WO2010143643A1 - 粘着剤組成物および粘着剤、ならびに光学部材用粘着剤、それを用いて得られる粘着剤層付き光学部材 - Google Patents
粘着剤組成物および粘着剤、ならびに光学部材用粘着剤、それを用いて得られる粘着剤層付き光学部材 Download PDFInfo
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- WO2010143643A1 WO2010143643A1 PCT/JP2010/059737 JP2010059737W WO2010143643A1 WO 2010143643 A1 WO2010143643 A1 WO 2010143643A1 JP 2010059737 W JP2010059737 W JP 2010059737W WO 2010143643 A1 WO2010143643 A1 WO 2010143643A1
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- pressure
- sensitive adhesive
- meth
- acrylate
- adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive, a pressure-sensitive adhesive for optical members, and an optical member with a pressure-sensitive adhesive layer obtained using the same.
- an optical film polarizing film, retardation film, optical compensation film, brightness enhancement film, etc.
- liquid crystal display devices organic EL display devices
- image display devices such as PDP, etc.
- the present invention relates to an optical member with an adhesive layer, particularly a polarizing plate with an adhesive layer.
- a polarizing film for example, a polarizing plate coated with a cellulose film, for example, a cellulose triacetate film, on both sides of a polarizing film, for example, a polyvinyl alcohol film having a polarizing property
- a polarizing film for example, a polyvinyl alcohol film having a polarizing property
- Lamination is carried out on the surface of the sandwiched liquid crystal cell to form a liquid crystal display panel. This lamination to the liquid crystal cell surface is performed by bringing the pressure-sensitive adhesive layer provided on the polarizing plate surface into contact with the liquid crystal cell surface. This is usually done by pressing.
- the pressure-sensitive adhesive layer provided on the surface of the optical member such as the polarizing plate is provided with a separator for the purpose of preventing scratches or dirt, or the surface for the purpose of preventing scratches or dirt generated during processing and transporting processes.
- a protective film or the like is provided, these separators and the surface protective film are not necessary and are peeled and removed when they are bonded to a liquid crystal cell or the like. Static electricity is generated when the separator or the surface protection film is peeled off from such an optical member, and this static electricity causes dust to adhere to the optical member, causes an abnormal display due to disorder of the liquid crystal alignment, and peripheral circuit elements. There is a problem that problems such as electrostatic breakdown occur.
- an antistatic pressure-sensitive adhesive composition containing an acrylic polymer and a lithium imide salt having a perfluoroalkyl group as an antistatic agent is used as an antistatic surface protective film (for example, see Patent Document 2).
- An ionic liquid having a fluorine-containing imide anion, and a pressure-sensitive adhesive composition containing a polymer having a glass transition temperature Tg of 0 ° C. or less as a base polymer see, for example, Patent Document 3).
- Patent Document 1 describes that the ionic liquid is simply blended with the acrylic polymer, the type of the ionic liquid to be used has not been optimized, and antistatic Durability and light leakage prevention performance, which are important when using such pressure-sensitive adhesives in optical members, particularly polarizing plate applications, are not considered at all and are not sufficient. .
- an imide salt having a perfluoroalkyl group is used as the fluorine-containing imide salt.
- an imide salt having a perfluoroalkyl group needs to use an electrolytic fluorination method for fluorine substitution of an alkyl group in its production, and its production is very difficult and costly.
- liquid crystal display panels using polarizing plates are widely used as display devices for personal computers, liquid crystal televisions, car navigation systems, etc., and the use environment has become very harsh. It is required to be excellent in durability even in use, for example, there is no phenomenon such as foaming or peeling between the pressure-sensitive adhesive layer and the glass plate even under a severe environment such as high temperature and high humidity, In a high-temperature, high-humidity environment, the polarizing film contracts, whereas the adhesive layer cannot follow the contraction of the polarizing film, and light leaks from the peripheral edge of the liquid crystal display panel. It is required that there is no so-called light leakage phenomenon.
- the antistatic performance is excellent, and further, even under high temperature and high humidity conditions, the optical laminate, particularly, the adhesive property between the polarizing plate and the glass substrate is excellent, and the pressure-sensitive adhesive.
- the gist of the present invention is that the pressure-sensitive adhesive composition [I] comprising the acrylic resin (A) and the ionic compound (B) which has a bis (fluorosulfonyl) imide anion and is solid at room temperature
- the present invention relates to a pressure-sensitive adhesive that is crosslinked.
- the present invention also relates to a pressure-sensitive adhesive composition comprising an acrylic resin (A) and a ionic compound (B) which has a bis (fluorosulfonyl) imide anion and is solid at room temperature.
- the present invention relates to an optical member with an adhesive layer, wherein the adhesive for an optical member using the above-mentioned adhesive and the adhesive for an optical member are laminated on the optical member.
- the pressure-sensitive adhesive of the present invention can be suitably used particularly for optical member applications, has an excellent balance between pressure-sensitive adhesive properties and antistatic performance, and is also an optical laminate, particularly polarized light, even under high temperature and high humidity conditions. Excellent adhesion between the plate and the glass substrate, no foaming or peeling between the pressure-sensitive adhesive layer and the glass substrate, and prevention of light leakage caused by contraction of the polarizing film In addition, an excellent liquid crystal display panel can be obtained.
- the pressure-sensitive adhesive of the present invention can also be used as a temporary surface-protecting pressure-sensitive adhesive; various displays such as word processors, computers, mobile phones, and televisions; optical components such as polarizing plates and laminates equivalent thereto; electronic substrates
- a transparent surface protection sheet such as polyethylene, polyester, or polypropylene is laminated via an adhesive for the purpose of surface protection and functionalization.
- the sheet often finishes the role of surface protection after the incorporation of a liquid crystal display or the like is completed and is peeled and removed. In this case, static electricity is generated when the surface protective adhesive sheet is peeled off, and surrounding dust is involved.
- the liquid crystal substrate and the electronic circuit are destroyed by the peeling charge generated when the surface protective adhesive sheet is peeled off. Le is what also has effects such unlikely to occur.
- (meth) acryl means acryl or methacryl
- (meth) acryloyl means acryloyl or methacryloyl
- (meth) acrylate means acrylate or methacrylate.
- the pressure-sensitive adhesive composition of the present invention comprises an acrylic resin (A) and an ionic compound (B) having a bis (fluorosulfonyl) imide anion.
- a copolymer component containing a (meth) acrylic monomer (a1) represented by the following general formula (1) is copolymerized with other copolymer components or homopolymerized. It is preferable from the viewpoint of further improving the antistatic performance.
- X in the general formula (1) is an alkylene group, and among them, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 4 carbon atoms such as an ethylene group, a propylene group, or a tetramethylene group is particularly preferable. And ethylene group is particularly preferable. Further, when n is a polyoxyalkylene chain moiety having 2 or more, a homopolymer of the same oxyalkylene chain may be used, or different oxyalkylene chains may be copolymerized randomly or in a block form.
- Y in the general formula (1) is any one of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group.
- a hydrogen atom, an alkyl group, and an aryl group are preferable, a hydrogen atom, an alkyl group, and a phenyl group are particularly preferable, and an acrylic resin (A) is easily manufactured and an antistatic property is more preferable.
- an alkyl group is preferable, and a methyl group is particularly preferable.
- the alkyl group preferably has a relatively short carbon number, specifically 1 to 15 carbon atoms, particularly preferably 1 to 10 carbon atoms, further preferably 1 to 6 carbon atoms.
- Y) is preferably a methyl group, an ethyl group or a propyl group, and particularly preferably a methyl group. If the number of carbon atoms is too long, the HLB is lowered and the antistatic performance tends to be lowered due to the lipophilicity.
- aryl group those having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms are usually used, and specific examples include phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, and the like. Among these, a phenyl group is preferable.
- aralkyl group those having 7 to 20 carbon atoms, preferably 7 to 15 carbon atoms are usually used, and specific examples include a benzyl group.
- the alkyl group, aryl group, and aralkyl group may have a substituent.
- the substituent is usually a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a hydroxyl group, an alkoxy group.
- a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a hydroxyl group, an alkoxy group.
- R 1 in the general formula (1) is a hydrogen atom or a methyl group.
- n is an integer of 1 or more, preferably 1 to 10, particularly preferably 1 to 2, and further preferably 1. If the value of n is too large, the moisture and heat resistance of the acrylic resin tends to decrease, and n is preferably small from the viewpoint of easy production of an acrylic resin among the raw materials that can be procured.
- Secondary hydroxyl group-containing monomer secondary hydroxyl group-containing monomer such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2,2-dimethyl-2 -Hydroxyethyl (Meth) tertiary hydroxyl group-containing monomers such as acrylate.
- Examples of the monomer having n of 2 or more include polyethylene glycol derivatives such as polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, poly (Ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, and the like.
- polyethylene glycol derivatives such as polyethylene glycol mono (meth) acrylate
- polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, poly (Ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (me
- Y in the general formula (1) is an alkyl group, for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxy Ethyl (meth) acrylate, 2-butoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, octoxypolyethylene glycol-polypropylene glycol-mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate DOO, (meth) acrylic acid esters of aliphatic, such as stearoxy polyethylene glycol mono (meth)
- Y in the general formula (1) is an aryl group
- examples thereof include phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and ethylene oxide-modified nonylphenol (meth) acrylate.
- Y in the general formula (1) is an aralkyl group
- examples thereof include benzyloxyethyl (meth) acrylate and benzyloxydiethylene glycol (meth) acrylate.
- a hydroxyl group-containing monomer and a methoxy group-containing monomer are preferable from the viewpoint of effectively imparting hydrophilicity, in particular, a primary hydroxyl group-containing monomer and a methoxy group-containing monomer are more preferable. Hydroxyethyl acrylate and 2-methoxyethyl acrylate are preferred. Moreover, it is also preferable to use 2 or more types of said monomers together, and it is especially preferable to use 2 types together.
- the (meth) acrylic monomer (a1) is preferably contained in an amount of 5 to 100% by weight, particularly preferably 8 to 70% by weight, based on the entire copolymerization component, as a copolymerization component of the acrylic resin (A). More preferably, it is 10 to 50% by weight, particularly preferably 20 to 40% by weight. If the content of the (meth) acrylic monomer (a1) is too small, the antistatic performance tends to be insufficient.
- copolymer components other than the above (meth) acrylic monomer (a1) include (meth) acrylic acid ester monomer (a2), and if necessary, a functional group-containing monomer other than (meth) acrylic monomer (a1) And (a3) and other copolymerizable monomers (a4).
- Examples of the (meth) acrylic acid ester monomer (a2) include (meth) acrylic acid alkyl esters.
- the alkyl group usually has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 4 to 8 carbon atoms, and specifically, methyl (meth) acrylate.
- n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable in terms of copolymerizability, adhesive properties, ease of handling, and availability of raw materials.
- N-butyl (meth) acrylate is preferably used because it is preferably used and more preferably has excellent antistatic performance.
- Examples of the functional group-containing monomer (a3) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and (meth) acrylic acid.
- Michael adducts for example, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.
- 2- (meth) acryloyloxyethyl dicarboxylic acid monoester for example, 2- Acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hex Carboxyl group-containing monomers such as hydrophthalic acid monoester and 2-methacryloyloxyethyl hexahydrophthalic acid monoester); glycidyl group-containing monomers such as glycidyl (meth) acrylate and allyl glycidy
- carboxyl group-containing monomers glycidyl group-containing monomers, amide group-containing monomers, and nitrogen-containing monomers are preferably used. Furthermore, the carboxyl group-containing monomers have excellent release properties and are durable. It is particularly preferably used because it contributes to the properties.
- Examples of other copolymerizable monomer (a4) include acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, And monomers such as vinyl pyridine, vinyl pyrrolidone, dialkyl esters of itaconic acid, dialkyl esters of fumaric acid, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinylketone.
- ethylene glycol di (meth) acrylate For the purpose of increasing the molecular weight, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate
- a compound having two or more ethylenically unsaturated groups such as divinylbenzene can also be used in combination.
- the acrylic resin (A) is produced by polymerizing the copolymer component containing the monomer components (a1) to (a4).
- the polymerization is carried out by a conventionally known method. be able to.
- a polymerization monomer and a polymerization initiator azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.
- the content of the polymerization component other than the (meth) acrylic monomer (a1) is 0 to 95% by weight of the (meth) acrylic acid ester monomer (a2), particularly 30 to 92% by weight, and more preferably 50%. It is preferably 90 to 90% by weight, particularly 60 to 85% by weight, and the functional group-containing monomer (a3) other than the (meth) acrylic monomer (a1) is 0 to 40% by weight, particularly 0 to 30%. It is preferably 0 to 20% by weight, and the other copolymerizable monomer (a4) is 0 to 50% by weight, particularly 0 to 40% by weight, more preferably 0 to 30% by weight. preferable.
- the glass transition temperature (Tg) of the acrylic resin (A) is preferably 0 ° C. or less, particularly preferably ⁇ 15 ° C. or less, and further preferably ⁇ 30 ° C. or less.
- the lower limit of the glass transition temperature (Tg) is usually -75 ° C.
- the glass transition temperature (Tg) is calculated from the following Fox equation.
- the value of the glass transition temperature (Tg) of the acrylic resin (A) can be adjusted by changing the type and blending ratio of the acrylic monomer used as the copolymerization component.
- the weight average molecular weight of the acrylic resin (A) thus obtained is usually 100,000 to 3,000,000, preferably 300,000 to 2,500,000, particularly preferably 600,000 to 2,000,000, particularly preferably 1,000,000 to 1,500,000. It is. If the weight average molecular weight is too small, sufficient cohesive force tends not to be obtained. If the weight average molecular weight is too large, a large amount of diluent solvent is required, which tends to be undesirable in terms of coating properties and cost.
- the degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin (A) is preferably 20 or less, particularly preferably 15 or less, more preferably 10 or less, and particularly preferably 7 or less. preferable. When the degree of dispersion is too high, the pressure-sensitive adhesive layer tends to be inferior in durability performance such as heat and moisture resistance and light leakage.
- the lower limit of the degree of dispersion is usually 2 from the viewpoint of production limit.
- said weight average molecular weight and number average molecular weight are based on standard polystyrene molecular weight conversion, and are high performance liquid chromatography (The product made by Japan Waters, "Waters 2695 (main body)” and “Waters 2414 (detector)”).
- the particle size is 10 ⁇ m), and the degree of dispersion is determined from the weight average molecular weight and the number average molecular weight.
- the glass transition temperature is calculated from the Fox equation.
- the acrylic resin (A) it is also preferable to use an HLB value of 6.8 or more, particularly preferably 6.8 to 10, more preferably 7.0 to 8.2, Preferably it is 7.2 to 8.0. If the HLB value is too small, the antistatic ability tends to be lowered. In addition, when the value of HLB is too large, there exists a tendency for the heat-and-moisture resistance of acrylic resin to fall.
- HLB Hydrophilie-Lipophile Balance
- HLB ⁇ (base number of hydrophilic group) + ⁇ (base number of lipophilic group) +7.
- hydrophilic groups, types of lipophilic groups and values of the number of hydrophilic groups and lipophilic groups include those described in the following [Table 1]. For details, refer to the document “New Edition Surfactant Handbook” (Nippon Yushi Co., Ltd., Engineering Books Co., Ltd.), pages 234 to 242, 5.1.5. To 5.1.7. It is described in.
- the ionic compound (B) having a bis (fluorosulfonyl) imide anion in the present invention and solid at room temperature (hereinafter sometimes simply referred to as “ionic compound (B)”) is bis (fluoro) as an anion site. It only needs to have a sulfonyl) imide anion (see the following general formula (2)), and the cation moiety may have a known general cation.
- Examples of the cation component of the ionic compound (B) include metal cations such as alkali metals, alkaline earth metals, transition metals, rare earth metals, cations of nitrogen atom-containing heterocyclic compounds, and chain-like quaternary quaternary compounds. Examples thereof include an ammonium cation and a quaternary phosphonium cation. Among these, a metal cation and a cation of a nitrogen atom-containing heterocyclic compound are preferable.
- an alkali metal cation or an alkaline earth metal cation is preferably used, and an alkali metal cation is particularly preferable.
- Li +, Na +, K + are preferred, in particular, from the viewpoint of excellent solubility in acrylic polymers, Na +, K + is preferred.
- Ca + and Mg + are preferable.
- an imidazolium cation, a pyrrolidinium cation, a piperidinium cation, and a pyridinium cation are preferable, and an imidazolium cation, a pyridinium cation, and further an imidazolium cation are particularly used. Is preferable in view of good antistatic performance.
- an alkyl imidazolium cation is preferably used, and a dimethylimidazolium cation is particularly preferably used.
- imidazolium cation a polymerizable unsaturated group-containing imidazolium cation such as a (meth) acrylic imidazolium cation or a vinyl imidazolium cation can also be used.
- the ionic compound (B) in the present invention is solid at room temperature, it can be recrystallized by purification, and thus has an advantage that it becomes easy to produce a high-purity ionic compound. This is because if the purification is incomplete, undesired ions and the like are included, adversely affect the moisture and heat resistance, and the antistatic performance is inferior.
- normal temperature means 20 ° C. ⁇ 15 ° C. (5 to 35 ° C.).
- the imidazolium cation include 1,3-dimethylimidazolium bis (fluorosulfonyl) imide and are preferably used from the viewpoint of good antistatic performance.
- these ionic compounds (B) may be used independently and may use 2 or more types together.
- the content of the ionic compound (B) is preferably 0.01 to 30 parts by weight, particularly preferably 0.1 to 15 parts by weight, with respect to 100 parts by weight of the acrylic resin (A). Further, 0.5 to 10 parts by weight, particularly 2 to 5 parts by weight is preferable. When the content is too large, the heat and humidity resistance tends to be lowered, and when the content is too small, the antistatic performance tends to be insufficient.
- an acrylic resin composition containing the acrylic resin (A) and the ionic compound (B) of the present invention is obtained.
- the pressure-sensitive adhesive composition [I] containing the acrylic resin (A) and the ionic compound (B) is obtained.
- the pressure-sensitive adhesive composition [I] In addition to the above components (A) and (B), it is preferable to further contain an unsaturated group-containing compound (C) and a polymerization initiator (D) described later in order to improve durability, and further, a crosslinking agent. It is also preferable to contain (E) and an oxyalkylene group containing compound (F). And this adhesive composition [I] is bridge
- the pressure-sensitive adhesive of the present invention is obtained by crosslinking the above-mentioned pressure-sensitive adhesive composition [I].
- the pressure-sensitive adhesive composition [I] preferably contains the acrylic resin (A) as a main component.
- the “main component” means that the acrylic resin ( It means that A) is usually 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more based on the total amount of the pressure-sensitive adhesive composition [I].
- the upper limit is usually 99.9% by weight.
- the method [ ⁇ ], that is, the unsaturated group-containing compound (C) and the polymerization initiator (D) are contained, and the pressure-sensitive adhesive composition [I] is subjected to active energy rays and / or heat (active energy ray irradiation). And / or a method of crosslinking by heating) will be described.
- the above-mentioned acrylic resin (A) and ionic compound (B) are used as the pressure-sensitive adhesive composition [I].
- the pressure-sensitive adhesive composition [I] further containing an unsaturated group-containing compound (C) and a polymerization initiator (D) is used.
- the reaction at the time of active energy ray irradiation and / or a heating can be stabilized by containing the said polymerization initiator (D).
- the unsaturated group-containing compound (C) is polymerized (polymerized) with active energy rays and / or heat to cross-link (physical cross-linking) with the acrylic resin (A).
- the acrylic resin (A) is an unsaturated group-containing acrylic resin
- the unsaturated group-containing acrylic resin is not limited to polymerization of the unsaturated group-containing compound (C) by active energy rays and / or heat.
- Cross-linking accompanying polymerization of the resin (A) and the unsaturated group-containing compound (C) will also occur.
- the unsaturated group-containing compound (C) used in the present invention may be a monofunctional unsaturated group-containing compound having one unsaturated group in one molecule, or two or more in one molecule.
- a polyfunctional unsaturated group-containing compound having an unsaturated group may be used, but preferably an unsaturated group-containing compound having two or more unsaturated groups, more preferably an unsaturated group-containing compound having three or more unsaturated groups.
- a saturated group-containing compound is preferred from the viewpoint of curability during irradiation with active energy rays.
- Examples of the structure of the unsaturated group-containing compound (C) include urethane (meth) acrylate compounds, epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds, and one or more ethylene in one molecule.
- An ethylenically unsaturated monomer containing a polymerizable unsaturated group for example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher functional monomer, and the like can be used.
- the unsaturated group-containing compound (C) preferably contains an oxyalkylene chain, a hydroxyl group, or an acid-base ion pair and / or a structural portion exhibiting hydrophilicity such as a betaine structure from the viewpoint of antistatic performance.
- the urethane (meth) acrylate compound (c1) is a (meth) acrylate compound having a urethane bond in the molecule, a (meth) acrylic compound containing a hydroxyl group and a polyvalent isocyanate compound (if necessary, What is necessary is just to use what is obtained by making a polyol type compound) react by a well-known general method, and what is usually used is 300-4000 as the weight average molecular weight.
- the urethane (meth) acrylate compound is not particularly limited, but a polyol compound is not included, but a polyisocyanate compound directly reacted with a (meth) acrylic compound containing a hydroxyl group is preferred.
- Examples of the (meth) acrylic compound containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
- polyvalent isocyanate compound examples include aromatic, aliphatic, and alicyclic polyisocyanates. Among them, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified Diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, Lysine diisocyanate, lysine triisocyanate, naphthalenedi Polyisocyanates such as cyanate or trimer compounds or multimer compounds of these poly
- ethylenically unsaturated monomer (c2) used in the present invention a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer, and the like can be used.
- the monofunctional monomer may be any monomer containing one ethylenically unsaturated group.
- Examples of the ethylenically unsaturated monomer include, in addition to the above, a Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester.
- Examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid dimer, Examples include acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer.
- Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester that is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxy Examples thereof include ethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester and the like. Furthermore, oligoester acrylate is also mentioned.
- the bifunctional monomer may be any monomer containing two ethylenically unsaturated groups.
- the tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups.
- a urethane (meth) acrylate compound (c1) or an ethylenically unsaturated monomer (c2) containing an oxyalkylene chain is used in that it exhibits excellent antistatic performance. Is also preferable.
- an unsaturated group-containing compound containing an oxyalkylene chain and containing 3 or more unsaturated groups is preferred.
- These unsaturated group-containing compounds (C) may be used alone or in combination of two or more.
- the content of the unsaturated group-containing compound (C) is preferably 2 to 99 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 8 to 30 parts by weight based on 100 parts by weight of the acrylic resin (A). Parts by weight.
- compatibility with resin will worsen, the tendency which a coating film whitens will be seen, or a crosslinking density will rise too much and adhesive force will fall too much. Therefore, there is a tendency that peeling is likely to occur in the durability test.
- the amount is too small, the crosslinking density of the pressure-sensitive adhesive becomes insufficient, and the light leakage prevention property and durability tend to decrease.
- polymerization initiator (D) for example, various polymerization initiators such as a photopolymerization initiator (d1) and a thermal polymerization initiator (d2) can be used.
- d1) is preferable in that it can be crosslinked (cured) by irradiation with active energy rays such as ultraviolet rays for a very short time.
- adhesive composition [I] when using the said photoinitiator (d1), adhesive composition [I] is bridge
- Examples of the photopolymerization initiator (d1) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether etc.
- auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid.
- Ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.
- benzyl dimethyl ketal 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.
- thermal polymerization initiator (d2) examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexyl peroxide).
- the content of the polymerization initiator (D) is 0.01 to 10 parts by weight, particularly 0.1 to 7 parts by weight, and more preferably 0.3 to 100 parts by weight of the acrylic resin (A). It is preferably ⁇ 3 parts by weight. If the content of the polymerization initiator (D) is too small, the curability tends to be poor and the physical properties tend to become unstable, and if it is too much, no further effect can be obtained.
- UV ray irradiation far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays and other electromagnetic waves, X rays, ⁇ rays and other electromagnetic waves, as well as electron beams, proton rays, neutron rays, etc.
- Curing by ultraviolet irradiation is advantageous from the standpoint of availability of the device and price.
- electron beam irradiation it can harden
- a high pressure mercury lamp for example, 5 ⁇ 3000mJ / cm 2, preferably carried out at a 10 ⁇ 1000mJ / cm 2 conditions.
- the electrodeless lamp for example, 2 ⁇ 1500mJ / cm 2, preferably carried out at a 5 ⁇ 500mJ / cm 2 conditions.
- the irradiation time varies depending on the type of light source, the distance between the light source and the coating surface, the coating thickness, and other conditions, but it may be usually from several seconds to several tens of seconds, and in some cases, a fraction of a second.
- the electron beam irradiation for example, an electron beam having an energy in the range of 50 to 1000 Kev is used, and the irradiation amount is preferably 2 to 50 Mrad.
- the thermal polymerization initiator (d2) when used as the polymerization initiator (D), the polymerization reaction is started by heating and allowed to proceed.
- the treatment temperature and treatment time at the time of crosslinking by heating vary depending on the type of the thermal polymerization initiator (d2) used, and are usually calculated from the half-life of the initiator, but the treatment temperature is usually It is preferably 70 ° C. to 170 ° C., and the treatment time is usually preferably 0.2 to 20 minutes, particularly preferably 0.5 to 10 minutes.
- the pressure-sensitive adhesive composition [I] contains a cross-linking agent (E) in addition to the acrylic resin (A) and the ionic compound (B). Agent composition [I] is used.
- the acrylic resin (A) preferably has a functional group, and crosslinking (chemical crosslinking) is performed by reacting the functional group with the crosslinking agent.
- said crosslinking agent (E) what is necessary is just a compound which has a functional group which reacts with the functional group contained in the said acrylic resin (A), for example, an isocyanate type compound, an epoxy-type compound, an aziridine type compound, a melamine type Examples include compounds, aldehyde compounds, amine compounds, and metal chelate compounds. Among these, an isocyanate compound is preferably used from the viewpoint of improving the adhesion to the base material and the reactivity with the base polymer.
- isocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene diisocyanate.
- Diphenylmethane-4,4-diisocyanate isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and polyisocyanate compounds thereof
- Examples thereof include adducts with polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds.
- Examples of the epoxy compound include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, Examples include trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether, and the like.
- aziridine compounds examples include tetramethylolmethane-tri- ⁇ -aziridinylpropionate, trimethylolpropane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4 ′.
- Examples of the melamine compound include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, and melamine resin.
- aldehyde compounds examples include glyoxal, malondialdehyde, succindialdehyde, maleindialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, benzaldehyde and the like.
- amine compound examples include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resin, polyamide, and the like.
- Examples include aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, panadium, chromium, zirconium, and other multimetallic acetylacetone and acetoacetyl ester coordination compounds.
- cross-linking agents (E) may be used alone or in combination of two or more.
- the content of the crosslinking agent (E) can be appropriately selected depending on the amount of the functional group contained in the acrylic resin (A), the molecular weight of the acrylic resin (A), and the purpose of use.
- the amount is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 12 parts by weight, particularly 1.5 to 10 parts by weight, especially 0.5 to 100 parts by weight. It is preferably 3 parts by weight.
- the amount of the crosslinking agent (E) is too small, there is a tendency that the cohesive force is insufficient and sufficient durability cannot be obtained.
- the amount is too large, the flexibility and the adhesive strength are lowered, the durability is deteriorated, and peeling is caused. Tends to occur, and it tends to be difficult to bond to an optical film.
- a structure having an antistatic performance as a part of the crosslinking agent (E) is also preferable to use a cross-linking agent having an introduced site.
- sufficient crosslinking can be obtained only by the above-mentioned [ ⁇ ] active energy rays and / or heat (irradiation and / or heating of active energy rays). It is preferable to use in combination, and the cross-linking density of the pressure-sensitive adhesive is increased and the cohesive force is increased, so that a further superior one in terms of prevention of light leakage and durability can be obtained.
- the pressure-sensitive adhesive composition [I] which is a pressure-sensitive adhesive-forming material, further includes an oxyalkylene group-containing compound (F) (excluding (C)) (hereinafter simply referred to as an oxyalkylene group-containing compound ( F) may be described as follows.) Is further preferable in terms of further improving the antistatic function and improving adhesion to the optical member.
- the content of the oxyalkylene group-containing compound (F) is usually set to 0.1 to 90 parts by weight, preferably 1 to 50 parts by weight, particularly 100 parts by weight of the acrylic resin (A).
- the amount is preferably 3 to 30 parts by weight, particularly 5 to 10 parts by weight.
- the oxyalkylene group-containing compound (F) used in the present invention is not particularly limited as long as it is a compound having an oxyalkylene group (excluding unsaturated group-containing compounds), and a known oxyalkylene group-containing compound may be used. it can.
- a known oxyalkylene group-containing compound may be used. it can.
- the above oxyalkylene group-containing compounds (F) they are not incorporated into the crosslinking system and have a high degree of freedom in the molecular chain, so that they contain an oxyalkylene structure and do not contain a hydroxyl group at the end of the molecular chain.
- X in the general formula (3) is an alkylene group, and among them, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 4 carbon atoms such as an ethylene group, a propylene group, or a tetramethylene group is particularly preferable. And ethylene group is particularly preferable. Further, when n is a polyoxyalkylene chain moiety having 2 or more, a homopolymer of the same oxyalkylene chain may be used, or different oxyalkylene chains may be copolymerized randomly or in a block form.
- Y 1 and Y 2 in the general formula (3) are any of an alkyl group, an aryl group, an aralkyl group, and an amino group, and may be the same or different from each other.
- an alkyl group is particularly preferable in that it contributes to the improvement of the antistatic function without inhibiting the degree of freedom of the oxyalkylene chain.
- the alkyl group preferably has a relatively short carbon number, specifically 1 to 15 carbon atoms, particularly preferably 1 to 10 carbon atoms, and further preferably 1 to 6 carbon atoms.
- aryl group those having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms are usually used, and specific examples include phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, and the like. Among these, a phenyl group is preferable.
- aralkyl group those having 7 to 20 carbon atoms, preferably 7 to 15 carbon atoms are usually used, and specific examples include a benzyl group.
- the alkyl group, aryl group, aralkyl group, and amino group may have a substituent, and as the substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, Examples thereof include a hydroxyl group, an alkoxy group, an amino group, a sulfanyl group, an aryl group, and a heteroaryl group.
- n is an integer of 1 or more, preferably 1 to 10, particularly preferably 1 to 2, and further preferably 1.
- Specific examples of the compound represented by the general formula (3) for the oxyalkylene group-containing compound (F) used in the present invention include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether. And nonionic surfactants such as polyoxyalkylene alkylphenyl allyl ether, polyoxyalkylene alkylamines, polyoxyalkylene diamines and the like.
- oxyalkylene group-containing compound (F) compound other than the compound represented by the general formula (3) include polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkyl ether phosphate, polyoxy Anionic surfactants such as alkylene alkyl phenyl ether sulfates and polyoxyalkylene alkyl phenyl ether phosphates, cationic surfactants having both oxyalkylene groups and amphoteric surfactants, polyoxyalkylene glycol fatty acid esters , Polyoxyalkylene sorbitan fatty acid ester, oxyalkylene group-containing polyether ester and the like.
- oxyethylene group-containing compounds are preferable.
- polyoxyethylene alkylamines, polyoxyethylene diamines, oxyethylene group-containing polyether polymers, oxyethylene group-containing polyether ester amides, oxyethylene group-containing polymers are preferred.
- examples include ether amide imide, polyoxyethylene glycol fatty acid ester, polyoxysorbitan acid fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, etc., and polyether polymers or acrylic polymers having an oxyethylene group, It is preferably used because it is easy to balance the compatibility with the base polymer.
- polyether polymers containing oxyethylene groups include polypropylene glycol-polyethylene glycol-polypropylene glycol block copolymers, polypropylene glycol-polyethylene glycol block copolymers, polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymers, Examples thereof include random copolymers and block copolymers of polyethylene glycol and polypropylene glycol, such as a polypropylene glycol-polyethylene glycol random copolymer.
- the end of the glycol chain may be a hydroxyl group or may be substituted with an alkyl group, a phenyl group or the like.
- the polyethylene glycol ratio of the random copolymer or block copolymer of polyethylene glycol and polypropylene glycol is preferably 5 to 75% by weight, and more preferably 10 to 70% by weight. If the polyethylene glycol ratio is too small, the compatibility with the ionic liquid tends to be low, and sufficient antistatic properties tend to be difficult to obtain. If it is too high, the crystallinity becomes high and the compatibility with the acrylic polymer decreases. There is a tendency that sufficient antistatic properties cannot be obtained. These compounds may be used alone or in combination of two or more. Among the oxyethylene group-containing compounds, polyoxyethylene alkyl ether is preferable in terms of effectively increasing the antistatic ability.
- polyoxyethylene alkyl ether examples include diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether and the like having 2 repetitions, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether and the like. No. 3, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether, higher polyoxyethylene dimethyl ether, and the like. Among these, tetraethylene glycol dimethyl ether is preferably used.
- the oxyalkylene group content in the oxyalkylene group-containing compound (F) is preferably 5 to 85% by weight, more preferably 7 to 80% by weight, and more preferably 9 to 75%. More preferably, it is% by weight.
- the content is too low, the antistatic performance tends to be inferior, and when the content is too high, the composition becomes hydrophilic and tends to be inferior in heat and moisture resistance.
- the molecular weight of the oxyalkylene group-containing compound (F) is preferably a number average molecular weight of 100 to 10000, particularly preferably 180 to 1000, and more preferably 200 to 300.
- the pressure-sensitive adhesive composition [I], which is a pressure-sensitive adhesive forming material further contains a silane coupling agent (G) from the viewpoint of improving the adhesion to the optical member.
- the content of the silane coupling agent (G) is usually 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, with respect to 100 parts by weight of the acrylic resin (A). Particularly preferred is 0.03 to 0.8 parts by weight. If the content of the silane coupling agent (G) is too small, there is a tendency that the addition effect cannot be obtained. If the content is too large, the compatibility with the acrylic resin (A) is lowered, and adhesive strength and cohesive strength are obtained. There is a tendency to disappear.
- silane coupling agent (G) examples include an epoxy silane coupling agent, an acrylic silane coupling agent, a mercapto silane coupling agent, a hydroxyl group silane coupling agent, a carboxyl group silane coupling agent, and amino.
- examples thereof include a base silane coupling agent, an amide group silane coupling agent, and an isocyanate group silane coupling agent. These may be used alone or in combination of two or more.
- an epoxy silane coupling agent and a mercapto silane coupling agent are preferably used, and the combined use of an epoxy silane coupling agent and a mercapto silane coupling agent also improves wet heat durability and has adhesive strength. It is preferable in that it does not rise too much.
- epoxy-based silane coupling agent examples include, for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycid.
- examples include xylpropylmethyldimethoxysilane, methyltri (glycidyl) silane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
- ⁇ is preferable.
- mercapto silane coupling agent examples include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, and ⁇ -mercaptopropyldimethoxymethylsilane.
- the pressure-sensitive adhesive composition [I] which is a pressure-sensitive adhesive forming material, may further contain an antistatic agent (H) other than the ionic compound (B) described above.
- an antistatic agent (H) include imidazolium salts (excluding (B)), quaternary ammonium salt cationic antistatic agents such as tetraalkylammonium sulfonates, aliphatic sulfonates, and higher grades.
- Anionic antistatic agents such as alcohol sulfate ester salts, higher alcohol alkylene oxide adduct sulfate salts, higher alcohol phosphate ester salts, higher alcohol alcohol alkylene oxide adduct phosphate ester salts, lithium perchlorate, lithium chloride, etc.
- Examples include alkali metal salts, alkaline earth metal salts, higher alcohol alkylene oxide adducts, polyalkylene glycol fatty acid esters, and the like of organic acids or inorganic acids.
- the content of the antistatic agent (H) is usually 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, particularly 100 parts by weight of the acrylic resin (A).
- the amount is preferably 0.02 to 5 parts by weight. If the content of the antistatic agent (H) is too small, the effect of addition tends not to be obtained, and if it is too large, the durability may be lowered or the antistatic agent may bleed out.
- the pressure-sensitive adhesive composition [I] which is a pressure-sensitive adhesive-forming material, further includes other acrylic pressure-sensitive adhesives, other pressure-sensitive adhesives, urethane resins, rosins, and rosins, as long as the effects of the present invention are not impaired.
- Esters hydrogenated rosin esters, phenol resins, aromatic modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, styrene resins, xylene resins, tackifiers, colorants, fillers, anti-aging
- Conventionally known additives such as an agent, an ultraviolet absorber, a functional dye, and the like, and a compound that causes coloration or discoloration upon irradiation with ultraviolet rays or radiation can be blended.
- a small amount of impurities contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition [I] may be contained.
- a pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition [I] is obtained.
- the crosslinking method of the pressure-sensitive adhesive composition [I] containing the acrylic resin (A) and the ionic compound (B) is the pressure-sensitive adhesive composition [I].
- the pressure-sensitive adhesive composition [I] can be cross-linked by a method of irradiating active energy rays without containing an unsaturated group substantially.
- optical member with an adhesive layer can be obtained by laminating and forming the adhesive layer which consists of the said adhesive on an optical member (optical laminated body).
- the optical member with the pressure-sensitive adhesive layer it is preferable to further provide a release sheet on the surface opposite to the optical member surface of the pressure-sensitive adhesive layer.
- the manufacturing method of the said optical member with an adhesive layer after apply
- the adhesive composition [I] can be applied to the release sheet, dried, and then manufactured by a method of bonding an optical member.
- coats adhesive composition [I] on a release sheet which is the method of said [2] is preferable at the point with a low possibility of degrading an optical member with a dilution solvent.
- the release sheet is peeled off and used. And as said release sheet, it is preferable to use a silicon-type release sheet.
- the pressure-sensitive adhesive composition [I] is crosslinked by at least one of active energy ray irradiation and heating
- [1] after the pressure-sensitive adhesive composition [I] is applied on the optical member and dried A method in which a release sheet is bonded and a treatment by at least one of active energy ray irradiation and heating is performed.
- the adhesive composition [I] is applied and dried, and then an optical member is applied.
- a method of performing treatment by at least one of active energy ray irradiation and heating, and [3] applying and drying the adhesive composition [I] on the optical member, and further performing treatment by at least one of active energy ray irradiation and heating A method in which a release sheet is bonded and a treatment by at least one of active energy ray irradiation and heating is performed.
- the adhesive composition [I] is applied and dried, and then an optical member is applied.
- the pressure-sensitive adhesive composition [I] When the pressure-sensitive adhesive composition [I] is applied, it is preferable to dilute the pressure-sensitive adhesive composition [I] in a solvent, and the dilution concentration is preferably 5 to 60% by weight, particularly preferably 10%. ⁇ 30% by weight.
- the solvent is not particularly limited as long as it can dissolve the pressure-sensitive adhesive composition [I].
- ester solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, and ethyl acetoacetate
- ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
- aromatic solvents such as toluene and xylene
- alcohol solvents such as methanol, ethanol and propyl alcohol
- ethyl acetate and methyl ethyl ketone are preferably used from the viewpoints of solubility, drying property, price, and the like.
- the application of the pressure-sensitive adhesive composition [I] is performed by a conventional method such as roll coating, die coating, gravure coating, comma coating, or screen printing.
- adhesive composition [I] contains an unsaturated group containing compound (C) and a polymerization initiator (D), an active energy ray and / or In the case of crosslinking by heat, it is preferably 70% or more, particularly 90% or more from the viewpoint of durability performance and light leakage prevention performance. If the gel fraction is too low, durability and light leakage due to insufficient cohesion tend to deteriorate. In general, the upper limit of the gel fraction is 100%.
- the gel fraction of the pressure-sensitive adhesive layer produced by the above-described method is durable and light leaks. From the viewpoint of the balance of prevention performance, it is preferably 20 to 90%, particularly preferably 30 to 80%, more preferably 40 to 70%, and particularly preferably 50 to 60%. . If the gel fraction is too low, durability tends to be insufficient due to insufficient cohesive force. If the gel fraction is too high, light leakage due to increased cohesive force tends to deteriorate.
- adjusting the gel fraction of the optical member pressure-sensitive adhesive for example, adjusting the irradiation amount and irradiation intensity of the active energy ray, adjusting the type and amount of the unsaturated group-containing compound, This is achieved by adjusting the type of polymerization initiator and the combination ratio thereof, adjusting the blending amount of the polymerization initiator, adjusting the type and amount of the crosslinking agent, and the like.
- the gel fraction changes by each interaction, the irradiation amount and irradiation intensity
- the gel fraction is a measure of the degree of crosslinking, and is calculated, for example, by the following method. That is, a pressure-sensitive adhesive sheet (not provided with a separator) in which a pressure-sensitive adhesive layer is formed on a polymer sheet (for example, polyethylene terephthalate film) serving as a base material is wrapped with a 200-mesh SUS wire mesh, and 23 in toluene. The weight percentage of the insoluble pressure-sensitive adhesive component immersed in the wire mesh at 24 ° C. for 24 hours is defined as the gel fraction. However, the weight of the substrate is subtracted.
- the thickness of the pressure-sensitive adhesive layer in the obtained optical member with a pressure-sensitive adhesive layer is usually preferably 5 to 300 ⁇ m, particularly preferably 10 to 50 ⁇ m, and further preferably 12 to 30 ⁇ m. If the thickness of the pressure-sensitive adhesive layer is too thin, the adhesive physical properties tend to be difficult to stabilize, and if it is too thick, the thickness of the entire optical member tends to increase too much.
- the optical member with the pressure-sensitive adhesive layer of the present invention has a release sheet, and after the release sheet is peeled off, the pressure-sensitive adhesive layer surface is bonded to a glass substrate and used for a liquid crystal display plate, for example.
- the initial adhesive strength of the pressure-sensitive adhesive layer is appropriately determined according to the material of the adherend.
- it when adhering to a glass substrate, it preferably has an adhesive strength of 0.2 N / 25 mm to 20 N / 25 mm, and more preferably 0.5 N / 25 mm to 10 N / 25 mm.
- the initial adhesive strength is calculated as follows, for example. About the polarizing plate with an adhesive layer, it cuts to width 25mm width, peels a release film, presses the adhesive layer side to a non-alkali glass plate (Corning company make, "Corning 1737"), A glass plate is bonded. Then, after performing an autoclave process (50 degreeC, 0.5 MPa, 20 minutes), 23 degreeC and 50% R. H. After leaving for 24 hours, a 180 degree peel test is performed.
- the optical member in the present invention is not particularly limited, and is an optical film suitably used for an image display device such as a liquid crystal display device, an organic EL display device, or a PDP, such as a polarizing plate, a retardation plate, or an elliptical polarizing plate. , Optical compensation films, brightness enhancement films, and those in which these are laminated. Among them, a polarizing plate is particularly effective in the present invention.
- the polarizing plate used in the present invention is usually one obtained by laminating a cellulose triacetate film as a protective film on both sides of a polarizing film.
- the polarizing film has an average polymerization degree of 1,500 to 10,000,
- a uniaxially stretched film dyed with an aqueous solution of iodine-potassium iodide or a dichroic dye usually 2 to 10 times, preferably a film made of a polyvinyl alcohol resin having a degree of conversion of 85 to 100 mol% as a raw film. Is a stretching ratio of about 3 to 7 times.
- the polyvinyl alcohol-based resin is usually produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, but a small amount of unsaturated carboxylic acid (including salt, ester, amide, nitrile, etc.), olefins, vinyl ether And a component copolymerizable with vinyl acetate, such as an unsaturated sulfonate.
- unsaturated carboxylic acid including salt, ester, amide, nitrile, etc.
- olefins vinyl ether
- a component copolymerizable with vinyl acetate such as an unsaturated sulfonate.
- polyvinyl acetal resin and polyvinyl alcohol derivatives such as polybutyral resin and polyvinyl formal resin, which are obtained by reacting polyvinyl alcohol with an aldehyde in the presence of an acid are also exemplified.
- the pressure-sensitive adhesive of the present invention can also be used as a temporary surface protection pressure-sensitive adhesive in temporary surface protection applications. Since it is useful in terms of high-speed peelability depending on the case, an explanation about the use of the pressure-sensitive adhesive of the present invention for temporary surface protection will be described below.
- the pressure-sensitive adhesive composition [I] When used as a temporary surface-protecting pressure-sensitive adhesive, the pressure-sensitive adhesive composition [I] includes an ionic compound (B) component having the acrylic resin (A) and bis (fluorosulfonyl) imide anion as an electron beam.
- the pressure-sensitive adhesive composition [I] further contains at least one of the unsaturated group-containing compound (C), the polymerization initiator (D), and the crosslinking agent (E) component.
- the acrylic resin (A), the ionic compound (B) having a bis (fluorosulfonyl) imide anion, and the crosslinking agent (E) component it is preferably unsaturated. It is particularly preferred that the pressure-sensitive adhesive composition [I] containing the group-containing compound (C) and the polymerization initiator (D) is crosslinked to form a pressure-sensitive adhesive.
- acrylic resin (A) used as the temporary surface protecting adhesive the same acrylic resin (A) as described above can be used.
- the same unsaturated group-containing compound (C) as described above can be used.
- a polyfunctional that is, an unsaturated group-containing compound having 2 or more unsaturated groups, more preferably an unsaturated group-containing compound having 3 or more unsaturated groups.
- An unsaturated group-containing compound having 4 or more saturated groups is preferred, and an unsaturated group-containing compound having 5 or more unsaturated groups is particularly preferred.
- urethane (meth) acrylate compound containing an alkylene glycol chain or an ethylenically unsaturated monomer from the viewpoint of excellent antistatic performance.
- urethane (meth) acrylate compounds containing an alkylene glycol chain and containing 3 or more unsaturated groups are preferred.
- the content of the unsaturated group-containing compound (C) is preferably 200 parts by weight or less, more preferably 5 to 150 parts by weight, still more preferably 10 to 10 parts by weight based on 100 parts by weight of the acrylic resin (A). 100 parts by weight, particularly preferably 20 to 80 parts by weight. If the content of the unsaturated group-containing compound (C) is too small, the crosslinking is insufficient and the cohesive force tends to be reduced and the adherend tends to be contaminated. If the content is too large, the adhesive strength tends to decrease. .
- polymerization initiator (D) when used as the temporary surface protecting pressure-sensitive adhesive, the same ones as the polymerization initiator (D) described above can be used.
- crosslinking agent (E) when used as the temporary surface protecting adhesive the same crosslinking agent (E) as described above can be used.
- the temporary surface protecting adhesive obtained by curing the above-mentioned adhesive composition [I] can be usefully used as a temporary surface protecting adhesive sheet by being laminated on a substrate.
- the “sheet” in the present invention includes a film.
- polyester-type resins such as a polyethylene naphthalate, a polyethylene terephthalate, a boribylene terephthalate, a polyethylene terephthalate / isophthalate copolymer; Polyethylene, polypropylene Polyolefin resins such as polymethylpentene; Polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene; Polyamides such as nylon 6, nylon 6, 6; Polyvinyl chloride, polyvinyl chloride / vinyl acetate Polymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; polymethyl methacrylate, Acrylic resins such as ethyl methacrylate, Acrylic resins such as ethyl methacrylate, Acrylic resins such as e
- a synthetic resin film or sheet such as polyethylene terephthalate, polyethylene, or polypropylene is preferably used.
- the surface of the base material is treated to improve easy adhesion properties such as corona discharge treatment, plasma treatment, primer coating, degreasing treatment, and surface roughening treatment.
- an antistatic layer may be provided for further antistatic.
- the thickness of the substrate is not particularly limited, it can generally be exemplified by a thickness of about 500 ⁇ m or less, preferably 1 to 300 ⁇ m, more preferably 5 to 200 ⁇ m, and particularly preferably about 10 to 100 ⁇ m.
- the thickness of the pressure-sensitive adhesive composition [I] provided on the substrate is not particularly limited, but is generally 1 to 200 ⁇ m, preferably 2 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, and particularly preferably 5 to 30 ⁇ m after drying.
- the thickness of the degree can be exemplified. If it is too thick, the adhesive tends to remain on the surface of the adherend when peeling the temporary surface-protecting pressure-sensitive adhesive sheet from the adherend, and if it is too thin, the adhesive force to the adherend will be reduced. After sticking the temporary surface protective adhesive sheet to the adherend, the temporary surface protective adhesive sheet tends to peel off when the adherend and temporary surface protective adhesive sheet are exposed to high temperatures. There is.
- a separator can be laminated on the surface of the pressure-sensitive adhesive for the purpose of protecting the pressure-sensitive adhesive from contamination until the temporary surface-protective pressure-sensitive adhesive sheet is bonded to the adherend.
- a separator what carried out mold release processing of base materials, such as the synthetic resin film or sheet
- the pressure-sensitive adhesive composition [I] In providing the pressure-sensitive adhesive composition [I] on the substrate, it is usually applied as a solution of the pressure-sensitive adhesive composition [I], particularly to a viscosity suitable for application with a solvent, and then applied to the substrate. Drying is performed.
- a direct application method in which the solution-like pressure-sensitive adhesive composition [I] is directly applied to a substrate, or a solution-type pressure-sensitive adhesive composition [I] is applied to a separator and then attached to a substrate. Examples of the transfer coating method are as follows.
- the pressure-sensitive adhesive composition [I] is applied to a base material, heated and dried, then irradiated with active energy rays, and then a separator is attached, or the pressure-sensitive adhesive composition [I] ], And after drying by heating, a separator is attached, and then an active energy ray is irradiated.
- Coating is performed by methods such as roll coating, die coating, gravure coating, comma coating, and screen printing.
- the pressure-sensitive adhesive composition [I] is applied to the separator, heated and dried, then irradiated with active energy rays, and then the substrate is bonded to the pressure-sensitive adhesive composition [ After I] is applied and dried by heating, the substrates are bonded together, and then irradiated with active energy rays.
- the method similar to direct coating can be used.
- the temporary surface protecting adhesive sheet there are no particular restrictions on the type of adherend to which the temporary surface protecting adhesive sheet is applied, but for example, in addition to the metal foil, synthetic resin film or sheet, paper, woven fabric and non-woven fabric exemplified in the above substrate. Examples thereof include a glass plate, a synthetic resin plate, and a metal plate.
- the initial adhesive strength of the temporary surface protective adhesive sheet is appropriately determined according to the material of the adherend. For example, when sticking to a SUS304BA plate, it preferably has an adhesive strength of 0.01 N / 25 mm to 50 N / 25 mm, and when used for temporary protection (surface protection, masking), An adhesive strength of 01 N / 25 mm to 5 N / 25 mm is preferable, and an adhesive strength of 0.02 N / 25 mm to 1 N / 25 mm is particularly preferable.
- the above adhesive strength is calculated as follows. First, the obtained pressure-sensitive adhesive sheet was cut into 25 mm ⁇ 100 mm, and this was then applied to a stainless steel plate (SUS304BA plate) or acrylic plate (PMMA plate) as an adherend in an atmosphere at 23 ° C. and 50% relative humidity. A test piece is prepared by pressure bonding by reciprocating twice using a 2 kg rubber roller. After leaving this test piece for 30 minutes under the same atmosphere, a 180 ° peel test is performed at a peel rate of 0.3 m / min, and the measured adhesive strength (N / 25 mm) is taken as the initial adhesive strength.
- SUS304BA plate stainless steel plate
- PMMA plate acrylic plate
- the high-speed peel adhesive strength of the temporary surface protecting adhesive sheet is usually 6 times or less of the initial adhesive force, particularly preferably 4 times or less, and more preferably 2 times or less. preferable.
- a test piece prepared by the same method as the initial adhesion was left for 30 minutes in an atmosphere of 23 ° C. and 50% relative humidity. Thereafter, in the same atmosphere, a 180 ° peel test is performed at a high speed of 30 m / min, and the measured adhesive strength (N / 25 mm) is defined as the high speed peel adhesive strength.
- various acrylic resins and various unsaturated group-containing compounds were prepared as follows.
- the measurement of the weight average molecular weight of acrylic resin, dispersion degree, and glass transition temperature it measured according to the above-mentioned method.
- the measurement of a viscosity it measured according to the 4.5.3 rotational viscometer method of JISK5400 (1990).
- Acrylic resin (A-2) In a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet and a thermometer, 10 parts of 2-hydroxyethyl acrylate (a1), 40 parts of 2-methoxyethyl acrylate (a1), butyl acrylate (A2) 49 parts, acrylic acid (a3) 1 part and ethyl acetate 140 parts, acetone 45 parts were charged.
- azobisisobutyronitrile (AIBN) 0.03 part was added as a polymerization initiator, After reacting at the reflux temperature for 3 hours, the solution was diluted with ethyl acetate and diluted with an acrylic resin (A-2) solution (weight average molecular weight (Mw) 1,200,000, dispersity (Mw / Mn) 4.3, glass transition temperature -49. C, solid content 20%, viscosity 5,000 mPa ⁇ s (25 ° C)).
- the acrylic resin (A-2) had an HLB of 7.55.
- Acrylic resin (A-3) In a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet and a thermometer, 10 parts of 2-hydroxyethyl acrylate (a1), 40 parts of 2-methoxyethyl acrylate (a1), butyl acrylate (A2) 50 parts, 140 parts of ethyl acetate and 45 parts of acetone were added, and after heating and refluxing, 0.03 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the reaction was performed at reflux temperature for 3 hours.
- AIBN azobisisobutyronitrile
- Acrylic resin (A-3) solution diluted with ethyl acetate (weight average molecular weight (Mw) 1,200,000, dispersity (Mw / Mn) 4.6, glass transition temperature -50 ° C., solid content 20%, viscosity 4,700 mPa ⁇ s (25 ° C.)) was obtained.
- Acrylic resin (A-4) A 4-neck round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet and a thermometer was charged with 5 parts of 2-hydroxyethyl acrylate (a1), 94.5 parts of butyl acrylate (a2), acrylic acid ( a3) 0.5 parts, 100 parts of ethyl acetate and 45 parts of acetone were added, and after heating to reflux, 0.03 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the mixture was refluxed at ethyl acetate for 3 hours.
- AIBN azobisisobutyronitrile
- the reaction mixture was diluted with ethyl acetate, and the acrylic resin (A-4) solution (weight average molecular weight (Mw) 1.58 million, dispersity (Mw / Mn) 3.7, glass transition temperature ⁇ 50 ° C., solid content 18 %, Viscosity 8,000 mPa ⁇ s (25 ° C.)).
- the HLB of the acrylic resin (A-4) was 6.70.
- Acrylic resin (A-5) In a 4-neck round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet and a thermometer, 1.5 parts of 2-hydroxyethyl acrylate (a1), 98 parts of butyl acrylate (a2), acrylic acid ( a3) 0.5 parts, 100 parts of ethyl acetate and 45 parts of acetone were added, and after heating to reflux, 0.03 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the mixture was refluxed at ethyl acetate for 3 hours.
- AIBN azobisisobutyronitrile
- the acrylic resin (A-5) solution weight average molecular weight (Mw) 1.65 million, dispersity (Mw / Mn) 3.5, glass transition temperature -55 ° C. solid content 18% And a viscosity of 8,000 mPa ⁇ s (25 ° C.)).
- the acrylic resin (A-5) had an HLB of 6.60.
- the ionic compounds (B-1), (B-2), (B-3), (B′-1), (B′-2) and (B′-3) are all at room temperature. It is solid.
- Photopolymerization initiator (D) The following were prepared as the photopolymerization initiator (D-1). A mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1: 1 (Ciba Specialty Chemicals, “Irgacure 500”)
- Crosslinking agent (E) The following were prepared as the crosslinking agent (E-1). ⁇ 55% ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane (Nippon Polyurethane Co., Ltd., “Coronate L-55E”)
- Silane coupling agent (G) The following were prepared as the silane compound (G-1). ⁇ ⁇ -glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM403”)
- Examples 1 to 6, Comparative Examples 1 to 4 Each of the blended components prepared and prepared as described above is blended in the proportions shown in Tables 3 and 4 below to prepare a pressure-sensitive adhesive composition that becomes a pressure-sensitive adhesive forming material for an optical member. And diluted (viscosity [1000 to 10,000 mPa ⁇ s (25 ° C.)]) to prepare a pressure-sensitive adhesive composition solution.
- the formed adhesive composition layer side is made into polyethylene.
- a terephthalate (PET) film thickness 38 ⁇ m
- the film was aged for 10 days under the above conditions to obtain a PET film with an adhesive layer.
- Examples 7 to 12, Comparative Examples 5 and 6 Each of the blended components prepared and prepared as described above is blended in the proportions shown in Tables 3 and 4 below to prepare a pressure-sensitive adhesive composition that becomes a pressure-sensitive adhesive forming material for an optical member. And diluted (viscosity [1000 to 10,000 mPa ⁇ s (25 ° C.)]) to prepare a pressure-sensitive adhesive composition solution.
- the formed adhesive composition layer side is made into polyethylene.
- a terephthalate (PET) film thickness 38 ⁇ m
- the film was transferred at 23 ° C. ⁇ 65% H.
- the film was aged for 10 days under the above conditions to obtain a PET film with an adhesive layer.
- the obtained PET film with the pressure-sensitive adhesive layer was cut into a size of 40 ⁇ 40 mm, and this was left to stand for 3 hours under conditions of a temperature of 23 ° C. and a relative humidity of 65%, and then the release sheet was peeled off.
- the surface resistivity of the pressure-sensitive adhesive layer after 10 to 20 seconds was measured using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, Hiresta UP). In addition, it means that antistatic performance is so high that surface resistivity is small.
- the pressure-sensitive adhesive composition solutions of Examples 2 to 4 were applied to a polyester release sheet so that the thickness after drying was 25 ⁇ m, dried at 90 ° C. for 3 minutes, and then formed pressure-sensitive adhesive.
- the composition layer was transferred onto a polarizing plate (thickness: 190 ⁇ m), peak illuminance: 600 mW / cm 2 , integrated exposure amount: 240 mJ from the polyester release sheet side using an electrodeless lamp [H bulb of LH6UV lamp] manufactured by Fusion. / cm 2 performs UV irradiation at (120 mJ / cm 2 ⁇ 2 pass), then 23 °C ⁇ 65% R. H.
- the film was aged for 10 days under the above conditions to obtain a polarizing plate with an adhesive layer.
- the polarizing plate is laminated with a cellulose triacetate film having a thickness of 80 ⁇ m on both sides of a 30 ⁇ m-thick polyvinyl alcohol polarizing film (average polymerization degree 1700, average saponification degree 99 mol%, iodine staining, 4-fold stretching).
- the polarizing plate (the polyvinyl alcohol polarizing film was cut into 100 mm ⁇ 100 mm by tilting the direction of the stretching axis by 45 °) was used.
- ⁇ Adhesive force About the prepared polarizing plate with an adhesive layer, it cuts to width 25mm width, peels off a release film, presses the adhesive layer side to a non-alkali glass board (Corning company make, "Corning 1737"), and polarized light The plate and the glass plate were bonded together. Thereafter, autoclaving (50 ° C., 0.5 MPa, 20 minutes) was performed, and a 180-degree peel test was performed 24 hours later. In the peelability, it is desired that the adhesive strength is small, and the target is 10 N / 25 mm or less after one day.
- the pressure-sensitive adhesive containing a bis (fluorosulfonyl) imide anion which is a fluorine-containing imide anion not containing a carbon atom described in the examples is a pressure-sensitive adhesive containing a imide anion containing a perfluoroalkyl group having a carbon atom. It can be seen that the antistatic performance is effectively improved as compared with FIG. Furthermore, it has excellent durability and light leakage resistance as an adhesive for polarizing plates.
- the pressure-sensitive adhesive of the present invention is less likely to be charged with static electricity generated in each step, and is excellent in adhesiveness between the optical laminate and the glass substrate even under high temperature and high humidity conditions. In addition, foaming and peeling do not occur during this period, and the light leakage phenomenon caused by the shrinkage of the optical film can be suppressed. Therefore, a liquid crystal display panel having excellent durability can be obtained, which is very useful.
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Abstract
Description
このような静電気発生に起因した不具合の発生防止対策として、例えば、光学部材の片面または両面にガラス転移温度が0℃以下のポリマーとイオン性液体を有する粘着剤層を形成させて得られる粘着型光学部材が提案されている(例えば、特許文献1参照)。
また、アクリル系ポリマーと帯電防止剤としてパーフルオロアルキル基を有しているリチウムイミド塩を含有する帯電防止性粘着剤組成物を、帯電防止性表面保護フィルムとして用いること(例えば、特許文献2参照)や、フッ素含有イミドアニオンを有するイオン性液体、およびベースポリマーとしてガラス転移温度Tgが0℃以下のポリマーを含有する粘着剤組成物が提案されている(例えば、特許文献3参照)。
更には、上記粘着剤を用いてなる光学部材用粘着剤、および上記光学部材用粘着剤が光学部材に積層されてなることを特徴とする粘着剤層付き光学部材に関するものである。
なお、本発明において、(メタ)アクリルとはアクリルあるいはメタクリルを、(メタ)アクリロイルとはアクリロイルあるいはメタクリロイルを、(メタ)アクリレートとはアクリレートあるいはメタクリレートをそれぞれ意味するものである。
本発明の粘着剤組成物は、アクリル系樹脂(A)と、ビス(フルオロスルホニル)イミドアニオンを有するイオン性化合物(B)を含有してなるものである。
nが2以上のモノマーとしては、例えば、ポリエチレングリコールモノ(メタ)アクリレート等のポリエチレングリコール誘導体、ポリプロピレングリコールモノ(メタ)アクリレート等のポリプロピレングリコール誘導体、ポリエチレングリコール-ポリプロピレングリコール-モノ(メタ)アクリレート、ポリ(エチレングリコール-テトラメチレングリコール)モノ(メタ)アクリレート、ポリ(プロピレングリコール-テトラメチレングリコール)モノ(メタ)アクリレート等があげられる。
なお、ガラス転移温度(Tg)は、下記Foxの式より算出されるものである。
かかる親水基、親油基の種類および親水基、親油基の基数の値の例としては、下記[表1]に記載するものがあげられるが、詳細に関しては、文献「新版界面活性剤ハンドブック」(日本油脂株式会社著、工学図書株式会社版)の第234~242頁の5.1.5.~5.1.7.に記載されている。
更に、イミダゾリウムカチオンとしては、アルキルイミダゾリウムカチオンを用いることが好ましく、特にはジメチルイミダゾリウムカチオンを用いることが好ましい。
なお、本発明において常温とは、20℃±15℃(5~35℃)を意味する。
なお、これらイオン性化合物(B)は、単独で用いてもよいし、2種以上を併用してもよい。
本発明の粘着剤は、上述した粘着剤組成物[I]が架橋されてなるものである。
なお、本発明においては、粘着剤組成物[I]が、アクリル系樹脂(A)を主成分とするものであることが好ましく、ここで「主成分とする」とは、上記アクリル系樹脂(A)が粘着剤組成物[I]全量に対して、通常、50重量%以上、好ましくは60重量%以上、より好ましくは70重量%以上含有することを意味する。なお、上限としては通常99.9重量%である。
また、上記不飽和基含有化合物(C)は、オキシアルキレン鎖や水酸基、または酸塩基のイオン対および/またはベタイン構造等の親水性を示す構造部位を含有することも帯電防止性能からより好ましい。
上記架橋剤(E)を用いて架橋する場合は、粘着剤組成物[I]として、前記アクリル系樹脂(A)およびイオン性化合物(B)に加え、さらに架橋剤(E)を含有する粘着剤組成物[I]を用いる。
上記オキシアルキレン基含有化合物(F)の中でも、架橋システムに組み込まれず、分子鎖の自由度が高いため帯電防止機能を向上させる点で、オキシアルキレン構造を含有し、分子鎖末端に水酸基を含有しないものが好ましく、特に好ましくは、下記一般式(3)で示される化合物を使用することが、帯電防止能がより向上する点で好ましい。
また、上記一般式(3)で示される化合物以外のオキシアルキレン基含有化合物(F)化合物の具体例としては、ポリオキシアルキレンアルキルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルエーテルリン酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテルリン酸エステル塩等のアニオン性界面活性剤、オキシアルキレン基を有するカチオン性界面活性剤や両イオン性界面活性剤、ポリオキシアルキレングリコール脂肪酸エステル、ポリオキシアルキレンソルビタン脂肪酸エステル、オキシアルキレン基含有ポリエーテルエステル等があげられる。
これらの化合物は単独で使用してもよく、また2種以上を混合して使用してもよい。上記オキシエチレン基含有化合物のなかでも、ポリオキシエチレンアルキルエーテルが、効果的に帯電防止能を上げる点で好ましい。
また、上記添加剤の他にも、粘着剤組成物[I]の構成成分の製造原料等に含まれる不純物等が少量含有されたものであっても良い。
また、上記の架橋方法の他にも、アクリル系樹脂(A)およびイオン性化合物(B)を含有してなる粘着剤組成物[I]の架橋方法としては、粘着剤組成物[I]に実質的に不飽和基を含有させず、粘着剤組成物[I]に、活性エネルギー線を照射する方法により架橋させることもできる。なお、このときに重合開始剤(D)、架橋剤(E)、オキシアルキレン基含有化合物(F)、シランカップリング剤(G)を含有することが、上記と同様の理由で好ましい。
[アクリル系樹脂(A-1)]
還流冷却器、撹拌器、窒素ガスの吹き込み口および温度計を備えた4ツ口丸底フラスコに、酢酸エチル100部を仕込み、重合開始剤としてアゾビスイソブチロニトリル(AIBN)0.05部を加え、撹拌しながら昇温し、78℃で、2-ヒドロキシエチルアクリレート(a1)30部、ブチルアクリレート(a2)69部、アクリル酸(a3)1部の混合物を2時間にわたって滴下した。重合途中に酢酸エチル10部にAIBN0.05部を溶解させた重合開始剤液を逐次追加しながら、酢酸エチル還流温度で3.5時間重合させた後、希釈してアクリル系樹脂(A-1)溶液(重量平均分子量(Mw)80万、分散度(Mw/Mn)4.5、ガラス転移温度-45℃、固形分35%、粘度7,000mPa・s(25℃))を得た。
なお、アクリル系樹脂(A-1)のHLBに関しては、以下の計算により求め、7.42であった。
・重合時の2-ヒドロキシエチルアクリレートを各構成部分に分解すると、
(CH2:-0.475)(CH:-0.475)(COO:2.4)(CH2:-0.475)(CH2:-0.475)(OH:1.9)であるので、
HLB値=Σ疎水機の基数+Σ親水基の基数+7
={(-0.475)×4}+{(2.4)+(1.9)}+7
=9.4
・同様に、アクリル酸(CH2:-0.475)(CH:-0.475)(COOH:2.1)についても計算すると、
HLB値={(-0.475)×2}+(2.1)+7
=8.15
・同様に、ブチルアクリレート(CH2:-0.475)(CH:-0.475)(COO:-2.4)(CH2:-0.475)(CH2:-0.475)(CH2:-0.475)(CH3:-0.475)についても計算すると、
HLB値={(-0.475)×6}+(2.4)+7
=6.55
・アクリル系樹脂(A-1)
=BA/HEA/AAc
=69/30/1であるので、上記計算値に各モノマーの含有割合を掛け合わせると、
HLB値=(6.55×69+9.4×30+8.15×1)/100
=7.42
還流冷却器、撹拌器、窒素ガスの吹き込み口および温度計を備えた4ツ口丸底フラスコに、2-ヒドロキシエチルアクリレート(a1)10部、2-メトキシエチルアクリレート(a1)40部、ブチルアクリレート(a2)49部、アクリル酸(a3)1部および酢酸エチル140部、アセトン45部を仕込み、加熱還流開始後、重合開始剤としてアゾビスイソブチロニトリル(AIBN)0.03部を加え、還流温度で3時間反応後、酢酸エチルにて希釈してアクリル系樹脂(A-2)溶液(重量平均分子量(Mw)120万、分散度(Mw/Mn)4.3、ガラス転移温度-49℃、固形分20%、粘度5,000mPa・s(25℃))を得た。
なお、アクリル系樹脂(A-2)のHLBは7.55であった。
還流冷却器、撹拌器、窒素ガスの吹き込み口および温度計を備えた4ツ口丸底フラスコに、2-ヒドロキシエチルアクリレート(a1)10部、2-メトキシエチルアクリレート(a1)40部、ブチルアクリレート(a2)50部および酢酸エチル140部、アセトン45部を仕込み、加熱還流開始後、重合開始剤としてアゾビスイソブチロニトリル(AIBN)0.03部を加え、還流温度で3時間反応後、酢酸エチルにて希釈してアクリル系樹脂(A-3)溶液(重量平均分子量(Mw)120万、分散度(Mw/Mn)4.6、ガラス転移温度-50℃、固形分20%、粘度4,700mPa・s(25℃))を得た。
なお、アクリル系樹脂(A-3)のHLBは7.54であった。
還流冷却器、撹拌器、窒素ガスの吹き込み口および温度計を備えた4ツ口丸底フラスコに、2-ヒドロキシエチルアクリレート(a1)5部、ブチルアクリレート(a2)94.5部、アクリル酸(a3)0.5部および酢酸エチル100部、アセトン45部を仕込み、加熱還流開始後、重合開始剤としてアゾビスイソブチロニトリル(AIBN)0.03部を加え、酢酸エチル還流温度で3時間反応後、酢酸エチルにて希釈してアクリル系樹脂(A-4)溶液(重量平均分子量(Mw)158万、分散度(Mw/Mn)3.7、ガラス転移温度-50℃、固形分18%、粘度8,000mPa・s(25℃))を得た。
なお、アクリル系樹脂(A-4)のHLBに関しては、6.70であった。
還流冷却器、撹拌器、窒素ガスの吹き込み口および温度計を備えた4ツ口丸底フラスコに、2-ヒドロキシエチルアクリレート(a1)1.5部、ブチルアクリレート(a2)98部、アクリル酸(a3)0.5部および酢酸エチル100部、アセトン45部を仕込み、加熱還流開始後、重合開始剤としてアゾビスイソブチロニトリル(AIBN)0.03部を加え、酢酸エチル還流温度で3時間反応後、酢酸エチルにて希釈してアクリル系樹脂(A-5)溶液(重量平均分子量(Mw)165万、分散度(Mw/Mn)3.5、ガラス転移温度-55℃固形分18%、粘度8,000mPa・s(25℃))を得た。
なお、アクリル系樹脂(A-5)のHLBは6.60であった。
イオン性化合物(B-1)として、以下のものを用意した。
・カリウムビス(フルオロスルホニル)イミド
イオン性化合物(B-2)として、以下のものを用意した。
・1,3-ジメチルイミダゾリウムビス(フルオロスルホニル)イミド
イオン性化合物(B-3)として、以下のものを用意した。
・ナトリウムビス(フルオロスルホニル)イミド
イオン性化合物(B’-1)として、以下のものを用意した。
・カリウムビス(トリフルオロメチルスルホニル)イミド
イオン性化合物(B’-2)として、以下のものを用意した。
・カリウムビス(ノナフルオロブチルスルホニル)イミド
イオン性化合物(B’-3)として、以下のものを用意した。
・1-エチル-3-メチルイミダゾリウムビス(ノナフルオロブタンスルホニル)イミド
還流冷却器、撹拌器、窒素ガスの吹き込み口および温度計を備えた4ツ口丸底フラスコに、イソホロンジイソシアネート19.2部、ジ-t-ブチルヒドロキシフェノール0.05部、ジブチルスズジラウレート0.02部を仕込み、50℃以下で、ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートとの混合物(共栄社化学社製ライトアクリレートPE-3A、水酸基価120mgKOH/g)80.8部を、70℃で反応を継続し、不飽和基含有化合物(C-1)を得た。
光重合開始剤(D-1)として、以下のものを用意した。
・ベンゾフェノンと1-ヒドロキシシクロヘキシルフェニルケトンとの質量比1:1の混合物(チバ・スペシャリティ・ケミカルズ社製、「イルガキュア500」)
架橋剤(E-1)として、以下のものを用意した。
・トリメチロールプロパンのトリレンジイソシアネート付加物の55%酢酸エチル溶液(日本ポリウレタン社製、「コロネートL-55E」)
オキシアルキレン基含有化合物(F-1)として、以下のものを用意した。
・テトラエチレングリコールジメチルエーテル(東邦化学工業社製、「ハイソルブMTEM」)
シラン系化合物(G-1)として、以下のものを用意した。
・γ-グリシドキシプロピルトリメトキシシラン(信越化学社製、「KBM403」)
上記のようにして調製,準備した各配合成分を、下記の表3および表4に示す割合で配合することにより光学部材用粘着剤形成材料となる粘着剤組成物を調製し、これをメチルエチルケトンにて希釈し(粘度〔1000~10000mPa・s(25℃)〕)粘着剤組成物溶液を作製した。
上記のようにして調製,準備した各配合成分を、下記の表3および表4に示す割合で配合することにより光学部材用粘着剤形成材料となる粘着剤組成物を調製し、これをメチルエチルケトンにて希釈し(粘度〔1000~10000mPa・s(25℃)〕)粘着剤組成物溶液を作製した。
得られた粘着剤層付きPETフィルムを40×40mmの大きさに切断した後、これを温度23℃×相対湿度65%の条件下に3時間放置し調湿した後、離型シートを剥がして10~20秒後の粘着剤層について、抵抗率計(三菱化学社製、ハイレスターUP)を用いて表面抵抗率を測定した。なお、表面抵抗率が小さいほど帯電防止性能が高いことを意味する。
得られた粘着剤層付きPETフィルムを40×40mmに切断した後、離型シートを剥がし粘着剤層側を50×100mmのSUSメッシュシート(200メッシュ)に貼合してから、SUSメッシュシートの長手方向に対して中央部より折り返してサンプルを包み込んだ後、トルエン250gの入った密封容器にて浸漬した際の重量変化にてゲル分率の測定を行なった。
なお、上記偏光板には、膜厚30μmのポリビニルアルコール偏光フィルム(平均重合度1700、平均ケン化度99モル%、ヨウ素染色、4倍延伸)の両側を厚さ80μmの三酢酸セルロースフィルムで積層した偏光板(ポリビニルアルコール偏光フィルムの延伸軸方向を45°傾けて100mm×100mmに切断)を用いた。
得られた粘着剤層付き偏光板の離型シートを剥離して、粘着剤層側を無アルカリガラス板(コーニング社製、コーニング1737)に押圧して、偏光板とガラス板とを貼合した後、オートクレーブ処理(50℃、0.5MPa、20分)を行ない、その後、下記の耐久試験(耐湿熱試験、ヒートサイクル試験、耐熱試験)における発泡、剥がれ、光漏れ現象の評価を行なった。
なお、耐熱試験のみは、偏光板がクロスニコルになるように表と裏の両面に同じサンプルを貼合し、光漏れ観察用とした。
なお、使用した試験片サイズは、耐湿熱・ヒートサイクルでは10cm×10cmを使用し、耐熱試験では20cm×15cmのものを使用した。
(1)耐湿熱試験
60℃、90%R.H.100時間の耐久試験
(2)ヒートサイクル試験
-40℃で30分間放置した後、85℃で30分間放置する操作を1サイクルとして、100サイクル行なう耐久試験
(3)耐熱試験
80℃、100時間の耐久試験
(発泡)
○・・・発泡がほとんど見られない
△・・・発泡がわずかに見られる
×・・・発泡が多く見られる
(剥離)
○・・・0.5mm未満の剥がれ、もしくは浮き跡の発生
△・・・0.5mm以上10mm未満の剥がれ、もしくは浮き跡の発生
×・・・10mm以上の剥がれ、もしくは10mm以上の浮き跡の発生
(光漏れ)
上記(3)耐熱試験のみ光漏れに関する評価を行なった。
○・・・光漏れがほとんど見られない
△・・・光漏れが僅かに発生
×・・・4辺に光漏れが大きく発生
調製した粘着剤層付き偏光板について、幅25mm幅に裁断し、離型フィルムを剥離して、粘着剤層側を無アルカリガラス板(コーニング社製、「コーニング1737」)に押圧して、偏光板とガラス板とを貼合した。その後、オートクレーブ処理(50℃、0.5MPa、20分)を行い、24時間後に180度剥離試験を行った。剥離性においては粘着力が小さいことが望まれ、1日後で10N/25mm以下が目標となる。
更には、偏光板用粘着剤としての高耐久・耐光漏れ性にも優れるものである。
Claims (13)
- アクリル系樹脂(A)と、ビス(フルオロスルホニル)イミドアニオンを有し常温で固体のイオン性化合物(B)を含有してなることを特徴とする粘着剤組成物。
- アクリル系樹脂(A)のHLBが6.8以上であることを特徴とする請求項1記載の粘着剤組成物。
- ビス(フルオロスルホニル)イミドアニオンを有するイオン性化合物(B)のカチオン部が、金属カチオンまたは窒素原子含有ヘテロ環式化合物のカチオン類であることを特徴とする請求項1または2記載の粘着剤組成物。
- 金属カチオンが、アルカリ金属カチオンであることを特徴とする請求項3記載の粘着剤組成物。
- 窒素原子含有ヘテロ環式化合物のカチオン類が、イミダゾリウムカチオンであることを特徴とする請求項3記載の粘着剤組成物。
- 請求項1~5のいずれか一項に記載の粘着剤組成物が、架橋されてなることを特徴とする粘着剤。
- 粘着剤組成物が、さらに不飽和基含有化合物(C)および重合開始剤(D)を含有し、活性エネルギー線および/または熱により架橋されてなることを特徴とする請求項6記載の粘着剤。
- 粘着剤組成物が、さらに架橋剤(E)を含有し、この架橋剤(E)により架橋されてなることを特徴とする請求項6または7記載の粘着剤。
- 請求項6~8のいずれか一項に記載の粘着剤を用いてなる光学部材用粘着剤。
- 光学部材が偏光板であることを特徴とする請求項9記載の光学部材用粘着剤。
- 請求項9または10記載の光学部材用粘着剤が光学部材に積層されてなることを特徴とする粘着剤層付き光学部材。
- アクリル系樹脂(A)と、ビス(フルオロスルホニル)イミドアニオンを有するイオン性化合物(B)と、オキシアルキレン基含有化合物(F)とを含有してなる粘着剤組成物であって、上記オキシアルキレン基含有化合物(F)が、オキシアルキレン構造を含有し、分子鎖末端に水酸基を含有しない化合物であることを特徴とする粘着剤組成物。
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| CN2010800239830A CN102449092A (zh) | 2009-06-09 | 2010-06-09 | 粘合剂组合物和粘合剂、以及光学部件用粘合剂、使用其获得的带有粘合剂层的光学部件 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5615608B2 (ja) | 2014-10-29 |
| JP2011016990A (ja) | 2011-01-27 |
| JP2011016999A (ja) | 2011-01-27 |
| CN102449092A (zh) | 2012-05-09 |
| JP5700396B2 (ja) | 2015-04-15 |
| JP2011017000A (ja) | 2011-01-27 |
| TW201107437A (en) | 2011-03-01 |
| KR20120036829A (ko) | 2012-04-18 |
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