WO2013187508A1 - 重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法 - Google Patents
重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法 Download PDFInfo
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- WO2013187508A1 WO2013187508A1 PCT/JP2013/066496 JP2013066496W WO2013187508A1 WO 2013187508 A1 WO2013187508 A1 WO 2013187508A1 JP 2013066496 W JP2013066496 W JP 2013066496W WO 2013187508 A1 WO2013187508 A1 WO 2013187508A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
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- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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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
- C09J2423/00—Presence of polyolefin
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- C09J2451/00—Presence of graft polymer
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133331—Cover glasses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to a polymerizable composition used in an image display device such as a liquid crystal display device used in, for example, smartphones and tablet PCs, a polymer obtained by polymerizing the composition, and an image display using the composition
- an image display device such as a liquid crystal display device used in, for example, smartphones and tablet PCs
- a polymer obtained by polymerizing the composition and an image display using the composition
- the present invention relates to a device manufacturing method and an image display device manufactured by the manufacturing method.
- a liquid crystal display device 101 shown in FIG. 6 is known as this type of image display device.
- the liquid crystal display device 101 has a transparent protective part 103 made of, for example, glass or plastic on a liquid crystal display panel 102.
- a spacer 104 is interposed between the protective portion 103 and a gap between the liquid crystal display panel 102 and the protective portion 103.
- 105 is provided.
- the presence of the gap 105 between the liquid crystal display panel 102 and the protection unit 103 causes light scattering, resulting in a decrease in contrast and brightness, and the presence of the gap 105 hinders thinning of the panel. It has become.
- Patent Document 2 or Patent Document 3 uses a polyurethane acrylate or a polyisoprene polymer maleic anhydride adduct and an esterified product of 2-hydroxyethyl methacrylate with a low elastic modulus.
- a curable composition having a small volumetric shrinkage during curing is disclosed.
- the volume shrinkage ratio at the time of curing of the curable composition using polyurethane acrylate is large (greater than 4.0%), and the maleic anhydride adduct of polyisoprene polymer and ester of 2-hydroxyethyl methacrylate
- the curable composition using the chemicals has a small volume shrinkage at the time of curing, it has a problem that coloring of the cured cured product due to heat increases.
- a capacitive touch panel As an example of a capacitive touch panel, a polymer (layer) filled between the display unit and the touch panel in the Out-Cell capacitive touch panel display device shown in FIG. 2 or 3 (FIG. 2). And the polymer (layer) of 5b shown in FIG. 3) or a cover glass-polymerization filled between the display unit and the touch center integrated protection unit in the touch-panel-integrated capacitive touch panel display device.
- the material (layer) (5b polymer (layer) shown in FIGS. 4 and 5) is desired to have a low dielectric constant from the viewpoint of preventing malfunction and thinning.
- the present invention provides a polymerizable composition for producing a polymer having a small volume shrinkage during polymerization, a low dielectric constant, and little coloration by heat, and a composition obtained by polymerizing the composition. It is an object to provide a polymer (including an optical pressure-sensitive adhesive sheet) to be obtained, an image display device using the polymer, and a method for producing the image display device.
- a photopolymerizable composition containing a (meth) acryloyl group-containing compound having a specific structure has a small volume shrinkage during polymerization and is The heat-resistant colorability of the obtained polymer was reduced, and the dielectric constant was found to be lower, and the present invention was completed.
- the present invention (I) is a polymerizable composition for producing a polymer for forming a polymer layer interposed between an image display part and a translucent protective part of an image display device.
- the polymerizable composition is Component (1) (meth) acryloyl group-containing compound having polyolefin structural unit, (meth) acryloyl group-containing compound having hydrogenated polyolefin structural unit, (meth) acryloyl group-containing compound having (poly) ester structural unit and (poly ) At least one selected from the group consisting of (meth) acryloyl group-containing compounds having a carbonate structural unit;
- Polymeric composition comprising component (3) at least one selected from the group consisting of liquid hydrogenated polybutadiene polyol, liquid hydrogenated polyisoprene polyol and hydrogenated dimer diol, and component (4) photopolymerization initiator Related to
- the present invention (II) relates to a polymer obtained by polymerizing the polymerizable composition of the present invention (I).
- the present invention (III) is a thickness obtained by applying the polymerizable composition of the present invention (I), irradiating the polymerizable composition with light capable of being photosensitized by a photopolymerization initiator, and polymerizing the polymerizable composition.
- the present invention relates to an optical pressure-sensitive adhesive sheet having a polymer layer of 10 to 500 ⁇ m.
- the present invention (IV) is a method for manufacturing an image display device, comprising: a base having an image display portion; a translucent protective portion; and a polymer layer interposed between the base and the protective portion.
- the method comprises the step of interposing the polymerizable composition of the present invention (I) between the base part and the protective part, and polymerizing the polymerizable composition by irradiating the polymerizable composition with photosensitive light.
- the present invention relates to a method for manufacturing an image display device including a step of forming a physical layer.
- the present invention (V) is a method for producing an image display device having a step of attaching a polymer layer using an optical adhesive sheet between a base portion having an image display portion and a translucent protective portion,
- the optical pressure-sensitive adhesive sheet is an optical pressure-sensitive adhesive sheet according to the present invention (III).
- the present invention (VI) relates to an image display device produced by the method of the present invention (IV) or the present invention (V).
- a polymerizable composition for producing a polymer for forming a polymer layer interposed between an image display part and a translucent protective part of an image display device is, Component (1) (meth) acryloyl group-containing compound having polyolefin structural unit, (meth) acryloyl group-containing compound having hydrogenated polyolefin structural unit, (meth) acryloyl group-containing compound having (poly) ester structural unit and (poly ) At least one selected from the group consisting of (meth) acryloyl group-containing compounds having a carbonate structural unit; Component (2) Liquid (meth) acryloyl group-containing compound other than component (1), Polymeric composition comprising component (3) at least one selected from the group consisting of liquid hydrogenated polybutadiene polyol, liquid hydrogenated polyisoprene polyol and hydrogenated dimer diol, and component (4)
- Component (5) Hydrogenated polybutadiene, hydrogenated polyisoprene, poly ( ⁇ -olefin) liquid, ethylene-propylene copolymer liquid, propylene- ⁇ -olefin copolymer liquid, ethylene- ⁇ -olefin copolymer It further includes at least one selected from the group consisting of liquid, liquid polybutene, liquid hydrogenated polybutene, liquid polybutadiene, liquid hydrogenated polybutadiene, liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene polyol, and liquid polyisoprene polyol.
- the component (6) further comprising at least one selected from the group consisting of hydrogenated petroleum resins, terpene hydrogenated resins, and hydrogenated rosin esters Polymerizable composition.
- a polymerizable composition which is a composition.
- Optical pressure-sensitive adhesive having a polymer layer having a thickness of 10 to 500 ⁇ m, obtained by irradiating the polymerizable composition as described in [7] with light capable of being photosensitized by a photopolymerization initiator. Sheet.
- a method for manufacturing an image display device comprising: a base portion having an image display portion; a translucent protective portion; and a polymer layer interposed between the base portion and the protective portion.
- the manufacturing method of the image display apparatus characterized by including the process of irradiating and forming a polymer layer.
- a method for manufacturing an image display device comprising a step of attaching a polymer layer using an optical pressure-sensitive adhesive sheet between a base having an image display portion and a translucent protective portion, the optical pressure-sensitive adhesive
- the polymerizable composition of the present invention has a low volume shrinkage during polymerization, and the polymer obtained by polymerizing the polymerizable composition of the present invention is colored even when stored for a long time under high temperature conditions. The appearance change is less likely to occur, and good light transmission can be maintained.
- FIG. 1 is a cross-sectional view showing a main part of an embodiment of a display device according to the present invention.
- FIG. 2 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention.
- FIG. 3 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention.
- FIG. 4 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention.
- FIG. 5 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention.
- FIG. 6 is a cross-sectional view showing a main part of a display device according to the prior art.
- the present invention will be specifically described below.
- the “polymer layer interposed between the image display unit and the translucent protective unit” described in the present specification refers to all polymers between the image display unit and the translucent protective unit. Means a layer, for example, means that both 5a and 5b in FIG. 2 are included.
- (meth) acryloyl group in the present specification means an acryloyl group and / or a methacryloyl group.
- (poly) ester polyol in the present specification refers to a compound having one or more —COO— bonds (carboxylic acid ester bonds) in one molecule and having two or more alcoholic hydroxyl groups.
- (poly) carbonate polyol used herein means a compound having one or more —OCOO— bonds (carbonate bonds) in one molecule and two or more alcoholic hydroxyl groups. .
- the raw material of the (poly) ester polyol which can be a raw material of the component (1) which is an essential raw material component of the polymerizable composition of the present invention (I)
- the raw material of the (poly) ester polyol When a polyol (that is, a polyol having no —COO— bond (carboxylic acid ester bond)) remains, this polyol is also defined as being included in the (poly) ester polyol.
- a polyol which is a component in the raw material of the (poly) ester polyol to be used is newly added.
- component (1) which is an essential component of the polymerizable composition
- (poly) It shall be included in the ester polyol.
- the raw material of the (poly) carbonate polyol when manufacturing the (poly) carbonate polyol which can be a raw material of the component (1) which is an essential raw material component of the polymerizable composition of the present invention (I), the raw material of the (poly) carbonate polyol When a polyol (that is, a polyol having no carbonate bond) remains, this polyol is also included in the (poly) carbonate polyol.
- a polyol which is a component in the raw material of the (poly) carbonate polyol to be used is newly added.
- component (1) which is an essential component of the polymerizable composition is produced, this added polyol is included in the (poly) carbonate polyol.
- the present invention (I) is a polymerizable composition for forming a polymer layer interposed between an image display part and a translucent protective part of an image display device, the polymerizable composition comprising: A polymerizable composition comprising the following components (1) to (4) as essential components.
- Component (1) (meth) acryloyl group-containing compound having a polyolefin structural unit, (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit, (meth) acryloyl group-containing compound having a (poly) ester structural unit, (poly ) At least one selected from the group consisting of (meth) acryloyl group-containing compounds having a carbonate structural unit and (meth) acryloyl group-containing compounds having a polyether structural unit.
- Component (2) Liquid (meth) acryloyl other than component (1)
- Group-containing compound Component (3) At least one selected from the group consisting of liquid hydrogenated polybutadiene polyol, liquid hydrogenated polyisoprene polyol and hydrogenated dimer diol Component (4) Photopolymerization initiator
- the “structural unit derived from (poly) ester polyol” described in the present specification has one or more —COO— bond (carboxylic acid ester bond) in one molecule and two or more It means a structure obtained by removing H of at least one alcoholic hydroxyl group from a compound having an alcoholic hydroxyl group.
- the “structural unit derived from (poly) carbonate polyol” described in the present specification means at least one compound having one or more carbonate bonds and two or more alcoholic hydroxyl groups in one molecule. It means a structure excluding H of one alcoholic hydroxyl group.
- Component (1) which is an essential raw material component of the polymerizable composition of the present invention (I) is a (meth) acryloyl group-containing compound having a polyolefin structural unit, a (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit, It is at least one (meth) acryloyl group-containing compound selected from the group consisting of a (meth) acryloyl group-containing compound having a (poly) ester structural unit and a (meth) acryloyl group-containing compound having a (poly) carbonate structural unit. .
- the (meth) acryloyl group-containing compound having a polyolefin structural unit is not particularly limited as long as it is a compound having a polyolefin structural unit and a (meth) acryloyl group in one molecule.
- a compound having a polydiene structural unit is preferable.
- polydiene structural units obtained by polymerizing one or more dienes selected from the group consisting of 2,5-dimethyl-2,4-hexadiene and 1,3-octadiene.
- a polybutadiene structural unit, a polyisoprene structural unit or a poly (butadiene-isoprene) structural unit is preferable.
- Examples of commercially available (meth) acryloyl group-containing compounds having a polyolefin structural unit include, for example, Claprene UC-102, UC-203 (manufactured by Kuraray Co., Ltd.), polybutadiene structural units, which are methacryloyl group-containing compounds having a polyisoprene structural unit.
- NISSO-PB TE-2000 manufactured by Nippon Soda Co., Ltd.
- NISSO-PB TEA-1000 manufactured by Nippon Soda Co., Ltd.
- NISSO-PB TEA-1000 manufactured by Nippon Soda Co., Ltd.
- NISSO-PB TE-2000 and NISSO-PB TEA-1000 are polybutadiene polyols such as NISSO-PB G-1000 and G-2000 (manufactured by Nippon Soda Co., Ltd.), organic polyisocyanate compounds and alcoholic hydroxyl group-containing (meta) Reaction product of acrylate.
- polyolefin polyol is useful as a raw material for producing a (meth) acryloyl group-containing compound having a polyolefin structural unit, and these commercially available products include polybutadiene polyol which is a commercially available product of the aforementioned polyolefin polyol.
- NISSO PB G-1000, G-2000, and G-3000 manufactured by Nippon Soda Co., Ltd.
- Poly bd made by Idemitsu Kosan Co., Ltd.
- a hydroxyl group-terminated liquid polybutadiene Poly Ip (made by Idemitsu Kosan Co., Ltd.) Idemitsu Kosan Co., Ltd.)
- KRASOL produced by Cray Valley
- Polyolefin polyols typified by polybutadiene polyol and polyisoprene polyol have two or more hydroxyl groups in one molecule, but preferably have 2 to 4 hydroxyl groups.
- the hydroxyl value of the polyolefin polyol is preferably 10 to 80 mgKOH / g, more preferably 17 to 70 mgKOH / g, and particularly preferably 23 to 65 mgKOH / g.
- the hydroxyl value of the polyolefin polyol compound is smaller than 10 mgKOH / g, the molecular weight and viscosity of the resulting (meth) acryl group-containing polyolefin compound are too high, handling properties tend to be poor, and handling tends to be difficult.
- the polybutadiene polyol is a butadiene homopolymer containing a hydroxyl group.
- the polyisoprene polyol is a homopolymer of isoprene containing a hydroxyl group.
- the organic polyisocyanate compound is not particularly limited as long as it is an organic compound having two or more isocyanato groups in one molecule.
- the component (1) which is an essential component of the polymerizable composition of the present invention (I), desirably has a low viscosity in consideration of the degree of freedom of subsequent blending.
- organic polyisocyanate compounds that meet this purpose include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate, 2,2 1,4-trimethylhexanemethylene diisocyanate, 1,6-hexamethylene diisocyanate and norbornane diisocyanate are preferred, more preferably 1,3-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate and 2, 2,4-trimethylhexanemethylene diisocyanate, most preferred are 2,4,4-trimethylhexamethylene diisocyanate and 2,2,4-trimethylhexanemethylene diisocyanate It is.
- the alcoholic hydroxyl group-containing (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having an alcoholic hydroxyl group in one molecule.
- 2-hydroxyethyl acrylate 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2 -Hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate.
- 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is most preferable.
- polyolefin polyol As a method of reacting polyolefin polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate, polyolefin polyol, organic in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate and dioctyltin dilaurate
- a known urethanization catalyst such as dibutyltin dilaurate and dioctyltin dilaurate
- the reaction in the presence of a catalyst is preferable in terms of shortening the reaction time.
- the amount used is polyolefin polyol, organic polyisocyanate compound, alcoholic hydroxyl group-containing (meta)
- the amount is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of acrylate.
- an organic polyisocyanate compound and, if necessary, a urethanization catalyst are charged into a reactor and stirred, and then the temperature in the reactor is 40 ° C to 140 ° C, preferably 50 ° C to 120 ° C.
- a polyol and, if necessary, a polyol component other than the polyolefin polyol are sequentially added, and then these are reacted at a temperature in the reactor of 50 ° C. to 160 ° C., preferably 60 ° C.
- the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C.
- a polymerization inhibitor and a urethanization catalyst are added if necessary, and an alcoholic hydroxyl group-containing (meth) acrylate is added dropwise.
- the temperature in the reactor is preferably maintained at 30 ° C. to 120 ° C., desirably 50 ° C. to 100 ° C.
- the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., to complete the reaction.
- the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 110 ° C., and reacted. Thereafter, the reaction product is stirred in a reactor containing a polyolefin polyol and, if necessary, a polyol component other than the polyolefin polyol, and the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C. C. to 100.degree. C., and after the addition, the temperature in the reactor is maintained at 30.degree. C. to 120.degree. C., preferably 50.degree. C. to 100.degree. C. to complete the reaction.
- component (1) which is an essential component of the present invention (I)
- component (1) which is an essential component of the present invention (I)
- component (1) which is an essential component of the present invention (I)
- the number of polyolefin polyols used and polyols other than this polyolefin polyol are used. It is necessary to increase the total number of isocyanato groups of the organic polyisocyanate compound used compared to the total number of hydroxyl groups when the use number of these is combined.
- the feed molar ratio of the raw material is not particularly limited, but the ratio of the total number of hydroxyl groups when the number of isocyanate groups in the organic polyisocyanate compound is combined with the number of polyolefin polyols used and the number of polyols other than this polyolefin polyol is combined. Is preferably 1.5: 1 or more. If this ratio is less than 1.5: 1, the viscosity may be too high, which is not preferable.
- the number of polyolefin polyols used, other than this polyolefin polyol From the total number of isocyanato groups of the organic polyisocyanate compound used, the total number of hydroxyl groups when the number of polyols used and the number of compounds having one hydroxyl group containing an alcoholic hydroxyl group-containing (meth) acrylate in the molecule are combined. There is a need to do more.
- the number of polyolefin polyols used when the number of polyolefin polyols used, the number of polyols other than this polyolefin polyol, and the number of compounds having one hydroxyl group containing an alcoholic hydroxyl group-containing (meth) acrylate in the molecule are combined.
- the ratio of the total number of hydroxyl groups to the total number of isocyanato groups in the organic polyisocyanate compound is preferably 2: 1 or less. When this ratio is larger than 2: 1, the number of molecules having no acryloyl group increases, and the shape retention of the polymer after polymerization may deteriorate, which is not preferable.
- urethane (meth) acrylate having no polyolefin structural unit may be produced.
- the urethane (meth) acrylate having no polyolefin polyol structural unit is defined as not included in the component (1) which is an essential component of the present invention (I).
- the compound of the formula (1) is not included in the component (1) because it does not have a polyolefin structural unit.
- a (meth) acryloyl group-containing compound having a polyolefin structural unit is obtained using a polyolefin polyol and a (meth) acryloyl group-containing compound having one isocyanato group in one molecule as essential raw material components
- the polyolefin polyol is as described above.
- Examples of the (meth) acryloyl group-containing compound having an isocyanato group that can be used as the raw material include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
- Examples of 2-isocyanatoethyl acrylate include Karenz AOI (registered trademark) manufactured by Showa Denko KK.
- Examples of 2-isocyanatoethyl methacrylate include Kaerens MOI (registered trademark) manufactured by Showa Denko KK.
- the urethane (meth) acrylate obtained by reacting a (meth) acryloyl group-containing compound having a polyolefin structural unit containing a urethane bond in one molecule and having a (meth) acryloyl group at the terminal is generally as follows. It is synthesized by the method of Even if all the hydroxyl groups of the polyolefin polyol are reacted with the (meth) acryloyl group-containing compound having an isocyanato group, only a part of the hydroxyl groups of the polyolefin polyol are reacted with the (meth) acryloyl group-containing compound having an isocyanato group.
- the total number of hydroxyl groups of the polyolefin polyol is used. It is necessary to prepare a small total number of isocyanato groups of (meth) acrylate. At this time, there may be a polyolefin polyol which remains as it is without reacting with the (meth) acryloyl group-containing compound having an isocyanato group, but this polyolefin polyol is not included in the component (1).
- the polyolefin polyol is a liquid polybutadiene polyol or a liquid polyisoprene polyol, it is included in the component (5).
- the production method is not particularly limited, but generally, a polyolefin polyol, a polymerization inhibitor and, if necessary, a urethanization catalyst and an antioxidant are added, put into the reactor, stirring is started, The temperature is raised to 40 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C. Thereafter, a (meth) acryloyl group-containing compound having an isocyanato group is dropped. During the addition, the temperature in the reactor is controlled to 40 ° C to 130 ° C, preferably 50 ° C to 110 ° C. After completion of the dropwise addition, the temperature in the reactor is maintained at 40 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C. while stirring is continued to complete the reaction.
- a transesterification reaction between a polyolefin polyol and a (meth) acrylic acid ester and / or a polyolefin polyol and (meth) acrylic acid The desired product is obtained by dehydration condensation reaction.
- the number of (meth) acryloyl groups in the (meth) acrylate compound may be one or more per molecule, and more preferably 2 to 4.
- a (meth) acryloyl group-containing compound having a polyolefin structural unit that does not contain a urethane bond it is produced by a transesterification reaction between polybutadiene diol and acrylic acid ester, or a dehydration condensation reaction between polybutadiene diol and acrylic acid.
- the (meth) acrylate compound of component (1) is produced by transesterification of a polyolefin polyol and a (meth) acrylic acid ester
- the polyolefin polyol and a (meth) acrylic acid lower alkyl ester are esterified.
- a transesterification reaction is carried out by heating in the presence of an exchange catalyst, and a corresponding lower alkyl alcohol is distilled off to produce a component (1) (meth) acrylate. It can be produced by the methods described in 2011-195823 and JP-A-2006-45284.
- the esterification reaction is usually performed in the presence of a solvent azeotropic with water, such as cyclohexane and toluene, and the water generated by the dehydration condensation reaction is removed outside the reactor by azeotropically boiling the solvent and water.
- a solvent azeotropic with water such as cyclohexane and toluene
- the catalyst used in the esterification reaction include acid catalysts such as p-toluenesulfonic acid.
- a method of producing a (meth) acryloyl group-containing compound having a polyolefin structural unit that does not contain a urethane bond as component (1) a method of transesterifying a polyolefin polyol with a (meth) acrylic ester
- a solvent there are two types of methods for the dehydration condensation reaction of polyolefin polyol and (meth) acrylic acid, but it is not necessary to use a solvent, and it can be simplified even if it is not performed or performed, so industrially
- the method of producing a (meth) acryloyl group-containing compound having a polyolefin structural unit not containing the urethane bond of component (1) by a transesterification reaction between a polyolefin polyol and a (meth) acrylic acid ester is preferred.
- the (meth) acryloyl group containing compound which has a hydrogenated polyolefin structural unit is demonstrated.
- the (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit is not particularly limited as long as it is a compound having a hydrogenated polyolefin structural unit and a (meth) acryloyl group in one molecule.
- As the hydrogenated polyolefin structural unit a compound having a hydrogenated polydiene structural unit is preferable.
- a structural unit obtained by hydrogenating a polydiene structural unit obtained by polymerizing one or more dienes selected from 1,4-hexadiene, 2,5-dimethyl-2,4-hexadiene and 1,3-octadiene. can do.
- a structural unit obtained by hydrogenating a polybutadiene structural unit a structural unit obtained by hydrogenating a polyisoprene structural unit, or a structural unit obtained by hydrogenating a poly (butadiene-isoprene) structural unit. It is.
- Examples of commercially available (meth) acryloyl group-containing compounds having hydrogenated polyolefin structural units include, for example, NISSO-PB TEAI-1000 (manufactured by Nippon Soda Co., Ltd.), which is an acryloyl group-containing compound having hydrogenated polybutadiene structural units.
- NISSO-PB TEAI-1000 is a reaction product of a hydrogenated polybutadiene polyol such as NISSO-PB GI-1000 (manufactured by Nippon Soda Co., Ltd.), an organic polyisocyanate compound, and an alcoholic hydroxyl group-containing acrylate.
- hydrogenated polyolefin polyol is useful as a raw material for producing a (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit, and these commercially available products include commercially available hydrogenated polybutadiene polyols described above.
- NISSO PB GI-1000 which is a product
- NISSO PB GI-2000 and GI-3000 manufactured by Nippon Soda Co., Ltd.
- Epole manufactured by Idemitsu Kosan Co., Ltd.
- Idemitsu Kosan Co., Ltd. which is a hydroxyl-terminated liquid hydrogenated polyisoprene be able to.
- Hydrogenated polyolefin polyols typified by hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol have two or more hydroxyl groups in one molecule, but preferably have 2 to 4 hydroxyl groups.
- the hydroxyl value of the hydrogenated polyolefin polyol is preferably 10 to 80 mgKOH / g, more preferably 17 to 70 mgKOH / g, and particularly preferably 23 to 65 mgKOH / g.
- the hydroxyl value of the hydrogenated polyolefin polyol compound is less than 10 mgKOH / g, the molecular weight and viscosity of the resulting (meth) acrylic group-containing hydrogenated polyolefin compound become too high, handling properties tend to be poor, and handling tends to be difficult. is there.
- the hydroxyl value of the hydrogenated polyolefin polyol compound is greater than 80 mgKOH / g, the volumetric shrinkage during polymerization becomes too large, or the cohesive strength of the polymer becomes too high, and the adhesion performance of the polymer is not sufficiently exhibited. This is not preferable.
- the hydrogenated polybutadiene polyol is a hydride of a homopolymer of butadiene containing a hydroxyl group.
- Hydrogenated polyisoprene polyol is a hydride of a homopolymer of isoprene containing a hydroxyl group.
- the organic polyisocyanate compound is not particularly limited as long as it is an organic compound having two or more isocyanato groups in one molecule.
- the component (1) which is an essential component of the polymerizable composition of the present invention (I), desirably has a low viscosity in consideration of the degree of freedom of subsequent blending.
- organic polyisocyanate compounds that meet this purpose include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate, 2,2 1,4-trimethylhexanemethylene diisocyanate, 1,6-hexamethylene diisocyanate and norbornane diisocyanate are preferred, more preferably 1,3-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate and 2, 2,4-trimethylhexanemethylene diisocyanate, most preferred are 2,4,4-trimethylhexamethylene diisocyanate and 2,2,4-trimethylhexanemethylene diisocyanate It is.
- the alcoholic hydroxyl group-containing (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having an alcoholic hydroxyl group in one molecule.
- component 1 which is an essential component of the present invention (I)
- 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is most preferable.
- hydrogenation is performed in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate or dioctyltin dilaurate.
- Synthesis can be performed by reacting a polyolefin polyol, an organic polyisocyanate compound, and an alcoholic hydroxyl group-containing (meth) acrylate, but the reaction in the presence of a catalyst is preferred in terms of shortening the reaction time.
- the amount used is hydrogenated polyolefin polyol, organic polyisocyanate compound, alcoholic hydroxyl group-containing ( The amount is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of (meth) acrylate.
- a polyolefin component other than the hydrogenated polyolefin polyol and, if necessary, a polyol component other than the hydrogenated polyolefin polyol are sequentially added, and then these are reacted at a temperature in the reactor of 50 to 160 ° C., preferably 60 to 140 ° C. Thereafter, the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., a polymerization inhibitor and a urethanization catalyst are added if necessary, and an alcoholic hydroxyl group-containing (meth) acrylate is added dropwise. To do. During the dropping, the temperature in the reactor is preferably maintained at 30 ° C.
- the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., to complete the reaction.
- the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 110 ° C., and reacted. Thereafter, the reaction product was stirred in a reactor containing hydrogenated polyolefin polyol and, if necessary, a polyol component other than this hydrogenated polyolefin polyol, while the temperature in the reactor was 30 ° C. to 120 ° C.
- the reaction is preferably carried out so that the temperature can be maintained at 50 ° C. to 100 ° C.
- the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C. to complete the reaction.
- component (1) which is an essential component of the present invention (I)
- component (1) which is an essential component of the present invention (I)
- component (1) which is an essential component of the present invention (I)
- Charged molar ratio of raw materials that is, (total number of hydroxyl groups when the number of polyols other than hydrogenated polyolefin polyol and hydrogenated polyolefin polyol is combined) / (total number of isocyanato groups of organic polyisocyanate compound used) / ( The total number of hydroxyl groups when the number of compounds having one hydroxyl group in the molecule containing an alcoholic hydroxyl group-containing (meth) acrylate is combined) is adjusted according to the molecular weight of the target polyurethane.
- the ratio of the total number of hydroxyl groups when the number of hydrogenated polyolefin polyols used and the number of polyols other than this hydrogenated polyolefin polyol are combined to the total number of isocyanate groups in the organic polyisocyanate compound is 1.
- the molecular weight increases, and when it deviates from 1.0, the molecular weight decreases.
- the feed molar ratio of the raw material is not particularly limited, but the number of isocyanate groups in the organic polyisocyanate compound, the number of hydrogenated polyolefin polyols used and the number of polyols other than this hydrogenated polyolefin polyol are combined.
- the ratio of the total number is preferably 1.5: 1 or more. If this ratio is less than 1.5: 1, the viscosity may be too high, which is not preferable.
- the number of hydrogenated polyolefin polyols used, Isocyanato of the organic polyisocyanate compound to be used is the total number of hydroxyl groups when the number of polyols other than polyolefin polyol and the number of compounds having one hydroxyl group containing alcoholic hydroxyl group-containing (meth) acrylate are combined in the molecule. It needs to be more than the total number of groups.
- the number of hydrogenated polyolefin polyols used, the number of polyols other than this hydrogenated polyolefin polyol, and the number of compounds having one hydroxyl group in the molecule including an alcoholic hydroxyl group-containing (meth) acrylate is preferably 2: 1 or less. When this ratio is larger than 2: 1, the number of molecules having no acryloyl group increases, and the shape retention of the polymer after polymerization may deteriorate, which is not preferable.
- a hydrogenated polyolefin polyol 1,3-bis (isocyanatomethyl) cyclohexane and 2-hydroxyethyl acrylate
- a (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit as component (1) is prepared.
- a compound of the above formula (1) which is urethane (meth) acrylate having no hydrogenated polyolefin structural unit, is also produced, but the compound of formula (1) has a hydrogenated polyolefin structural unit. This means that it is not included in component (1).
- a hydrogenated polyolefin polyol and a (meth) acryloyl group-containing compound having one isocyanato group in one molecule are used as essential raw material components, a (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit is obtained. Will be described.
- the hydrogenated polyolefin polyol is as described above.
- Examples of the (meth) acryloyl group-containing compound having an isocyanato group that can be used as the raw material include the aforementioned 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
- a urethane (meth) acrylate obtained by reacting a (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit having a urethane bond in one molecule and having a (meth) acryloyl group at the terminal is generally used. Is synthesized by the following method. In addition, even if all the hydroxyl groups of the hydrogenated polyolefin polyol are reacted with the (meth) acryloyl group-containing compound having an isocyanato group, only a part of the hydroxyl groups of the hydrogenated polyolefin polyol has a (meth) acryloyl group having an isocyanato group.
- the total number of hydroxyl groups of the hydrogenated polyolefin polyol was used. It is necessary to prepare a small total number of isocyanato groups in the isocyanato group-containing (meth) acrylate. At this time, there may be a hydrogenated polyolefin polyol that remains as it is without reacting with the (meth) acryloyl group-containing compound having an isocyanato group, but this hydrogenated polyolefin polyol is not included in the component (1).
- the hydrogenated polyolefin polyol is a liquid hydrogenated polybutadiene polyol or a liquid hydrogenated polyisoprene polyol, it is included in the liquid polybutadiene polyol or liquid polyisoprene polyol, which will be described later.
- a hydrogenated polyolefin polyol, a polymerization inhibitor and, if necessary, a urethanization catalyst and an antioxidant are added, put into the reactor, and stirring is started.
- the temperature inside is raised to 40 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C.
- a (meth) acryloyl group-containing compound having an isocyanato group is dropped.
- the temperature in the reactor is controlled to 40 ° C to 130 ° C, preferably 50 ° C to 110 ° C.
- the temperature in the reactor is maintained at 40 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C. while stirring is continued to complete the reaction.
- the (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit does not contain a urethane bond
- a transesterification reaction between the hydrogenated polyolefin polyol and the (meth) acrylic acid ester and / or a hydrogenated polyolefin polyol The desired product is obtained by dehydration condensation reaction with (meth) acrylic acid.
- the number of (meth) acryloyl groups in the (meth) acrylate compound may be one or more per molecule, and more preferably 2 to 4.
- a (meth) acryloyl group-containing compound (1) When producing a (meth) acryloyl group-containing compound (1) by a transesterification reaction between a hydrogenated polyolefin polyol and a (meth) acrylic ester, in general, a hydrogenated polyolefin polyol and (meth) acrylic acid are used.
- a (meth) acryloyl group-containing compound of component (1) is produced by conducting a transesterification reaction by heating with a lower alkyl ester in the presence of a transesterification catalyst, and distilling off the corresponding lower alkyl alcohol generated. For example, it can be manufactured by the method described in JP 2011-195823 A or JP 2006-45284 A.
- the (meth) acryloyl group-containing compound of component 1 is produced by a dehydration condensation reaction between a hydrogenated polyolefin polyol and (meth) acrylic acid
- the hydrogenated polyolefin polyol and (meth) acrylic acid are converted into an esterification catalyst.
- the reaction is carried out by heating to a high temperature of 150 ° C. or higher, there is a risk of causing radical polymerization of the acryloyl group during the dehydration condensation reaction.
- the esterification reaction is usually performed in the presence of a solvent azeotropic with water, such as cyclohexane and toluene, and the water generated by the dehydration condensation reaction is removed outside the reactor by azeotropically boiling the solvent and water.
- a solvent azeotropic with water such as cyclohexane and toluene
- the catalyst used in the esterification reaction include acid catalysts such as p-toluenesulfonic acid.
- a method for producing a (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit not containing a urethane bond a method of transesterifying a hydrogenated polyolefin polyol and a (meth) acrylic ester
- it is not necessary to use a solvent and it can be simplified even if it is not performed or carried out in a refining process.
- the (meth) acryloyl group-containing compound having a (poly) ester structural unit is not particularly limited as long as it is a compound having a structural unit derived from a (poly) ester polyol and a (meth) acryloyl group in one molecule. Absent.
- a (poly) ester polyol that can be a raw material for a (meth) acryloyl group-containing compound having a (poly) ester structural unit has one or more —COO— bonds (carboxylic acid ester bonds) in one molecule and 2 If it is a compound which has one or more alcoholic hydroxyl groups, there will be no restriction
- Examples of the (poly) ester polyol that can be used as a raw material for a (meth) acryloyl group-containing compound having a (poly) ester structural unit include a structural unit derived from a polycarboxylic acid having a chain hydrocarbon chain and a chain (Poly) ester polyol having a structural unit derived from a polyol having a hydrocarbon chain, and a polyol having a structural unit derived from a polycarboxylic acid having a hydrocarbon chain containing an alicyclic structure and a chain hydrocarbon chain A (poly) ester polyol having a structural unit derived from, a structural unit derived from a polycarboxylic acid having a chain hydrocarbon chain, and a structural unit derived from a polyol having a hydrocarbon chain containing an alicyclic structure (Poly) ester polyol having a structure derived from a polycarboxylic acid having an alicyclic structure-containing hydrocarbon chain (Pol
- polyols preferred are those having 8 or more carbon atoms.
- the polyol having 8 or more carbon atoms include 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2-methyl-1,1-cyclohexanedimethanol, tricyclo [5.2. 1.0 2,6 ] decanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decadiol, 1,12-todecanediol, dimer diol, hydrogenated dimer A diol etc. can be mentioned.
- hydrogenated dimer diol is particularly preferable.
- polycarboxylic acids preferred is a polycarboxylic acid having 7 or more carbon atoms excluding carbon in the carboxylic acid structure (—COOH).
- these polycarboxylic acids include 1,9-nonannic acid, sebacic acid, 1,12-dodecanoic acid, dimer acid, hydrogenated dimer acid, and the like.
- polycarboxylic acids having 7 or more carbon atoms excluding carbon in the carboxylic acid structure (—COOH) particularly preferred are sebacic acid, 1,12-dodecanoic acid, and hydrogenated dimer acid.
- the number of carbon atoms excluding carbon having 8 or more carbon atoms and carbon in the carboxylic acid structure (—COOH) is 7 or more.
- a combination of polycarboxylic acids, particularly preferred is a combination of hydrogenated dimer diol and at least one selected from sebacic acid, 1,12-dodecanoic acid and hydrogenated dimer acid.
- dimer acid means a fatty acid having 14 to 22 carbon atoms (hereinafter referred to as unsaturated fatty acid A) having 2 to 4 ethylenic double bonds, preferably 14 carbon atoms having two ethylenic double bonds.
- 14 to 22 fatty acids having 1 to 4 fatty acids and 1 to 4 ethylenic double bonds hereinafter referred to as unsaturated fatty acids B
- unsaturated fatty acids B preferably 14 to 1 carbon atoms having 1 or 2 ethylenic double bonds
- the unsaturated fatty acid A includes tetradecadienoic acid, hexadecadienoic acid, octadecadienoic acid (linoleic acid, etc.), eicosadienoic acid, docosadienoic acid, octadecatrienoic acid (linolenic acid, etc.), eicosatetraenoic acid ( Arachidonic acid and the like), and linoleic acid is most preferable.
- unsaturated fatty acid B tetradecenoic acid (tuzuic acid, sperm acid, myristoleic acid) as a fatty acid having 14 to 22 carbon atoms having one ethylenic double bond in addition to those exemplified above , Hexadecenoic acid (such as palmitoleic acid), octadecenoic acid (such as oleic acid, elaidic acid, vaccenic acid), eicosenoic acid (such as gadoleic acid), docosenoic acid (such as erucic acid, cetreic acid, brassic acid), etc. Acid or linoleic acid is most preferred.
- the use ratio (molar ratio) of unsaturated fatty acid A and unsaturated fatty acid B is preferably about 1: 1.2 to 1.2: 1, and most preferably 1: 1.
- the dimerization reaction can be performed according to a known method, for example, a method described in JP-A-9-136861. That is, for example, an unsaturated fatty acid A and an unsaturated fatty acid B are mixed with a Lewis acid or Bronsted acid type liquid or solid catalyst, preferably montmorillonite-based activated clay, in an amount of 1 to 20% by weight, preferably 2 to It can be carried out by adding 8% by weight and heating to 200 to 270 ° C., preferably 220 to 250 ° C.
- the pressure during the reaction is usually a slightly pressurized state, but may be normal pressure.
- the reaction time varies depending on the amount of catalyst and the reaction temperature, but is usually 5 to 7 hours.
- the catalyst can be filtered off and then distilled under reduced pressure to distill off unreacted raw materials and isomerized fatty acids, and then dimer acid fraction can be distilled off.
- the dimerization reaction is thought to proceed through double bond transfer (isomerization) and Diels-Alder reaction, but the present invention is not limited thereto.
- the obtained dimer acid is usually a mixture of dimer acids having different structures depending on the bonding site or isomerization of the double bond, and may be used separately, but can be used as it is. Furthermore, the dimer acid obtained contains a small amount of monomeric acid (for example, 3% by weight or less, particularly 1% by weight or less), polymer acid or the like of trimer acid or more (for example, 3% by weight or less, particularly 1% by weight or less) May be.
- hydrophilic dimer acid refers to a saturated dicarboxylic acid obtained by hydrogenating the carbon-carbon double bond of the dimer acid.
- the dimer acid having 36 carbon atoms produced from, for example, linoleic acid and linoleic acid or oleic acid is used as the dimer acid
- the structure of the main component of the hydrogenated dimer acid has the following formula (6 ) And formula (7).
- Examples of commercially available hydrogenated dimer acid include PRIPOL (registered trademark) 1009 (manufactured by Croda), EMPOL (registered trademark) 1008, and EMPOL (registered trademark) 1062 (manufactured by BASF).
- the “hydrogenated dimer diol” described in the present specification refers to the reduction of at least one of the above dimer acid, the above hydrogenated dimer acid and the lower alcohol ester thereof in the presence of a catalyst,
- the main component is a diol obtained by hydrogenating the double bond.
- a hydrogenated dimer diol is produced by reducing a hydrogenated dimer acid containing a compound having a structure represented by formula (6) or formula (7) as a main component, the main component of the hydrogenated dimer diol is reduced.
- the structure is a structure represented by the following formulas (8) and (9).
- Examples of commercially available hydrogenated dimer diol include PRIPOL (registered trademark) 2033 (manufactured by Croda) and SoVermol (registered trademark) 908 (manufactured by BASF).
- the (poly) ester polyol which can be a raw material for the (meth) acryloyl group-containing compound having a (poly) ester structural unit, comprises the above-described polycarboxylic acid and a polyol component containing the polyol as an essential component for the esterification catalyst. It can manufacture by performing a condensation reaction in presence. Since the esterification reaction removes water, the reaction is generally performed at a reaction temperature of about 150 to 250 ° C. In general, the reaction is performed under normal pressure or reduced pressure.
- the (poly) ester polyol that can be a raw material for the (meth) acryloyl group-containing compound having a (poly) ester structural unit includes a lower alkyl ester of the carboxylic acid and a polyol component as the polyol essential component. It can also be produced by conducting a transesterification reaction in the presence of a transesterification catalyst. In the transesterification reaction, alcohol is removed, so that the reaction is generally performed at a reaction temperature of about 120 to 230 ° C. In general, the reaction is performed under normal pressure or reduced pressure.
- a polyol that is, a raw material for the (poly) ester polyol (ie, When a polyol having no —COO— bond (carboxylic ester bond) remains, this polyol is also included in the (poly) ester polyol. That is, when 8% by mass of the raw material polyol remains in the (poly) ester polyol, this means that this polyol is also included in the (poly) ester polyol.
- a hydrogenated dimer diol which is a raw material of 8 parts by mass in 100 parts by mass of the synthesized product
- the component (1) is produced by adding 5 parts by mass of the hydrogenated dimer diol, the raw material hydrogenated dimer diol remaining during the synthesis of the component (1), and the hydrogenated dimer added thereafter It means that both diols are included in the (poly) ester polyol.
- the hydroxyl value of the (poly) ester polyol used as a raw material for the (meth) acryloyl group-containing compound having the (poly) ester structural unit of the component (1) of the present invention (I) is preferably 20 to 100 mgKOH / g, more preferably 25 to 80 mg KOH / g, and still more preferably 30 to 65 mg KOH / g.
- the (poly) ester polyol 100 mass 30 parts by mass or less is preferable with respect to parts, and preferably 25 parts by mass or less.
- the method for synthesizing the (meth) acryloyl group-containing compound having a (poly) ester structural unit is not particularly limited.
- (poly) ester polyol, an organic polyisocyanate compound, and an alcoholic hydroxyl group-containing (meth) acrylate are essential raw materials.
- (Meth) acryloyl group-containing compound having a (poly) ester structural unit obtained by addition reaction, (poly) ester polyol and (meth) acryloyl group-containing one isocyanato group in one molecule The (meth) acryloyl group containing compound which has a (poly) ester structural unit obtained by carrying out an addition reaction using a compound as an essential raw material can be mentioned.
- (poly) ester polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate are used as essential raw material components, and (meth) acryloyl group containing (poly) ester structural unit obtained by addition reaction
- the compound will be described.
- the (poly) ester polyol is as described above.
- the organic polyisocyanate compound is the same as the organic polyisocyanate compound described in the raw material component of the (meth) acryloyl group-containing compound having a polyolefin structural unit or the (meth) acryloyl group-containing compound having an added polyolefin structural unit.
- the alcoholic hydroxyl group-containing (meth) acrylate is the same as described in the raw material components of the (meth) acryloyl group-containing compound having a polyolefin structural unit and the (meth) acryloyl group-containing compound having an added polyolefin structural unit.
- the synthesis method is to replace the polyolefin polyol and the (poly) ester polyol, thereby using the polyolefin polyol, the organic polyisocyanate compound and the alcoholic hydroxyl group-containing (meth) acrylate as essential raw material components, and a polyolefin structural unit. It can be produced by a method similar to the method described in the description of the case of obtaining a (meth) acryloyl group-containing compound having.
- a (meth) acryloyl group-containing compound having one isocyanato group in one molecule is obtained.
- the case of obtaining will be described.
- the (poly) ester polyol is as described above.
- Examples of the (meth) acryloyl group-containing compound having an isocyanato group that can be used as the raw material include the aforementioned 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
- a method for obtaining a (meth) acryloyl group-containing compound having a (poly) ester structural unit using a (poly) ester polyol and a (meth) acryloyl group-containing compound having one isocyanato group in one molecule as essential raw material components By replacing the polyolefin polyol with a (poly) ester polyol, the above-mentioned polyolefin polyol and the (meth) acryloyl group-containing compound having one isocyanato group in one molecule are used as essential raw material components, and a hydrogenated polyolefin structural unit is obtained. It can carry out by the method similar to the method of obtaining the (meth) acryloyl group containing compound which has.
- a (meth) acryloyl group-containing compound having a (poly) carbonate structural unit is not particularly limited as long as it is a compound having a structural unit derived from a (poly) carbonate polyol and a (meth) acryloyl group in one molecule. There is no. One or more (meth) acryloyl groups and one or more urethane bonds may be contained in one molecule.
- the (poly) carbonate polyol that can be used as a raw material is not particularly limited as long as it is a compound having one or more carbonate bonds (—OCOO—) in one molecule and having two or more alcoholic hydroxyl groups. .
- the (poly) carbonate polyol that can be a raw material for a (meth) acryloyl group-containing compound having a (poly) carbonate structural unit, for example, it is produced using a polyol having a chain hydrocarbon chain as a raw material (poly) Manufactured using carbonate polyol, polyol having alicyclic structure-containing hydrocarbon chain as a raw material (poly) carbonate polyol, manufactured using polyol having aromatic ring structure-containing hydrocarbon chain as a raw material (poly) A carbonate polyol etc. can be mentioned.
- polyols that can be used as a raw material for the (poly) carbonate polyol
- preferred polyols having 8 or more carbon atoms include 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2-methyl-1,1-cyclohexanedimethanol, tricyclo [5.2.
- (Poly) carbonate polyol which can be a raw material for a (meth) acryloyl group-containing compound having a (poly) carbonate structural unit is a transesterification of the polyol component and a dialkyl carbonate, diaryl carbonate or alkylene carbonate in the presence of a transesterification catalyst. It can also be produced by carrying out a reaction. In the transesterification reaction, alcohol is removed, so that the reaction is generally performed at a reaction temperature of about 80 to 230 ° C. In general, the reaction is performed under normal pressure or reduced pressure.
- the (poly) carbonate polyol which can be a raw material for the (meth) acryloyl group-containing compound having a (poly) carbonate structural unit can also be produced by a reaction between the polyol and phosgene.
- the above reaction is generally performed at a reaction temperature of 100 ° C. or less, and hydrochloric acid is generated. Therefore, it is general to trap hydrochloric acid using a base.
- the raw material of the (poly) carbonate polyol which can be a raw material of the component (1) which is an essential raw material component of the polymerizable composition of the present invention (I)
- the raw material of the (poly) carbonate polyol When a polyol (that is, a polyol having no carbonate bond) remains, this polyol is also included in the (poly) carbonate polyol. That is, when 8% by mass of the raw material polyol remains in the (poly) carbonate polyol, it means that the residual polyol is contained in the (poly) ester polyol.
- the hydroxyl value of the (poly) carbonate polyol used as a raw material for the (meth) acryloyl group-containing compound having the (poly) carbonate structural unit of the present invention (I) is preferably in the range of 20 to 100 mgKOH / g. More preferably, it is 25 to 80 mgKOH / g, and further preferably 30 to 65 mgKOH / g.
- a polyol that can be a raw material for a (poly) carbonate polyol is used as a raw material for a (meth) acryloyl group-containing compound having a (poly) carbonate structural unit, 30 parts by mass with respect to 100 parts by mass of the (poly) carbonate polyol. Or less, more preferably 25 parts by mass or less.
- the method for synthesizing the (meth) acryloyl group-containing compound having a (poly) carbonate structural unit is not particularly limited.
- (poly) carbonate polyol, an organic polyisocyanate compound and an alcoholic hydroxyl group-containing (meth) acrylate are essential raw materials.
- (Meth) acryloyl group-containing compound having a (poly) carbonate structural unit obtained by addition reaction, and (poly) carbonate polyol and (meth) acryloyl group-containing one isocyanato group in one molecule A (meth) acryloyl group-containing compound having a (poly) carbonate structural unit obtained by addition reaction using the compound as an essential raw material can be mentioned.
- (poly) carbonate polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate are used as essential raw material components, and (meth) acryloyl group containing (poly) carbonate structural unit obtained by addition reaction
- the compound will be described.
- the (poly) carbonate polyol is as described above.
- the organic polyisocyanate compound is the same as the organic polyisocyanate compound described in the raw material component of the (meth) acryloyl group-containing compound having a polyolefin structural unit or the (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit.
- the alcoholic hydroxyl group-containing (meth) acrylate is the same as described in the raw material components of the (meth) acryloyl group-containing compound having a polyolefin structural unit and the (meth) acryloyl group-containing compound having a hydrogenated polyolefin structural unit.
- (poly) carbonate polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate are used as essential raw material components, and (meth) acryloyl group containing (poly) carbonate structural unit obtained by addition reaction
- the method for synthesizing the compound also uses the polyolefin polyol, the organic polyisocyanate compound, and the alcoholic hydroxyl group-containing (meth) acrylate as essential raw material components by replacing the polyolefin polyol and the (poly) carbonate polyol.
- the (meth) acryloyl group-containing compound can be produced by the same method as described in the description of the case of obtaining the compound.
- (poly) carbonate polyol, 1,3-bis (isocyanatomethyl) cyclohexane and 2-hydroxyethyl acrylate are used to contain (meth) acryloyl group having (poly) carbonate structural unit as component (1)
- component (1) When the compound is produced, the compound of the above formula (1), which is a urethane (meth) acrylate having no (poly) carbonate structural unit, is also produced, but the compound of the formula (1) is a (poly) carbonate. Since it does not have a structural unit, it means that it is not contained in component (1).
- a (meth) acryloyl group-containing compound having one isocyanato group per molecule is obtained.
- the case of obtaining will be described.
- the (poly) carbonate polyol is as described above.
- Examples of the (meth) acryloyl group-containing compound having an isocyanato group that can be used as the raw material include the aforementioned 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
- a method for obtaining a (meth) acryloyl group-containing compound having a (poly) carbonate structural unit by using (poly) carbonate polyol and a (meth) acryloyl group-containing compound having one isocyanato group in one molecule as essential raw material components By replacing the polyolefin polyol with a (poly) carbonate polyol, the above-mentioned polyolefin polyol and the (meth) acryloyl group-containing compound having one isocyanato group in one molecule are used as essential raw material components, and a hydrogenated polyolefin structural unit is obtained. It can carry out by the method similar to the method of obtaining the (meth) acryloyl group containing compound which has.
- the amount of component (1) used in the present invention (I) is preferably 10 to 50% by weight, more preferably 12 to 40% by weight, based on the total amount of the polymerizable composition of the present invention (I). Particularly preferred is 13 to 35% by mass.
- the amount of the component (1) used is less than 10% by mass with respect to the total amount of the polymerizable composition of the present invention (I)
- the volumetric shrinkage during polymerization of the polymerizable composition of the present invention (I) May be difficult to polymerize or polymerization, which is not preferable.
- the viscosity of the polymeric composition of this invention (I) becomes high. In some cases, it is not preferable.
- Component (2) is a liquid (meth) acryloyl group-containing compound and is not particularly limited as long as it is other than component (1).
- a (meth) acryloyl group-containing compound having a chain aliphatic hydrocarbon group a (meth) acryloyl group-containing compound having a cyclic aliphatic group, a (meth) acryloyl group-containing compound having an aromatic ring structure, a heterocyclic structure
- Examples include (meth) acryloyl group-containing compounds.
- a (meth) acryloyl group-containing compound having a hydrocarbon group having 6 or more carbon atoms is preferable.
- the (meth) acryloyl group-containing compound having a hydrocarbon group having 6 or more carbon atoms include benzyl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and dicyclopentanyl acrylate.
- cyclohexyl acrylate isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentanyloxyethyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopenta are preferable.
- Nyl methacrylate dicyclopentanyl ethyl methacrylate, methoxytriethylene acrylate, ethyl carbitol acrylate, lauryl acrylate, isononyl acrylate, 2-propylheptyl acrylate, 4-methyl-2-propylhexyl acrylate, lauryl methacrylate, isononyl methacrylate, 2-propylheptyl methacrylate, 4-methyl-2-propylhexyl methacrylate, which will be described later.
- the polymerizable composition of the present invention (I) can preferably contain a (meth) acryloyl group-containing compound having an alcoholic hydroxyl group in the component (2).
- a (meth) acryloyl group-containing compound having an alcoholic hydroxyl group include, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2 -Hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy 3- (o-phenylphenoxy) propyl methacryl
- 2-hydroxybutyl acrylate preferred among these are 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl Acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, more preferably 4- Hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, most preferred - hydroxypropyl methacrylate.
- the amount of the component (2) used is preferably 10 to 30% by mass, more preferably 13 to 25% by mass, particularly preferably the total amount of the polymerizable composition of the present invention (I). 15 to 22% by mass.
- the amount of the component (2) used is less than 10% by mass relative to the total amount of the polymerizable composition of the present invention (I)
- the viscosity of the polymerizable composition of the present invention (I) may increase. It is not preferable.
- the usage-amount of a component (2) is more than 30 mass% with respect to the total amount of the polymeric composition of this invention (I), the volume at the time of superposition
- Component (3) is at least one selected from the group consisting of liquid hydrogenated polybutadiene polyol, liquid hydrogenated polyisoprene polyol and hydrogenated dimer diol.
- the liquid hydrogenated polybutadiene polyol is a liquid polyol having a structure obtained by reductive hydrogenation of polybutadiene polyol or polybutadiene polycarboxylic acid, manufactured by Nippon Soda Co., Ltd., NISSO-PB GI-1000, NISSO-PB GI-2000, NISSO. -PB GI-3000 and the like.
- the liquid hydrogenated polyisoprene polyol is a liquid polyol having a structure obtained by reductive hydrogenation of polyisoprene polyol or polyisoprene polycarboxylic acid. Since the hydrogenated dimer diol has been described above, it is omitted here.
- liquid hydrogenated polybutadiene polyol and liquid hydrogenated polyisoprene polyol are preferable in consideration of heat resistant colorability, and liquid hydrogenated polybutadiene polyol is particularly preferable, considering low dielectric constant.
- liquid hydrogenated polybutadiene polyol and liquid hydrogenated polyisoprene polyol are preferable, and liquid hydrogenated polybutadiene polyol is particularly preferable.
- the amount of the component (3) used is preferably 10 to 45% by mass, more preferably 12 to 40% by mass, particularly preferably the total amount of the polymerizable composition of the present invention (I). 15 to 37% by mass.
- the amount of the component (3) used is less than 10% by mass relative to the total amount of the polymerizable composition of the present invention (I)
- the dielectric constant of the polymerizable composition of the present invention (I) may increase. Yes, not preferred.
- the amount of component (3) used is more than 45% by mass with respect to the total amount of the polymerizable composition of the present invention (I)
- curing during polymerization of the polymerizable composition of the present invention (I) The strength of the object may be reduced, which is not preferable.
- Component (4) which is an essential component of the polymerizable composition of the present invention (I)
- Component (4) which is an essential component of the present invention (I)
- the photopolymerization initiator of component (4) is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.
- photopolymerization initiator of component (4) examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl.
- bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, (2,5,6-trimethylbenzo
- a metallocene compound can be used as a photopolymerization initiator.
- transition elements represented by Fe, TI, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound.
- An example is bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.
- photopolymerization initiators can be used alone or in combination of two or more.
- the translucent protection unit 103 in FIGS. 1 and 2 is often provided with a function of cutting the ultraviolet region from the viewpoint of ultraviolet protection for the image display unit 105.
- the amount of component (4) used is preferably 0.1 to 4.0% by weight, more preferably 0.3 to 3.0% by weight based on the total amount of the polymerizable composition of the present invention (I). % By mass, particularly preferably 0.5 to 2.0% by mass. When the amount of component (4) used is less than 0.1% by mass relative to the total amount of the polymerizable composition of the present invention (I), the polymerization initiation performance of the polymerization initiator may be insufficient, such being undesirable.
- the amount of the component (4) used is more than 4.0% by mass with respect to the total amount of the polymerizable composition of the present invention (I), the polymer of the present invention (II) to be described later is allowed to In the case of odor, it may be easy to color, which is not preferable.
- the polymerizable composition of the present invention (I) can contain the following component (5) and is preferable.
- Component (5) Hydrogenated polybutadiene, hydrogenated polyisoprene, poly ( ⁇ -olefin) liquid, ethylene-propylene copolymer liquid, propylene- ⁇ -olefin copolymer liquid, ethylene- ⁇ -olefin copolymer liquid, At least one selected from the group consisting of liquid polybutene, liquid hydrogenated polybutene, liquid polybutadiene, liquid hydrogenated polybutadiene, liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene polyol, and liquid polyisoprene polyol.
- Hydrogenated polyptadiene is a liquid product at room temperature obtained by reductive hydrogenation of a butadiene polymer, and examples thereof include NISSO-PB BI-2000, NISSO-PB BI-3000 manufactured by Nippon Soda Co., Ltd. it can.
- Hydrogenated polyisoprene is a compound that is obtained by reductive hydrogenation of an isoprene polymer and is liquid at room temperature, and examples thereof include LIR-200 manufactured by Kuraray.
- the poly ( ⁇ -olefin) liquid is a liquid produced by polymerization of ⁇ -olefin, and the ⁇ -olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end.
- the propylene and ⁇ -olefin copolymer liquid material is a liquid polymer produced by copolymerizing propylene and ⁇ -olefin.
- An ⁇ -olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end, such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene and the like.
- the ethylene and ⁇ -olefin copolymer liquid is a liquid polymer produced by copolymerizing ethylene and ⁇ -olefin.
- An ⁇ -olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end, such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene and the like.
- Liquid polybutene is a liquid polymer containing isobutene or n-butene as a (co) polymerization component, such as homopolymerization of isobutene, homopolymerization of n-butene, copolymerization of isobutene and n-butene. It is a compound having a carbon-carbon unsaturated bond.
- Commercially available liquid polybutenes include, for example, Nisseki Polybutene LV-7, LV-50, LV-100, HV-15, HV-35, HV-50, HV-100, HV- manufactured by JX Nippon Mining & Energy. 300 or the like.
- the liquid hydrogenated polybutene is a liquid material having a side chain obtained by hydrogenating the liquid polybutene.
- palm reel 4 palm reel 6, palm reel 18, palm reel 24, palm A reel EX can be used.
- Liquid polybutadiene is a butadiene polymer that is liquid at room temperature.
- POLYVEST110, POLYVEST130 manufactured by Evonik Degussa NISSO-PB B-1000, NISSO-PB B-2000, NISSO-PB B- manufactured by Nippon Soda Co., Ltd. 3000 etc. can be mentioned.
- Liquid polyisoprene is an isoprene polymer that is liquid at room temperature, and examples thereof include Kuraray Kuraprene LIR-30.
- the liquid polybutadiene polyol is a polymer that is liquid at room temperature and has two or more hydroxyl groups at the molecular terminals and has a polybutadiene structural unit.
- Examples thereof include G-2000, NISSO-PB G-3000, and Poly bd manufactured by Idemitsu Kosan Co., Ltd.
- the liquid polyisoprene polyol is a polymer that is liquid at room temperature and has two or more hydroxyl groups at the molecular ends and a polyisoprene structural unit, and examples thereof include poly ip manufactured by Idemitsu Kosan Co., Ltd. .
- the amount of the component (5) used is preferably 5 to 35% by mass, more preferably 7 to 32% by mass, particularly preferably the total amount of the polymerizable composition of the present invention (I). 10 to 30% by mass.
- the amount of the component (5) used is less than 5% by mass based on the total amount of the polymerizable composition of the present invention (I)
- the dielectric constant and viscosity of the polymerizable composition of the present invention (I) increase. In some cases, it is not preferable.
- the amount of component (5) used is more than 35% by mass relative to the total amount of the polymerizable composition of the present invention (I), curing during polymerization of the polymerizable composition of the present invention (I) It is not preferable because the strength of the object may be reduced.
- the polymerizable composition of the present invention (I) can contain the following component (6) and is preferable.
- Component (6) At least one selected from the group consisting of hydrogenated petroleum resins, terpene-based hydrogenated resins, and hydrogenated rosin esters
- Hydrogenated petroleum resin is a resin obtained by hydrogen reduction of petroleum-based resin.
- Examples of petroleum resins that are raw materials for hydrogenated petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and the like.
- Modified products such as hydrogenated products of The synthetic petroleum resin may be C5 or C9.
- the terpene-based hydrogenated resin is a resin obtained by hydrogen reduction of a terpene-based resin.
- Terpenic resins that are raw materials for terpene hydrogenated resins include ⁇ -pinene resins, ⁇ -pinene resins, ⁇ -limonene resins, ⁇ -limonene resins, pinene-limonene copolymer resins, and pinene-limonene-styrene copolymer resins.
- the hydrogenated rosin ester is a resin obtained by hydrogenating a rosin ester obtained by esterifying a hydrogenated rosin obtained by hydrogenating a rosin resin or esterifying a rosin.
- the rosin resin tackifier include modified rosins such as gum rosin, tall oil rosin, wood rosin, disproportionated rosin, polymerized rosin and maleated rosin.
- the amount of component (6) used in the present invention (I) is preferably 10 to 50% by weight, more preferably 12 to 40% by weight, based on the total amount of the polymerizable composition of the present invention (I). Particularly preferred is 13 to 35% by mass.
- the amount of component (6) used is less than 10% by mass relative to the total amount of the polymerizable composition of the present invention (I)
- the cured film during polymerization of the polymerizable composition of the present invention (I) It may be difficult to maintain the shape, which is not preferable.
- the usage-amount of a component (6) is more than 50 mass% with respect to the total amount of the polymeric composition of this invention (I), the viscosity of the polymeric composition of this invention (I) becomes high. In some cases, it is not preferable.
- the volume shrinkage ratio at the time of polymerization of the polymerizable composition of the present invention (I). Is preferably 3.5% or less, more preferably 2.7% or less, and most preferably 2.3% or less.
- the volume shrinkage during polymerization of the polymerizable composition of the present invention (I) is larger than 3.5%, the internal stress accumulated in the polymer increases when the polymerizable composition is polymerized. This is not preferable because the interface between the polymer layer 5a or 5b and the image display unit 2, the protection unit 3 or the touch panel 7 in contact with the polymer layer 5a or 5b is distorted.
- the viscosity at 25 ° C. of the polymerizable composition of the present invention (I) is not particularly limited, but is preferably 10000 mPa ⁇ s or less, more preferably 7000 mPa ⁇ s or less, particularly preferably for handling. 5000 mPa ⁇ s or less.
- the viscosity described in this specification is a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model: CPE- 42), and measured under conditions of a temperature of 25.0 ° C. and a rotation speed of 10 rpm.
- the viscosity of the polymerizable composition of the present invention (I) at 25 ° C. is set to 1000 mPa ⁇ s or less
- a coating is applied. Thereafter, the spread of the liquid is facilitated, and as a result, it becomes easy for the composition to spread in a required thickness at a uniform thickness, and the entrainment of bubbles is easily suppressed.
- a polymerization inhibitor In the polymerizable composition of the present invention (I), a polymerization inhibitor, an inhibitor and an antioxidant can be added and are preferable.
- the polymerization inhibitor and the polymerization inhibitor are not particularly limited as long as they have a polymerization inhibition ability or a function to inhibit polymerization.
- the polymerization inhibitor can be adjusted so as to be added in an amount of 0.01 to 5% by mass relative to the total amount of the polymerizable composition of the present invention (I).
- the amount of the polymerization inhibitor is a value in consideration of the polymerization inhibitor previously contained in the component (1), the component (2) and the component (5). That is, in general, the polymerization inhibitor is previously contained in the component (1), the component (2) and the component (5), but the total amount of the polymerization inhibitor and the newly added polymerization inhibitor is This means that the addition amount is 0.01 to 5% by mass relative to the total amount of the polymerizable composition of the polymerizable composition of the present invention (I).
- the antioxidant is not particularly limited.
- pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
- octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate
- thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
- 3,5-di-tert-butyl-4 7-C9 alkyl ester of hydroxybenzenepropanoic acid 4,6-bis (octylthiomethyl) -o-cresol, 3,9-bis [2- [3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxy Spiro [5,5] -undecane, 2,2'
- pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
- Tadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
- pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate].
- the antioxidant can be adjusted so as to be added in an amount of 0.01 to 5% by mass relative to the total amount of the polymerizable composition of the present invention (I).
- the amount of the polymerization inhibitor is a value in consideration of the antioxidant contained in advance in other components such as the components (1) to (6). That is, in general, an antioxidant may be contained in advance in the component (2) or the like, but the total amount of this antioxidant and the newly added antioxidant is the present invention (I). It means that the added amount is 0.01 to 5% by mass with respect to the total amount of the polymerizable composition.
- the present invention (II) is a polymer obtained by polymerizing the polymerizable composition described in the present invention (I).
- the polymer of the present invention (II) uses a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, an LED, etc. It is obtained by polymerizing the polymerizable composition by irradiation through a glass or plastic substrate.
- the polymer of the present invention (II) is a polymer used as a polymer layer interposed between the image display part of the image display device and the translucent protective part.
- This polymer was adjusted to a thickness of 200 ⁇ m in which the dielectric constant of the polymer having a thickness of 2 mm under conditions of 23 ° C., a frequency of 1 MHz and an applied voltage of 100 mV is 3.1 or less and exists between two glasses. It is preferable that the color coordinate b * value described in JIS Z 8729 after the polymer is stored at 95 ° C. for 500 hours is less than 1.0.
- the dielectric constant of the polymer under the conditions of 23 ° C., frequency 1 MHz, applied voltage 100 mV means that a 2 mm-thick test piece (polymer) is obtained under an environment of 23 ° C. 4294A Precision Impedance Analyzer 40Hz-110MHz is used as an impedance analyzer made by Agilent Technologies, and a frequency of 1MHz, measured using 16451B dielectric test fixture made by Agilent Technologies, as a test fixture. It is a dielectric constant of the polymer under the condition of a voltage of 100 mV.
- the polymer of the present invention (II) is used for the polymer (layer 5b) shown in FIGS. 4 and 5, the dielectric constant of the polymer of the present invention (II) is preferably low.
- a polymer having a dielectric constant of 3.1 or less more preferably 23 ° C., at a temperature of 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV.
- polymerized to a thickness of 200 ⁇ m existing between two glasses means two optical glasses having a thickness of 0.7 mm (trade name: Eagle XG manufactured by Corning). In between, a polymer obtained by sandwiching a 200 ⁇ m sheet-like polymer, or a polymerizable composition between two optical glasses having a thickness of 0.7 mm (trade name: Eagle XG manufactured by Corning) Intervene and irradiate light through which the photopolymerization initiator can be sensitized through the optical glass using a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc. as a light source.
- a polymer having a thickness of 200 ⁇ m obtained by the process, and the portion sandwiched between the two pieces of glass outside the polymer layer contains no spacers, gaskets, or sealants. Without those.
- the “color coordinate b * value described in JIS Z 8729 after storage at 95 ° C. for 500 hours” described in the present specification is adjusted to a thickness of 200 ⁇ m existing between the two glasses.
- the polymer was held at 95 ° C. for 500 hours, and then measured at 23 ° C. in accordance with the method described in JIS Z 8729 using the value of b * of the psychometric chroma coordinates measured. is there.
- the reference used when measuring the value of b * is one optical glass having a thickness of 0.7 mm (trade name: Eagle XG manufactured by Corning).
- the value of b * measured under the above conditions must be less than 1.0.
- the transmittance of light at 370 to 450 nm decreases with time, which is not preferable.
- the refractive index of the polymer of the present invention (II) at 25 ° C. is preferably 1.48 to 1.52.
- the refractive index at 25 ° C. is less than 1.48 or larger than 1.52
- the refractive index is too low compared with the refractive index of acrylic resin such as optical glass or polymethyl methacrylate, which is the material of the protective part.
- the difference in refractive index at the interface between the protective part and the protective part becomes slightly large, and the scattering and attenuation of image light from the display part become slightly large, which is not preferable.
- the tensile modulus of the polymer of the present invention (II) at 23 ° C. is preferably 1 ⁇ 10 7 Pa or less, and more preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa.
- the tensile modulus at 23 ° C. is preferably 1 ⁇ 10 7 Pa or less, and more preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa.
- the image display portion and the protection portion are prevented from being distorted due to the influence of stress due to volume shrinkage during polymerization of the polymerizable composition. be able to.
- the tensile elasticity modulus as described in this specification is a value when a test is performed at a tensile speed of 500 mm / min.
- the present invention (III) is obtained by coating the polymerizable composition of the present invention (I), irradiating the composition with light capable of being photosensitized by a photopolymerization initiator, and polymerizing the composition. It is an optical pressure-sensitive adhesive sheet having a polymer layer of 500 ⁇ m.
- the optical pressure-sensitive adhesive sheet of the present invention (III) may be a double-sided pressure-sensitive adhesive sheet in which both surfaces of the sheet are pressure-sensitive adhesive surfaces (pressure-sensitive adhesive layer surface), or only one surface of the sheet is a pressure-sensitive adhesive surface (pressure-sensitive adhesive layer surface) It may be a single-sided pressure-sensitive adhesive sheet. Especially, it is preferable that it is a double-sided adhesive sheet from a viewpoint of bonding two members together.
- the term “adhesive sheet” includes a tape-shaped material, that is, “adhesive tape”.
- optical pressure-sensitive adhesive sheet does not have a base material (base material layer), and is called a “base-less type” optical pressure-sensitive adhesive sheet (hereinafter referred to as “base-material-less optical pressure-sensitive adhesive sheet”).
- base-material-less optical pressure-sensitive adhesive sheet There may also be an optical pressure-sensitive adhesive sheet having a base material.
- the substrate-less optical pressure-sensitive adhesive sheet include, for example, a double-sided pressure-sensitive adhesive sheet composed only of the polymer layer composed of the polymer of the present invention, and a polymer layer composed of the polymer of the present invention and a pressure-sensitive adhesive other than the polymer layer. Examples thereof include a double-sided pressure-sensitive adhesive sheet composed of layers.
- a pressure-sensitive adhesive sheet for substrate-less optics (a pressure-sensitive adhesive sheet for substrate-less double-sided optics) is preferable, and more preferably, It is a base-less double-sided optical pressure-sensitive adhesive sheet consisting only of a polymer layer made of a product.
- the “base material (base material layer)” does not include a separator (release liner) that is peeled off when the pressure-sensitive adhesive sheet is used (attached).
- the thickness of the polymer layer of the optical pressure-sensitive adhesive sheet of the present invention (III) is preferably 10 to 500 ⁇ m, more preferably 10 to 350 ⁇ m, and further preferably 10 to 300 ⁇ m. If the thickness of the polymer layer exceeds 500 ⁇ m, wrinkles may occur during winding during coating, or white turbidity may easily occur due to humidification, which is not preferable. When the thickness of the polymer layer is less than 10 ⁇ m, since the polymer layer is thin, the stress cannot be dispersed and peeling may easily occur.
- the optical pressure-sensitive adhesive sheet of the present invention (III) is used as a polymer layer interposed between an image display part of an image display device and a translucent protective part.
- 5b polymer (layer)) or a polymer (layer) filled between the display unit and the touch center integrated protection unit in the cover glass-touch center integrated capacitive touch panel display device When the optical pressure-sensitive adhesive sheet of the present invention (III) is used for the polymer (layer 5b described in FIGS.
- the dielectric constant of the optical pressure-sensitive adhesive sheet of the present invention (III) is Preferably it is low. Specifically, it is preferable to use a 2 mm-thick optical adhesive sheet having a dielectric constant of 3.1 or less under the conditions of 23 ° C., frequency 1 MHz, and applied voltage 100 mV, more preferably 23 ° C. In other words, a 2 mm-thick optical adhesive sheet having a frequency of 1 MHz and an applied voltage of 100 mV has a dielectric constant of 3.0 or less.
- the color coordinate b * value described in JIS Z 8729 after storing the pressure-sensitive adhesive sheet adjusted to a thickness of 200 ⁇ m existing between two glasses at 95 ° C. for 500 hours is less than 1.0. It is preferable that it exists in.
- the optical pressure-sensitive adhesive sheet of the present invention (III) is capable of sensitizing a photopolymerization initiator using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, an LED or the like as a light source. It is obtained by irradiating light to polymerize the polymerizable composition.
- the value of b * measured under the above conditions is preferably less than 1.0. Furthermore, it is preferably less than 0.9, and most preferably less than 0.8. When the value of b * measured under the above conditions is 1.0 or more, the transmittance of light at 370 to 450 nm decreases with time, which is not preferable.
- the refractive index of the optical pressure-sensitive adhesive sheet of the present invention (III) at 25 ° C. is preferably 1.48 to 1.52.
- the refractive index at 25 ° C. is less than 1.48 or larger than 1.52
- the refractive index is too low compared with the refractive index of acrylic resin such as optical glass or polymethyl methacrylate, which is the material of the protective part.
- the difference in refractive index at the interface between the protective part and the protective part becomes slightly large, and the scattering and attenuation of image light from the display part become slightly large, which is not preferable.
- the method for forming the polymer layer of the optical pressure-sensitive adhesive sheet of the present invention (III) can be a known or conventional method for forming a polymer layer, and is not particularly limited.
- the following methods (1) to (3) can be mentioned.
- a composition containing an additive, if necessary, on a polymerizable composition having an acryloyl group containing a photopolymerization initiator is applied (coated) on a substrate or a separator (release liner), and a low-pressure mercury lamp , Using a light source such as a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, or an LED, the photopolymerization initiator irradiates light capable of being polymerized to polymerize the composition. Thus, a polymer layer is formed.
- a light source such as a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, or an LED
- a polymerizable composition having an acryloyl group containing a photopolymerization initiator is further coated with a composition (solution) containing a solvent and, if necessary, an additive on a substrate or a separator (release liner). And then irradiate the photopolymerization initiator with sensitive light using a light source such as a dry and low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, and LED. Then, a polymer layer is formed by polymerizing the composition. (3) The polymer layer formed in (1) above is further dried.
- a known coating method can be used for coating (coating) in the above polymer layer forming method, and a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, or a dip coater can be used.
- a roll coater, bar coater, knife coater, spray coater, comma coater, direct coater and the like can be used.
- the substrate is not particularly limited, and examples thereof include various optical films such as a plastic film, an antireflection (AR) film, a polarizing plate, and a retardation plate. It is done.
- the material for the plastic film include (poly) ester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), (poly) carbonate, triacetyl cellulose (TAC), and polysulfone.
- polyarylate Polyimide, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name “ARTON (cyclic olefin polymer; manufactured by JSR)”, trade name “ZEONOR (cyclic olefin polymer; Plastic materials such as cyclic olefin polymers such as “manufactured by Nippon Zeon”.
- a plastic material can be used individually or in combination of 2 or more types.
- the above-mentioned “base material” is a portion that is attached to the adherend together with the adhesive layer when the optical adhesive sheet is used (attached) to the adherend (optical member or the like).
- a separator (release liner) that is peeled off when the adhesive sheet is used (attached) is not included in the “base material”.
- a transparent substrate is preferable as the substrate.
- the “transparent substrate” means, for example, a substrate having a total light transmittance (according to JIS K7361) in the visible light wavelength region of 85% or more, more preferably 88% or more. Further, the haze (according to JIS K7361) of the base material is preferably 1.5% or less, and more preferably 1.0% or less.
- the transparent substrate include PET films and non-oriented films such as trade names “Arton” and trade names “Zeonoa”.
- the thickness of the substrate is not particularly limited, and is preferably 12 to 75 ⁇ m, for example.
- the said base material may have any form of a single layer and a multilayer.
- the surface of the substrate may be appropriately subjected to known and conventional surface treatments such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoating treatment.
- various functional films can be used as the substrate.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive functional film having the pressure-sensitive adhesive layer of the present invention on at least one side of the functional film.
- optical functionality polarizability, photorefractive property, light reflectivity, light transmittance, light absorption property, light diffraction property, optical rotation property, visibility, etc.
- a film having conductivity a film having conductivity (such as an ITO film), a film having ultraviolet cutting property, a film having hard coat properties (scratch resistance), and the like.
- a hard coat film (a film on which at least one surface of a plastic film such as a PET film is hard-coated), a polarizing film, a wave plate, a retardation film, an optical compensation film, a brightness enhancement film, a light guide plate , Reflective film, antireflection film, transparent conductive film (ITO film, etc.), design film, decorative film, surface protective film, prism, color filter and the like.
- said "plate” and “film” shall include forms, such as plate shape, film shape, and sheet shape, respectively, for example, “polarizing film” shall also include “polarizing plate” and “polarizing sheet”.
- the “functional film” includes “functional plate” and “functional sheet”.
- the other pressure-sensitive adhesive layer is not particularly limited. Adhesives, silicone adhesives, (poly) ester adhesives, polyamide adhesives, epoxy adhesives, vinyl alkyl ether adhesives, known adhesives formed from known adhesives such as fluorine adhesives An adhesive layer is mentioned.
- the above pressure-sensitive adhesives can be used alone or in combination of two or more.
- a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) when neither the substrate nor other pressure-sensitive adhesive layers are contained, a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I), When other pressure-sensitive adhesive layers are included, a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) and a layer obtained by combining the other pressure-sensitive adhesive layers, or a substrate, In the case of including a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) and a layer in which the base material is combined, or when including both other pressure-sensitive adhesive layer and the base material, The layer obtained by polymerizing the polymerizable composition of the present invention (I), the other pressure-sensitive adhesive layer and the base material is defined as “pressure-sensitive adhesive layer”.
- the pressure-sensitive adhesive layer surface (adhesive surface) of the optical pressure-sensitive adhesive sheet of the present invention (III) may be protected by a separator (release liner) until use.
- a separator release liner
- each pressure-sensitive adhesive surface may be protected by two separators, respectively, or a single separator whose both surfaces are release surfaces, You may protect in the form wound by the shape.
- the separator is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when being applied to an adherend.
- the separator also serves as a support for the pressure-sensitive adhesive layer.
- the separator is not necessarily provided.
- a conventional release paper or the like can be used, and is not particularly limited.
- a substrate having a release treatment layer, a low adhesive substrate made of a fluoropolymer, a low adhesive substrate made of a nonpolar polymer, etc. can be used.
- a base material which has the said peeling process layer the plastic film, paper, etc.
- fluorine-based polymer in the low-adhesive substrate made of the above-mentioned fluoropolymer examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro Examples include fluoroethylene-vinylidene fluoride copolymer.
- nonpolar polymer for example, polyethylene, a polypropylene, etc.
- olefin resin for example, polyethylene, a polypropylene, etc.
- the separator can be formed by a known or common method. Further, the thickness of the separator is not particularly limited.
- the present invention (IV) is a method for manufacturing an image display device, comprising a base portion having an image display portion, a translucent protective portion, and a polymer layer interposed between the base portion and the protective portion.
- the step of interposing the polymerizable composition of the present invention (I) between the base part and the protective part, and polymerization by irradiating the polymerizable composition with light that can be photosensitized It is a manufacturing method of an image display device characterized by including the process of forming a physical layer.
- “between the base portion and the protective portion” described in the present specification means all portions between the base portion having the image display portion and the translucent protective portion.
- FIG. 1, FIG. 2, and FIG. 4 are cross-sectional views showing the main parts of an embodiment of an image display device according to the present invention.
- an image display device 1 according to the present embodiment is connected to a drive circuit (not shown) and displays an image display unit 2 that performs a predetermined image display.
- a translucent protective portion 3 disposed in close proximity to each other at a predetermined distance.
- the “image display device” described in the present specification is not particularly limited as long as it is a device that displays an image, and can be applied to various devices.
- the image display unit 2 of the present embodiment is a liquid crystal display panel of a liquid crystal display device.
- polarizing plates 6a and 6b are provided on the surface thereof.
- the spacer 4 and a jetty portion are provided on the peripheral edge portion of the image display portion 2, and the region of the present invention (I) is provided inside these regions.
- a predetermined amount of the polymerizable composition is dropped.
- a protective portion 3 is disposed on the spacer 4 of the image display portion (liquid crystal display panel) 2, and the present invention (I)
- the polymerizable composition is filled without gaps.
- the component (4) which is an essential component of the polymerizable composition of the present invention (I)
- the protective part 3 with respect to the polymerizable composition of the present invention (I).
- the polymerizable composition of the present invention (I) is polymerized. Thereby, the target image display apparatus 1 is obtained.
- the refractive index of the polymer layer 5 and the protection part 3 is equivalent, a brightness
- the polymer of the present invention (II) is used for the polymer layer 5b in FIG. 2 or FIG. 4, the dielectric constant of the polymer in the polymer layer 5b is kept low. Even if the thickness of the physical layer is reduced, the malfunction of the image display device can be prevented, and the image display device can be reduced in thickness.
- the present invention (V) is a method for producing an image display device having a step of attaching a polymer layer using an optical pressure-sensitive adhesive sheet between a base portion having an image display portion and a translucent protective portion,
- the optical pressure-sensitive adhesive sheet is the optical pressure-sensitive adhesive sheet of the present invention (III).
- attaching a polymer layer using an optical pressure-sensitive adhesive sheet between a base portion having an image display portion and a translucent protective portion means a base portion having an image display portion; Even if any part between the translucent protective part is pasted, "the base having the image display part and the translucent protective part are pasted using an optical adhesive sheet” Means that it is included in the expression, for example, even if it is attached to either 5a or 5b in FIG. This means that it is included in the expression “paste using”.
- the first base material is a touch sensor integrated protective portion
- a manufacturing process in the display device of FIG. 5 in which the base material is a display unit with a polarizing plate will be described as an example.
- the optical adhesive sheet of the present invention (III) is disposed adjacent to the touch sensor mounting surface side of the touch sensor-integrated protector that is the first substrate, and the polarizing plate that is the second substrate.
- the step of arranging the surface of the display part adjacent to the optical pressure-sensitive adhesive sheet of the present invention (III), and the step of heating and / or pressurizing the optical pressure-sensitive adhesive sheet of the present invention (III) to follow a step or a bump Furthermore, it can be manufactured by a method including a step of irradiating the optical pressure-sensitive adhesive sheet of the present invention (III) with light that can be photosensitized by the photopolymerization initiator, if necessary. These steps can be performed in various orders.
- one surface of the optical pressure-sensitive adhesive sheet of the present invention (III) is adjacent to the touch sensor mounting surface side of the touch sensor-integrated protection portion which is the first substrate. It arrange
- the optical pressure-sensitive adhesive sheet of the present invention (III) is heated and / or pressurized to cause the pressure-sensitive adhesive sheet to follow a step or a bump. Thereafter, the present invention (III) is passed through these substrates from the touch sensor-integrated protection unit (first substrate) side and / or the display unit with the polarizing plate (second substrate) side as necessary.
- the optical pressure-sensitive adhesive sheet is irradiated with light capable of being photosensitized by the photopolymerization initiator. In this way, the touch sensor integrated protection part (first base material) and the polarizing plate are provided without forming a gap near the step or the bulge of the touch sensor integrated protection part (first base material).
- the display portion (second base material) can be adhered.
- the touch sensor integrated protection part (first base material) and the display part with the polarizing plate (second base material) are adjacent to the optical pressure-sensitive adhesive sheet of the present invention (III), and then In order to heat and / or pressurize the pressure-sensitive adhesive sheet, when there is a step or a bulge on the adherend surface of the display part with the polarizing plate (second base material) (that is, on the polarizing plate attached to the image display module)
- the pressure-sensitive adhesive sheet can be made to follow the steps and bulges of the display portion (second base material) with a polarizing plate to prevent the formation of voids in the vicinity of the shape. it can.
- the photopolymerization initiator when the photopolymerization initiator irradiates photosensitive light, at least one of the first base material and the second base material passes through them to the optical pressure-sensitive adhesive sheet of the present invention (IV). It is at least partially transparent so that the photoinitiator can irradiate light that can be sensitized.
- the step or bulge portion of the first base material does not transmit ultraviolet light
- the ultraviolet light when the ultraviolet light is irradiated from the first base material side, the ultraviolet light is not irradiated directly below the step or bulge portion, but the irradiated portion
- the polymerization of the pressure-sensitive adhesive sheet proceeds to some extent even in the non-irradiated part due to the movement of radicals generated in the above.
- one surface of the optical pressure-sensitive adhesive sheet of the present invention (III) is provided on the surface side (that is, the touch sensor) having a step or a bulge on the touch sensor integrated protective part (first base material).
- the pressure-sensitive adhesive sheet After being placed adjacent to each other on the mounting surface side, the pressure-sensitive adhesive sheet is heated and / or pressurized to cause the pressure-sensitive adhesive sheet to follow a step or a bump. Then, if necessary, after irradiating the open surface of the optical pressure-sensitive adhesive sheet of the present invention (III) with ultraviolet rays to further polymerize the pressure-sensitive adhesive sheet, the display unit with the polarizing plate (second base material) is formed.
- the second base material is attached to the pressure-sensitive adhesive sheet so as to be adjacent to the other surface of the pressure-sensitive adhesive sheet.
- the release film is transparent, the pressure-sensitive adhesive sheet can be irradiated with ultraviolet rays through the release film, if necessary.
- the pressure-sensitive adhesive sheet can be polymerized more uniformly.
- the first base material is at least partially transparent so that the photopolymerization initiator necessary for the polymerization of the pressure-sensitive adhesive sheet can irradiate light capable of being sensitized, from the first base material side, if necessary. Irradiation with ultraviolet rays is also possible. In this way, the first base material and the second base material can be bonded together without forming a gap near the step or bulge of the first base material.
- the heating step can be performed using a convection oven, a hot plate, a heat laminator, an autoclave, or the like.
- a convection oven a hot plate
- a heat laminator a heat laminator
- an autoclave a heat laminator
- Pressurization using an autoclave is particularly advantageous for defoaming the optical pressure-sensitive adhesive sheet.
- the heating temperature of the optical pressure-sensitive adhesive sheet of the present invention may be any temperature as long as the pressure-sensitive adhesive sheet softens or flows and sufficiently follows a step or a bump, and is generally about 30 ° C. or higher, about 40 ° C. or higher, or about 60 ° C.
- the temperature may be about 150 ° C. or lower, about 120 ° C. or lower, or about 100 ° C. or lower.
- the applied pressure can be generally about 0.05 MPa or more, or about 0.1 MPa or more, about 2 MPa or less, or about 1 MPa or less.
- the process of irradiating light that can be photosensitized by the photopolymerization initiator, which is performed as necessary, uses a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, etc. It can carry out using the general ultraviolet irradiation device used as, for example, a belt conveyor type ultraviolet irradiation device. UV irradiation dose is generally from about 1000 mJ / cm 2 ⁇ about 5000 mJ / cm 2.
- the present invention (VI) is an image display device produced by the method described in the present invention (IV) or the present invention (V).
- the image display device of the present invention (VI) generally has a refractive index (n D ) of 1.49 to 1.52 when the main body of the display device is made of optical glass.
- n D refractive index
- the protection unit 3 is formed of a plate-like, sheet-like, or film-like translucent member having the same size as the image display unit 2.
- optical glass or plastic acrylic resin such as polymethyl methacrylate
- An optical layer such as an antireflection film, a light shielding film, or a viewing angle control film may be formed on the front surface or the back surface of the protection unit 3.
- the protective part 3 is made of an acrylic resin, its refractive index (n D ) is generally 1.49 to 1.51.
- the protection unit 3 is provided on the image display unit 2 via a spacer 4 provided at the peripheral edge of the image display unit 2.
- the thickness of the spacer 4 is about 0.05 to 1.5 mm, so that the distance between the surfaces of the image display unit 2 and the protection unit 3 is maintained at about 1 mm.
- a frame-shaped light shielding portion (not shown) is provided at the peripheral portion of the protection portion 3 in order to improve luminance and contrast.
- the image display device manufactured by the method for manufacturing an image display device of the present invention (IV) will be described in detail. Between the image display part 2 and the protection part 3, polymer layers 5a and 5b are interposed.
- the polymer of the present invention (II) is interposed in the polymer layer 5a and the polymer layer 5b.
- the transmittance in the visible light region is 90% or more.
- the thickness of the polymer layer 5a or the polymer layer 5b is preferably 10 to 500 ⁇ m. More preferably, it is 10 to 350 ⁇ m, and particularly preferably 10 to 300 ⁇ m.
- the refractive index (n D ) at 25 ° C. is 1.45 to 1.55, preferably 1 .48 to 1.52 is preferable because it is almost equal to the refractive index of the image display unit 2 and the protection unit 3. Thereby, the brightness
- the polymer of the present invention (II) is interposed in the polymer layer 5a and the polymer layer 5b, so
- the elastic modulus is 1 ⁇ 10 7 Pa or less, preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa. Therefore, it is possible to prevent the image display portion and the protection portion from being distorted due to the influence of stress caused by volume shrinkage during polymerization of the polymerizable composition.
- the polymer composition of the present invention (I) is interposed in the polymer layer 5a and the polymer layer 5b.
- the volume shrinkage during polymerization is 4.0% or less, preferably 3.5% or less, and more preferably 2.7% or less.
- the scattering of light generated at the interface between the polymer layer 5 and the image display unit 2, the protection unit 3, and the touch panel 7 can be reduced, and the brightness of the display image is increased and the visibility is improved. Can be made.
- the thickness of the polymer layer 5b can be made thin.
- the image display device manufactured by the method for manufacturing the image display device of the present invention (V) will be described in detail.
- polymer layers 5a and 5b are interposed.
- the optical adhesive sheet of the present invention (III) is interposed in the polymer layer 5a and the polymer layer 5b. Therefore, the transmittance in the visible light region is 90% or more.
- the thickness of the polymer layer 5a or the polymer layer 5b is preferably 10 to 500 ⁇ m. More preferably, it is 10 to 350 ⁇ m, and particularly preferably 10 to 300 ⁇ m.
- the refractive index (n D ) at 25 ° C. is 1.45 to 1.55, preferably 1.48 to 1.52 is preferable because it is almost equal to the refractive index of the image display unit 2 and the protection unit 3. Thereby, the brightness
- an image display device is produced by the method for producing an image display device of the present invention (V)
- the optical adhesive sheet of the present invention (III) is interposed in the polymer layer 5a and the polymer layer 5b,
- the pressure-sensitive adhesive sheet can be made to follow the steps and bulges of the image display unit and the protection unit, and the formation of voids can be prevented even in the vicinity of these shapes.
- the optical adhesive sheet of this invention (III) has flexibility, even if the protection part 3, the image display part 2, and the touch panel 7 have uneven
- the display surface (for example, a polarizing plate) of the image display unit 2 can be used even in a high temperature and high humidity environment. No bubbles or peeling occur at the interface with the optical pressure-sensitive adhesive sheet (that is, the polymer layer 5b) and at the interface between the optical pressure-sensitive adhesive sheet (that is, the polymer layer 5b) and the touch sensor integrated protection portion 3a. No whitening occurs.
- optical glass plate used in the image display device of the present invention those used as a glass plate for sandwiching the liquid crystal of the liquid crystal cell or a protective plate for the liquid crystal cell can be preferably used.
- acrylic resin board used what is used as a protective plate of a liquid crystal cell can be used preferably.
- the average surface roughness of these optical glass plates and acrylic resin plates is usually 1.0 nm or less.
- the image display device of the present invention (VI) is a polymer obtained by using the polymer of the present invention (I) or the optical pressure-sensitive adhesive sheet of the present invention (III) between the image display unit 2 and the protection unit 3. Since layer 5 is filled, it is resistant to impact. In addition, it can be formed thinner than the conventional example in which a gap is provided between the image display unit 2 and the protection unit 3. Further, the image display device of the present invention (VI) can take various forms. For example, as shown in FIGS. 3 and 5, the spacer 4 may be omitted and the image display device 1 may be manufactured. In the case of the polymer layer 5b of FIG.
- the photopolymerizable composition of the present invention (I) is applied on the polarizing plate 6a on the image display unit 2, and the touch panel 7 is overlaid thereon.
- a laminate on the image display unit 2 is formed of a laminate composed of the protection unit 3, the polymer layer 5a, the touch panel 7, and the polymer layer 5b (that is, the optical pressure-sensitive adhesive sheet 5b). It can be obtained by bonding to the surface (that is, the surface of the polarizing plate 6a).
- the photopolymerizable composition of the present invention (I) is applied onto the polarizing plate 6a on the image display unit 2, and the touch sensor integrated type is applied thereon.
- the protective part 3a is overlapped and photopolymerization is performed in the same manner as described above, or, for example, a laminate composed of the touch sensor integrated protective part 3a and the polymer layer 5b (that is, the optical pressure-sensitive adhesive sheet 5b) is used as the image display part 2. It can be obtained by bonding to the upper display surface (that is, the surface of the polarizing plate 6a).
- the present invention can be applied not only to the liquid crystal display device described above but also to various panel displays such as an organic EL and a plasma display device.
- the viscosity was measured by the following method. Using a 1 mL sample, the viscosity was measured at a temperature of 25.0 ° C. and a rotation speed of 10 rpm using a cone / plate viscometer (Brookfield, model: DV-II + Pro, spindle model: CPE-42). The value when it became almost constant was measured.
- the number average molecular weight is a value in terms of polystyrene measured by GPC under the following conditions.
- Device name HPLC unit HSS-2000 manufactured by JASCO Corporation Column: Shodex column LF-804
- Mobile phase Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI-2031Plus manufactured by JASCO Corporation Temperature: 40.0 ° C
- Sample volume Sample loop 100 ⁇ L
- Sample concentration prepared at around 0.5 wt%
- Example 1 In a 300 mL separable flask equipped with a condenser, dropping funnel, thermometer and stirrer, 180 g of polybutadiene polyol (trade name: NISSO-PB G-2000 hydroxyl value 47.3 mgKOH / g, manufactured by Nippon Soda Co., Ltd.), pentaerythritol tetrakis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF) 1.17 g and dioctyltin dilaurate 20 mg were added, and the internal temperature was 50 ° C. using an oil bath.
- polybutadiene polyol trade name: NISSO-PB G-2000 hydroxyl value 47.3 mgKOH / g, manufactured by Nippon Soda Co., Ltd.
- pentaerythritol tetrakis [3 -(
- Example 2 In a 1-liter four-necked flask equipped with a stirrer and a distillation apparatus, 540.0 g of polybutadiene polyol (trade name: NISSO-PB G-3000, hydroxyl value 29.5 mgKOH / g, manufactured by Nippon Soda Co., Ltd.), 101 g of n-butyl acrylate , 0.81 g of dioctyltin dilaurate and 3.51 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF) Then, the mixture of n-butanol and n-butyl acrylate produced by heating to 130 ° C.
- polybutadiene polyol trade name: NISSO-PB G-3000, hydroxyl value 29.5 mgKOH / g, manufactured by Nippon
- reaction product ⁇ a reaction product (hereinafter referred to as reaction product ⁇ ).
- reaction product ⁇ a reaction product (hereinafter referred to as reaction product ⁇ ).
- 150 g of polyisoprene polyol (trade name: Poly ip hydroxyl value: 47.3 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd.) and 12 mg of dioctyltin dilaurate are added and stirred. Started.
- reaction product ⁇ 46.1 g maintained at a temperature of 60 ° C. was introduced into the reaction vessel in several portions. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 65 to 70 ° C., and stirring was continued. The reaction was terminated after confirming that the absorption of C ⁇ O stretching vibration of the isocyanato group disappeared by IR.
- This reaction product of 4-hydroxybutyl acrylate: VESTANAT (registered trademark) TMDI 2: 1 (molar ratio) is defined as urethane acrylate monomer ⁇ . Moreover, what remove
- Example 4 In a 300 mL separable flask equipped with a condenser, a dropping funnel, a thermometer and a stirrer, hydrogenated polybutadiene polyol (trade name: NISSO-PB GI-2000, hydroxyl value: 47.3 mgKOH / g, manufactured by Nippon Soda Co., Ltd.) 180 g, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF, trade name: IRGANOX1010) 1.17 g and dioctyltin dilaurate 20 mg were added, and the internal temperature was adjusted using an oil bath.
- hydrogenated polybutadiene polyol trade name: NISSO-PB GI-2000, hydroxyl value: 47.3 mgKOH / g, manufactured by Nippon Soda Co., Ltd.
- BASF trade name: IRGANOX1010
- Example 5 A 1 liter four-necked flask equipped with a stirrer and a distillation apparatus was charged with hydrogenated polybutadiene polyol (trade name: NISSO-PB GI-3000, hydroxyl value 29.5 mgKOH / g, manufactured by Nippon Soda Co., Ltd.) 540.0 g, acrylic acid n- 101 g of butyl, 0.81 g of dioctyltin dilaurate and 3.51 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010 manufactured by BASF) Under a stream of air, the mixture of n-butanol and n-butyl acrylate produced by heating to 130 ° C.
- hydrogenated polybutadiene polyol trade name: NISSO-PB GI-3000, hydroxyl value 29.5 mgKOH /
- Example synthesis 6 In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI Evonik Degussa) 23.93 g, dioctyltin dilaurate 11 mg and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010 manufactured by BASF) 74 g was charged into the reaction vessel, and 16.41 g of 4-hydroxybutyl acrylate was added dropwise with a dropping funnel.
- VESTANAT® 2,2,4-trimethylhexamethylene diisocyanate
- TMDI Evonik Degussa 23.93 g
- reaction product ⁇ was adjusted to 70 ° C. or lower. After completion of the dropping, stirring was continued for 2 hours while maintaining the temperature in the reactor at 65 to 70 ° C. to obtain a reaction product ⁇ .
- a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with 150 g of hydrogenated polyisoprene polyol (trade name: Epaul hydroxyl group value 47.3 mgKOH / g) manufactured by Idemitsu Kosan Co., Ltd. and 12 mg of dioctyltin dilaurate. Started. Thereafter, the reaction product ⁇ 46.1 g maintained at a temperature of 60 ° C. was introduced into the reaction vessel in several portions.
- a product obtained by removing the urethane acrylate monomer ⁇ from the reaction product is referred to as a (meth) acryloyl group-containing compound 6 having a hydrogenated polyolefin structural unit containing a urethane group.
- Example synthesis 7 In a reaction vessel equipped with a stirrer and a water separator, Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, hydrogenated dimer diol purity 97.5% by mass), 270.0 g, EMPOL (registered trademark) 1008 (hydrogenated by BASF) Dimer acid, hydrogenated dimer acid purity 92.0 %%) 171.0 g and dioctyltin dilaurate 100 mg were charged, and dehydration esterification reaction was carried out at about 240 ° C. starting from normal pressure while flowing out condensed water and depressurizing.
- polyester polyol A A mixture of polyester polyol and hydrogenated dimer diol (hereinafter referred to as “polyester polyol A”) having a value of 59 mg KOH / g and a number average molecular weight of 2000 and containing 15% by mass of hydrogenated dimer diol was obtained.
- Example 8 In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI Evonik Degussa) 21.89 g, dioctyltin dilaurate 12 mg and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010 manufactured by BASF) 74 g was charged into the reaction vessel, and 15.16 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel.
- IRGANOX 1010 manufactured by BASF
- reaction product ⁇ a reaction product (hereinafter referred to as reaction product ⁇ ).
- reaction product ⁇ a reaction product
- 180.0 g of the (poly) ester polyol A and 12 mg of dioctyltin dilaurate were added, and stirring was started. Thereafter, 33.7 g of the reaction product ⁇ maintained at a temperature of 60 ° C. was introduced into the reaction vessel in several portions. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C.
- Example synthesis 9 In a 300 mL reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 180.0 g of the above-mentioned (poly) ester polyol A, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy) were added. Phenyl) propionate] (trade name: IRGANOX 1010, manufactured by BASF) 5.74 g and dioctyltin dilaurate 20 mg were added, and stirring was started.
- 2-isocyanatoethyl acrylate (trade name: Karenz (registered trademark) AOI, Showa Denko) was added dropwise. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 65 to 70 ° C., and stirring was continued. The reaction was terminated after confirming that the absorption of C ⁇ O stretching vibration of the isocyanato group disappeared by IR.
- the manufactured urethane acrylate be the (meth) acryloyl group containing compound 8 which has a polyester structural unit.
- Example synthesis example 10 Pripol (registered trademark) 2033 (clad hydrogenated dimer diol, hydroxyl value 202 mg KOH / g) 366.6 g, diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 54 in a 500 ml reaction vessel equipped with a stirrer and refluxing distillation apparatus .3 g, titanium tetrabutoxide 0.2 g, dioctyl tin oxide (trade name: DOTO Hokuko Chemical Co., Ltd.) 0.12 g are charged, heated to 130 ° C. using an oil bath, and then the reaction proceeds. The temperature was raised to 180 ° C.
- the transesterification reaction was carried out while reducing the pressure while allowing ethanol to flow out, starting from normal pressure.
- ethanol was distilled, the amount of diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) distilled together was confirmed by gas chromatography, and diethyl carbonate corresponding to the amount of distillation was added.
- the total amount of ethanol distilled was 29.5 g.
- Example synthesis 11 In a 300 mL reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 177.8 g of the above-mentioned (poly) carbonate polyol A, Pripol (registered trademark) 2033 (clad hydrogenated dimer diol, hydroxyl value 202 mgKOH / g) ) 2.2 g, 5.74 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF) and 20 mg of dioctyltin dilaurate were added.
- Example synthesis 12 In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI Evonik Degussa) 21.89 g, dioctyltin dilaurate 12 mg and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010 manufactured by BASF) 74 g was charged into the reaction vessel, and 15.16 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel.
- VESTANAT® 2,2,4-trimethylhexamethylene diisocyanate
- TMDI Evonik Degussa 21.89 g
- reaction product ⁇ a reaction product (hereinafter referred to as reaction product ⁇ ).
- reaction product ⁇ a reaction product
- a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser the above-mentioned (poly) carbonate polyol A 178.9 g, Pripol (registered trademark) 2033 (clad hydrogenated dimer diol, hydroxyl value 202 mgKOH / g) 1.1 g And 12 mg of dioctyltin dilaurate was added and stirring was started.
- Example formulation 1 60.0 parts by mass of (meth) acryloyl group-containing compound 1 having the above-mentioned polyolefin structural unit, 20.0 parts by mass of isostearyl acrylate (trade name: ISTA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), hydrogenated dimer diol (product of Croda) Name: Pripol 2033) 20.0 parts by mass, 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name: Irgacure 184) 0.8 parts by mass and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Lambson, trade name: SpeedCure TPO ) 0.4 part by mass was mixed using a rotating / revolving mixer (trade name: Awatori Rentaro ARE-310, manufactured by Shinky Corporation). This blend was designated as a polymerizable composition A1. The viscosity at 25 ° C. of the polymerizide,
- Example Formulation Example 2 to Example Formulation Example 11 and Comparative Formulation Example 1 to Comparative Formulation Example 2 In the same manner as in Example 1 of blending, blending was performed according to the blending composition shown in Table 1.
- the formulations prepared in Examples Formulation Examples 2 to 11 were designated as Polymerizable Composition A2 to Polymerizable Composition A11, respectively, and the formulations prepared in Comparative Formulation Example 1 and Comparative Formulation Example 2 were respectively polymerizable compositions B1. And polymerizable composition B2.
- PET After coating on a film (100 mm ⁇ 100 mm ⁇ 50 ⁇ m) and covering the upper surface with a 25 ⁇ m thick silicone-coated PET film, a conveyor type ultraviolet irradiation device using a metal halide lamp (Co., Ltd.) GS Yuasa Lighting Co., Ltd., trade name: GSN2-40), with an irradiation intensity of 190 mW / cm 2 (value of 365 nm) and dose of 2800 mJ / cm 2 (value of 365 nm) through a PET film coated with silicone.
- a metal halide lamp Co., Ltd.
- GSN2-40 metal halide lamp
- optical pressure-sensitive adhesive sheet having a film thickness of about 200 ⁇ m was obtained.
- the optical pressure-sensitive adhesive sheets produced using the polymerizable composition A1 to the polymerizable composition A11, the polymerizable composition B1 and the polymerizable composition B2 are respectively referred to as the pressure-sensitive adhesive sheet A1 to the pressure-sensitive adhesive sheet A11, the pressure-sensitive adhesive sheet B1 and the pressure-sensitive adhesive sheet B1. It was set as adhesive sheet B2.
- ⁇ Method for preparing test piece using the pressure-sensitive adhesive sheet and evaluation of initial optical properties Two glass plates (50 mm ⁇ 50 mm ⁇ 0.7 mm, glass type, product name: EAGLE so that air bubbles do not enter the interface in the pressure-sensitive adhesive sheets A1 to A11, pressure-sensitive adhesive sheet B1 and pressure-sensitive adhesive sheet B2, respectively.
- a test piece was prepared by pasting the adhesive sheet so as to be sandwiched from both sides with XG (registered trademark), manufactured by CORNING.
- test pieces prepared using the pressure-sensitive adhesive sheets A1 to A11, the pressure-sensitive adhesive sheet B1, and the pressure-sensitive adhesive sheet B2 were designated as a test piece AS1 to a test piece AS11, a test piece BS1, and a test piece BS2, respectively.
- the total light transmittance, b * was measured by the method described later. The results are shown in Table 3.
- the polymerizable composition A4 to the polymerizable composition A11, the polymerizable composition B1 and the polymerizable composition B2 were each made of glass plates (50 mm ⁇ 50 mm ⁇ 0.00 mm) so as to have a film thickness of 200 ⁇ m using a bar coater.
- a polymer film for evaluation tests having a film thickness of about 2 mm sandwiched between PET films coated with silicone by polymerizing by irradiation with ultraviolet rays under the condition of an irradiation amount of 2800 mJ / cm 2 (value of 365 nm). Obtained.
- the polymer film was peeled off from the PET film coated with silicone, and measured using an impedance analyzer (trade name: 4294A Precision Impedance Analyzer 40 Hz-110 MHz, manufactured by Agilent Technologies, Inc.). The results are shown in Table 2.
- test piece AS1 to test piece AS11, test piece AL4 to test piece AL11, test piece BS1, test piece BS2, test piece BL1 and test piece BL2 are placed in a thermostat of 70 ° C., 85 ° C. and 95 ° C., respectively, 500 Using the test piece after the lapse of time, the total light transmittance, b * value and haze were measured by the above-described method. The results are shown in Table 3.
- ⁇ Measurement of total light transmittance, b * value and haze when stored under high temperature and high humidity conditions Place the test piece AS1 to test piece AS11, test piece AL4 to test piece AL11, test piece BS1, test piece BS2, test piece BL1 and test piece BL2 in a constant temperature and humidity machine with a temperature of 60 ° C. and a humidity of 90% RH, respectively.
- the total light transmittance, b * value and haze were measured by the above-described method using the test piece after 500 hours. The results are shown in Table 3.
- the polymerizable composition of the present invention (I) has a low volume shrinkage during polymerization and is a polymer obtained by polymerizing the polymerizable composition of the present invention (II). It was found that even when stored for a long time under high temperature conditions, the appearance change such as coloring hardly occurs, and good light transmittance can be maintained.
- the polymerizable composition of the present invention (I) has a low volume shrinkage during polymerization, and the polymer film obtained by polymerizing the polymerizable composition of the present invention (I) has a high temperature. Even when stored for a long time under conditions, appearance changes such as coloring are unlikely to occur, and good light transmittance can be maintained. Therefore, when the polymer film is used as a transparent optical resin layer interposed between the image display portion and the translucent protective portion of the image display device, a good optical adhesive layer can be provided. . That is, it is useful to use the polymer in an image display device.
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Description
図6に示すように、この液晶表示装置101は、液晶表示パネル102上に、例えば、ガラスやプラスチックスからなる透明な保護部103を有している。
この場合、液晶表示パネル102表面および偏光板(図示せず)を保護するため、保護部103との間にスペ-サ104を介在させることによって液晶表示パネル102と保護部103との間に空隙105が設けられている。
しかし、液晶表示パネル102と保護部103との間の空隙105の存在により、光の散乱がおき、それに起因してコントラストや輝度が低下し、また空隙105の存在はパネルの薄型化の妨げとなっている。
成分(1)ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、(ポリ)エステル構造単位を有する(メタ)アクリロイル基含有化合物および(ポリ)カーボネート構造単位を有する(メタ)アクリロイル基含有化合物からなる群より選ばれる少なくとも1種、
成分(2)成分(1)以外の液状(メタ)アクリロイル基含有化合物、
成分(3)液状水添ポリブタジエンポリオール、液状水添ポリイソプレンポリオールおよび水添ダイマージオールからなる群より選ばれる少なくとも1種、および
成分(4)光重合開始剤
を含むことを特徴とする重合性組成物に関する。
本発明(II)は、本発明(I)の重合性組成物を重合して得られる重合物に関する。
本発明(III)は、本発明(I)の重合性組成物を塗布し、光重合開始剤が感光可能な光を該重合性組成物に照射して、重合させることによって得られる、厚さ10~500μmの重合物層を有する光学用粘着シートに関する。
本発明(IV)は、画像表示部を有する基部と、透光性の保護部と、前記基部と前記保護部との間に介在する重合物層とを含む画像表示装置の製造方法であって、該方法が本発明(I)の重合性組成物を前記基部と前記保護部との間に介在させる工程、および光重合開始剤が感光可能な光を前記重合性組成物に照射して重合物層を形成する工程を含むことを特徴とする画像表示装置の製造方法に関する。
本発明(V)は、画像表示部を有する基部と透光性の保護部との間に光学用粘着シートを用いて重合物層を貼り付ける工程を有する画像表示装置の製造方法であって、該光学用粘着シートが本発明(III)の光学用粘着シートであることを特徴とする画像表示装置の製造方法に関する。
本発明(VI)は、本発明(IV)または本発明(V)の方法によって製造された画像表示装置に関する。
[1] 画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合物を製造するための重合性組成物であって、該重合性組成物が、
成分(1)ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、(ポリ)エステル構造単位を有する(メタ)アクリロイル基含有化合物および(ポリ)カーボネート構造単位を有する(メタ)アクリロイル基含有化合物からなる群より選ばれる少なくとも1種、
成分(2)成分(1)以外の液状(メタ)アクリロイル基含有化合物、
成分(3)液状水添ポリブタジエンポリオール、液状水添ポリイソプレンポリオールおよび水添ダイマージオールからなる群より選ばれる少なくとも1種、および
成分(4)光重合開始剤
を含むことを特徴とする重合性組成物。
[2] 成分(5)水添ポリブタジエン、水添ポリイソプレン、ポリ(α-オレフィン)液状物、エチレン-プロピレン共重合液状物、プロピレン-α-オレフィン共重合液状物、エチレン-α-オレフィン共重合液状物、液状ポリブテン、液状水添ポリブテン、液状ポリブタジエン、液状水添ポリブタジエン、液状ポリイソプレン、液状水添ポリイソプレン、液状ポリブタジエンポリオール、および液状ポリイソプレンポリオールからなる群より選ばれる少なくとも1種
をさらに含むことを特徴とする請求項1に記載の重合性組成物。
[3] 成分(6)水添石油樹脂、テルペン系水添樹脂、および水添ロジンエステルからなる群より選ばれる少なくとも1種
をさらに含むことを特徴とする[1]または[2]に記載の重合性組成物。
[4] 成分(2)が炭素数6以上の炭化水素基を有する(メタ)アクリロイル基含有化合物を含むことを特徴とする[1]~[3]のいずれか1つに記載の重合性組成物。
[5] 成分(2)がアルコール性水酸基を有する(メタ)アクリロイル基含有化合物を含むことを特徴とする[1]~[4]のいずれか1つに記載の重合性組成物。
[6] [1]~[5]のいずれか1つに記載の重合性組成物を重合して得られる重合物。
[7] 前記重合物層に用いられる光学用粘着シートを製造するための重合性組成物であって、該重合性組成物が[1]~[5]のいずれか1つに記載の重合性組成物であることを特徴とする重合性組成物。
[8] [7]に記載の重合性組成物に、光重合開始剤が感光可能な光を照射して、重合させることによって得られる、厚さ10~500μmの重合物層を有する光学用粘着シート。
[9] 画像表示部を有する基部と、透光性の保護部と、前記基部と前記保護部との間に介在する重合物層とを含む画像表示装置の製造方法であって、該方法が
[1]~[5]のいずれか1つに記載の重合性組成物を前記基部と前記保護部との間に介在させる工程、および
光重合開始剤が感光可能な光を前記重合性組成物に照射して重合物層を形成する工程
を含むことを特徴とする画像表示装置の製造方法。
[10] 画像表示部を有する基部と透光性の保護部との間に光学用粘着シートを用いて重合物層を貼り付ける工程を有する画像表示装置の製造方法であって、該光学用粘着シートが[8]に記載の光学用粘着シートであることを特徴とする画像表示装置の製造方法。
[11] [9]または[10]に記載の方法によって製造された画像表示装置。
[12] 画像表示部が液晶表示パネルであることを特徴とする[11]に記載の画像表示装置。
なお、本明細書に記載の「重合物」とは、重合性組成物を重合して得られる重合物であれば、形態等に特に制限はなく、本明細書に記載の「光学用粘着シート」も重合物に含まれることを意味する。
また、本明細書に記載の「画像表示部と透光性の保護部との間に介在させる重合物層」とは、画像表示部と透光性の保護部との間の全ての重合物層を意味し、例えば、図2の5aと5bのいずれも含まれることを意味する。
また、本明細書における「(メタ)アクリロイル基」とは、アクリロイル基および/またはメタクリロイル基を意味する。
さらに、本明細書における「(ポリ)エステルポリオール」とは、1分子中に1つ以上の-COO-結合(カルボン酸エステル結合)を有し、かつ2つ以上のアルコール性水酸基を有する化合物を意味し、本明細書における「(ポリ)カーボネートポリオール」とは、1分子中に1つ以上の-OCOO-結合(カーボネート結合)を有しかつ2つ以上のアルコール性水酸基を有する化合物を意味する。
また、本明細書では、本発明(I)の重合性組成物の必須原料成分である成分(1)の原料になり得る(ポリ)カーボネートポリオールを製造する際に、(ポリ)カーボネートポリオールの原料であるポリオール(即ち、カーボネート結合を有さないポリオール)が残存する場合には、このポリオールも(ポリ)カーボネートポリオールには含まれるものとする。加えて、本明細書では、(ポリ)カーボネートポリオール中に含まれる原料ポリオールの他に、新たに、使用する(ポリ)カーボネートポリオールの原料で成分であるポリオールを加えて、本発明(I)の重合性組成物の必須成分である成分(1)が製造された場合、この加えられたポリオールは、(ポリ)カーボネートポリオールに含まれるものとする。
本発明(I)は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、下記成分(1)~成分(4)を必須成分として含むことを特徴とする重合性組成物である。
成分(1) ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、(ポリ)エステル構造単位を有する(メタ)アクリロイル基含有化合物、(ポリ)カーボネート構造単位を有する(メタ)アクリロイル基含有化合物およびポリエーテル構造単位有する(メタ)アクリロイル基含有化合物からなる群より選ばれる少なくとも1種
成分(2) 成分(1)以外の液状(メタ)アクリロイル基含有化合物
成分(3) 液状水添ポリブタジエンポリオール、液状水添ポリイソプレンポリオールおよび水添ダイマージオールからなる群より選ばれる少なくとも1種
成分(4) 光重合開始剤
また、本明細書に記載の「(ポリ)カーボネートポリオールから誘導された構造単位」とは、1分子中に1つ以上のカーボネート結合を有しかつ2つ以上のアルコール性水酸基を有する化合物から少なくとも1つのアルコール性水酸基のHを除いた構造を意味する。
本発明(I)の重合性組成物の必須原料成分である成分(1)は、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、(ポリ)エステル構造単位を有する(メタ)アクリロイル基含有化合物および(ポリ)カーボネート構造単位を有する(メタ)アクリロイル基含有化合物からなる群より選ばれる少なくとも1種の(メタ)アクリロイル基含有化合物である。
これらの中で好ましいものとしては、ポリブタジエン構造単位、ポリイソプレン構造単位あるいはポリ(ブタジエン-イソプレン)構造単位である。
なお、NISSO-PB TE-2000やNISSO-PB TEA-1000はNISSO-PB G-1000、G-2000(日本曹達株式会社製)等のポリブタジエンポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有(メタ)アクリレートの反応生成物である。このように、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物を製造するための原料として、ポリオレフィンポリオールは有用であり、これらの市販品としては、前述のポリオレフィンポリオールの市販品であるポリブタジエンポリオールであるNISSO PB G-1000、G-2000、G-3000(日本曹達株式会社製)以外に、水酸基末端液状ポリブタジエンであるPoly bd(出光興産株式会社製)、水酸基末端液状ポリイソプレンであるPoly Ip(出光興産株式会社製)、液状ポリブタジエンジオールであるKRASOL(Cray Valley社製)等を挙げることができる。
まず、ポリオレフィンポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有(メタ)アクリレートを必須原料成分に用いて、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物を得る場合について説明する。
なお、ポリブタジエンポリオールとは、水酸基を含有するブタジエンのホモポリマーである。ポリイソプレンポリオールは、水酸基を含有するイソプレンのホモポリマーのことである。
本発明(I)の重合性組成物の必須成分である成分(1)は、その後の配合の自由度を考慮すると、粘度が低いことが望ましい。この目的に合致する有機ポリイソシアネート化合物としては、1,3-ビス(イソシアナトメチル)シクロヘキサン、1,4-ビス(イソシアナトメチル)シクロヘキサン、2,4,4-トリメチルヘキサメチレンジイソシアネート、2,2,4-トリメチルヘキサンメチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネートおよびノルボルナンジイソシアネートが好ましく、さらに好ましくは、1,3-ビス(イソシアナトメチル)シクロヘキサン、2,4,4-トリメチルヘキサメチレンジイソシアネートおよび2,2,4-トリメチルヘキサンメチレンジイソシアネートであり、最も好ましいのは、2,4,4-トリメチルヘキサメチレンジイソシアネートおよび2,2,4-トリメチルヘキサンメチレンジイソシアネートである。
これらの中で、本発明(I)の必須成分である成分(1)の重合速度を考慮すると、好ましいものとしては、2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレート、3-ヒドロキシプロピルアクリレート、2-ヒドロキシブチルアクリレート、4-ヒドロキシブチルアクリレート、2-ヒドロキシ-3-フェノキシプロピルアクリレート、2-ヒドロキシ-3-(o-フェニルフェノキシ)プロピルアクリレートである。イソシアネート基との反応性を考慮すると、2-ヒドロキシエチルアクリレート、3-ヒドロキシプロピルアクリレート、4-ヒドロキシブチルアクリレートが好ましく、最も好ましいのは、4-ヒドロキシブチルアクリレートである。
ただし、化合物の末端を、アルコール性水酸基含有(メタ)アクリレートを含む水酸基を分子中に1つ有する化合物でほぼ完全に封止される場合には、ポリオレフィンポリオールの使用数およびこのポリオレフィンポリオール以外のポリオールの使用数を合わせたときの水酸基の総数より使用される有機ポリイソシアネート化合物のイソシアナト基の総数を多くする必要がある。
この場合には、ポリオレフィンポリオールの使用数およびこのポリオレフィンポリオール以外のポリオールの使用数を合わせたときの水酸基の総数と、有機ポリイソシアネート化合物中のイソシアナト基の総数の比が、1.0に近いと分子量が大きくなり、1.0からずれて小さくなると分子量は小さくなる。
この比が1.5:1よりも小さい場合には、粘度が高くなりすぎる場合があり、好ましいこととは言えない。
ただし、この場合には、ポリオレフィンポリオールの使用数、このポリオレフィンポリオール以外のポリオールの使用数およびアルコール性水酸基含有(メタ)アクリレートを含む水酸基を分子中に1つ有する化合物の使用数を合わせたときの水酸基の総数と、有機ポリイソシアネート化合物中のイソシアナト基の総数の比は、2:1以下であることが好ましい。
この比が2:1よりも大きい場合には、アクリロイル基を有さない分子が多くなり、重合後の重合物の形状保持性が悪化あることがあり、好ましいこととは言えない。
ポリオレフィンポリオールは前述の通りである。
上記の原料になり得るイソシアナト基を有する(メタ)アクリロイル基含有化合物としては、例えば、2-イソシアナトエチルアクリレート、2-イソシアナトエチルメタクリレート等を挙げることができる。
2-イソシアナトエチルアクリレートとしては、例えば、昭和電工株式会社製のカレンズAOI(登録商標)等を挙げることができる。
2-イソシアナトエチルメタクリレートとしては、例えば、昭和電工株式会社製のカエレンズMOI(登録商標)等を挙げることができる。
なお、ポリオレフィンポリオールの水酸基の全てをイソシアナト基を有する(メタ)アクリロイル基含有化合物と反応させても、ポリオレフィンポリオールの水酸基の一部のみを、イソシアナト基を有する(メタ)アクリロイル基含有化合物と反応させて、一部の水酸基を残してもいっこうにかまわない。
ポリオレフィンポリオールの水酸基の全てをイソシアナト基を有する(メタ)アクリロイル基含有化合物と反応させる場合には、ポリオレフィンポリオールの水酸基の総数と、使用したイソシアナト基含有(メタ)アクリレートのイソシアナト基の総数の比が1以上である必要がある。
ポリオレフィンポリオールの水酸基の一部のみを、イソシアナト基を有する(メタ)アクリロイル基含有化合物と反応させて、一部の水酸基を残す場合には、ポリオレフィンポリオールの水酸基の総数より、使用したイソシアナト基含有(メタ)アクリレートのイソシアナト基の総数を少なく仕込む必要がある。
なお、この時イソシアナト基を有する(メタ)アクリロイル基含有化合物と反応せずにそのまま残るポリオレフィンポリオールが存在しうるが、このポリオレフィンポリオールは、成分(1)には含まれないものとする。ポリオレフィンポリオールが液状ポリブタジエンポリオール、液状ポリイソプレンポリオールである場合には、成分(5)に含まれる。
ウレタン結合を含有しないポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物の代表的な合成例として、ポリブタジエンジオールとアクリル酸エステルとのエステル交換反応、あるいはポリブタジエンジオールとアクリル酸との脱水縮合反応によって生成する(メタ)アクリレート化合物の構造式、およびポリイソプレンジオールとアクリル酸エステルとのエステル交換反応、あるいはポリイソプレンジオールとアクリル酸との脱水縮合反応によって生成する(メタ)アクリレート化合物の構造式を、それぞれ、式(2)および式(3)に示す。
水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物とは、1分子中に、水添ポリオレフィン構造単位と(メタ)アクリロイル基を有する化合物であれば、特に制限はない。水添ポリオレフィン構造単位としては、水添ポリジエン構造単位を有する化合物が好ましく、例えば、1,3-ブタジエン、1,3-ペンタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエン、2-フェニル-1,3-ブタジエン、2-プロピル-1,3-ブタジエン、1,3-ヘプタジエン、6-メチル-1,3-ヘプタジエン、1,3-ヘキサジエン、5-メチル-1,3-ヘキサジエン、2,4-ヘキサジエン、2,5-ジメチル-2,4-ヘキサジエンおよび1,3-オクタジエンから選ばれる1種以上のジエンを重合させて得られるポリジエン構造単位を水素化して得られる構造単位を挙げることができる。
これらの中で好ましいものとしては、ポリブタジエン構造単位を水素化して得られる構造単位、ポリイソプレン構造単位を水素化して得られる構造単位あるいはポリ(ブタジエン-イソプレン)構造単位を水素化して得られる構造単位である。
なお、NISSO-PB TEAI-1000は、NISSO-PB GI-1000(日本曹達株式会社製)等の水添ポリブタジエンポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有アクリレートの反応生成物である。このように、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物を製造するための原料として、水添ポリオレフィンポリオールは有用であり、これらの市販品としては、前述の水添ポリブタジエンポリオールの市販品であるNISSO PB GI-1000以外に、NISSO PB GI-2000、GI-3000(日本曹達株式会社製)以外に、水酸基末端液状水添ポリイソプレンであるエポール(出光興産株式会社製)等を挙げることができる。
まず、水添ポリオレフィンポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有(メタ)アクリレートを必須原料成分に用いて、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物を得る場合について説明する。
なお、水添ポリブタジエンポリオールとは、水酸基を含有するブタジエンのホモポリマーの水素化物である。水添ポリイソプレンポリオールは、水酸基を含有するイソプレンのホモポリマーの水素化物のことである。
本発明(I)の重合性組成物の必須成分である成分(1)は、その後の配合の自由度を考慮すると、粘度が低いことが望ましい。この目的に合致する有機ポリイソシアネート化合物としては、1,3-ビス(イソシアナトメチル)シクロヘキサン、1,4-ビス(イソシアナトメチル)シクロヘキサン、2,4,4-トリメチルヘキサメチレンジイソシアネート、2,2,4-トリメチルヘキサンメチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネートおよびノルボルナンジイソシアネートが好ましく、さらに好ましくは、1,3-ビス(イソシアナトメチル)シクロヘキサン、2,4,4-トリメチルヘキサメチレンジイソシアネートおよび2,2,4-トリメチルヘキサンメチレンジイソシアネートであり、最も好ましいのは、2,4,4-トリメチルヘキサメチレンジイソシアネートおよび2,2,4-トリメチルヘキサンメチレンジイソシアネートである。
これらの中で、本発明(I)の必須成分である成分1の重合速度を考慮すると、好ましいものとしては、2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレート、3-ヒドロキシプロピルアクリレート、2-ヒドロキシブチルアクリレート、4-ヒドロキシブチルアクリレート、2-ヒドロキシ-3-フェノキシプロピルアクリレート、2-ヒドロキシ-3-(o-フェニルフェノキシ)プロピルアクリレートである。イソシアネート基との反応性を考慮すると、2-ヒドロキシエチルアクリレート、3-ヒドロキシプロピルアクリレート、4-ヒドロキシブチルアクリレートが好ましく、最も好ましいのは、4-ヒドロキシブチルアクリレートである。
ただし、化合物の末端を、アルコール性水酸基含有(メタ)アクリレートを含む水酸基を分子中に1つ有する化合物でほぼ完全に封止される場合には、水添ポリオレフィンポリオールの使用数およびこの水添ポリオレフィンポリオール以外のポリオールの使用数を合わせたときの水酸基の総数より使用される有機ポリイソシアネート化合物のイソシアナト基の総数を多くする必要がある。
この場合には、水添ポリオレフィンポリオールの使用数およびこの水添ポリオレフィンポリオール以外のポリオールの使用数を合わせたときの水酸基の総数と、有機ポリイソシアネート化合物中のイソシアナト基の総数の比が、1.0に近いと分子量が大きくなり、1.0からずれて小さくなると分子量は小さくなる。
この比が1.5:1よりも小さい場合には、粘度が高くなりすぎる場合があり、好ましいこととは言えない。
ただし、この場合には、水添ポリオレフィンポリオールの使用数、この水添ポリオレフィンポリオール以外のポリオールの使用数およびアルコール性水酸基含有(メタ)アクリレートを含む水酸基を分子中に1つ有する化合物の使用数を合わせたときの水酸基の総数と、有機ポリイソシアネート化合物中のイソシアナト基の総数の比は、2:1以下であることが好ましい。
この比が2:1よりも大きい場合には、アクリロイル基を有さない分子が多くなり、重合後の重合物の形状保持性が悪化あることがあり、好ましいこととは言えない。
水添ポリオレフィンポリオールは前述の通りである。
上記の原料になり得るイソシアナト基を有する(メタ)アクリロイル基含有化合物としては、例えば、前述の2-イソシアナトエチルアクリレート、2-イソシアナトエチルメタクリレート等を挙げることができる。
なお、水添ポリオレフィンポリオールの水酸基の全てをイソシアナト基を有する(メタ)アクリロイル基含有化合物と反応させても、水添ポリオレフィンポリオールの水酸基の一部のみを、イソシアナト基を有する(メタ)アクリロイル基含有化合物と反応させて、一部の水酸基を残してもいっこうにかまわない。
水添ポリオレフィンポリオールの水酸基の全てをイソシアナト基を有する(メタ)アクリロイル基含有化合物と反応させる場合には、水添ポリオレフィンポリオールの水酸基の総数と、使用したイソシアナト基含有(メタ)アクリレートのイソシアナト基の総数の比が1以上である必要がある。
水添ポリオレフィンポリオールの水酸基の一部のみを、イソシアナト基を有する(メタ)アクリロイル基含有化合物と反応させて、一部の水酸基を残す場合には、水添ポリオレフィンポリオールの水酸基の総数より、使用したイソシアナト基含有(メタ)アクリレートのイソシアナト基の総数を少なく仕込む必要がある。
なお、この時イソシアナト基を有する(メタ)アクリロイル基含有化合物と反応せずにそのまま残る水添ポリオレフィンポリオールが存在しうるが、この水添ポリオレフィンポリオールは、成分(1)には含まれないものとする。この水添ポリオレフィンポリオールが液状水添ポリブタジエンポリオール、液状水添ポリイソプレンポリオールである場合には、後述の成分(2)の液状ポリブタジエンポリオール、液状ポリイソプレンポリオールに含まれる。
ウレタン結合を含有しない水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物の代表的な合成例として、水添ポリブタジエンジオールとアクリル酸エステルとのエステル交換反応、あるいは水添ポリブタジエンジオールとアクリル酸との脱水縮合反応によって生成する(メタ)アクリレート化合物の構造式、および水添ポリイソプレンジオールとアクリル酸エステルとのエステル交換反応、あるいは水添ポリイソプレンジオールとアクリル酸との脱水縮合反応によって生成する(メタ)アクリレート化合物の構造式を、それぞれ、式(4)および式(5)に示す。
(ポリ)エステル構造単位を有する(メタ)アクリロイル基含有化合物とは、1分子中に(ポリ)エステルポリオールから誘導された構造単位と、(メタ)アクロイル基を有する化合物であれば、特に制限はない。
(ポリ)エステル構造単位を有する(メタ)アクリロイル基含有化合物の原料になり得る(ポリ)エステルポリオールは、1分子中に1つ以上の-COO-結合(カルボン酸エステル結合)を有しかつ2つ以上のアルコール性水酸基を有する化合物であれば、特に制限はない。
炭素数8以上のポリオールとしては、1,4-シクロヘキサンジメタノール、1,2-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、2-メチル-1,1-シクロヘキサンジメタノール、トリシクロ[5.2.1.02,6]デカンジメタノール、1,9-ノナンジオール、2-メチル-1,8-オクタンジオール、1,10-デカジオール、1,12-トデカンジオール、ダイマージオール、水添ダイマージオール等を挙げることができる。
これらの炭素数8以上のポリオールの中で、特に好ましいものは、水添ダイマージオールである。
これらのポリカルボン酸としては、1,9-ノナンニ酸、セバシン酸、1,12-ドデカンニ酸、ダイマー酸、水添ダイマー酸等を挙げることができる。
カルボン酸構造(-COOH)中の炭素を除いた炭素数が7個以上であるポリカルボン酸の中で、特に好ましいものは、セバシン酸、1,12-ドデカンニ酸、水添ダイマー酸である。
例えば、式(6)および式(7)で表される構造の化合物を主成分とする水添ダイマー酸を還元して水添ダイマージオールを製造した場合には、水添ダイマージオールの主成分の構造は、以下の式(8)および式(9)で表される構造である。
上記エステル化反応は、水を除去するので、150~250℃程度の反応温度で反応を行うことが一般的である。反応時の圧力は、常圧または減圧条件下で反応することが一般的である。
上記エステル交換反応は、アルコールを除去するので、120~230℃程度の反応温度で反応を行うことが一般的である。反応時の圧力は、常圧または減圧条件下で反応することが一般的である。
即ち、(ポリ)エステルポリオール中に、8質量%の原料ポリオールが残存している場合、このポリオールも(ポリ)エステルポリオールに含まれることを意味する。
即ち、(ポリ)エステルポリオールの原料ポリオール成分に水添ダイマージオールを使用して、(ポリ)エステルポリオールを合成した際に、合成品100質量部中に8質量部の原料である水添ダイマージオールが残存し、さらに、水添ダイマージオール5質量部を加えて成分(1)が製造された場合、成分(1)の合成の際に残存した原料水添ダイマージオール、およびその後加えた水添ダイマージオールもともに(ポリ)エステルポリオールに含まれることを意味する。
(ポリ)エステルポリオールは、前述の通りである。
有機ポリイソシアネート化合物は、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物や添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物の原料成分で説明した有機ポリイソシアネート化合物と同様のものである。
アルコール性水酸基含有(メタ)アクリレートも、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物や添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物の原料成分で説明したと同様のものである。
また、その合成法も、ポリオレフィンポリオールと(ポリ)エステルポリオールを置き換えることによって、前述の、ポリオレフィンポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有(メタ)アクリレートを必須原料成分に用いて、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物を得る場合についての説明の際に記載した方法と同様の方法により製造することができる。
(ポリ)エステルポリオールは、前述の通りである。
上記の原料になり得るイソシアナト基を有する(メタ)アクリロイル基含有化合物としては、例えば、前述の2-イソシアナトエチルアクリレート、2-イソシアナトエチルメタクリレート等を挙げることができる。
(ポリ)エステルポリオールおよび1分子中に1つイソシアナト基を有する(メタ)アクリロイル基含有化合物を必須原料成分に用いて、(ポリ)エステル構造単位を有する(メタ)アクリロイル基含有化合物を得る方法は、ポリオレフィンポリオールを(ポリ)エステルポリオールに置き換えることによって、前述のポリオレフィンポリオールおよび1分子中に1つイソシアナト基を有する(メタ)アクリロイル基含有化合物を必須原料成分に用いて、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物を得る方法と同様の方法により行うことができる。
(ポリ)カーボネート構造単位を有する(メタ)アクリロイル基含有化合物とは、1分子中に、(ポリ)カーボネートポリオールから誘導された構造単位と、(メタ)アクロイル基を有する化合物であれば、特に制限はない。1分子中に1つ以上の(メタ)アクリロイル基と1つ以上のウレタン結合が共に含有してもよい。また、原料になり得る(ポリ)カーボネートポリオールは、1分子中に1つ以上のカーボネート結合(-OCOO-)を有しかつ2つ以上のアルコール性水酸基を有する化合物であれば、特に制限はない。
炭素数8以上のポリオールとしては、1,4-シクロヘキサンジメタノール、1,2-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、2-メチル-1,1-シクロヘキサンジメタノール、トリシクロ[5.2.1.02,6]デカンジメタノール、1,9-ノナンジオール、2-メチル-1,8-オクタンジオール、1,10-デカジオール、1,12-トデカンジオール、ダイマージオール、水添ダイマージオール等を挙げることができる。これらの炭素数8以上のポリオールの中で、さらに好ましいものは、1,10-デカジオール、1,12-トデカンジオール、水添ダイマージオールであり、最も好ましいものは、水添ダイマージオールである。
上記エステル交換反応は、アルコールを除去するので、80~230℃程度の反応温度で反応を行うことが一般的である。反応時の圧力は、常圧または減圧条件下で反応することが一般的である。
上記の反応は、100℃以下の反応温度で反応を行うことが一般的であり、塩酸が発生するので、塩基を用いて塩酸をトラップすることが一般的である。
即ち、(ポリ)カーボネートポリオール中に、原料であるポリオールが8質量%残存している場合、この残存ポリオールは(ポリ)エステルポリオールには含まれることを意味する。
(ポリ)カーボネートポリオールは、前述の通りである。
有機ポリイソシアネート化合物は、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物や水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物の原料成分で説明した有機ポリイソシアネート化合物と同様のものである。
アルコール性水酸基含有(メタ)アクリレートも、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物や水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物の原料成分で説明したと同様のものである。
(ポリ)カーボネートポリオールは前述の通りである。
上記の原料になり得るイソシアナト基を有する(メタ)アクリロイル基含有化合物としては、例えば、前述の2-イソシアナトエチルアクリレート、2-イソシアナトエチルメタクリレート等を挙げることができる。
(ポリ)カーボネートポリオールおよび1分子中に1つイソシアナト基を有する(メタ)アクリロイル基含有化合物を必須原料成分に用いて、(ポリ)カーボネート構造単位を有する(メタ)アクリロイル基含有化合物を得る方法は、ポリオレフィンポリオールを(ポリ)カーボネートポリオールに置き換えることによって、前述のポリオレフィンポリオールおよび1分子中に1つイソシアナト基を有する(メタ)アクリロイル基含有化合物を必須原料成分に用いて、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物を得る方法と同様の方法により行うことができる。
成分(2)は、液状(メタ)アクリロイル基含有化合物であり、成分(1)以外のものであれば、特に制限はない。例えば、鎖状脂肪族炭化水素基を有する(メタ)アクリロイル基含有化合物、環状脂肪族基を有する(メタ)アクリロイル基含有化合物、芳香環構造を有する(メタ)アクリロイル基含有化合物、複素環構造を有する(メタ)アクリロイル基含有化合物等を挙げることができる。
アルコール性水酸基を有する(メタ)アクリロイル基含有化合物の具体例としては、例えば、2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレート、3-ヒドロキシプロピルアクリレート、2-ヒドロキシブチルアクリレート、4-ヒドロキシブチルアクリレート、2-ヒドロキシ-3-フェノキシプロピルアクリレート、2-ヒドロキシ-3-(o-フェニルフェノキシ)プロピルアクリレート、2-ヒドロキシエチルアクリルアミド、2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルメタクリレート、3-ヒドロキシプロピルメタクリレート、2-ヒドロキシブチルメタクリレート、4-ヒドロキシブチルメタクリレート、2-ヒドロキシ-3-フェノキシプロピルメタクリレート、2-ヒドロキシ-3-(o-フェニルフェノキシ)プロピルメタクリレート等を挙げることができる。
成分(3)は、液状水添ポリブタジエンポリオール、液状水添ポリイソプレンポリオールおよび水添ダイマージオールからなる群より選ばれる少なくとも1種である。
水添ダイマージオールは、上記で説明してあるので、ここでは省略する。
本発明(I)の必須成分である成分(4)は、光重合開始剤である。
成分(4)の光重合開始剤は、近赤外線、可視光線、紫外線等の光の照射により、ラジカル重合の開始に寄与するラジカルを発生する化合物であれば、特に制限はない。
成分(5) 水添ポリブタジエン、水添ポリイソプレン、ポリ(α-オレフィン)液状物、エチレン-プロピレン共重合液状物、プロピレン-α-オレフィン共重合液状物、エチレン-α-オレフィン共重合液状物、液状ポリブテン、液状水添ポリブテン、液状ポリブタジエン、液状水添ポリブタジエン、液状ポリイソプレン、液状水添ポリイソプレン、液状ポリブタジエンポリオール、および液状ポリイソプレンポリオールからなる群より選ばれる少なくとも1種
成分(6) 水添石油樹脂、テルペン系水添樹脂、および水添ロジンエステルからなる群より選ばれる少なくとも1種
水添ロジンエステルとは、ロジン系樹脂を水添して得られる水添ロジンをエステル化あるいはロジンをエステル化して得られるロジンエステルを水素還元して得られた樹脂である。ロジン系樹脂粘着付与剤としては、ガムロジン、トール油ロジン、ウッドロジン、不均化ロジン、重合ロジン、マレイン化ロジンなどの変性ロジンなどが挙げられる。
本発明(I)の重合性組成物の25℃における粘度は、特に制限はないが、ハンドリング上、10000mPa・s以下であることが好ましく、さらに好ましくは、7000mPa・s以下であり、特に好ましくは、5000mPa・s以下である。
25℃における、本発明(I)の重合性組成物の粘度が1000mPa・s以下にすると、本発明(I)の重合性組成物をディスペンサーを用いた線引き塗布法で塗布する場合には、塗布後、液の広がりが容易になり、その結果、必要箇所に均一の厚みで該組成物がいきわたることが容易になり、さらに、気泡の巻き込みが抑制されやすくなる。
これらは単独でも、あるいは2種以上を適宜組み合わせて使用することができる。
本発明(II)は、本発明(I)に記載の重合性組成物を重合して得られる重合物である。
本発明(II)の重合物は、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプ、LED等を光源として、光重合開始剤が感光可能な光を、ガラスやプラスチックの基材を介して照射して、重合性組成物を重合することにより得られるものである。
なお、本明細書に記載の引張弾性率は、500mm/minの引張速度で試験を行ったときの値である。
本発明(III)は、本発明(I)の重合性組成物を塗布し、光重合開始剤が感光可能な光を該組成物に照射して、重合させることによって得られる、厚さ10~500μmの重合物層を有する光学用粘着シートである。
本発明(III)の光学用粘着シートは、シートの両面が粘着面(粘着剤層表面)となっている両面粘着シートであってもよいし、シートの片面のみが粘着面(粘着剤層表面)となっている片面粘着シートであってもよい。中でも、2つの部材同士を貼り合わせる観点からは、両面粘着シートであることが好ましい。なお、本明細書において、「粘着シート」という場合には、テープ状のもの、即ち、「粘着テープ」も含まれるものとする。
本発明(III)の光学用粘着シートの重合物層の形成方法は、公知あるいは慣用の重合物層の形成方法を用いることが可能であり、特に限定されないが、本発明の重合性組成物のようなアクリロイル基を有する重合性組成物を重合させて、光学用粘着シートの重合物層を形成させる場合には、例えば、以下の(1)~(3)などの方法が挙げることができる。
(1)光重合開始剤を含むアクリロイル基を有する重合性組成物に、必要に応じて添加剤を含む組成物を、基材またはセパレータ(剥離ライナー)上に塗布(塗工)し、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプ、LED等の光源を用いて、光重合開始剤が感光可能な光を照射して、該組成物を重合することにより重合物層を形成する。
(2)光重合開始剤を含むアクリロイル基を有する重合性組成物に、さらに溶剤、必要に応じて添加剤を含む組成物(溶液)を、基材またはセパレータ(剥離ライナー)上に塗布(塗工)し、乾燥および低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプ、LED等の光源を用いて、光重合開始剤が感光可能な光を照射して、該組成物を重合することにより重合物層を形成する。
(3)上記(1)で形成した重合物層をさらに乾燥させる。
なお、上記の重合物層の形成方法における塗布(塗工)には、公知のコーティング法を用いることが可能であり、慣用のコーター、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーターなどを用いることができる。
本発明(III)の光学用粘着シートが基材を有する場合、基材としては、特に制限されないが、プラスチックフィルム、反射防止(AR)フィルム、偏光板、位相差板などの各種光学フィルムが挙げられる。上記プラスチックフィルムなどの素材としては、例えば、ポリエチレンテレフタレート(PET)等の(ポリ)エステル系樹脂、ポリメチルメタクリレート(PMMA)等のアクリル系樹脂、(ポリ)カーボネート、トリアセチルセルロース(TAC)、ポリサルフォン、ポリアリレート、ポリイミド、ポリ塩化ビニル、ポリ酢酸ビニル、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、商品名「アートン(環状オレフィン系ポリマー;JSR製)」、商品名「ゼオノア(環状オレフィン系ポリマー;日本ゼオン製)」等の環状オレフィン系ポリマーなどのプラスチック材料が挙げられる。なお、プラスチック材料は単独で、または2種以上を組み合わせて使用することができる。また、上記の「基材」とは、光学用粘着シートを被着体(光学部材等)に使用(貼付)する際には、粘着剤層とともに被着体に貼付される部分である。粘着シートの使用時(貼付時)に剥離されるセパレータ(剥離ライナー)は「基材」には含まない。
上記の中でも、基材としては、透明基材が好ましい。上記「透明基材」とは、例えば、可視光波長領域における全光線透過率(JIS K7361に準じる)が85%以上である基材が好ましく、さらに好ましくは88%以上である基材をいう。また、基材のヘーズ(JIS K7361に準じる)は、例えば、1.5%以下が好ましく、より好ましくは1.0%以下である。上記透明基材としては、PETフィルムや、商品名「アートン」、商品名「ゼオノア」などの無配向フィルムなどが挙げられる。
上記基材の厚さは、特に限定されず、例えば、12~75μmが好ましい。なお、上記基材は単層および複層のいずれの形態を有していてもよい。また、基材表面には、例えば、コロナ放電処理、プラズマ処理等の物理的処理、下塗り処理等の化学的処理などの公知慣用の表面処理が適宜施されていてもよい。
本発明(III)の光学用粘着シートが基材を有する場合、基材としては各種の機能性フィルムを用いることができる。その場合、本発明の粘着シートは、機能性フィルムの少なくとも片面に本発明の粘着剤層を有する粘着型機能性フィルムとなる。上記の機能性フィルムとしては、特に限定されないが、例えば、光学的機能性(偏光性、光屈折性、光反射性、光透過性、光吸収性、光回折性、旋光性、視認性など)を有するフィルム、導電性を有するフィルム(ITOフィルムなど)、紫外線カット性を有するフィルム、ハードコート性(耐傷付き性)を有するフィルム等が挙げられる。さらに具体的には、ハードコートフィルム(PETフィルムなどのプラスチックフィルムの少なくとも片面にハードコート処理が施されたフィルム)、偏光フィルム、波長板、位相差フィルム、光学補償フィルム、輝度向上フィルム、導光板、反射フィルム、反射防止フィルム、透明導電フィルム(ITOフィルムなど)、意匠フィルム、装飾フィルム、表面保護フィルム、プリズム、カラーフィルターなどが挙げられる。なお、上記の「板」および「フィルム」は、それぞれ板状、フィルム状、シート状等の形態を含むものとし、たとえば、「偏光フィルム」は、「偏光板」、「偏光シート」も含むものとする。また、「機能性フィルム」は「機能性板」、「機能性シート」を含むものとする。
また、本発明(III)の光学用粘着シートが、他の粘着剤層を有する場合、他の粘着剤層としては、特に制限されず、例えば、ウレタン系粘着剤、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、(ポリ)エステル系粘着剤、ポリアミド系粘着剤、エポキシ系粘着剤、ビニルアルキルエーテル系粘着剤、フッ素系粘着剤などの公知の粘着剤から形成された公知慣用の粘着剤層が挙げられる。上記粘着剤は単独で、または2種以上を組み合わせて用いることができる。
なお、本発明(III)の光学用粘着シートにおいては、基材も他の粘着剤層も含まない場合には、本発明(I)の重合性組成物を重合して得られる重合物層、また、他の粘着剤層を含む場合には、本発明(I)の重合性組成物を重合して得られる重合物層と、この他の粘着剤層を合わせた層、また、基材を含む場合には本発明(I)の重合性組成物を重合して得られる重合物層と、この基材を合わせた層、また、他の粘着剤層と基材をともに含む場合には、本発明(I)の重合性組成物を重合して得られる重合物層、他の粘着剤層および基材を合わせた層を「粘着剤層」と定義する。
本発明(III)の光学用粘着シートの粘着剤層表面(粘着面)は、使用時まではセパレータ(剥離ライナー)により保護されていてもよい。なお、本発明の光学用粘着シートが両面粘着シートである場合、各粘着面は、2枚のセパレータによりそれぞれ保護されていてもよいし、両面が剥離面となっているセパレータ1枚により、ロール状に巻回される形態で保護されていてもよい。セパレータは粘着剤層の保護材として用いられており、被着体に貼付する際に剥がされる。また、本発明の粘着シートが基材レス粘着シートの場合には、セパレータは粘着層の支持体の役割も担う。なお、セパレータは必ずしも設けられていなくてもよい。上記セパレータとしては、慣用の剥離紙などを使用でき、特に限定されないが、例えば、剥離処理層を有する基材、フッ素ポリマーからなる低接着性基材や無極性ポリマーからなる低接着性基材などを用いることができる。上記剥離処理層を有する基材としては、例えば、シリコーン系、長鎖アルキル系、フッ素系、硫化モリブデン等の剥離処理剤により表面処理されたプラスチックフィルムや紙等が挙げられる。上記フッ素ポリマーからなる低接着性基材におけるフッ素系ポリマーとしては、例えば、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン-フッ化ビニリデン共重合体等が挙げられる。また、上記無極性ポリマーとしては、例えば、オレフィン系樹脂(例えば、ポリエチレン、ポリプロピレンなど)等が挙げられる。なお、セパレータは公知乃至慣用の方法により形成することができる。また、セパレータの厚さ等も特に制限されない。
本発明(IV)は、画像表示部を有する基部と、透光性の保護部と、前記基部と前記保護部との間に介在する重合物層とを含む画像表示装置の製造方法であって、該方法が本発明(I)の重合性組成物を前記基部と前記保護部との間に介在させる工程、および光重合開始剤が感光可能な光を前記重合性組成物に照射して重合物層を形成する工程を含むことを特徴とする画像表示装置の製造方法である。
なお、本明細書に記載の「前記基部と前記保護部との間」とは、画像表示部を有する基部と透光性の保護部との間の全て部分を意味し、例えば、図2の5aと5bのいずれの場所も「前記基部と前記保護部との間」という表現に含まれることを意味する。
例えば、図1、図2および図4は、本発明に係る画像表示装置の一実施形態の要部を示す断面図である。
図1、図2および図4に示すように、本実施の形態の画像表示装置1は、図示しない駆動回路に接続され、所定の画像表示を行う画像表示部2と、この画像表示部2に所定の距離をおいて近接対向配置された透光性の保護部3とを有している。
なお、本明細書に記載の「画像表示装置」としては、画像を表示する装置であれば、特に限定されるものではなく、種々のものに適用することができる。例えば、携帯電話、携帯ゲーム機器等の液晶表示装置あるいは有機EL表示装置があげられる。本実施形態の画像表示部2は、液晶表示装置の液晶表示パネルである。
なお、画像表示部2が液晶表示パネルである場合には、図2あるいは図4に示すように、その表面に偏光板6a、6bが設けられている。
そして、画像表示部(液晶表示パネル)2のスペ-サ4上に保護部3を配置し、画像表示部(液晶表示パネル)2と保護部3との間の空隙に、本発明(I)の重合性組成物を隙間なく充填する。
その後、保護部3を介して、本発明(I)の重合性組成物に対して、本発明(I)の重合性組成物の必須成分である成分(4)が感光可能な光を照射することにより、本発明(I)の重合性組成物を重合させる。これにより、目的とする画像表示装置1を得る。
また、画像表示部(液晶表示パネル)2および保護部3に対し、重合性組成物の重合時の体積収縮により引き起こされる応力の影響を最小限に抑えることができるので、液晶表示パネル2および保護部3において歪みがほとんど発生せず、その結果、画像表示部(液晶表示パネル)2に変形が発生しないので、表示不良のない高輝度および高コントラストの画像表示が可能になる。
また、図2や図4の5bの重合物層に本発明(II)の重合物が用いられた場合には、5bの重合物層の重合物の誘電率は低く維持されるので、この重合物層の厚みを薄くしても、画像表示装置の誤作動を防止することができ、画像表示装置の薄型化に寄与できる。
本発明(V)は、画像表示部を有する基部と透光性の保護部との間に光学用粘着シートを用いて重合物層を貼り付ける工程を有する画像表示装置の製造方法であって、該光学用粘着シートが、本発明(III)の光学用粘着シートであることを特徴とする画像表示装置の製造方法である。
なお、本明細書に記載の「画像表示部を有する基部と透光性の保護部との間に光学用粘着シートを用いて重合物層を貼り付ける」とは、画像表示部を有する基部と透光性の保護部との間のいずれの部分を貼り付けても、「画像表示部を有する基部と透光性の保護部とを光学用粘着シートを用いて重合物層を貼り付ける」という表現に含まれることを意味し、例えば、図2の5aと5bのどちらに粘着シートを用いて貼り付けても、「画像表示部を有する基部と透光性の保護部とを光学用粘着シートを用いて貼り付ける」という表現に含まれることを意味する。
本発明(III)の光学用粘着シートを、第1の基材であるタッチセンサー一体型保護部のタッチセンサー搭載面側で隣接させて配置する工程と、第2の基材である偏光板付きの表示部の表面を本発明(III)の光学用粘着シートと隣接させて配置する工程と、本発明(III)の光学用粘着シートを加熱および/または加圧して段差または隆起に追従させる工程と、さらに、必要に応じて本発明(III)の光学用粘着シートに光重合開始剤が感光可能な光を照射する工程を含む方法によって製造することができる。これらの工程は様々な順序で行うことができる。
本発明(VI)は、本発明(IV)または本発明(V)に記載の方法によって製造された画像表示装置である。
本発明(VI)の画像表示装置は、表示装置の本体が光学ガラスから形成されている場合、一般的にその屈折率(nD)は、1.49~1.52となる。なお、屈折率(nD)が、1.55程度の強化ガラスも存在する。
保護部3は、画像表示部2と同程度の大きさの板状、シート状またはフィルム状の透光性部材から形成されている。この透光性部材としては、例えば、光学ガラスやプラスチック(ポリメタクリル酸メチル等のアクリル樹脂等)を好適に用いることができる。保護部3の表面もしくは裏面には、反射防止膜、遮光膜、視野角制御膜等の光学層を形成してもよい。
保護部3がアクリル樹脂から形成されている場合には、一般的にその屈折率(nD)は1.49~1.51となる。
保護部3は、画像表示部2の周縁部に設けられたスペ-サ4を介して画像表示部2上に設けられている。このスペ-サ4の厚さは0.05~1.5mm程度であり、これにより画像表示部2と保護部3との表面間距離が1mm程度に保持される。
また、保護部3の周縁部には、輝度およびコントラストを向上させるため、図示しない枠状の遮光部が設けられている。
画像表示部2と保護部3との間には、重合物層5a、5bが介在している。本発明(IV)の画像表示装置の製造方法によって製造された画像表示装置の場合には、この重合物層5aや重合物層5bには、本発明(II)の重合物が介在するため、可視光領域の透過率が90%以上になる。ここで、重合物層5aや重合物層5bの厚みは10~500μmとなるようにすることが好ましい。さらに好ましくは、10~350μmであり、特に好ましくは、10~300μmである。
また、重合物層5aや重合物層5bには、本発明(II)の重合物が介在するため、25℃における屈折率(nD)は、1.45~1.55、好ましくは、1.48~1.52になるので、画像表示部2や保護部3の屈折率とほぼ同等になるので好ましい。これにより、画像表示部2からの映像光の輝度やコントラストを高め、視認性を向上させることができる。
本発明(IV)の画像表示装置の製造方法によって画像表示装置を製造する場合、重合物層5aや重合物層5bには、本発明(II)の重合物が介在するため、23℃における引張弾性率を、1×107Pa以下、好ましくは、1×103~1×106Paになる。従って、画像表示部および保護部に対して、重合性組成物の重合時に体積収縮に起因する応力の影響による歪みの発生を防止することができる。
本発明(IV)の画像表示装置の製造方法によって画像表示装置を製造する場合、重合物層5aや重合物層5bには、本発明(I)の重合物が介在するため、重合性組成物の重合時の体積収縮率が、4.0%以下、好ましくは3.5%以下、さらに好ましくは2.7%以下になる。これにより、重合性組成物が重合する際に重合物層に蓄積される内部応力を低減させることができ、重合物層5aとタッチパネル7または保護部3との界面や、重合物層5bとタッチパネル7、画像表示部2あるいは保護部3との界面に歪みができることを防止できる。したがって、重合性組成物を、タッチパネル7と保護部3との間、タッチパネル7と画像表示部2との間、あるいは画像表示部2と保護部3との間に介在させ、その重合性組成物を重合させた場合に、重合物層5と画像表示部2、保護部3、タッチパネル7との界面で生じる光の散乱を低減させることができ、表示画像の輝度を高めると共に、視認性を向上させることができる。
また、本発明(I)の重合物を重合物層5bに用いる場合には、これらの重合物の誘電率が低いので、重合物層5bの厚みを薄くすることができる。
画像表示部2と保護部3との間には、重合物層5a、5bが介在している。本発明(V)の画像表示装置の製造方法によって製造された画像表示装置の場合には、この重合物層5aや重合物層5bには、本発明(III)の光学用粘着シートが介在するため、可視光領域の透過率が90%以上になる。ここで、重合物層5aや重合物層5bの厚みは10~500μmとなるようにすることが好ましい。さらに好ましくは、10~350μmであり、特に好ましくは、10~300μmである。
また、重合物層5aや重合物層5bには、本発明(III)の光学用粘着シートが介在するため、25℃における屈折率(nD)は、1.45~1.55、好ましくは、1.48~1.52になるので、画像表示部2や保護部3の屈折率とほぼ同等になるので好ましい。これにより、画像表示部2からの映像光の輝度やコントラストを高め、視認性を向上させることができる。
また、本発明(V)の画像表示装置の製造方法によって画像表示装置を製造する場合、重合物層5aや重合物層5bには、本発明(III)の光学用粘着シートが介在するため、画像表示部や保護部の段差や隆起にも当該粘着シートを追従させて、それらの形状近傍においても空隙の形成を防止することができる。
また、本発明(III)の光学用粘着シートは柔軟性を有するので、保護部3や画像表示部2、タッチパネル7が凹凸形状を有していても、さらには、画像表示ユニットの表示面に凹凸表面形状を有する層(例えば、偏光板)が設けられていたとしても、シート自体の内部残留応力が緩和されており、画像表示装置における表示ムラを防止することができる。例えば、図4の表示装置の場合、光学用粘着シートは充分な接着力および親水性を有しているため、高温高湿環境下でも、画像表示部2の表示面(例えば、偏光板)と光学用粘着シート(即ち、重合物層5b)との界面、および光学用粘着シート(即ち、重合物層5b)とタッチセンサー一体型保護部3aとの界面で気泡や剥がれが発生せず、また、白化も生じない。
加えて、画像表示部2と保護部3との間に空隙を設けていた従来例に比して薄型に形成することができる。
また、本発明(VI)の画像表示装置は種々の態様をとることができる。例えば、図3や図5に示すように、スペーサ4を省略して画像表示装置1を製造してもよい。図3の重合物層5bの場合には、例えば、画像表示部2上の偏光板6a上に、本発明(I)の光重合性組成物を塗布し、その上にタッチパネル7を重ね、前述と同様に光重合を行うか、あるいは、例えば、保護部3、重合物層5a、タッチパネル7および重合物層5b(即ち、光学用粘着シート5b)からなる積層体を画像表示部2上の表示面(即ち、偏光板6a表面)に貼り合わせることで得られる。
また、図5の重合物層5bの場合には、例えば、画像表示部2上の偏光板6a上に、本発明(I)の光重合性組成物を塗布し、その上にタッチセンサー一体型保護部3aを重ね、前述と同様に光重合を行うか、あるいは、例えば、タッチセンサー一体型保護部3aおよび重合物層5b(即ち、光学用粘着シート5b)からなる積層体を画像表示部2上の表示面(即ち、偏光板6a表面)に貼り合わせることで得られる。
また、本発明は、上述した液晶表示装置のみならず、例えば、有機EL、プラズマディスプレイ装置等の種々のパネルディスプレイに適用することができる。
粘度は以下の方法により測定した。
試料1mLを使用して、コーン/プレート型粘度計(Brookfield社製、型式:DV-II+Pro、スピンドルの型番:CPE-42)を用いて、温度25.0℃、回転数10rpmの条件で粘度がほぼ一定になったときの値を測定した。
数平均分子量は下記条件でGPCにより測定したポリスチレン換算の値である。
装置名:日本分光株式会社製HPLCユニット HSS-2000
カラム:ShodexカラムLF-804
移動相:テトラヒドロフラン
流速:1.0mL/min
検出器:日本分光株式会社製 RI-2031Plus
温度:40.0℃
試料量:サンプルループ 100μL
試料濃度:0.5wt%前後に調製
コンデンサー、滴下ロート、温度計および撹拌機付きの300mLセパラブルフラスコに、ポリブタジエンポリオール(日本曹達株式会社製 商品名:NISSO-PB G-2000 水酸基価47.3mgKOH/g)180g、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)1.17gおよびジオクチル錫ジラウレート20mgを入れ、オイルバスを用いて、内温を50℃に昇温した。その後、2-イソシアナトエチルメタクリレート(商品名;カレンズMOI 昭和電工株式会社製)22.86gを滴下ロートから15分かけて滴下した。滴下している間、内温が70℃を超えないようにした。滴下終了後、70±2℃の内温を管理して、撹拌を継続した。赤外吸収スペクトルでイソシアネート基のC=O伸縮振動の吸収が見られなくなったので、撹拌を止め反応を終了し、ウレタン基を含有するポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物1を得た。
撹拌機および蒸留装置のついた1リットル四口フラスコに、ポリブタジエンポリオール(日本曹達株式会社製 商品名:NISSO-PB G-3000 水酸基価29.5mgKOH/g)540.0g、アクリル酸n-ブチル101g、ジオクチル錫ジラウレート0.81gおよびペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)3.51gを投入し、空気気流下で、130℃に加熱して生成してくるn-ブタノールおよびアクリル酸n-ブチルの混合液を還流しながら、10時間程度かけて徐々に反応系外に留去した。n-ブタノールおよびアクリル酸n-ブチルが出なくなった後、真空ポンプを用いて、反応系内を10kPaまで減圧にし、再度n-ブタノールとアクリル酸n-ブチルを系外に留去した。1.5時間程度50Pa保持した後、反応器を冷却して、ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物2を得た。
攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた100mLの反応容器に、2,2,4-トリメチルヘキサメチレンジイソシアネートと2,4,4-トリメチルヘキサメチレンジイソシアネートの混合物(商品名:VESTANAT(登録商標) TMDI エボニックデグサ製)23.93g、ジオクチル錫ジラウレート11mgおよびペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)5.74gを反応容器に投入し、4-ヒドロキシブチルアクリレート16.41gを滴下ロートで滴下投入した。滴下中、反応容器内の温度は70℃以下になるようにした。滴下終了後、2時間、反応器内の温度を65~70℃に維持したまま、撹拌を継続して反応生成物(以下、反応生成物αと記す。)を得た。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に、ポリイソプレンポリオール(出光興産株式会社製 商品名:Poly ip 水酸基価47.3mgKOH/g)150gおよびジオクチル錫ジラウレート12mgを投入し、撹拌を開始した。その後、60℃に温度を維持した反応生成物α46.1gを数回に分けて反応容器内に投入した。その間、反応器内の温度は、70℃より高くならないようにした。その後、反応器内の温度を65~70℃に維持して撹拌を継続した。IRでイソシアナト基のC=O伸縮振動の吸収がなくなったことを確認して反応を終了した。液体クロマトグラフィーで分析した結果、生成物中に、4-ヒドロキシブチルアクリレート:VESTANAT(登録商標) TMDI=2:1(モル比)の反応生成物(即ち、下記式(10)と下記式(11)の混合物)が3質量%存在することが確認された。この4-ヒドロキシブチルアクリレート:VESTANAT(登録商標) TMDI=2:1(モル比)の反応生成物をウレタンアクリレートモノマーαとする。また、反応生成物から前記ウレタンアクリレートモノマーαを除いたものをウレタン基を含有するポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物3とする。
コンデンサー、滴下ロート、温度計および撹拌機付きの300mLセパラブルフラスコに、水添ポリブタジエンポリオール(日本曹達株式会社製 商品名:NISSO-PB GI-2000 水酸基価47.3mgKOH/g)180g、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)1.17gおよびジオクチル錫ジラウレート20mgを入れ、オイルバスを用いて、内温を50℃に昇温した。その後、2-イソシアナトエチルメタクリレート(商品名;カレンズMOI 昭和電工株式会社製)22.86gを滴下ロートから15分かけて滴下した。滴下している間、内温が70℃を超えないようにした。滴下終了後、70±2℃の内温を管理して、撹拌を継続した。赤外吸収スペクトルでイソシアネート基のC=O伸縮振動の吸収が見られなくなったので、撹拌を止め反応を終了し、ウレタン基を含有する水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物4を得た。
撹拌機および蒸留装置のついた1リットル四口フラスコに、水添ポリブタジエンポリオール(日本曹達株式会社製 商品名:NISSO-PB GI-3000 水酸基価29.5mgKOH/g)540.0g、アクリル酸n-ブチル101g、ジオクチル錫ジラウレート0.81gおよびペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)3.51gを投入し、空気気流下で、130℃に加熱して生成してくるn-ブタノールおよびアクリル酸n-ブチルの混合液を還流しながら、10時間程度かけて徐々に反応系外に留去した。n-ブタノールおよびアクリル酸n-ブチルが出なくなった後、真空ポンプを用いて、反応系内を10kPaまで減圧にし、再度n-ブタノールとアクリル酸n-ブチルを系外に留去した。1.5時間程度50Pa保持した後、反応器を冷却して、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物5を得た。
攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた100mLの反応容器に、2,2,4-トリメチルヘキサメチレンジイソシアネートと2,4,4-トリメチルヘキサメチレンジイソシアネートの混合物(商品名:VESTANAT(登録商標) TMDI エボニックデグサ製)23.93g、ジオクチル錫ジラウレート11mgおよびペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)5.74gを反応容器に投入し、4-ヒドロキシブチルアクリレート16.41gを滴下ロートで滴下投入した。滴下中、反応容器内の温度は70℃以下になるようにした。滴下終了後、2時間、反応器内の温度を65~70℃に維持したまま、撹拌を継続して反応生成物αを得た。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に水添ポリイソプレンポリオール(出光興産株式会社製 商品名:エポール 水酸基価47.3mgKOH/g)150gおよびジオクチル錫ジラウレート12mgを投入し、撹拌を開始した。その後、60℃に温度を維持した反応生成物α46.1gを数回に分けて反応容器内に投入した。その間、反応器内の温度は、70℃より高くならないようにした。その後、反応器内の温度を65~70℃に維持して撹拌を継続した。IRでイソシアナト基のC=O伸縮振動の吸収がなくなったことを確認して反応を終了した。液体クロマトグラフィーで分析した結果、実施合成例3と同様に生成物中に、4-ヒドロキシブチルアクリレート:VESTANAT(登録商標) TMDI=2:1(モル比)の反応生成物(即ち、上記式(I)と上記式(II)の混合物)が3質量%存在することが確認された。この4-ヒドロキシブチルアクリレート:VESTANAT(登録商標) TMDI=2:1(モル比)の反応生成物をウレタンアクリレートモノマーαとする。また、反応生成物から前記ウレタンアクリレートモノマーαを除いたものをウレタン基を含有する水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物6とする。
攪拌機、水分離器付き反応容器中にSovermol(登録商標)908(BASF製水添ダイマージオール、水添ダイマージオール純度97.5質量%)270.0g、EMPOL(登録商標)1008(BASF製水添ダイマー酸、水添ダイマー酸純度92.0%%)171.0gおよびジオクチル錫ジラウレート100mgを仕込み、約240℃ 、常圧下から始めて縮合水を流出させながら減圧しつつ脱水エステル化反応を行い、水酸基価59mgKOH/g、数平均分子量2000で、水添ダイマージオールを15質量%含む、ポリエステルポリオールと水添ダイマージオールの混合物(以下、「ポリエステルポリオールA」と記す。)を得た。
攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた100mLの反応容器に、2,2,4-トリメチルヘキサメチレンジイソシアネートと2,4,4-トリメチルヘキサメチレンジイソシアネートの混合物(商品名:VESTANAT(登録商標) TMDI エボニックデグサ製)21.89g、ジオクチル錫ジラウレート12mgおよびペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)5.74gを反応容器に投入し、4-ヒドロキシブチルアクリレート15.16gを滴下ロートを用いて滴下投入した。滴下中、反応容器内の温度は70℃以下になるようにした。滴下終了後、2時間、反応器内の温度を65~70℃に維持したまま、撹拌を継続して反応生成物(以下、反応生成物αと記す。)を得た。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に、前述の(ポリ)エステルポリオールA 180.0gおよびジオクチル錫ジラウレート12mgを投入し、撹拌を開始した。その後、60℃に温度を維持した反応生成物α33.7gを数回に分けて反応容器内に投入した。その間、反応器内の温度は、70℃より高くならないようにした。その後、反応器内の温度を65~70℃に維持して撹拌を継続した。IRでイソシアナト基のC=O伸縮振動の吸収がなくなったことを確認して反応を終了した。液体クロマトグラフィーで分析した結果、実施合成例3と同様に生成物中に、4-ヒドロキシブチルアクリレート:VESTANAT(登録商標) TMDI=2:1(モル比)の反応生成物αが3質量%存在することが確認された。反応生成物から前記ウレタンアクリレートモノマーαを除いたものをウレタン基を含有するポリエステル構造単位を有する(メタ)アクリロイル基含有化合物7とする。
攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた300mLの反応容器に、前述の(ポリ)エステルポリオールA180.0g、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)5.74gおよびジオクチル錫ジラウレート20mgを投入し、撹拌を開始した。その後、2-イソシアナトエチルアクリレート(商品名:カレンズ(登録商標)AOI 昭和電工製)13.4gを滴下して投入した。その間、反応器内の温度は、70℃より高くならないようにした。その後、反応器内の温度を65~70℃に維持して撹拌を継続した。IRでイソシアナト基のC=O伸縮振動の吸収がなくなったことを確認して反応を終了した。製造されたウレタンアクリレートをポリエステル構造単位を有する(メタ)アクリロイル基含有化合物8とする。
攪拌装置および還流可能な蒸留装置を備えた500mlの反応容器中にPripol(登録商標)2033(クローダ製水添ダイマージオール、水酸基価202mgKOH/g)366.6g、ジエチルカーボネート(東京化成工業製)54.3g、チタンテトラブトキシド0.2g、ジオクチル錫オキシド(商品名:DOTO 北興化学工業株式会社製)0.12gを仕込み、オイルバスを用いて、130℃に昇温し、その後反応の進行に伴い温度180℃まで昇温した。圧力も常圧下から始めてエタノールを流出させながら減圧しつつエステル交換反応を行った。なお、エタノールが留出の際に、一緒に留出したジエチルカーボネート(東京化成工業製)の量をガスクロマトグラフィーで確認して、留出量分のジエチルカーボネートを追添した。エタノールの総留出量は29.5gであった。水酸基価57.3mgKOH/gである(ポリ)カーボネートポリオール(以下、(ポリ)カーボネートポリオールAと記す。)を得た。
攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた300mLの反応容器に、前述の(ポリ)カーボネートポリオールA 177.8g、Pripol(登録商標)2033(クローダ製水添ダイマージオール、水酸基価202mgKOH/g)2.2g、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)5.74gおよびジオクチル錫ジラウレート20mgを投入し、撹拌を開始した。その後、2-イソシアナトエチルメタクリレート(商品名:カレンズ(登録商標)MOI 昭和電工製)14.7gを滴下して投入した。その間、反応器内の温度は、70℃より高くならないようにした。その後、反応器内の温度を65~70℃に維持して撹拌を継続した。IRでイソシアナト基のC=O伸縮振動の吸収がなくなったことを確認して反応を終了した。製造されたウレタンメタクリレートをポリカーボネート構造単位を有する(メタ)アクリロイル基含有化合物9とする。
攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた100mLの反応容器に、2,2,4-トリメチルヘキサメチレンジイソシアネートと2,4,4-トリメチルヘキサメチレンジイソシアネートの混合物(商品名:VESTANAT(登録商標) TMDI エボニックデグサ製)21.89g、ジオクチル錫ジラウレート12mgおよびペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 商品名:IRGANOX1010)5.74gを反応容器に投入し、4-ヒドロキシブチルアクリレート15.16gを滴下ロートを用いて滴下投入した。滴下中、反応容器内の温度は70℃以下になるようにした。滴下終了後、2時間、反応器内の温度を65~70℃に維持したまま、撹拌を継続して反応生成物(以下、反応生成物αと記す。)を得た。
攪拌装置、温度計およびコンデンサーを備えた300mLの反応容器に、前述の(ポリ)カーボネートポリオールA178.9g、Pripol(登録商標)2033(クローダ製水添ダイマージオール、水酸基価202mgKOH/g)1.1gおよびジオクチル錫ジラウレート12mgを投入し、撹拌を開始した。その後、反応器内の温度を65~70℃に維持して撹拌を継続した。IRでイソシアナト基のC=O伸縮振動の吸収がなくなったことを確認して反応を終了した。液体クロマトグラフィーで分析した結果、実施合成例3と同様に生成物中に、4-ヒドロキシブチルアクリレート:VESTANAT(登録商標) TMDI=2:1(モル比)の反応生成物αが3質量%存在することが確認された。反応生成物から前記ウレタンアクリレートモノマーαを除いたものをウレタン基を含有するポリカーボネート構造単位を有する(メタ)アクリロイル基含有化合物10とする。
前記ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物1 60.0質量部、イソステアリルアクリレート(大阪有機化学工業株式会社製 商品名:ISTA)20.0質量部、水添ダイマージオール(クローダ製 商品名:Pripol2033)20.0質量部、1-ヒドロキシシクロヘキシルフェニルケトン(BASF製 商品名:Irgacure 184)0.8質量部および2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド(Lambson製 商品名:SpeedCure TPO)0.4質量部を自転・公転ミキサー(株式会社シンキー製、商品名:あわとり錬太郎 ARE-310)を用いて混合した。この配合物を重合性組成物A1とした。重合性組成物A1の25℃での粘度は5700mPa・sであった。
実施配合例1と同様の方法によって、表1に示す配合組成に従って配合した。実施配合例2~11で調製した配合物を、それぞれ重合性組成物A2~重合性組成物A11とし、比較配合例1および比較配合例2で調製した配合物を、それぞれ、重合性組成物B1と重合性組成物B2とした。
※2 クラプレン UC-203(ポリイソプレン重合物の無水マレイン酸付加物と2-ヒドロキシエチルメタクリレートとのエステル化物 株式会社クラレ製)
※3 イソボルニルアクリレート (商品名;IBXA 大阪有機化学工業株式会社製)
※4 ジシクロペンテニルオキシエチルメタクリレート (商品名;FA-512M 日立化成工業株式会社製)
※5 ラウリルアクリレート (商品名;ブレンマーLA 日油株式会社製)
※6 イソステアリルアクリレート (商品名;ISTA 大阪有機化学工業株式会社製)
※7 2-ヒドロキシプロピルメタクリレート (商品名;HPMA 三菱レイヨン株式会社製)
※8 4-ヒドロキシブチルアクリレート (商品名;4HBA 大阪有機化学工業株式会社製)
※9 2-ヒドロキシブチルメタクリレート (商品名;ライトエステルHOB(N) 共栄社化学株式会社製)
※10 テルペン系水添樹脂 CLEARON(登録商標) P85 (ヤスハラケミカル株式会社製)
※11 テルペン系水添樹脂 CLEARON(登録商標) K100 (ヤスハラケミカル株式会社製)
※12 テルペン系水添樹脂 CLEARON(登録商標) M105 (ヤスハラケミカル株式会社製)
※13 水添ポリブタジエンポリオール NISSO-PB GI-1000 (日本曹達株式会社製)
※14 水添ポリイソプレンポリオール エポール (出光興産株式会社製)
※15 水添ダイマージオール Pripol(登録商標)2033 (クローダ製)
※16 水添ポリブタジエン NISSO-PB BI-2000 (日本曹達株式会社製)
※17 ポリ(α-オレフィン)液状物 Spectrasyn40 (エクソンモービル株式会社製)
※18 エチレン-α-オレフィン共重合液状物 HC-40 (三井化学株式会社製)
※19 液状ポリブテン HV-35 (JX日鉱日石エネルギー株式会社製)
※20 液状ポリブタジエン POLYVEST 110 (エボニックデグサ製)
※21 IRGANOX1010 (化合物名:ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート] BASF製)
※22 光重合開始剤 SpeedCure TPO (化合物名:2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド Lambson製)
※23 光重合開始剤 IRGACURE 184 (化合物名:1-ヒドロキシシクロヘキシルフェニルケトン BASF製)
表1に示す重合性組成物A1~重合性組成物A11、重合性組成物B1および重合性組成物B2を、それぞれ、アプリケーターを用い、膜厚が200μmとなるようにシリコーンでコートされたポリエチレンテレフタレート(以下、PETと記す。)フィルム(100mm×100mm×50μm)に塗布し、上面を25μm厚のシリコーンでコートされたPETフィルムで覆った後、メタルハライドランプを用いたコンベア式紫外線照射装置(株式会社ジーエス・ユアサライティング製、商品名:GSN2-40)を用い、シリコーンでコートされたPETフィルム越しに、照射強度190mW/cm2(365nmの値)、照射量2800mJ/cm2(365nmの値)の条件で紫外線を照射して重合させ、離型PETフィルムに挟まれた膜厚が約200μmの光学用粘着シートを得た。重合性組成物A1~重合性組成物A11、重合性組成物B1および重合性組成物B2を用いて製造された前記光学用粘着シートを、それぞれ、粘着シートA1~粘着シートA11、粘着シートB1および粘着シートB2とした。
前記粘着シートA1~粘着シートA11、粘着シートB1および粘着シートB2で、それぞれ、気泡が界面に入らないように、2枚のガラス板(50mm×50mm×0.7mm、ガラスの種類 商品名:EAGLE XG(登録商標)、CORNING製)で該粘着シートの両面から挟むように貼りつけることにより、試験片を作成した。
粘着シートA1~粘着シートA11、粘着シートB1および粘着シートB2を用いて、作成された試験片を、それぞれ、試験片AS1~試験片AS11、試験片BS1および試験片BS2とした。これらの試験片の全光線透過率、b*を後述の方法により測定した。その結果を表3に記す。
前記重合性組成物A4~重合性組成物A11、重合性組成物B1および重合性組成物B2を、それぞれ、バーコーターを用い、膜厚が200μmとなるようにガラス板(50mm×50mm×0.7mm、ガラスの種類 商品名:EAGLE XG(登録商標)、CORNING製)に塗布し、同種同形のガラス板で挟みこみ、メタルハライドランプを用いたコンベア式紫外線照射装置(株式会社ジーエス・ユアサライティング製、商品名:GSN2-40)を用い、ガラス板越しに、照射強度190mW/cm2(365nmの値)、照射量2800mJ/cm2(365nmの値)の条件で紫外線を照射して重合させ、ガラス板に挟まれた膜厚が約200μmの評価試験用の重合物膜を得た。重合性組成物A4~A11、重合性組成物B1および重合性組成物B2を用いて製造された、前記ガラス板に挟まれた膜厚が約200μmの評価試験用の重合物膜を、それぞれ試験片AL4~試験片AL11、試験片BL1および試験片BL2とした。これらの試験片の全光線透過率、b*を後述の方法により測定した。その結果を表3に記す。
ガラス板(50mm×50mm×0.7mm ガラスの種類 商品名:EAGLE XG(登録商標) CORNING製)1枚をリファレンスに用いて、前記試験片AS1~試験片AS11、試験片AL4~試験片AL11、試験片BS1、試験片BS2、試験片BL1および試験片BL2の全光線透過率を、JIS K 7361-1に準拠して測定した。その結果を表3に記す。
ガラス板(50mm×50mm×0.7mm ガラスの種類 商品名:EAGLE XG(登録商標) CORNING製)1枚をリファレンスに用いて、前記試験片AS1~試験片AS11、試験片AL4~試験片AL11、試験片BS1、試験片BS2、試験片BL1および試験片BL2のb*を、JIS Z 8729に準拠して測定した。その結果を表3に記す。
ガラス板(50mm×50mm×0.7mm ガラスの種類 商品名:EAGLE XG(登録商標) CORNING製)1枚をリファレンスに用いて、前記試験片AS1~試験片AS11、試験片AL4~試験片AL11、試験片BS1、試験片BS2、試験片BL1および試験片BL2のヘーズを、JIS K 7136に準拠して測定した。その結果を表3に記す。
2枚のシリコーンでコートされたPETフィルムを用いて、その間に、重合性組成物A1~重合性組成物A11、重合性組成物B1および重合性組成物B2を、膜厚が2mmになるように挟み込み、メタルハライドランプを用いたコンベア式紫外線照射装置(株式会社ジーエス・ユアサライティング製、商品名:GSN2-40)を用い、シリコーンでコートされたPETフィルム越しに、照射強度190mW/cm2(365nmの値)、照射量2800mJ/cm2(365nmの値)の条件で紫外線を照射して重合させ、シリコーンでコートされたPETフィルムに挟まれた膜厚が約2mmの評価試験用の重合物膜を得た。この重合物膜をシリコーンでコートされたPETフィルムから剥離し、インピーダンスアナライザ(アジレント・テクノロジー株式会社製、商品名:4294A プレシジョン・インピーダンス・アナライザ 40Hz-110MHz)を用いて測定した。その結果を表2に記す。
重合前の重合性組成物A1~A11、重合性組成物B1および重合性組成物B2と、それらを重合した重合物の密度を、自動比重計(型式:DMA-220H、新光電子株式会社製)を用いて、23℃の温度条件で測定し、下記の式から重合時の体積収縮率を求めた。
重合時の体積収縮率(%)=(重合物の密度-重合性組成物の密度)/(重合物の密度)×100
その結果を表2に記す。
前記重合物膜A1~重合物膜A11、重合物膜B1および重合物膜B2を使用して、JIS K 7105に準拠して測定した。その結果を表2に記す。
前記重合物膜A1~重合物膜A11、重合物膜B1および重合物膜B2を、それぞれ引張り試験機(株式会社島津製作所製、EZ Test/CE)に固定し、23℃において、引っ張り速度500mm/minで試験を行い、引張弾性率を求めた。その結果を表2に記す。
前記試験片AS1~試験片AS11、試験片AL4~試験片AL11、試験片BS1、試験片BS2、試験片BL1および試験片BL2を、それぞれ70℃、85℃および95℃の恒温機に入れ、500時間経過後の試験片を用いて、前記の方法により、全光線透過率、b*値およびへーズを測定した。その結果を表3に記す。
前記試験片AS1~試験片AS11、試験片AL4~試験片AL11、試験片BS1、試験片BS2、試験片BL1および試験片BL2を、それぞれ温度60℃,湿度90%RHの恒温恒湿機に入れ、500時間経過後の試験片を用いて、前記の方法により、全光線透過率、b*値およびへーズを測定した。その結果を表3に記す。
すなわち、該重合物を画像表示装置に使用することは有用である。
2 画像表示部
3 保護部
3a タッチセンサー一体型保護部
4 スペーサ
5a、5b 重合物(層)
6a、6b 偏光板
Claims (12)
- 画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合物を製造するための重合性組成物であって、該重合性組成物が、
成分(1)ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、水添ポリオレフィン構造単位を有する(メタ)アクリロイル基含有化合物、(ポリ)エステル構造単位を有する(メタ)アクリロイル基含有化合物および(ポリ)カーボネート構造単位を有する(メタ)アクリロイル基含有化合物からなる群より選ばれる少なくとも1種、
成分(2)成分(1)以外の液状(メタ)アクリロイル基含有化合物、
成分(3)液状水添ポリブタジエンポリオール、液状水添ポリイソプレンポリオールおよび水添ダイマージオールからなる群より選ばれる少なくとも1種、および
成分(4)光重合開始剤
を含むことを特徴とする重合性組成物。 - 成分(5)水添ポリブタジエン、水添ポリイソプレン、ポリ(α-オレフィン)液状物、エチレン-プロピレン共重合液状物、プロピレン-α-オレフィン共重合液状物、エチレン-α-オレフィン共重合液状物、液状ポリブテン、液状水添ポリブテン、液状ポリブタジエン、液状水添ポリブタジエン、液状ポリイソプレン、液状水添ポリイソプレン、液状ポリブタジエンポリオール、および液状ポリイソプレンポリオールからなる群より選ばれる少なくとも1種
をさらに含むことを特徴とする請求項1に記載の重合性組成物。 - 成分(6)水添石油樹脂、テルペン系水添樹脂、および水添ロジンエステルからなる群より選ばれる少なくとも1種
をさらに含むことを特徴とする請求項1または2に記載の重合性組成物。 - 成分(2)が炭素数6以上の炭化水素基を有する(メタ)アクリロイル基含有化合物を含むことを特徴とする請求項1~3のいずれか1項に記載の重合性組成物。
- 成分(2)がアルコール性水酸基を有する(メタ)アクリロイル基含有化合物を含むことを特徴とする請求項1~4のいずれか1項に記載の重合性組成物。
- 請求項1~5のいずれか1項に記載の重合性組成物を重合して得られる重合物。
- 前記重合物層に用いられる光学用粘着シートを製造するための重合性組成物であって、該重合性組成物が請求項1~5のいずれか1項に記載の重合性組成物であることを特徴とする重合性組成物。
- 請求項7に記載の重合性組成物に、光重合開始剤が感光可能な光を照射して、重合させることによって得られる、厚さ10~500μmの重合物層を有する光学用粘着シート。
- 画像表示部を有する基部と、透光性の保護部と、前記基部と前記保護部との間に介在する重合物層とを含む画像表示装置の製造方法であって、該方法が
請求項1~5のいずれか1項に記載の重合性組成物を前記基部と前記保護部との間に介在させる工程、および
光重合開始剤が感光可能な光を前記重合性組成物に照射して重合物層を形成する工程
を含むことを特徴とする画像表示装置の製造方法。 - 画像表示部を有する基部と透光性の保護部との間に光学用粘着シートを用いて重合物層を貼り付ける工程を有する画像表示装置の製造方法であって、該光学用粘着シートが請求項8に記載の光学用粘着シートであることを特徴とする画像表示装置の製造方法。
- 請求項9または請求項10に記載の方法によって製造された画像表示装置。
- 画像表示部が液晶表示パネルであることを特徴とする請求項11に記載の画像表示装置。
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| US14/397,259 US20150079379A1 (en) | 2012-06-15 | 2013-06-14 | Polymerizable composition, polymer, optical adhesive sheet, image display device, and method for manufacturing image display device |
| JP2014521433A JP6104244B2 (ja) | 2012-06-15 | 2013-06-14 | 重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法 |
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| CN114195922B (zh) * | 2021-12-17 | 2022-08-23 | 东北林业大学 | 一种聚丁二烯基柔性快速光固化树脂的制备方法 |
| CN115197664B (zh) * | 2022-08-01 | 2023-06-02 | 业成科技(成都)有限公司 | 光学胶组合物、光学胶膜及制造光学胶膜之方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101642375B1 (ko) | 2016-07-25 |
| KR20140119172A (ko) | 2014-10-08 |
| JPWO2013187508A1 (ja) | 2016-02-08 |
| JP6104244B2 (ja) | 2017-03-29 |
| US20150079379A1 (en) | 2015-03-19 |
| CN104364282A (zh) | 2015-02-18 |
| CN104364282B (zh) | 2017-04-12 |
| TW201412872A (zh) | 2014-04-01 |
| TWI510550B (zh) | 2015-12-01 |
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