WO2017022770A1 - 粘着シート、粘着剤層付き積層体の製造方法、粘着剤層付き積層体、画像表示装置およびタッチパネル - Google Patents
粘着シート、粘着剤層付き積層体の製造方法、粘着剤層付き積層体、画像表示装置およびタッチパネル Download PDFInfo
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- WO2017022770A1 WO2017022770A1 PCT/JP2016/072682 JP2016072682W WO2017022770A1 WO 2017022770 A1 WO2017022770 A1 WO 2017022770A1 JP 2016072682 W JP2016072682 W JP 2016072682W WO 2017022770 A1 WO2017022770 A1 WO 2017022770A1
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- sensitive adhesive
- pressure
- adhesive layer
- acrylate
- meth
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
-
- 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
Definitions
- the present invention relates to a pressure-sensitive adhesive sheet, a method for producing a laminate with a pressure-sensitive adhesive layer, a laminate with a pressure-sensitive adhesive layer, an image display device, and a touch panel.
- the present invention relates to a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer with a good balance between pressure-sensitive adhesive properties and heat and moisture resistance.
- a transparent adhesive sheet is used for bonding.
- a transparent double-sided PSA sheet is used to attach the touch panel and various display devices and optical members (protective plates, etc.).
- step following ability is required.
- a plastic material such as polycarbonate resin, acrylic resin, or (cyclic) olefin resin is used as a member constituting the touch panel, the adherend (member) and the adhesive layer are caused by gas or moisture generated from the member. In some cases, foaming or peeling may occur between them, and blister resistance that can suppress them is also required.
- step following ability there is a method using a soft adhesive layer.
- the step following ability is improved by softening the adhesive layer, deformation and distortion are likely to occur. Furthermore, there was a problem that the durability was inferior.
- Patent Document 1 discloses crosslinking of an acrylic resin with a thermally crosslinkable crosslinking agent, and ethylenic property.
- a type of pressure-sensitive adhesive sheet that combines curing with irradiation of active energy rays of an unsaturated monomer, and includes a base polymer, a monomer having at least one polymerizable unsaturated group, a crosslinking agent that reacts with the base polymer by heat, and polymerization
- a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive obtained by semi-curing a pressure-sensitive adhesive composition containing an initiator and a solvent by heating has been proposed.
- the pressure-sensitive adhesive sheet disclosed in Patent Document 1 is also excellent in step followability, but is not sufficient in terms of blister resistance, and a pressure-sensitive adhesive sheet excellent in step followability and blister resistance is required.
- the present invention under such a background, it is a pressure-sensitive adhesive sheet excellent in level difference followability and blister resistance, and has a high level of reliability that is well balanced in adhesive physical properties (adhesive strength, holding power) and wet heat resistance. It aims at providing the adhesive sheet which has property.
- an acrylic resin in which the glass transition temperature is usually used as an adhesive in an adhesive sheet having an adhesive layer in which the acrylic resin is crosslinked with a crosslinking agent By using an acrylic resin higher than the glass transition temperature of the adhesive sheet, the resulting adhesive sheet exhibits excellent step following capability when bonded to an uneven substrate, and also when bonded to a plastic substrate.
- the present invention was completed by finding out that foaming and peeling do not occur between the base material and the pressure-sensitive adhesive layer, and that it is excellent in blister resistance, adhesive physical properties (adhesive strength, holding power), and wet heat resistance. .
- the gist of the present invention is the following (1) to (9).
- a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a crosslinked product of a functional group-containing acrylic resin (A) and a crosslinking agent (B), and an ethylenically unsaturated compound (C) having one ethylenically unsaturated group A pressure-sensitive adhesive sheet in which the functional group-containing acrylic resin (A) has a glass transition temperature of ⁇ 35 ° C. or higher.
- the functional group-containing acrylic resin (A) is an acrylic resin obtained by polymerizing a monomer component containing a methacrylic acid alkyl ester monomer having an alkyl group having 1 to 8 carbon atoms.
- the image display apparatus which has a laminated body with an adhesive layer as described in said (7).
- the touch panel which has a laminated body with an adhesive layer as described in said (7).
- the present invention is characterized in that an acrylic resin having a high glass transition temperature, which is usually difficult to use for pressure sensitive adhesives that require a step following ability, is characterized by the use of an ethylenically unsaturated group.
- One ethylenically unsaturated compound is contained in the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet excellent in step following ability and excellent in blister resistance, because it has a well-balanced adhesive property (adhesive strength, holding power), moisture and heat resistance, and excellent reworkability.
- it is useful as an adhesive sheet used for pasting a touch panel or an image display device.
- (meth) acryl means acryl or methacryl
- (meth) acryloyl means acryloyl or methacryloyl
- (meth) acrylate means acrylate or methacrylate.
- the acrylic resin is a resin obtained by polymerizing a monomer component containing at least one (meth) acrylic monomer.
- the pressure-sensitive adhesive sheet of the present invention comprises a crosslinked product of a functional group-containing acrylic resin (A) having a specific glass transition temperature and a crosslinking agent (B), and an ethylenically unsaturated compound having one ethylenically unsaturated group (C ) Containing a pressure-sensitive adhesive layer.
- A functional group-containing acrylic resin
- B crosslinking agent
- C ethylenically unsaturated compound having one ethylenically unsaturated group
- the pressure-sensitive adhesive sheet of the present invention is characterized by using a functional group-containing acrylic resin (A) having a glass transition temperature of ⁇ 35 ° C. or higher.
- the glass transition temperature of the functional group-containing acrylic resin (A) is preferably ⁇ 35 ° C. to 30 ° C., more preferably ⁇ 35 ° C. to 0 ° C., particularly preferably ⁇ 35 ° C. to ⁇ 10 ° C., particularly preferably. Is ⁇ 30 ° C. to ⁇ 10 ° C. If the glass transition temperature of the functional group-containing acrylic resin (A) is too low, the blister resistance is deteriorated and the object of the present invention cannot be achieved. Further, even if the glass transition temperature is too high, the step following ability tends to be lowered.
- the type and blending ratio of the monomer components constituting the functional group-containing acrylic resin (A) may be adjusted as appropriate.
- the above glass transition temperature is calculated from the following Fox equation.
- Tg Glass transition temperature of copolymer (K)
- Tga Glass transition temperature (K) of homopolymer of monomer A
- Wa weight fraction of monomer A
- Tgb glass transition temperature (K) of homopolymer of monomer B
- Tgn glass transition temperature (K) of homopolymer of monomer N
- the functional group-containing acrylic resin (A) contains a functional group that can become a crosslinking point by reacting with a cross-linking agent (B) described later.
- the functional group include a hydroxyl group, a carboxyl group, and an amino group. Acetoacetyl group, isocyanate group, glycidyl group and the like. Among these, it is preferable to contain a hydroxyl group and a carboxyl group from the viewpoint that the crosslinking reaction can be efficiently carried out, and it is preferable to contain a hydroxyl group from the viewpoint of improving the heat and moisture resistance.
- the functional group-containing acrylic resin (A) used in the present invention contains the functional group-containing monomer (a1) as an essential component as a monomer component, and a (meth) acrylic acid alkyl ester monomer (a2), necessary In accordance with the above, a monomer component containing another polymerizable monomer (a3) is further polymerized.
- the functional group-containing monomer (a1) may be any monomer containing a functional group that can become a crosslinking point by reacting with the later-described crosslinking agent (B).
- a hydroxyl group-containing monomer and a carboxyl group-containing monomer from the viewpoint that the crosslinking reaction can be efficiently performed, and it is preferable to use a hydroxyl group-containing monomer from the viewpoint that wet heat resistance can be improved.
- a carboxyl group-containing monomer since it becomes easy to corrode when a to-be-adhered body is a metal or its oxide, it is preferable not to use a carboxyl group-containing monomer.
- hydroxyl group-containing monomer examples include: (Meth) acrylic such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, etc.
- Acid hydroxyalkyl esters include caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, oxyalkylene-modified monomers such as diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and others, 2-acryloyloxyethyl-2 -Primary hydroxyl group-containing monomers such as hydroxyethylphthalic acid; Secondary hydroxyl group-containing monomers such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 3-chloro-2-hydroxypropyl (meth) acrylate; Examples thereof include tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.
- a primary hydroxyl group-containing monomer is preferable from the viewpoint of excellent reactivity with a crosslinking agent, and 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly preferable.
- hydroxyl-containing monomer used by this invention it is also preferable to use a thing with the content rate of di (meth) acrylate which is an impurity 0.5% or less, especially 0.2% or less, Furthermore, 0 It is preferable to use those having a content of 1% or less, specifically 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate.
- carboxyl group-containing monomer examples include (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide-N-glycolic acid, cinnamon An acid etc. are mentioned, Especially, (meth) acrylic acid is used preferably.
- amino group-containing monomer examples include t-butylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.
- acetoacetyl group-containing monomer examples include 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate.
- isocyanate group-containing monomer examples include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.
- Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate.
- These functional group-containing monomers (a1) may be used alone or in combination of two or more.
- the content of the functional group-containing monomer (a1) in the monomer component is preferably 0.01 to 70% by weight, particularly preferably 0.1 to 50% by weight, more preferably 1 to 35% by weight, Particularly preferred is 10 to 30% by weight. If the content ratio of the functional group-containing monomer (a1) is too small, the durability of the acrylic resin tends to deteriorate due to insufficient cohesive strength of the acrylic resin, and if it is too large, the viscosity of the acrylic resin increases or is preserved. There is a tendency for stability to decrease.
- the content ratio of the hydroxyl group-containing monomer is preferably 5 to 50% by weight, particularly 7 to 40% by weight, based on the entire copolymerization component. %, More preferably 10 to 35% by weight, especially 15 to 30% by weight. If the content of the hydroxyl group-containing monomer is too small, the adhesive strength tends to decrease or the heat-and-moisture resistance tends to decrease. If the content is too large, the viscosity of the acrylic resin increases and a good coating film can be formed. It tends to be difficult.
- Examples of the (meth) acrylic acid alkyl ester monomer (a2) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, isodecyl (meth) acrylate, Lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, n-stearyl (meth) acrylate, iso-stearyl (meth) acrylate, behenyl (meth)
- acrylic acid alkyl ester monomers (a2) may be used alone or in combination of two or more.
- a methacrylic acid alkyl ester monomer (a2-1) having 1 to 8 carbon atoms in the alkyl group such as methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, etc. from the viewpoint of increasing the cohesive force.
- the alkyl group has 4 to 8 carbon atoms in terms of efficiently increasing the rigidity of the main chain and improving the blister resistance and excellent copolymerizability with the monomer (polymerization stability).
- a methacrylic acid alkyl ester monomer particularly tert-butyl methacrylate.
- the content of the (meth) acrylic acid alkyl ester monomer (a2) in the monomer component is preferably 5 to 99% by weight, particularly preferably 20 to 80% by weight, and more preferably 40 to 70% by weight. It is.
- the content ratio of the (meth) acrylic acid alkyl ester monomer (a2) is too small, the blister resistance and cohesive force tend to decrease, and when too large, the adhesive physical properties when used as an adhesive tend to decrease. It is in.
- the content in the monomer component is preferably 10 to 70% by weight, particularly preferably 15%. -60% by weight, more preferably 20-50% by weight. If the content is too small, the blister resistance tends to decrease due to a decrease in cohesive force, and if it is too large, the step following property tends to deteriorate.
- the total content is preferably 1 to 70% by weight, particularly preferably 5 to 60% by weight, more preferably 7 to 55% by weight, and particularly preferably 10 to 50% by weight. If the content ratio of the (meth) acrylic acid alkyl ester monomer (a2-2) is too small, the blister resistance tends to decrease, and if it is too large, the viscosity of the acrylic resin increases and handling becomes difficult.
- the adhesive properties when used as an adhesive tend to decrease.
- Alicyclic (meth) acrylic acid ester monomers such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate;
- One fragrance such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyldiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, styrene, ⁇ -methylstyrene, etc.
- the content of the other polymerizable monomer (a3) in the monomer component is preferably 0 to 40% by weight, particularly preferably 0 to 30% by weight, and further preferably 0 to 25% by weight.
- the content of the other polymerizable monomer (a3) in the monomer component is preferably 0 to 40% by weight, particularly preferably 0 to 30% by weight, and further preferably 0 to 25% by weight.
- a functional group-containing acrylic resin (A) can be produced by polymerizing the monomer components.
- the polymerization method of the functional group-containing acrylic resin (A) for example, conventionally known polymerization methods such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization and the like can be used. Polymerization can be carried out according to typical polymerization conditions, but production by solution polymerization is preferred in that the functional group-containing acrylic resin (A) can be produced safely and stably with any monomer composition.
- the monomer components (a1) to (a3) and the polymerization initiator are mixed or dropped in an organic solvent, and the mixture is polymerized at reflux or at 50 to 98 ° C. for 0.1 to 20 hours. That's fine.
- organic solvent used in the polymerization reaction examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, N-propyl alcohol, and isopropyl alcohol.
- aromatic hydrocarbons such as toluene and xylene
- aliphatic hydrocarbons such as hexane
- esters such as ethyl acetate and butyl acetate
- N-propyl alcohol and isopropyl alcohol.
- Aliphatic alcohols such as acetone, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- ethyl acetate, acetone, methyl ethyl ketone, butyl acetate, toluene, methyl isobutyl ketone are preferred because of their ease of polymerization reaction, chain transfer effect, ease of drying during adhesive coating, and safety.
- ethyl acetate, acetone, and methyl ethyl ketone are more preferable.
- polymerization initiators examples include azo-based polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile, which are ordinary radical polymerization initiators, benzoyl peroxide, lauroyl peroxide, and di-t-butyl peroxide.
- azo-based polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile
- benzoyl peroxide lauroyl peroxide
- di-t-butyl peroxide examples include peroxide polymerization initiators such as cumene hydroperoxide.
- the weight average molecular weight of the functional group-containing acrylic resin (A) is usually 50,000 to 2,000,000, preferably 200,000 to 1,000,000, particularly preferably 300,000 to 800,000. When the weight average molecular weight is too small, the durability performance tends to decrease, and when it is too large, the step following ability tends to decrease.
- the dispersity (weight average molecular weight / number average molecular weight) of the functional group-containing acrylic resin (A) is preferably 20 or less, particularly preferably 15 or less, more preferably 10 or less, especially 7 or less. Is preferred. If the degree of dispersion is too high, the durability performance of the pressure-sensitive adhesive layer tends to decrease.
- the lower limit of the degree of dispersion is usually 1.1 from the viewpoint of production limit.
- the weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: Shodex is used in high performance liquid chromatography (manufactured by Waters, Japan, “Waters 2695 (main body)” and “Waters 2414 (detector)”).
- GPC KF-806L exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size : 10 ⁇ m
- the degree of dispersion is determined from the weight average molecular weight and the number average molecular weight.
- the functional group containing acrylic resin (A) used by this invention the functional group containing acrylic resin which has an active energy ray reactive structure site
- the ethylenically unsaturated group-containing acrylic resin is obtained by reacting the functional group of the functional group-containing acrylic resin (A) with an ethylenically unsaturated compound having a functional group that reacts with the functional group. It is something that can be done.
- the ethylenically unsaturated compound include the carboxyl group-containing unsaturated monomer, the hydroxyl group-containing unsaturated monomer, the glycidyl group-containing unsaturated monomer, the isocyanate group-containing unsaturated monomer, the amide group-containing unsaturated monomer, and the amino group-containing unsaturated monomer. Examples thereof include monomers and sulfonic acid group-containing unsaturated monomers.
- the functional group in the acrylic resin is a carboxyl group
- the glycidyl group-containing unsaturated monomer or the isocyanate group-containing unsaturated monomer is used.
- the functional group is a hydroxyl group
- the isocyanate group-containing unsaturated monomer is used.
- a carboxyl group-containing unsaturated monomer or an amide group-containing unsaturated monomer is selected, and in the case where the functional group is an amino group, a glycidyl group-containing unsaturated monomer is selected and used.
- the functional group in acrylic resin is a hydroxyl group
- an ethylenically unsaturated compound is an isocyanate group containing unsaturated compound.
- the adhesive sheet when used for an information label used for bonding to a transparent electrode such as a touch panel or other electronic member, particularly a precision electronic member, or used for fixing an electronic member, the corrosion resistance is low. Since it is calculated
- the crosslinking agent (B) used in the present invention exhibits an excellent adhesive force by mainly reacting with the functional group contained in the functional group-containing acrylic resin (A).
- an isocyanate-based crosslinking agent Epoxy crosslinking agents, aziridine crosslinking agents, melamine crosslinking agents, aldehyde crosslinking agents, amine crosslinking agents, metal chelate crosslinking agents, and the like.
- an isocyanate-based crosslinking agent is preferably used in terms of improving the adhesion to the substrate and the reactivity with the functional group-containing acrylic resin (A).
- isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene.
- epoxy-based crosslinking agent examples include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol diglycidyl ether. , Trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether and the like.
- aziridine-based crosslinking agent examples include tetramethylolmethane-tri- ⁇ -aziridinylpropionate, trimethylolpropane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4.
- Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, and melamine resin. .
- aldehyde-based crosslinking agent examples include glyoxal, malondialdehyde, succindialdehyde, maleindialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, benzaldehyde and the like.
- amine-based crosslinking agent examples include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resin, and polyamide.
- metal chelate-based crosslinking agent examples include acetylacetone and acetoacetyl ester coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, panadium, chromium, and zirconium. Can be mentioned.
- crosslinking agents (B) may be used alone or in combination of two or more.
- the amount of the crosslinking agent (B) is usually preferably 0.001 to 10 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the functional group-containing acrylic resin (A). 5 parts by weight, particularly preferably 0.1 to 2 parts by weight. If the amount of the crosslinking agent (B) used is too small, the cohesive force is insufficient, and there is a tendency that sufficient durability cannot be obtained. Be looked at.
- the reaction temperature when the acrylic resin (A) and the cross-linking agent (B) are cross-linked to form a cross-linked product may be room temperature or may be heated at 20 to 60 ° C., for example.
- the ethylenically unsaturated compound (C) containing one ethylenically unsaturated group used in the present invention (hereinafter sometimes referred to as a monofunctional unsaturated compound (C)) is an ethylenically unsaturated group.
- (Meth) acrylic acid ester compound (C1) (excluding (C2) described later. Hereinafter, it may be described as “monofunctional (meth) acrylic acid ester compound (C1)”).
- An ethylenically unsaturated compound (C2) containing one ethylenically unsaturated group containing a nitrogen atom (hereinafter sometimes referred to as “nitrogen-containing monofunctional unsaturated compound (C2)”) is used. Is preferred.
- Examples of the monofunctional (meth) acrylic ester compound (C1) include long chain aliphatic (meth) acrylate (C1-1), alicyclic (meth) acrylate (C1-2), and aromatic (meth) acrylate. (C1-3), and an oxyalkylene structure-modified compound (C1-4) of these (meth) acrylates.
- Examples of the long chain aliphatic (meth) acrylate (C1-1) include decane (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isotridecyl (meth) acrylate, and isomyristyl.
- Examples of the alicyclic (meth) acrylate (C1-2) include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate.
- aromatic (meth) acrylate (C1-3) examples include biphenyl (meth) acrylate, naphthalene (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl ( And (meth) acrylate.
- Examples of the (C1-1) to (C1-3) oxyalkylene structure-modified compound (C1-4) include the following.
- Examples of the (C1-1) oxyalkylene structure-modified compound include 2-ethylhexyl diethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, alkyl polyethylene glycol (meth) acrylate, and methoxydi Examples include propylene glycol (meth) acrylate, alkylene glycol monoalkyl ester (meth) acrylate, and alkylene glycol mono (meth) acrylate.
- Examples of the (C1-2) oxyalkylene structure-modified compound include t-butylcyclohexyloxyethyl (meth) acrylate, cyclohexyloxyalkyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyloxyethyl. (Meth) acrylate etc. are mentioned.
- Examples of the (C1-3) oxyalkylene structure-modified compound include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyldiethylene glycol (meth) acrylate, phenyltriethylene glycol (meth) acrylate, and phenyltetraglycol (meth).
- Examples include acrylate, biphenyloxyethyl (meth) acrylate, nonylphenol ethylene oxide modified (repeated 4) (meth) acrylate, nonylphenol ethylene oxide modified (repeated 8) (meth) acrylate, and the like.
- the nitrogen-containing monofunctional unsaturated compound (C2) can be used to improve the adhesive strength of the adhesive.
- acrylamide, methacrylamide, butoxymethylacrylamide, hydroxyethylacrylamide, dimethylaminopropylacrylamide, dye Examples include (meth) acrylamide unsaturated monomers such as acetone acrylamide, N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, oxazolidone acrylate, etc.
- (meth) acrylamide unsaturated monomers should be used. Is preferable in terms of being well-balanced in terms of poor volatility and adhesive performance, and particularly preferred is butoxymethylacrylamide and diacetoneacrylamide.
- a long-chain aliphatic acrylate (C1-1) is used in that an optically transparent pressure-sensitive adhesive layer that is difficult to be colored is obtained, and further, hydrophobicity can be imparted to the pressure-sensitive adhesive layer.
- C1-1 a long-chain aliphatic acrylate
- isomyristyl acrylate, isotridecyl acrylate, isostearyl acrylate, and 2-decyl tetradecanyl acrylate are particularly preferred.
- the monofunctional unsaturated compound (C) is present as a polymer in the pressure-sensitive adhesive layer by being cured using at least one of active energy rays and heat as described later.
- the monofunctional unsaturated compound (C) is preferably selected so that the glass transition temperature of the polymer is -80 to 80 ° C.
- the glass transition temperature is particularly preferably ⁇ 60 to 40 ° C., more preferably ⁇ 55 to 10 ° C., and particularly preferably ⁇ 20 to 0 ° C. If the glass transition temperature is too high, the adhesive performance tends to be difficult to exhibit, and if it is too low, the cohesive force tends to decrease.
- the glass transition temperature is calculated from the Fox equation described above.
- the monofunctional unsaturated compound (C) has the effect of improving the drying property at the time of coating using an organic solvent at the same time as making the pressure-sensitive adhesive flexible, and during coating drying (particularly, thick film coating). At the time of drying, a material that is less volatile than an organic solvent and easily stays in the pressure-sensitive adhesive layer is used.
- the flash point of the monofunctional unsaturated compound (C) is preferably 40 ° C. or higher, particularly preferably 80 ° C. or higher, more preferably 100 ° C. or higher, particularly preferably 140 ° C. or higher. If the flash point is too low, it tends to volatilize in the drying process.
- the upper limit of the normal flash point is 350 ° C.
- the weight average molecular weight of the monofunctional unsaturated compound (C) is preferably 100 to 2,000, particularly preferably 120 to 1,000, more preferably 160 to 600, and particularly preferably 200 to 400. is there. If the molecular weight is too large, the physical properties of the adhesive tend to be lowered, and if it is too small, it tends to volatilize in the drying process.
- the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer containing a crosslinked product of a functional group-containing acrylic resin (A) having a specific glass transition temperature and a crosslinking agent (B), and a monofunctional unsaturated compound (C). It is an adhesive sheet.
- A functional group-containing acrylic resin
- B crosslinking agent
- C monofunctional unsaturated compound
- the content ratio of the monofunctional unsaturated compound (C) is preferably 5 to 70% by weight, particularly 9 to 50% by weight, more preferably 12 to It is preferably 40% by weight, particularly preferably 15 to 30% by weight. If the content ratio of the monofunctional unsaturated compound (C) is too small, the step following ability tends to be lowered, and if it is too large, the elastic modulus at the time of creating the sheet becomes too low, and the handleability and the stability of the coating film are low. There is a tendency to decrease.
- the pressure-sensitive adhesive layer may be obtained by cross-linking the functional group-containing acrylic resin (A) and the cross-linking agent (B) and then blending the monofunctional unsaturated compound (C).
- C) may be blended and the functional group-containing acrylic resin (A) and the cross-linking agent (B) may be cross-linked in the presence of the monofunctional unsaturated compound (C). It is preferable that the functional group-containing acrylic resin (A) and the cross-linking agent (B) are cross-linked in the presence of the monofunctional unsaturated compound (C) in that an adhesive sheet can be easily obtained.
- the blending amount of the monofunctional unsaturated compound (C) is preferably 50:50 to 95: 5 (weight ratio), particularly 65:35 to 90: 9, more preferably 70:30 to 85: 15 is preferable.
- the amount of the monofunctional unsaturated compound (C) added to the functional group-containing acrylic resin (A) is too large, the stability of the coating film tends to be lowered, and when it is too small, the step following ability tends to be lowered.
- the blending amount of the crosslinking agent (B) and the blending amount of the monofunctional unsaturated compound (C) is preferably 0.1: 99.9 to 20:80 (weight ratio), particularly 0.3: 99. 0.7-2: 98, and more preferably 0.5: 99.5-1: 99.0.
- the amount of the monofunctional unsaturated compound (C) is too large relative to the amount of the crosslinking agent (B), the stability of the coating film tends to decrease, and when it is too small, the step following ability tends to decrease.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention includes an ethylenically unsaturated compound in addition to the cross-linked product of the functional group-containing acrylic resin (A) and the cross-linking agent (B) and the monofunctional unsaturated compound (C). Containing the ethylenically unsaturated compound (D) containing two or more saturated groups (hereinafter sometimes abbreviated as “polyfunctional unsaturated compound (D)”) adjusts the cohesive force of the entire pressure-sensitive adhesive layer. It is preferable at the point which can be performed, and also containing a polymerization initiator (E) is preferable at the point which can stabilize reaction at the time of active energy ray irradiation and / or a heating.
- Examples of the polyfunctional unsaturated compound (D) include an ethylenically unsaturated monomer containing two or more ethylenically unsaturated groups in one molecule, such as a bifunctional monomer, a trifunctional or higher monomer, and urethane.
- a (meth) acrylate compound, an epoxy (meth) acrylate compound, or a polyester (meth) acrylate compound can be used.
- 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.
- the urethane (meth) acrylate compound 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, a polyol What is necessary is just to use what is obtained by making it react by a well-known general method.
- the weight average molecular weight of the urethane (meth) acrylate compound is usually 300 to 4000.
- the content of the polyfunctional unsaturated compound (D) is preferably 20 to 0.1% by weight, particularly 10 to 0.2% by weight, based on the whole pressure-sensitive adhesive layer. Further, it is preferably 5 to 0.3% by weight, particularly 1 to 0.5% by weight. If the content ratio of the polyfunctional unsaturated compound (D) is too small, the reliability when cured by irradiation with active energy rays tends to decrease, and if too large, the cohesive force when cured by irradiation with active energy rays is high. There is a tendency that the adhesive performance is lowered due to excessive shrinkage and curing shrinkage.
- the content of the polyfunctional unsaturated compound (D) in the pressure-sensitive adhesive layer is preferably 0.01 to 50 parts by weight, particularly preferably 100 parts by weight of the monofunctional unsaturated compound (C). Is 0.5 to 20 parts by weight, more preferably 1 to 5 parts by weight.
- the content of the polyfunctional unsaturated compound (D) is too large, the cohesive force is excessively increased in the post-curing step, and the shrinkage of the curing occurs and the adhesive performance tends to decrease.
- the content is too small, the holding power is insufficient. Tend.
- the functional group-containing acrylic resin (A), the crosslinking agent (B), and the monofunctional unsaturated compound (C) are further used with the polyfunctional unsaturated compound (D) to produce the pressure-sensitive adhesive sheet of the present invention.
- the compounding amount of the polyfunctional unsaturated compound (D) is preferably 0.01 to 50 parts by weight, particularly preferably 0.1 to 30 parts by weight based on 100 parts by weight of the functional group-containing acrylic resin (A). Parts by weight, more preferably 0.5 to 20 parts by weight, particularly preferably 1 to 5 parts by weight.
- polymerization initiator (E) for example, various polymerization initiators such as a photopolymerization initiator (e1) and a thermal polymerization initiator (e2) can be used. It is preferable to use e1) in that it can be cured by irradiation with active energy rays such as ultraviolet rays for a very short time. Moreover, it is also preferable to use both together as needed.
- a known general polymerization initiator may be used as the photopolymerization initiator (e1) and the thermal polymerization initiator (e2).
- Examples of the photopolymerization initiator (e1) 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
- 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 (e2) examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexyl peroxide).
- About content in the adhesive layer of the said polymerization initiator (E), when using monofunctional unsaturated compound (C) 100 weight part (when using polyfunctional unsaturated compound (D), (C) and ( D) is preferably 0.01 to 50 parts by weight, particularly preferably 0.1 to 20 parts by weight, more preferably 0.3 to 12 parts by weight, particularly preferably 100 parts by weight of D). Is 0.5 to 5 parts by weight. If the content of the polymerization initiator (E) 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.
- the pressure-sensitive adhesive sheet of the present invention does not have a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer provided on a base sheet, a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer provided on a release sheet, and a base material sheet when bonding an adherend.
- Examples include a substrate-less double-sided pressure-sensitive adhesive sheet used in a state, but a substrate-less double-sided pressure-sensitive adhesive sheet is preferable in terms of excellent transparency and high adhesive force with respect to the thickness to be formed.
- a functional group-containing acrylic resin (A), a cross-linking agent (B), and a monofunctional unsaturated compound (C) are contained as essential components, and further ethylene if necessary.
- An adhesive composition containing an ethylenically unsaturated compound (D) containing two or more polymerizable unsaturated groups and a polymerization initiator (E) is coated on a base sheet or a release sheet, dried, and if necessary By curing, the pressure-sensitive adhesive sheet of the present invention having a pressure-sensitive adhesive layer containing a cross-linked product of the functional group-containing acrylic resin (A) and the cross-linking agent (B) and the monofunctional unsaturated compound (C) is obtained.
- a substrate-less double-sided pressure-sensitive adhesive sheet for example, after a pressure-sensitive adhesive layer is formed by coating a pressure-sensitive adhesive composition on a release sheet and drying, there is no release sheet for the pressure-sensitive adhesive layer. It can manufacture by sticking another release sheet to the side, and curing as needed.
- the base sheet examples include polyester resins such as polyethylene naphthalate, polyethylene terephthalate, boribylene terephthalate, polyethylene terephthalate / isophthalate copolymer; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; Examples include cyclic olefin resins such as Arton (cyclic olefin polymer; manufactured by JSR) and trade name “Zeonoa (cyclic olefin polymer; manufactured by Nippon Zeon)”; polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene.
- polyester resins such as polyethylene naphthalate, polyethylene terephthalate, boribylene terephthalate, polyethylene terephthalate / isophthalate copolymer
- polyolefin resins such as polyethylene, polypropylene, and polymethylpentene
- Polyfluorinated ethylene resins such as nylon 6, polyamides such as nylon 6,6; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer Vinyl polymers such as polyvinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; polystyrene; polycarbonate; Polyarylate; synthetic resin sheets such as polyimide, metal foils of aluminum, copper, and iron, paper such as fine paper and glassine paper, woven fabrics and nonwoven fabrics made of glass fibers, natural fibers, synthetic fibers, and the like. These base material sheets can be used as a single layer body or a multilayer body in which two or more kinds are laminated.
- ITO indium tin
- Cu mesh As a base material sheet, ITO (acid value indium tin) electrode film, Cu mesh, Ag mesh, Ag nanofiber, or transparent electrode films such as organic conductive curtains such as polythiophene, or the above various types with electrode films
- optical members such as a base material, a polarizing plate, a phase difference plate, an elliptical polarizing plate, an optical compensation film, a brightness enhancement film, an electromagnetic wave shielding film, a near-infrared absorption film, and an AR (anti-reflection) film.
- the release sheet it is possible to use various synthetic resin sheets exemplified in the base sheet, paper, cloth, non-woven fabric, and the like, for example, a silicon release sheet, an olefin-based release sheet, and the like. Examples include a release sheet, a fluorine release sheet, a long-chain alkyl release sheet, and an alkyd release sheet.
- a gravure roll coater for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater or the like may be used.
- the drying temperature is usually 50 ° C. to 250 ° C., preferably 60 ° C. to 120 ° C., more preferably 65 ° C. to 95 ° C.
- the drying time is usually 10 seconds to 10 minutes.
- the temperature is usually room temperature to 70 ° C.
- the time is usually 1 day to 30 days.
- the temperature is 23 ° C. for 1 day to 20 days, preferably 23 ° C. for 3 to 3 days.
- the treatment may be performed for 10 days at 40 ° C. for 1 to 7 days.
- the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is usually preferably 5 to 300 ⁇ m, particularly preferably 10 to 250 ⁇ m, more preferably 25 to 200 ⁇ m, particularly preferably 50 to 175 ⁇ m. If the thickness of the pressure-sensitive adhesive layer is too thin, the step following ability tends to decrease, and if it is too thick, the thickness of the entire optical member tends to increase too much.
- a thick adhesive layer when a thick adhesive layer is obtained, it is preferably applied with a film thickness of 10 ⁇ m or more, particularly preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more.
- the film thickness at the time of coating is usually 800 ⁇ m.
- the above-mentioned film thickness is a value obtained by subtracting the measured value of the thickness of components other than the pressure-sensitive adhesive layer from the measured value of the thickness of the entire pressure-sensitive adhesive sheet using “ID-C112B” manufactured by Mitutoyo Corporation. .
- the gel fraction of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention (before curing by irradiation with active energy rays and / or heating) is preferably 5 to 60% from the viewpoint of pressure-sensitive adhesive strength and step following ability, It is preferably 10 to 50%, particularly 20 to 45%. If the gel fraction is too low, the pressure-sensitive adhesive sheet tends to be traced by foreign substances due to a decrease in cohesive force, or the pressure-sensitive adhesive sheet tends to sag. On the other hand, if the gel fraction is too high, the step following ability decreases due to the increase in cohesive force, the adhesion to the adherend tends to decrease, and the blister resistance tends to deteriorate.
- the gel fraction of the pressure-sensitive adhesive layer after curing by irradiation with active energy rays and / or heating of the pressure-sensitive adhesive sheet of the present invention is preferably 10 to 95%, particularly 20 to 90% is preferable, and 30 to 80% is particularly preferable. If the gel fraction is too low, the durability of the pressure-sensitive adhesive layer tends to deteriorate due to a decrease in cohesive force. On the other hand, if the gel fraction is too high, the adhesion with the interface tends to decrease due to an increase in cohesive force.
- the gel fraction is a measure of the degree of crosslinking (curing degree), 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 or the like) 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 pressure-sensitive adhesive sheet of the present invention thus obtained includes a monofunctional unsaturated compound in addition to the cross-linked product of the functional group-containing acrylic resin (A) having a specific glass transition temperature in the pressure-sensitive adhesive layer and the cross-linking agent (B). Since (C) is contained, the monofunctional unsaturated compound (C) imparts a plastic effect to the pressure-sensitive adhesive, so that the elastic modulus of the pressure-sensitive adhesive layer is lowered, so that the level difference (unevenness) of the adherend is reduced. Excellent follow-up performance.
- the glass transition temperature of the functional group-containing acrylic resin (A) is higher than usual, so that the content of the crosslinking agent can be reduced, and therefore, the decrease in adhesion due to thermal crosslinking of the acrylic resin is minimized. can do.
- the monofunctional unsaturated compound (C) contained in an adhesive layer superposes
- the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet is bonded to the adherend, and then heated and pressurized with an autoclave or the like (for example, 50 ° C./0.5 MPa). X30 minutes).
- a transparent material is used for at least one of the base sheet and the adherend, and the active energy rays may be irradiated from such a transparent surface.
- 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 at a 50 ⁇ 2000mJ / cm 2 conditions.
- the electrodeless lamp for example, it is performed under the conditions of 2 to 2000 mJ / cm 2 , preferably 10 to 1000 mJ / cm 2 .
- 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 (e2) is used as the polymerization initiator (E), and the polymerization reaction is started by heating and is allowed to proceed.
- the treatment temperature and treatment time at the time of curing by heating vary depending on the type of the thermal polymerization initiator (e2) to be used, and are usually calculated from the half-life of the initiator, but the treatment temperature is usually The temperature is preferably 70 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 sheet of the present invention is laminated to the adherend by laminating the pressure-sensitive adhesive sheet of the present invention to the adherend and performing at least one of active energy ray irradiation and heating.
- a laminate with an adhesive layer [adhered body / adhesive layer / adhesive body] when [adhered body / adhesive layer / base material sheet] or base material-less double-sided adhesive sheet). it can.
- the adherend is not particularly limited.
- the optical member include a plate, an optical compensation film, a brightness enhancement film, an electromagnetic wave shielding film, a near-infrared absorbing film, and an AR (anti-reflection) film.
- the adherend having a step on the surface exhibits the effect of the pressure-sensitive adhesive sheet excellent in followability of the present invention, and is preferably 1 to 100 ⁇ m, particularly 3 to 50 ⁇ m, Even an adherend having a step of 5 to 30 ⁇ m on the surface exhibits good followability.
- the storage elastic modulus of the pressure-sensitive adhesive layer is 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 at 23 ° C. and 1 Hz, and tan ⁇ at 50 ° C. and 1 Hz is 0.5 to It is preferable that it is 0.7. Further, the storage elastic modulus of the pressure-sensitive adhesive layer after curing with active energy rays and / or heat is 1.0 ⁇ 10 4 or more at 23 ° C. and 1 Hz, and tan ⁇ at 50 ° C. and 1 Hz is less than 0.5. It is preferable that
- the adhesive sheet of the present invention is made of glass, ITO transparent electrode sheet, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA) and other optical sheets, polarizing plate, retardation plate, optical compensation film, and brightness enhancement. This is useful for attaching optical members such as films. Furthermore, it can be suitably used for an image display device such as a touch panel including these optical members.
- azobisisobutyronitrile (AIBN) was added as a polymerization initiator, reacted at methyl ethyl ketone reflux temperature for 3 hours, 0.02 part of azobisisobutyronitrile (AIBN), 3 parts of ethyl acetate The mixture was further reacted for 4 hours and diluted with ethyl acetate to obtain an acrylic resin solution. To 100 parts of the resulting acrylic resin solution (resin content), 0.03 part of 2-methacryloyloxyethyl isocyanate was charged and reacted at 50 ° C. for 12 hours. Ethylenically unsaturated groups were added to the side chain with respect to hydroxyethyl acrylate.
- AIBN azobisisobutyronitrile
- HEA 2-hydroxyethyl acrylate
- 2EHA 2-ethylhexyl acrylate
- tBMA tert-butyl methacrylate
- 2EHMA 2-ethylhexyl methacrylate
- ISTA isostearyl acrylate
- Crosslinking agent (B) The following were prepared as the crosslinking agent (B-1). -55% ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane ("Coronate L-55E" manufactured by Nippon Polyurethane)
- Polymerization initiator (E) The following were prepared as the polymerization initiator (E-1).
- a 1 1 mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone (“Irgacure 500” manufactured by Ciba Japan)
- Example 1 100 parts (resin part) of the functional group-containing acrylic resin (A-1), 0.2 part of a crosslinking agent (B-1), 40 parts of a monofunctional unsaturated compound (C-1), a polyfunctional unsaturated compound 1 part of (D-1) and 1 part of photopolymerization initiator (E-1) were blended to prepare an adhesive composition solution.
- This pressure-sensitive adhesive composition solution was applied to a polyester release sheet so that the thickness after drying was 100 ⁇ m, and dried at 90 ° C. for 5 minutes to form a pressure-sensitive adhesive layer.
- the obtained pressure-sensitive adhesive layer was sandwiched between polyester release sheets and aged at 40 ° C. for 3 days to obtain a substrate-less double-sided pressure-sensitive adhesive sheet [I-1].
- the release sheet on one side is peeled off from the pressure-sensitive adhesive layer of the base-less double-sided pressure-sensitive adhesive sheet obtained above, and pressed onto a 125 ⁇ m-thick easy-adhesion-treated polyethylene terephthalate (PET) sheet, and the film thickness of the pressure-sensitive adhesive layer Gave a PET sheet [II-1] with an adhesive layer of 100 ⁇ m. Furthermore, the release sheet on one side is peeled off from the pressure-sensitive adhesive layer of the substrate-less double-sided pressure-sensitive adhesive sheet, pressed against a polyethylene terephthalate (PET) sheet having a thickness of 50 ⁇ m, and the pressure-sensitive adhesive layer has a thickness of 100 ⁇ m. A PET sheet [III-1] was obtained.
- Example 3 The film of the pressure-sensitive adhesive layer was changed in the same manner as in Example 1 except that the blending ratio of the components (A) to (E) was changed to the blending ratio shown in Table 2 and the thickness after drying was 160 ⁇ m. Substrate-less double-sided pressure-sensitive adhesive sheet [I-3] and PET sheets with pressure-sensitive adhesive layers [II-3] and [III-3] having a thickness of 160 ⁇ m were obtained.
- the pressure-sensitive adhesive layer side is bonded to a 50 mm ⁇ 100 mm SUS mesh sheet (200 mesh), and then the other release sheet is peeled off to the longitudinal direction of the SUS mesh sheet.
- the gel fraction (%) was measured by the change in weight when immersed in a sealed container containing 250 g of toluene for 24 hours.
- PET film with adhesive layer [II-1] to [II-3], [II'-1], [II'-2] is cut into a width of 25 mm and a length of 100 mm, respectively, and the release sheet is peeled off Then, the pressure-sensitive adhesive layer side was pressure-applied to a non-alkali glass in an atmosphere of 23 ° C. and a relative humidity of 50% by reciprocating 2 kg rubber rollers, and left for 30 minutes in an atmosphere of 23 ° C. and a relative humidity of 50%.
- the 180 degree peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min at room temperature.
- PET film with adhesive layer [II-1] to [II-3], [II'-1], [II'-2] is cut into a width of 25 mm and a length of 100 mm, respectively, and the release sheet is peeled off Then, the pressure-sensitive adhesive layer side is pressure-applied by reciprocating 2kg rubber roller in non-alkali glass at 23 ° C and relative humidity of 50%, and is heated by autoclave at 50 ° C and 0.5MPa x 20min. Went.
- UV irradiation was performed from the PET film side with a high-pressure mercury UV irradiation device at a peak illuminance of 150 mW / cm 2 and an integrated exposure amount of 1000 mJ / cm 2 (500 mJ / cm 2 ⁇ 2 passes), and 23 ° C. ⁇ 50% R . H.
- the 180 ° peel strength was measured at room temperature and a peel rate of 300 mm / min.
- PET films of 25 ⁇ m, 38 ⁇ m, 50 ⁇ m, 70 ⁇ m, and 100 ⁇ m were respectively fixed with cellophane tape to produce a stepped glass.
- the above PET sheets [II-1] to [II-3], [II′-1], and [II′-2] with the pressure-sensitive adhesive layer are respectively 23 ° C. and 50% relative humidity with respect to the stepped glass.
- pressure was applied by two reciprocations of a 2 kg rubber roller, and a pressure heat treatment at 50 ° C. and 0.5 MPa ⁇ 20 minutes was performed by an autoclave.
- UV irradiation was performed from the PET film side with a high-pressure mercury UV irradiation device at a peak illuminance of 150 mW / cm 2 and an integrated exposure amount of 1000 mJ / cm 2 (500 mJ / cm 2 ⁇ 2 passes), and 23 ° C. ⁇ 50% R . H.
- the ability to follow a step was visually evaluated as follows. (Evaluation) ⁇ ⁇ ⁇ ⁇ No air entrainment or lifting was confirmed at the step. ⁇ : Air can be slightly caught in a part of the step portion, but no floating was confirmed. ⁇ : Air can be seen biting or floating in part of the step. X: A large float was confirmed at the step.
- haze value and color difference b * value were measured.
- haze value diffuse transmittance and total light transmittance are measured using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the obtained diffuse transmittance and total light transmittance value are substituted into the following formula. The haze was calculated. This machine conforms to JIS K7361-1.
- Haze value (%) (diffuse transmittance (%) / total light transmittance (%)) ⁇ 100 [Color difference]
- the color difference b * value was measured according to JIS K7105, and the measurement was performed under transmission conditions using a spectral color difference meter (SE6000: manufactured by Nippon Denshoku Industries Co., Ltd.).
- SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.
- UV irradiation was performed from the PET film side with a high-pressure mercury UV irradiation device at a peak illuminance of 150 mW / cm 2 and an integrated exposure amount of 1000 mJ / cm 2 (500 mJ / cm 2 ⁇ 2 passes), and 23 ° C. ⁇ 50% R . H.
- the test piece having the configuration of “slide glass / adhesive layer / PET film” was produced by leaving it for 30 minutes under the above conditions.
- the heat and humidity resistance test for 168 hours was performed under the above atmosphere, and the haze values after the start of the moisture and heat resistance test and after the moisture and heat resistance test were measured and evaluated according to the following criteria.
- the haze value was measured by the same method as the optical property measurement of the pressure-sensitive adhesive layer. (Evaluation) ⁇ : The haze value after the moist heat resistance test is less than 2.0%, and the rate of increase in the haze value before and after the moist heat resistance test is within 1.2 times.
- ⁇ The haze value immediately after the moist heat resistance test is less than 2.0%, and the rate of increase in the haze value before and after the moist heat resistance test is greater than 1.2 times.
- X The haze value immediately after the wet heat resistance test is 2.0% or more.
- ⁇ Foaming of ⁇ 0.5 mm or less was observed, but no foaming exceeding ⁇ 0.5 mm was observed.
- ⁇ Foaming exceeding ⁇ 0.5 mm occurs in less than 1/3 of the entire pasting surface.
- X Foaming exceeding ⁇ 0.5 mm occurs in 1/3 or more of the entire pasting surface.
- the pressure-sensitive adhesive sheets of Examples 1 and 2 having a pressure-sensitive adhesive layer thickness of 100 ⁇ m exhibit very excellent followability with respect to steps of 25 ⁇ m and 38 ⁇ m, and the pressure-sensitive adhesive sheet of Example 1 is 50 ⁇ m. It can be seen that sufficient followability is exhibited even with respect to the level difference.
- the pressure-sensitive adhesive sheet of Example 3 having a pressure-sensitive adhesive layer thickness of 160 ⁇ m exhibits very excellent followability to steps of 25 ⁇ m, 38 ⁇ m, and 50 ⁇ m, and sufficiently follows steps of 75 ⁇ m. It turns out that it shows sex.
- the pressure-sensitive adhesive sheets of Examples 1 to 3 have properties required when the pressure-sensitive adhesive sheet is used for laminating optical members such as a touch panel, such as strong adhesive strength, moisture and heat whitening resistance, and blister resistance. It turns out that it is also excellent.
- the pressure-sensitive adhesive sheet of the present invention is excellent in step following ability, and further has high adhesive strength, high light transmittance, and hardly generates haze, so that glass, ITO transparent electrode sheet, polyethylene terephthalate (PET) is used. ), Polycarbonate (PC), polymethyl methacrylate (PMMA), and other optical sheets, polarizing plates, retardation plates, optical compensation films, brightness enhancement films, and other optical member application applications. Furthermore, it can be suitably used for a touch panel including these optical members.
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Abstract
Description
例えば、タッチパネルと各種表示装置や光学部材(保護板等)の貼付に透明な両面粘着シートが使用されているが、かかる用途においては、近年のタッチパネルにおける構成変化に伴い様々な段差に追従すること(以下、段差追従性という。)が要求される。さらに、タッチパネルを構成する部材として、ポリカーボネート樹脂、アクリル樹脂、(環状)オレフィン樹脂等のプラスチック材料が用いられる場合には、かかる部材から発生するガスや水分により被着体(部材)と粘着剤層との間に発泡や剥離が生じることがあり、これらを抑制できるような耐ブリスター性も要求される。
(1)官能基含有アクリル系樹脂(A)と架橋剤(B)の架橋物、およびエチレン性不飽和基を一つ有するエチレン性不飽和化合物(C)を含有する粘着剤層を有する粘着シートであり、前記官能基含有アクリル系樹脂(A)のガラス転移温度が-35℃以上である粘着シート。
(2)前記官能基含有アクリル系樹脂(A)が、アルキル基の炭素数が1~8のメタクリル酸アルキルエステル系モノマーを含有する単量体成分を重合してなるアクリル系樹脂である、前記(1)記載の粘着シート。
(3)前記粘着剤層の厚みが5~300μmである、前記(1)または(2)に記載の粘着シート。
(4)前記粘着剤層の両側に離型シートが積層されてなる両面粘着シートである、前記(1)~(3)のいずれか1つに記載の粘着シート。
(5)前記(1)~(4)のいずれか1つに記載の粘着シートの粘着剤層面を、被着体に貼合し、活性エネルギー線照射及び加熱のうちの少なくとも一方を行う粘着剤層付き積層体の製造方法。
(6)前記被着体の表面に1~100μmの段差がある、前記(5)記載の粘着剤層付き積層体の製造方法。
(7)前記(5)または(6)記載の粘着剤層付き積層体の製造方法により得られる粘着剤層付き積層体。
(8)前記(7)記載の粘着剤層付き積層体を有する画像表示装置。
(9)前記(7)記載の粘着剤層付き積層体を有するタッチパネル。
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。
またアクリル系樹脂とは(メタ)アクリル系モノマーを少なくとも1種含有するモノマー成分を重合して得られる樹脂である。
本発明の粘着シートにおいては、ガラス転移温度が-35℃以上である官能基含有アクリル系樹脂(A)を用いることを最大の特徴とする。官能基含有アクリル系樹脂(A)のガラス転移温度は-35℃~30℃であることが好ましく、更に好ましくは-35℃~0℃、特に好ましくは-35℃~-10℃、殊に好ましくは-30℃~-10℃である。官能基含有アクリル系樹脂(A)のガラス転移温度が低すぎると耐ブリスター性が悪化し本発明の目的を達成することができない。また、ガラス転移温度が高すぎても段差追従性が低下しやすい傾向がある。
Tg:共重合体のガラス転移温度(K)
Tga:単量体Aのホモポリマーのガラス転移温度(K)
Wa:単量体Aの重量分率
Tgb:単量体Bのホモポリマーのガラス転移温度(K)
Wb:単量体Bの重量分率
Tgn:単量体Nのホモポリマーのガラス転移温度(K)
Wn:単量体Nの重量分率
(ただし、Wa+Wb+・・・+Wn=1)
である。
これらの中でも、効率的に架橋反応ができる点で水酸基、カルボキシル基を含有することが好ましく、更に耐湿熱性も向上できる点で水酸基を含有することが好ましい。
これらの中でも、効率的に架橋反応ができる点で水酸基含有モノマー、カルボキシル基含有モノマーを用いることが好ましく、更に耐湿熱性も向上できる点で水酸基含有モノマーを用いることが好ましい。
なお、被着体が金属又はその酸化物である場合には腐食しやすくなるため、カルボキシル基含有モノマーを用いないことが好ましい。
2-ヒドロキシエチル(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、5-ヒドロキシペンチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、8-ヒドロキシオクチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキルエステル、カプロラクトン変性2-ヒドロキシエチル(メタ)アクリレート等のカプロラクトン変性モノマー、ジエチレングリコール(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート等のオキシアルキレン変性モノマー、その他、2-アクリロイロキシエチル-2-ヒドロキシエチルフタル酸等の1級水酸基含有モノマー;
2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-クロロ2-ヒドロキシプロピル(メタ)アクリレート等の2級水酸基含有モノマー;
2,2-ジメチル2-ヒドロキシエチル(メタ)アクリレート等の3級水酸基含有モノマーを挙げることができる。
これらの中でも重合安定性、疎水性に優れる点で2-エチルヘキシルメタクリレート、イソステアリルアクリレートが好ましく用いられる。
シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等の脂環族の(メタ)アクリル酸エステル系モノマー;
フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェニルジエチレングリコール(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、スチレン、α-メチルスチレン等の1つの芳香環を含有するモノマー;
ビフェニルオキシエチル(メタ)アクリレート等のビフェニルオキシ構造含有(メタ)アクリル酸エステル系モノマー;
2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、2-ブトキシエチル(メタ)アクリレート、2-ブトキシジエチレングリコール(メタ)アクリレート、メトキシジエチレングリコール(メタ)アクリレート、メトキシトリエチレングリコール(メタ)アクリレート、エトキシジエチレングリコール(メタ)アクリレート、メトキシジプロピレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、オクトキシ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、ラウロキシポリエチレングリコールモノ(メタ)アクリレート、ステアロキシポリエチレングリコールモノ(メタ)アクリレート等のエーテル鎖含有(メタ)アクリル酸エステル系モノマー;
アクリロニトリル、メタクリロニトリル、酢酸ビニル、プロピオン酸ビニル、ステアリン酸ビニル、塩化ビニル、塩化ビニリデン、アルキルビニルエーテル、ビニルトルエン、ビニルピリジン、ビニルピロリドン、イタコン酸ジアルキルエステル、フマル酸ジアルキルエステル、アリルアルコール、アクリルクロライド、メチルビニルケトン、N-アクリルアミドメチルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン、(メタ)アクリロイルモルホリン等を用いることができる。
これらは単独でもしくは2種以上併せて用いられる。
かかる溶液重合では、例えば、有機溶媒中に、(a1)~(a3)の単量体成分、重合開始剤を混合あるいは滴下し、還流状態あるいは50~98℃で0.1~20時間重合すればよい。
本発明で用いられる架橋剤(B)は、主として官能基含有アクリル系樹脂(A)が含有する官能基と反応することで、優れた粘着力を発揮するものであり、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、メラミン系架橋剤、アルデヒド系架橋剤、アミン系架橋剤、金属キレート系架橋剤等が挙げられる。これらの中でも、基材との密着性を向上させる点や官能基含有アクリル系樹脂(A)との反応性の点で、イソシアネート系架橋剤が好適に用いられる。
本発明で用いられるエチレン性不飽和基を一つ含有するエチレン性不飽和化合物(C)(以下、単官能不飽和化合物(C)と記載することがある。)としては、エチレン性不飽和基を一つ有する(メタ)アクリル酸エステル系化合物(C1)(後述の(C2)を除く。以下、「単官能(メタ)アクリル酸エステル系化合物(C1)」と記載することがある。)や、窒素原子を含有するエチレン性不飽和基を一つ含有するエチレン性不飽和化合物(C2)(以下、「窒素含有単官能不飽和化合物(C2)」と記載することがある。)を用いることが好ましい。
(C1-1)のオキシアルキレン構造変性化合物として、例えば、2-エチルヘキシルジエチレングリコール(メタ)アクリレート、メトキシトリエチレングリコール(メタ)アクリレート、エトキシジエチレングリコール(メタ)アクリレート、アルキルポリエチレングリコール(メタ)アクリレート、メトキシジプロピレングリコール(メタ)アクリレート、アルキレングリコールモノアルキルエステル(メタ)アクリレート、アルキレングリコールモノ(メタ)アクリレート等が挙げられる。
(C1-2)のオキシアルキレン構造変性化合物として、例えば、t-ブチルシクロヘキシルオキシエチル(メタ)アクリレート、シクロヘキシルオキシアルキル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、ジシクロペンタニルオキシエチル(メタ)アクリレート等が挙げられる。
(C1-3)のオキシアルキレン構造変性化合物として、例えば、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェニルジエチレングリコール(メタ)アクリレート、フェニルトリエチレングリコール(メタ)アクリレート、フェニルテトラグリコール(メタ)アクリレート、ビフェニルオキシエチル(メタ)アクリレート、ノニルフェノールエチレンオキサイド変性(繰り返し4)(メタ)アクリレート、ノニルフェノールエチレンオキサイド変性(繰り返し8)(メタ)アクリレート等が挙げられる。
なお、ガラス転移温度は上述したFoxの式より算出されるものである。
かかる分子量が大きすぎると、粘着物性が低下する傾向があり、小さすぎると乾燥工程で揮発しやすくなる傾向がある。
本発明の粘着シートは、特定のガラス転移温度を有する官能基含有アクリル系樹脂(A)と架橋剤(B)の架橋物、および単官能不飽和化合物(C)を含有する粘着剤層を有する粘着シートである。
かかる単官能不飽和化合物(C)の含有割合が少なすぎると段差追従性が低下する傾向があり、多すぎるとシート作成時の弾性率が低くなりすぎて、取り扱い性や塗膜の安定性が低下する傾向がある。
官能基含有アクリル系樹脂(A)に対する単官能不飽和化合物(C)の配合量が多すぎると塗膜の安定性が低下する傾向があり、少なすぎると段差追従性が低下する傾向がある。
架橋剤(B)の配合量に対する単官能不飽和化合物(C)の配合量が多すぎると塗膜の安定性が低下する傾向があり、少なすぎると段差追従性が低下する傾向がある。
かかる多官能不飽和化合物(D)の含有割合が少なすぎると活性エネルギー線照射により硬化した際の信頼性が低下する傾向があり、多すぎると、活性エネルギー線照射により硬化した際の凝集力が上がりすぎ、硬化収縮が起こり粘着性能が低下する傾向がある。
また、必要に応じて、両方を併用することも好ましい。
上記光重合開始剤(e1)としては、例えば、ジエトキシアセトフェノン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、ベンジルジメチルケタール、4-(2-ヒドロキシエトキシ)フェニル-(2-ヒドロキシ-2-プロピル)ケトン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-2-モルホリノ(4-チオメチルフェニル)プロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン、2-ヒドロキシ-2-メチル-1-[4-(1-メチルビニル)フェニル]プロパノンオリゴマー等のアセトフェノン類;ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類;ベンゾフェノン、o-ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、4-ベンゾイル-4′-メチル-ジフェニルサルファイド、3,3′,4,4′-テトラ(t-ブチルパーオキシカルボニル)ベンゾフェノン、2,4,6-トリメチルベンゾフェノン、4-ベンゾイル-N,N-ジメチル-N-[2-(1-オキソ-2-プロペニルオキシ)エチル]ベンゼンメタナミニウムブロミド、(4-ベンゾイルベンジル)トリメチルアンモニウムクロリド等のベンゾフェノン類;2-イソプロピルチオキサントン、4-イソプロピルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジクロロチオキサントン、1-クロロ-4-プロポキシチオキサントン、2-(3-ジメチルアミノ-2-ヒドロキシ)-3,4-ジメチル-9H-チオキサントン-9-オンメソクロリド等のチオキサントン類;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、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルフォスフィンオキサイド、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等のアシルフォスフォンオキサイド類;等が挙げられる。なお、これら光重合開始剤(e1)は、1種のみが単独で用いられてもよいし、2種以上が併用されてもよい。
これらの中でも、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、ベンゾイルイソプロピルエーテル、4-(2-ヒドロキシエトキシ)-フェニル(2-ヒドロキシ-2-プロピル)ケトン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オンを用いることが好ましい。
基材レス両面粘着シートの場合は、例えば、離型シート上に粘着剤組成物を塗工し、乾燥することにより得られる粘着剤層を形成した後、該粘着剤層の離型シートのない側に、更に別の離型シートを貼合し、必要により養生することにより製造することができる。
かかる粘着剤層の厚みが薄すぎると段差追従性が低下する傾向があり、厚すぎると光学部材全体の厚みが増しすぎてしまう傾向がある。
そして、被着体を貼合した後には、粘着剤層に活性エネルギー線照射及び/又は加熱することで、粘着剤層中に含まれる単官能不飽和化合物(C)が重合し、被着体とより強固に接着することが可能となるものである。
また、活性エネルギー線及び/又は熱による硬化後の粘着剤層の貯蔵弾性率が23℃、1Hzにて1.0×104以上であり、かつ50℃、1Hzにおけるtanδが、0.5未満であることが好ましい。
[官能基含有アクリル系樹脂(A-1)]
還流冷却器、撹拌器、窒素ガスの吹き込み口及び温度計を備えた4ツ口丸底フラスコに、2-エチルヘキシルアクリレート(a2)29部、2-ヒドロキシエチルアクリレート(a1)30部、2-エチルヘキシルメタクリレート(a2-2)15部、イソステアリルアクリレート(a2-2)15部、tert-ブチルメタクリレート(a2-1)11部、及びアセトン8部、メチルエチルケトン41部、酢酸エチル5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)0.04部を加え、メチルエチルケトン還流温度で3時間反応後、アゾビスイソブチロニトリル(AIBN)0.02部、酢酸エチル3部を加え、更に4時間反応し、酢酸エチルにて希釈してアクリル系樹脂溶液を得た。得られたアクリル系樹脂溶液100部(樹脂分)に、2-メタクリロイルオキシエチルイソシアネート0.03部を仕込み、50℃で12時間反応させ、側鎖にエチレン性不飽和基をヒドロキシエチルアクリレートに対して0.13モル%付加した官能基含有アクリル系樹脂(A-1)溶液(重量平均分子量29.6万、分散度3.72、ガラス転移温度-25.4℃、固形分60%、粘度12,000mPa・s(25℃))を得た。
還流冷却器、撹拌器、窒素ガスの吹き込み口及び温度計を備えた4ツ口丸底フラスコに、2-エチルヘキシルアクリレート(a2)50部、2-ヒドロキシエチルアクリレート(a1)30部、tert-ブチルメタクリレート(a2-1)20部、及び酢酸エチル76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)0.04部を加え、酢酸エチル還流温度で3時間反応後、アゾビスイソブチロニトリル(AIBN)0.02部、酢酸エチル3部を加え、更に3時間反応し、酢酸エチルにて希釈してアクリル系樹脂溶液を得た。得られたアクリル系樹脂溶液100部(樹脂分)に、2-メタクリロイルオキシエチルイソシアネート0.03部を仕込み、50℃で12時間反応させ、側鎖にエチレン性不飽和基をヒドロキシエチルアクリレートに対して0.08モル%付加した官能基含有アクリル系樹脂(A-2)溶液(重量平均分子量62.2万、分散度4.95、ガラス転移温度-32.2℃、固形分49.1%、粘度16,000mPa・s(25℃))を得た。
還流冷却器、撹拌器、窒素ガスの吹き込み口及び温度計を備えた4ツ口丸底フラスコに、2-エチルヘキシルアクリレート(a2)70部、2-ヒドロキシエチルアクリレート(a1)30部、及び酢酸エチル150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)0.04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溶液を得た。得られたアクリル系樹脂溶液100部(樹脂分)に、2-メタクリロイルオキシエチルイソシアネート0.03部を仕込み、50℃で12時間反応させ、側鎖にエチレン性不飽和基をヒドロキシエチルアクリレートに対して0.17モル%付加した官能基含有アクリル系樹脂(A’-1)溶液(重量平均分子量69.1万、分散度4.99、ガラス転移温度-56.1℃、固形分51.7%、粘度20,000mPa・s(25℃))を得た。
HEA:2-ヒドロキシエチルアクリレート
2EHA:2-エチルヘキシルアクリレート
tBMA:tert-ブチルメタクリレート
2EHMA:2-エチルヘキシルメタクリレート
ISTA:イソステアリルアクリレート
架橋剤(B-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」)
単官能不飽和化合物(C)として以下のものを用意した。
・(C1-1a)イソトリデシルアクリレート(日立化成社製「FA-113A」)
・(C1-1b)2-デシルテトラデカニルアクリレート(共栄社化学社製「DTD-A」)
・(C1-1c)イソステアリルアクリレート(大阪有機化学工業社製「ISTA」)
多官能不飽和化合物(D-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トリアクリレート(TMPTA)
重合開始剤(E-1)として以下のものを用意した。
・1-ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンの1:1の混合物(チバジャパン社製「イルガキュア500」)
上記官能基含有アクリル系樹脂(A-1)100部(樹脂分)に、架橋剤(B-1)0.2部、単官能不飽和化合物(C-1)40部、多官能不飽和化合物(D-1)1部、光重合開始剤(E-1)1部を配合し、粘着剤組成物溶液を調製した。
かかる粘着剤組成物溶液を、ポリエステル系離型シートに、乾燥後の厚みが100μmとなるように塗布し、90℃で5分間乾燥し、粘着剤層を形成させた。得られた粘着剤層をポリエステル系離型シートではさみ、40℃条件下で3日間エージングさせて基材レス両面粘着シート[I-1]を得た。
また、上記で得られた基材レス両面粘着シートの粘着剤層から一方の面の離型シートを剥がし、厚み125μmの易接着処理ポリエチレンテレフタレート(PET)シートに押圧し、粘着剤層の膜厚が100μmの粘着剤層付きPETシート[II-1]を得た。
さらに、上記基材レス両面粘着シートの粘着剤層から一方の面の離型シートを剥がし、厚み50μmのポリエチレンテレフタレート(PET)シートに押圧し、粘着剤層の膜厚が100μmの粘着剤層付きPETシート[III-1]を得た。
(A)~(E)成分の配合割合を表2に記載の配合割合に変更した以外は実施例1と同様にして基材レス両面粘着シート[I-2]、[I’-1]、[I’-2]および粘着剤層付きPETシート[II-2]、[II’-1]、[II’-2]、[III-2]、[III’-1],[III’-2]を得た。
(A)~(E)成分の配合割合を表2に記載の配合割合に変更し、乾燥後の厚みが160μmとなるように塗布した以外は実施例1と同様にして、粘着剤層の膜厚が160μmの基材レス両面粘着シート[I-3]および粘着剤層付きPETシート[II-3]、[III-3]を得た。
上記基材レス両面粘着シート[I-1]~[I-3]、[I’-1]、[I’-2]をそれぞれ40mm×40mmに裁断した後、23℃×50%R.H.の条件下で30分放置した。その後、一方の離型シートを剥がし、粘着剤層側を50mm×100mmのSUSメッシュシート(200メッシュ)に貼合した後、もう一方の離型シートを剥離し、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24時間浸漬した際の重量変化にてゲル分率(%)の測定を行った。
上記基材レス両面粘着シート[I-1]~[I-3]、[I’-1]、[I’-2]をそれぞれをそれぞれ40mm×40mmに裁断した後、高圧水銀UV照射装置にてピーク照度:150mW/cm2,積算露光量:1000mJ/cm2で紫外線照射を行い(500mJ/cm2×2パス)、23℃×50%R.H.の条件下で30分放置した。その後、一方の離型シートを剥がし、粘着剤層側を50mm×100mmのSUSメッシュシート(200メッシュ)に貼合した後、もう一方の離型シートを剥離し、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24時間浸漬した際の重量変化にてゲル分率(%)の測定を行った。
上記粘着剤層付きPETフィルム[II-1]~[II~3]、[II’-1]、[II’-2]をそれぞれ、幅25mm×長さ100mmに裁断し、離型シートを剥離して、粘着剤層側を無アルカリガラスに23℃、相対湿度50%の雰囲気下で2kgゴムローラー2往復で加圧貼付し、23℃、相対湿度50%の雰囲気下で30分放置し、常温で剥離速度300mm/minで180度剥離強度(N/25mm)を測定した。
上記粘着剤層付きPETフィルム[II-1]~[II~3]、[II’-1]、[II’-2]をそれぞれ、幅25mm×長さ100mmに裁断し、離型シートを剥離して、粘着剤層側を無アルカリガラスに23℃、相対湿度50%の雰囲気下で2kgゴムローラー2往復で加圧貼付し、オートクレーブで50℃・0.5MPa×20分の加圧加熱処理を行った。その後、PETフィルム側から高圧水銀UV照射装置にてピーク照度:150mW/cm2,積算露光量:1000mJ/cm2で紫外線照射を行い(500mJ/cm2×2パス)、23℃×50%R.H.の条件下で30分放置した後、常温で剥離速度300mm/minで180度剥離強度(N/25mm)を測定した。
無アルカリガラス上に、25μm、38μm、50μm、70μm、100μmのPETフィルムをそれぞれセロハンテープで固定し、段差付きのガラスを作製した。上記粘着剤層付きPETシート[II-1]~[II~3]、[II’-1]、[II’-2]をそれぞれ、その段差付きガラスに対し、23℃、相対湿度50%の雰囲気下で2kgゴムローラー2往復で加圧貼付し、オートクレーブで50℃・0.5MPa×20分の加圧加熱処理を行った。その後、PETフィルム側から高圧水銀UV照射装置にてピーク照度:150mW/cm2,積算露光量:1000mJ/cm2で紫外線照射を行い(500mJ/cm2×2パス)、23℃×50%R.H.の条件下で30分放置した後、段差への追従性を目視で下記のとおり評価した。
(評価)
◎・・・段差部に空気の噛みこみや浮きが確認できなかった。
○・・・段差部の一部に空気の噛み込みがわずかに確認できるが、浮きは確認できなかった。
△・・・段差部の一部に空気の噛み込みや浮きが確認できた。
×・・・段差部に大きな浮きが確認できた。
[光学測定用サンプルの作製]
上記基材レス両面粘着シート[I-1]~[I-3]、[I’-1]、[I’-2]をそれぞれ25mm×25mmになるよう裁断し、高圧水銀UV照射装置にてピーク照度:150mW/cm2,積算露光量:1000mJ/cm2で紫外線照射を行った(500mJ/cm2×2パス)。その後、粘着剤層から一方の面の離型シートを剥がし、粘着剤層側をスライドガラス(コーニング社製、イーグルXG)に貼り合わせた後、オートクレーブ処理(50℃、0.5MPa、20分)を行い、23℃×50%R.H.の条件下で30分放置した。最後にもう一方の離型シートを剥がし「スライドガラス/粘着剤層」の構成を有する試験片を作製した。
[ヘイズ値]
ヘイズ値は、拡散透過率及び全光線透過率を、HAZE MATER NDH2000(日本電色工業社製)を用いて測定し、得られた拡散透過率と全光線透過率の値を下記式に代入して、ヘイズを算出した。なお、本機はJIS K7361-1に準拠している。
ヘイズ値(%)=(拡散透過率(%)/全光線透過率(%))×100
[色差]
色差b*値は、JIS K7105に準拠して測定したものであり、測定は、分光色差計(SE6000:日本電色工業社製)を用いて、透過条件で行った。
なお、本発明における、ヘイズ、全光線透過率、色差b*値の測定は、粘着剤層のみを、無アルカリガラス(全光線透過率=93、ヘイズ=0.06、b*値=0.16)に貼着し測定した値である。
上記粘着剤層付きPETフィルム[III-1]~[III-3]、[III’-1]、[III’-2]をそれぞれ25mm×25mmになるよう裁断し、離型シートを剥離して、粘着剤層側をスライドガラス(コーニング社製、イーグルXG)に貼り合わせた後、オートクレーブ処理(50℃、0.5MPa、20分)を行った。その後、PETフィルム側から高圧水銀UV照射装置にてピーク照度:150mW/cm2,積算露光量:1000mJ/cm2で紫外線照射を行い(500mJ/cm2×2パス)、23℃×50%R.H.の条件下で30分放置し、「スライドガラス/粘着剤層/PETフィルム」の構成を有する試験片を作製した。
(評価)
○・・・耐湿熱性試験後のヘイズ値が2.0%未満であり、耐湿熱性試験前後でヘイズ値の上昇割合が1.2倍以内。
△・・・耐湿熱性試験直後のヘイズ値が2.0%未満であり、耐湿熱性試験前後でヘイズ値の上昇割合が1.2倍よりも大きい。
×・・・耐湿熱性試験直後のヘイズ値が2.0%以上。
上記粘着剤層付きPETフィルム[II-1]~[II-3]、[II’-1]、[II’-2]をそれぞれ25mm×50mmになるよう裁断し、離型シートを剥離して、粘着剤層側を厚み2mmの未処理ポリカーボネート板に貼り付け、オートクレーブ処理(50℃、0.5MPa、20分)を行った。次いで、PETフィルム側から高圧水銀UV照射装置にてピーク照度:150mW/cm2,積算露光量:1000mJ/cm2で紫外線照射を行い(500mJ/cm2×2パス)、23℃×50%R.H.の条件下で30分放置し、「ポリカーボネート板/アクリル系粘着剤層/PETフィルム」の構成を有する試験片を作製した。
その後、85℃×85%R.H.の雰囲気下で24時間静置し、静置前後のブリスター発生程度を目視で観察した。評価基準は以下の通りである。
(評価)
◎…発泡がない。
○…φ0.5mm以下の発泡がみられたが、φ0.5mmを超える発泡がなかった。
△…φ0.5mmを超える発泡が貼付面全体の1/3未満に発生。
×…φ0.5mmを超える発泡が貼付面全体の1/3以上に発生。
また、粘着剤層の厚みが160μmの実施例3の粘着シートは、25μm、38μm、50μmの段差に対して非常に優れた追従性を示すものであり、75μmの段差に対しても十分な追従性を示すことがわかる。これは、粘着剤層の厚みに対して47%程度の段差に対して十分な追従性を示すものであり、粘着剤層の厚みに対して50%の段差に対して十分な追従性を示す実施例1の粘着シートと同程度に優れた段差追従性を有するものであることがわかる。
更に、実施例1~3の粘着シートは、粘着シートをタッチパネル等の光学部材の貼合せ用途に使用する場合に要求される物性である、強粘着力、耐湿熱白化性、耐ブリスター性等にも優れるものであることがわかる。
Claims (9)
- 官能基含有アクリル系樹脂(A)と架橋剤(B)の架橋物、およびエチレン性不飽和基を一つ有するエチレン性不飽和化合物(C)を含有する粘着剤層を有する粘着シートであり、前記官能基含有アクリル系樹脂(A)のガラス転移温度が-35℃以上である粘着シート。
- 前記官能基含有アクリル系樹脂(A)が、アルキル基の炭素数が1~8のメタクリル酸アルキルエステル系モノマーを含有する単量体成分を重合してなるアクリル系樹脂である、請求項1記載の粘着シート。
- 前記粘着剤層の厚みが5~300μmである、請求項1または2に記載の粘着シート。
- 前記粘着剤層の両側に離型シートが積層されてなる両面粘着シートである、請求項1~3のいずれか1項に記載の粘着シート。
- 請求項1~4のいずれか1項に記載の粘着シートの粘着剤層面を、被着体に貼合し、活性エネルギー線照射及び加熱のうちの少なくとも一方を行う粘着剤層付き積層体の製造方法。
- 前記被着体の表面に1~100μmの段差がある、請求項5記載の粘着剤層付き積層体の製造方法。
- 請求項5または6記載の粘着剤層付き積層体の製造方法により得られる粘着剤層付き積層体。
- 請求項7記載の粘着剤層付き積層体を有する画像表示装置。
- 請求項7記載の粘着剤層付き積層体を有するタッチパネル。
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Cited By (16)
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WO2017159788A1 (ja) * | 2016-03-17 | 2017-09-21 | 王子ホールディングス株式会社 | 粘着剤組成物及び粘着シート |
WO2017159789A1 (ja) * | 2016-03-17 | 2017-09-21 | 王子ホールディングス株式会社 | 粘着シート及び積層体 |
WO2019065817A1 (ja) * | 2017-09-29 | 2019-04-04 | サイデン化学株式会社 | 粘着シート |
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KR102501683B1 (ko) | 2022-01-18 | 2023-02-21 | 오르바이오 주식회사 | 마이크로나노 버블을 포함하는 초음파 조영제 및 이의 제조방법 |
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CN107849397B (zh) | 2021-05-07 |
CN107849397A (zh) | 2018-03-27 |
JPWO2017022770A1 (ja) | 2018-05-24 |
TW201726849A (zh) | 2017-08-01 |
KR102496512B1 (ko) | 2023-02-06 |
KR20180036968A (ko) | 2018-04-10 |
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