenic situation of the generation such as Yin Gaowen facestock is few, particularly preferably.
Also can pass through and use the methods such as Photoepolymerizationinitiater initiater and thermal polymerization, carry out at the same time or separately the incompatible raising solidified nature of photopolymerization and hot polymerization.
In addition, by the method that curable resin composition of the present invention is manufactured duplexer, be not limited to the method for above-mentioned embodiment, can suitably use known method.
Embodiment
Below, the example of implementing in order to confirm validity of the present invention is shown.Example 1～5,9 and 10 is embodiment, and example 6～8 is comparative example.
(storing the measuring method of shearing modulus of elasticity and loss tangent thereof)
Storage shearing modulus of elasticity and the loss tangent (tan δ) thereof of the resin layer after solidifying are measured as follows: use rheometer (Anton Paar company (ア ント ンパール society) system, Physica MCR301), uncured resin layer is formed with Photocurable resin composition and is held on the platform of soda-lime glass system and rotor (Anton Paar company system for mensuration, D-PP20/AL/S07) gap of the 0.4mm between, under nitrogen atmosphere in 35 ℃ by being arranged on black lamp (Nippon Electric Company, Ltd. (the Japanese ElectricityGenki society) system of platform bottom, FL15BL) irradiate 2mW/cm 2light 30 minutes, apply 1% dynamic shearing distortion simultaneously, resin layer is formed with Photocurable resin composition and solidifies, thereby measure.Resin layer forms while solidifying with Photocurable resin composition, and automatic tracing is adjusted the position of rotor, makes the normal direction of rotor not produce stress.
Exposure intensity is used luxmeter (oxtail Electric Co., Ltd (ウ シ オElectricity Machine society) system, ultraviolet ray intensity meter UNIMETER UIT-101) to form on the platform with Photocurable resin composition and measure resin layer is set.
(number-average molecular weight)
The number-average molecular weight of oligopolymer is used GPC device, and (TOSOH Co., Ltd (TOSOH society) system, HLC-8020) tries to achieve.
(viscosity)
By E type viscometer, (Toki Sangyo Co., Ltd. (EastMachine industry society) system, RE-85U) measures the viscosity of Photocurable resin composition.
(haze value)
The Haze-gard II that haze value is used Toyo Co., Ltd.'s essence mechanism to make institute (East Yang Jing Machine Systemzuosuo society) system is measured according to ASTM D1003.
[example 1]
(display device)
From 17 inches of commercially available LCD monitors, (Acer (Acer society) system V137b) is taken out liquid crystal display device.The display format of liquid crystal display device is TN (twisted nematic, Twisted Nematic) type, and display part is of a size of long 338mm, wide 270mm.The two sides of liquid crystal display device is bonded with polaroid, and a side engagement on long limit has 6 driving FPC, and a side engagement of minor face has 3 driving FPC, and the engaged at end of the FPC of long side has printed wiring board.This liquid crystal display device is denoted as to display device A.
(sheet glass)
Using the soda-lime glass of long 355mm, wide 290mm, thick 2.8mm as the sheet glass B that becomes protecting sheet.
(sealing formation Photocurable resin composition)
By molecular end addition in 1 molecule of oxyethane, have 2 officials of 2 hydroxyls can polypropylene glycol (the number-average molecular weights of being calculated by hydroxyl value: 4000, ethylene oxide content 24 quality % in polypropylene glycol molecule) and 1, hexamethylene-diisocyanate is with 6 to 7 mixed in molar ratio, use again isobornyl acrylate (Osaka Organic Chemical Industry Co., Ltd. (Osaka You Machine chemical industry society) system, IBXA) after dilution, under existing, the catalyzer of tin compound makes its reaction in 70 ℃, to the mol ratio with approximately 1 to 2 in the prepolymer of gained, add 2-Hydroxy ethyl acrylate and add 0.03 mass parts 2, 5-di-tert-butyl hydroquinone (stopper) makes its reaction in 70 ℃, thereby obtain urethane acrylate oligomer (the being denoted as below UC-1) solution with isobornyl acrylate dilution of 30 quality %.The solidified nature group number of UC-1 is 2, and number-average molecular weight is approximately 55000.Viscosity during 60 ℃ of UC-1 solution is about 580Pas.
90 mass parts UC-1 solution and 10 mass parts methacrylic acid-2-hydroxyl butyl ester (Kyoeisha Chemical Co., Ltd. (chemistry society of GongSakae society) system, Light Ester HOB) are mixed equably and obtain mixture.By this mixture of 100 mass parts, 3 mass parts 1-hydroxycyclohexylphenylketone (Photoepolymerizationinitiater initiaters, Ciba company (チ バ ス ペ シ ャ Le テ ィ ケミカル ズ society) system, IRGACURE 184) mix equably, obtain sealing formation Photocurable resin composition C.
Sealing is formed and adds container and be arranged in reliever with open state with Photocurable resin composition C, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when sealing is formed to 25 ℃ with Photocurable resin composition C is measured, and result is about 1300Pas.
(resin layer formation Photocurable resin composition)
By molecular end addition in 1 molecule of oxyethane, have 2 officials of 2 hydroxyls can polypropylene glycol (the number-average molecular weights of being calculated by hydroxyl value: 4000, ethylene oxide content 24 quality % in polypropylene glycol molecule) and isophorone diisocyanate with 4 to 5 mixed in molar ratio, under existing, the catalyzer of tin compound makes its reaction in 70 ℃, to the mol ratio with approximately 1 to 2 in the prepolymer of gained, add 2-Hydroxy ethyl acrylate and add 0.03 mass parts 2, 5-di-tert-butyl hydroquinone (stopper) makes its reaction in 70 ℃, thereby obtain urethane acrylate oligomer (being denoted as below UA-2) solution.The solidified nature group number of UA-2 is 2, and viscosity when number-average molecular weight is approximately 24000,25 ℃ is about 830Pas.
By 40 mass parts UA-2,30 mass parts methacrylic acid-2-hydroxyl butyl ester (Kyoeisha Chemical Co., Ltd.'s systems, Light Ester HOB), 30 mass parts methacrylic acid dodecyl esters mix equably, in this mixture of 100 mass parts, dissolve equably 0.5 mass parts two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba company system, IRGACURE 819), obtain resin layer formation Photocurable resin composition PD.
Then, the molecular end addition that the compound that uses while making 40 mass parts PD, 60 mass parts and UA-2 synthetic is same in 1 molecule of oxyethane, there are 2 officials of 2 hydroxyls can the polypropylene glycol (number-average molecular weights of being calculated by hydroxyl value: 4000, ethylene oxide content 24 quality % in polypropylene glycol molecule) dissolve equably, obtain resin layer formation Photocurable resin composition D.
Resin layer is formed and adds container and be arranged in reliever with open state with Photocurable resin composition D, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when resin layer is formed to 25 ℃ with Photocurable resin composition D is measured, and result is about 1.3Pas.
For resin layer, form with the Photoepolymerizationinitiater initiater (above-mentioned IRGACURE 819) of Photocurable resin composition D and have than the absorbing wavelength region (about 440nm is following) that forms the more close long wavelength side in absorbing wavelength region (about 380nm is following) with the Photoepolymerizationinitiater initiater (above-mentioned IRGACURE 184) of Photocurable resin composition C for sealing.
Then, use rheometer that resin layer is formed and measured with the viscoelastic property after the photocuring of Photocurable resin composition D, storing shearing modulus of elasticity is 3.7 * 10 3pa, its loss tangent (tan δ) is 0.61.
(operation (a))
The complete cycle of the position of the approximately 3mm outside the image display area of display device A is coated with sealing formation according to the condition of wide about 1mm, the about 0.6mm of coating thickness by divider and uses Photocurable resin composition C, forms uncured sealing.
(operation (b))
In the region of uncured sealing inner side of coating the image display area periphery of display device A, use divider with the total mass of 38g, resin layer to be formed and is supplied to many places with Photocurable resin composition D.
Supply with resin layer and form with Photocurable resin composition D therebetween, the shape of uncured sealing is maintained.
(operation (c))
Display device A is formed to the upper surface of the lower platform in the reliever that the mode towards upper with Photocurable resin composition D lies in the lifting device that is provided with a pair of platform with resin layer.
Use electrostatic chuck to make sheet glass B to be formed with the surface mode relative with display device A of a side of shading Printing Department, remain on the lower surface of the upper mounting plate of the lifting device in reliever, while observing from above, the image display area of the transmittance section without shading Printing Department of sheet glass B and display device A is positioned at same position to leave the state on the border of about 1mm, is 30mm in the vertical direction with the distance of display device A.
Make reliever be sealed state, the pressure being vented in reliever reaches about 10Pa.By the lifting device in reliever, upper and lower platform is approached, display device A and sheet glass B Jie are formed to the pressure crimping with 2kPa with Photocurable resin composition D with resin layer, keep 1 minute.By electrostatic chuck power-off, make sheet glass B leave upper mounting plate, will in reliever, return to normal atmosphere with approximately 15 seconds, obtain resin layer and form the stacked precursor E by Photocurable resin composition D shown device A, sheet glass B and uncured both seals.
In stacked precursor E, the shape of uncured sealing maintains initial state substantially.
(operation (d))
From the face of the sheet glass B side of stacked precursor E, irradiate equably from the ultraviolet ray of black lamp and the visible ray below 450nm 30 minutes, resin layer is formed with Photocurable resin composition D and solidify, thereby form resin layer, obtain display unit F.Although required bubble is not removed operation when display unit F does not need to adopt injection method to manufacture in the past, unconfirmed to defects such as residual bubbles in resin layer.In addition, also unconfirmedly to resin layer, form with Photocurable resin composition from defects such as sealing spill.In addition, the thickness of resin layer is target thickness (about 0.4mm).
Use the roughly sheet glass of same size to replace display device A similarly to make Sparent laminate, the haze value of the part without printing light shielding part is measured, result is below 1%, and transparency is high.
Display unit F is put back to the LCD monitor that takes out liquid crystal display device, reconnect after wiring, the framework of LCD monitor is set in the vertical mode of display device A engaging with sheet glass B.Energize after standing 5 days, is connected with computer and shows image, and whole of result display frame obtains homogeneous and good demonstration image, and display comparison degree is higher than originally.Firmly pressing image display surface is pointed in i.e. use does not have anamorphose yet, and sheet glass B has protected display device A effectively.
Then, display unit F is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
[example 2]
(resin layer formation Photocurable resin composition)
The resin layer using in 30 mass parts examples 1 is formed by 2 officials' energy polypropylene glycol (number-average molecular weights of being calculated by hydroxyl value: 2000 in Photocurable resin composition PD and 70 mass parts 1 molecules with 2 hydroxyls, EO content 0 quality % in polypropylene glycol molecule) dissolve equably, obtain resin layer formation Photocurable resin composition D2.
Resin layer is formed and adds container and be arranged in reliever with open state with Photocurable resin composition D2, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when resin layer is formed to 25 ℃ with Photocurable resin composition D2 is measured, and result is 0.6Pas.
Then, use rheometer that resin layer is formed and measured with the viscoelastic property after the photocuring of Photocurable resin composition D2, storing shearing modulus of elasticity is 9 * 10 2pa, its loss tangent (tan δ) is 0.84.
As sealing formation Photocurable resin composition, except using composition D2 to form with Photocurable resin composition as resin layer, similarly obtain display unit F2 with example 1 with the same composition C that uses of example 1.Display unit F2 is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.Energize after standing 5 days, is connected with computer and shows image, and whole of result display frame obtains homogeneous and good demonstration image, and display comparison degree is higher than originally.Firmly pressing image display surface is pointed in i.e. use does not have anamorphose yet, and sheet glass B has protected display device A effectively.
Then, display unit F2 is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
[example 3]
(resin layer formation Photocurable resin composition)
By the UA-2 using in 40 mass parts examples 1, 30 mass parts methacrylic acid-2-hydroxyl butyl ester (Kyoeisha Chemical Co., Ltd.'s systems, Light Ester HOB), 30 mass parts methacrylic acid dodecyl esters mix equably, in this mixture of 100 mass parts, dissolve equably 0.5 mass parts two (2, 4, 6-Three methyl Benzene formyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba company system, IRGACURE819), 0.5 mass parts n-dodecyl mercaptan (chain-transfer agent, Kao Corp (Hua Wangshe) system, THIOKALCOL 20), obtain resin layer formation Photocurable resin composition PG.
Then, the molecular end addition that the compound that uses while making 60 mass parts PG, 40 mass parts and UA-2 synthetic is same in 1 molecule of oxyethane, there are 2 officials of 2 hydroxyls can the polypropylene glycol (number-average molecular weights of being calculated by hydroxyl value: 4000, ethylene oxide content 24 quality % in polypropylene glycol molecule) dissolve equably, obtain resin layer formation Photocurable resin composition G.
Resin layer is formed and adds container and be arranged in reliever with open state with Photocurable resin composition G, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when resin layer is formed to 25 ℃ with Photocurable resin composition G is measured, and result is 1.7Pas.
Then, use rheometer that resin layer is formed and measured with the viscoelastic property after the photocuring of Photocurable resin composition G, storing shearing modulus of elasticity is 1.0 * 10 4pa, its loss tangent (tan δ) is 0.83.
As sealing formation Photocurable resin composition, except using composition G to form with Photocurable resin composition as resin layer, similarly obtain display unit H with example 1 with the same composition C that uses of example 1.
Display unit H is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.Energize after standing 5 days, is connected with computer and shows image, and whole of result display frame obtains homogeneous and good demonstration image, and display comparison degree is higher than originally.Firmly pressing image display surface is pointed in i.e. use does not have anamorphose yet, and sheet glass B has protected display device A effectively.
Then, display unit H is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
[example 4]
(resin layer formation Photocurable resin composition)
By molecular end addition in 1 molecule of oxyethane, have 2 officials of 2 hydroxyls can polypropylene glycol (the number-average molecular weights of being calculated by hydroxyl value: 4000, ethylene oxide content 24 quality % in polypropylene glycol molecule) and isophorone diisocyanate with 3 to 4 mixed in molar ratio, under existing, the catalyzer of tin compound makes its reaction in 70 ℃, to the mol ratio with approximately 1 to 2 in the prepolymer of gained, add 2-Hydroxy ethyl acrylate and add 0.03 mass parts 2, 5-di-tert-butyl hydroquinone (stopper) makes its reaction in 70 ℃, thereby obtain urethane acrylate oligomer (being denoted as below UA-3).The solidified nature group number of UA-3 is 2, and viscosity when number-average molecular weight is approximately 21000,25 ℃ is about 350Pas.
By 80 mass parts UA-3,20 mass parts methacrylic acid-2-hydroxyl butyl ester (Kyoeisha Chemical Co., Ltd.'s systems, Light Ester HOB) mix equably, in this mixture of 100 mass parts, dissolve equably 0.5 mass parts two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba company system, IRGACURE 819), obtain resin layer formation Photocurable resin composition PI.
Make to have in 30 mass parts PI and 70 mass parts 1 molecules 2 officials' energy polypropylene glycol (number-average molecular weights of being calculated by hydroxyl value: 2000 of 2 hydroxyls, EO content 0 quality % in polypropylene glycol molecule) dissolve equably, obtain resin layer formation Photocurable resin composition I.
Resin layer is formed and adds container and be arranged in reliever with open state with Photocurable resin composition I, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when resin layer is formed to 25 ℃ with Photocurable resin composition I is measured, and result is 2.0Pas.
Then, use rheometer that resin layer is formed and measured with the viscoelastic property after the photocuring of Photocurable resin composition I, storing shearing modulus of elasticity is 2.5 * 10 4pa, its loss tangent (tan δ) is 0.06.
As sealing formation Photocurable resin composition, except using composition I to form with Photocurable resin composition as resin layer, similarly obtain display unit J with example 1 with the same composition C that uses of example 1.
Display unit J is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.Energize after standing 5 days, whole of result display frame obtains homogeneous and good demonstration image, and display comparison degree is higher than originally.Firmly pressing image display surface is pointed in i.e. use does not have anamorphose yet, and sheet glass B has protected display device A effectively.
Then, display unit J is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
[example 5]
(resin layer formation Photocurable resin composition)
2 officials that make in 20 mass parts examples 4 to have in the PI that uses and 80 mass parts 1 molecules 2 hydroxyls can the polypropylene glycol (number-average molecular weights of being calculated by hydroxyl value: 2000, EO content 0 quality % in polypropylene glycol molecule) dissolve equably, obtain resin layer formation Photocurable resin composition I2.
Resin layer is formed and adds container and be arranged in reliever with open state with Photocurable resin composition I2, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when resin layer is formed to 25 ℃ with Photocurable resin composition I2 is measured, and result is 1.0Pas.
Then, use rheometer that resin layer is formed and measured with the viscoelastic property after the photocuring of Photocurable resin composition I2, storing shearing modulus of elasticity is 4.0 * 10 3pa, its loss tangent (tan δ) is 0.07.
As sealing formation Photocurable resin composition, except using composition I 2 to form with Photocurable resin composition as resin layer, similarly obtain display unit J2 with example 1 with the same composition C that uses of example 1.
Display unit J2 is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.Energize after standing 5 days, whole of result display frame obtains homogeneous and good demonstration image, and display comparison degree is higher than originally.Firmly pressing image display surface is pointed in i.e. use does not have anamorphose yet, and sheet glass B has protected display device A effectively.
Then, display unit J2 is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
[example 6]
(resin layer formation Photocurable resin composition)
In the resin combination PD using, do not add uncured oligomers and obtain resin layer formation Photocurable resin composition K in example 1.
Resin layer is formed and adds container and be arranged in reliever with open state with Photocurable resin composition K, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when resin layer is formed to 25 ℃ with Photocurable resin composition K is measured, and result is 2.2Pas.
Then, use rheometer that resin layer is formed and measured with the viscoelastic property after the photocuring of Photocurable resin composition K, storing shearing modulus of elasticity is 3.1 * 10 5pa, its loss tangent (tan δ) is 0.32.
As sealing formation Photocurable resin composition, except using composition K to form with Photocurable resin composition as resin layer, similarly obtain display unit L with example 1 with the same composition C that uses of example 1.
Display unit L is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.Energize after standing 5 days, is connected with computer and shows that image, the circumference of result display frame produce the demonstration inequality that is frame shape, particularly can confirm significantly this demonstration uneven in the demonstration of shadow tone.Do not show uneven part, obtaining contrast gradient than original higher image.
Then, display unit L is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
[example 7]
(resin layer formation Photocurable resin composition)
In the resin combination PG using, do not add uncured oligomers and obtain resin layer formation Photocurable resin composition M in example 3.
Resin layer is formed and adds container and be arranged in reliever with open state with Photocurable resin composition M, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when resin layer is formed to 25 ℃ with Photocurable resin composition M is measured, and result is 2.1Pas.
Then, use rheometer that resin layer is formed and measured with the viscoelastic property after the photocuring of Photocurable resin composition M, storing shearing modulus of elasticity is 1.6 * 10 5pa, its loss tangent (tan δ) is 0.46.
As sealing formation Photocurable resin composition, except using composition M to form with Photocurable resin composition as resin layer, similarly obtain display unit N with example 1 with the same composition C that uses of example 1.
Display unit N is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.Energize after standing 5 days, is connected with computer and shows that image, the circumference of result display frame produce the demonstration inequality that is frame shape, particularly can confirm significantly this demonstration uneven in the demonstration of shadow tone.Do not show uneven part, obtaining contrast gradient than original higher image.
Then, display unit N is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
[example 8]
(resin layer formation Photocurable resin composition)
By the UA-2 using in 40 mass parts examples 1, 20 mass parts methacrylic acid-2-hydroxyl butyl ester (Kyoeisha Chemical Co., Ltd.'s systems, Light Ester HOB), 40 mass parts methacrylic acid dodecyl esters mix equably, in this mixture of 100 mass parts, dissolve equably 0.3 mass parts two (2, 4, 6-Three methyl Benzene formyl) phenyl phosphine oxide (Photoepolymerizationinitiater initiater, Ciba company system, IRGACURE 819), 1.5 mass parts n-dodecyl mercaptan (chain-transfer agents, Kao Corp (Hua Wangshe) system, THIOKALCOL 20), obtain resin layer formation Photocurable resin composition O.
Resin layer is formed and adds container and be arranged in reliever with open state with Photocurable resin composition O, will in reliever, be decompressed to about 20Pa and keep 10 minutes, thereby carry out deaeration processing.Viscosity when resin layer is formed to 25 ℃ with Photocurable resin composition O is measured, and result is 1.9Pas.
Then, use rheometer that resin layer is formed and measured with the viscoelastic property after the photocuring of Photocurable resin composition O, storing shearing modulus of elasticity is 7.5 * 10 3pa, its loss tangent (tan δ) is 1.8.
As sealing formation Photocurable resin composition, except using composition O to form with Photocurable resin composition as resin layer, similarly obtain display unit P with example 1 with the same composition C that uses of example 1.
Display unit P is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.After approximately 1 hour, confirmed the bonding station of display device, result display device is counted mm left and right from sheet glass landing, display device cannot be held in to sheet glass well.
So, to be engaged in the mode of the display device A level of sheet glass B, display unit P is set, energize after standing 5 days, the skew of result display device is unchanged, the central part of display frame obtains homogeneous and good demonstration image, and display comparison degree is higher than originally.Firmly pressing image display surface is pointed in i.e. use does not have anamorphose yet, and sheet glass B has protected display device A effectively.
[example 9]
Can polypropylene glycols except molecular end not being there are to 2 officials of 2 hydroxyls in 1 molecule of addition of ethylene oxide (number-average molecular weight of being calculated by hydroxyl value: 5500) with comprise 2 of equivalent almost, 2,4-trimethylammonium-1, hexamethylene-diisocyanate and 2, beyond the mixed in molar ratio of the mixture of 4,4-trimethylammonium-hexamethylene diisocyanate with 1:2, similarly operate synthesis of carbamates origoester acrylate (UA-4) with example 1.The solidified nature group number of UA-4 is 2, and viscosity when number-average molecular weight is approximately 16000,25 ℃ is about 39Pas.
In example 1, use UA-4 to replace UA-2, similarly obtain resin layer formation Photocurable resin composition PQ with example 1.Use 4 mass parts PQ and with for the same molecular end of the synthetic compound of UA-4 not 1 molecule of addition of ethylene oxide there are 2 officials of 2 hydroxyls can polypropylene glycols (the number-average molecular weight of being calculated by hydroxyl value: 5500), obtain resin layer and form and uses Photocurable resin composition Q.Viscosity when resin layer forms 25 ℃ with Photocurable resin composition Q is 0.8Pas.
Adopting the resin layer formation that rheometer records is that storing shearing modulus of elasticity is 2.4 * 10 with the viscoelastic property after the photocuring of Photocurable resin composition Q 4pa, its loss tangent (tan δ) is 0.13.
As sealing formation Photocurable resin composition, except using composition Q to form with Photocurable resin composition as resin layer, similarly obtain display unit R with example 1 with the same composition C that uses of example 1.
Display unit R is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.Energize after standing 5 days, whole of result display frame obtains homogeneous and good demonstration image, and display comparison degree is higher than originally.Firmly pressing image display surface is pointed in i.e. use does not have anamorphose yet, and sheet glass B has protected display device A effectively.
Then, display unit R is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
[example 10]
Can polypropylene glycols except molecular end not being there are to 2 officials of 2 hydroxyls in 1 molecule of addition of ethylene oxide (number-average molecular weight of being calculated by hydroxyl value: 2000) with the mixed in molar ratio of isophorone diisocyanate with 5:6, similarly operate synthesis of carbamates origoester acrylate (UA-5) with example 1.The solidified nature group number of UA-5 is 2, and viscosity when number-average molecular weight is approximately 18000,25 ℃ is about 620Pas.
In example 1, use UA-5 to replace UA-2, similarly obtain resin layer formation Photocurable resin composition PS with example 1.2000), the large molecular end of the compound that uses when synthetic of 30 mass parts molecular weight ratio UA-5 does not have 2 officials of 2 hydroxyls in 1 molecule of addition of ethylene oxide can the polypropylene glycols (number-average molecular weight of being calculated by hydroxyl value: 5500), obtain resin layer and form and uses Photocurable resin composition S the (number-average molecular weight of being calculated by hydroxyl value: that the same molecular end of the compound that uses while using 40 mass parts PS, 30 mass parts and UA-5 synthetic does not have 2 officials of 2 hydroxyls in 1 molecule of addition of ethylene oxide can polypropylene glycols.Viscosity when resin layer forms 25 ℃ with Photocurable resin composition S is 0.9Pas.
Adopting the resin layer formation that rheometer records is that storing shearing modulus of elasticity is 2.0 * 10 with the viscoelastic property after the photocuring of Photocurable resin composition Q 4pa, its loss tangent (tan δ) is 0.15.
As sealing formation Photocurable resin composition, except using composition S to form with Photocurable resin composition as resin layer, similarly obtain display unit T with example 1 with the same composition C that uses of example 1.
Display unit T is put back to the framework of the LCD monitor that takes out liquid crystal display device, reconnect after wiring, in the vertical mode of display device A engaging with sheet glass B, LCD monitor is set.Energize after standing 5 days, whole of result display frame obtains homogeneous and good demonstration image, and display comparison degree is higher than originally.Firmly pressing image display surface is pointed in i.e. use does not have anamorphose yet, and sheet glass B has protected display device A effectively.
Then, display unit T is similarly set, after 1 month, confirms the bonding station of display device, there is no position skew, be held in well sheet glass.
Known solidified nature compound (II) and uncured oligomers (D) and the content that should (D) of comprising of the present invention is the stress that the contraction can reduce resin layer and solidify time of the example 1～5,9 and 10 of 10～90 quality % in curable resin composition produces, and whole of display frame, obtains homogeneous and good demonstration image.
Comprise solidified nature compound of the present invention (II) but containing the example 6 of uncured oligomers (D), example 7, at the circumference of liquid crystal display picture, do not produce and show unevenly, particularly in the demonstration of shadow tone, confirming significantly this demonstrations inequality.In addition, particularly with the example 8 comprising with respect to 100 mass parts solidified nature compounds (II) over 1.5 mass parts chain-transfer agents, display device cannot be held in to sheet glass well.
The possibility of utilizing in industry
Curable resin composition of the present invention is useful in the manufacture of the duplexer for display unit.
In addition, all the elements of specification sheets, claims, accompanying drawing and summary of quoting No. 2010-137532, the Japanese patent application of filing an application on June 16th, 2010 are here as the announcement of specification sheets of the present invention.
The explanation of symbol
1 display unit
10 transparent facestock
12 uncured sealings
13 regions
14 resin layer formation Photocurable resin compositions
40 resin layers
42 sealings
50 display devices
55 shading Printing Departments (light shielding part)
56 transmittance sections

Claims (12)

1. curable resin composition, it is for by uncured curable resin composition being held between a facestock and making the curable resin composition of its duplexer being solidified to form, it is characterized in that, at least one party's plane materiel is transparent, comprise following solidified nature compound (II) and following uncured oligomers (D), the content of this uncured oligomers (D) is 10～90 quality %;
Solidified nature compound (II) comprises a kind of above solidified nature compound that curing reaction occurs when curable resin composition solidifies, in this solidified nature compound at least a kind has the hydroxyl not reacting when described curable resin composition solidifies, and this solidified nature compound comprises the above following monomer of a kind of above following oligopolymer (A ') and a kind (B ');
Oligopolymer (A '): there is solidified nature group and number-average molecular weight and be 1000～100000, by polyoxyalkylene polyol and polyisocyanates as raw material and synthetic oligourethane;
Monomer (B '): there is solidified nature group and molecular weight and be 125～600 monomer;
Uncured oligomers (D) is that curable resin composition with described solidified nature compound (II), curing reaction does not occur while solidifying, and average every 1 molecule has the polyoxyalkylene polyol of 0.8～3 hydroxyl.
2. curable resin composition as claimed in claim 1, is characterized in that, the content of described uncured oligomers (D) is 30～80 quality %.
3. curable resin composition as claimed in claim 1, is characterized in that, described solidified nature compound (II) comprises the monomer simultaneously with solidified nature group and hydroxyl.
4. curable resin composition as claimed in claim 3, it is characterized in that, described solidified nature compound (II) comprises and has the oligopolymer that solidified nature group and molecular weight are 1000～100000 (A ') and have solidified nature group and monomer that molecular weight is 125～600 (B '), and this monomer (B ') comprises the monomer (B3) with hydroxyl.
5. curable resin composition as claimed in claim 4, is characterized in that, described oligopolymer (A ') has acryl, and at least a portion of described monomer (B ') has methacryloyl.
6. the curable resin composition as described in claim 4 or 5, is characterized in that, described monomer (B3) comprise there is hydroxyl value 1～2, the hydroxyl-metacrylate of the hydroxyalkyl of carbon number 3～8.
7. the curable resin composition as described in claim 4 or 5, is characterized in that, described monomer (B ') comprises the monomer (B4) of the alkyl methacrylate that is selected from the alkyl with carbon number 8～22.
8. curable resin composition as claimed in claim 1 or 2, is characterized in that, containing chain-transfer agent, or comprise chain-transfer agent and its content with respect to 100 mass parts solidified nature compounds (II) below 1 mass parts.
9. duplexer, is characterized in that, stacked integrated the forming of resin layer that the cured article that the facestock that at least one party is transparent facestock is situated between with the curable resin composition described in any one by claim 1～8 forms.
10. duplexer as claimed in claim 9, is characterized in that, a side of a described facestock is transparent facestock, and the opposing party is display device.
The manufacture method of 11. duplexers, it be manufacture the first plane materiel that the either party comprise in the first plane materiel and the second plane materiel is transparent facestock and the second plane materiel, by the resin layer of this first plane materiel and the second plane materiel clamping, the method for surrounding the duplexer of resin layer sealing around, it is characterized in that thering is following operation (a)～(d):
(a) the surperficial circumference at the first plane materiel is coated with the aqueous sealing formation curable resin composition that comprises solidified nature compound (I) and polymerization starter, forms the operation of uncured sealing;
(b) region surrounding to the sealing by uncured is supplied with the resin layer being formed by the curable resin composition described in any one in claim 1～8 and is formed the operation with curable resin composition;
(c) under the reduced atmosphere below 100Pa, the second plane materiel is overlapped in to resin layer and forms with on curable resin composition, obtain resin layer and form with curable resin composition by the operation of the stacked precursor of the first plane materiel, the second plane materiel and uncured both seals;
(d), so that stacked precursor is placed in to the state under pressure atmosphere more than 50kPa, uncured sealing and resin layer are formed by the curing operation of curable resin composition.
The manufacture method of 12. duplexers as claimed in claim 11, is characterized in that, a side of described the first plane materiel and the second plane materiel is transparent facestock, and the opposing party is display device.
CN201180029238.1A 2010-06-16 2011-06-14 Curable resin composition, laminate comprising same, and process for production of the laminate Expired - Fee Related CN102939312B (en)

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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5738641B2 (en) * 2011-03-25 2015-06-24 株式会社日本触媒 Optical UV-curable resin composition, cured product, and display device
TW201317315A (en) * 2011-08-26 2013-05-01 Denki Kagaku Kogyo Kk Curable resin composition
JP5969375B2 (en) * 2012-12-18 2016-08-17 オリジン電気株式会社 UV-curable adhesive composition and laminate using the same
JPWO2014104231A1 (en) * 2012-12-28 2017-01-19 旭硝子株式会社 Transparent surface material with adhesive layer, laminate, display device, and production method thereof
JP6226652B2 (en) * 2013-09-09 2017-11-08 昭和電工株式会社 Manufacturing method of image display device
JPWO2015159957A1 (en) * 2014-04-17 2017-04-13 旭硝子株式会社 Transparent surface material with adhesive layer, display device, manufacturing method thereof, and adhesive sheet
CN106536584B (en) * 2014-07-28 2019-08-23 Ａｇｃ株式会社 Hardening resin composition, the manufacturing method of hardening resin composition, the manufacturing method of laminated body and display device
JP6425119B2 (en) 2014-08-05 2018-11-21 Ｔｉａｎｍａ Ｊａｐａｎ株式会社 Device and method of manufacturing device
JP2016169335A (en) * 2015-03-13 2016-09-23 旭硝子株式会社 Curable composition, cured article, laminate and picture display device
JP6730006B2 (en) * 2015-05-21 2020-07-29 株式会社きもと Optical shading member and manufacturing method thereof
JP6983039B2 (en) * 2016-11-29 2021-12-17 住友化学株式会社 Gas barrier film and flexible electronic device
WO2019004160A1 (en) * 2017-06-26 2019-01-03 大日本印刷株式会社 Light modulating member, sun visor, and movable body
JP6904161B2 (en) * 2017-08-24 2021-07-14 デクセリアルズ株式会社 Manufacturing method of image display device
JP2019174739A (en) * 2018-03-29 2019-10-10 三菱電機株式会社 Manufacturing method of image display device

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58138766A (en) * 1982-02-10 1983-08-17 Nippon Synthetic Chem Ind Co Ltd:The Photo-setting type adhesive composition for glass
JP2909661B2 (en) * 1990-11-16 1999-06-23 大阪有機化学工業株式会社 Radiation-curable pressure-sensitive adhesive composition
JPH083266A (en) * 1994-06-27 1996-01-09 Japan Energy Corp Photocurable resin composition
CN1259146A (en) * 1997-04-08 2000-07-05 Dsm有限公司 Radiation-curable binder compositions having high elongation and toughness after cure
JP4741257B2 (en) * 2004-03-04 2011-08-03 ノーテープ工業株式会社 UV curable liquid adhesive composition
JP5343391B2 (en) * 2007-07-17 2013-11-13 デクセリアルズ株式会社 Resin composition and image display device
CN101765497B (en) * 2007-07-30 2013-05-29 旭硝子株式会社 Curable resin composition, transparent laminate using the same, and method for producing the transparent laminate
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
JP5098722B2 (en) * 2008-03-17 2012-12-12 Ｊｓｒ株式会社 Curable resin composition, film laminate for sticking, and laminate for impact absorption
JP5590030B2 (en) * 2009-05-20 2014-09-17 旭硝子株式会社 Curable resin composition, transparent laminate and method for producing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JP特开2009-46620A 2009.03.05 *
JP特开平8-3266A 1996.01.09 *

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