WO2008029766A1 - Agent adhésif sensible à la pression et film adhésif sensible à la pression - Google Patents

Agent adhésif sensible à la pression et film adhésif sensible à la pression Download PDF

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Publication number
WO2008029766A1
WO2008029766A1 PCT/JP2007/067140 JP2007067140W WO2008029766A1 WO 2008029766 A1 WO2008029766 A1 WO 2008029766A1 JP 2007067140 W JP2007067140 W JP 2007067140W WO 2008029766 A1 WO2008029766 A1 WO 2008029766A1
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Prior art keywords
molecular weight
copolymer
peak
pressure
weight component
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PCT/JP2007/067140
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English (en)
Japanese (ja)
Inventor
Hiroyuki Kobayashi
Issei Haruta
Noboru Kojima
Ichirou Sawatari
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Toyo Ink Mfg. Co., Ltd.
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Priority to JP2008533147A priority Critical patent/JP5151982B2/ja
Publication of WO2008029766A1 publication Critical patent/WO2008029766A1/fr

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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
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • the present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive film using the pressure-sensitive adhesive.
  • the present invention relates to a pressure-sensitive adhesive suitably used when an optical film is attached to an adherend such as glass. More specifically, it can be used to form a pressure-sensitive adhesive film (pressure-sensitive adhesive film) that can be peeled off without being contaminated even if it is placed under high temperature, high pressure, high temperature, and high temperature and high humidity. It relates to adhesives.
  • Various optical films such as a polarizing film and a retardation film are attached to glass or other optical films as adherends using a pressure-sensitive adhesive. After affixing to an adherend, if a defect is found in the adhering state, the polarizing film or retardation film is peeled off from the glass or the like, and a new polarizing film or retardation film is attached. This work is called “rework”. During rework, it is required that the pressure-sensitive adhesive layer does not remain on the surface of the adherend.
  • the polarizing film has a structure in which a stretched polybutyl alcohol film dyed with a pigment is sandwiched between a triacetyl cellulose-based protective film or a cycloolefin-based protective film.
  • Polarizing films have poor dimensional stability due to the characteristics of these materials, and the change in dimensions due to film shrinkage is particularly severe under high temperature or high temperature and high humidity conditions.
  • the adhesive strength is increased to resist the dimensional change of the optical film and foam, float and peel even in harsh environments. Attempts have been made to prevent this from occurring.
  • a high molecular weight (meth) acrylic copolymer which is a copolymer of an alkyl (meth) acrylate and a polymerizable monomer having reactivity with a crosslinking agent and has a weight average molecular weight of 1 million or more.
  • a low molecular weight (meth) acrylic copolymer having a weight average molecular weight of 30,000 or less and a polyfunctional compound having at least two functional groups capable of forming a crosslinked structure in the molecule.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-279907
  • An adhesive layer containing a (meth) acrylic resin and a dye is provided on one surface of the light-transmitting film, and the (meth) acrylic resin has a weight average molecular weight of 200,000 or more and a high molecular weight polymer.
  • a resin component As a resin component, (A) a (meth) acrylic acid ester homopolymer or copolymer having a weight average molecular weight of 500,000 to 2,000,000, and (B) a (meth) having a weight average molecular weight of 5,000 to less than 500,000 And (meth) acrylic acid ester having at least one of (A) component and (B) component having a nitrogen-containing functional group in the molecule.
  • a pressure-sensitive adhesive composition which is a ter copolymer has been proposed! (Patent Document 3: Japanese Patent Laid-Open No. 2001-89731).
  • a pressure-sensitive adhesive composed of a polyfunctional compound having at least two reactive functional groups capable of reacting with the coalescence (B), and a pressure-sensitive adhesive layer composed of this pressure-sensitive adhesive are formed on at least one surface of the optical member.
  • An optical member has been proposed! (Patent Document 4: Japanese Patent Laid-Open No. 2004-331697).
  • Patent Document 5 Japanese Patent Laid-Open No. 2003-49143.
  • Patent Documents 1 to 5 have been improved so that they can withstand use under severe conditions, but after being attached to an adherend such as glass, high-temperature and high-pressure
  • an adherend such as glass, high-temperature and high-pressure
  • the adhesion between the pressure-sensitive adhesive and the glass that is the adherend has increased, so the pressure-sensitive adhesive is applied to the glass that is the adherend. a call and the force s in which the adhesive is left.
  • the present invention provides an adhesive interface even when an optical film having good adhesion to an optical film is attached to an adherend and exposed to a high temperature, a high pressure, a high temperature, and a high temperature and high humidity for a long time.
  • Pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer with excellent reworkability as well as no foaming, no floating or peeling, and no light leakage phenomenon, and using this pressure-sensitive adhesive It is an object of the present invention to provide a pressure-sensitive adhesive film.
  • a copolymer (C) having a hydroxyl group and / or a carboxyl group and having a glass transition temperature of 60 to 0 ° C and an isocyanate curing agent (D) are provided.
  • the copolymer (C) is a copolymer (C)
  • a peak of a high molecular weight component (A3) consisting of polymer molecules having a molecular weight of 150,000 or more and a weight average molecular weight of 500,000 to 2,200,000, and a polymer having a molecular weight of less than 150,000
  • a pressure sensitive adhesive is provided.
  • a method for producing a pressure-sensitive adhesive comprising the following (I) to (III): (I) Alkyl metatalylate having no substituent (a): 15 to 35% by weight, V having no substituent, alkyl attalate (b), and other copolymerizable with the above (a) and (b) A monomer (c) having an ethylenically unsaturated double bond and comprising a monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond ( c) radically copolymerizing the polymerization conversion rate to 60 to 90% to obtain a copolymer containing a high molecular weight component having a weight average molecular weight of 500,000 to 2,200,000;
  • a peak of a high molecular weight component (A3) consisting of polymer molecules having a molecular weight of 150,000 or more and a weight average molecular weight of 500,000 to 2,200,000, and a polymer having a molecular weight of less than 150,000
  • a copolymer (C) comprising a high molecular weight component (A) and a low molecular weight component (B), having a hydroxyl group and / or a carboxyl group, and having a glass transition temperature of ⁇ 60 to 0 ° C. Obtaining a copolymer (C); and
  • an optical film selected from the group consisting of a polarizing film and a retardation film, and a pressure-sensitive adhesive layer provided on at least one surface of the optical film,
  • a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive according to one aspect of the present invention.
  • the pressure-sensitive adhesive according to the present invention includes a copolymer (C), which is a main component of the pressure-sensitive adhesive, and an isocyanate curing agent (D). Is formed.
  • the copolymer (C) has a hydroxyl group and / or a carboxyl group, and its glass transition temperature (hereinafter also referred to as “Tg”) is ⁇ 60 to 0 ° C.
  • the copolymer (C) has an alkyl metatalylate (a) having no substituent, an alkyl acrylate (b) having no substituent, and other ethylenic copolymerizable with the above (a) (b).
  • the monomer (c) having an unsaturated double bond is a constituent component.
  • the monomer (c) includes at least a monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond.
  • the copolymer (C) contains a high molecular weight component (A) and a low molecular weight component (B).
  • (2-2) A type that shows a continuous peak in which the high molecular weight component (A2) and the low molecular weight component (B2) are connected by the minimum value (valley) on the GPC emission curve. From this minimum value, the high molecular weight component (A2) is the high molecular weight component and the low molecular component (B2) is the low molecular component. In many cases, the minimum value is between about 20,000 and 200,000 molecular weight.
  • (2-3) A type in which the high molecular weight component (A3) and the low molecular weight component (B3) show continuous peaks on the GPC emission curve and do not have a clear minimum value.
  • the high molecular weight side is the high molecular weight component (A3) and the low molecular weight side is the low molecular weight component (B3).
  • the high molecular weight component (A) is defined as having a weight average molecular weight of 500,000 to 2,200,000
  • the low molecular weight component (B) is defined as having a weight average molecular weight of 1,000 to 100,000;
  • the alkyl methacrylate having no substituent that constitutes the copolymer (C) is an alkyl methacrylate having no functional group such as a hydroxyl group or a carboxyl group (that is, an alkyl in the ester part).
  • the group is an alkyl group without these functional groups).
  • the alkyl group may be linear, may have a branched structure, or may have a cyclic structure.
  • the number of carbon atoms of the alkyl group is preferably from! To 6 from the viewpoint of reactivity (polymerizability).
  • Alkyl acrylate (b) is an alkyl acrylate having no functional group such as a hydroxyl group or a carboxyl group (that is, the alkyl group in the ester portion has these functional groups. No alkyl group.)
  • the alkyl group may be linear, may have a branched structure, or may have a cyclic structure.
  • the carbon number of the alkynole group is preferably 2 to 6 because it becomes difficult to foam in the durability test after sticking.
  • Examples of the other monomer (c) having an ethylenically unsaturated double bond copolymerizable with the above (a) and (b) include the following (cl) to (c3).
  • (c l) A monomer having a hydroxyl group and / or a carboxyl group and having an ethylenically unsaturated double bond. Used to introduce a hydroxyl group and / or a carboxyl group into the copolymer (C).
  • (c2) A monomer having a substituent other than a hydroxyl group or a carboxyl group and an ethylenically unsaturated double bond.
  • Monomers ( C2 ) and (c3) are optional components.
  • Monomers (cl) having a hydroxyl group and an ethylenically unsaturated double bond include (meth) acrylates having a hydroxyl group in the ester moiety, such as a (meth) acrylic ester of polyol. Is preferred.
  • 2-hydroxyethyl (meth) acrylate is an abbreviation of “2-hydroxyethyl acrylate” and “2-hydroxyethyl methacrylate”. is there. Others are the same.
  • Monomers (cl) having a carboxyl group and an ethylenically unsaturated double bond include acrylic acid, methacrylic acid, / 3-carboxyethyl acrylate, itaconic acid, maleic acid, maleic anhydride, croton An acid, fumaric acid, fumaric anhydride, etc. are mentioned.
  • Any one of these exemplified monomers (cl) may be used, or a plurality of these monomers may be arbitrarily combined. They may be used together.
  • Examples of other substituents that can be used in combination with the monomer (cl) and the monomer (c2) having an ethylenically unsaturated double bond include an amino group, an amide group, a maleimide group, an itaconimide group, Examples thereof include a monomer having at least one substituent selected from the group consisting of a nucleenimide group and an epoxy group, and an ethylenically unsaturated double bond.
  • a plurality of types of monomers (c2) can also be used in combination.
  • Monomers (c2) having an amino group and an ethylenically unsaturated double bond include aminomethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate. Rate, dimethylaminopropyl (meth) ate, and the like.
  • Examples of the monomer (c2) having an amide group and an ethylenically unsaturated double bond include (meth) acrylamide, N-substituted (meth) acrylamide, and N-butylpyrrolidone.
  • Examples of the monomer (c2) having a maleimide group and an ethylenically unsaturated double bond include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like. .
  • N— (meth) attaroyloxymethylene nucleenimide, N— (meth) attaroyl yl 6-oxyhexamethylene nucleenimide, N— (meth) attaroyl yl 8- oxyota tamethylene nucleimide Can be mentioned.
  • Examples of the monomer (c2) having an epoxy group and an ethylenically unsaturated double bond include glycidyl (meth) acrylate.
  • Bulle monomers such as styrene, methylstyrene, butyltoluene, and acetic acid butyl; dibule monomers such as dibylbenzene; 14-Butyldiatalylate, i 6-Hexyldiatalylate, Hexanediol di (meth) atarylate, (Poly) ethyleneglycol di (meth) acrylate, (Poly) propylene diol Di (meth) acrylate And diatalylate monomers such as neopentyl glycol di (meth) acrylate and pentaerythritol di (meth) acrylate; and
  • phosphoric acid group-containing monomers such as 2-hydroxyethyl allyloyl phosphate.
  • the durability (heat resistance, heat and moisture resistance) of the formed pressure-sensitive adhesive layer is improved. I like it.
  • a polyfunctional monomer such as a dibule monomer or a ditalylate monomer
  • gelation is likely to occur, and therefore it is preferable to use a small amount.
  • the compounding amount of the polyfunctional monomer is 0.00. Preferably in the range of 3% by weight.
  • the Tg of the copolymer (C) is 1600 ° C, and it is preferable that it is 555 ° C.
  • this Tg is lower than ⁇ 60 ° C., the pressure-sensitive adhesive layer is liable to be lifted and foamed at high temperatures and high humidity.
  • the main component for forming a pressure-sensitive adhesive layer requires a force S that Tg is in the region of 0 ° C or less.
  • an alkyl acrylate (b) ) Must be the main component.
  • the alkyl methacrylate having no substituent, which is a component that raises Tg is not used at all, or even if it is used, it is not used in a very small amount to control Tg.
  • the monomer used for forming the copolymer (C) is quantitatively used. It is necessary that the alkyl acrylate (b) having no substituent is the main component. However, according to the knowledge of the present inventors, when the alkyl acrylate (b) having no substituent is too much, the flexibility of the main chain of the copolymer to be formed becomes too high. As a result, the pressure-sensitive adhesive layer formed by the reaction between such a copolymer and the curing agent (D) described later is excessively softened at high temperature or high temperature and high humidity, so that the adherend is not sensitive. It has been found that if a pressure-sensitive adhesive film is applied and exposed to a high temperature or high temperature and high humidity for a long period of time, it will be liable to float and foam.
  • the alkyl methacrylate without a substituent (Ha) exceeds 35% by weight, the translation, vibration and rotational movement of the main chain are excessively suppressed, and the pressure-sensitive adhesive layer becomes rigid.
  • the rigid pressure-sensitive adhesive layer resists the dimensional change too much, and the resistance force is around the optical film as the substrate. As a result, the light leakage phenomenon occurs at the peripheral edge.
  • the copolymer (C) needs to have a hydroxyl group and / or a carboxyl group as a functional group for reacting with the isocyanate curing agent (D) described later.
  • the amount of the monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond used for introducing a hydroxyl group or a carboxyl group constitutes the copolymer (C).
  • 0.01 to 10% is preferable.
  • 0.05 to 8% % Is more preferable.
  • this monomer (cl) When this monomer (cl) is less than 0.01% by weight, the cohesive force as a pressure-sensitive adhesive layer is insufficient, and the pressure-sensitive adhesive film is not easily lifted or peeled off at high temperature or high humidity. It tends to occur. On the other hand, if the monomer (cl) force exceeds 0% by weight, the degree of crosslinking becomes too high and pressure-sensitive adhesiveness (tackiness) becomes poor, which is not preferable.
  • the amount of alkyl methacrylate (ha) having no substituent, the amount of monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond In consideration of the Tg of the copolymer (C) and the amount of monomers other than (a) and (c 1) used for the formation of the copolymer (C), that is, alkyl having no substituent Atallate (b), a monomer having a substituent other than a hydroxyl group or a carboxyl group and an ethylenically unsaturated double bond (c2), and an ethylenically unsaturated double bond not classified as any of the above monomers
  • the amount of the other monomer (c3) having can be appropriately selected.
  • the alkyl acrylate (b) having no substituent is preferably 45% by weight or more, more preferably 50 to 78% by weight.
  • the copolymer (C) contains two copolymer components, a high molecular weight component (A) and a low molecular weight component (B) as described above. These two copolymer components are divided into the following three types according to the peak shape of the GPC emission curve.
  • copolymer (C) has a completely independent peak on the GPC emission curve
  • copolymer (C) has a high molecular weight component (A1) And (A1) and (B1) are contained with the low molecular weight side as the low molecular weight component (B1).
  • Copolymer (C) has a continuous peak on the GPC emission curve, with a minimum value (valley), specifically a minimum value between about 20,000 and 200,000 in molecular weight.
  • the high molecular weight component is defined as the high molecular weight component (A2) and the low molecular weight component is defined as the low molecular weight component (B2). Contains B2).
  • the copolymer (C) does not have a clear minimum between about 20,000 and 200,000 in the GPC emission curve, the copolymer (C) has a molecular weight of 150,000.
  • a copolymer composed of polymer molecules having a molecular weight of 150,000 or more is defined as a high molecular weight component (A3), and a copolymer component composed of polymer molecules having a molecular weight of less than 150,000 is defined as a low molecular weight component (B3).
  • A3 high molecular weight component
  • B3 low molecular weight component
  • the weight average molecular weights of the high molecular weight components (Al), (A2), and (A3) specified as described above are 500,000 to 2,200,000, and preferably 700,000 to 2,000,000.
  • the weight average molecular weights of the low molecular weight components (Bl), (B2), and (B3) specified as described above are 1000 to 100,000, preferably 5,000 to 80,000.
  • the weight average molecular weight of the high molecular weight component (A) is less than 500,000, the cohesive force of the pressure-sensitive adhesive layer will be insufficient even when reacted with the isocyanate curing agent (D) described later, causing floating and peeling, foaming, etc. Occurs.
  • the weight average molecular weight of the high molecular weight component (A) is larger than 2.2 million, the viscosity becomes high and the workability such as coating becomes inferior, and the optical properties cannot be maintained.
  • Such a copolymer (C) can be obtained by various methods.
  • the high molecular weight component (A) and the low molecular weight component (B) can be obtained separately and mixed together, or the high molecular weight component (i.e., the above (Al) to (A3 A high-molecular-weight component comprising a high-molecular-weight component), and a low-molecular-weight component obtained by polymerizing the monomer in the presence of the obtained copolymer.
  • the high molecular weight component (A) and the low molecular weight component (B) can be obtained separately and mixed together, or the high molecular weight component (i.e., the above (Al) to (A3 A high-molecular-weight component comprising a high-molecular-weight component), and a low-molecular-weight component obtained by polymerizing the monomer in the presence of the obtained copolymer.
  • the latter method is more preferable.
  • first stage polymerization which is a more preferred method
  • the monomer is polymerized (second stage polymerization) in the presence of the obtained high molecular weight component.
  • second stage polymerization The method for obtaining the low molecular weight component will be described in more detail.
  • the high molecular weight component is 0.0;! To 1 part by weight of a polymerization initiator, more preferably 100 parts by weight of the monomers (a) to (c) used in the first stage, It is obtained by a method such as bulk polymerization or solution polymerization, preferably solution polymerization, using a polymerization initiator of 0.01 to 0.1.
  • polymerization initiator an azo compound or an organic peroxide is used, and two or more polymerization initiators may be used in combination.
  • polymerization solvents include methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n propanol, isopropanol, etc. Is used. Two or more polymerization solvents can be mixed and used.
  • examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1, 1'-azobis. (Cyclohexane 1 carbonitryl), 2, 2 'azobis (2, 4 dimethylvaleronitrile), 2, 2' azobis (2, 4 dimethyl-4-methoxyvaleronitryl), dimethyl 2, 2 'azobis (2 methyl) Norepropionate), 4, 4'-azobis (4 cyanovaleric acid), 2, 2 'azobis (2-hydroxymethylpropionitrile), 2, 2'-azobis (2- (2-imidazoline-2-i) E) Propane) and the like.
  • organic peroxide examples include benzoyl peroxide, t-butyl perbenzoate, tamen hydroperoxide, diisopropyl peroxydicarbonate, di-n-propylenoperoxydicarbonate, di (2— Etoxyshettinore) peroxydicarbonate, tert-butenoreperoxyneodecanoate, tert-butenoreperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionylperoxide, diacetylperper An oxide etc. are mentioned.
  • the first stage polymerization a copolymer constituting the high molecular weight component (A) of the copolymer (C) can be first obtained in the system.
  • the copolymer obtained by the first-stage polymerization mainly comprises the high molecular weight component (A), but may contain other copolymer components.
  • the polymerization conversion rate is a value obtained by dividing the weight of the copolymer obtained by polymerizing the monomer by the total weight of the monomers used as raw materials. More specifically, a very small amount of the solution during polymerization is sampled and heated at 150 ° C for about 20 minutes to obtain the solid content. The monomer volatilizes under the heating conditions, but the copolymer does not volatilize. Therefore, by determining the solid content of the solution, the amount of the copolymer contained can be determined, and the polymerization conversion rate is calculated based on that.
  • the new monomer (a) to (c) and / or the polymerization initiator is removed, and the second stage polymerization is carried out in the system after the first stage polymerization.
  • the remaining monomer (and a new monomer added if necessary) is further radically polymerized to form a low molecular weight component ( ⁇ ).
  • the force S can be obtained to obtain a copolymer (C) containing a high molecular weight component ( ⁇ ) and a low molecular weight component ( ⁇ ).
  • the polymerization conversion rate of the copolymer (C) in the second stage polymerization is 80 to 100%, preferably 90 to 100%, more preferably 95 to 100%. More preferably. That is, out of the total 100% by weight of the monomers used in the polymerization, including the monomers added as necessary in the second stage polymerization process, the monomers remaining in the reaction system are preferred. Is copolymerized by forming a low molecular weight component by radical copolymerization until it is less than 20% by weight, more preferably less than 10% by weight, and even more preferably less than 5% by weight. C) can be obtained.
  • a monomer (c) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond is preferred, even though it is preferable to add a new monomer (c). It is more preferable to add cl).
  • the monomer (cl) is 0% in total of 100% by weight of all monomers used for the polymerization of the high molecular weight component (A) and the low molecular weight component (B). 01 to 10% by weight is preferred. 0.05 to 8% by weight is more preferred.
  • the amount of monomer (cl) used in the first stage polymerization is preferably 0.008 to 8% by weight, preferably 0.04 to 6% by weight. More preferably, the amount of monomer (c2) newly added during the second stage polymerization is preferably 0.002 to 2% by weight 0.0;! To 2% by weight It is more preferable that Pressure sensitive adhesive from the end when optical film is cut by adding monomer (cl) and actively introducing hydroxyl and / or carboxyl groups into low molecular weight component (B) This is effective in preventing the protrusion of spills.
  • the polymerization initiator used in the first stage is more than the polymerization initiator used in the first stage. It is preferable to use about 5 to 50 times the amount of the polymerization initiator. More specifically, 0.05 to 50 parts by weight of the polymerization initiator, more preferably 0. 5 parts by weight with respect to 100 parts by weight of the total of the monomers (a) to (c) used in the second stage. It is preferable to use 05 to 5 parts by weight of a polymerization initiator.
  • a chain transfer agent such as n-lauryl mercaptan or n-dodecyl mercaptan, ⁇ -methylstyrene dimer or limonene is used for the synthesis of the low molecular weight component (B). May be.
  • the ability to obtain a pressure-sensitive adhesive by mixing the copolymer (C) having a hydroxyl group and / or a carboxyl group obtained as described above and an isocyanate curing agent (D). S can.
  • the isocyanate curing agent (D) reacts with the hydroxyl group and / or carboxyl group of the copolymer (C) when forming a pressure-sensitive adhesive film to form a pressure-sensitive adhesive layer.
  • the copolymer (C) is preferably in a solution state dissolved in an organic solvent.
  • isocyanate curing agent (D) those having two or more isocyanate groups in one molecule are preferable, and those having 2 to 4 are more preferable.
  • the isocyanate curing agent (D) By using the isocyanate curing agent (D), a stable pressure-sensitive adhesive property can be obtained, and the adhesiveness to the base material is reduced, so that it is a useful curing agent.
  • Examples of the isocyanate curing agent (D) include: toxylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane dianocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. , Polyisocyanate compounds such as polymethylenpolyphenyl isocyanate;
  • Adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane are Adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane;
  • Examples include burettes or isocyanurates of these polyisocyanate compounds; and adducts of these polyisocyanate compounds with known polyether polyols or polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like. These can be used alone or in any combination of two or more! /.
  • the isocyanate curing agent (D) is preferably used in an amount of 0.01 to 15 parts by weight with respect to 100 parts by weight of the copolymer (C). If the amount is less than 01 parts by weight, the cohesive force of the pressure-sensitive adhesive layer decreases, and if it exceeds 15 parts by weight immediately, the pressure-sensitive adhesiveness to the adherend becomes poor. More preferably, 0.03 to 10 parts by weight, and particularly preferably 0.05 to 2 parts by weight.
  • the pressure-sensitive adhesive contains at least one curing agent other than the isocyanate curing agent (D), for example, an epoxy curing agent, an ethyleneimine curing agent, a metal chelate curing agent, and an amine curing agent. It can be used in combination with an isocyanate curing agent (D).
  • the blending amount is preferably 0.0;! To 8 parts by weight per 100 parts by weight of the copolymer (C).
  • Examples of the epoxy curing agent include bisphenol A-epoxychlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidino enoate, glycerin diglycidino enotenole, glycerin ligine Ginole etherol, 1,6 monohexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl dilin, N, N, ⁇ ', ⁇ '-tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N, monodiglycidinoleaminomethinole) cyclohexane, N, N, ⁇ ', ⁇ '— Examples include tetraglycidylaminophenyl methane.
  • Examples of the ethyleneimine curing agent include N, N, -diphenylmethane 4, 4'-bis (1 aziridine canolepoxysite), N, N'-tonolene 2, 4-bis (1 aziridine) Canorepoxite), bisisophthalloy 1 (2-methylaziridine), tree 1 aziridinyl phosphate oxide, N, N 'hexamethylene 1, 6-bis (1-aziridinecarboxite), 2, 2, 1-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], trimethylolpropane tri- ⁇ -aziridinylpropionate, tetramethylol methanetree / 3-aziridinylpropionate, Tris-2, 4, 6- (1 aziridinyl) -1,3,5-triazine and the like.
  • Examples of the metal chelate curing agent include aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and acetylacetone or acetoacetic acid. And a coordination compound with ethyl.
  • examples of amine curing agents include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine. And amino resins and methylene resins.
  • the pressure-sensitive adhesive preferably further contains a silane coupling agent.
  • silane coupling agents examples include butyltrimethoxysilane, butyltriethoxysilane,
  • 2- (3,4 epoxy epoxyaminopropyltriethoxysilane, ⁇ -aminopropylmethylmethoxysilane, ⁇ - (2-aminoethyl) 3 aminopropyl Examples include trimethoxysilane, ⁇ - (2 aminoethyl) 3 aminopropropyltriethoxysilane, mercaptobutyltrimethoxysilane, ⁇ -mercaptopropinolemethyldimethoxysilane, etc. These may be used in combination of two or more. .
  • Silane coupling agents are effective in improving the adhesion between pressure-sensitive adhesive layers and glass, This is particularly effective for preventing the pressure-sensitive adhesive film from floating and peeling off and foaming under high humidity.
  • the content of the silane coupling agent in the pressure-sensitive adhesive is preferably 0.0;! 2 parts by weight with respect to 100 parts by weight of the copolymer (C). If the amount is less than 01 parts by weight, the effect of improving the physical properties is insufficient. If the amount exceeds 2 parts by weight, the pressure-sensitive adhesive is not only expensive, but also may cause floating and peeling, foaming, etc. There is.
  • the pressure-sensitive adhesive does not inhibit the effect of the present invention! /, As far as it is concerned, an ultraviolet absorber, an antioxidant, a pressure-sensitive adhesive resin, a plasticizer, an antifoaming agent, and a leveling agent.
  • an ultraviolet absorber As far as it is concerned, an antioxidant, a pressure-sensitive adhesive resin, a plasticizer, an antifoaming agent, and a leveling agent.
  • One or more known additives such as a regulator may be optionally blended.
  • the adhesiveness to the optical film is good, and after the optical film is attached to the adherend, it is long under high temperature and high pressure, high temperature or high temperature and high humidity. Even if it is exposed for a period of time, it is possible to form a pressure-sensitive adhesive layer that does not cause foaming at the sticking interface, does not float or peel off, and has excellent reworkability as well as no light leakage phenomenon.
  • a pressure-sensitive adhesive film obtained using the pressure-sensitive adhesive will be described.
  • a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive is used for various display members.
  • the pressure-sensitive adhesive film that is formed on at least one surface of the optical film is suitably used for forming various display members, for example, suitably pasted and used on the glass of a liquid crystal display member.
  • optical film examples include a polarizing film and a retardation film, and a polarizing film is preferable.
  • the pressure-sensitive adhesive film can be formed by applying a pressure-sensitive adhesive to the surface of the optical film and drying to form a pressure-sensitive adhesive layer.
  • a release sheet is laminated on the obtained pressure-sensitive adhesive layer. If necessary, the adhesive layer may be aged.
  • the pressure-sensitive adhesive layer on the optical film can be formed by applying a pressure-sensitive adhesive to the release sheet, drying to form a pressure-sensitive adhesive layer, and then bonding it to the optical film, The so-called "transfer method" that transfers the pressure-sensitive adhesive layer on the optical film According to that.
  • the pressure-sensitive adhesive layer can be formed using a commonly used coating apparatus.
  • the coating apparatus include a roll knife coater, a die coater, a roll coater, a no coater, a gravure rhino recoater, a reno-kuno slow coater, a datebing, and a blade coater.
  • the thickness of the pressure-sensitive adhesive layer (after drying) is preferably; If it is less than m, pressure-sensitive adhesiveness may be poor, and if it exceeds 200 m, it may be difficult to produce and handle a pressure-sensitive adhesive film.
  • pressure-sensitive adhesive layer obtained as described above is preferably a storage modulus force 0. 01 X 10 5 Pa ⁇ 5 X 10 5 Pa at 25 ° C. More preferably, it is 0.05 x 10 5 to 3 x 10 5 .
  • the storage elastic modulus can be measured by using a viscoelasticity tester “RDA-III” manufactured by TA Instruments Japan.
  • the storage elastic modulus at 25 ° C of the pressure-sensitive adhesive layer is less than 0.01 X 10 5 Pa, after bonding to an adherend such as glass, the pressure sensitive adhesive layer is long under high temperature or high humidity. When exposed for a period of time, the pressure-sensitive adhesive layer may be softened, and may be easily lifted, peeled off, or foamed.
  • the storage elastic modulus of the pressure-sensitive adhesive layer at 25 ° C is greater than 5 ⁇ 10 5 Pa, the heat resistance is sufficiently high.
  • the pressure-sensitive adhesive layer is hard at room temperature, so the pressure-sensitive adhesive layer When laminating an adhesive film, the pressure-sensitive adhesive layer does not sufficiently adhere to the adherend, and the pressure-sensitive adhesive force tends to decrease.
  • part means “part by weight”
  • % means “% by weight”.
  • a copolymer component having a weight average molecular weight of 100,000 or more is referred to as “high molecular weight component (A)”, and a copolymer component having a weight average molecular weight of less than 100,000 is referred to as “low and high.
  • the molecular weight component (B) ” was assigned a sequential number.
  • the copolymer was numbered consecutively as “C” regardless of whether it was an embodiment of the present invention.
  • reaction vessel In a reaction vessel (hereinafter simply referred to as “reaction vessel”) equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen inlet tube, 76 parts of n-butyl acrylate and 22 parts of methyl metatalylate 1 ⁇ 5 parts of attalinoleic acid, 100 parts of acetone, ⁇ (2, 2'-azobisisobutyronitrile, hereinafter referred to as “AIBN”) 0. 03 parts are charged, and the air in the reaction vessel is filled with nitrogen. Replaced with gas.
  • reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen inlet tube
  • AIBN 2, 2'-azobisisobutyronitrile
  • the copolymer (C1) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 1 million, a high molecular weight component (A1-1) having a Tg of -29.9 ° C, a molecular weight of 15 It contained no more than ten thousand polymers and contained a low molecular weight component (B1-1) having a weight average molecular weight of 30,000 and a Tg of -28 ° C.
  • the Tg of the high molecular weight component (A1-1) is based on the glass transition temperature of the homopolymer obtained from each monomer, assuming that each monomer used is uniformly polymerized. The value obtained from the following equation (1).
  • the Tg of the low molecular weight component (B1-1) is based on the unreacted remaining monomer, the amount of each added monomer, and the glass transition temperature of the homopolymer obtained from each monomer. The value obtained by the following equation (1).
  • the Tg of the copolymer (C1) is expressed by the following formula (based on the glass transition temperature of the homopolymer obtained from each monomer constituting the copolymer (C1) (that is, the blended monomer): The value obtained by 1).
  • Tgn Glass transition temperature of homopolymer consisting of monomer n
  • ⁇ Production Example 2> In a reaction vessel, 73-98 parts of n-butyl acrylate, 24 parts of n-butinomethacrylate, 1.5 parts of attalic acid, light acrylate 4EG-A (PEG # 200 diatalylate, manufactured by Kyoeisha Chemical Co., Ltd.) The same shall apply hereinafter.) 0.02 part, 100 parts of acetone, and 03 parts of AIBNO. 03 parts were prepared and reacted in the same manner as in Production Example 1 for 4.5 hours until the conversion reached 75%. The weight average molecular weight was 980,000. A mixed solution of a polymer and a monomer was obtained.
  • Copolymer (C2) having a Tg of -37.8 ° C Got a solution of
  • the copolymer (C2) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 980,000, a Tg of -38.2 ° C, a high molecular weight component (A1-2), and a molecular weight of 15 It contained no more than 10,000 polymers and contained a low molecular weight component (B1-2) with a weight average molecular weight of 31,000 and a Tg of -36.4 ° C.
  • Tg was determined by excluding the light amount of light acrylate 4EG-A.
  • a reaction vessel was charged with 74 parts of n-butyl acrylate, 24 parts of methyl methacrylate, 1 ⁇ 5 parts of acrylic acid, 100 parts of acetone, 0.03 parts of AIBN, and the conversion rate was 65% as in Production Example 1.
  • the reaction was allowed to proceed for 4 hours until a mixture solution of a copolymer having a weight average molecular weight of 1,010,000 and a monomer was obtained.
  • Copolymer (C3) does not contain a polymer with a molecular weight of less than 150,000, has a weight average molecular weight of 1010,000, a Tg of -27.6 ° C, a high molecular weight component (A1-3), and a molecular weight of 15 It contained no more than 10,000 polymers and contained a low molecular weight component (B1-3) having a weight average molecular weight of 28,000 and a Tg of ⁇ 26.3 ° C.
  • a reaction vessel was charged with 83 parts of n-butyl acrylate, 15 parts of methyl methacrylate, 1 ⁇ 5 parts of acrylic acid, 100 parts of acetone and 03 parts of AIBNO. The reaction was allowed to proceed for 5 hours until a mixture solution of a copolymer having a weight average molecular weight of 1 million and a monomer was obtained.
  • Copolymer (C4) having a Tg of -37.1 ° C Got a solution of
  • the copolymer (C4) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 1 million, a Tg of -37.6 ° C, a high molecular weight component (A1-4), and a molecular weight of 15 It contained no more than ten thousand polymers and contained a low molecular weight component (B1-4) with a weight average molecular weight of 37,000 and a Tg of -35.8 ° C.
  • the monomer yarns were n-fu, chinore accreta ⁇ 82. methinomethacrylate 15 2, 2-hydroxyxetyl metatalylate 1 ⁇ 5 parts, light acrylate 4EG— A 0.02 parts. Except for the above, the reaction was carried out in the same manner as in Production Example 2 until the conversion rate reached 75% to obtain a mixed solution of a copolymer having a weight average molecular weight of 1,000,000 and a monomer.
  • the copolymer (C5) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 1 million, a high molecular weight component (A1-5) having a Tg of -37.9 ° C, a molecular weight of 15 It contained no more than 10,000 polymers, and contained a low molecular weight component (B1-5) having a weight average molecular weight of 31,000 and a Tg of -35.6 ° C.
  • Tg was determined by excluding the light amount of light acrylate 4EG-A.
  • a reaction vessel was charged with 78 parts of n-butyl acrylate, 20 parts of methyl methacrylate, 2 parts of acrylic acid, 100 parts of acetone, and 03 parts of AIBNO. 03, and the air in the reaction container was replaced with nitrogen gas. Then, while stirring in a nitrogen atmosphere, this reaction solution is reacted for 6 hours at a reflux temperature until the conversion rate reaches 100%, and does not contain a component having a weight average molecular weight of 1,050,000 and a molecular weight of less than 150,000, Tg 31. A solution of high molecular weight copolymer (A1-6) at 7 ° C was obtained. The obtained copolymer solution was diluted with toluene to adjust the nonvolatile content concentration to 40%.
  • the weight specific force S between the high molecular weight component (A1-6) and the low molecular weight component (B1-6) S, (A1-6) / ( ⁇ 1-6) 75/25
  • the polymer solution was mixed to obtain a copolymer (C6) solution having a Tg of ⁇ 31 ⁇ 7 ° C., and GPC was measured.
  • Tg was determined by excluding the light amount of light acrylate 4EG-A.
  • Monomer yarns are made with n,, and chinole acreole ⁇ 82. methinoremethacrylate ⁇ 15, 2 hydrochetyl methacrylate 1 ⁇ 5 parts, light acrylate 4EG— A 0.02 parts
  • the reaction was carried out until the conversion rate reached 75% to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 980,000.
  • Monomer yarns are made with n,, and chinole acreole ⁇ 82. methinoremethacrylate ⁇ 15, 2 hydrochetyl methacrylate 1 ⁇ 5 parts, light acrylate 4EG— A 0.02 parts
  • the reaction was carried out until the conversion rate reached 75% to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 950,000.
  • Copolymer (C9) shows a continuous peak having no clear minimum value in GPC, a high molecular weight component (A3-9) having a molecular weight of 150,000 or more, and a molecular weight of less than 150,000.
  • Low molecular weight component (B3-9) the high molecular weight component (A3-9) has a weight average molecular weight of 1,000,000, and the low molecular weight component (B3-9) has a weight average molecular weight of 80,000.
  • the copolymer (CC10) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 1600,000, a Tg of -54.3 ° C, a high molecular weight component (A1-10), and a molecular weight It contained no more than 150,000 polymers and had a low molecular weight component (B1-10) with a weight average molecular weight of 34,000 and a Tg of -53.4 ° C.
  • the copolymer (C11) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 100,000, a Tg of 7.4 ° C, a high molecular weight component (A1-11), and a molecular weight. Contains over 150,000 polymers And a low molecular weight component (B1-11) having a weight average molecular weight of 25,000 and a Tg of -5.8 ° C.
  • the copolymer (C12) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 104,000, a Tg of -32.1 ° C and a high molecular weight component (A1-12), It contained no polymer with a molecular weight of 150,000 or more, and contained a low molecular weight component (B1-12) having a weight average molecular weight of 30,000 and a Tg of -32.9 ° C.
  • Copolymer (C13) does not contain a polymer with a molecular weight of less than 150,000, has a weight average molecular weight of 11,000,000, a Tg of 32.1 ° C, a high molecular weight component (A1-13), It contained no more than 150,000 polymers and contained a low molecular weight component (B1-13) with a weight average molecular weight of 28,000 and a Tg of -34.9 ° C.
  • the conversion rate is 75% in the same manner as in Production Example 1, except that the monomer yarn is made of 76 parts of n-butenorea talelate, 22 parts of methinoremethalate, and 1.5 parts of attalinoleic acid. The mixture was reacted for 4.5 hours until a mixed solution of copolymer and monomer having a weight average molecular weight of 1 million was obtained.
  • Copolymer (C14) shows a continuous peak having a minimum value at a molecular weight of 180,000 in GPC, a high molecular weight component (A2-14) on the higher molecular weight side than this minimum value, and a minimum value. It contains a low molecular weight component (B2-14) on the low molecular weight side.
  • the weight average molecular weight of the high molecular weight component (A2-14) is 1 million
  • the weight average molecular weight of the low molecular weight component (B2-14) is 120,000
  • the monomer yarn is composed of 76 parts of n-butenorea tallylate, 22 parts of methenoremethalate, 1.5 parts of attalinoleic acid, 75 parts of toluene, 25 parts of acetone and 0.03 parts of AIBN.
  • the reaction was carried out until the conversion rate reached 75% to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 450,000 and Tg of -32.1 ° C.
  • Copolymer (C15) shows a continuous peak without a clear minimum value in GPC, a high molecular weight component (A3-15) having a molecular weight of 150,000 or more, and a molecular weight of 150,000. Containing less than low molecular weight components (B3-15)!
  • the weight average molecular weight of the high molecular weight component (A3-15) is 450,000
  • the weight average molecular weight of the low molecular weight component (B3-15) is 30,000
  • the copolymer (C16) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 250,000, a Tg of 32. 1 ° C, a high molecular weight component (A1-16), It contained no more than 150,000 polymers and contained a low molecular weight component (B1-16) with a weight average molecular weight of 30,000 and a Tg of -33.2 ° C.
  • the monomer composition is 95 parts of n-butinorea tallylate and 5 parts of atalinoleic acid, and 100 parts of ethynole acetate and 0.2 parts of benzoyl peroxide instead of 100 parts of acetone and 03 parts of AIBNO.
  • the reaction was allowed to proceed for 10 hours until the conversion reached 100%, and the Tg was 49.3 ° C, the weight average molecular weight was 1,500,000, and the high molecular weight copolymer (A1 — A solution of 17) was obtained.
  • the resulting copolymer solution was diluted with ethyl acetate to adjust the nonvolatile concentration to 20%.
  • the monomer composition was 65 parts of n-butenorea talelate, 30 parts of methenoremethalate, 5 parts of atharinoleamide, and instead of 150 parts of toluene and 03 parts of AIBNO. Except for using 2 parts of AIBN and 2 parts of n-lauryl mercaptan, the reaction was conducted for 6 hours until the conversion reached 100% in the same manner as in Production Example 6, Tg was -17.2 ° C, and the weight average molecular weight was 10,000. A solution of a low molecular weight copolymer (B1-17) containing no component having a molecular weight of 150,000 or more was obtained. The obtained copolymer solution was diluted with toluene to adjust the nonvolatile content concentration to 40%.
  • Copolymer (C17) does not contain a polymer with a molecular weight of less than 150,000, has a weight average molecular weight of 150,000, a Tg of 49.3 ° C, a high molecular weight component (A1-17), and a molecular weight of 150,000 or more. And a low molecular weight component (B1-17) having a weight average molecular weight of 10,000 and a Tg of ⁇ 17.2 ° C.
  • the alkyl methacrylate (a) had no substituents constituting the copolymer (C17) and was about 18%.
  • the monomer composition is 95 parts of ⁇ -butinorea tallylate and 5 parts of attalinoleic acid. Instead of 100 parts of acetone and 0.03 parts of acetone, 0.3 part of benzoyl peroxide, 40 parts of ethyl acetate, 60 parts of toluene In the same manner as in Production Example 6, except that the reaction was carried out for 10 hours until the conversion rate reached 100%, and it contained components with a Tg of -49.3 ° C, a weight average molecular weight of 1 million, and a molecular weight of less than 15. A high molecular weight copolymer (A1-18) solution was obtained. The obtained copolymer solution was diluted with ethyl acetate to adjust the nonvolatile content concentration to 20%.
  • the monomer composition was 99 parts methyl metatalylate and 1 part acrylic acid, but instead of 150 parts toluene and AIBN 0.03 parts, AIBN 1 part, ethyl acetate 40 parts, toluene 60 parts
  • the reaction was allowed to proceed for 6 hours until the conversion reached 100%, and the Tg was 105 ° C, the weight average molecular weight was 20,000, and the low molecular weight A polymer (B1-18) solution (nonvolatile content: 50%) was obtained.
  • Both copolymer solutions were mixed to obtain a copolymer (C18) solution having a Tg of 10.5 ° C.
  • GPC was measured for copolymer (C18)
  • the alkyl methacrylate (a) had no substituents constituting the copolymer (C18) and was about 51.5%.
  • the monomer composition is 98 parts of n-butyl acrylate, 1 part of acrylic acid, 1 part of acrylamide, and 100 parts of ethyl acetate and 0.03 parts of AIBN instead of 100 parts of acetone and AIBNO. 03 parts.
  • the reaction is allowed to proceed for 8 hours until the conversion reaches 100%.
  • a high molecular weight copolymer (A3-19) solution was obtained.
  • the resulting copolymer solution was diluted with ethyl acetate to adjust the nonvolatile content concentration to 25%.
  • the monomer composition is 86.4 parts of n-butinorea tallylate and 13.6 parts of methinoremethalate, and instead of 150 parts of toluene and 0.03 parts of AIBN, 200 parts of ethyl acetate, Except for AIBN of 0.03 part, the reaction was conducted for 4 hours until the conversion rate reached 100% in the same manner as in Production Example 6, the Tg was -40.7 ° C, the weight average molecular weight was 300,000, and the molecular weight A high molecular weight copolymer (A3-19 ′) solution containing more than 100,000 components was obtained. The obtained copolymer solution was diluted with ethyl acetate to adjust the nonvolatile content concentration to 25%.
  • a copolymer (C 19) solution having a Tg of ⁇ 49 ⁇ 7 ° C. was obtained.
  • the alkylmetatalate (a) was about 3.1%.
  • the copolymer (C19) shows a continuous peak without a clear minimum value in GPC, and the area ratio between the high molecular weight side and the low molecular weight side with a molecular weight of 150,000 is 83/17.
  • the weight average molecular weight on both sides of the high molecular weight was 550,000, and the weight average molecular weight on the low molecular weight side was 80,000.
  • Manufacture example 6 except that the monomer composition was 95 parts of n-butinorea tallylate and 5 parts of atalinoleic acid, and instead of 100 parts of acetone and 0.03 parts of AIBN, 100 parts of ethyl acetate and 0.2 parts of AIBN were used.
  • the reaction is allowed to proceed for 12 hours until the conversion reaches 100%, the Tg is 49.3 ° C, the weight average molecular weight is 1.5 million, and the high molecular weight copolymer containing no component with a molecular weight of less than 150,000 is contained.
  • a polymer (A1-20) solution was obtained.
  • the resulting copolymer solution was diluted with ethyl acetate to adjust the nonvolatile content concentration to 20%.
  • the monomer composition was changed to 100 parts of n-butinorea tallylate, and instead of 150 parts of toluene and 03 parts of AIB NO. 03 parts of toluene, 5 parts of ⁇ -methylstyrene dimer as a chain transfer agent, In the same manner as in Production Example 6 except that 2 parts were used, the reaction was allowed to proceed for 6 hours until the conversion reached 100%, the Tg was -54 ° C, the weight average molecular weight was 7000, and the molecular weight was 150,000 or more. A low molecular weight copolymer (B1-20) solution containing no components was obtained. The resulting copolymer solution was diluted with toluene to adjust the nonvolatile content concentration to 40%.
  • the solution was mixed to obtain a copolymer (C19) solution having a Tg of -5.1.7 ° C.
  • the copolymer (C120) had no substituent! /, And the alkyl methacrylate (a) was 0%. GPC of copolymer (C20) was measured and found to have two independent peaks.
  • the weight average molecular weight of the copolymer is the polystyrene-reduced weight average molecular weight determined by GPC measurement, and the GPC measurement conditions are as follows.
  • an isocyanate curing agent (trimethylolpropane adduct of tolylene diisocyanate; the same shall apply hereinafter) is used as an active ingredient.
  • Silane Coupling Agent 1 3-glycidoxypropyltrimethoxysilane; the same shall apply hereinafter
  • Adhesive composition in the same manner as in Example 1 except that each of the copolymer (C2) to (C3) solutions obtained in Production Examples 2 to 3 was used instead of the copolymer (C1) solution. And evaluated in the same manner as in Example 1.
  • the obtained adhesive composition was evaluated in the same manner as in Example 1. As a result, the substrate adhesion was remarkably poor, and remarkable foaming was observed in the heat resistance test and the moist heat resistance test.
  • epoxy hardener 2 ethylene glycol diglycidyl ether; the same shall apply hereinafter
  • an adhesive composition 100 parts of epoxy hardener 2 (ethylene glycol diglycidyl ether; the same shall apply hereinafter) as an active ingredient to 100 parts of the solid content of the copolymer (C18) solution obtained in Comparative Production Example 9. And stirred well to obtain an adhesive composition.
  • epoxy hardener 2 ethylene glycol diglycidyl ether; the same shall apply hereinafter
  • the obtained adhesive composition was evaluated in the same manner as in Example 1. As a result, a light leakage phenomenon in which the substrate adhesion and reworkability were remarkably deteriorated, and remarkable foaming was observed in the heat resistance test and the moist heat resistance test. It was.
  • a pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the epoxy-based curing agent 1 was used instead of the isocyanate curing agent, and evaluated in the same manner as in Example 1. As a result of evaluation, the substrate adhesion was remarkably poor.
  • the adhesive composition obtained in each Example and each Comparative Example was applied to a polyester release film (thickness 38 m) and dried at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 25 m. .
  • a polarizing film (thickness 180 m) was bonded to the obtained adhesive layer, and the reaction was allowed to proceed for 7 days in an atmosphere of 23 ° C. and 50% RH (aging) to obtain an adhesive film 1.
  • the resulting adhesive film 1 was cut to a width of 25 mm, the release film was peeled off, and the exposed adhesive layer was attached to a 0.7 mm thick glass plate in a 23 ° C, 50% RH atmosphere, and a 50 ° C atmosphere. Then, after applying pressure of 5 kg / cm 2 and holding for 15 minutes, bonding was performed in accordance with JIS Z 0237.
  • the pressure-sensitive adhesive layer has not been transferred to the glass plate surface at all, and the pressure-sensitive adhesive layer surface is also smooth.
  • the pressure-sensitive adhesive layer has not transferred to the glass plate surface, but slight unevenness is generated on the surface of the pressure-sensitive adhesive layer.
  • Adhesive film 2 was obtained by cutting into 200 mm ⁇ 200 mm so that the axial direction force of the absorption axis of the polarizing film was at an angle of 45 ° to the side.
  • Foaming is a state in which relatively large bubbles are generated at the interface between the adhesive layer and the glass (other than the peripheral edge).
  • Isocyanate curing agent Trimethylolpropane adduct of tolylene diisocyanate
  • Epoxy curing agent 1 N, N, ⁇ ', ⁇ '-tetraglycidinole m-xylene diamine
  • Epoxy curing agent 2 Ethylene glycol di Glycidyl ether
  • Ethyleneimine curing agent trimethylol propane tree ⁇ aziridinyl propionate
  • Antioxidants 3,5-di-tert-butyl 4-hydroxy-benzylphosphonate ethinoleestenole
  • Silane coupling agent 1 3-glycidoxypropyltrimethoxysilane
  • Silane coupling agent 2 3 Aminopropyltrimethoxysilane

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Abstract

L'invention concerne un agent adhésif sensible à la pression comprenant un copolymère (C) ayant un groupe hydroxyle et/ou un groupe carboxyle et ayant une température de transition vitreuse de -60 à 0 °C et un agent de durcissement de type isocyanate (D), dans lequel : (1) le copolymère (C) est obtenu par la polymérisation radicalaire de 15 à 35 % en poids d'un méthacrylate d'alkyle (a) n'ayant pas de substituant, un acrylate d'alkyle (b) n'ayant pas de substituant et un monomère (c) qui a d'autre double liaison insaturée éthylénique copolymérisable avec les composants (a) et (b) et comprend un monomère (c1) ayant un groupe hydroxyle et/ou un groupe carboxyle et une double liaison insaturée éthylénique (à la condition que la somme totale des composants (a) à (c) soit de 100 % en poids) ; et (2) le copolymère (C) comprend un composant à masse moléculaire élevée (A) et un composant à faible masse moléculaire (B).
PCT/JP2007/067140 2006-09-08 2007-09-03 Agent adhésif sensible à la pression et film adhésif sensible à la pression WO2008029766A1 (fr)

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Cited By (25)

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JP2012153816A (ja) * 2011-01-27 2012-08-16 Soken Chem & Eng Co Ltd アクリル系重合体の製造方法並びにこの方法により得られるアクリル系重合体およびこれを利用するアクリル系粘着剤組成物
JP2012214543A (ja) * 2011-03-31 2012-11-08 Lintec Corp 粘着剤および粘着シート
JP2012214544A (ja) * 2011-03-31 2012-11-08 Lintec Corp 粘着剤および粘着シート
JP2013530414A (ja) * 2010-11-10 2013-07-25 エルジー・ケム・リミテッド 光学素子
JP2013189601A (ja) * 2012-03-15 2013-09-26 Toyo Ink Sc Holdings Co Ltd 粘着剤およびそれを用いた粘着フィルム
JP2013194151A (ja) * 2012-03-21 2013-09-30 Sumitomo Chemical Co Ltd 粘着剤シート、粘着剤付き光学フィルム及び光学積層体
JP5348343B1 (ja) * 2013-04-25 2013-11-20 東洋インキＳｃホールディングス株式会社 感圧式接着剤組成物、及びそれを用いてなる感圧式接着シート
WO2017043241A1 (fr) * 2015-09-07 2017-03-16 綜研化学株式会社 Procédé de production de polymère (méth)acrylique et procédé de production de couche adhésive
CN108698396A (zh) * 2016-02-19 2018-10-23 理研科技株式会社 装饰片
US10596739B2 (en) 2015-03-18 2020-03-24 Riken Technos Corporation Molded body
JP2020128470A (ja) * 2019-02-07 2020-08-27 日東電工株式会社 粘着シート、光学積層体、および画像表示装置
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JP2012041453A (ja) * 2010-08-19 2012-03-01 Lintec Corp 粘着性組成物、粘着剤および粘着シート
US8758869B2 (en) 2010-11-10 2014-06-24 Lg Chem Ltd. Optical element
JP2013530414A (ja) * 2010-11-10 2013-07-25 エルジー・ケム・リミテッド 光学素子
US9239491B2 (en) 2010-11-10 2016-01-19 Lg Chem, Ltd. Optical element
JP2012153816A (ja) * 2011-01-27 2012-08-16 Soken Chem & Eng Co Ltd アクリル系重合体の製造方法並びにこの方法により得られるアクリル系重合体およびこれを利用するアクリル系粘着剤組成物
JP2012214543A (ja) * 2011-03-31 2012-11-08 Lintec Corp 粘着剤および粘着シート
JP2012214544A (ja) * 2011-03-31 2012-11-08 Lintec Corp 粘着剤および粘着シート
JP2013189601A (ja) * 2012-03-15 2013-09-26 Toyo Ink Sc Holdings Co Ltd 粘着剤およびそれを用いた粘着フィルム
JP2013194151A (ja) * 2012-03-21 2013-09-30 Sumitomo Chemical Co Ltd 粘着剤シート、粘着剤付き光学フィルム及び光学積層体
WO2014175341A1 (fr) * 2013-04-25 2014-10-30 東洋インキＳｃホールディングス株式会社 Composition adhésive autocollante et feuille adhésive autocollante l'utilisant
JP5348343B1 (ja) * 2013-04-25 2013-11-20 東洋インキＳｃホールディングス株式会社 感圧式接着剤組成物、及びそれを用いてなる感圧式接着シート
EP2990454A4 (fr) * 2013-04-25 2016-10-19 Toyo Ink Sc Holdings Co Ltd Composition adhésive autocollante et feuille adhésive autocollante l'utilisant
US9598616B2 (en) 2013-04-25 2017-03-21 Toyo Ink Sc Holdings Co., Ltd. Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using same
US10596739B2 (en) 2015-03-18 2020-03-24 Riken Technos Corporation Molded body
US11065851B2 (en) 2015-03-18 2021-07-20 Riken Technos Corporation Multilayer hard coating film
US11512176B2 (en) 2015-03-18 2022-11-29 Riken Technos Corporation Anti-glare hard coat laminated film
US11433651B2 (en) 2015-03-18 2022-09-06 Riken Technos Corporation Hard coat laminated film
US11352473B2 (en) 2015-03-18 2022-06-07 Riken Technos Corporation Hard coat laminated film and method for producing same
US11065852B2 (en) 2015-03-18 2021-07-20 Riken Technos Corporation Adhesive film
US10809418B2 (en) 2015-03-18 2020-10-20 Riken Technos Corporation Anti-glare hard coat laminated film
US10780685B2 (en) 2015-03-18 2020-09-22 Riken Technos Corporation Hard coat laminated film
WO2017043241A1 (fr) * 2015-09-07 2017-03-16 綜研化学株式会社 Procédé de production de polymère (méth)acrylique et procédé de production de couche adhésive
JPWO2017043241A1 (ja) * 2015-09-07 2018-06-28 綜研化学株式会社 （メタ）アクリル系重合体の製造方法および粘着剤層の製造方法
CN111852277A (zh) * 2015-11-25 2020-10-30 理研科技株式会社 门体
US11774166B2 (en) 2015-11-25 2023-10-03 Riken Technos Corporation Door body
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US10816700B2 (en) 2015-12-08 2020-10-27 Riken Technos Corporation Hard coat layered film
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KR20180116258A (ko) * 2016-02-19 2018-10-24 리껭테크노스 가부시키가이샤 화장 시트
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US11407870B2 (en) 2016-09-14 2022-08-09 Riken Technos Corporation Hard coat laminated film
US11639428B2 (en) 2016-11-25 2023-05-02 Riken Technos Corporation Hardcoat multilayer film
JP2020128470A (ja) * 2019-02-07 2020-08-27 日東電工株式会社 粘着シート、光学積層体、および画像表示装置
JP7365772B2 (ja) 2019-02-07 2023-10-20 日東電工株式会社 粘着シート、光学積層体、および画像表示装置
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