WO2011010599A1 - 光硬化性樹脂組成物とその硬化物、樹脂シートとその製造法、及び表示装置 - Google Patents
光硬化性樹脂組成物とその硬化物、樹脂シートとその製造法、及び表示装置 Download PDFInfo
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- WO2011010599A1 WO2011010599A1 PCT/JP2010/061982 JP2010061982W WO2011010599A1 WO 2011010599 A1 WO2011010599 A1 WO 2011010599A1 JP 2010061982 W JP2010061982 W JP 2010061982W WO 2011010599 A1 WO2011010599 A1 WO 2011010599A1
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- Prior art keywords
- meth
- component
- resin composition
- acrylic
- acrylate
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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
- C08F290/06—Polymers provided for in subclass C08G
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L33/04—Homopolymers or copolymers of esters
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
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- Y10T428/00—Stock material or miscellaneous articles
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Definitions
- the present invention relates to a photocurable resin composition and a cured product thereof, a resin sheet and a method for producing the same, and a display device.
- the display devices can be made thin by thinning the constituent members and directly bonding the front optical member to the display members.
- improvement of contrast is being promoted.
- a thin display is used as a display member and an optical member is directly bonded to the front surface of the display member, internal stress is generated due to stress derived from expansion and contraction of each member and residual stress at the time of bonding. , Tends to cause display unevenness. Therefore, in recent years, various studies have been made on the resin layer material interposed between the display member and the optical member.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2001-316447 discloses a polyol having a functional group number of 2.4 to 3.0 and a molecular weight of 3,000 to 6,000, and a secondary serving as a tackifier.
- a more efficient production method than cast molding for example, a method for producing a thick film sheet in which a composition is continuously applied on a film as a base material so that bubbles are not mixed therein. It is unsuitable.
- Patent Document 2 Japanese Patent Laid-Open No. 2004-359808 discloses a transparent gel pressure-sensitive adhesive and sheet in which a three-dimensional cross-linked polymer is swollen with a liquid containing a plasticizer and inorganic fine particles as a resin layer material.
- this pressure-sensitive adhesive and sheet contain a plasticizer, breathing due to the plasticizer is likely to occur, and the adherend such as the display member may be contaminated or eroded.
- Patent Document 3 Japanese Patent Laid-Open No. 2006-309114 discloses an adhesive sheet having a storage elastic modulus G ′ of 3 ⁇ 10 5 to 1 ⁇ 10 7 Pa at 23 ° C. and a frequency of 1 Hz as a resin layer material.
- the pressure-sensitive adhesive sheet preferably has an appropriate elastic modulus at least in the temperature range of 0 ° C to 50 ° C.
- the above disclosure does not mention the elastic modulus of the pressure-sensitive adhesive sheet at a low temperature.
- the elastic modulus When the elastic modulus is high at low temperatures, when the display device is used in a low temperature environment, the stress relaxation property and adhesiveness of the sheet may be insufficient, resulting in problems. More specifically, for example, when the above-mentioned pressure-sensitive adhesive sheet is applied to a display device such as a mobile phone that is easily affected by temperature, display unevenness is likely to occur in a low-temperature environment, and due to impact such as dropping. There is a possibility of peeling from the adhesive sheet interface. Furthermore, when the elastic modulus in a high temperature environment of 50 ° C. or higher is too low, distortion of various optical members cannot be suppressed, and peeling or display unevenness may occur.
- Patent Document 4 Japanese Patent Laid-Open No. 2008-56757.
- the cohesive force of this sheet tends to extremely decrease under a high temperature environment.
- a plastic plate such as an acrylic plate
- the peripheral portion of the sheet may be lifted or peeled due to thermal deformation of the plastic plate.
- any disclosure directed to the resin layer material of a display device can improve display unevenness of the display device, while mass productivity, non-contamination, low temperature impact resistance, and high temperature It does not have reliability. Therefore, there is a resin layer material that exhibits excellent stress relaxation properties and improves display unevenness, is excellent in non-contamination, and has excellent reliability in various usage environments, and a method for efficiently producing such a resin layer material. It is desired.
- the present invention has been made in view of the above-described situation, and can be used for bonding a display member such as a thin display and a front optical member, and in a wide temperature environment, expansion and contraction of each member. It is an object of the present invention to provide a pressure-sensitive adhesive sheet and a material thereof that can reduce the occurrence of internal stress due to the stress derived from the above and the residual stress due to the residual stress at the time of bonding, and can suppress display unevenness of the display.
- an acrylic photocurable resin composition containing a specific urethane (meth) acrylate oligomer has excellent stress relaxation properties, little display unevenness, adhesive strength,
- the present invention has been completed by finding that it can be a suitable material for a sheet having excellent transparency and various environmental reliability.
- the photocurable resin composition according to the present invention is for forming the resin layer of a display device having a display member and an optical member installed on the front surface of the display member via a resin layer.
- A a urethane (meth) acrylate oligomer having a polyoxyalkylene structure
- B a (meth) acrylic polymer
- C a (meth) acrylic monomer
- D a photopolymerization initiator
- the component (A) comprises (a1) at least one polyoxyalkylene polyol, (a2) at least one polyisocyanate, (a3) at least one hydroxyl group-containing mono (meth) acrylate compound, And the total mass n1 of the three or more monomer components and the acrylic component in the three or more monomer components.
- the component (B) includes a (meth) acrylic polymer having a carboxyl group
- the component (C) includes a (meth) acrylic monomer having a carboxyl group.
- the component (A) is preferably a mixture of a urethane (meth) acrylate oligomer having one (meth) acryloyl group and a urethane (meth) acrylate oligomer having two or more (meth) acryloyl groups.
- the component (B) is preferably a (meth) acrylic polymer having a weight average molecular weight of 10 ⁇ 10 4 to 200 ⁇ 10 4 .
- Component (B) is preferably a copolymer obtained by polymerizing a monomer mixture containing (b1) (meth) acrylic acid and (b2) (meth) acrylic acid ester.
- the monomer mixture preferably contains 5 to 45 mol% of the (meth) acrylic acid (b1).
- the component (C) is preferably a monomer mixture containing (c1) (meth) acrylic acid and (c2) (meth) acrylic acid ester.
- the monomer mixture preferably contains 5 to 45 mol% of the (meth) acrylic acid (c1).
- the monomer mixture constituting the component (B) and the component (C) preferably contain the same kind of compounds.
- the photocurable resin composition according to the present invention comprises (A) 1 to 50% by mass, (B) 5 to 40% by mass, based on the total mass of the components (A), (B) and (C). And (C) in a proportion of 5 to 85% by mass, and 0.1 to 20 parts by mass of the component (D) with respect to 100 parts by mass in total of the components (A), (B) and (C). It is preferable to include by a ratio.
- the cured product according to the present invention is obtained by photocuring the above-mentioned photocurable resin composition, and the storage elastic modulus and loss elastic modulus at each temperature are within the ranges of the following formulas (1) to (3). It is characterized by satisfaction.
- Storage elastic modulus at 70 ° C. is 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa and loss elastic modulus is 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa.
- Storage elastic modulus at 23 ° C. is 1 ⁇ 10 4 to 5 ⁇ 10 6 Pa and loss elastic modulus is 1 ⁇ 10 4 to 5 ⁇ 10 6 Pa.
- Storage elastic modulus at 0 ° C. is 5 ⁇ 10 4 to 1 ⁇ 10 7 Pa and loss elastic modulus is 5 ⁇ 10 4 to 1 ⁇ 10 7 Pa.
- the resin sheet member by this invention is for forming the said resin layer of the display apparatus which has a display member and the optical member installed through the resin layer in the front surface of this display member, The 1st film And a resin sheet made of the above-described cured product provided on the first film, and a second film provided on the resin sheet.
- the first and second films are plastic films subjected to release treatment, and the release forces of the first and second films are different from each other.
- the manufacturing method of the resin sheet member by this invention manufactures the resin sheet member for forming the said resin layer of the display apparatus which has a display member and the optical member installed through the resin layer in the front surface of this display member.
- the photocurable resin composition described above for applying the photocurable resin composition described above to one side of the first film in a sheet form and then covering the second film with the first film and the first film. And irradiating light from at least one main surface of the film of 2 to cure the photocurable resin composition.
- the light to be irradiated is ultraviolet light having a peak wavelength of 365 nm that does not substantially include a wavelength of less than 280 nm, and the ultraviolet light is irradiated at an illuminance of 0.01 to 20.0 mW / cm 2 for 2 minutes or more. It is preferable.
- the display device has a display member and an optical member installed on the front surface of the display member via a resin layer, and the resin layer includes a cured product of a photocurable resin composition.
- a photocurable resin composition suitable as the resin layer material of a display device having a display member and an optical member disposed on the viewing side of the display member, that is, the front surface via a resin layer. can be provided.
- the photocurable resin composition according to the present invention it has excellent stress relaxation properties, can be designed in a wide range of adhesive strength, is excellent in transparency without containing bubbles, and is non-staining.
- the resin sheet excellent also in productivity can be provided. Further, by using such a resin sheet, it is possible to realize a thin display device in which display unevenness is suppressed and the reliability with respect to the use environment is high. Since the display device according to the present invention does not use secondary means such as a plasticizer as a sheet material, contamination of the adherend is suppressed, and the reliability during long-term use is excellent.
- the urethane (meth) acrylate oligomer having a polyoxyalkylene structure as the component (A) in the photocurable resin composition of the present invention comprises (a1) at least one polyoxyalkylene polyol and (a2) at least one polyoxyalkylene polyol.
- the polyoxyalkylene polyol of component (a1) used in the present invention is a compound that contains two or more hydroxyl groups in the molecule and is also called a polyether polyol.
- a compound having two or more active hydrogens in the molecule such as polyhydric alcohols, polyhydric phenols, and amines as an initiator, and alkylene oxide with respect to the initiator. It can be obtained by addition polycondensation of the compound.
- the compound having two or more active hydrogens in the molecule used as the initiator may be any of aliphatic, alicyclic, and aromatic compounds.
- the alkylene oxide compound is preferably a compound having 2 to 4 carbon atoms.
- polyethylene glycol polypropylene glycol, polybutylene glycol, and tetramethylene glycol.
- a copolymer comprising two or more of these exemplified compounds for example, a copolymer of ethylene oxide and propylene oxide or a copolymer of ethylene oxide and tetrahydrofuran can be suitably used.
- This polyoxyalkylene polyol (a1) can be used in combination of bifunctional and / or trifunctional or more. This number of functional groups depends on the initiator used in the synthesis of the polyoxyalkylene polyol, that is, the polyhydric alcohols, polyhydric phenols, and polyhydric amines having two or more active hydrogens in the molecule. Synthesis methods using such initiators are well known, depending on the type of compound.
- bifunctional polyols use diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol as initiators, such as Obtained by adding an alkylene oxide to a simple initiator.
- a tri- or higher functional polyol can be obtained by using glycerin, trimethylolpropane, pentaerythritol, sorbitol or the like as an initiator, and adding an alkylene oxide to such an initiator.
- diols and triols having 2 to 4 carbon atoms are preferable, and ethylene glycol, propylene glycol, and glycerin are particularly preferable.
- component (a1) only one kind of polyoxyalkylene polyol may be used, or a plurality of kinds thereof may be used in combination. Further, a plurality of types of polyoxyalkylene polyols having different numbers of hydroxyl groups in the molecule may be used in combination.
- the polyoxyalkylene polyols that can be used as the component (a1) compounds having a number average molecular weight in the range of 1000 to 20000 are particularly preferred from the viewpoints of suppressing display unevenness and stress relaxation.
- the polyoxyalkylene polyol (a1) is preferably a compound that becomes liquid at the reaction temperature described below.
- the “hydroxyl value” is a value obtained by measurement according to JIS K1557 6.4.
- the polyoxyalkylene polyol (a1) preferably contains an ethylene oxide unit as a copolymerization component from the viewpoint of transparency, particularly heat and moisture resistance.
- the polymerization method of ethylene oxide may be random or block.
- the copolymerization ratio of the ethylene oxide component is 3% to 60%, preferably 5% to 40% by weight based on the polyoxyalkylene polyol of component (A).
- the heat and moisture resistance tends to be inferior. More specifically, it is difficult to maintain sufficient transparency as a resin layer material of a display device when a heat and humidity resistance test evaluated by placing it in a humid heat environment at 50 ° C. and a relative humidity of 95% for 7 days is performed. And haze (white turbidity) may occur.
- the copolymerization ratio exceeds 60%, the hardness of the cured product becomes too high, and sufficient stress relaxation may not be obtained when applied as a resin layer material.
- the polyisocyanate of component (a2) used in the present invention is an aromatic, alicyclic or aliphatic polyisocyanate having two or more isocyanate groups, a mixture of two or more of them, and modified them.
- the resulting modified polyisocyanate may be used.
- diisocyanate compounds having two isocyanate groups are preferred.
- tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI) ), Xylylene diisocyanate (XDI), trimethylxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), norbornene diisocyanate (NBDI), hydrogenated MDI and other polyisocyanate compounds and their prepolymer modifications Body, nurate modified body, urea modified body, carbodiimide modified body, and the like.
- aliphatic diisocyanates having 3 to 9 carbon atoms such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated XDI, and hydrogenated MDI.
- HDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- XDI hydrogenated XDI
- MDI hydrogenated MDI
- the hydroxyl group-containing mono (meth) acrylate compound of component (a3) used in the present invention is preferably an ester of (meth) acrylic acid and an aliphatic, alicyclic or aromatic diol.
- an ester of (meth) acrylic acid and an alkanediol having 1 to 8 carbon atoms is preferable.
- any compound having compatibility within a range in which turbidity does not occur as a photocurable composition such as polycaprolactone acrylate and hydroxyl group-containing alicyclic acrylate, can be used without particular limitation.
- the component (A) in the present invention is substantially produced using the three components (a1), (a2) and (a3) described above, but the effect expressed by the oligomer of the component (A) is impaired.
- Other monomer components may be used in combination as necessary.
- monool may be used in combination in order to adjust the number of functional groups involved in the reaction.
- Monool is a compound containing one hydroxyl group in the molecule. Specifically, one or two hydroxyl groups existing in the compound exemplified above as component (a1) are replaced with hydrogen atoms.
- the acrylic monool may be an acrylic polymer having one hydroxyl group in the molecule.
- the castor oil-based monool may be a higher monool having 18 carbon atoms obtained from ricinoleic acid which is a castor oil hydrolyzate.
- Natural or synthetic monoalcohol is a monofunctional alcohol having 6 or more carbon atoms, preferably 6 to 30 carbon atoms, such as 2-ethylhexyl alcohol, sec-stearyl alcohol, ⁇ -terpineol, diacetone alcohol, and capryl alcohol. It may be.
- the number average molecular weight of monool is preferably in the range of 100 to 10,000.
- the number average molecular weight of the monool can also be determined by the same method as in the case of the polyoxyalkylene polyol (a1).
- silane coupling agent means a silane compound having a so-called coupling action, and a silane compound having an active hydrogen group that reacts with an isocyanate group can be used.
- the silane coupling agent that can be suitably used in the present invention is a silane coupling agent having an alkoxysilyl group at one end and an active hydrogen group such as a mercapto group or an amino group at the other end.
- a silane coupling agent having an alkoxysilyl group at one end and a mercapto group at the other end is particularly preferred.
- the monomer component used in combination has a molar ratio of 1. to the amount of component (a3). It is preferably 5 times or less, more preferably 0.2 to 1 times.
- the amount of the monomer component used in combination exceeds 1.5 times in terms of molar ratio, the properties that are inherently expressed by the component (A) are reduced, and display unevenness resistance, adhesive properties, and non-staining properties are achieved in a well-balanced manner. Tend to be difficult.
- the photocurable resin composition of the present invention in order to obtain the effect of the component (A) oligomer, it is necessary to appropriately control the molecular weight of the oligomer and the average number of functional groups of the acryloyl group in the molecule.
- the molecular weight of the oligomer is too small, the adhesive strength is weak and the adhesiveness tends to be insufficient in applications where strong adhesiveness is required.
- the molecular weight is too large, the viscosity of the oligomer becomes too high, and the handleability and workability tend to be lowered.
- the average number of functional groups of the acryloyl group accompanying the urethanization reaction is maximized to 2 and the value varies depending on the type and ratio of each monomer component used. If the value of the average number of functional groups of the acryloyl group is too small, the cohesive force at high temperature becomes insufficient and the urethane component tends to bleed out from the cured product. On the other hand, the peel adhesion strength tends to decrease as the average number of functional groups of the acryloyl group approaches 2.
- the number average molecular weight of the oligomer used as component (A) is typically preferably in the range of 10,000 to 300,000, and in the range of 30,000 to 200,000. Is more preferable. Further, the average number of functional groups in the oligomer is typically preferably in the range of 0.7 to 1.8.
- the peel adhesive strength can be easily increased.
- the upper limit value of n1 / n2 is not particularly limited, but the upper limit is practically about 10,000 to 100,000 considering that the handleability decreases due to an increase in viscosity or the like.
- the urethane (meth) acrylate oligomer used as the component (A) does not substantially contain an unreacted isocyanate group.
- substantially free means that it contains no unreacted isocyanate groups, that is, it cannot be detected or contains a trace amount of unreacted isocyanate groups, but the amount is very small. That is, it means that the optical quality such as transparency and smoothness is not adversely affected.
- the concentration of the unreacted isocyanate group present in the oligomer is preferably 0.3% by mass or less, and most preferably 0.
- the concentration of the unreacted isocyanate group present in the oligomer is preferably 0.3% by mass or less, and most preferably 0.
- swelling due to carbon dioxide gas generated by reaction with moisture and the like causes a decrease in transparency and smoothness, optical quality such as bubble inclusion, and adhesion.
- optical quality such as bubble inclusion, and adhesion.
- the problem of floating at the interface is likely to occur.
- the urethane reaction can proceed completely or at least almost completely in accordance with a well-known technique. Therefore, each component is charged in a stoichiometric amount that satisfies the above formula (I). It is possible to have substantially no unreacted isocyanate groups present in the oligomer by reacting the components completely or at least almost completely.
- Whether or not an unreacted isocyanate group is present in the final composition or the product of each reaction step, and further in the oligomer, is determined by, for example, an infrared absorption spectrum as described later in Examples. The determination can be made based on whether or not the group absorption (2250 cm ⁇ 1 ) can be confirmed.
- the component (A) can be prepared by reacting the three components (a1), (a2) and (a3) which are essential components at the same time (one-shot method) or by reacting them sequentially. May be.
- a sequential reaction in which at least one of these components is reacted sequentially is preferable.
- any of the following methods (I) to (III) can be applied.
- component (I) A step of reacting component (a1) and component (a2) in excess of component (a1) to obtain a prepolymer having a hydroxyl group at the terminal, while component (a2) and component (a3) are 1 : A step of obtaining a (meth) acryloylated isocyanate compound by reacting at a molar ratio of 1: and a step of reacting the resulting prepolymer with the (meth) acryloylated isocyanate compound after each step Method.
- component (II) A step of reacting component (a1) and component (a2) in excess of component (a2) to obtain a prepolymer having an isocyanate group at the terminal, and then reacting the prepolymer with component (a3)
- a method comprising a step of (meth) acryloylating a part of the isocyanate group in the prepolymer, and a step of reacting the remaining isocyanate group with the monool component as the component (a1), if necessary.
- (III) A step of reacting component (a1) and component (a2) in excess of component (a2) to obtain a prepolymer having isocyanate groups at both ends, and then reacting component (a3) with the resulting prepolymer
- a method comprising reacting the prepolymer 1 and the prepolymer 2 obtained in each step.
- each component is finally reacted at a desired ratio of excess hydroxyl groups.
- how to advance a sequential reaction is not limited to the method illustrated previously.
- urethanization reactions that is, the bonding reaction between the isocyanate group of component (a2) and the hydroxyl group of other components
- a known catalyst can be used as necessary.
- typical catalysts include organometallic compounds having metals such as tin, lead and titanium, and tertiary amines such as triethylamine and triethylenediamine.
- organic tin compounds are preferable, and typical examples thereof include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin maleate, dibutyltin mercaptopropionate, dibutyltin bisisooctylthioglycolate. , Dibutyltin dodecyl mercaptide, tin 2-ethylhexanoate, stannous octoate, stannous oleate, and the like.
- the catalyst is used by appropriately selecting an amount capable of appropriately adjusting the reaction rate between the isocyanate group and the hydroxyl group. Although not particularly limited, in general, the catalyst amount is preferably 0.001 to 10% by weight based on all components used as raw materials.
- the proportion of the reaction mixture is usually 50 to 2000 ppm in order to prevent gelation due to radical polymerization during the reaction. It is preferable to add a polymerization inhibitor.
- Specific examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, and p-benzoquinone.
- the reaction temperature in this (meth) acrylate formation is usually in the range of normal temperature to 100 ° C., preferably in the range of 50 to 85 ° C.
- the reaction mixture obtained by the above-described various urethanization reactions generally contains a plurality of types of urethane (meth) acrylate oligomers as main components, and may further contain subcomponents.
- an oligomer having an appropriate molecular weight and average number of functional groups can be obtained as a main component by reacting each monomer component used as a raw material at a blending ratio satisfying the formula (I).
- the urethane (meth) acrylate oligomer (reaction mixture) used as the component (A) preferably does not contain an unreacted isocyanate group. Therefore, the urethanization reaction is preferably continued until there are no unreacted isocyanate groups in the reaction mixture. Whether or not unreacted isocyanate groups are present in the reaction mixture can be determined by collecting a part of the reaction mixture, measuring the infrared absorption spectrum, and confirming whether the isocyanate group absorption can be confirmed. . Each urethanization reaction varies depending on the reaction temperature and other conditions, but is usually completed in a reaction time of about 1 to 6 hours.
- the component (B) in the photocurable resin composition of the present invention is a (meth) acrylic polymer, and this component causes the resin composition and the sheet to exhibit adhesiveness, and the adhesion reliability in a high-temperature environment. Has the effect of improving.
- the (meth) acrylic polymer used as the component (B) may be a polymer obtained by polymerizing a (meth) acrylic monomer compound, and is not particularly limited. However, a polymer having a weight average molecular weight of 10 ⁇ 10 4 to 200 ⁇ 10 4 is preferable from the viewpoint of enhancing the adhesion reliability in a high temperature environment.
- the “weight average molecular weight” means a value obtained as a standard polystyrene conversion value measured by gel permeation chromatography.
- the component (B) preferably has a carboxyl group in the polymer molecule.
- the component (B) suitable for the present invention comprises (b1) a (meth) acrylic monomer mixture having a carboxyl group-containing (meth) acrylic monomer as an essential component, and a known heavy polymer such as solution polymerization. It can be obtained by polymerizing according to a legal method.
- the (meth) acrylic monomer (b1) having a carboxyl group examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Among these, acrylic acid or methacrylic acid is preferable from the viewpoint of polymer synthesis.
- the (meth) acrylic monomer (b1) having a carboxyl group is 3 to 50 mol% with respect to the total amount of the monomer mixture used for the production of the component (B). It is preferably present in a proportion, more preferably in a proportion of 5 to 45 mol%.
- component (B) is an acrylic copolymer obtained by polymerizing a monomer mixture containing (b1) (meth) acrylic acid and (b2) (meth) acrylic acid ester,
- the monomer mixture preferably contains component (b1) in a proportion of 3 to 50 mol%, more preferably 5 to 45 mol%.
- (b2) (meth) acrylic acid esters compounds having an alkyl group or hydroxyalkyl group having 1 to 20 carbon atoms in the ester moiety are preferred.
- Specific compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate and the like. These may be used alone or in combination of two or more.
- examples of the (meth) acrylate compound having a hydroxyl group include an alkylene oxide adduct of (meth) acrylic acid, a dehydration condensate of polyhydric alcohols and (meth) acrylic acid, and these compounds as starting materials.
- examples thereof include (meth) acrylic acid adducts of derivatives and epoxy group-containing compounds.
- Specific compounds include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxy Mono (meth) acrylate of alkanediol having 1 to 8 carbon atoms such as octyl (meth) acrylate; alkanetriol mono (meth) acrylate, alkanetriol di (meth) acrylate, alkanetetraol mono (meth) acrylate, alkanetetraol Di (meth) acrylate, alkanepentaol mono (meth) acrylate, alkanepentaol di (meth) acrylate, alkanehexaol mono (meth) acrylate , Alkanehexaol di (meth) acrylate,
- mono (meth) acrylate of alkane polyol having 1 to 8 carbon atoms di (meth) acrylate of alkane polyol, polyether poly (meth) acrylate, diethylene glycol mono (meth) Examples thereof include polyalkylene glycol mono (meth) acrylates such as acrylate, dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate.
- the (meth) acrylic monomer used as component (C) in the present invention may be a compound well known as a (meth) acrylic compound. Although it does not specifically limit, It is preferable that the component (C) used by this invention contains the (meth) acrylic-type monomer which has a carboxyl group. As a specific example, the various compounds illustrated as a monomer component which comprises a component (B) previously can be used.
- component (C) Assuming an application as a resin layer material in a display device, from the viewpoint of adhesion durability under a high temperature environment, a (meth) acrylic group having a carboxyl group with respect to the total amount of monomers constituting the component (C)
- the monomer (c1) is preferably present in a proportion of 3 to 50 mol%, more preferably 5 to 45 mol%.
- component (C) is a monomer mixture comprising (c1) (meth) acrylic acid and (c2) (meth) acrylic acid ester, and the monomer mixture comprises component (c1). Preferably, it is contained in a proportion of 3 to 50 mol%, more preferably 5 to 45 mol%.
- the monomer mixture constituting the component (B) and the monomer mixture of the component (C) contain the same kind of compounds.
- an acrylic rubber obtained by polymerizing acrylic acid and 2-ethylhexyl acrylate is used as component (B), and a mixture of acrylic acid and 2-ethylhexyl acrylate is used as component (C).
- component (B) an acrylic rubber obtained by polymerizing acrylic acid and 2-ethylhexyl acrylate
- component (C) a mixture of acrylic acid and 2-ethylhexyl acrylate
- the component (C) in addition to the above-mentioned carboxyl group-containing (meth) acrylate, other acrylic compounds such as a hydroxyl group-containing (meth) acrylate compound may be used in combination.
- a hydroxyl group-containing (meth) acrylate compound is contained as the component (C) in the resin composition, it is preferable because antifogging properties can be imparted in a humid heat environment of, for example, 50 ° C. and a relative humidity of 95%.
- the addition amount of the hydroxyl group-containing (meth) acrylate compound is preferably in the range of 1 to 30% by mass based on the total mass of the components (A), (B) and (C) of the photocurable resin composition of the present invention, A range of 3 to 20% by mass is more preferable.
- the addition amount is less than 1% by mass, the component (A) may not have sufficient antifogging property during wet heat.
- the addition amount exceeds 30% by weight, physical properties such as flexibility and toughness of the cured product may be deteriorated.
- Specific examples of the hydroxyl group-containing (meth) acrylate compound include the same compounds exemplified above as the monomer component constituting the component (B).
- the above component (B) and component (C) may be used as independent raw materials at the time of preparing the composition, but by using them in a premixed state as an acrylic syrup, the compatibility of these components is increased. Is preferable.
- Acrylic syrup is prepared by dissolving the (meth) acrylic polymer of component (B) obtained in advance in the polymerization reaction in the (meth) acrylic monomer of component (C) or polymerizing the monomer component of the (meth) acrylic compound. It can be obtained by terminating the reaction in an intermediate stage.
- the ratio of the component (B) and the component (C) in the acrylic syrup is not particularly limited, but the weight of the component (C) is 50 to 2000 with the weight of the polymer compound as the component (B) being 100. It is a range.
- the weight average molecular weight of the component (B) in the acrylic syrup is preferably 10 ⁇ 10 4 to 200 ⁇ 10 4 as described above.
- the acrylic syrup preferably contains a monomer and / or polymer of a carboxyl group-containing compound.
- the total ratio of the monomer and / or polymer of the carboxyl group-containing compound in the acrylic syrup is preferably in the range of 3 to 60 mol%, more preferably in the range of 5 to 55 mol%, based on the total amount of the acrylic syrup. preferable.
- the mixing ratio of each of the components (A), (B), and (C) described above is (A) 1 to 50% by mass based on the total mass of each component, A blending ratio of (B) 5 to 40% by mass and (C) component 5 to 85% by mass is preferable in terms of both non-display unevenness and adhesion durability in a high temperature environment. Further, the blending ratio of (A) 5 to 30% by mass, (B) 10 to 20% by mass, and (C) 50 to 85% by mass results in non-display unevenness and adhesion durability in a high temperature environment. And the viscosity of the coating solution, that is, the handling property of the coating solution is preferable.
- the monomer component used for preparation of the (meth) acrylic-type polymer of a component (B) and the (meth) acrylic-type monomer component used as a component (C) are the same kind of compounds.
- component (C) a carboxyl group-containing (meth) acrylic monomer and (meth) acrylic acid alkyl ester are used, and a polymer obtained by polymerizing a monomer mixture containing the same compound is used as component (B). In this case, it is preferable in that excellent transparency can be obtained.
- the photopolymerization initiator used as the component (D) in the present invention may be a known compound that can be used for photopolymerizing a vinyl monomer.
- Specific examples of compounds that can be used as photopolymerization initiators include ⁇ -hydroxyisobutylphenone benzoin, isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, acetophenone diethyl ketal, benzyl Dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl
- the photopolymerization initiator is selected in consideration of the absorption characteristics of the light irradiation device and is not particularly limited.
- benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy -2-Methyl-1-phenylpropan-1-one is preferred.
- the amount of component (D) added is not particularly limited. However, in general, when the internal curability is insufficient, unreacted components may migrate to the surface of the cured product over time and become sticky. It is necessary to adjust the addition amount appropriately.
- the amount of the component (D) added is the total amount of the photocurable component in the composition, that is, the components (A), (B) and (C).
- the range of 0.1 to 20 parts by mass is preferable with respect to 100 parts by mass in total, and the range of 0.5 to 5 parts by mass is more preferable.
- tackifier means a so-called tackifying resin, and can be used within a range that is transparently dissolved in the resin composition according to the present invention.
- specific tackifiers that can be used in the present invention include, for example, gum rosin, tall rosin, wood rosin, disproportionated rosin, polymerized rosin, glycerin ester and pentaerythritol ester of these rosins, and hydrogens thereof.
- Rosin resins such as additives, terpene resins, hydrocarbon-modified terpene resins, terpene resins such as these hydrogenated products, terpene phenol resins, terpene phenol resins such as hydrogenated terpene phenol resins, aliphatic petroleum Resins, alicyclic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, dicyclopentadiene petroleum resins, pure monomer petroleum resins, petroleum resins such as hydrogenated products, styrene resins, polymers Maron indene resin, alkylphenol resin, xylene resin, Nmaru, copal, shellac, and the like.
- the amount used is preferably in the range of 1 to 20% by weight with respect to the total mass of the photocurable resin composition.
- the photocurable resin composition of the present invention is not limited to the above-described tackifier, and may further contain various components known in the polyurethane technical field as necessary. Examples thereof include various additives such as a catalyst involved in the urethanization reaction, an anti-aging agent, an antifoaming agent, and a flame retardant.
- anti-aging agent examples include hindered phenol-based, benzotriazole-based, and hindered amine-based anti-aging agents such as butylated hydroxytoluene (BHT) and butylhydroxyanisole (BHA).
- BHT butylated hydroxytoluene
- BHA butylhydroxyanisole
- Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methyl phosphate, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and bromine / phosphorus compound.
- Examples of the antifoaming agent include Disparon OX-710 (trade name, manufactured by Enomoto Kasei Co., Ltd.).
- the concentration of these additives is not particularly limited as long as it does not adversely affect the characteristics exhibited by the resin composition according to the present invention. Usually, it is desirable to use in the range of 10 wt% or less, more preferably 5 wt% or less with respect to the total mass of the photocurable resin composition.
- the photocurable resin composition of the present invention is suitable as a material for forming the resin layer of a display device having a display member and an optical member installed on the front surface of the display member via a resin layer.
- a resin layer having excellent stress relaxation properties and transparency can be formed.
- the formation of the resin layer is not particularly limited, and a method in which the photocurable resin composition is filled between the display member and the optical member and then photocured, or the photocurable resin composition is used as the display member and the optical member. It can be carried out by a method of photocuring after applying to any one of the members and subsequently attaching the other member.
- the cured product of the photocurable resin composition according to the present invention exhibits tackiness. Therefore, as another method of forming the resin layer, a resin sheet made of a cured product of the photocurable resin composition can be produced, and the display member and the cover member can be attached using the resin sheet.
- the resin sheet can be obtained by coating the photocurable resin composition on a film that has been subjected to a release treatment, and then irradiating light to cure the coating layer. When irradiating light, in order to prevent polymerization inhibition by oxygen, it is preferable to purge the inert gas or to coat the coated surface with a protective film.
- a cured product of the photocurable resin composition exhibits excellent adhesion durability in an environment where it is normally used.
- the cured product has appropriate elastic characteristics in the above temperature range. More specifically, it is preferable that the storage elastic modulus and loss elastic modulus of the cured product simultaneously satisfy the following ranges (1) to (3).
- the storage elastic modulus at 70 ° C. is 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa, more preferably 1 ⁇ 10 4 to 1 ⁇ 10 5 Pa, and the loss elastic modulus is 1 ⁇ 10 3 to 1 ⁇ 10. 6 Pa, more preferably 1 ⁇ 10 4 to 1 ⁇ 10 5 Pa.
- the storage elastic modulus at 23 ° C. is 1 ⁇ 10 4 to 5 ⁇ 10 6 Pa, more preferably 3 ⁇ 10 4 to 1 ⁇ 10 6 Pa, and still more preferably 5 ⁇ 10 4 to 1 ⁇ 10 6 Pa.
- the loss elastic modulus is 1 ⁇ 10 4 to 5 ⁇ 10 6 Pa, more preferably 3 ⁇ 10 4 to 1 ⁇ 10 6 Pa, and still more preferably 5 ⁇ 10 4 to 1 ⁇ 10 6 Pa.
- the storage elastic modulus at 0 ° C. is 5 ⁇ 10 4 to 1 ⁇ 10 7 Pa, more preferably 2 ⁇ 10 5 to 1 ⁇ 10 7 Pa, and still more preferably 5 ⁇ 10 5 to 1 ⁇ 10 7 Pa.
- the loss elastic modulus is 5 ⁇ 10 4 to 1 ⁇ 10 7 Pa, more preferably 2 ⁇ 10 5 to 1 ⁇ 10 7 Pa, and still more preferably 5 ⁇ 10 5 to 1 ⁇ 10 7 Pa.
- the “storage elastic modulus” and “loss elastic modulus” described in the present specification serve as indexes of the adhesiveness and stress relaxation property of the cured product of the resin composition, and are values measured by the following methods.
- Measurement method of elastic modulus By laminating and laminating sheets of various thicknesses, a strip-shaped sheet having a length of 5 mm, a width of 12.0 mm, and a thickness of 1.0 mm is prepared, and this is used as a test piece. The specimen is measured by the film shear mode under the following conditions. Measuring device: DMS6100 manufactured by SII Nano Technology Frequency: 10Hz Temperature: -100 ° C to 100 ° C (Temperature increase rate: 2 ° C / min)
- a material for forming a resin layer in a display device photocuring is performed with a light surface and a heavy surface protective film (first and second films) subjected to release treatment with different release forces.
- a resin sheet member obtained by sandwiching the conductive resin composition and then photocuring the resin composition can be provided. Since such a resin sheet member exhibits adhesiveness, the resin sheet can be directly adhered to one installation surface after the light surface protective film is peeled off. Next, after the heavy surface protective film is peeled off, the other installation surface can be attached to obtain a display device without an air layer.
- the thickness of the resin sheet is not particularly limited, but is preferably about 0.02 to 2.0 mm, more preferably 0.05 to 1.0 mm, from the viewpoint of reaction uniformity in the thickness direction.
- the resin sheet has an appropriate adhesive strength. More specifically, a resin sheet having a peel adhesion measured at room temperature (23 ° C.) of 0.2 to 40 N / 25 mm, more preferably 0.5 to 30 N / 25 mm, and further preferably 1 to 20 N / 25 mm. Is preferred.
- the peel adhesion measured at 80 ° C. is 0.2 to 30 N / 25 mm, more preferably 0.5 to 20 N / 25 mm, and further preferably 1 to 10 N / 25 mm.
- a resin sheet is preferred.
- the value of the said peeling adhesive force intends the value obtained by measuring according to the method prescribed
- a plastic film is preferable, and it is preferable that at least a surface of each film forming the resin sheet is subjected to a release treatment.
- the plastic film include polyethylene films, polypropylene films, polyester films, polyvinyl chloride films, cellulose films such as triacetyl cellulose, acrylic films, polyethylene films, polypropylene films, polyolefin films having a cyclo or norbornene structure, and the like. It is done.
- the thickness of the first and second films used as the protective film is not particularly limited, but generally a film having a thickness of 0.5 to 0.2 mm is used.
- the mold release treatment for the film can be carried out by using various known methods such as addition reaction type or condensation reaction type silicone treatment, long chain alkyl treatment, and fluorine treatment.
- the first and second films are preferably subjected to a release treatment so as to have different release forces from the viewpoint of handleability of the resin sheet member.
- the above-mentioned resin sheet member is a step of applying the photocurable resin composition of the present invention in a sheet form on one side of one protective film and then covering the other protective film, and at least one main surface of each protective film And irradiating light to cure the photocurable resin composition.
- the light source lamp used for light irradiation preferably has a light emission distribution at a wavelength of 400 nm or less.
- a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a metal halide lamp, a microwave excitation mercury lamp, or the like can be used.
- a chemical lamp or black light that can irradiate ultraviolet light having a peak wavelength of 365 nm that does not substantially include a wavelength of less than 280 nm.
- the curing step it is preferable to carry out the curing step by using ultraviolet rays having a peak wavelength of 365 nm and irradiating such ultraviolet rays at an illuminance of 0.1 to 20.0 mW / cm 2 for 2 minutes or more.
- more preferable irradiation conditions are ultraviolet illuminance of 0.5 to 1.5 mW / cm 2 and irradiation time of 3 minutes or more.
- the ultraviolet illuminance is higher than 20.0 mW / cm 2 , the molecular weight of the resulting cured product tends to decrease, and the holding power at high temperatures tends to decrease.
- the ultraviolet illuminance when the ultraviolet illuminance is lower than 0.1 mW / cm 2, the time required for completing the polymerization in the curing step becomes long, which is not practical.
- light may be irradiated with an illuminance exceeding this range as long as it is irradiated with ultraviolet rays having a peak wavelength of 365 nm at an illuminance of 0.01 to 20.0 mW / cm 2 for 2 minutes or more.
- a display device including a resin layer made of a cured product such as the photocurable resin composition and the resin sheet described above can be configured.
- the display device of the present invention may have any structure as long as it has a structure in which an optical member is disposed via a resin layer on the front surface of the display member on the visual recognition side of the display member. Is not particularly limited.
- the resin layer can improve visibility by suppressing light scattering.
- the impact from the outside can be reduced by the elastic characteristics of the resin itself constituting the resin layer, and damage to the optical member such as the cover member and the module of the display device can be suppressed. Even if the cover member is damaged, it is possible to prevent scattering of the fragments of the cover member.
- the display device includes display devices in mobile phones, personal computers, televisions, other various electric appliances, and electronic devices.
- Such a display device can be manufactured by applying or filling a photocurable resin composition according to the present invention between a display member and an optical member, and then curing the resin composition to form a resin layer. it can. It is also possible to use the resin sheet member described above as the resin layer material.
- the photocurable resin composition of the present invention and the cured product thereof have excellent stress relaxation properties, and can be designed in accordance with the purpose from an appropriate adhesive force to a strong adhesive force. Therefore, the resin sheet which shows desired adhesiveness can be easily produced by adjusting the adhesiveness of a photocurable resin composition appropriately beforehand. When such a resin sheet is used, the resin sheet itself can serve as a resin layer and function as an adhesive. Therefore, a display apparatus can be easily manufactured only by sticking a display member and a cover member through a resin sheet.
- the thickness of the resin layer is preferably about 0.02 to 2.0 mm, more preferably 0.05 to 1.0 mm, from the viewpoint of reaction uniformity in the thickness direction.
- a resin sheet having a desired thickness may be used.
- a display member constituting the display device various display panels such as a liquid crystal display, an organic EL display, and a plasma display can be used.
- a cover member installed on the front surface of the display member can be cited.
- a transparent substrate made of various known materials such as an acrylic resin plate such as PMMA, a polycarbonate resin plate, and a glass plate can be used.
- various functional layers known in the art such as a touch panel may be added to the cover member. When providing such various functional layers, it is preferable to use the resin sheet according to the present invention for attachment to the cover member.
- the resin layer of the display device according to the present invention is excellent in stress relaxation, exhibits moderate tackiness, does not contain bubbles or the like with respect to a desired thickness, has no cloudiness under high humidity, and has excellent transparency. Therefore, according to the present invention, it is possible to realize a display device that is improved in defects such as display unevenness and has excellent visibility and high reliability.
- Polyoxyalkylene polyol (a1-1) Polyoxypropylene diol having a hydroxyl value of 56.0 mgKOH / g obtained by further adding PO to propylene oxide (PO) adduct of propylene glycol (PG) (hydroxyl value 112 mgKOH / g) using potassium hydroxide. .
- Polyoxyalkylene polyol (a1-2) The propylene oxide (PO) adduct of propylene glycol (PG) (hydroxyl value 36 mgKOH / g) was further added with ethylene oxide (EO) using potassium hydroxide, and the oxyethylene group content was 12 mass. % Polyoxypropylene-ethylenediol having a hydroxyl value of 28.0 mgKOH / g.
- PO propylene oxide
- PG propylene glycol
- EO ethylene oxide
- Acrylic syrup (B1) A 2 liter round bottom flask equipped with a condenser, nitrogen gas inlet tube, thermometer, and stirrer was charged with 92% by weight 2-ethylhexyl acrylate (2-EHA) and 8% by weight acrylic acid (AA). 500 g of an acrylic rubber having a weight average molecular weight (Mw) of 60 ⁇ 10 4 , 460 g of 2-ethylhexyl acrylate (2-EHA), and 40 g of acrylic acid (AA) are prepared. The mixture was stirred and mixed until the acrylic rubber was completely dissolved.
- Mw weight average molecular weight
- Acrylic syrup (B2) In a 2 liter round bottom flask equipped with a condenser, a nitrogen gas inlet tube, a thermometer, and a stirrer, 97 wt% 2-ethylhexyl acrylate (2-EHA) and 3 wt% acrylic acid (AA) were added. 500 g of an acrylic rubber having a weight average molecular weight (Mw) of 60 ⁇ 10 4 , 485 g of 2-ethylhexyl acrylate (2-EHA), and 15 g of acrylic acid (AA) were prepared. The mixture was stirred and mixed at 0 ° C. until the acrylic rubber was completely dissolved.
- Mw weight average molecular weight
- Acrylic syrup (B3) A 2 liter round bottom flask equipped with a condenser, a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 80 wt% 2-ethylhexyl acrylate (2-EHA) and 20 wt% 2-hydroxyethyl acrylate ( 500 g of acrylic rubber having a weight average molecular weight (Mw) of 10 ⁇ 10 4 , 400 g of 2-ethylhexyl acrylate (2-EHA), and 2-hydroxyethyl acrylate (2-HEA) ) was added to each of them, and these raw materials were stirred and mixed at 50 ° C. until the acrylic rubber was completely dissolved.
- Mw weight average molecular weight
- Acrylic syrup (B4) To a 2-liter round bottom flask equipped with a condenser, a nitrogen gas inlet tube, a thermometer, and a stirrer, 70% by weight of 2-ethylhexyl acrylate (2-EHA) and 30% by weight of acrylic acid (AA) 500 g of acrylic rubber having a weight average molecular weight (Mw) of 60 ⁇ 10 4 , 350 g of 2-ethylhexyl acrylate (2-EHA), and 150 g of acrylic acid (AA) were charged, respectively, and these raw materials were charged at 50 ° C. The mixture was stirred and mixed until the acrylic rubber was completely dissolved.
- Mw weight average molecular weight
- Acrylic syrup (B5) A 2-liter round bottom flask equipped with a condenser, a nitrogen gas inlet tube, a thermometer, and a stirrer was charged with 92% by weight of 2-ethylhexyl acrylate (2-EHA) and 8% by weight of acrylic acid (AA).
- 2-EHA 2-ethylhexyl acrylate
- AA acrylic acid
- the obtained monoisocyanate was calculated to have an isocyanate concentration of 13.6% using an automatic potentiometric titrator (trade name “AT-400” manufactured by Kyoto Electronics Industry Co., Ltd.).
- Urethane acrylate oligomer (A1) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-1), 78 g of isophorone diisocyanate (IPDI), 2-acrylic acid 2- 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- 2-acrylic acid 2- 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- Urethane acrylate oligomer (A2) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of the previously prepared polyoxyalkylene polyol (a1-1), 100 g of isophorone diisocyanate (IPDI), and a diluent 700 g of 2-ethylhexyl acrylate and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- Urethane acrylate oligomer (A3) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-1), 106 g of isophorone diisocyanate (IPDI), and 2-acrylic acid acrylic acid as a diluent. 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate as a catalyst were respectively charged and reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- Urethane acrylate oligomer (A4) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-1), 166 g of isophorone diisocyanate (IPDI), 2-acrylic acid 2- 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours. Next, 57 g of hydroxyethyl acrylate (HEA) was added to the reaction mixture, and further reacted at a temperature of 100 ° C. for 2 hours. The infrared absorption spectrum of the reaction mixture thus obtained was measured, and it was confirmed that the isocyanate group absorption (2250 cm ⁇ 1 ) disappeared.
- IPDI isophorone diisocyanate
- Urethane acrylate oligomer (A5) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-1), 100 g of isophorone diisocyanate (IPDI), and 2-acrylic acid acrylic acid as a diluent. 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- Urethane acrylate oligomer (A6) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-1), 56 g of isophorone diisocyanate (IPDI), and 2-acrylic acid acrylic acid as a diluent. 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate as a catalyst were respectively charged and reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- Urethane acrylate oligomer (A7) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-1), 222 g of isophorone diisocyanate (IPDI), 2-acrylic acid 2- 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- 2-acrylic acid 2- 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- the reaction mixture was mixed with polyoxy 840 g of alkylene monool (commercial product “Preminol S 1004”, manufactured by Asahi Glass Co., Ltd., hydroxyl value 16.7 mgKOH / g) and 87 g of hydroxyethyl acrylate (HEA) were added, and further reacted at a temperature of 100 ° C. for 2 hours.
- the reaction mixture thus obtained was measured by automatic infrared absorption spectrum, and it was confirmed that the isocyanate group absorption (2250 cm ⁇ 1 ) disappeared.
- Urethane acrylate oligomer (A8) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-1), 100 g of isophorone diisocyanate (IPDI), and 2-acrylic acid acrylic acid as a diluent. 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- Urethane acrylate oligomer (A9) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-1), 100 g of isophorone diisocyanate (IPDI), and 2-acrylic acid acrylic acid as a diluent. 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- Urethane acrylate oligomer (A10) In a four-necked flask equipped with a stirrer, dropping funnel, nitrogen inlet tube and thermometer, 1,000 g of polyoxyalkylene polyol (a1-2), 54 g of isophorone diisocyanate (IPDI), and 2-acrylic acid acrylic acid as a diluent. 700 g of ethylhexyl and 0.1 g of dibutyltin dilaurate were charged as a catalyst, and these were reacted at a temperature of 100 ° C. for 4 hours.
- IPDI isophorone diisocyanate
- Example 1 Production of sheet material
- 200 g of A1 prepared previously as urethane acrylate oligomer and 800 g of B1 prepared previously as acrylic syrup were charged and mixed at 30 ° C. for 1 hour. Then, the mixture was defoamed by mixing for 15 minutes under a pressure of 100 mmHg.
- 10 g of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator was added to this reaction mixture, mixed at 30 ° C. for 1 hour, and then mixed with degassing under a pressure of 100 mmHg for 15 minutes.
- the varnish thus obtained was sandwiched between two PET separator films that had been previously treated with silicone so as to have different peel forces, and the thickness of the varnish layer was adjusted to 175 ⁇ m.
- ultraviolet rays having an illuminance of 0.5 mW / cm 2 were irradiated from the outer surface of each PET separator film using a black light for 7 minutes to cure the varnish layer to obtain a sheet member.
- each test piece was placed in a tensile tester and peeled at room temperature (23 ° C.) at a peeling angle of 200 mm / min at 180 °. The sheet was peeled from the glass interface at a speed, and the stress at the time of peeling was measured.
- each measured value described in Table 1 is evaluated as follows. A: Stress during peeling is 4 N / 25 mm or more B: Stress during peeling is 2 N / 25 mm or more and less than 4 N / 25 mm C: Stress at peeling is 0.5 N / 25 mm or more and less than 2 N / 25 mm D: Stress during peeling is less than 0.5 N / 25 mm
- B About one test piece among two test pieces, slight peeling, floating, and foaming are observed between the sheet and the polarizing plate.
- C About two test pieces, slight peeling, floating, and foaming are observed between the sheet and the polarizing plate.
- D Clear peeling, floating, and foaming are observed between the sheet and the polarizing plate of the two test pieces.
- the prepared test piece is fixed so that the longitudinal direction is the vertical direction, and a steel ball having a weight of 110 g is dropped from a height of 1 m toward the end of the test piece (that is, the bonding surface) and collided. After that, the presence or absence of peeling of the test piece was visually confirmed.
- the evaluation criteria in Table 1 are as follows. P: No peeling F: Peeling
- the previously produced sheet member was cut to 40 ⁇ 60 mm, and the light separator film of the sheet member was peeled off, and then the sheet surface was float glass (80 mm ⁇ 60 mm ⁇ thickness 1.0 mm) that was regarded as a cover member ( Compliant with JIS R 3202).
- the heavy surface separator of the sheet member is peeled off and bonded to one side of the above-mentioned structure as if it were a liquid crystal panel, and it is placed in an autoclave adjusted to 50 ° C. and 5 atm for 20 minutes to produce a test plate. did.
- test piece was prepared by using an acrylic plate (“Acrylite MR-200”) of 85 mm ⁇ 45 mm ⁇ 2 mm in thickness as a cover member.
- an acrylic plate (“Acrylite MR-200”) of 85 mm ⁇ 45 mm ⁇ 2 mm in thickness as a cover member.
- Example 2 A varnish was prepared by exactly the same formulation and method as in Example 1 except that A2 prepared previously as a urethane acrylate oligomer was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 3 A varnish was prepared by exactly the same formulation and method as in Example 1 except that A3 prepared previously as a urethane acrylate oligomer was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 4 A varnish was prepared by exactly the same formulation and method as in Example 1 except that A5 prepared previously as urethane acrylate was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 5 A varnish was prepared by exactly the same formulation and method as in Example 1 except that A9 prepared previously as urethane acrylate was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 6 A varnish was prepared by exactly the same formulation and method as in Example 2 except that B2 prepared earlier was used as an acrylic syrup, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 7 A varnish was prepared by exactly the same composition and method as in Example 2 except that B3 prepared previously as an acrylic syrup was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Example 8 A varnish was prepared by exactly the same composition and method as in Example 2 except that B5 prepared previously as an acrylic syrup was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.
- Example 9 The same reaction mixture as the varnish of Example 1 was prepared in the same manner as Example 1 except that A2 prepared earlier was used as the urethane acrylate and B1 prepared earlier was used as the acrylic syrup. Subsequently, 5 g of 3-glycidoxypropylmethyldiethoxysilane was added to the reaction mixture, and the mixture was further mixed at 30 ° C. for 15 minutes, and then mixed under a pressure of 100 mmHg for 15 minutes to degas. The varnish thus obtained was cured by the same method as in Example 1 to produce a sheet member and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.
- Example 10 In a four-necked flask equipped with a stirrer, a vacuum tube and a thermometer, 200 g of A2 prepared previously as urethane acrylate, 800 g of B3 prepared earlier as acrylic syrup, and Mitsui Chemicals' “ FTR6100 "(trade name), 50 g, was charged, mixed at 50 ° C for 2 hours, and then mixed for 15 minutes under a pressure of 100 mmHg to degas.
- Example 11 A varnish was prepared by exactly the same composition and method as in Example 2 except that A10 prepared previously as urethane acrylate was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.
- Example 12 A varnish was prepared by exactly the same formulation and method as in Example 1 except that A8 prepared previously as urethane acrylate was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.
- Example 13 A varnish was prepared by exactly the same composition and method as in Example 2 except that B4 prepared previously as an acrylic syrup was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.
- Example 14 A four-necked flask equipped with a stirrer, a vacuum tube and a thermometer was charged with 300 g of A9 as urethane acrylate and 700 g of B1 as acrylic syrup, and these were mixed at 30 ° C. for 1 hour, and then at a pressure of 100 mmHg for 15 minutes. Mix and degas. Next, 10 g of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator was added to this reaction mixture and mixed at 30 ° C. for 1 hour, and then mixed for 15 minutes under a pressure of 100 mmHg to degas.
- the varnish thus obtained was sandwiched between two PET separator films whose surfaces were previously silicone-treated so as to have different peeling forces, and the thickness of the varnish layer was adjusted to 175 ⁇ m.
- ultraviolet light having an illuminance of 400 mW / cm 2 was irradiated with an integrated light amount of 3,000 mJcm 2 to cure the varnish layer, thereby obtaining a sheet member.
- a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.
- Example 1 A varnish was prepared by exactly the same composition and method as in Example 1 except that A6 prepared previously as urethane acrylate was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
- Example 2 A varnish was prepared by exactly the same formulation and method as in Example 1 except that A4 prepared previously as urethane acrylate was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
- Example 3 A varnish was prepared by exactly the same formulation and method as in Example 1 except that A7 prepared previously as urethane acrylate was used, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
- Comparative Example 4 A varnish was prepared by exactly the same composition and method as Comparative Example 3 except that B3 prepared earlier was used as an acrylic syrup, and then a sheet member was prepared and evaluated. Further, a display device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
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Abstract
Description
4000≦N(=n1/n2)・・・式(I)
を満足し、未反応のイソシアネート基を実質的に含まないことを特徴とする。
(1)70℃における貯蔵弾性率が1×103~1×106Paかつ損失弾性率が1×103~1×106Pa
(2)23℃における貯蔵弾性率が1×104~5×106Pa、かつ損失弾性率が1×104~5×106Pa
(3)0℃における貯蔵弾性率が5×104~1×107Pa、かつ損失弾性率が5×104~1×107Pa
なお、本出願は、同出願人により2009年7月22日に出願された日本国特願2009-171200号に基づく優先権主張を伴うものであって、この出願明細書を参照して全体的に本明細書に組み込むものとする。
成分(A)
本発明の光硬化性樹脂組成物における成分(A)のポリオキシアルキレン構造を有するウレタン(メタ)アクリレートオリゴマーは、(a1)少なくとも1種のポリオキシアルキレンポリオールと、(a2)少なくとも1種のポリイソシアネートと、(a3)少なくとも1種の水酸基含有モノ(メタ)アクリレート化合物とを含む3種以上のモノマー成分を用いて製造され、3種以上のモノマー成分の合計質量n1と、3種以上のモノマー成分におけるアクリロイル基の合計等量数n2との関係N(=n1/n2)が下式
4000≦N(=n1/n2)・・・式(I)
を満足するものであり、未反応のイソシアネート基を実質的に含まないことを特徴とする。このように、成分(A)として使用するオリゴマーは、少なくとも(a1)~(a3)のモノマー成分を式(I)の関係を満足するような特定の割合で反応させることによって、その分子量及び分子内におけるアクリロイル基の平均官能基数が適切に制御される。
本発明で使用する成分(a1)のポリオキシアルキレンポリオールは、分子内に2個以上の水酸基を含有し、ポリエーテルポリオールとも呼ばれる化合物である。このような化合物は、例えば、多価アルコール類、多価フェノール類、及びアミン類等の分子内に2個以上の活性水素を有する化合物を開始剤として使用し、その開始剤に対してアルキレンオキサイド化合物を付加重縮合させることによって得ることができる。開始剤として使用する分子内に2個以上の活性水素を有する化合物は、脂肪族、脂環式、及び芳香族のいずれの化合物であってもよい。一方、アルキレンオキサイド化合物は、炭素数2~4の化合物が好ましい。
数平均分子量=(56100/OHv)×1分子当たりの平均官能基数
を用いて計算して得られた値をいう。また「水酸基価」とは、JIS K1557 6.4に準拠し測定して得られた値である。
本発明で使用する成分(a2)のポリイソシアネートは、イソシアネート基を2個以上有する芳香族系、脂環族系及び脂肪族系のポリイソシアネート、それら2種類以上の混合物、並びにそれらを変性して得られる変性ポリイソシアネートであってよい。上述のポリイソシアネート化合物の中でも、イソシアネート基を2個有するジイソシアネート化合物が好ましい。
本発明で使用する成分(a3)の水酸基含有モノ(メタ)アクリレート化合物は、(メタ)アクリル酸と、脂肪族、脂環式又は芳香族ジオールとのエステルが好ましい。特に、(メタ)アクリル酸と、炭素数1~8のアルカンジオールとのエステルが好ましい。例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート(平均値としてn=2~10)、ポリプロピレングリコールモノ(メタ)アクリレート(平均値としてn=2~10)、2-ヒドロキシ-3-フェニルオキシプロピル(メタ)アクリレート等が挙げられる。その他、ポリカプロラクトンアクリレートや水酸基含有脂環族アクリレート等の、光硬化性組成物として濁りが発生しない範囲の相溶性を有する化合物であれば、特に制限なく使用することができる。
4000≦N(=n1/n2)・・・式(I)
を満足するような割合で反応させることによって、得られるオリゴマーの分子量及び平均官能基数を適切に制御することができる。
本発明の光硬化性樹脂組成物における成分(B)は、(メタ)アクリル系ポリマーであり、この成分は、樹脂組成物及びシートに粘着性を発現させ、かつ高温環境下での粘着信頼性を向上させる効果を有する。成分(B)として使用する(メタ)アクリル系ポリマーは、(メタ)アクリル系のモノマー化合物を重合して得られるポリマーであってよく、特に限定されない。しかし、高温環境下における粘着信頼性を高める観点から、10×104~200×104の重量平均分子量を有するポリマーが好ましい。ここで「重量平均分子量」は、ゲル浸透クロマトグラフィーによって測定した標準ポリスチレン換算値として求めた値を意味する。
本発明において成分(C)として使用する(メタ)アクリル系モノマーは、(メタ)アクリル系化合物として周知の化合物であってよい。特に限定するものではないが、本発明で使用する成分(C)は、カルボキシル基を有する(メタ)アクリル系モノマーを含むことが好ましい。具体例としては、先に成分(B)を構成するモノマー成分として例示した各種化合物を使用することができる。なお、表示装置における樹脂層材料としての用途を想定すると、高温環境下での粘着耐久性の観点から、成分(C)を構成するモノマーの総量に対して、カルボキシル基を有する(メタ)アクリル系モノマー(c1)が好ましくは3~50モル%、より好ましくは5~45モル%の割合で存在することが望ましい。本発明の好ましい一実施形態において、成分(C)は(c1)(メタ)アクリル酸と、(c2)(メタ)アクリル酸エステルとを含むモノマー混合物であり、上記モノマー混合物は成分(c1)を好ましくは3~50モル%、より好ましくは5~45モル%の割合で含む。
本発明で成分(D)として使用する光重合開始剤は、ビニル系モノマーを光重合させるために使用可能な周知の化合物であってよい。光重合開始剤として使用可能な化合物の具体例として、α-ヒドロキシイソブチルフェノンベンゾイン、イソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、ベンゾフェノン、ミヒラーケトン、クロロチオキサントン、ドデシルチオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、アセトフェノンジエチルケタール、ベンジルジメチルケタール、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-ジフェニルフォスフィンオキサイド、オキシ-フェニル-アセチックアシッド2-[2-オキソ-2-フェニル-アセトキシ-エトキシ]-エチルエステルとオキシ-フェニル-アセチックアシッド2-[2-ヒドロキシ-エトキシ]-エチルエステルの混合物等が挙げられる。
本発明による光硬化性樹脂組成物は、上述の必須成分(A)~(D)に加えて、必要に応じて、その他の成分を追加してもよい。特に、本発明では、樹脂層材料としてシート部材を作製する場合を想定し、シートの粘着性を向上させるために、樹脂組成物にタッキファイアを追加してもよい。
(弾性率の測定方法)
各種厚さのシートを貼合積層することによって、長さ:5mm、幅:12.0mm、厚さ:1.0mmの短冊状シートを作製し、これを試験片として使用する。試験片を以下の条件下でフィルムずりモードによって測定する。
測定装置:エスアイアイ・ナノテクノロジー社製 DMS6100
周波数:10Hz
温度:-100℃~100℃(昇温速度:2℃/min)
プロピレングリコール(PG)のプロピレンオキサイド(PO)付加体(水酸基価112mgKOH/g)に、水酸化カリウムを用いてさらにPOを付加することによって得た、水酸基価56.0mgKOH/gのポリオキシプロピレンジオール。
プロピレングリコール(PG)のプロピレンオキサイド(PO)付加体(水酸基価36mgKOH/g)に、水酸化カリウムを用いてさらにエチレンオキサイド(EO)を付加することによって得た、オキシエチレン基含有量が12質量%であり、水酸基価28.0mgKOH/gのポリオキシプロピレン-エチレンジオール。
コンデンサー、窒素ガス導入管、温度計、及び攪拌装置を備えた容量2リットルの丸底フラスコに、92重量%のアクリル酸2-エチルヘキシル(2-EHA)と8重量%のアクリル酸(AA)とから構成される重量平均分子量(Mw)が60×104のアクリルゴムを500g、アクリル酸2-エチルヘキシル(2-EHA)を460g、及びアクリル酸(AA)を40gそれぞれ仕込み、これら原料を50℃にてアクリルゴムが完全に溶解するまで攪拌混合した。
コンデンサー、窒素ガス導入管、温度計、及び攪拌装置を備えた容量2リットルの丸底フラスコに、97重量%のアクリル酸2-エチルヘキシル(2-EHA)と3重量%のアクリル酸(AA)とから構成される重量平均分子量(Mw)が60×104のアクリルゴムを500g、アクリル酸2-エチルヘキシル(2-EHA)を485g、及びアクリル酸(AA)を15g、それぞれ仕込み、これら原料を50℃にてアクリルゴムが完全に溶解するまで攪拌混合した。
コンデンサー、窒素ガス導入管、温度計、攪拌装置を備えた容量2リットルの丸底フラスコに、80重量%のアクリル酸2-エチルヘキシル(2-EHA)と20重量%のアクリル酸2-ヒドロキシエチル(2-HEA)とから構成される重量平均分子量(Mw)が10×104のアクリルゴムを500g、アクリル酸2-エチルヘキシル(2-EHA)を400g、及びアクリル酸2-ヒドロキシエチル(2-HEA)を100g、それぞれ仕込み、これら原料を50℃にてアクリルゴムが完全に溶解するまで攪拌混合した。
コンデンサー、窒素ガス導入管、温度計、攪拌装置を備えた容量2リットルの丸底フラスコに、70重量%のアクリル酸2-エチルヘキシル(2-EHA)と30重量%のアクリル酸(AA)とから構成される重量平均分子量(Mw)が60×104のアクリルゴムを500g、アクリル酸2-エチルヘキシル(2-EHA)を350g、及びアクリル酸(AA)を150g、それぞれ仕込み、これら原料を50℃にてアクリルゴムが完全に溶解するまで攪拌混合した。
コンデンサー、窒素ガス導入管、温度計、攪拌装置を備えた容量2リットルの丸底フラスコに、92重量%のアクリル酸2-エチルヘキシル(2-EHA)と8重量%のアクリル酸(AA)とから構成される重量平均分子量(Mw)が10×104のアクリルゴムを500g、アクリル酸2-エチルヘキシル(2-EHA)を460g、及びアクリル酸(AA)を40g、それぞれ仕込み、これら原料を50℃にてアクリルゴムが完全に溶解するまで攪拌混合した。
本発明で使用するウレタン(メタ)アクリレートオリゴマーの製造方法を以下に例示する。
モノイソシアネート(HEA-H6XDI)の製造:
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、水添キシリレンジイソシアネート(b2)194gと、ヒドロキシエチルアクリレート116gと、ジブチル錫ジラウレート0.005gをそれぞれ仕込み、これらの反応混合物の温度を80℃以下に保持しながら3時間反応させた。その後、反応混合物の温度が40℃になるまで冷却したところで追加のジブチル錫ジラウレートを0.005g入れて、温度上昇がないことを確認することによって反応を終了した。得られたモノイソシアネートについて電位差自動滴定装置(京都電子工業(株)製、商品名「AT-400」を用いて、イソシアネート濃度を算出したところ13.6%であった。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート (IPDI)78gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、これらを温度100℃で4時間反応させた。反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した後、反応混合物にモノイソシアネート(HEA-H6XDI)を69g入れて、さらに温度100℃で2時間反応させた。得られた反応混合物の赤外吸収スペクトルを再度測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、先に調製したポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート(IPDI)100gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、これらを温度100℃で4時間反応させた。反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した後、反応混合物にモノイソシアネート(HEA-H6XDI)を23g入れて、さらに温度100℃で2時間反応させた。その後、得られた反応混合物の赤外吸収スペクトルを再度測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート (IPDI)106gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、温度100℃で4時間反応させた。反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した後、反応混合物にモノイソシアネート(HEA-H6XDI)を10.6g入れて、さらに温度100℃で2時間反応させた。このようにして得られた反応混合物の赤外吸収スペクトルを再度測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート (IPDI)166gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、これらを温度100℃で4時間反応させた。次いで、反応混合物にヒドロキシエチルアクリレート(HEA)を57g入れて、さらに温度100℃で2時間反応させた。このようにして得られた反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート (IPDI)100gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、これらを温度100℃で4時間反応させた。反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した後、モノイソシアネート(HEA-H6XDI)を31g入れて、さらに温度100℃で2時間反応させた。このようにして得られた反応混合物の赤外吸収スペクトルを再度測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート (IPDI)56gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、温度100℃で4時間反応させた。反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した後、モノイソシアネート(HEA-H6XDI)を115g入れて、さらに温度100℃で2時間反応させた。このようにして得られた反応混合物の赤外吸収スペクトルを再度測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート (IPDI)222gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、これらを温度100℃で4時間反応させた。AT-400電位差自動測定装置(京都電子工業株式会社製)を使用して反応混合物におけるイソシアネート濃度を測定し、その濃度が0.75%になったことを確認した後に、反応混合物に、ポリオキシアルキレンモノオール(市販品「プレミノールS 1004」、旭硝子株式会社製 水酸基価16.7mgKOH/g)840gと、ヒドロキシエチルアクリレート(HEA)87gとを入れて、さらに温度100℃で2時間反応させた。このようにして得られた反応混合物を自動赤外吸収スペクトルで測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート (IPDI)100gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、これらを温度100℃で4時間反応させた。反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した後に、反応混合物にモノイソシアネート(HEA-H6XDI)を7.8g入れて、さらに温度100℃で2時間反応させた。このようにして得られた反応混合物の赤外吸収スペクトルを再度測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-1)1,000gと、イソホロンジイソシアネート (IPDI)100gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとをそれぞれ仕込み、これらを温度100℃で4時間反応させた。反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した後に、反応混合物にモノイソシアネート(HEA-H6XDI)を31g入れて、さらに温度100℃で2時間反応させた。このようにして得られた反応混合物の赤外吸収スペクトルを再度測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
撹拌機、滴下ロート、窒素導入管及び温度計を取り付けた4ツ口フラスコに、ポリオキシアルキレンポリオール(a1-2)1,000gと、イソホロンジイソシアネート (IPDI)54gと、希釈剤としてアクリル酸2-エチルヘキシル700gと、触媒としてジブチル錫ジラウレート0.1gとを仕込み、これらを温度100℃で4時間反応させた。反応混合物の赤外吸収スペクトルを測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した後、反応混合物にモノイソシアネート(HEA-H6XDI)を6.5g入れて、さらに温度100℃で2時間反応させた。このようにして得られた反応混合物の赤外吸収スペクトルを再度測定し、イソシアネート基の吸収(2250cm-1)が消えたことを確認した。
1.シート部材の作製
撹拌機、真空管及び温度計を取り付けた4ツ口フラスコに、ウレタンアクリレートオリゴマーとして先に調製したA1を200g、及びアクリルシロップとして先に調製したB1を800gそれぞれ仕込み、これらを30℃で1時間混合した後に、100mmHgの圧力下で15分混合して脱泡した。この反応混合物に、次いで、光重合開始剤として1-ヒドロキシシクロヘキシルフェニルケトンを10g入れて、30℃で1時間混合した後に、100mmHgの圧力下で15分にわたって脱泡しながら混合した。このようにして得られたワニスを、予め互いに異なる剥離力となるようにシリコーン処理を施した2枚のPETセパレータフィルムで挟み込み、ワニス層の厚さが175μmとなるように調整した。次いで、各PETセパレータフィルムの外面から、ブラックライトを用いて照度0.5mW/cm2の紫外線を7分照射し、ワニス層を硬化させ、シート部材を得た。
先に作製したシート部材を使用して以下に示す各種試験を実施した。各種試験における評価結果を表1に示す。
(剥離接着強さ)
シート部材を25×100mmの寸法に切断し、軽面セパレータフィルムを剥がしてから、シート面を厚さ38μmの易接着性PET支持体に貼り合わせた。次いで、シート部材の重面セパレータフィルムを剥がして、他方のシート面を幅30mm×長さ100mm×厚み2.0mmのフロートガラス(JIS R 3202に準拠)上に貼り合わせ、試験片とした。この試験片を23℃及び80℃の各温度条件下にそれぞれ2時間放置した後、各試験片を引張試験機に設置し、室温下(23℃)、180°の剥離角度200mm/分の剥離速度でガラス界面からシートを剥離させ、剥離時の応力を測定した。表示装置の樹脂層材料としての用途を考慮すると、表1に記載した各測定値は以下のように評価される。
A:剥離時の応力が4N/25mm以上
B:剥離時の応力が2N/25mm以上、4N/25mm未満
C:剥離時の応力が0.5N/25mm以上、2N/25mm未満
D:剥離時の応力が0.5N/25mm未満
剥離接着強さの試験に向けて作製した試験片と同様にして、一面にPET支持体を有し、他面にフロートガラスを有する試験片を作製し、この試験片を80℃の温度条件下で24時間放置した。その後、試験片のシート層とガラスとをそれらの界面で剥離し、ガラスの剥離面を目視にて観察し、ブリード成分の有無について評価した。表1における評価基準は、以下のとおりである。
P:ガラス表面にブリード成分が見られない。
P-:ガラス表面にブリード成分がほとんど見られない。
F:ガラス表面にブリード成分が見られる。
先に作製したシート部材を40×60mmの寸法に切断し、軽面セパレータフィルムを剥離してから、シート面を、カバー部材に見立てた80mm×60mm×厚み1.0mmのフロートガラス(JIS R 3202に準拠)上に貼り合わせ、偏光板を貼った80mm×60mm×厚み1.0mmのフロートガラスの偏向板に対して貼り合せ、オートクレーブで50℃、0.5MPa条件で30分脱泡処理した後、80℃環境下に放置した。また、同様にして、カバー部材として85mm×45mm×厚み2mmのアクリル板(三菱レイヨン株式会社製の商品名「アクリライトMR-200」)を使用して試験片を作製し、同様の処理を施した。上述のようにカバー部材としてフロートガラス及びアクリル板を使用した各試験片を2つずつ準備し、それぞれ6時間放置後に偏光板界面を目視にて観察した。すなわち、各試験片につき2回の評価を行い、さらに以下の基準に従って評価した。その結果を表1に示す。
(評価基準)
A:2つの試験片について、シートと偏光板との間に剥れや浮き、発泡が見られない。
B:試験片2つのうち1つの試験片について、シートと偏光板との間に軽微な剥れや浮き、発泡が見られる。
C:2つの試験片についてシートと偏光板との間に軽微な剥れや浮き、発泡が見られる。
D:2つの試験片についてシートと偏光板との間に明らかな剥れや浮き、発泡が見られる。
先に作製したシート部材を20mm×40mmの寸法に切断し、軽面セパレータフィルムを剥がした後に、そのシート面を松浪硝子工業株式会社製のマイクロスライドガラス「S3233」(厚さ1.3mm、寸法48×28mm)上に気泡の巻き込みなく貼り合わせて試験片を作製した。この試験片のヘイズを、JIS K 7105適合のヘイズメータを用いて測定し、以下の基準に従って評価した。
P:ヘイズ0.3%以下
F:ヘイズ0.4%以上
先に作製したシート部材を40mm×40mmの寸法に切断し、一方のセパレータフィルムを剥離してシート面を露出させ第1のアクリル板に貼り付けた。次いで、上記シート部材の残りのセパレータフィルムを剥離してシート面を露出させた後、第1のアクリル板に対して、互いに長手方向に継ぎ手状に第2のアクリル板を配置し、重なり部位が60mmとなるように貼り合わせて試験片を作製した。なお、上記試験片の作製では、第1および第2のアクリル板として、85mm×45mm×厚み2mmの寸法を有する、三菱レイヨン株式会社製の商品名「アクリライトMR-200」)を使用した。
作製した試験片の長手方向が鉛直方向となるように固定し、試験片の端部(すなわち、貼り合せ面)に向かって、重さ110gの鋼球を1mの高さから落下させて衝突させた後に、試験片の剥れの有無を目視にて確認した。表1における評価基準は以下のとおりである。
P:剥れなし
F:剥れあり
80mm×60mm×厚み0.55mmのフロートガラス(JIS R 3202に準拠)2枚を、日立化成ポリマー株式会社製の透明粘着テープYY621-3(厚み0.1mm)を介して、互いに気泡なく貼り付け、無アルカリガラス板として使用した。このガラス板の両面に対して、偏光板2枚を互いに直交ニコル位になるように、ラミネーターロールを用いて貼着した後、これを50℃、5気圧に調整したオートクレーブ内に入れ20分間保持した。このようにして得た偏光板/無アルカリガラス板/偏光板からなる構造体を液晶パネルに見立てた。
B:光漏れはほぼ見られなかった。
C:わずかに光漏れが見られた。
D:明らかな光漏れが見られた。
ウレタンアクリレートオリゴマーとして先に調製したA2を使用した以外は、実施例1と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表1に示す。
ウレタンアクリレートオリゴマーとして先に調製したA3を使用した以外は、実施例1と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表1に示す。
ウレタンアクリレートとして先に調製したA5を使用した以外は、実施例1と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表1に示す。
ウレタンアクリレートとして先に調製したA9を使用した以外は、実施例1と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表1に示す。
アクリルシロップとして先に調製したB2を使用した以外は、実施例2と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表1に示す。
アクリルシロップとして先に調製したB3を使用した以外は、実施例2と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表1に示す。
アクリルシロップとして先に調製したB5を使用した以外は、実施例2と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表2に示す。
ウレタンアクリレートとして先に調製したA2を使用し、またアクリルシロップとして先に調製したB1を使用すること以外は全て実施例1と同様して、実施例1のワニスと同じ反応混合物を調製した。この反応混合物に、引き続き3-グリシドキシプロピルメチルジエトキシシランを5g入れて、さらに30℃で15分間混合した後、100mmHgの圧力下で15分混合し脱泡した。このようにして得られたワニスを実施例1と同じ方法によって硬化させてシート部材を作製し、評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表2に示す。
撹拌機、真空管及び温度計を取り付けた4ツ口フラスコに、ウレタンアクリレートとして先に調製したA2を200gと、アクリルシロップとして先に調製したB3を800gと、タッキファイアとして三井化学株式会社製の「FTR6100」(商品名)を50g、それぞれ仕込み、これらを50℃で2時間混合した後、100mmHgの圧力下で15分混合して脱泡した。反応混合物の温度が30℃になるまで冷却した後に、反応混合物に光重合開始剤として1-ヒドロキシシクロヘキシルフェニルケトンを10g入れて、30℃で1時間混合し、引き続き100mmHgの圧力下で15分混合して脱泡した。このようにして得られたワニスを、実施例1と同様にして、予め互いに異なる剥離力となるように表面をシリコーン処理した2枚のPETセパレータフィルムで挟み込み、ワニス層の厚さが175μmとなるように調整した。次いで、各PETセパレータフィルムの主面側から、ブラックライトを用いて、照度0.5mW/cm2の紫外線を7分照射し、ワニス層を硬化させ、シート部材を得た。作製したシート部材について、実施例1と同様にして各種試験を実施するとともに、表示装置を作製し、評価した。その結果を表2に示す。
ウレタンアクリレートとして先に調製したA10を使用した以外は、実施例2と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表2に示す。
ウレタンアクリレートとして先に調製したA8を使用した以外は、実施例1と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。その結果を表2に示す。
アクリルシロップとして先に調製したB4を使用した以外は、実施例2と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。結果を表2に示す。
撹拌機、真空管及び温度計を取り付けた4ツ口フラスコに、ウレタンアクリレートとしてA9を300g及びアクリルシロップとしてB1を700gそれぞれ仕込み、これらを30℃で1時間混合した後、100mmHgの圧力下で15分混合して脱泡した。次いで、この反応混合物に、光重合開始剤として1-ヒドロキシシクロヘキシルフェニルケトンを10g入れて30℃で1時間混合した後、100mmHgの圧力下で15分混合して脱泡した。このようにして得られたワニスを、予め互いに異なる剥離力となるように表面をシリコーン処理した2枚のPETセパレータフィルムで挟み込み、ワニス層の厚さが175μmとなるように調整した。次いで、各PETセパレータフィルムの外面から、メタルハライドランプを用いて、照度400mW/cm2の紫外線を積算光量で3,000mJcm2照射し、ワニス層を硬化させ、シート部材を得た。さらに実施例1と同様にして表示装置を作製し、評価した。結果を表2に示す。
ウレタンアクリレートとして先に調製したA6を使用した以外は、実施例1と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。結果を表3に示す。
ウレタンアクリレートとして先に調製したA4を使用した以外は、実施例1と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。結果を表3に示す。
ウレタンアクリレートとして先に調製したA7を使用した以外は、実施例1と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。結果を表3に示す。
アクリルシロップとして先に調製したB3を使用した以外は、比較例3と全く同じ配合及び方法でワニスを調製し、次いでシート部材を作製して評価した。さらに実施例1と同様にして表示装置を作製し、評価した。結果を表3に示す。
Claims (17)
- 表示部材と、該表示部材の前面に樹脂層を介して設置される光学部材とを有する表示装置の前記樹脂層を形成するための光硬化性樹脂組成物であって、
(A)ポリオキシアルキレン構造を有するウレタン(メタ)アクリレートオリゴマーと、
(B)(メタ)アクリル系ポリマーと、
(C)(メタ)アクリル系モノマーと、
(D)光重合開始剤と
を含有し、
前記成分(A)が、(a1)少なくとも1種のポリオキシアルキレンポリオールと、(a2)少なくとも1種のポリイソシアネートと、(a3)少なくとも1種の水酸基含有モノ(メタ)アクリレート化合物を含む3種以上のモノマー成分を用いて製造され、
前記3種以上のモノマー成分の合計質量n1と、前記3種以上のモノマー成分におけるアクリロイル基の合計等量数n2との関係Nが下式
4000≦N(=n1/n2)・・・式(I)
を満足し、未反応のイソシアネート基を実質的に含まないことを特徴とする、光硬化性樹脂組成物。 - 前記成分(B)がカルボキシル基を有する(メタ)アクリル系ポリマーを含み、前記成分(C)がカルボキシル基を有する(メタ)アクリル系モノマーを含むことを特徴とする、請求項1に記載の光硬化性樹脂組成物。
- 前記成分(A)が、(メタ)アクリロイル基を1つ有するウレタン(メタ)アクリレートオリゴマーと、(メタ)アクリロイル基を2つ以上有するウレタン(メタ)アクリレートオリゴマーとの混合物であることを特徴とする、請求項1又は2に記載の光硬化性樹脂組成物。
- 前記成分(B)が、重量平均分子量10×104~200×104の(メタ)アクリル系ポリマーであることを特徴とする、請求項1~3のいずれか1項に記載の光硬化性樹脂組成物。
- 前記成分(B)が、(b1)(メタ)アクリル酸と、(b2)(メタ)アクリル酸エステルとを含むモノマー混合物を重合して得られるコポリマーであることを特徴とする、請求項2~4のいずれか1項に記載の光硬化性樹脂組成物。
- 前記モノマー混合物が、前記(メタ)アクリル酸(b1)を5~45モル%含むことを特徴とする、請求項5に記載の光硬化性樹脂組成物。
- 前記成分(C)が、(c1)(メタ)アクリル酸と、(c2)(メタ)アクリル酸エステルとを含むモノマー混合物であることを特徴とする、請求項2~6のいずれか1項に記載の光硬化性樹脂組成物。
- 前記モノマー混合物が、前記(メタ)アクリル酸(c1)を5~45モル%含むことを特徴とする、請求項7に記載の光硬化性樹脂組成物。
- 前記成分(B)を構成するモノマー混合物及び前記成分(C)が、互いに同種類の化合物を含むことを特徴とする、請求項1~8のいずれか1項に記載の光硬化性樹脂組成物。
- 前記成分(A)、(B)及び(C)を、これらの合計質量を基準として、(A)1~50質量%、(B)5~40質量%、(C)5~85質量%の割合で含み、及び前記成分(D)を前記成分(A)、(B)及び(C)の合計100質量部に対して0.1~20質量部の割合で含むことを特徴とする、請求項1~9のいずれか1項に記載の光硬化性樹脂組成物。
- 請求項1~10のいずれか1項に記載の光硬化性樹脂組成物を光硬化させて得られることを特徴とする硬化物。
- 各温度における貯蔵弾性率及び損失弾性率が下式(1)~(3)の範囲を同時に満足することを特徴とする、請求項11に記載の硬化物。
(1)70℃における貯蔵弾性率が1×103~1×106Paかつ損失弾性率が1×103~1×106Pa
(2)23℃における貯蔵弾性率が1×104~5×106Pa、かつ損失弾性率が1×104~5×106Pa
(3)0℃における貯蔵弾性率が5×104~1×107Pa、かつ損失弾性率が5×104~1×107Pa - 表示部材と、該表示部材の前面に樹脂層を介して設置される光学部材とを有する表示装置の前記樹脂層を形成するための樹脂シート部材であって、第1のフィルムと、該第1のフィルム上に設けられた請求項11又は12に記載の硬化物からなる樹脂シートと、該樹脂シート上に設けられた第2のフィルムとを有することを特徴とする樹脂シート部材。
- 前記第1及び第2のフィルムが、それぞれ離型処理したプラスチックフィルムであり、前記第1及び第2のフィルムの離型力が互いに異なることを特徴とする、請求項13に記載の樹脂シート部材。
- 表示部材と、該表示部材の前面に樹脂層を介して設置される光学部材とを有する表示装置の前記樹脂層を形成するための樹脂シート部材の製造方法であって、
第1のフィルムの片面に、請求項1~10のいずれか1項に記載の光硬化性樹脂組成物をシート状に塗布し、次いで第2のフィルムを被せる工程と、
前記第1のフィルム及び前記第2のフィルムの少なくとも一方の主面から光を照射し、前記光硬化性樹脂組成物を硬化させる工程と
を含むことを特徴とする樹脂シート部材の製造方法。 - 前記硬化工程において、前記照射する光は280nm未満の波長を実質的に含まないピーク波長365nmの紫外線であり、該紫外線を照度0.01~20.0mW/cm2で2分以上照射することを特徴とする、請求項15に記載の樹脂シート部材の製造方法。
- 表示部材と、該表示部材の前面に樹脂層を介して設置される光学部材とを有する表示装置であって、前記樹脂層が請求項11又は12に記載の硬化物を含むことを特徴とする表示装置。
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Also Published As
Publication number | Publication date |
---|---|
CN102471426B (zh) | 2013-10-30 |
EP2457935A1 (en) | 2012-05-30 |
JP5545296B2 (ja) | 2014-07-09 |
EP2457935A4 (en) | 2013-12-04 |
US20120114953A1 (en) | 2012-05-10 |
US8697240B2 (en) | 2014-04-15 |
KR20120040225A (ko) | 2012-04-26 |
TW201107416A (en) | 2011-03-01 |
CN102471426A (zh) | 2012-05-23 |
KR101470912B1 (ko) | 2014-12-09 |
JPWO2011010599A1 (ja) | 2012-12-27 |
TWI476248B (zh) | 2015-03-11 |
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