WO2013057959A1 - 光学部材の製造方法及びそのための紫外線硬化型樹脂組成物の使用 - Google Patents
光学部材の製造方法及びそのための紫外線硬化型樹脂組成物の使用 Download PDFInfo
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- WO2013057959A1 WO2013057959A1 PCT/JP2012/006713 JP2012006713W WO2013057959A1 WO 2013057959 A1 WO2013057959 A1 WO 2013057959A1 JP 2012006713 W JP2012006713 W JP 2012006713W WO 2013057959 A1 WO2013057959 A1 WO 2013057959A1
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- acrylate
- resin composition
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- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- IFZUFHWISBKFJP-UHFFFAOYSA-N n'-[4-[dimethoxy(methyl)silyl]oxybutyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)OCCCCNCCN IFZUFHWISBKFJP-UHFFFAOYSA-N 0.000 description 1
- FDAKZQLBIFPGSV-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCNC1CC(C)(C)NC(C)(C)C1 FDAKZQLBIFPGSV-UHFFFAOYSA-N 0.000 description 1
- HRYSOBDFNHXNTM-UHFFFAOYSA-N n-butylbutan-1-amine;1,3,5-triazine Chemical compound C1=NC=NC=N1.CCCCNCCCC HRYSOBDFNHXNTM-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 239000011029 spinel Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
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- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
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- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- 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
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
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- 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
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- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0412—Digitisers structurally integrated in a display
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- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
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- 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
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- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
Definitions
- the present invention relates to a method for producing an optical member by laminating an optical substrate having a light-shielding portion and another optical substrate, and the use of an ultraviolet curable resin composition therefor.
- a touch panel that enable screen input by attaching a touch panel to a display screen of a display device such as a liquid crystal display, a plasma display, or an organic EL display are widely used.
- a glass plate or resin film on which a transparent electrode is formed is bonded with a slight gap facing each other, and if necessary, a transparent protective plate made of glass or resin on the touch surface Has a structure of bonding.
- the transparent protective plate is provided with a strip-shaped light shielding portion at the outermost edge in order to improve the contrast of the display image.
- a transparent protective plate provided with a light shielding part is bonded with an ultraviolet curable resin composition, sufficient ultraviolet light does not reach the light shielding area behind the light shielding part of the ultraviolet curable resin by the light shielding part, Curing of the resin in the light shielding region becomes insufficient. If the resin is not sufficiently cured, problems such as display unevenness in the display image near the light shielding portion occur.
- Patent Document 1 discloses a technique for curing the resin in the light shielding region by containing an organic peroxide in the ultraviolet curable resin and heating it after the ultraviolet irradiation. Yes.
- the heating process may damage the liquid crystal display device and the like.
- Patent Document 2 discloses a technique for curing the resin in the light shielding region by irradiating ultraviolet rays from the outer side surface of the light shielding portion forming surface.
- Patent Document 3 discloses a technique using the slow-acting property of a cationic polymerizable ultraviolet curable resin, but the cured resin is inferior in flexibility.
- the present invention provides an optical member with little damage to the optical base material, good productivity, and an optical member such as a touch panel or a display unit, a high degree of curing of the resin composition, and high reliability. It aims at providing the manufacturing method of the optical member using the ultraviolet curable resin composition which can be obtained.
- the inventors of the present invention used an ultraviolet curable resin composition to form an optical substrate having a light-shielding portion and another optical substrate to be bonded to the specific step 1 to It has been found that the above-mentioned problems can be solved by manufacturing by a method including step 3, and the present invention has been completed. That is, the present invention relates to the following (1) to (21).
- the light shielding region is a state where the two optical base materials are bonded together, and the ultraviolet light is shielded by the light shielding portion when the coating layer is irradiated with the ultraviolet light through the transparent optical base material having the light shielding portion on the surface, It means the coating layer part not exposed to ultraviolet rays, Step 2: Step of bonding both optical substrates by sandwiching the coating layer obtained in Step 1 between the bonding surfaces of the two optical substrates.
- Step 3 The laminate having at least one pair of optical substrates bonded together in the above steps 1 and 2 is irradiated with ultraviolet rays through the transparent optical substrate having the light-shielding portion, and between the two optical substrates.
- Process 4 The process of applying a pressure with respect to the bonded optical base material.
- step 1 when the light shielding region is cured, a portion to be left uncured other than the light shielding region of the coating layer is masked with an ultraviolet shielding plate and irradiated with ultraviolet rays. Manufacturing method of the optical member.
- step 1 The method for producing an optical member according to any one of the above (1) to (3), wherein in the step 1, the amount of ultraviolet irradiation is at least 200 mJ / cm 2 .
- step 1 an ultraviolet curable resin composition is provided on at least one of the surface of the optical substrate having the light shielding portion on the surface and the display surface of the display unit that is an optical substrate bonded to the optical substrate.
- the above-mentioned (1) is applied so that the surface of the optical substrate having the light-shielding portion on the surface and the display surface of the display unit face each other with the obtained coating layer interposed therebetween.
- the optical base material having a light shielding part on the surface is at least one selected from the group consisting of a transparent glass substrate having a light shielding part, a transparent resin substrate having a light shielding part, and a glass substrate having a light shielding part and a transparent electrode formed thereon.
- the optical substrate according to any one of the above (1) to (5), wherein the optical substrate to be bonded thereto is at least one selected from the group consisting of a liquid crystal display unit, a plasma display unit, and an organic EL display unit. Manufacturing method of member.
- the (meth) acrylate (A) is at least one selected from the group consisting of urethane (meth) acrylate, (meth) acrylate having a polyisoprene skeleton, and a (meth) acrylate monomer. Manufacturing method.
- the urethane (meth) acrylate is a urethane (meth) acrylate obtained by reacting polypropylene glycol, polyisocyanate, and a hydroxy group-containing (meth) acrylate, as described in any one of (8) to (10) above. Manufacturing method of the optical member.
- (meth) acrylate (A) is urethane (meth) acrylate with respect to the total amount of the ultraviolet curable resin composition. 20 to 80% by weight and 5 to 70% by weight of (meth) acrylate monomer, 0.2 to 5% by weight of photopolymerization initiator (B) based on the total amount of the UV curable resin composition, the balance being other
- a touch panel obtained by the method for manufacturing an optical member according to any one of (1) to (13).
- the display apparatus which has the optical base material which has the light-shielding part on the surface obtained by the manufacturing method of the optical member as described in said (5) on the display screen of a display unit.
- An ultraviolet curable resin composition containing (meth) acrylate (A) and a photopolymerization initiator (B) for the method for producing an optical member according to any one of (1) to (6) above use.
- Use of mold resin composition Use of mold resin composition.
- a curable resin composition Use of a curable resin composition.
- the ultraviolet curable resin composition as described in said (21) containing a softening component.
- a bonded optical member having little damage to the optical substrate, good productivity, good curability and adhesion for example, a touch panel having the optical substrate having a light shielding portion or the same display A body unit etc. can be obtained. Furthermore, since the degree of curing of the resin at the light shielding portion is high, problems such as display unevenness of the display image in the vicinity of the light shielding portion do not occur, and a highly reliable optical member can be provided.
- Step 1 An ultraviolet curable resin composition was applied to at least one of the bonding surfaces of a transparent optical substrate having a light-shielding portion on the surface and another optical substrate to be bonded thereto to form a coating layer.
- Step 2 Step of bonding both optical substrates by sandwiching the coating layer obtained in Step 1 between the bonding surfaces of the two optical substrates.
- Step 3 Uncured sandwiched between the two optical substrates by irradiating the laminated body having at least one pair of optical substrates bonded together with ultraviolet rays through the transparent optical substrate having the light shielding part. Curing the coating layer.
- the “light-shielding region” or “light-shielding region at the time of bonding” means that the two optical substrates are bonded together, and the coating layer is irradiated with ultraviolet rays through a transparent optical substrate having a light-shielding part on the surface. In this case, the coating layer portion where the ultraviolet ray is blocked by the light shielding portion and not irradiated with the ultraviolet ray.
- FIG. 1 is a process diagram showing a first embodiment of a method for producing an optical member using the ultraviolet curable resin composition of the present invention.
- the first embodiment is a method of obtaining an optical member (a liquid crystal display unit having a light shielding part) by bonding the liquid crystal display unit 1 and a transparent substrate 2 having a light shielding part.
- the liquid crystal display unit 1 is a unit in which a liquid crystal material is sealed between a pair of substrates on which electrodes are formed, and a polarizing plate, a driving circuit, a signal input cable, and a backlight unit are provided.
- the transparent substrate 2 having a light shielding part is black on the surface of the bonding surface of the transparent substrate 3 such as a glass plate, a polymethyl methacrylate (PMMA) plate, a polycarbonate (PC) plate or an alicyclic polyolefin polymer (COP) plate.
- a frame-shaped light-shielding portion 4 is provided.
- the light-shielding portion 4 is provided by attaching a tape, applying a paint, printing, or the like.
- an ultraviolet curable resin composition is apply
- the coating method include a slit coater, a roll coater, a spin coater, and a screen printing method.
- the ultraviolet curable resin composition applied to the surfaces of the liquid crystal display unit 1 and the transparent substrate 2 having the light shielding portion may be the same or different ultraviolet curable resin compositions. Usually, it is preferable that both are the same ultraviolet curable resin composition.
- the film thickness of the cured product of each ultraviolet curable resin composition is adjusted so that the cured resin layer 7 after bonding has a thickness of 50 to 500 ⁇ m, preferably 50 to 350 ⁇ m, more preferably 100 to 350 ⁇ m.
- UV curable resin composition in which when UV light is irradiated, the UV light is selectively irradiated to the part of the coating layer in the light blocking area where the UV light is blocked by the light blocking part, and the light blocking area is selectively cured at the time of bonding.
- a product coating layer 7 is obtained.
- the exposure area at the time of bonding (the portion of the coating layer exposed to ultraviolet rays when the laminated body in which both optical base materials are bonded together is irradiated with ultraviolet rays from the transparent substrate 2 side having a light shielding portion) does not cure.
- region at the time of a bonding is masked with an ultraviolet-ray shielding board.
- the irradiation amount of ultraviolet rays is preferably 200 mJ / cm 2 or more, and particularly preferably 1000 mJ / cm 2 or more. If the amount of irradiation is too small, the degree of cure of the light shielding part of the optical member that is finally bonded may be insufficient.
- the upper limit is not particularly limited, but is preferably 4000 mJ / cm 2 or less, more preferably 3000 mJ / cm 2 or less.
- the light source used for ultraviolet to near ultraviolet irradiation is not limited as long as it is a lamp that emits ultraviolet to near ultraviolet light.
- a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
- the technique of masking with an ultraviolet light-shielding plate has been described as an example.
- the method of selectively irradiating the light shielding region with ultraviolet rays is not limited to this method.
- Any method that can selectively cure the light-shielding region such as a scanning method (a method using spot UV), can be applied without particular limitation. From the viewpoint of simplicity, a method using an ultraviolet light shielding plate is more preferable.
- ultraviolet irradiation is performed from the upper surface of the coating layer (on the opposite side of the liquid crystal display unit side or the transparent substrate side as viewed from the ultraviolet curable resin composition) (normal air side surface). Is done.
- the irradiation with ultraviolet rays can be performed in the atmosphere, and depending on the purpose, it is performed in a vacuum, or under reduced pressure or non-depressurized, in the presence or absence of a curing inhibiting gas such as oxygen or ozone. It doesn't matter. Further, depending on the purpose, after the vacuum is applied, ultraviolet rays may be irradiated while spraying a curing-inhibiting gas or an inert gas on the upper surface of the coating layer.
- a curing-inhibiting gas or an inert gas on the upper surface of the coating layer.
- UV irradiation is performed on the upper surface of the coating layer in the presence of air or a curing-inhibiting gas such as oxygen and ozone. It is preferable to carry out with.
- the liquid crystal display unit 1 is formed in such a manner that the coating layers 7 (coating layers of the ultraviolet curable resin composition in which the light-shielding region at the time of bonding is selectively cured) face each other. And a transparent substrate 2 having a light shielding portion are bonded together. Bonding can be performed either in air or in vacuum. Here, in order to prevent bubbles from being generated during bonding, it is preferable to perform bonding in a vacuum. As described above, when the liquid crystal display unit 1 and the transparent substrate 2 are bonded to each other after the application layer 7 of the ultraviolet curable resin composition having the light-shielding region is cured, an improvement in adhesive strength can be expected. .
- the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 is irradiated with the ultraviolet-ray 9 from the transparent substrate 2 side which has a light-shielding part, and ultraviolet curable type
- the resin composition layer (coating layer) is cured.
- Irradiation of the ultraviolet in the step 3 is preferably from about 100 ⁇ 4000mJ / cm 2, particularly preferably 200 ⁇ 3000mJ / cm 2 approximately.
- the light source used for irradiation of ultraviolet to near ultraviolet light may be any type of light source as long as it is a lamp that irradiates ultraviolet to near ultraviolet light.
- a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used. In this way, an optical member as shown in FIG. 4 can be obtained.
- step 4 pressure can be applied to the obtained optical member to strengthen the adhesion.
- pressure is applied, the adhesive strength of the cured product layer in the light shielding region during bonding is improved.
- an effect of preventing peeling due to an external pressure or an environmental change at an interface where the coating layers 7 are adhered to each other can be expected.
- the adhesive force with respect to the liquid crystal display unit 1 of the resin cured material layer 8 or the transparent substrate 2 having a light-shielding portion becomes stronger. Therefore, it is preferable to go through step 4.
- FIG. 2 is a process diagram showing a second embodiment of a method for producing an optical member using the ultraviolet curable resin composition of the present invention.
- symbol is attached
- the liquid crystal display unit 1 and the transparent substrate having the light-shielding portion are formed in such a manner that the coating layer 7 of the transparent substrate 2 having the light-shielding portion and the display surface of the liquid crystal display unit 1 face each other.
- Bonding can be performed either in air or in vacuum.
- FIG. 2C the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 is irradiated with ultraviolet rays 9 from the side of the transparent substrate 2 having the light-shielding portion, and then bonded.
- the ultraviolet curable resin composition in the exposed region is cured.
- the optical member shown in FIG. 4 can be obtained.
- the optical member of the present invention can be manufactured by applying the third embodiment modified as follows.
- Process 1 First, after the ultraviolet curable resin composition is applied to the display surface of the liquid crystal display unit 1, the ultraviolet light is applied to the light shielding region at the time of bonding, and the ultraviolet curable resin composition in which the light shielding region at the time of bonding is cured is applied. Layer 7 is obtained.
- the exposure region at the time of bonding is masked by the ultraviolet shielding plate 6 so that the resin composition in the exposure region is not cured when the ultraviolet ray is irradiated.
- the optical member of the present invention can be manufactured according to the fourth embodiment modified as follows.
- the ultraviolet curable resin composition is applied to each of the display surface of the liquid crystal display unit 1 and the surface provided with the light shielding part 4 of the transparent substrate 2 having the light shielding part. Then, the ultraviolet-ray is irradiated to the light shielding area
- acylphosphine oxide is contained in the ultraviolet curable resin composition, and the amount of ultraviolet irradiation is adjusted so that the coating layer 7 is placed on the lower side of the coating layer 7 (the liquid crystal display unit 1 or the light shielding portion.
- the exposure area at the time of bonding is masked by the ultraviolet shielding plate 6 so that the resin composition in the exposure area is not cured when the ultraviolet ray is irradiated.
- optical base materials some of the embodiments of the method for producing an optical member of the present invention are described with specific examples of optical base materials.
- Each embodiment has been described using a liquid crystal display unit and a transparent substrate having a light-shielding portion.
- various substrates described later can be used as an optical substrate instead of the liquid crystal display unit.
- various base materials described later can be used as the optical base material instead of the transparent substrate.
- these various substrates are further bonded to another optical substrate layer (for example, a film bonded with a cured product layer of an ultraviolet curable resin composition). Or what laminated
- the ultraviolet curable resin composition coating method described in the first embodiment the film thickness of the cured resin, the irradiation amount and the light source in the ultraviolet irradiation, and selectively irradiating the light shielding area with ultraviolet rays
- Both the method and the step of applying pressure to the optical member to strengthen the adhesion are not applied only to each of the above embodiments, but can be applied to any manufacturing method included in the present invention.
- optical substrate is an optical substrate
- the optical substrate bonded thereto is at least one display body unit selected from the group consisting of a liquid crystal display unit, a plasma display unit, and an organic EL display unit, and the obtained optical member is the light shielding portion
- One optical base material is a protective base material having a light-shielding portion, and another optical base material bonded thereto is a touch panel or a display unit having a touch panel, and at least two optical base materials are bonded together.
- the optical member is a touch panel having a protective base material having a light shielding portion or a display unit having the same.
- the ultraviolet curable resin composition is applied to either one or both of the surface of the protective base material having the light shielding portion and the touch surface of the touch panel. It is preferable to do this.
- One optical substrate is an optical substrate having a light shielding portion, the other optical substrate bonded thereto is a display unit, and an optical member having at least two optical substrates bonded is a light shielding portion.
- the aspect which is a display body unit which has an optical base material which has.
- the ultraviolet curable resin composition is applied to either the surface of the optical substrate having the light shielding portion on the side where the light shielding portion is provided, the display surface of the display unit, or both. Is preferably applied.
- the optical substrate having a light shielding part include a display screen protective plate having a light shielding part, or a touch panel provided with a protective substrate having a light shielding part.
- the optical substrate having the light-shielding portion is a protective plate for a display screen having the light-shielding portion
- the surface of the optical substrate having the light-shielding portion is provided on the side on which the light-shielding portion is provided. It is the surface on the side where the part is provided.
- the optical base material having the light shielding part is a touch panel having a protective base material having the light shielding part
- the protective base material having the light shielding part is bonded to the touch surface of the touch panel.
- the surface of the optical substrate having the light-shielding portion on the side where the light-shielding portion is provided refers to the substrate surface of the touch panel opposite to the touch surface of the touch panel.
- the light-shielding part of the optical base material having the light-shielding part may be in any part of the optical base material, but is usually made in a frame shape around the transparent plate-like or sheet-like optical base material,
- the width is about 0.5 to 10 mm, preferably about 1 to 8 mm, more preferably about 2 to 8 mm.
- the ultraviolet curable resin composition used in the method for producing an optical member of the present invention is not particularly limited as long as it is a resin that is cured by ultraviolet irradiation, but (meth) acrylate (A) and a photopolymerization initiator (B). It is preferable to use an ultraviolet curable resin composition containing benzene (hereinafter also referred to as “the ultraviolet curable resin composition of the present invention”).
- the ultraviolet curable resin composition containing the (meth) acrylate (A) and the photopolymerization initiator (B) contains, as optional components, other components that can be added to the ultraviolet curable resin composition used for optics. can do.
- the phrase “can be added to an ultraviolet curable resin composition used for optics” means that an additive that lowers the transparency of the cured product to an extent that it cannot be used for optics is not included.
- a preferable average transmittance of the sheet with light having a wavelength of 400 to 800 nm is: At least 90%.
- the composition ratio of the ultraviolet curable resin composition is such that (meth) acrylate (A) is 25 to 90% by weight and the photopolymerization initiator (B) is 0. 0% with respect to the total amount of the ultraviolet curable resin composition. 2 to 5% by weight, other components are the balance.
- any photopolymerization initiator that is usually used can be used as the photopolymerization initiator (B).
- the (meth) acrylate (A) in the ultraviolet curable resin composition is not particularly limited, but is selected from the group consisting of urethane (meth) acrylate, (meth) acrylate having a polyisoprene skeleton, and (meth) acrylate monomer. It is preferable to use at least one of these. More preferably, it is an embodiment containing both (i) at least one of urethane (meth) acrylate or (meth) acrylate having a polyisoprene skeleton and (ii) (meth) acrylate monomer.
- “(meth) acrylate” means either one or both of methacrylate and acrylate. The same applies to “(meth) acrylic acid” and the like.
- the said (ii) (meth) acrylate monomer is used by the meaning of (meth) acrylate except said (i).
- the urethane (meth) acrylate can be obtained by reacting three kinds of polyhydric alcohol, polyisocyanate and hydroxy group-containing (meth) acrylate.
- polyhydric alcohol examples have 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol.
- Polyester polyol obtained by reaction with acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc .; obtained by reaction of polyhydric alcohol with ⁇ -caprolactone Caprolactone alcohol; polycarbonate polyol (for example, polycarbonate diol obtained by reaction of 1,6-hexanediol and diphenyl carbonate); or polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and ethylene oxide-modified bisphenol
- Polypropylene glycol is preferred as the polyhydric alcohol from the viewpoint of compatibility with other components (A) and adhesion, and weight average molecular weight from the viewpoint of adhesion between the substrate and the cured product layer or between the cured product layers.
- polypropylene glycol having a molecular weight of 2000 or more is particularly preferably polypropylene glycol having a molecular weight of 2000 or more.
- polypropylene glycol having a weight average molecular weight of 2000 or more is used, the adhesive strength of the cured product layer is improved, and when the optical base material such as a liquid crystal display unit and a transparent substrate is bonded, the light shielding region is cured at the time of bonding.
- the upper limit of the weight average molecular weight of the polypropylene glycol at this time is not particularly limited, but is preferably 10,000 or less, and more preferably 5000 or less.
- organic polyisocyanate examples include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate and dicyclopentanyl isocyanate.
- hydroxy group-containing (meth) acrylates include hydroxy C2-C4 alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; dimethylolcyclohexyl mono ( (Meth) acrylate; hydroxycaprolactone (meth) acrylate; and hydroxy group-terminated polyalkylene glycol (meth) acrylate can be used.
- hydroxy C2-C4 alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate
- dimethylolcyclohexyl mono (Meth) acrylate
- hydroxycaprolactone (meth) acrylate hydroxycaprolactone
- hydroxy group-terminated polyalkylene glycol (meth) acrylate can be used.
- the above reaction for obtaining urethane (meth) acrylate is performed as follows, for example. That is, the polyhydric alcohol is mixed with the polyhydric alcohol so that the isocyanate group of the organic polyisocyanate per equivalent of hydroxyl group of the polyhydric alcohol is preferably 1.1 to 2.0 equivalents, more preferably 1.1 to 1.5 equivalents.
- a urethane oligomer is synthesized by mixing the organic polyisocyanate and reacting at 70 to 90 ° C. preferably.
- the obtained urethane oligomer and the above hydroxy group-containing (hydroxyl group-containing (meth) acrylate) are preferably 1 to 1.5 equivalents with respect to 1 equivalent of the isocyanate group of the obtained urethane oligomer.
- the target urethane (meth) acrylate can be obtained by mixing and reacting at 70 to 90 ° C.
- the weight average molecular weight of the urethane (meth) acrylate is preferably about 7000 to 25000, and more preferably 10,000 to 20000. If the weight average molecular weight is too small, shrinkage may increase, and if the weight average molecular weight is too large, curability may be poor.
- the urethane (meth) acrylate in the ultraviolet curable resin composition of the present invention may be used alone or in combination of two or more. When using 2 or more types, it can mix and use in arbitrary ratios.
- the weight ratio of urethane (meth) acrylate in the ultraviolet curable resin composition of the present invention is usually 20 to 80% by weight, preferably 30 to 70% by weight.
- the (meth) acrylate having the polyisoprene skeleton is a compound having a (meth) acryloyl group at the terminal or side chain of the polyisoprene molecule.
- a (meth) acrylate having a polyisoprene skeleton can be obtained, for example, as “UC-203” (manufactured by Kuraray Co., Ltd.).
- the (meth) acrylate having a polyisoprene skeleton preferably has a polystyrene-equivalent number average molecular weight of 10,000 to 50,000, more preferably about 25,000 to 45,000.
- the weight ratio of the (meth) acrylate having a polyisoprene skeleton in the ultraviolet curable resin composition of the present invention is usually 20 to 80% by weight, preferably 30 to 70% by weight.
- the (meth) acrylate monomer a (meth) acrylate having one (meth) acryloyl group in the molecule can be preferably used.
- the (meth) acrylate monomer indicates (meth) acrylate excluding the urethane (meth) acrylate, the following epoxy (meth) acrylate, and the (meth) acrylate having the polyisoprene skeleton.
- the (meth) acrylate having one (meth) acryloyl group in the molecule include isooctyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, and stearyl.
- Alkyl (meth) acrylates having 5 to 20 carbon atoms such as (meth) acrylate, cetyl (meth) acrylate, isomyristyl (meth) acrylate and tridecyl (meth) acrylate; benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Acryloylmorpholine, phenylglycidyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate, polypropylene oxide modified nonylphen
- Examples of the (meth) acrylate having one (meth) acryloyl group in the molecule include alkyl (meth) acrylate having 10 to 20 carbon atoms, 2-ethylhexyl carbitol acrylate, acryloylmorpholine, 4-hydroxybutyl (meth) It is preferable to use a compound selected from the group consisting of acrylate, tetrahydrofurfuryl (meth) acrylate, isostearyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and polypropylene oxide modified nonylphenyl (meth) acrylate. .
- alkyl (meth) acrylate having 10 to 20 carbon atoms dicyclopentenyloxyethyl (meth) acrylate, polypropylene oxide-modified nonylphenyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. It is preferable to use a compound selected from the group consisting of, more preferably an alkyl (meth) acrylate having 10 to 20 carbon atoms, and still more preferably lauryl (meth) acrylate.
- alkyl (meth) acrylate having 1 to 5 carbon atoms having a hydroxyl group and acryloylmorpholine is preferable to use at least one of alkyl (meth) acrylate having 1 to 5 carbon atoms having a hydroxyl group and acryloylmorpholine as the (meth) acrylate monomer. It is particularly preferred to use acryloylmorpholine.
- the (meth) acrylate monomer preferably contains both an alkyl (meth) acrylate having 10 to 20 carbon atoms and an alkyl (meth) acrylate having 1 to 5 carbon atoms having a hydroxyl group or acryloylmorpholine. It is preferable to contain both (meth) acrylate and acryloylmorpholine.
- composition of this invention can contain polyfunctional (meth) acrylate monomers other than (meth) acrylate which has one (meth) acryloyl group in the range which does not impair the characteristic of this invention.
- polyfunctional (meth) acrylate monomers other than (meth) acrylate which has one (meth) acryloyl group in the range which does not impair the characteristic of this invention.
- Specific examples thereof include, for example, tricyclodecane dimethylol di (meth) acrylate, dioxane glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, alkylene oxide modified bisphenol A Type di (meth) acrylate, bifunctional (meth) acrylate such as caprolactone-modified hydroxypivalate neopentyl glycol di (meth) acrylate and ethylene oxide-modified di (meth) acrylate; tri
- trimethylol C2-C10 alkane polyalkoxy tri (meth) acrylate tris [(meth) acryloyloxy Ethyl] isocyanurate, pentaerythritol tri (meth) acrylate, and alkylene oxide modified trimethylolpropane tri (meth), such as ethylene oxide modified trimethylolpropane tri (meth) acrylate and propylene oxide modified trimethylolpropane tri (meth) acrylate ) Trifunctional (meth) acrylates such as acrylate; and pentaerythritol polyethoxytetra (meth) acrylate, pentaerythritol Propoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta
- the ultraviolet curable resin composition of this invention about these (meth) acrylate monomer components, 1 type (s) or 2 or more types can be used. When using 2 or more types, it can mix and use in arbitrary ratios.
- the weight ratio of the (meth) acrylate monomer in the ultraviolet curable resin composition of the present invention is usually 5 to 70% by weight, preferably 10 to 50% by weight. If it is less than 5% by weight, the curability may be poor, and if it is more than 70% by weight, shrinkage may be increased.
- both (i) urethane (meth) acrylate or (meth) acrylate having a polyisoprene skeleton and (ii) (meth) acrylate monomer in the ultraviolet curable resin composition The total content of both (i) and (ii) is usually 25 to 90% by weight, preferably 40 to 90% by weight, more preferably 40 to 80% by weight, based on the total amount of the resin composition. .
- the light-shielding region obtained in step 1 is selectively cured, and is excellent in adhesiveness after curing in the coating layer of the ultraviolet curable resin composition in which other portions are uncured.
- (meth) acrylate having a polypropylene oxide structure is used, the adhesive strength of the cured product layer is improved, and when the optical base material such as a liquid crystal display unit and a transparent substrate is bonded, the light shielding region is cured at the time of bonding.
- the adhesive force with respect to optical base materials such as the liquid crystal display unit 1 of the resin cured material layer 8, or the transparent substrate 2 which has a light-shielding part, also improves.
- examples of the (meth) acrylate having a polypropylene oxide structure include urethane (meth) acrylate having a polypropylene oxide structure and (meth) acrylate monomers having a polypropylene oxide structure.
- urethane (meth) acrylate which has a polypropylene oxide structure is included as (meth) acrylate (A).
- urethane (meth) acrylate having a polypropylene oxide structure examples include urethane (meth) acrylate obtained by reacting three of polypropylene glycol, polyisocyanate and hydroxy group-containing (meth) acrylate.
- Specific examples of the (meth) acrylate monomer having a polypropylene oxide structure include polypropylene glycol (meth) acrylate, polypropylene oxide-modified nonylphenyl (meth) acrylate, polypropylene glycol di (meth) acrylate and propylene oxide-modified trimethylolpropane tri (meth) ) Acrylates.
- epoxy (meth) acrylate can be used as the (meth) acrylate (A) as long as the characteristics of the present invention are not impaired.
- Epoxy (meth) acrylate has a function of improving curability and improving the hardness and curing speed of a cured product. Any epoxy (meth) acrylate may be used as long as it is obtained by reacting a glycidyl ether type epoxy compound with (meth) acrylic acid.
- Examples of glycidyl ether type epoxy compounds for obtaining epoxy (meth) acrylates preferably used include diglycidyl ether of bisphenol A or its alkylene oxide adduct, diglycidyl ether of bisphenol F or its alkylene oxide adduct, and hydrogenated bisphenol.
- Diglycidyl ether of A or its alkylene oxide adduct diglycidyl ether of hydrogenated bisphenol F or its alkylene oxide adduct, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl Ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether And, and polypropylene glycol diglycidyl ether.
- Epoxy (meth) acrylate is obtained by reacting these glycidyl ether type epoxy compounds with (meth) acrylic acid under the following conditions.
- (Meth) acrylic acid is reacted at a ratio of 0.9 to 1.5 mol, more preferably 0.95 to 1.1 mol, per 1 equivalent of epoxy group of the glycidyl ether type epoxy compound.
- the reaction temperature is preferably 80 to 120 ° C., and the reaction time is about 10 to 35 hours.
- a catalyst such as triphenylphosphine, TAP, triethanolamine and tetraethylammonium chloride.
- paramethoxyphenol and methylhydroquinone can be used as a polymerization inhibitor in order to prevent polymerization during the reaction.
- Examples of the epoxy (meth) acrylate that can be suitably used in the present invention include bisphenol A type epoxy (meth) acrylate obtained from a bisphenol A type epoxy compound.
- the weight average molecular weight of the epoxy (meth) acrylate that can be used in the present invention is preferably 500 to 10,000.
- the weight ratio of the epoxy (meth) acrylate in the ultraviolet curable resin composition of the present invention is usually 1 to 80% by weight, preferably 5 to 30% by weight.
- the content ratio of (meth) acrylate (A) in the ultraviolet curable resin composition of the present invention is 25 to 90% by weight, preferably 40 to 90% by weight, based on the total amount of the ultraviolet curable resin composition. More preferably, it is 40 to 80% by weight.
- the (meth) acrylate (A) is selected from the group consisting of the urethane (meth) acrylate, the (meth) acrylate having the polyisoprene skeleton, and the (meth) acrylate monomer.
- the urethane (meth) acrylate content is 20 to 80 wt%, preferably 30 to 70 wt%; the polyisoprene skeleton-containing (meth) acrylate content Is 20 to 80% by weight, preferably 30 to 70% by weight, more preferably when the content ratio of the (meth) acrylate monomer is 5 to 70% by weight, preferably 10 to 50% by weight.
- the urethane (meth) acrylate or the (meth) acrylate having a polyisoprene skeleton is 20 to 80% by weight, preferably 30 to 70% by weight. Further, it is more preferable when it contains 5 to 70% by weight, preferably 10 to 50% by weight of the (meth) acrylate monomer as (meth) acrylate (A).
- photopolymerization initiator can be used as the photopolymerization initiator (B) contained in the ultraviolet curable resin composition of the present invention.
- Specific examples of the photopolymerization initiator (B) include, for example, 1-hydroxycyclohexyl phenyl ketone (Irgacure (registered trademark, the same applies hereinafter) 184; manufactured by BASF), 2-hydroxy-2-methyl- [4- (1 -Methylvinyl) phenyl] propanol oligomer (Esacure ONE; manufactured by Lamberti), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959) Manufactured by BASF), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one (Irgacure 127; BASF 2,
- an acylphosphine oxide compound such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- 2,4,6-trimethylbenzoyldiphenylphosphine oxide is particularly preferable as the photopolymerization initiator (B) from the viewpoint of easy formation of an uncured portion and transparency of the cured resin layer.
- the amount of ultraviolet irradiation in the step 1 is preferably 5 to 200 mJ / cm 2 , particularly preferably 10 to 100 mJ / cm 2 .
- one or more of these photopolymerization initiators (B) can be used. When using 2 or more types, it can mix and use in arbitrary ratios.
- the weight ratio of the photopolymerization initiator (B) in the ultraviolet curable resin composition of the present invention is usually 0.2 to 5% by weight, preferably 0.3 to 3% by weight. Within this range, transparency is good and curability is also good. If it is too much, the transparency of the cured resin layer may be deteriorated. Moreover, when there are too few photoinitiators (B), the cure degree of a resin composition will become inadequate.
- the ultraviolet curable resin composition of the present invention includes, as other components, a photopolymerization initiation assistant described below, a general formula (1 ), A softening component to be described later, an additive to be described later, and the like.
- the content ratio of the other components with respect to the total amount of the ultraviolet curable resin composition of the present invention is the balance obtained by subtracting the total amount of the (meth) acrylate (A) and the photopolymerization initiator (B) from the total amount. is there.
- the total amount of the other components is 0 to 74.8% by weight, preferably about 5 to 70% by weight, based on the total amount of the ultraviolet curable resin composition of the present invention.
- an amine that can be a photopolymerization initiation assistant can be used in combination with the photopolymerization initiator (B).
- amines that can be used include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylaminobenzoic acid isoamyl ester.
- the content in the ultraviolet curable resin composition of the present invention is usually 0.005 to 5% by weight, preferably 0.01 to 3% by weight.
- the ultraviolet curable resin composition of this invention can be made to contain the compound which has a structure shown by General formula (1) as needed.
- n represents an integer of 0 to 40
- m represents an integer of 10 to 50.
- R 1 and R 2 may be the same or different.
- R 1 and R 2 each have 1 to 18 alkyl groups, alkenyl groups having 1 to 18 carbon atoms, alkynyl groups having 1 to 18 carbon atoms, and aryl groups having 5 to 18 carbon atoms.
- the compound having the structure represented by the general formula (1) can be obtained as, for example, Unisafe PKA-5017 (product name, polyethylene glycol-polypropylene glycol allyl butyl ether) manufactured by NOF Corporation.
- the weight ratio of the compound having the structure represented by the general formula (1) in the ultraviolet curable resin composition is usually 10 to 80% by weight, preferably 10 to 70% by weight.
- a softening component other than the above can be used as necessary.
- known softening components and plasticizers that are usually used in ultraviolet curable resins can be used.
- Specific examples of the softening component that can be used include polymers or oligomers excluding the (meth) acrylate or the compound having the structure represented by the general formula (1), phthalic acid esters, phosphoric acid esters, glycol esters, Examples thereof include citric acid esters, aliphatic dibasic acid esters, fatty acid esters, epoxy plasticizers, castor oils, and terpene hydrogenated resins.
- polymer or oligomer examples include a polymer or oligomer having a polyisoprene skeleton, a polybutadiene skeleton or a xylene skeleton, and an esterified product thereof. In some cases, a polymer or oligomer having a polybutadiene skeleton and an esterified product thereof are used. It is preferable to do.
- the polymer or oligomer having a polybutadiene skeleton and esterified products thereof include butadiene homopolymer, epoxy-modified polybutadiene, butadiene-styrene random copolymer, maleic acid-modified polybutadiene, and terminal hydroxyl group-modified liquid polybutadiene.
- the weight ratio in the ultraviolet curable resin composition is usually 10 to 80% by weight, preferably 10 to 70% by weight.
- the ultraviolet curable resin composition of the present invention includes an antioxidant, an organic solvent, a coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, and a light stabilizer as necessary. You may add additives, such as a hindered amine compound (for example) and a filler.
- antioxidants include, for example, BHT, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, , N-hexamethylenebis (3,5-di-di
- organic solvent examples include alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene and xylene.
- the coupling agent examples include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent.
- Specific examples of the silane coupling agent include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, ⁇ -mercapropropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (
- titanium coupling agent examples include isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate. And neoalkoxytri (pN- ( ⁇ -aminoethyl) aminophenyl) titanate.
- zirconium-based coupling agent and the aluminum-based coupling agent include, for example, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodecanoylzirconate, neoalkoxytris.
- polymerization inhibitor examples include paramethoxyphenol and methylhydroquinone.
- the light stabilizer include, for example, 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetramethyl-4-piperidyl alcohol, 1,2,2, 6,6-pentamethyl-4-piperidyl (meth) acrylate (manufactured by Adeka Co., Ltd., product name LA-82), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3 , 4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic Acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [ 5.5] Mixed esterified product with undecan
- Benzotriazole compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5 -Triazine-2-yl) -5-[(hexyl) oxy] phenol and the like.
- Particularly preferred light stabilizers are hindered amine compounds.
- the filler include, for example, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania and talc.
- examples thereof include powder or beads obtained by spheroidizing these.
- the content ratio of the additives added as necessary to the total amount of the ultraviolet curable resin composition is about 0 to 3% by weight in total of the additives.
- the content ratio of the various additives to the total amount of the composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, more preferably 0.02 to 0.5%. % By weight.
- the ultraviolet curable resin composition of the present invention is obtained by mixing and dissolving the (meth) acrylate (A), the photopolymerization initiator (B), and, if necessary, the other components at room temperature to 80 ° C. be able to. Moreover, you may remove impurities by operation, such as filtration, as needed.
- the cure shrinkage of the cured product of the ultraviolet curable resin composition of the present invention is preferably 3.0% or less, and particularly preferably 2.0% or less.
- the transmittance in the wavelength region of 400 nm to 800 nm is preferably 90% or more. This is because when the transmittance is less than 90%, it is difficult for light to pass through, and when the cured product is used in a display device, the visibility of the display image may be reduced. Further, when the cured product has a high transmittance in the wavelength region of 400 to 450 nm, the visibility of the display image can be further improved. Therefore, when the cured product is the film, the transmittance in the wavelength region of 400 to 450 nm is preferably 90% or more.
- UV curable resin composition containing the (meth) acrylate (A) and the photopolymerization initiator (B) used in the production method of the present invention are described below.
- “Wt%” in the content of each component indicates a content ratio with respect to the total amount of the ultraviolet curable resin composition of the present invention.
- (I) Containing (meth) acrylate (A) and photopolymerization initiator (B), (meth) acrylate (A) is composed of urethane (meth) acrylate, (meth) acrylate having a polyisoprene skeleton and (meth) acrylate monomer
- An ultraviolet curable resin composition which is at least one (meth) acrylate selected from the group.
- (II) As the (meth) acrylate (A), (I) urethane (meth) acrylate or (meth) acrylate having a polyisoprene skeleton, and (Ii) (meth) acrylate monomers, The ultraviolet curable resin composition as described in said (I) containing both of these. (III) The ultraviolet curing according to (I) or (II) above, wherein the urethane (meth) acrylate or the (meth) acrylate monomer is a urethane (meth) acrylate having a polypropylene oxide structure or a (meth) acrylate monomer having a polypropylene oxide structure. Mold resin composition.
- (IV) The ultraviolet ray according to the above (I) or (II), wherein the urethane (meth) acrylate is a urethane (meth) acrylate obtained by reacting three of polypropylene glycol, polyisocyanate and hydroxy group-containing (meth) acrylate.
- a curable resin composition A curable resin composition.
- the weight average molecular weight of the urethane (meth) acrylate is 7000 to 25000, and the number average molecular weight of the (meth) acrylate having a polyisoprene skeleton is 15000 to 50000, according to any one of the above (I) to (IV) UV curable resin composition.
- (VII) An ultraviolet curable resin composition containing (meth) acrylate (A) and a photopolymerization initiator (B), and further containing other components in addition to the component (A) and the component (B), or (A The ultraviolet curable resin composition according to any one of the above (I) to (VI), which further contains other components in addition to the component (B) and the component (B).
- the content ratio of (meth) acrylate (A) is 25 to 90% by weight
- the content ratio of photopolymerization initiator (B) is 0.2 to 5% by weight
- the other components are the balance as described in (VII) above UV curable resin composition.
- (X) The ultraviolet curable resin composition according to any one of the above (VII) to (IX), which contains 10 to 80% by weight of the compound represented by the general formula (1) as another component.
- (XI) An ultraviolet curable resin composition containing (meth) acrylate (A) and a photopolymerization initiator (B), wherein the cured shrinkage of the cured product of the ultraviolet curable resin composition is 3% or less, or
- (I) The ultraviolet curable resin composition according to any one of (1) to (X).
- the light transmittance of a sheet made of a cured product of an ultraviolet curable resin composition having a film thickness of 200 ⁇ m has an average transmittance of at least 90% in a wavelength region of 400 to 450 nm, and a wavelength region of 400 to 800 nm.
- an ultraviolet curable resin composition containing (meth) acrylate (A) and a photopolymerization initiator (B) having an average transmittance of at least 90%, or any of (I) to (XI) above The ultraviolet curable resin composition according to one item.
- the ultraviolet curable resin composition of the present invention is suitably used as an adhesive for producing an optical member by laminating a plurality of optical substrates by the steps including Step 1 to Step 3 and Optional Step 4. be able to.
- an optical base material used in the manufacturing method of the optical member of this invention a transparent plate, a sheet
- optical substrate means both an optical substrate having no light-shielding portion on the surface and an optical substrate having a light-shielding portion on the surface.
- at least one of a plurality of optical base materials used is an optical base material having a light shielding portion.
- the optical substrate having a light shielding part can be used without particular limitation as long as the light shielding part is formed on the surface of the optical substrate made of the above material.
- the position of the light shielding part in the optical substrate having the light shielding part is not particularly limited.
- a band-shaped light shielding portion having a width of about 0.05 to 20 mm, preferably about 0.05 to 10 mm, more preferably about 0.1 to 6 mm is provided in the peripheral portion of the optical substrate.
- the light-shielding part on the optical substrate can be formed by attaching a tape, applying a paint or printing.
- the optical base material to be bonded to the optical base material having the light shielding portion does not have the light shielding portion even if it has the light shielding portion on the surface. It doesn't matter.
- optical substrate used in the present invention Various materials can be used as the material of the optical substrate used in the present invention. Specific examples include PET, PC, PMMA, a composite of PC and PMMA, glass, COC, COP, and an acrylic resin.
- an optical substrate used in the present invention for example, a transparent plate or sheet, a transparent plate or sheet in which a plurality of films or sheets such as polarizing plates are laminated; a transparent plate or sheet that is not laminated; and a transparent made from inorganic glass Plates (inorganic glass plates and processed products thereof, such as lenses, prisms, ITO glass) and the like can be used.
- the optical base material used for this invention is a laminated body (henceforth "functionality") which consists of several functional boards or sheets, such as a touch panel (touch panel input sensor) or the following display body unit other than the above-mentioned polarizing plate. Also referred to as “laminated body”.
- Examples of the sheet that can be used as the optical substrate used in the present invention include an icon sheet, a decorative sheet, and a protective sheet.
- Examples of the plate (transparent plate) that can be used in the method for producing an optical member of the present invention include a decorative plate and a protective plate.
- materials for these sheets or plates those listed as materials for the transparent plate or sheet can be applied.
- Examples of the material of the surface of the touch panel that can be used as the optical substrate used in the present invention include glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP.
- the thickness of a plate-like or sheet-like optical substrate such as a transparent plate or a sheet is not particularly limited, and is usually about 5 ⁇ m to 5 cm, preferably about 10 ⁇ m to 10 mm, more preferably about 50 ⁇ m to 3 mm. Is the thickness.
- a plate-shaped or sheet-shaped transparent optical base material having a light-shielding portion and the functional laminate are cured products of the ultraviolet curable resin composition of the present invention. Examples of the optical member bonded together.
- an optical functional material is used by using a display unit such as a liquid crystal display device as one of optical substrates, and using an optical functional material having a light-shielding portion as another optical substrate.
- An attached display unit (hereinafter also referred to as a display panel) can be manufactured.
- display apparatuses such as LCD which adheres a polarizing plate to glass, an organic or inorganic EL display, EL illumination, electronic paper, and a plasma display, are mentioned, for example.
- transparent plastic plates such as an acrylic board, PC board, PET board, and PEN board, tempered glass, and a touch panel are mentioned.
- the ultraviolet curable resin composition of the present invention When used as an adhesive for laminating an optical substrate, the visibility of a display image is further improved when the refractive index of the cured product is 1.45 to 1.55. Therefore, it is more preferable. If the refractive index of the cured product is within the range, it is possible to reduce the difference in refractive index from the base material used as the optical base material, and it is possible to reduce light loss by suppressing irregular reflection of light. Become.
- Preferred embodiments of the optical member obtained by the production method of the present invention include the following (i) to (vii).
- An optical base selected from the group consisting of a transparent glass substrate having a light shielding part, a transparent resin substrate having a light shielding part, and a glass substrate having a light shielding part and a transparent electrode formed thereon, wherein the optical substrate having the light shielding part is used.
- the optical member according to (i), which is a material and the functional laminate is a display unit or a touch panel.
- the display unit is any one of a liquid crystal display unit, a plasma display unit, and an organic EL display unit.
- a touch panel or touch panel input sensor in which a plate-shaped or sheet-shaped optical substrate having a light-shielding portion is bonded to the surface on the touch surface side of the touch panel using the cured product of the ultraviolet curable resin composition of the present invention ).
- V A display panel in which a plate-like or sheet-like optical substrate having a light-shielding part is bonded to the display screen of the display unit using the cured product of the ultraviolet curable resin composition of the present invention.
- the ultraviolet curable resin composition of the present invention By using the ultraviolet curable resin composition of the present invention, a plurality of optical substrates selected from each of the optical substrates described above are bonded together by the methods of Steps 1 to 3 and Step 4 optionally performed.
- the optical member is obtained.
- the ultraviolet curable resin composition may be applied to only one of the surfaces facing each other through the cured product layer in the two optical substrates to be bonded, or to both surfaces. May be.
- the functional laminate is a touch panel or a display unit
- any one surface of the protective base material having a light shielding part, preferably the light shielding part is provided.
- the resin composition may be applied to only one of the provided surface and the touch surface of the touch panel or the display surface of the display unit, or may be applied to both of them.
- a light shielding portion of the protective base material is provided in Step 1, in which a protective base material or a touch panel for protecting the display screen of the display body unit is bonded to the display body unit.
- the resin composition may be applied to only one of the substrate surface opposite to the surface or the touch surface of the touch panel and the display surface of the display unit, or to both of them.
- the display unit including an optical base material having a light-shielding portion obtained by the manufacturing method of the present invention can be incorporated into an electronic device such as a television, a small game machine, a mobile phone, or a personal computer.
- UV-curable resin composition Urethane acrylate (reaction product obtained by reacting three components of polypropylene glycol (molecular weight 3000), isophorone diisocyanate and 2-hydroxyethyl acrylate in a molar ratio of 1: 1.3: 2) 45 Parts by weight, 25 parts by weight of Unisafe PKA-5017 (polyethylene glycol-polypropylene glycol allyl butyl ether, manufactured by NOF Corporation), 10 parts by weight of ACMO (acryloylmorpholine, manufactured by Kojin Co., Ltd.), LA (lauryl acrylate, Osaka Organic Chemical Industry) 20 parts by weight (made by Co., Ltd.) and 0.5 parts by weight of speed cure TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by LAMBSON) were prepared by heating and mixing (UV curable resin composition A). .
- Unisafe PKA-5017 polyethylene glycol-polypropylene glycol allyl butyl
- Example 1 As shown in FIG. 1A, the display surface of the liquid crystal display unit 1 having an area of 3.5 inches and the surface of the transparent glass substrate 2 having the light shielding part 4 (width 5 mm) provided with the light shielding part.
- the prepared ultraviolet curable resin composition A was applied so that each film thickness was 125 ⁇ m.
- the obtained coating layer 5 is irradiated with ultraviolet rays 9 having an integrated light quantity of 2000 mJ / cm 2 from the atmosphere side with a high-pressure mercury lamp (80 W / cm, ozone-less) with an ultraviolet shielding plate 6 interposed in the exposure area at the time of bonding.
- the coating layer in the light shielding area was cured during bonding.
- the liquid crystal display unit 1 and the transparent substrate 2 having the light-shielding portion were bonded together so that the coating layers 7 in which the respective light-shielding regions were cured face each other.
- an ultraviolet ray 9 with an integrated light quantity of 2000 mJ / cm 2 is applied to the coating layer 7 from the transparent glass substrate 2 side having a light-shielding portion with a high-pressure mercury lamp (80 W / cm, ozone-less).
- a high-pressure mercury lamp 80 W / cm, ozone-less
- Example 2 As shown in FIG. 2 (a), the prepared ultraviolet curable resin composition A on a transparent glass substrate 2 having a light shielding part 4 (width 5 mm) having an area of 3.5 inches has a film thickness of 250 ⁇ m. It applied so that it might become.
- the obtained coating layer 5 is irradiated with ultraviolet rays 9 having an integrated light quantity of 2000 mJ / cm 2 from the atmosphere side with a high-pressure mercury lamp (80 W / cm, ozone-less) with an ultraviolet shielding plate 6 interposed in the exposure area at the time of bonding.
- the coating layer in the light shielding area was cured during bonding.
- the liquid crystal display unit 1 and the light shielding portion are arranged so that the coating layer 7 in which the light shielding region in the transparent substrate 2 having the light shielding portion is cured and the display surface of the liquid crystal display unit 1 face each other.
- the transparent substrate 2 having Finally, as shown in FIG. 2 (c), ultraviolet rays 9 with an integrated light quantity of 2000 mJ / cm 2 are applied to the coating layer 7 from the transparent glass substrate 2 side having a light-shielding part with a high-pressure mercury lamp (80 W / cm, ozone-less). By irradiating, the uncured coating layer was cured to produce the optical member of the present invention (a liquid crystal display unit having a transparent glass substrate having a light shielding part).
- Comparative Example 1 As shown in FIG. 3A, an ultraviolet curable resin prepared on each of the display surface of the liquid crystal display unit 1 and the surface provided with the light shielding portion on the transparent substrate 2 having the light shielding portion 4 (width 5 mm). Composition A was applied so that each film thickness was 125 ⁇ m.
- the liquid crystal display unit 1 and the transparent substrate 2 having a light shielding portion were bonded together so that the coating layers 5 face each other.
- an ultra high pressure mercury lamp (TOSCURE752, manufactured by Harrison Toshiba Lighting Co., Ltd.) is used to irradiate ultraviolet rays 9 with an integrated light quantity of 2000 mJ / cm 2 from the transparent glass substrate 2 side having a light shielding portion.
- TOSCURE752 manufactured by Harrison Toshiba Lighting Co., Ltd.
- the cured resin layer in the light shielding region has a high degree of curing even if the ultraviolet light is shielded by the light shielding part of the protective substrate. It was.
- Two glass slides having a thickness of 1 mm coated with a fluorine-based mold release agent are prepared, and the obtained ultraviolet curable resin composition A is formed to have a film thickness of 200 ⁇ m on one of the mold release agent application surfaces. It was applied to. Thereafter, the two slide glasses were bonded so that the respective release agent application surfaces face each other. Through the glass, an ultraviolet ray having an accumulated light amount of 2000 mJ / cm 2 was irradiated to the coating layer sandwiched between two slide glasses with a high-pressure mercury lamp (80 W / cm, ozone-less) to cure the coating layer. Thereafter, the two slide glasses were peeled off to produce a cured film for measuring the film specific gravity.
- a high-pressure mercury lamp 80 W / cm, ozone-less
- a slide glass having a thickness of 0.8 mm and an acrylic plate having a thickness of 0.8 mm are prepared, and the obtained ultraviolet curable resin composition A is applied so that the film thickness becomes 200 ⁇ m, and the obtained application is obtained.
- the other was bonded so as to sandwich the layer.
- the sandwiched coating layer was irradiated with ultraviolet light with an integrated light quantity of 2000 mJ / cm 2 through a slide glass with a high-pressure mercury lamp (80 W / cm, ozone-less), the coating layer was cured, and a sample for evaluating adhesiveness was produced. This was left to stand at 85 ° C. and 85% RH for 250 hours. In the sample for evaluation, peeling of the slide glass or the acrylic plate from the cured resin was visually confirmed, but there was no peeling.
- the obtained ultraviolet curable resin composition A was sufficiently cured, and the durometer E hardness was measured using a durometer hardness meter (type E) by a method based on JIS K7215 to evaluate flexibility. More specifically, the ultraviolet curable resin composition A was poured into a cylindrical mold so as to have a film thickness of 1 cm, and the resin composition was sufficiently cured by irradiation with ultraviolet rays. The hardness of the obtained cured product was measured with a durometer hardness meter (type E). As a result, the measured value was less than 10, and the flexibility was excellent.
- the transmittance in the wavelength region of 400 to 800 nm and 400 to 450 nm was measured using a spectrophotometer (U-3310, Hitachi High-Technologies Corporation). As a result, the transmittance at 400 to 800 nm was 90% or more, and the transmittance at 400 to 450 nm was also 90% or more.
- 1 liquid crystal display unit 2 transparent substrate with light-shielding part, 3 transparent substrate, 4 light-shielding part, 5 UV-curable resin composition coating layer, 6 UV-shielding plate (UV mask), 7 light-shielding area when cured UV curable resin composition coating layer, 8 resin cured product layer, 9 UV
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Abstract
Description
表面上に遮光部を有する透明光学基材とそれと貼り合わされる他の光学基材の両者を、紫外線硬化型樹脂組成物を用いて、下記工程1~工程3を含む工程により貼り合わされた少なくとも一対の光学基材を含む光学部材の製造方法、
工程1:表面上に遮光部を有する透明光学基材およびそれと貼り合わされる他の光学基材の少なくとも何れか一方の貼り合わせ面に、紫外線硬化型樹脂組成物を塗布し、塗布層を形成した後、得られた塗布層における、下記する遮光領域に選択的に紫外線を照射して、該遮光領域を選択的に硬化させ、他の部分を未硬化のままの塗布層とする工程、
なお、上記の遮光領域とは、上記二つの光学基材を貼り合わせて、表面上に遮光部を有する透明光学基材を通して紫外線を塗布層に照射した際に、遮光部によって紫外線が遮られ、紫外線が当たらない塗布層部分を意味する、
工程2:工程1で得られた塗布層を上記両光学基材の貼り合わせ面の間に挟んで、両光学基材を貼り合わせる工程、
工程3:上記工程1及び2により貼り合わされた一対の光学基材を少なくとも一つ有する積層体に、上記遮光部を有する透明光学基材を通して紫外線を照射して、該二つの光学基材の間に挟まれた未硬化の塗布層を硬化させる工程。
(2)
前記工程3の後に、更に、下記工程4を有する上記(1)に記載の光学部材の製造方法、
工程4:貼り合わされた光学基材に対して圧力をかける工程。
(3)
前記工程1において、前記遮光領域を硬化させる際に、前記塗布層の遮光領域以外の未硬化で残す部分を紫外線遮蔽板でマスクして、紫外線を照射する上記(1)又は(2)に記載の光学部材の製造方法。
前記工程1において、紫外線照射量が少なくとも200mJ/cm2である上記(1)~(3)のいずれか一項に記載の光学部材の製造方法。
(5)
工程1において、表面上に遮光部を有する光学基材の遮光部が設けられた面、又は、それと貼り合わされる光学基材である表示ユニットの表示面の少なくとも何れか一方に紫外線硬化型樹脂組成物を塗布し、得られた塗布層を挟んで、表面上に遮光部を有する光学基材の遮光部を有する側の面と、表示ユニットの表示面とが向かい合うように貼り合わされる上記(1)~(4)のいずれか一項に記載の光学部材の製造方法。
(6)
前記表面上に遮光部を有する光学基材が遮光部を有する透明ガラス基板、遮光部を有する透明樹脂基板および遮光部と透明電極が形成してあるガラス基板からなる群から選ばれる少なくとも一つであり、それと貼り合わされる光学基材が液晶表示ユニット、プラズマ表示ユニットおよび有機EL表示ユニットからなる群から選ばれる少なくとも一つである上記(1)~(5)のいずれか一項に記載の光学部材の製造方法。
紫外線硬化型樹脂組成物が、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物である上記(1)~(6)のいずれか一項に記載の光学部材の製造方法。
(8)
前記(メタ)アクリレート(A)がウレタン(メタ)アクリレート、ポリイソプレン骨格を有する(メタ)アクリレートおよび(メタ)アクリレートモノマーからなる群から選ばれる少なくとも一つである上記(7)に記載の光学部材の製造方法。
(9)
前記(メタ)アクリレート(A)として、(i)ウレタン(メタ)アクリレート又はポリイソプレン骨格を有する(メタ)アクリレート、及び(ii)(メタ)アクリレートモノマーの両者を含む上記(7)又は(8)に記載の光学部材の製造方法。
ポリプロピレンオキサイド構造を有する、ウレタン(メタ)アクリレートまたは(メタ)アクリレートモノマーである上記(8)又は(9)に記載の光学部材の製造方法。
(11)
前記ウレタン(メタ)アクリレートが、ポリプロピレングリコール、ポリイソシアネート及びヒドロキシ基含有(メタ)アクリレートを反応させることによって得られるウレタン(メタ)アクリレートである上記(8)~(10)のいずれか一項に記載の光学部材の製造方法。
(12)
ウレタン(メタ)アクリレートの重量平均分子量が7000~25000であり、ポリイソプレン骨格を有する(メタ)アクリレートの数平均分子量が15000~50000である上記(8)又は(9)に記載の光学部材の製造方法。
(メタ)アクリレート(A)および光重合開始剤(B)以外のその他の成分を含み、(メタ)アクリレート(A)として、紫外線硬化型樹脂組成物の総量に対して、ウレタン(メタ)アクリレートを20~80重量%および(メタ)アクリレートモノマーを5~70重量%含み、光重合開始剤(B)を紫外線硬化型樹脂組成物の総量に対して0.2~5重量%含み、残部がその他の成分である上記(8)~(12)のいずれか一項に記載の光学部材の製造方法。
(14)
上記(1)~(13)のいずれか一項に記載の光学部材の製造方法により得られた光学部材。
(15)
上記(1)~(13)のいずれか一項に記載の光学部材の製造方法により得られたタッチパネル。
上記(5)に記載の光学部材の製造方法により得られた、表面上に遮光部を有する光学基材を表示ユニットの表示画面上に有する表示装置。
(17)
上記(1)~(6)のいずれか一項に記載の光学部材の製造方法のための、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物の使用。
(18)
前記(メタ)アクリレート(A)がウレタン(メタ)アクリレート、ポリイソプレン骨格を有する(メタ)アクリレートおよび(メタ)アクリレートモノマーからなる群から選ばれる少なくとも1つである上記(17)に記載の紫外線硬化型樹脂組成物の使用。
前記(メタ)アクリレート(A)として、(i)ウレタン(メタ)アクリレート又はポリイソプレン骨格を有する(メタ)アクリレート、及び(ii)(メタ)アクリレートモノマーの両者を含む上記(17)に記載の紫外線硬化型樹脂組成物の使用。
(20)
前記ウレタン(メタ)アクリレートが、ポリプロピレングリコール、ポリイソシアネート及びヒドロキシ基含有(メタ)アクリレートを反応させることによって得られるウレタン(メタ)アクリレートである上記(18)又は(19)に記載の紫外線硬化型樹脂組成物の使用。
(21)
上記(1)~(13)のいずれか一項に記載の光学部材の製造方法に使用するための、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物。
(22)
前記(メタ)アクリレート(A)がウレタン(メタ)アクリレート、ポリイソプレン骨格を有する(メタ)アクリレートおよび(メタ)アクリレートモノマーからなる群から選ばれる少なくとも1つである上記(21)に記載の紫外線硬化型樹脂組成物。
(23)
紫外線硬化型樹脂組成物が、更に柔軟化成分を含有する紫外線硬化型樹脂組成物である上記(7)に記載の光学部材の製造方法。
(24)
更に柔軟化成分を含有する上記(21)に記載の紫外線硬化型樹脂組成物。
本発明の光学部材の製造方法は、表面上に遮光部を有する透明光学基材と、それと貼り合わされる他の光学基材とを、紫外線硬化型樹脂組成物を用いて、下記工程1~工程3を含む工程により、貼り合わせることを特徴とする。
工程1:表面上に遮光部を有する透明光学基材およびそれと貼り合わされる他の光学基材の少なくとも何れか一方の貼り合わせ面に、紫外線硬化型樹脂組成物を塗布し、塗布層を形成した後、得られた塗布層における、下記する遮光領域に選択的に紫外線を照射して、該遮光領域を選択的に硬化させ、他の部分を未硬化のままの塗布層とする工程、
工程2:工程1で得られた塗布層を上記両光学基材の貼り合わせ面の間に挟んで、両光学基材を貼り合わせる工程、
工程3:貼り合わされた一対の光学基材を少なくとも一つ有する積層体に、上記遮光部を有する透明光学基材を通して紫外線を照射して、該二つの光学基材の間に挟まれた未硬化の塗布層を硬化させる工程。
本明細書において、「遮光領域」又は「貼り合わせ時遮光領域」とは、上記二つの光学基材を貼り合わせて、表面上に遮光部を有する透明光学基材を通して紫外線を塗布層に照射した際に、遮光部によって紫外線が遮られ、紫外線が当たらない塗布層部分をいう。
図1は、本発明の紫外線硬化型樹脂組成物を使用する光学部材の製造方法の第1の実施形態を示す工程図である。
この第1の実施形態は、液晶表示ユニット1と遮光部を有する透明基板2を貼り合わせることにより光学部材(遮光部を有する液晶表示ユニット)を得る方法である。
液晶表示ユニット1は、電極を形成した一対の基板間に液晶材料が封入されたものに、偏光板、駆動用回路、信号入力ケーブルおよびバックライトユニットが備わったものを言う。
遮光部を有する透明基板2は、ガラス板、ポリメチルメタクリレート(PMMA)板、ポリカーボネート(PC)板又は脂環式ポリオレフィンポリマー(COP)板等の透明基板3の貼り合わせ面の表面上に、黒色枠状の遮光部4が設けられたものである。
ここで、遮光部4はテープの貼付や塗料の塗布又は印刷等によって設けられている。
まず、図1(a)に示すように、紫外線硬化型樹脂組成物を、液晶表示ユニット1の表示面と遮光部を有する透明基板2の遮光部が設けられた面のそれぞれの表面に塗布する。塗布の方法としては、スリットコーター、ロールコーター、スピンコーター、スクリーン印刷法等が挙げられる。ここで、液晶表示ユニット1と遮光部を有する透明基板2の表面に塗布する紫外線硬化型樹脂組成物は、同一であってもよいし、異なる紫外線硬化型樹脂組成物を用いても構わない。通常は両者が同じ紫外線硬化型樹脂組成物であることが好ましい。
各紫外線硬化型樹脂組成物の硬化物の膜厚は、貼り合わせた後の樹脂硬化物層7が50~500μm、好ましくは50~350μm、更に好ましくは100~350μmとなるように調整される。
このときの紫外線の照射量は200mJ/cm2以上であるのが好ましく、特に好ましくは、1000mJ/cm2以上である。照射量が少な過ぎると、最終的に貼り合わせた光学部材の遮光部部分の硬化度が不十分となるおそれがある。紫外線の照射量は、上限は特に限定されないが、4000mJ/cm2以下であるのが好ましく、3000mJ/cm2以下であるのがより好ましい。
紫外~近紫外の紫外線照射に使用する光源については、紫外~近紫外の光線を照射するランプであれば光源の種類を問わない。例えば、低圧、高圧若しくは超高圧水銀灯、メタルハライドランプ、(パルス)キセノンランプ、または無電極ランプ等が挙げられる。
工程1において、紫外線の照射は、塗布層の上部側表面(紫外線硬化型樹脂組成物から見て、液晶表示ユニット側と反対側または透明基板側と反対側)(通常大気側の面)から照射される。該紫外線の照射は、大気中で行うことができ、目的に応じて、真空中、又は、減圧下又は非減圧下で、酸素又はオゾンなどの硬化阻害性気体の存在下又は非存在下で行っても構わない。また、目的に応じて、真空にした後に、硬化阻害性気体又は不活性ガスを塗布層の上部表面に噴霧しながら紫外線を照射しても構わない。大気中で該遮光領域の樹脂組成物を硬化した場合には、液晶表示ユニット側と反対側または透明基板側と反対側は大気側となる。
遮光領域にある塗布層の表面に粘着性を残し、接着性を向上させる観点から、紫外線の照射を、塗布層の上部表面上に、大気又は、酸素及びオゾン等の硬化阻害性ガスの存在下で行うことが好ましい。
次に、図1(b)に示すように、塗布層7(貼り合わせ時遮光領域が選択的に硬化された紫外線硬化型樹脂組成物の塗布層)同士が対向する形で、液晶表示ユニット1と遮光部を有する透明基板2を貼り合わせる。貼り合わせは、大気中及び真空中のいずれでもできる。
ここで、貼り合わせの際に気泡が生じることを防ぐためには、真空中で貼り合わせることが好適である。
このように、液晶表示ユニット1及び透明基板2の各々に、遮光領域が硬化された紫外線硬化型樹脂組成物の塗布層7を設けてから貼り合わせると、粘着力の向上を期待することができる。
次に、図1(c)に示すように、透明基板2及び液晶表示ユニット1を貼り合わせて得た光学部材に、遮光部を有する透明基板2側から紫外線9を照射して、紫外線硬化型樹脂組成物層(塗布層)を硬化させる。
工程3における紫外線の照射量は約100~4000mJ/cm2が好ましく、特に好ましくは、200~3000mJ/cm2程度である。紫外~近紫外の光線照射に使用する光源については、紫外~近紫外の光線を照射するランプであれば光源の種類を問わない。例えば、低圧、高圧若しくは超高圧水銀灯、メタルハライドランプ、(パルス)キセノンランプ、または無電極ランプ等が挙げられる。
こうして、図4に示すような光学部材を得ることができる。
さらに、必要により(工程4)として、得られた光学部材に圧力をかけて粘着を強固にすることもできる。
圧力をかけると、貼り合わせ時遮光領域における硬化物層の粘着力が向上する。これにより、液晶表示ユニット1及び透明基板2を貼り合わせた際に、該塗布層7同士を粘着させた界面における外部圧力や環境変化による剥離を防止する効果が期待できる。また、樹脂硬化物層8の液晶表示ユニット1または遮光部を有する透明基板2に対する粘着力も、より強固なものとなる。
従って、工程4を経由させることが好ましい。
図2は、本発明の紫外線硬化型樹脂組成物を使用する光学部材の製造方法の第2の実施形態を示す工程図である。
なお、上述した第1の実施形態における構成基材と同じ基材については図中で同一の符号を付し、その説明はここでは繰り返さない。
まず、図2(a)に示すように、紫外線硬化型樹脂組成物を、遮光部を有する透明基板2の遮光部4が設けられた面に塗布した。その後、貼り合わせ時遮光領域に紫外線を照射して、貼り合わせ時遮光領域が硬化された紫外線硬化型樹脂組成物の塗布層7を得る。ここで、貼り合わせ時露光領域を紫外線遮蔽板6でマスクすることにより、紫外線を照射する際に該露光領域にある樹脂組成物を硬化させないようにする。
(工程2)
次に、図2(b)に示すように、遮光部を有する透明基板2の該塗布層7と液晶表示ユニット1の表示面が対向する形で、液晶表示ユニット1と遮光部を有する透明基板2を貼り合わせる。貼り合わせは、大気中及び真空中のいずれでもできる。
(工程3)
次に、図2(c)に示すように、透明基板2及び液晶表示ユニット1を貼り合わせて得た光学部材に、遮光部を有する透明基板2側から紫外線9を照射して、貼り合わせ時露光領域にある紫外線硬化型樹脂組成物を硬化させる。
こうして、図4に示された光学部材を得ることが出来る。
第1の実施形態、第2の実施形態の他に、次のように変更した第3の実施形態を適用して本発明の光学部材を製造することができる。
(工程1)
まず、紫外線硬化型樹脂組成物を液晶表示ユニット1の表示面に塗布した後、貼り合わせ時遮光領域に紫外線を照射して、貼り合わせ時遮光領域が硬化された紫外線硬化型樹脂組成物の塗布層7を得る。ここで、貼り合わせ時露光領域を紫外線遮蔽板6でマスクすることにより、紫外線を照射する際に該露光領域にある樹脂組成物を硬化させないようにする。
(工程2)
次に、液晶表示ユニット1の該塗布層7と遮光部を有する透明基板2の遮光部4が設けられた面が対向する形で、液晶表示ユニット1と遮光部を有する透明基板2を貼り合わせる。貼り合わせは、大気中及び真空中のいずれでもできる。
(工程3)
次に、透明基板2及び液晶表示ユニット1を貼り合わせて得た光学部材に、遮光部を有する透明基板2側から紫外線9を照射して、貼り合わせ時露光領域にある紫外線硬化型樹脂組成物を硬化させる。
こうして、図4に示された光学部材を得ることが出来る。
前記第1の実施形態、第2の実施形態、第3の実施形態に加えて、次のように変更した第4の実施形態により本発明の光学部材を製造することができる。
まず、紫外線硬化型樹脂組成物を液晶表示ユニット1の表示面、及び、遮光部を有する透明基板2の遮光部4が設けられた面のそれぞれに塗布する。その後、貼り合わせ時遮光領域に紫外線を照射して、貼り合わせ時遮光領域が硬化された紫外線硬化型樹脂組成物の塗布層7を得る。ここで、紫外線硬化型樹脂組成物にアシルフォスフィンオキサイドを含有させ、紫外線の照射量を調整することで、該塗布層7を、該塗布層7の下部側(液晶表示ユニット1または遮光部を有する透明基板2側)に存在する硬化部分と、該塗布層7の上部側(液晶表示ユニット1または遮光部を有する透明基板2側と反対側)に存在する未硬化部分とを有する硬化物層とすることができる。一方、貼り合わせ時露光領域を紫外線遮蔽板6でマスクすることにより、紫外線を照射する際に該露光領域にある樹脂組成物を硬化させないようにする。
次に、該塗布層7同士が対向する形で、液晶表示ユニット1と遮光部を有する透明基板2を貼り合わせる。貼り合わせは、大気中及び真空中のいずれでもできる。
(工程3)
次に、透明基板2及び液晶表示ユニット1を貼り合わせて得た光学部材に、遮光部を有する透明基板2側から紫外線9を照射して、貼り合わせ時露光領域にある紫外線硬化型樹脂組成物を硬化させる。
こうして、図4に示された光学部材を得ることが出来る。
それだけでなく、液晶表示ユニット及び透明基板等の光学基材としては、これら各種基材に、更に、他の光学基材層(例えば、紫外線硬化型樹脂組成物の硬化物層で貼り合わされたフィルム又はその他の光学基材層)を積層したものを使用しても構わない。
さらに、第1の実施形態の項で記載した、紫外線硬化型樹脂組成物の塗布方法、樹脂硬化物の膜厚、紫外線照射の際の照射量及び光源、遮光領域に選択的に紫外線を照射する手法、及び、光学部材に圧力をかけて粘着を強固にする工程等はいずれも、上記各実施形態にのみ適用されるものでは無く、本発明に含まれるいずれの製造方法にも適用できる。
(i) 遮光部を有する光学基材が、遮光部を有する透明ガラス基板、遮光部を有する透明樹脂基板、及び遮光部と透明電極が形成してあるガラス基板からなる群から選ばれる少なくとも一つの光学基材であり、それと貼り合わされる光学基材が液晶表示ユニット、プラズマ表示ユニットおよび有機EL表示ユニットからなる群から選ばれる少なくとも一つの表示体ユニットであり、得られる光学部材が、該遮光部を有する光学基材を有する表示体ユニットである態様。
(ii) 一方の光学基材が遮光部を有する保護基材であり、それと貼り合わされる他の光学基材がタッチパネル又はタッチパネルを有する表示体ユニットであり、少なくとも2つの光学基材が貼り合わされた光学部材が、遮光部を有する保護基材を有するタッチパネル又はそれを有する表示体ユニットである態様。
この場合、工程1においては、遮光部を有する保護基材の遮光部が設けられた面、又は、タッチパネルのタッチ面の、何れか一方の面又はその両者に、紫外線硬化型樹脂組成物を塗布するのが好ましい。
(iii) 一方の光学基材が遮光部を有する光学基材であり、それと貼り合わされる他の光学基材が表示体ユニットであり、少なくとも2つの光学基材が貼り合わされた光学部材が遮光部を有する光学基材を有する表示体ユニットである態様。
この場合、工程1において、遮光部を有する光学基材の遮光部が設けられた側の面、又は、表示体ユニットの表示面の何れか一方、又は、その両者に、紫外線硬化型樹脂組成物を塗布するのが好ましい。
遮光部を有する光学基材の遮光部が設けられた側の面とは、例えば、遮光部を有する光学基材が遮光部を有する表示画面用の保護板であるときは、該保護板の遮光部が設けられた側の面である。また、遮光部を有する光学基材が、遮光部を有する保護基材を有するタッチパネルであるときには、遮光部を有する保護基材は遮光部を有する面がタッチパネルのタッチ面に貼り合わされることから、遮光部を有する光学基材の遮光部が設けられた側の面とは、該タッチパネルのタッチ面とは反対のタッチパネルの基材面を意味する。
遮光部を有する光学基材の遮光部は、光学基材の何れの箇所にあっても良いが、通常、透明な板状又はシート状の光学基材の周囲に、枠状に作製され、その幅は、0.5~10mm程度であり、好ましくは1~8mm程度、より好ましくは2~8mm程度である。
本発明の光学部材の製造方法で使用される紫外線硬化型樹脂組成物は、紫外線の照射により硬化する樹脂であれば特に限定されないが、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物(以下、「本発明の紫外線硬化型樹脂組成物」とも言う。)を使用することが好ましい。(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物は、任意成分として、光学用に使用する紫外線硬化型樹脂組成物に添加可能なその他の成分を含有することができる。
なお、「光学用に使用する紫外線硬化型樹脂組成物に添加可能」とは、硬化物の透明性を、光学用に使用出来ない程度に低下させる添加物が含まれないことを意味する。
該紫外線硬化型樹脂組成物の組成割合としては、該紫外線硬化型樹脂組成物の総量に対して、(メタ)アクリレート(A)が25~90重量%、光重合開始剤(B)が0.2~5重量%、その他の成分が残部である。
本発明の紫外線硬化型樹脂組成物において、光重合開始剤(B)としては、通常使用されている光重合開始剤は何れも使用出来る。
なお、本明細書において「(メタ)アクリレート」とは、メタクリレート及びアクリレートのいずれか一方又は両者を意味する。「(メタ)アクリル酸」等についても同様である。
また、上記(ii)(メタ)アクリレートモノマーは、上記(i)を除く、(メタ)アクリレートの意味で使用される。
このときのポリプロピレングリコールの重量平均分子量の上限は特に限定されないが、10000以下が好ましく、5000以下がより好ましい。
上記ポリイソプレン骨格を有する(メタ)アクリレートの本発明の紫外線硬化型樹脂組成物中における重量割合は、通常20~80重量%、好ましくは30~70重量%である。
ここで、(メタ)アクリレートモノマーとは、上記ウレタン(メタ)アクリレート、下記エポキシ(メタ)アクリレート、及び、上記ポリイソプレン骨格を有する(メタ)アクリレートを除いた(メタ)アクリレートを示す。
上記(メタ)アクリレートモノマーとして、炭素数10~20のアルキル(メタ)アクリレート、及び、水酸基を有する炭素数1~5のアルキル(メタ)アクリレート又はアクリロイルモルホリンの両者を含有することが好ましく、ラウリル(メタ)アクリレート及びアクリロイルモルホリンの両者を含有することが好ましい。
その具体例としては、例えば、トリシクロデカンジメチロールジ(メタ)アクリレート、ジオキサングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ポリテトラメチレングリコールジ(メタ)アクリレート、アルキレンオキサイド変性ビスフェノールA型ジ(メタ)アクリレート、カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート及びエチレンオキシド変性リン酸ジ(メタ)アクリレート等の2官能(メタ)アクリレート;トリメチロールプロパントリ(メタ)アクリレート、トリメチロールオクタントリ(メタ)アクリレート等のトリメチロールC2~C10アルカントリ(メタ)アクリレート、トリメチロールプロパンポリエトキシトリ(メタ)アクリレート、トリメチロールプロパンポリプロポキシトリ(メタ)アクリレート、トリメチロールプロパンポリエトキシポリプロポキシトリ(メタ)アクリレート等のトリメチロールC2~C10アルカンポリアルコキシトリ(メタ)アクリレート、トリス[(メタ)アクロイルオキシエチル]イソシアヌレ-ト、ペンタエリスリトールトリ(メタ)アクリレート、及び、エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート及びプロピレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート等のアルキレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート等の3官能(メタ)アクリレート;及び、ペンタエリスリトールポリエトキシテトラ(メタ)アクリレート、ペンタエリスリトールポリプロポキシテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート及びジペンタエリスリトールヘキサ(メタ)アクリレート等の4官能以上の(メタ)アクリレートを挙げることができる。
本発明においては、上記多官能(メタ)アクリレートを併用する場合は、硬化収縮を抑えるために、2官能の(メタ)アクリレートを使用することが好ましい。
該紫外線硬化型樹脂組成物における(i)ウレタン(メタ)アクリレート又はポリイソプレン骨格を有する(メタ)アクリレートの少なくとも何れか一方、及び、(ii)(メタ)アクリレートモノマーの両者を含む態様においては、(i)及び(ii)の両者の合計含量が、該樹脂組成物の総量に対して、通常、25~90重量%、好ましくは40~90重量%、より好ましくは40~80重量%である。
本発明の紫外線硬化型樹脂組成物においては、(メタ)アクリレート(A)として、ポリプロピレンオキサイド構造を有するウレタン(メタ)アクリレートを含む場合より好ましい。
ポリプロピレンオキサイド構造を有するウレタン(メタ)アクリレートの具体例としては、ポリプロピレングリコール、ポリイソシアネート及びヒドロキシ基含有(メタ)アクリレートの3者を反応させて得られるウレタン(メタ)アクリレートが挙げられる。
ポリプロピレンオキサイド構造を有する(メタ)アクリレートモノマーの具体例としては、ポリプロピレングリコール(メタ)アクリレート、ポリプロピレンオキサイド変性ノニルフェニル(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート及びプロピレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレートが挙げられる。
エポキシ(メタ)アクリレートは、硬化性の向上や硬化物の硬度や硬化速度を向上させる機能がある。エポキシ(メタ)アクリレートとしては、グリシジルエーテル型エポキシ化合物と、(メタ)アクリル酸を反応させることにより得られたものであればいずれも使用できる。
好ましく使用されるエポキシ(メタ)アクリレートを得るためのグリシジルエーテル型エポキシ化合物としては、ビスフェノールA或いはそのアルキレンオキサイド付加体のジグリシジルエーテル、ビスフェノールF或いはそのアルキレンオキサイド付加体のジグリシジルエーテル、水素添加ビスフェノールA或いはそのアルキレンオキサイド付加体のジグリシジルエーテル、水素添加ビスフェノールF或いはそのアルキレンオキサイド付加体のジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ブタンジオールジグリシジルエーテル、へキサンジオールジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、及び、ポリプロピレングリコールジグリシジルエーテル等を挙げることができる。
エポキシ(メタ)アクリレートの本発明の紫外線硬化型樹脂組成物中における重量割合は通常1~80重量%、好ましくは5~30重量%である。
本発明の紫外線硬化型樹脂組成物において、(メタ)アクリレート(A)として、前記ウレタン(メタ)アクリレート、前記ポリイソプレン骨格を有する(メタ)アクリレート及び前記(メタ)アクリレートモノマーからなる群から選択される少なくとも一つを含有することが好ましく;前記ウレタン(メタ)アクリレートの含有割合が20~80重量%、好ましくは30~70重量%であり;前記ポリイソプレン骨格を有する(メタ)アクリレートの含有割合が20~80重量%、好ましくは30~70重量%であり、前記(メタ)アクリレートモノマーの含有割合が5~70重量%、好ましくは10~50重量%であるとき、より好ましい。
本発明の紫外線硬化型樹脂組成物において、(メタ)アクリレート(A)として、前記ウレタン(メタ)アクリレート又はポリイソプレン骨格を有する(メタ)アクリレートを20~80重量%、好ましくは30~70重量%含有し、且つ、(メタ)アクリレート(A)として前記(メタ)アクリレートモノマーを5~70重量%、好ましくは10~50重量%含有するとき、更に好ましい。
光重合開始剤(B)の具体例としては、例えば、1-ヒドロキシシクロヘキシルフェニルケトン(イルガキュア(登録商標、以下同じ)184;BASF社製)、2-ヒドロキシ-2-メチル-[4-(1-メチルビニル)フェニル]プロパノールオリゴマー(エサキュアONE;ランバルティ社製)、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン(イルガキュア2959;BASF社製)、2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]-フェニル}-2-メチル-プロパン-1-オン(イルガキュア127;BASF社製)、2,2-ジメトキシ-2-フェニルアセトフェノン(イルガキュア651;BASF社製)、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(ダロキュア(登録商標)1173;BASF社製)、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン(イルガキュア907;BASF社製)、オキシ-フェニル-アセチックアシッド2-[2-オキソ-2-フェニル-アセトキシ-エトキシ]-エチルエステルとオキシ-フェニル-アセチックアシッド2-[2-ヒドロキシ-エトキシ]-エチルエステルの混合物(イルガキュア754;BASF社製)、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタン-1-オン、2-クロロチオキサントン、2,4-ジメチルチオキサントン、2,4-ジイソプロピルチオキサントン、イソプロピルチオキサントン、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、2,4,6-トリメチルベンゾイルフェニルエトキシフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド及びビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルフォスフィンオキサイド等を挙げることができる。
(式中、nは0~40の整数、mは10~50の整数を示す。R1およびR2はそれぞれ同一であっても異なっていてもよい。R1およびR2は炭素数1~18のアルキル基、炭素数1~18のアルケニル基、炭素数1~18のアルキニル基、炭素数5~18のアリール基である。)
一般式(1)で示される構造を有する化合物は、例えば、日油株式会社製ユニセーフPKA-5017(製品名、ポリエチレングリコール-ポリプロピレングリコールアリルブチルエーテル)等として入手することができる。
一般式(1)で示される構造を有する化合物を使用する際の紫外線硬化型樹脂組成物中における重量割合は、通常10~80重量%、好ましくは10~70重量%である。
かかる柔軟化成分を使用する場合の紫外線硬化型樹脂組成物中における重量割合は、通常10~80重量%、好ましくは10~70重量%である。
シランカップリング剤の具体例としては、例えば、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、N-(2-アミノエチル)3-アミノプロピルメチルジメトキシシラン、γ-メルカプロプロピルトリメトキシシラン、N-(2-アミノエチル)3-アミノプロピルメチルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、ビニルトリメトキシシラン、N-(2-(ビニルベンジルアミノ)エチル)3-アミノプロピルトリメトキシシラン塩酸塩、3-メタクリロキシプロピルトリメトキシシラン、3-クロロプロピルメチルジメトキシシラン、及び、3-クロロプロピルトリメトキシシラン等が挙げられる。
ジルコニウム系カップリング剤及びアルミニウム系カップリング剤の具体例としては、例えば、Zr-アセチルアセトネート、Zr-メタクリレート、Zr-プロピオネート、ネオアルコキシジルコネート、ネオアルコキシトリスネオデカノイルジルコネート、ネオアルコキシトリス(ドデカノイル)ベンゼンスルフォニルジルコネート、ネオアルコキシトリス(エチレンジアミノエチル)ジルコネート、ネオアルコキシトリス(m-アミノフェニル)ジルコネート、アンモニウムジルコニウムカーボネート、Al-アセチルアセトネート、Al-メタクリレート、及び、Al-プロピオネート等が挙げられる。
本発明の紫外線硬化型樹脂組成物は、塗布性を考え、25℃の粘度が300~15000mPa・sの範囲となるように、成分の配合比を適宜調節することが好ましい。
また、ガラス等の基材が薄い場合には、硬化収縮率が大きい場合には硬化時の反りが大きくなることから、表示性能に大きな悪影響を及ぼす。当該観点からも、硬化収縮率は少ない方が好ましい。
また、硬化物の400~450nmの波長領域における透過率が高いと、表示画像の視認性の向上が一層期待できる。そのため、上記硬化物を上記フィルムとしたとき、400~450nmの波長領域における透過率が90%以上であることが好ましい。
(I)
(メタ)アクリレート(A)及び光重合開始剤(B)を含有し、(メタ)アクリレート(A)がウレタン(メタ)アクリレート、ポリイソプレン骨格を有する(メタ)アクリレートおよび(メタ)アクリレートモノマーからなる群から選ばれる少なくとも一つの(メタ)アクリレートである紫外線硬化型樹脂組成物。
(II)
前記(メタ)アクリレート(A)として、
(i)ウレタン(メタ)アクリレート又はポリイソプレン骨格を有する(メタ)アクリレート、及び、
(ii)(メタ)アクリレートモノマー、
の両者を含む上記(I)に記載の紫外線硬化型樹脂組成物。
(III)
前記ウレタン(メタ)アクリレートまたは前記(メタ)アクリレートモノマーがポリプロピレンオキサイド構造を有するウレタン(メタ)アクリレート又はポリプロピレンオキサイド構造を有する(メタ)アクリレートモノマーである上記(I)又は(II)に記載の紫外線硬化型樹脂組成物。
前記ウレタン(メタ)アクリレートが、ポリプロピレングリコール、ポリイソシアネート及びヒドロキシ基含有(メタ)アクリレートの3者を反応させることによって得られるウレタン(メタ)アクリレートである上記(I)又は(II)に記載の紫外線硬化型樹脂組成物。
(V)
ウレタン(メタ)アクリレートの重量平均分子量が7000~25000であり、ポリイソプレン骨格を有する(メタ)アクリレートの数平均分子量が15000~50000である上記(I)~(IV)のいずれか一項に記載の紫外線硬化型樹脂組成物。
(VI)
(メタ)アクリレート(A)及び光重合開始剤(B)を含有し、光重合開始剤(B)として、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイドを含有する紫外線硬化型樹脂組成物、又は、光重合開始剤(B)として、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイドを含有する上記(I)~(V)のいずれか一項に記載の紫外線硬化型樹脂組成物。
(メタ)アクリレート(A)及び光重合開始剤(B)を含有し、(A)成分及び(B)成分以外に、更に、その他の成分を含有する紫外線硬化型樹脂組成物、又は、(A)成分及び(B)成分以外に、更に、その他の成分を含有する上記(I)~(VI)のいずれか一項に記載の紫外線硬化型樹脂組成物。
(VIII)
(メタ)アクリレート(A)の含有割合が25~90重量%、光重合開始剤(B)の含有割合が0.2~5重量%、その他の成分が残部である上記(VII)に記載の紫外線硬化型樹脂組成物。
(IX)
(メタ)アクリレート(A)として、(i)ウレタン(メタ)アクリレート又はポリイソプレン(メタ)アクリレートの少なくとも一方を20~80重量%、及び、(ii)(メタ)アクリレートモノマーを5~70重量%含み、両者の合計含有割合が40~90重量%である上記(VIII)に記載の紫外線硬化型樹脂組成物。
その他の成分として、前記一般式(1)で表される化合物を10~80重量%含む上記(VII)~(IX)の何れか一項に記載の紫外線硬化型樹脂組成物。
(XI)
紫外線硬化型樹脂組成物の硬化物の硬化収縮率が3%以下である、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物、又は、上記(I)~(X)の何れか一項に記載の紫外線硬化型樹脂組成物。
(XII)
膜厚が200μmである紫外線硬化型樹脂組成物の硬化物からなるシートの光透過率が、400~450nmの波長域での平均透過率が少なくとも90%であり、且つ、400~800nmの波長域での平均透過率が少なくとも90%である、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物、又は、上記(I)~(XI)の何れか一項に記載の紫外線硬化型樹脂組成物。
本発明の光学部材の製造方法において使用する光学基材としては、例えば、透明板、シート、タッチパネル及び表示体ユニット等を挙げることができる。
本明細書において「光学基材」とは、表面に遮光部を有さない光学基材と、表面に遮光部を有する光学基材の両者を意味する。本発明の光学部材の製造方法においては、複数用いられる光学基材のうち少なくとも一つが、遮光部を有する光学基材である。
遮光部を有する光学基材としては、上記材質の光学基材の表面上に遮光部を形成したものであれば、特に限定することなく使用することができる。遮光部を有する光学基材における遮光部の位置は、特に限定されない。好ましい態様としては、該光学基材の周辺部に、幅0.05~20mm、好ましくは0.05~10mm程度、より好ましくは0.1~6mm程度の幅を有する帯状の遮光部が設けられる場合が挙げられる。光学基材上の遮光部は、テープの貼付や塗料の塗布又は印刷等によって形成することができる。
また、本発明の光学部材の製造方法において、遮光部を有する光学基材と貼り合わせる光学基材は、表面上に遮光部を有するものであっても、遮光部を有していないものであっても構わない。
また、本発明に用いる光学基材は、上記した偏光板などの他、タッチパネル(タッチパネル入力センサー)又は下記の表示体ユニット等の、複数の機能板又はシートからなる積層体(以下、「機能性積層体」とも言う。)を含む。
本発明に用いる光学基材として使用することができるタッチパネルの表面の材質としては、ガラス、PET、PC、PMMA、PCとPMMAの複合体、COC及びCOPが挙げられる。
透明板又はシート等の板状又はシート状の光学基材の厚さは、特に制限されず、通常は、5μm程度から5cm程度、好ましくは10μm程度から10mm程度、より好ましくは50μm~3mm程度の厚さである。
また、本発明の製造方法において、光学基材の一つとして液晶表示装置等の表示体ユニットを使用し、他の光学基材として遮光部を有する光学機能材料を使用することにより、光学機能材料付き表示体ユニット(以下表示パネルともいう)を製造することができる。上記の表示体ユニットとしては、例えば、ガラスに偏光板を貼り付けてなるLCD、有機又は無機ELディスプレイ、EL照明、電子ペーパー及びプラズマディスプレイ等の表示装置が挙げられる。また、上記光学機能材料としては、アクリル板、PC板、PET板及びPEN板等の透明プラスチック板、強化ガラス及びタッチパネルが挙げられる。
硬化物の屈折率が当該範囲内であれば、光学基材として使用される基材との屈折率の差を低減させることができ、光の乱反射を抑えて光損失を低減させることが可能となる。
(i)遮光部を有する光学基材と前記機能性積層体とを、本発明の紫外線硬化型樹脂組成物の硬化物を用いて貼り合わせた光学部材。
(ii)遮光部を有する光学基材が、遮光部を有する透明ガラス基板、遮光部を有する透明樹脂基板、及び、遮光部と透明電極が形成してあるガラス基板からなる群から選ばれる光学基材であり、機能性積層体が表示体ユニット又はタッチパネルである上記(i)に記載の光学部材。
(iii)表示体ユニットが液晶表示ユニット、プラズマ表示ユニット及び有機EL表示ユニットのいずれかである上記(ii)に記載の光学部材。
(iv)遮光部を有する板状又はシート状の光学基材を、タッチパネルのタッチ面側の表面に本発明の紫外線硬化型樹脂組成物の硬化物を用いて貼り合わせたタッチパネル(又はタッチパネル入力センサー)。
(v)遮光部を有する板状又はシート状の光学基材を、表示体ユニットの表示画面上に本発明の紫外線硬化型樹脂組成物の硬化物を用いて貼り合わせた表示パネル。
(vi)遮光部を有する板状又はシート状の光学基材が、表示体ユニットの表示画面を保護するための保護基材又はタッチパネルである、上記(v)に記載の表示パネル。
(vii)紫外線硬化型樹脂組成物が、前記(I)~(XII)のいずれか一項に記載の紫外線硬化型樹脂組成物である、上記(i)~(vi)のいずれか一項に記載の光学部材、タッチパネル又は表示パネル。
例えば、前記機能性積層体がタッチパネル又は表示体ユニットである上記(ii)に記載の光学部材の場合、工程1において、遮光部を有する保護基材のいずれか一方の面、好ましくは遮光部が設けられた面、及び、タッチパネルのタッチ面又は表示体ユニットの表示面の何れか一方のみに該樹脂組成物を塗布しても良いし、その両方に塗布しても良い。
また、表示体ユニットの表示画面を保護するための保護基材又はタッチパネルを表示体ユニットと貼り合わせた上記(vi)の光学部材の場合、工程1において、保護基材の遮光部が設けられた面又はタッチパネルのタッチ面とは反対の基材面、及び、表示体ユニットの表示面の何れか一方のみに該樹脂組成物を塗布しても良いし、その両方に塗布しても良い。
ウレタンアクリレート(ポリプロピレングリコール(分子量3000)、イソホロンジイソシアネート及び2-ヒドロキシエチルアクリレートの3成分をモル比1:1.3:2で反応させて得られた反応物)45重量部、ユニセーフPKA-5017(ポリエチレングリコール-ポリプロピレングリコールアリルブチルエーテル、日油株式会社製)25重量部、ACMO(アクリロイルモルホリン、株式会社興人製)10重量部、LA(ラウリルアクリレート、大阪有機化学工業株式会社製)20重量部、スピードキュアTPO(2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、LAMBSON社製)0.5重量部を加熱混合して調製した(紫外線硬化型樹脂組成物A)。
実施例1
図1(a)に示すように面積が3.5インチの液晶表示ユニット1の表示面、及び、遮光部4(幅5mm)を有する透明ガラス基板2の遮光部が設けられた面のそれぞれに、調製した紫外線硬化型樹脂組成物Aを、それぞれの膜厚が125μmとなるように塗布した。ついで、得られた塗布層5に、貼り合わせ時露光領域に紫外線遮蔽板6を介在させ、高圧水銀灯(80W/cm、オゾンレス)で、大気側から積算光量2000mJ/cm2の紫外線9を照射し、貼り合わせ時遮光領域にある塗布層を硬化した。
図2(a)に示すように面積が3.5インチの、遮光部4(幅5mm)を有する透明ガラス基板2上に、調製した紫外線硬化型樹脂組成物Aを、その膜厚が250μmとなるように塗布した。ついで、得られた塗布層5に、貼り合わせ時露光領域に紫外線遮蔽板6を介在させ、高圧水銀灯(80W/cm、オゾンレス)で、大気側から積算光量2000mJ/cm2の紫外線9を照射し、貼り合わせ時遮光領域にある塗布層を硬化した。
図3(a)に示すように液晶表示ユニット1の表示面、及び、遮光部4(幅5mm)を有する透明基板2上の遮光部が設けられた面のそれぞれに、調製した紫外線硬化型樹脂組成物Aを、それぞれの膜厚が125μmとなるように塗布した。
得られた光学部材から透明基板を外して、遮光部により遮光された領域にある樹脂硬化物層をイソプロピルアルコールで洗い流した。これにより、未硬化の樹脂組成物は除去される。その後、遮光領域にある樹脂硬化物層の硬化状態を確認することにより、硬化度を測定した。硬化度の評価は下記の基準に基づいて行った。
硬化度:
○・・・硬化(未硬化の樹脂組成物が除去された形跡が確認できない。)
△・・・半硬化(硬化物が残存しているが、未硬化の樹脂組成物が除去された形跡も確認できる。)
×・・・全く硬化していない(硬化物が全く残存していない。)
厚さ1mmのスライドガラス2枚を用意し、そのうちの1枚に得られた紫外線硬化型樹脂組成物Aを膜厚が200μmとなるように塗布した。得られた塗布層上に他方のスライドガラスを貼り合わせた。ガラス越しに高圧水銀灯(80W/cm、オゾンレス)で積算光量2000mJ/cm2の紫外線を、2枚のスライドガラスに挟まれた塗布層に照射した。硬化物の硬化状態を目視で確認したところ完全に硬化していた。
フッ素系離型剤を塗布した厚さ1mmのスライドガラス2枚を用意し、そのうちの1枚の離型剤塗布面に、得られた紫外線硬化型樹脂組成物Aを膜厚が200μmとなるように塗布した。その後、2枚のスライドガラスを、それぞれの離型剤塗布面が互いに向かい合うように貼り合わせた。ガラス越しに、高圧水銀灯(80W/cm、オゾンレス)で積算光量2000mJ/cm2の紫外線を2枚のスライドガラスに挟まれた塗布層に照射し、塗布層を硬化させた。その後、2枚のスライドガラスを剥離し、膜比重測定用の硬化物フィルムを作製した。
JIS K7112 B法に準拠し、硬化物の比重(DS)を測定した。また、25℃での紫外線硬化型樹脂組成物の液比重(DL)を測定した。DS及びDLの測定結果から、次式より硬化収縮率を算出したところ、2.0%未満であった。
硬化収縮率(%)=(DS-DL)÷DS×100
厚さ0.8mmのスライドガラスと厚さ0.8mmのアクリル板を用意し、その一方に得られた紫外線硬化型樹脂組成物Aを膜厚が200μmとなるように塗布し、得られた塗布層を挟むように他方を貼り合わせた。挟まれた塗布層に、スライドガラス越しに、高圧水銀灯(80W/cm、オゾンレス)で積算光量2000mJ/cm2の紫外線を照射し、塗布層を硬化させ、接着性評価用サンプルを作製した。これを、85℃、85%RH環境下、250時間放置した。その評価用サンプルにおいて、目視にてスライドガラス又はアクリル板の樹脂硬化物からの剥がれを確認したが、剥がれはなかった。
得られた紫外線硬化型樹脂組成物Aを充分に硬化させ、JIS K7215に準拠する方法により、デュロメータ硬度計(タイプE)を用いてデュロメータE硬さを測定し、柔軟性を評価した。より具体的には、紫外線硬化型樹脂組成物Aを膜厚が1cmとなるように円柱状の型に流し込み、紫外線を照射して該樹脂組成物を十分に硬化させた。得られた硬化物の硬度をデュロメータ硬度計(タイプE)で測定した。その結果、測定値は10未満であり、柔軟性に優れていた。
フッ素系離型剤を塗布した厚さ1mmのスライドガラス2枚を用意し、そのうちの1枚の離型剤塗布面に、得られた紫外線硬化型樹脂組成物を硬化後の膜厚が200μmとなるように塗布した。その後、2枚のスライドガラスを、それぞれの離型剤塗布面が互いに向かい合うように貼り合わせた。ガラス越しに、高圧水銀灯(80W/cm、オゾンレス)で積算光量2000mJ/cm2の紫外線を該樹脂組成物に照射し、該樹脂組成物を硬化させた。その後、2枚のスライドガラスを剥離し、透明性測定用の硬化物を作製した。得られた硬化物の透過性については、分光光度計(U-3310、日立ハイテクノロジーズ株式会社)を用いて、400~800nm及び400~450nmの波長領域における透過率を測定した。その結果、400~800nmの透過率は90%以上であり、かつ、400~450nmの透過率も90%以上であった。
Claims (24)
- 表面上に遮光部を有する透明光学基材とそれと貼り合わされる他の光学基材の両者を、紫外線硬化型樹脂組成物を用いて、下記工程1~工程3を含む工程により貼り合わされた少なくとも一対の光学基材を含む光学部材の製造方法、
工程1:表面上に遮光部を有する透明光学基材およびそれと貼り合わされる他の光学基材の少なくとも何れか一方の貼り合わせ面に、紫外線硬化型樹脂組成物を塗布し、塗布層を形成した後、得られた塗布層における、下記する遮光領域に選択的に紫外線を照射して、該遮光領域を選択的に硬化させ、他の部分を未硬化のままの塗布層とする工程、
なお、上記の遮光領域とは、上記二つの光学基材を貼り合わせて、表面上に遮光部を有する透明光学基材を通して紫外線を塗布層に照射した際に、遮光部によって紫外線が遮られ、紫外線が当たらない塗布層部分を意味する、
工程2:工程1で得られた塗布層を上記両光学基材の貼り合わせ面の間に挟んで、両光学基材を貼り合わせる工程、
工程3:上記工程1及び2により貼り合わされた一対の光学基材を少なくとも一つ有する積層体に、上記遮光部を有する透明光学基材を通して紫外線を照射して、該二つの光学基材の間に挟まれた未硬化の塗布層を硬化させる工程。 - 前記工程3の後に、更に、下記工程4を有する請求項1に記載の光学部材の製造方法、
工程4:貼り合わされた光学基材に対して圧力をかける工程。 - 前記工程1において、前記遮光領域を硬化させる際に、前記塗布層の遮光領域以外の未硬化で残す部分を紫外線遮蔽板でマスクして、紫外線を照射する請求項1に記載の光学部材の製造方法。
- 前記工程1において、紫外線照射量が少なくとも200mJ/cm2である請求項1に記載の光学部材の製造方法。
- 工程1において、表面上に遮光部を有する光学基材の遮光部が設けられた面、又は、それと貼り合わされる光学基材である表示ユニットの表示面の少なくとも何れか一方に紫外線硬化型樹脂組成物を塗布し、得られた塗布層を挟んで、表面上に遮光部を有する光学基材の遮光部を有する側の面と、表示ユニットの表示面とが向かい合うように貼り合わされる請求項1に記載の光学部材の製造方法。
- 前記表面上に遮光部を有する光学基材が遮光部を有する透明ガラス基板、遮光部を有する透明樹脂基板および遮光部と透明電極が形成してあるガラス基板からなる群から選ばれる少なくとも一つであり、それと貼り合わされる光学基材が液晶表示ユニット、プラズマ表示ユニットおよび有機EL表示ユニットからなる群から選ばれる少なくとも一つである請求項1に記載の光学部材の製造方法。
- 紫外線硬化型樹脂組成物が、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物である請求項1に記載の光学部材の製造方法。
- 前記(メタ)アクリレート(A)がウレタン(メタ)アクリレート、ポリイソプレン骨格を有する(メタ)アクリレートおよび(メタ)アクリレートモノマーからなる群から選ばれる少なくとも一つである請求項7に記載の光学部材の製造方法。
- 前記(メタ)アクリレート(A)として、(i)ウレタン(メタ)アクリレート又はポリイソプレン骨格を有する(メタ)アクリレート、及び(ii)(メタ)アクリレートモノマーの両者を含む請求項8に記載の光学部材の製造方法。
- ポリプロピレンオキサイド構造を有する、ウレタン(メタ)アクリレートまたは(メタ)アクリレートモノマーである請求項8又は9に記載の光学部材の製造方法。
- 前記ウレタン(メタ)アクリレートが、ポリプロピレングリコール、ポリイソシアネート及びヒドロキシ基含有(メタ)アクリレートを反応させることによって得られるウレタン(メタ)アクリレートである請求項10に記載の光学部材の製造方法。
- ウレタン(メタ)アクリレートの重量平均分子量が7000~25000であり、ポリイソプレン骨格を有する(メタ)アクリレートの数平均分子量が15000~50000である請求項8又は9に記載の光学部材の製造方法。
- (メタ)アクリレート(A)および光重合開始剤(B)以外のその他の成分を含み、(メタ)アクリレート(A)として、紫外線硬化型樹脂組成物の総量に対して、ウレタン(メタ)アクリレートを20~80重量%および(メタ)アクリレートモノマーを5~70重量%含み、光重合開始剤(B)を紫外線硬化型樹脂組成物の総量に対して0.2~5重量%含み、残部がその他の成分である請求項8又は9に記載の光学部材の製造方法。
- 請求項1、3、6、8及び12のいずれか一項に記載の光学部材の製造方法により得られた光学部材。
- 請求項1に記載の光学部材の製造方法により得られたタッチパネル。
- 請求項5に記載の光学部材の製造方法により得られた、表面上に遮光部を有する光学基材を表示ユニットの表示画面上に有する表示装置。
- 請求項1~5のいずれか一項に記載の光学部材の製造方法のための、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物の使用。
- 前記(メタ)アクリレート(A)がウレタン(メタ)アクリレート、ポリイソプレン骨格を有する(メタ)アクリレートおよび(メタ)アクリレートモノマーからなる群から選ばれる少なくとも1つである請求項17に記載の紫外線硬化型樹脂組成物の使用。
- 前記(メタ)アクリレート(A)として、(i)ウレタン(メタ)アクリレート又はポリイソプレン骨格を有する(メタ)アクリレート、及び(ii)(メタ)アクリレートモノマーの両者を含む請求項17に記載の紫外線硬化型樹脂組成物の使用。
- 前記ウレタン(メタ)アクリレートが、ポリプロピレングリコール、ポリイソシアネート及びヒドロキシ基含有(メタ)アクリレートを反応させることによって得られるウレタン(メタ)アクリレートである請求項18に記載の紫外線硬化型樹脂組成物の使用。
- 請求項1に記載の光学部材の製造方法に使用するための、(メタ)アクリレート(A)及び光重合開始剤(B)を含有する紫外線硬化型樹脂組成物。
- 前記(メタ)アクリレート(A)がウレタン(メタ)アクリレート、ポリイソプレン骨格を有する(メタ)アクリレートおよび(メタ)アクリレートモノマーからなる群から選ばれる少なくとも1つである請求項21に記載の紫外線硬化型樹脂組成物。
- 紫外線硬化型樹脂組成物が、更に柔軟化成分を含有する紫外線硬化型樹脂組成物である請求項7に記載の光学部材の製造方法。
- 更に柔軟化成分を含有する請求項21に記載の紫外線硬化型樹脂組成物。
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US14/353,121 US9182527B2 (en) | 2011-10-21 | 2012-10-19 | Method for producing optical member and use of UV-curable resin composition therefor |
KR1020147006265A KR20140066184A (ko) | 2011-10-21 | 2012-10-19 | 광학부재의 제조방법 및 그것을 위한 자외선 경화형 수지 조성물의 사용 |
KR1020147020791A KR20140103184A (ko) | 2011-10-21 | 2012-10-19 | 광학부재의 제조방법 및 그것을 위한 자외선 경화형 수지 조성물의 사용 |
JP2013521328A JP5331271B1 (ja) | 2011-10-21 | 2012-10-19 | 光学部材の製造方法及びそのための紫外線硬化型樹脂組成物の使用 |
KR20137034564A KR101493251B1 (ko) | 2011-10-21 | 2012-10-19 | 광학부재의 제조방법 및 그것을 위한 자외선 경화형 수지 조성물의 사용 |
CN201280036583.2A CN103826855B (zh) | 2011-10-21 | 2012-10-19 | 光学构件的制造方法及用于该制造方法的紫外线固化型树脂组合物的应用 |
EP12842131.0A EP2769843B1 (en) | 2011-10-21 | 2012-10-19 | Method for producing optical member and use of uv-curable resin composition therefor |
HK14111983.0A HK1198438A1 (zh) | 2011-10-21 | 2014-11-27 | 光學構件的製造方法及用於該製造方法的紫外線固化型樹脂組合物的應用 |
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EP2769843A1 (en) | 2014-08-27 |
KR20140045961A (ko) | 2014-04-17 |
KR101493251B1 (ko) | 2015-02-16 |
JPWO2013057959A1 (ja) | 2015-04-02 |
CN103826855B (zh) | 2015-12-02 |
KR20140103184A (ko) | 2014-08-25 |
HK1198438A1 (zh) | 2015-04-24 |
EP2769843B1 (en) | 2016-06-29 |
EP2769843A4 (en) | 2015-06-03 |
TWI560063B (en) | 2016-12-01 |
CN103826855A (zh) | 2014-05-28 |
US9182527B2 (en) | 2015-11-10 |
TW201323216A (zh) | 2013-06-16 |
US20140256842A1 (en) | 2014-09-11 |
KR20140066184A (ko) | 2014-05-30 |
TWI438095B (zh) | 2014-05-21 |
TW201427829A (zh) | 2014-07-16 |
JP5331271B1 (ja) | 2013-10-30 |
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