WO2020105256A1 - Composition adhésive, adhésif, et feuille adhésive - Google Patents

Composition adhésive, adhésif, et feuille adhésive

Info

Publication number
WO2020105256A1
WO2020105256A1 PCT/JP2019/036182 JP2019036182W WO2020105256A1 WO 2020105256 A1 WO2020105256 A1 WO 2020105256A1 JP 2019036182 W JP2019036182 W JP 2019036182W WO 2020105256 A1 WO2020105256 A1 WO 2020105256A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
meth
group
ethylenically unsaturated
Prior art date
Application number
PCT/JP2019/036182
Other languages
English (en)
Japanese (ja)
Inventor
卓也 畠山
Original Assignee
三菱ケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to JP2019551484A priority Critical patent/JPWO2020105256A1/ja
Publication of WO2020105256A1 publication Critical patent/WO2020105256A1/fr

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive composition, an adhesive and an adhesive sheet.
  • the pressure-sensitive adhesive for example, a strong pressure-sensitive adhesive for the purpose of firmly sticking the pressure-sensitive adhesive sheet to an adherend for a long period of time, or peeling from the adherend after sticking the pressure-sensitive adhesive sheet.
  • a strong pressure-sensitive adhesive for the purpose of firmly sticking the pressure-sensitive adhesive sheet to an adherend for a long period of time, or peeling from the adherend after sticking the pressure-sensitive adhesive sheet.
  • target release type adhesives There are various types such as target release type adhesives, and the optimum adhesive is designed and used in each field.
  • the strong adhesive type adhesive is useful not only for attaching an adhesive sheet to an adherend but also for attaching members to each other, for example, attaching optical members to each other or building members to each other.
  • the step followability and the impact resistance are required in the bonding of such members, it is necessary to make the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet a thick film.
  • Patent Document 1 As a method of increasing the cohesive force of the pressure-sensitive adhesive, for example, a method of blending a polyfunctional monomer with the pressure-sensitive adhesive is known (for example, Patent Document 1).
  • An object is to provide a pressure-sensitive adhesive composition that can be used. Another object of the present invention is to provide a pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive.
  • the ethylenically unsaturated compound (B) contains an ethylenically unsaturated compound (B1) having one ethylenically unsaturated group and an ethylenically unsaturated compound (B2) having two or more ethylenically unsaturated groups.
  • the ethylenically unsaturated compound (B1) is an ethylenically unsaturated compound (B1-1) having a polar group and one ethylenically unsaturated group, an alkyl group having 1 to 20 carbon atoms and one ethylenically unsaturated Containing an ethylenically unsaturated compound (B1-2) having a group,
  • R is an atom or a group selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group and a phenyl group, and n is an integer of 0 to 5. However, when n is 2 or more, all 2 or more R may be the same or at least 1 may differ.
  • ⁇ 2> The pressure-sensitive adhesive composition according to ⁇ 1>, wherein the ethylenically unsaturated compound (B1-1) is a carboxy group-containing monomer or an amide group-containing monomer.
  • ⁇ 3> The adhesive as described in ⁇ 1> or ⁇ 2>, wherein the content ratio of the ethylenically unsaturated compound (B1-1) in the ethylenically unsaturated compound (B1) is 0.1 to 50% by weight.
  • Agent composition ⁇ 4> The pressure-sensitive adhesive composition according to any one of ⁇ 1> to ⁇ 3>, wherein the acrylic resin (A) is a functional group-containing acrylic resin.
  • ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the content of the ethylenically unsaturated compound (B1) is 1 to 1000 parts by weight with respect to 100 parts by weight of the acrylic resin (A).
  • ⁇ 6> Any of ⁇ 1> to ⁇ 5>, wherein the content of the ethylenically unsaturated compound (B2) is 0.01 to 5 parts by weight with respect to 100 parts by weight of the acrylic resin (A).
  • the polymerization initiator (C) is further at least one of a radical cleavage type polymerization initiator (C2) and a hydrogen abstraction type polymerization initiator (C3) (however, the polymerization initiator (C1) is excluded).
  • ⁇ 8> The pressure-sensitive adhesive composition according to any one of ⁇ 1> to ⁇ 7>, in which the content of the polymerization initiator (C1) in the polymerization initiator (C) is 10% by weight or more.
  • ⁇ 10> A pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition according to any one of ⁇ 1> to ⁇ 9> by irradiation with active energy rays.
  • ⁇ 11> A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive according to ⁇ 10>.
  • ⁇ 12> The pressure-sensitive adhesive sheet according to ⁇ 11>, which is a double-sided pressure-sensitive adhesive sheet in which a release sheet is laminated on both surfaces of the pressure-sensitive adhesive layer.
  • the "adhesive sheet" in the present invention conceptually includes a long adhesive tape. Further, the “adhesive” in the present invention is not only those whose adhesive force when applied to an adherend hardly changes, but also those which have a function as an adhesive whose adhesive force increases after being applied to an adherend. Include.
  • the pressure-sensitive adhesive composition of the present invention has a high curing rate and good curability, and the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition has an adherend (metal , Polyolefin, etc.), and also has excellent tensile strength and toughness.
  • (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 contains an acrylic resin (A), an ethylenically unsaturated compound (B) and a polymerization initiator (C).
  • A acrylic resin
  • B ethylenically unsaturated compound
  • C polymerization initiator
  • the acrylic resin (A) used in the present invention is a polymer obtained by polymerizing a polymerizable monomer containing the (meth) acrylic acid alkyl ester (a1) as an essential monomer.
  • the acrylic resin (A) is a functional group-containing acrylic resin obtained by polymerizing a polymerizable monomer further containing a functional group-containing monomer (a2) in addition to the (meth) acrylic acid alkyl ester (a1).
  • the above-mentioned polymerizable monomer may contain other copolymerizable monomer (a3), if necessary.
  • the (meth) acrylic acid alkyl ester (a1), the functional group-containing monomer (a2) and the other copolymerizable monomer (a3) one type or two or more types can be used.
  • the (meth) acrylic acid alkyl ester (a1) is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms, and the carbon number is particularly preferably 1 to 10, further preferably 1 to 8. ..
  • the (meth) acrylic acid alkyl ester (a1) include, for example, nonyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- Examples thereof include butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and particularly 2- Ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate are preferable.
  • Examples of the functional group-containing monomer (a2) include a carboxy group-containing monomer, a hydroxyl group-containing monomer, an amino group-containing monomer, an amide group-containing monomer, an oxyalkylene group-containing monomer, an acetoacetyl group-containing monomer, an isocyanate group-containing monomer, and a glycidyl group. Examples thereof include a contained monomer, a phosphoric acid group-containing monomer, and a sulfonic acid group-containing monomer.
  • the carboxy group also includes an acid anhydride group that is a derivative of the carboxy group.
  • carboxy group-containing monomer examples include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamido-N-glycolic acid, cinnamic acid, ( Michael adduct of (meth) acrylic acid (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-acryloyloxyethy
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( Hydroxyalkyl (meth) acrylate monomers such as (meth) acrylate; Caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate; Diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol-polypropylene Oxyalkylene-modified mono (meth) acrylate monomers such as glycol-mono (meth) acrylate, lauroxy polyethylene glycol-mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate; 2-acryloyloxyethyl-2-hydroxy Primary
  • amino group-containing monomer examples include primary amino group-containing monomers such as aminoalkyl (meth) acrylates such as aminomethyl (meth) acrylate and aminoethyl (meth) acrylate; tert-butylaminoethyl (meth) acrylate and the like. Secondary amino group-containing monomers; tertiary amino group-containing monomers such as dialkylaminoethyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; heterocyclic groups such as (meth) acryloylmorpholine Examples include amine structure-containing monomers, and quaternized products thereof.
  • amide group-containing monomer examples include (meth) acrylamide; N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth).
  • N-alkoxyalkyl (meth) acrylamides such as acrylamide, N- (n-butoxymethyl) (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl N, N-dialkyl (meth) acrylamide such as (meth) acrylamide; N, N-dialkylaminoalkyl (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide; cyclic structure containing N-acryloylmorpholine Examples thereof include amide.
  • Examples of the oxyalkylene group-containing monomer include 2-methoxyethyl (meth) acrylate, 3-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate and 2-butoxy.
  • Alkoxyalkyl mono (meth) acrylates such as ethyl (meth) acrylate, 2-butoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydi Alkoxy such as propylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate Aliphatic (meth) acrylic acid ester such as (poly) alkylene glycol mono (meth) acrylate; 2-phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxy poly
  • acetoacetyl group-containing monomer examples include 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate.
  • isocyanate group-containing monomer examples include 2- (meth) acryloyloxyethyl isocyanate and its alkylene oxide adduct.
  • Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allylglycidyl (meth) acrylate.
  • Examples of the phosphoric acid group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, phosphoric acid ester of polyethylene glycol monomethacrylate, and polyethylene glycol monoacrylate.
  • Phosphoric acid ester Phosphoric acid ester, phosphoric acid ester of polypropylene glycol monomethacrylate, phosphoric acid ester of polyalkylene glycol mono (meth) acrylate such as phosphoric acid ester of polypropylene glycol monoacrylate, methylene (meth) acrylate phosphate, trimethylene (meth) phosphate
  • Examples thereof include acrylates, propylene (meth) acrylate phosphates, and alkylene (meth) acrylate phosphates such as tetramethylene (meth) acrylate phosphates.
  • sulfonic acid group-containing monomer examples include olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid and salts thereof. ..
  • Examples of the other copolymerizable monomer (a3) include allyl compounds such as N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride and dimethylallylvinylketone; N-vinylpyrrolidone, vinyl propionate, vinyl stearate, and the like.
  • Vinyl-based monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, and styrene; and (meth) acrylic acid alkyl esters other than the (meth) acrylic acid alkyl ester (a1).
  • the (meth) acrylic acid alkyl ester (a1), the functional group-containing monomer (a2), and optionally a polymerizable monomer further containing another copolymerizable monomer (a3) are (co) polymerized to obtain an acrylic resin.
  • a system resin (A) is obtained.
  • the acrylic resin (A) For the polymerization of the acrylic resin (A), conventionally known methods such as solution radical polymerization, suspension polymerization, bulk polymerization, emulsion polymerization and the like can be adopted.
  • the acrylic resin (A) is preferably a solvent-based acrylic resin obtained by solution radical polymerization, from the viewpoint that an acrylic resin can be safely and stably produced with an arbitrary monomer composition.
  • a (meth) acrylic acid alkyl ester (a1) and a functional group-containing monomer (a2), a polymerizable monomer further containing another copolymerizable monomer (a3) as necessary, and a polymerization initiator are added.
  • the solvent-based acrylic resin (A) is obtained by mixing or dropping, and polymerizing at reflux or at 50 to 99 ° C. for 2 to 20 hours.
  • the weight average molecular weight (Mw) of the acrylic resin (A) in the present invention is usually 100,000 to 2,500,000, preferably 200,000 to 2,200,000, and particularly preferably 400,000 to 2,000,000. If the weight average molecular weight is too small, the cohesive force of the pressure-sensitive adhesive obtained by irradiation with active energy rays tends to decrease, and if the weight-average molecular weight is too large, a uniformly compatible pressure-sensitive adhesive composition tends to be difficult to obtain. is there.
  • the dispersity (weight average molecular weight / number average molecular weight) of the acrylic resin (A) is usually 20 or less, preferably 15 or less, particularly preferably 10 or less, and the lower limit of the dispersity is usually 1.1. Is. If the dispersity is too high, the cohesive force and the sticking property tend to increase due to the active energy ray irradiation conditions.
  • the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and is 3 in the high performance liquid chromatography (manufactured by Japan Waters, "Waters 2695 (main body)” and “Waters 2414 (detector)”).
  • Main column in series Shodex GPC KF-806L (Exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / line, packing material: styrene-divinylbenzene co-weight It is measured by using coalescence and filler particle size: 10 ⁇ m).
  • the number average molecular weight can be measured by the same method.
  • the polymer may be derivatized at the time of measurement, and the type of eluent may be appropriately changed.
  • the glass transition temperature (Tg) of the acrylic resin (A) is preferably ⁇ 70 to 20 ° C., particularly preferably ⁇ 60 to 0 ° C., further preferably ⁇ 55 to ⁇ 10 ° C. If the glass transition temperature (Tg) of the acrylic resin (A) is too low, the cohesive force tends to decrease, and if the glass transition temperature (Tg) of the acrylic resin (A) is too high, the pressure-sensitive adhesive becomes brittle. Tend to be induced.
  • the glass transition temperature (Tg) of the acrylic resin (A) is calculated by applying the glass transition temperature and the weight fraction when the monomers constituting the acrylic resin (A) are homopolymers to the Fox equation. It is the calculated value.
  • the glass transition temperature when the monomer that constitutes the acrylic resin (A) is a homopolymer is usually measured by a differential scanning calorimeter (DSC), and may be measured according to JIS K7121-1987 or JIS K6240. It can be measured by a method in conformity with.
  • DSC differential scanning calorimeter
  • the content of the acrylic resin (A) in the pressure-sensitive adhesive composition of the present invention is preferably 1 to 99% by weight, particularly preferably 5 to 80% by weight, based on the total amount of the pressure-sensitive adhesive composition. It is preferably 7 to 70% by weight.
  • the content ratio of the acrylic resin (A) is too high, the processability (handling property) is lowered, and the dispersibility of the filler (D) at the time of blending the below-mentioned filler (D) is lowered and the mixture is mixed. Tend to be difficult or less reactive.
  • the content of the acrylic resin (A) is too low, the workability is lowered and it becomes difficult to form the pressure-sensitive adhesive layer into a thick film, or the dispersibility of the filler (D) is lowered.
  • the filler (D) tends to precipitate or float.
  • the ethylenically unsaturated compound (B) used in the present invention is an ethylenically unsaturated compound (B1) having one ethylenically unsaturated group and an ethylenically unsaturated compound having two or more ethylenically unsaturated groups. (B2) is contained.
  • ethylenically unsaturated compound (B1) having one ethylenically unsaturated group will be described.
  • an ethylenically unsaturated compound (B1) having one ethylenically unsaturated group is referred to as a “monofunctional monomer (B1)”, and an ethylenically unsaturated compound having two or more ethylenically unsaturated groups is used.
  • (B2) may be referred to as a "polyfunctional monomer (B2)".
  • the monofunctional monomer (B1) is an ethylenically unsaturated compound (B1-1) having a polar group and one ethylenically unsaturated group (hereinafter, may be referred to as “monofunctional monomer (B1-1)”). And an ethylenically unsaturated compound (B1-2) having an alkyl group having 1 to 20 carbon atoms and one ethylenically unsaturated group (hereinafter may be referred to as “monofunctional monomer (B1-2)”). Contains.
  • the monofunctional monomers (B1-1) and (B1-2) one type or two or more types can be used.
  • Examples of the polar group in the monofunctional monomer (B1-1) include a carboxy group, a hydroxyl group, an amino group, an amide group, an oxyalkylene group, an acetoacetyl group, an isocyanate group, a glycidyl group, a phosphoric acid group and a sulfonic acid group. Can be mentioned.
  • the carboxy group also includes an acid anhydride group that is a derivative of the carboxy group.
  • a (meth) acryloyl group is preferable from the viewpoint of reactivity.
  • Examples of the monofunctional monomer (B1-1) include a carboxy group-containing monomer, a hydroxyl group-containing monomer, an amino group-containing monomer, an amide group-containing monomer, an oxyalkylene group-containing monomer, an acetoacetyl group-containing monomer, an isocyanate group-containing monomer, and glycidyl.
  • Examples thereof include a group-containing monomer, a phosphoric acid group-containing monomer, and a sulfonic acid group-containing monomer. Specific examples thereof include the same as the above-mentioned functional group-containing monomer (a2).
  • the monofunctional monomer (B1-1) a carboxy group-containing monomer and an amide group-containing monomer are preferable in terms of reactivity, and (meth) acrylic acid is particularly preferable in terms of adhesive strength, and acrylic acid is more preferable.
  • the content ratio of the monofunctional monomer (B1-1) in the monofunctional monomer (B1) is preferably 0.1 to 50% by weight, particularly preferably 1 to 40% by weight, and further preferably 5 to 20% by weight. Is. If the content of the monofunctional monomer (B1-1) is too high, the contamination of the member and the deterioration of weather resistance and adhesiveness tend to be caused. If the content of the monofunctional monomer (B1-1) is too low, curing will occur. Property tends to decrease and strength tends to decrease.
  • the alkyl group having 1 to 20 carbon atoms in the monofunctional monomer (B1-2) may be linear, branched or alicyclic.
  • a (meth) acryloyl group is preferable from the viewpoint of reactivity.
  • the alkyl group when the alkyl group is linear or branched, the alkyl group preferably has 2 to 20 carbon atoms, particularly preferably 4 to 18 carbon atoms, and further preferably 4 to 10 carbon atoms.
  • Examples of the monofunctional monomer (B1-2) having a linear or branched alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth).
  • the carbon number of the alkyl group is preferably 4-20, particularly preferably 6-10.
  • Examples of the monofunctional monomer (B1-2) having an alicyclic alkyl group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and 2-methylcyclohexyl (meth) acrylate.
  • cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate are preferable, and cyclohexyl acrylate is particularly preferable, in terms of excellent compatibility with the acrylic resin (A). Is.
  • the ethylenically unsaturated compound having an alkyl group having 1 to 20 carbon atoms and one ethylenically unsaturated group, and further having a polar group is a monofunctional monomer (B1- It is classified into 1).
  • the content ratio of the monofunctional monomer (B1-2) in the monofunctional monomer (B1) is preferably 50 to 99% by weight, particularly preferably 70 to 98% by weight, and further preferably 80 to 95% by weight. .. If the content ratio of the monofunctional monomer (B1-2) is too high, the polarity tends to decrease, and thus the adhesion or reactivity with the member tends to decrease, and the content ratio of the monofunctional monomer (B1-2) tends to be low. If it is too much, the weather resistance tends to decrease and the member tends to be contaminated.
  • the monofunctional monomer (B1) may contain, in addition to the monofunctional monomers (B1-1) and (B1-2), another ethylenically unsaturated compound having one ethylenically unsaturated group.
  • the content of the monofunctional monomer (B1) in the pressure-sensitive adhesive composition of the present invention is preferably 1 to 1000 parts by weight, more preferably 50 to 800 parts by weight, based on 100 parts by weight of the acrylic resin (A). Parts, particularly preferably 150 to 500 parts by weight, more preferably 200 to 300 parts by weight.
  • the content of the monofunctional monomer (B1) is too large, the processability is lowered and it becomes difficult to form the pressure-sensitive adhesive layer into a thick film, or the dispersibility of the filler (D) described later is lowered.
  • the filler (D) tends to precipitate or float.
  • the content of the monofunctional monomer (B1) is too small, the processability (handling property) is reduced, the dispersibility of the filler (D) is reduced, and mixing is difficult, or the reactivity is reduced. Tend to do.
  • the content ratio of the monofunctional monomer (B1) in the ethylenically unsaturated compound (B) is preferably 20 to 99% by weight, particularly preferably 50 to 98% by weight, further preferably 60 to 97% by weight. Is. If the content ratio of the monofunctional monomer (B1) is too large, the curability tends to be deteriorated and the strength tends to be lowered. If the content ratio of the monofunctional monomer (B1) is too small, the adhesive force tends to be decreased. ..
  • the polyfunctional monomer (B2) contains two or more ethylenically unsaturated groups in one molecule.
  • Examples of the polyfunctional monomer (B2) include a bifunctional (meth) acrylate-based monomer, a trifunctional or higher-functional (meth) acrylate-based monomer, a urethane (meth) acrylate-based compound, an epoxy (meth) acrylate-based compound, and a polyester ( A (meth) acrylate compound can be used.
  • 1 type (s) or 2 or more types can be used.
  • the bifunctional (meth) acrylate-based monomer may be a monomer containing two (meth) acryloyl groups, and examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and tetraethylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol ethylene oxide modified di (Meth) acrylate, gly
  • the trifunctional or higher functional (meth) acrylate-based monomer may be a monomer containing three or more (meth) acryloyl groups, and examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and penta.
  • the urethane (meth) acrylate-based compound is a (meth) acrylate-based compound having a urethane bond in the molecule, and contains a hydroxyl group-containing (meth) acrylic-based compound and a polyvalent isocyanate-based compound (if necessary, a polyol-based compound).
  • a compound obtained by reacting a compound) by a known general method is used.
  • the weight average molecular weight is usually 300 to 4000.
  • the content of the polyfunctional monomer (B2) in the pressure-sensitive adhesive composition of the present invention is preferably 0.01 to 5 parts by weight, particularly preferably 0.1 parts by weight, based on 100 parts by weight of the acrylic resin (A).
  • the amount is 05 to 1 part by weight, more preferably 0.1 to 0.5 part by weight. If the content of the polyfunctional monomer (B2) is too large, the adhesive force tends to decrease, and if the content of the polyfunctional monomer (B2) is too small, the cohesive force tends to decrease.
  • the content ratio of the polyfunctional monomer (B2) in the ethylenically unsaturated compound (B) is preferably 0.01 to 30% by weight, particularly preferably 0.05 to 10% by weight, and further preferably 0. 0.08 to 5% by weight. If the content ratio of the polyfunctional monomer (B2) is too large, it tends to be too hard and the adhesive strength tends to be lowered, and if the content ratio of the monofunctional monomer (B2) is too small, the strength tends to be lowered.
  • the polymerization initiator (C) used in the present invention contains a polymerization initiator (C1) having at least one structural site represented by the following formula (1) in the molecule.
  • R is a substituent on the benzene ring and is an atom or group selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group and a phenyl group.
  • the alkyl group is, for example, a straight chain or branched chain having 1 to 12 carbon atoms such as methyl group, ethyl group, n- or iso-propyl group, n- or tert-butyl group, n-hexyl group and cyclohexyl group.
  • a cyclic alkyl group and the like can be mentioned.
  • the alkoxy group includes, for example, a straight chain having 1 to 12 carbon atoms such as methoxy group, ethoxy group, n- or iso-propoxy group, n- or tert-butoxy group, n-hexyloxy group and cyclohexyloxy group, Examples thereof include branched or cyclic alkoxy groups.
  • n is an integer of 0 to 5, and any of the five hydrogen atoms of the benzene ring may be substituted.
  • n is 2 or more, all 2 or more R may be the same or at least 1 may differ.
  • a structure in which n in the above formula (1) is 0, that is, a structure in which any hydrogen atom of the benzene ring is not substituted is preferable.
  • the polymerization initiator (C1) is a hydrogen abstraction type polymerization initiator and can abstract hydrogen in the molecule and generate radicals. Therefore, when the polymerization initiator (C) used in the present invention contains the polymerization initiator (C1), the polymerization initiator (C1) reacts with the unsaturated group of the monomer, and hydrogen in the polymer after the polymerization is added. Is extracted and reacted to form a crosslinked structure, so that the strength of the pressure-sensitive adhesive after polymerization can be increased.
  • Examples of the polymerization initiator (C1) include oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester (for example, “Omnirad754” manufactured by IGM Resins BV) and oxyphenylacetic acid 2- (2). -Hydroxyethoxy) ethyl ester and the like, and oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester (for example, "Omnirad754" manufactured by IGM Resins BV) is particularly preferable.
  • the polymerization initiator (C) is at least one polymerization initiator of a radical cleavage type polymerization initiator (C2) and a hydrogen abstraction type polymerization initiator (C3) (however, excluding the polymerization initiator (C1)). It is preferable to contain
  • radical cleavage type polymerization initiator (C2) examples include 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2- Hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone (for example, "Omnirad184" manufactured by IGM Resins BV), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobuty
  • 1-hydroxycyclohexyl phenyl ketone eg, “Omnirad 184” manufactured by IGM Resins B.V.
  • 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferable.
  • 1 type (s) or 2 or more types can be used.
  • Examples of the hydrogen abstraction type polymerization initiator (C3) include 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2,2-dimethoxy-1,2-diphenyl.
  • Acylphosphon oxides; camphorquinone, di Examples thereof include benzosuberone, 2-ethylanthraquinone, methyl 2- (phenyl) -2-oxoethanoate, and 9,10-phenanthrenequinone.
  • benzophenone, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone are preferable.
  • 1 type (s) or 2 or more types can be used.
  • auxiliary agent of the polymerization initiator (C) for example, triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid , Ethyl 4-dimethylaminobenzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2 It is also possible to use 4,4-diisopropylthioxanthone and the like together.
  • the content ratio of the polymerization initiator (C1) in the polymerization initiator (C) is preferably 10% by weight or more, particularly preferably 20 to 80% by weight, further preferably 30 to 70% by weight.
  • the content of the radical cleavage type polymerization initiator (C2) in the polymerization initiator (C) is preferably 0.001 to 50% by weight, particularly preferably 10 to 40% by weight, further preferably 15 to 30% by weight. Is.
  • the content ratio of the hydrogen abstraction type polymerization initiator (C3) in the polymerization initiator (C) is preferably 0.001 to 50% by weight, particularly preferably 10 to 45% by weight, further preferably 15 to 40% by weight. Is.
  • the radical cleavage type polymerization initiator (C2) and the hydrogen abstraction type polymerization initiator (C3) contains at least one of the radical cleavage type polymerization initiator (C2) and the hydrogen abstraction type polymerization initiator (C3)
  • the content ratio of the agent (C3) [weight of radical cleavage type polymerization initiator (C2): weight of hydrogen abstraction type polymerization initiator (C3)] is preferably 0: 100 to 100: 0, and more preferably 20. : 80 to 80:20, more preferably 30:70 to 70:30.
  • the content of the polymerization initiator (C) in the pressure-sensitive adhesive composition of the present invention is preferably 0.01 to 10 parts by weight, particularly preferably 0. 0, based on 100 parts by weight of the acrylic resin (A).
  • the amount is 04 to 5 parts by weight, more preferably 0.1 to 2 parts by weight. If the content of the polymerization initiator (C) is too large, it tends to be colored or the weather resistance is deteriorated, and if the content of the polymerization initiator (C) is too small, the reactivity is decreased and the strength is decreased. Tend to invite.
  • the above-mentioned polymerization initiators (C1) to (C3) are all photopolymerization initiators for initiating polymerization by irradiation with active energy rays, but if necessary, in addition to curing by irradiation with active energy rays, Curing by heating can also be performed. At that time, the polymerization initiators (C1) to (C3) and the thermal polymerization initiator may be used in combination.
  • thermal polymerization initiator for example, known general thermal radical polymerization initiators such as organic peroxide type initiators and azo type initiators can be used. Among these, 1 type (s) or 2 or more types can be used.
  • the pressure-sensitive adhesive composition of the present invention preferably further contains a filler (D).
  • a filler D
  • the apparent viscosity of the solution of the pressure-sensitive adhesive composition is lowered, and moldability (productivity of pressure-sensitive adhesive sheet: coatability) can be improved.
  • the strength of the pressure-sensitive adhesive layer after curing can be improved.
  • Examples of the filler (D) include hollow particles, inorganic particles such as silica and alumina, glass particles, metal particles, polymer particles, and rubber particles.
  • the filler (D) can be used alone or in combination of two or more kinds.
  • silicic acid-based hollow particles such as shirasu, barlite, glass, silica, and flasheye; non-silicic acid-based hollow particles such as alumina, zirconia, and carbon; thermosetting of phenol resin, epoxy resin, urea resin, etc. Resin-based hollow particles; thermoplastic resin-based hollow particles such as polyvinylidene chloride, polystyrene, polymethyl methacrylate, polyacrylonitrile, and copolymers thereof.
  • the average particle diameter (D50) of the hollow particles is preferably 1 to 500 ⁇ m, particularly preferably 5 to 200 ⁇ m, and further preferably 20 to 80 ⁇ m.
  • the average particle diameter (D50) of the hollow particles is measured using a laser scattering type particle size distribution measuring device.
  • the specific gravity of the hollow particles is preferably 0.1 to 0.8 g / cm 3 , and particularly preferably 0.15 to 0.5 g / cm 3 .
  • the content of the filler (D) in the pressure-sensitive adhesive composition of the present invention is preferably 0.5 to 30 parts by weight, particularly preferably 1 to 28, relative to 100 parts by weight of the acrylic resin (A). Parts by weight, more preferably 5 to 25 parts by weight.
  • the content of the filler (D) is too large, the pressure-sensitive adhesive tends to become brittle, and the reactivity and the tackiness are deteriorated due to inhibition of curing, and the content of the filler (D) is too small. If so, the shear adhesive strength tends to decrease due to the decrease in the adhesive strength.
  • the pressure-sensitive adhesive composition of the present invention may contain a crosslinking agent, if necessary, within a range that does not impair the effects of the present invention.
  • cross-linking agent isocyanate-based, epoxy-based, metal salt, metal alcoside, aldehyde-based compound, non-amino resin-based amino compound, urea-based, metal chelate-based, melamine-based, aziridine-based, etc. Can be mentioned.
  • the pressure-sensitive adhesive composition of the present invention within the range that does not impair the effects of the present invention, other acrylic pressure-sensitive adhesive, other pressure-sensitive adhesive, urethane resin, rosin, rosin ester, hydrogenated rosin ester, phenol resin, aroma Group-modified terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, styrene resin, xylene resin, etc. tackifier, antistatic agent, colorant, antiaging agent, ultraviolet absorber, functional dye, etc.
  • the above-mentioned known additives and compounds that cause coloration or discoloration upon irradiation with ultraviolet rays or radiation may be contained.
  • the pressure-sensitive adhesive composition of the present invention may contain, in addition to the above-mentioned additives, a small amount of impurities and the like contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition.
  • the content of the above-mentioned additive is usually preferably 50% by weight or less, particularly preferably 30% by weight or less, further preferably 20% by weight or less, based on the entire pressure-sensitive adhesive composition. If the content is too large, the pressure-sensitive adhesive is likely to be colored, and adhesive sagging tends to occur due to the plasticizing effect of the additive.
  • the pressure-sensitive adhesive composition of the present invention does not substantially contain water, an aqueous solvent or an organic solvent, and the acrylic resin (A) and the polymerization initiator (C), and other components added as necessary. Is in a state of being dissolved or uniformly dispersed in the ethylenically unsaturated compound (B).
  • the acrylic resin (A), the ethylenically unsaturated compound (B), the polymerization initiator (C), and other components optionally added are added at room temperature or in some cases 60 It can be prepared by heating to about 0 ° C. and mixing.
  • the active energy rays for example, light rays such as far-ultraviolet rays, ultraviolet rays, near-ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and ⁇ -rays, electron rays, proton rays, neutron rays, etc. can be used, but curing speed Curing by ultraviolet irradiation is advantageous because of the availability of the equipment and the price.
  • a high pressure mercury lamp that emits light in the wavelength range of 150 to 450 nm
  • an ultrahigh pressure mercury lamp a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED lamp, etc.
  • a high pressure mercury lamp that emits light in the wavelength range of 150 to 450 nm
  • an ultrahigh pressure mercury lamp a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED lamp, etc.
  • the exposure dose of the actinic energy ray is preferably at 500 mJ / cm 2 or more, further 1000 mJ / cm 2 or more, and particularly preferably at 1500 mJ / cm 2 or more. If the irradiation amount is too small, the polymerization due to irradiation with active energy rays tends to be uneven. The upper limit of the dose is usually 10,000 mJ / cm 2 . If the irradiation amount is too large, it is not practical due to the device and cost.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive of the present invention.
  • the pressure-sensitive adhesive layer is preferably on the base sheet.
  • the pressure-sensitive adhesive sheet of the present invention is preferably a double-sided pressure-sensitive adhesive sheet in which a release sheet is laminated on both sides of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention is obtained by, for example, applying the pressure-sensitive adhesive composition of the present invention onto a substrate sheet, irradiating with active energy rays to form a pressure-sensitive adhesive layer, and then sticking a release sheet to the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive layer by bonding the release sheet to the pressure-sensitive adhesive composition-side surface of the base material sheet coated with the pressure-sensitive adhesive composition, and then irradiating with active energy rays. , Can be manufactured.
  • the pressure-sensitive adhesive sheet of the present invention is obtained by applying the pressure-sensitive adhesive composition of the present invention onto a release sheet, irradiating an active energy ray to form a pressure-sensitive adhesive layer, and then sticking a base sheet or a release sheet. It can also be manufactured by a method of forming a pressure-sensitive adhesive layer by irradiating active energy rays after bonding the base material sheet or the release sheet.
  • the pressure-sensitive adhesive sheet of the present invention can also be used for a double-sided tape or the like by using a non-woven fabric, a foam base material or the like as a base material sheet.
  • polyester resins such as polyethylene naphthalate, polyethylene terephthalate (PET), polybutylene terephthalate and polyethylene terephthalate / isophthalate copolymers
  • polyolefin resins such as polyethylene, polypropylene and polymethylpentene
  • Cyclic olefin resins such as trade name "Arton (cyclic olefin polymer; manufactured by JSR)" and trade name “Zeonoa (cyclic olefin polymer; manufactured by Nippon Zeon Co.)”
  • Polyfluorinated ethylene resins such as; polyamides such as nylon 6, nylon 6,6; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polyvinyl alcohol , Vinyl polymers such as
  • an ITO (acid-valued indium tin) electrode film a transparent electrode film such as Cu mesh, Ag mesh, Ag nanofiber, or an organic conductive film such as polythiophene, and the above various types with the transparent electrode film are used.
  • Optical members such as a base sheet, a polarizing plate, a retardation plate, an elliptically polarizing plate, an optical compensation film, a brightness enhancement film, an electromagnetic wave shielding film, a near infrared ray absorbing film, and an AR (antireflection) film may be used.
  • release sheet those obtained by performing release treatment on various base material sheets exemplified as the base material sheet can be used.
  • a silicone-based release sheet an olefin-based release sheet, and a fluorine-based release sheet.
  • examples thereof include a release sheet, a long-chain alkyl release sheet, and an alkyd release sheet.
  • a gravure roll coater for the application of the pressure-sensitive adhesive composition, for example, a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater or the like can be used.
  • the pressure-sensitive adhesive composition When applying the pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition may be diluted with a solvent and then applied.
  • the dilution concentration of the pressure-sensitive adhesive composition at that time is preferably 5 to 60% by weight, particularly preferably 10 to 30% by weight, as the concentration of the heating residue.
  • the solvent is not particularly limited as long as it can dissolve the pressure-sensitive adhesive composition, for example, methyl acetate, ethyl acetate, methyl acetoacetate, ester solvents such as ethyl acetoacetate, acetone, methyl ethyl ketone, A ketone solvent such as methyl isobutyl ketone, an aromatic solvent such as toluene or xylene, or an alcohol solvent such as methanol, ethanol or propyl alcohol can be used.
  • ethyl acetate and methyl ethyl ketone are preferably used in terms of solubility, drying property, price, and the like.
  • the drying temperature at that time is usually 50 ° C. to 250 ° C., preferably 60 ° C. to 120 ° C., and more preferably 65 ° C. to 95.
  • the drying time is usually 10 seconds to 10 minutes.
  • the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is preferably 20 to 2000 ⁇ m, particularly preferably 50 to 1500 ⁇ m, further preferably 100 to 1200 ⁇ m, and particularly preferably 200 to 1000 ⁇ m. If the thickness is too thin, the step followability tends to decrease, and if the thickness is too thick, the thickness of the entire adaptive member tends to increase too much.
  • the film thickness of the pressure-sensitive adhesive composition when applied is preferably 50 ⁇ m or more, particularly preferably 100 ⁇ m or more, further preferably 200 ⁇ m or more.
  • the upper limit of the thickness is usually 1000 ⁇ m.
  • the film thickness is a value obtained by subtracting the measured value of the thickness of the constituent members other than the adhesive layer from the measured value of the thickness of the entire adhesive sheet using "ID-C112B" manufactured by Mitutoyo. ..
  • the gel fraction of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is preferably 30 to 95%, particularly preferably 50 to 93%, and further preferably 60 to 90%, from the viewpoint of durability performance and adhesive strength. .. If the gel fraction is too low, the cohesive force will decrease and the durability will tend to decrease.
  • the above gel fraction is a measure of the degree of cross-linking, and is calculated by the following method, for example. That is, an adhesive sheet (without a separator) formed by forming an adhesive layer on a polymer sheet (for example, PET film) as a base material is wrapped with a 200-mesh SUS (Steel Special Use Stainless) wire mesh. It is immersed in ethyl acetate adjusted to 23 ° C. for 24 hours, and the weight percentage of the insoluble pressure-sensitive adhesive component remaining in the wire netting is taken as the gel fraction. However, the weight of the base material is subtracted.
  • SUS Steel Special Use Stainless
  • Examples of the method for sticking the pressure-sensitive adhesive sheet of the present invention to the adherend include, for example, bonding the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet of the present invention to the adherend, and then applying heat and pressure in an autoclave or the like (for example, 50 ° C.). , 0.5 MPa ⁇ 30 minutes).
  • the pressure-sensitive adhesive layer is cured by irradiation with active energy rays
  • a laminate with a pressure-sensitive adhesive layer obtained by laminating the pressure-sensitive adhesive sheet of the present invention on an adherend, and laminating the pressure-sensitive adhesive layer on the adherend [adherent / adhesive layer / base material sheet], or base material).
  • adherend / adhesive layer / base material sheet or base material.
  • the acrylic resin solution obtained above was allowed to stand for 1 hour at a jacket temperature of 80 ° C. in a flask in which the solvent could be distilled out of the system by using a V-shaped connecting tube, and then to 10 kPa.
  • the solvent was distilled off by reducing the pressure and leaving it at a jacket temperature of 90 ° C. for 2 hours to obtain an acrylic resin (A-1) (weight average molecular weight: 500,000).
  • the premixed solution was added dropwise over 3 hours. After 30 minutes from the end of the dropping, 0.30 part of ADVN was added dropwise over 1 hour to react, and then 1.3 parts of "Irganox 1010" (manufactured by BASF) as an antioxidant was added to obtain an acrylic resin solution. It was
  • the acrylic resin solution obtained above was allowed to stand for 1 hour at a jacket temperature of 80 ° C. in a flask in which the solvent could be distilled out of the system by using a V-shaped connecting tube, and then to 10 kPa.
  • the solvent was distilled off by reducing the pressure and leaving it at a jacket temperature of 90 ° C. for 2 hours to obtain an acrylic resin (A-2) (weight average molecular weight: 510,000).
  • Examples 1 to 7, Comparative Examples 1 to 4 The components were mixed in the blending amounts shown in Table 1 below to prepare a pressure-sensitive adhesive composition.
  • the numbers of the components (A) to (D) in Table 1 represent parts by weight, and "-" indicates that they are not contained.
  • AAc acrylic acid DMAA: N, N-dimethylacrylamide
  • ACMO acryloylmorpholine
  • EHA 2-ethylhexyl acrylate
  • HDDA 1,6-hexanediol diacrylate
  • 754 oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy)
  • Ethyl ester (“Omnirad 754” manufactured by IGM Resins BV)
  • 184 1-hydroxycyclohexyl phenyl ketone (IGM Resins BV “Omnirad 184”)
  • MBP 4-methylbenzophenone (MBP)
  • VS5500 Glass Bubbles (3M, average particle size (D50) 40 ⁇ m, specific gravity 0.38 g / cm 3 ).
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive was produced by the following method using the pressure-sensitive adhesive compositions of the above Examples and Comparative Examples.
  • the physical properties of the obtained pressure sensitive adhesive were measured by the following methods, and the results are summarized in Table 2. In addition, "-" in Table 2 indicates not measured.
  • the obtained pressure-sensitive adhesive composition was sandwiched between two PET films (SP-PET-01BU, 38 ⁇ m; manufactured by Mitsui Chemicals Tohcello) which had been subjected to a mold release treatment, and a spacer (a glass plate having a thickness of 1 mm) was placed between the two PET films. ) was put.
  • the pressure-sensitive adhesive composition was molded to a thickness of 1 mm by pressing the PET film with another glass plate.
  • the pressure-sensitive adhesive sheet produced under the above condition (2) was cut into 10 cm ⁇ 1 cm, and the release PET on one side was peeled off.
  • the cut adhesive sheet was attached to an untreated PET (Lumirror T60, manufactured by Toray Industries, Inc.) having a thickness of 38 ⁇ m by using a 2 kg hand roller and reciprocating twice at a speed of 1 cm / sec. After that, the release PET on the other side was peeled off, and a hand roller of 2 kg was used to reciprocate twice at a speed of 1 cm / sec to bond the adherend to the adherend (SUS304).
  • the pressure-sensitive adhesive sheet produced under the above condition (2) was cut into 2.5 cm ⁇ 1.25 cm, and the release PET on one side was peeled off.
  • the pressure-sensitive adhesive sheet after cutting was attached to an adherend (SUS304) by using a 2 kg hand roller and reciprocating twice at a speed of 1 cm / sec. After that, the release PET on the other side was peeled off, and a hand roller of 2 kg was used to reciprocate twice at a speed of 1 cm / sec to bond the adherend to the adherend (SUS304).
  • the adhesive compositions are excellent in curability because the gel fractions in Examples 1 to 7 are high. Further, even if the pressure-sensitive adhesive layer is a thick film having a thickness of 1 mm, since the peel strength, the shear adhesive strength and the tensile strength are high, the pressure-sensitive adhesive layer has an excellent balance between the adhesiveness to the adherend and the strength. I understand.
  • the monofunctional monomer (B1-2) when the monofunctional monomer (B1-2) is not contained, for example, when only acrylic acid is used as the monofunctional monomer (B1), the pressure-sensitive adhesive becomes too hard and adhesive properties cannot be obtained. ..
  • the pressure-sensitive adhesive composition of the present invention has a high curing rate and good curability, and the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition has an adherend (metal , Polyolefin, etc.), and has excellent tensile strength and toughness. Therefore, the pressure-sensitive adhesive composition of the present invention is, for example, an ITO film, a Cu mesh, a transparent electrode film such as an organic conductive film such as Ag nanofiber or polythiophene, a polarizing plate, a retardation plate, an elliptically polarizing plate, an optical compensation film.
  • Optical materials such as brightness enhancement film, electromagnetic wave shielding film, near infrared ray absorbing film, AR (anti-reflection) film; mortar, concrete, calcium silicate, marble, wood, melamine decorative board, glass, metal, vinyl chloride material, plastic, It can be used for building materials such as rubber; and for vehicle members such as moldings, emblems, side mirrors, room mirrors, back cameras, frames, door panels, front panels, bumpers, and interior materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition adhésive contenant une résine acrylique (A), un composé (B) qui contient un composé (B1) ayant un groupe éthylénique insaturé et un composé (B2) ayant deux groupes éthyléniques insaturés ou plus, et un initiateur de polymérisation (C) qui a un site structural de formule (1), le composé (B1) contenant un composé (B1-1) qui a un groupe polaire et un composé (B1-2) qui a un groupe alkyle en C1-20. [Dans la formule (1), R et n sont chacun tels que définis dans la description. ]
PCT/JP2019/036182 2018-11-22 2019-09-13 Composition adhésive, adhésif, et feuille adhésive WO2020105256A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019551484A JPWO2020105256A1 (ja) 2018-11-22 2019-09-13 粘着剤組成物、粘着剤および粘着シート

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018219702 2018-11-22
JP2018-219702 2018-11-22

Publications (1)

Publication Number Publication Date
WO2020105256A1 true WO2020105256A1 (fr) 2020-05-28

Family

ID=70774230

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/036182 WO2020105256A1 (fr) 2018-11-22 2019-09-13 Composition adhésive, adhésif, et feuille adhésive

Country Status (2)

Country Link
JP (1) JPWO2020105256A1 (fr)
WO (1) WO2020105256A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007217674A (ja) * 2006-01-18 2007-08-30 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線重合性組成物、粘着剤、および粘着テープ
JP2012012506A (ja) * 2010-06-30 2012-01-19 Dainippon Printing Co Ltd エネルギー線易剥離型粘着剤組成物
JP2013036024A (ja) * 2011-07-11 2013-02-21 Sanyo Chem Ind Ltd 感光性樹脂組成物
CN107099256A (zh) * 2017-03-20 2017-08-29 苏州凡赛特材料科技有限公司 一种uv阻隔光学胶粘剂以及光学胶膜、触摸屏和显示器

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007217674A (ja) * 2006-01-18 2007-08-30 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線重合性組成物、粘着剤、および粘着テープ
JP2012012506A (ja) * 2010-06-30 2012-01-19 Dainippon Printing Co Ltd エネルギー線易剥離型粘着剤組成物
JP2013036024A (ja) * 2011-07-11 2013-02-21 Sanyo Chem Ind Ltd 感光性樹脂組成物
CN107099256A (zh) * 2017-03-20 2017-08-29 苏州凡赛特材料科技有限公司 一种uv阻隔光学胶粘剂以及光学胶膜、触摸屏和显示器

Also Published As

Publication number Publication date
JPWO2020105256A1 (ja) 2021-10-14

Similar Documents

Publication Publication Date Title
JP6729380B2 (ja) 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
KR101928727B1 (ko) 점착 시트 및 그 사용 방법 그리고 적층체
JP6699544B2 (ja) 粘着剤組成物、粘着剤、粘着シート、粘着剤層付き積層体の製造方法、画像表示装置、およびタッチパネル
KR101806813B1 (ko) 점착 시트 및 적층체와 그 제조 방법
JP5954972B2 (ja) 粘着剤組成物、粘着剤、およびそれを用いてなる粘着シート
JP6319039B2 (ja) 粘着シート、積層体及び積層体の製造方法
JP5415115B2 (ja) 一時表面保護用粘着剤組成物、それにより得られる粘着剤、粘着シート、およびその粘着シートの使用方法
JP2012153788A (ja) 光学用粘着シート
JP2014214198A (ja) 粘着シート及びその使用方法並びに積層体
JP2009084372A (ja) 電子線硬化性樹脂組成物、積層体、及び、粘着シート又は粘着フィルム
WO2017010501A1 (fr) Feuille adhésive, stratifié, et leur procédé de production
JP2012140497A (ja) 活性エネルギー線硬化型組成物及び粘着剤
JP5483565B2 (ja) 活性エネルギー線硬化型粘着剤用樹脂組成物、それにより得られる粘着剤、および粘着シート
JP6032695B2 (ja) 粘着剤組成物、粘着剤、およびそれを用いてなる粘着シート
JP6132463B2 (ja) 粘着剤組成物、粘着剤、およびそれを用いてなる粘着シート
WO2017204247A1 (fr) Feuille adhésive sensible à la pression
WO2020105256A1 (fr) Composition adhésive, adhésif, et feuille adhésive
JP7172058B2 (ja) 積層粘着シート及び積層粘着シートの製造方法
JP6958180B2 (ja) 無溶剤型粘着剤組成物、それを用いて得られる粘着剤、光学部材用粘着シート、光学部材用基材レス両面粘着シート、粘着剤層付き光学部材、画像表示装置
JP2022170568A (ja) 活性エネルギー線硬化型粘着シート及び表示装置
JP2021055101A (ja) 透明両面粘着シート
JP2020033417A (ja) 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法
JP2020033416A (ja) 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法
JP6747475B2 (ja) 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法
WO2023074556A1 (fr) Feuille adhésive sensible à la pression optique

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019551484

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19887408

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19887408

Country of ref document: EP

Kind code of ref document: A1