WO2015041266A1 - Composition adhésive durcissable par des rayons d'énergie active - Google Patents

Composition adhésive durcissable par des rayons d'énergie active Download PDF

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Publication number
WO2015041266A1
WO2015041266A1 PCT/JP2014/074611 JP2014074611W WO2015041266A1 WO 2015041266 A1 WO2015041266 A1 WO 2015041266A1 JP 2014074611 W JP2014074611 W JP 2014074611W WO 2015041266 A1 WO2015041266 A1 WO 2015041266A1
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Prior art keywords
meth
active energy
energy ray
acrylate
sensitive adhesive
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PCT/JP2014/074611
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English (en)
Japanese (ja)
Inventor
慎哉 神戸
隆之 牧
洋輔 浅井
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東亞合成株式会社
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Priority to JP2015537953A priority Critical patent/JP6044720B2/ja
Publication of WO2015041266A1 publication Critical patent/WO2015041266A1/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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Definitions

  • the present invention relates to an active energy ray-curable pressure-sensitive adhesive composition, and in particular, contains a macromonomer having a (meth) acryloyl group at the terminal, has good curability and excellent adhesive performance, and causes corrosion to metals.
  • the present invention relates to an active energy ray-curable pressure-sensitive adhesive composition.
  • Adhesives also called pressure sensitive adhesives
  • adherends are widely used in applications such as tapes, labels, stickers and seals
  • adherends are also applied to various substances such as plastics, papers, metals, glass and ceramics.
  • shape of the adherend varies widely, such as planar or curved.
  • pressure-sensitive adhesives are classified into natural rubber, synthetic rubber, and acrylic based on the main components. Among them, acrylic pressure-sensitive adhesives are excellent in tackiness and weather resistance, and can be changed by changing the monomer composition. Since it is possible to impart a wide range of adhesive properties, it is used in many adhesive products. In general, in order to exhibit performance such as adhesiveness and cohesive force, the pressure-sensitive adhesive is desired to be a high molecular weight body having a weight average molecular weight of about 300,000 or more.
  • acrylic pressure-sensitive adhesive examples include solvent-based pressure-sensitive adhesives, water-dispersed (emulsion-type) pressure-sensitive adhesives, and solventless pressure-sensitive adhesives.
  • solvent-type pressure-sensitive adhesives have been pointed out to have problems in environmental hygiene and safety due to the solvent.
  • the water-dispersed pressure-sensitive adhesive requires a large amount of drying energy in order to evaporate water as a medium, and lowers water resistance due to the mixing of emulsifiers and the like into the obtained coating film. ing.
  • solventless pressure-sensitive adhesives, particularly active energy ray-curable pressure-sensitive adhesives have attracted attention because they do not have the above-mentioned problems caused by the solvent and can provide good pressure-sensitive adhesive performance. For this reason, various proposals have been made regarding active energy ray-curable pressure-sensitive adhesives and pressure-sensitive adhesive products using the same.
  • Patent Document 1 discloses a pressure-sensitive adhesive product by irradiating a photopolymerizable composition containing an alkyl acrylate ester or the like as a main component and containing no organic solvent with ultraviolet light having a wavelength of 300 nm to 400 nm with an intensity not exceeding 7 mW / cm 2.
  • Patent Document 2 discloses an adhesive tape that uses an ultraviolet curable adhesive composition comprising an alkyl acrylate ester, a monofunctional monomer, a specific polyfunctional oligoacrylate, and a photopolymerization initiator, and performs ultraviolet irradiation in two stages. A manufacturing method is described.
  • Patent Document 3 discloses a photopolymerizable composition containing an acrylate monomer, a vinyl compound monomer, a macromonomer, and a photopolymerization initiator.
  • Patent Document 1 exhibits good adhesive performance by irradiating ultraviolet rays having low light intensity to obtain a polymer having a high molecular weight. For this reason, the polymerization reaction rate was slow and it was difficult to put it to practical use in terms of low productivity.
  • the ultraviolet curable adhesive composition of patent document 2 uses polyfunctional acrylate as an essential component, when the compounding quantity is increased, it exists in the tendency for adhesive force to reduce large, and it is difficult to take a balance of adhesive physical property. There was a problem. Also, the productivity was not sufficient.
  • the photopolymerizable composition described in Patent Document 3 can obtain a pressure-sensitive adhesive product by light irradiation for a short time, and has a good pressure-sensitive adhesive property even if the molecular weight is not sufficiently high due to the microphase separation structure of the macromonomer portion. Performance can be demonstrated.
  • the present invention has been made in view of the above circumstances, and its purpose is that the curing speed is fast, the adhesive force and the cohesive force are excellent, and the turbidity of the cured product, coloring, and metal corrosion can be suppressed.
  • the present invention is to provide an active energy ray-curable pressure-sensitive adhesive composition that can be used for applications of electronic materials and optical materials.
  • a cured product is obtained by using a vinyl monomer having no acid group and a specific macromonomer having a (meth) acryloyl group at one end.
  • the present invention has found that it is possible to provide an active energy ray-curable resin composition that achieves both a high level of adhesive strength and holding power, less turbidity and coloring of the cured product, and can suppress metal corrosion. It came to complete.
  • An active energy ray-curable pressure-sensitive adhesive containing a vinyl monomer (A) having no acid group, a macromonomer (B) having a (meth) acryloyl group at one end, and a photopolymerization initiator (C)
  • a composition comprising: (B) has a glass transition temperature of 30 ° C. or higher and does not use a raw material having an acid group in the production thereof.
  • An active energy ray-curable pressure-sensitive adhesive composition, wherein the cured adhesive has a glass transition temperature of ⁇ 20 ° C. or lower.
  • a method for producing an adhesive product Supplying the active energy ray-curable pressure-sensitive adhesive composition according to any one of [1] to [4] to at least a part of one or more base materials; Curing the composition by irradiating the composition with an active energy ray to exhibit adhesiveness;
  • a manufacturing method comprising: [9] The production method according to [8], wherein the adhesive product is an electronic material or an optical material.
  • the active energy ray-curable pressure-sensitive adhesive composition of the present invention has good curability, has both adhesive strength and cohesive strength at a high level, has less turbidity and coloring of the cured product, and can suppress metal corrosion. Adhesive products can be given.
  • acrylic and / or methacryl are represented as (meth) acrylic, acrylate and / or methacrylate as (meth) acrylate, and acryloyl and / or methacryloyl as (meth) acryloyl.
  • the vinyl monomer (A) having no acid group in the present invention (hereinafter also referred to as “component (A)”) is other than a vinyl monomer having an acid group such as a carboxyl group or a sulfonic acid group.
  • the monomer of is shown.
  • the component (A) is a monomer having no acid group, but it is allowed when the monomer used as a raw material contains an acid group as an impurity.
  • an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms in terms of obtaining a polymer having a low Tg and having an adhesive property.
  • Examples include n-decyl (meth) acrylate, lauryl (meth) acrylate, and the like.
  • Preferred monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl ( (Meth) acrylate, n-nonyl Meth) acrylates, alkyl (meth) acrylate. Having an alkyl group having 4 to 9 carbon atoms such as isononyl (meth) acrylate, can be used one or two or more of them.
  • the amount of the alkyl (meth) acrylate used is preferably in the range of 30 to 100 parts by mass, more preferably 50 to 98 parts by mass in 100 parts by mass of the component (A), in order to obtain a polymer having good adhesion. 60 to 95 parts by mass is more preferable.
  • the component (A) in addition to the alkyl (meth) acrylate, other monomers copolymerizable with this can be used as long as the adhesive performance is not impaired.
  • the copolymerizable monomer include alkyl having 1 to 3 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate ( (Meth) acrylates; vinyl aromatic monomers such as styrene, ⁇ -methylstyrene, vinyltoluene; cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) Aliphatic vinyl monomers such as acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (me
  • Ethylenically unsaturated carboxylic acid amides and N-substituted compounds unsaturated alcohols such as allyl alcohol; (meth) acrylonitrile, vinyl acetate, glycidyl (meth) acrylate, diacetone acrylate Luamide and the like can be mentioned, and one or more of these can be used.
  • a polyfunctional monomer having two or more vinyl groups in the molecule may be used.
  • the polyfunctional monomer include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2- Ethyl-1,3-nonanediol diacrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 2-hydroxy-3- ( (Meth) acrylate
  • polyfunctional (meth) acrylate oligomers can also be used, and specifically, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and the like can be mentioned. Two or more types can be used.
  • the amount of the polyfunctional monomer used is preferably less than 5% by mass of the total component (A).
  • the polyfunctional monomer is used in an amount of 5% by mass or more, the cohesive force of the obtained pressure-sensitive adhesive is increased, but the pressure-sensitive adhesive force tends to be inferior.
  • the cure rate at the time of hardening with an active energy ray may fall.
  • the component (A) is preferably selected so that the calculated glass transition temperature (Tg) of the polymer is less than -45 ° C.
  • Tg glass transition temperature
  • Tg Tg of polymer W (a): Weight fraction of structural unit composed of monomer (a) in polymer W (b): Weight fraction of structural unit composed of monomer (b) in polymer W (c): Heavy Weight fraction of structural unit consisting of monomer (c) in coalescence
  • Tg Glass transition temperature of homopolymer of monomer (a)
  • Glass transition temperature of Tg (c) Glass transition temperature of homopolymer of monomer (c)
  • the macromonomer (B) having a (meth) acryloyl group at one end (hereinafter also referred to as “component (B)”) is a polymer having a vinyl monomer as a main structural unit, Having a (meth) acryloyl group.
  • component (B) is a polymer having a vinyl monomer as a main structural unit, Having a (meth) acryloyl group.
  • (B) As a compound (D) which has a (meth) acryloyl group used in order to obtain a component, the thing corresponding to the reactive functional group which the said chain transfer agent has is used.
  • the reactive functional group is a hydroxyl group or an amino group
  • a compound (D) having an isocyanato group is used.
  • the reactive functional group is a hydroxyl group
  • the compound (D) having a chloro group is used.
  • the reactive functional group is an alkoxysilyl group
  • a compound (D) having an alkoxysilyl group is used.
  • the reactive functional group is a hydroxyl group and the compound (D) has an isocyanato group in terms of few side reactions, ease of post-reaction treatment, raw material availability, and the like. preferable.
  • the said 1st process and 2nd process at the time of using the chain transfer agent which has a hydroxyl group, and the compound (D) which has an isocyanato group are explained in full detail.
  • ⁇ 1st step Synthesis of a polymer having a hydroxyl group at one end
  • a vinyl monomer is polymerized with a polymerization initiator in the presence of a chain transfer agent having a hydroxyl group, thereby having a hydroxyl group at one end.
  • a polymer is obtained.
  • the vinyl monomer include (meth) acrylate, (meth) acrylamide, styrene, ⁇ -methylstyrene, acrylonitrile, vinyl acetate, and the like.
  • (Meth) acrylate is preferable because of its excellent properties and water resistance.
  • As an example of (meth) acrylate the same compound as the vinyl monomer that can be used as the component (A) can be used.
  • chain transfer agent having a hydroxyl group examples include 2-mercaptoethanol, 3-mercapto-1-propanol, 6-mercapto-1-hexanol, 3-mercapto-1-hexanol, thioglycerol and thiophenol. 1 type, or 2 or more types of these can be used. Among these, 2-mercaptoethanol is preferably used from the viewpoint that a hydroxyl group can be efficiently introduced in a small amount.
  • any initiator that generates radicals at a predetermined reaction temperature may be used.
  • organic peroxides such as di-t-butyl peroxide and di-t-hexyl peroxide, azobisisobutyronitrile, azobiscyclohexacarbonitrile, azobis (2-methylbutyronitrile) Azo compounds such as azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4-cyanovaleric acid). It is preferable to use an azo compound because it is difficult to cause side reactions with various monomers.
  • the polymer having a hydroxyl group at one end is preferably obtained by solution polymerization using an appropriate organic solvent.
  • the organic solvent to be used is not particularly limited, but organic hydrocarbon compounds, cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; acetone , Ketones such as methyl ethyl ketone and cyclohexanone can be used.
  • a dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate can be added to remove water in the organic solvent.
  • the polymerization temperature is appropriately adjusted depending on the conditions such as the type of monomer and solvent used and the monomer concentration, but is usually in the range of 50 to 150 ° C, more preferably in the range of 60 to 120 ° C. .
  • Second step introduction of (meth) acryloyl group at one end
  • a macromonomer (B) having a (meth) acryloyl group at one end is obtained.
  • a catalyst for promoting the reaction in order to make the reaction proceed stably in a short time, it is preferable to add a catalyst for promoting the reaction and a polymerization inhibitor.
  • Examples of the compound having a (meth) acryloyl group and an isocyanato group include 2-isocyanatoethyl (meth) acrylate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, (meth) acryloyl isocyanate, and the like. .
  • compounds having an acryloyl group are preferable from the viewpoint of curing speed, and 2-isocyanatoethyl acrylate is particularly preferable because of few side reactions.
  • the amount of the compound having a (meth) acryloyl group and an isocyanato group is preferably 0.8 to 1.2 molar equivalents with respect to the hydroxyl group at one end.
  • Examples of the catalyst for accelerating the reaction include metal compounds, tertiary amines, quaternary ammonium salts, phosphine compounds, phosphonium salts, and the like, but metal compounds that can provide high effects in a small amount are preferable.
  • Specific examples of the metal compound include di-n-butyltin oxide, di-n-butyltin dilaurate, di-n-butyltin, di-n-butyltin diacetate, di-n-octyltin oxide, and di-n-octyl.
  • Organotin compounds such as tin dilaurate, monobutyltin trichloride, di-n-butyltin dialkyl mercaptan, di-n-octyltin dialkyl mercaptan; lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.
  • the amount of catalyst used is preferably 0.05 parts by weight or less when the total amount of the polymer having a hydroxyl group at one end and the compound having a (meth) acryloyl group and an isocyanate group is 100 parts by weight. . When 0.05 weight part or more is used, problems, such as coloring derived from a catalyst, will arise.
  • Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene and the like.
  • the amount of the polymerization inhibitor used is 0.002 to 0.02 parts by weight when the total amount of the polymer having a hydroxyl group at one end and the compound having a (meth) acryloyl group and an isocyanate group is 100 parts by weight. It is preferable to do.
  • the amount is 0.002 part by weight or less, the polymerization inhibition effect is not sufficiently exhibited, and when 0.02 part by weight or more is used, problems such as coloring due to the polymerization inhibitor occur and the subsequent curing rate is slowed. .
  • component (B) When an organic solvent is used during the synthesis of component (B), it is preferable to provide a solvent removal step for drying and removing the organic solvent after the first and second steps. By removing the organic solvent through this step, it is possible to avoid problems such as a flammable explosion caused by the organic solvent and problems such as odor.
  • the organic solvent is removed and dried by heating at about 50 to 200 ° C. under normal pressure or reduced pressure. Vacuum heating that can complete drying at a relatively low temperature in a short time is recommended.
  • the component (B) in the present invention preferably has a weight average molecular weight of 5,000 to 20,000.
  • the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
  • the glass transition temperature (Tg) of the (B) component in this invention is 30 degreeC or more, Preferably it is 55 degreeC or more, More preferably, it is 90 degreeC or more. By setting Tg to 30 ° C. or higher, the holding power when the obtained cured product is used as an adhesive is improved. In the present invention, the glass transition temperature is measured by the midpoint of the endothermic peak detected in the differential scanning calorimeter.
  • the mass ratio of the component (A) to the component (B) is such that when the total of the component (A) and the component (B) is 100 parts by mass, the component (B) is 2 parts by mass or more and 10 parts by mass or less. Is preferred. When it is 2 parts by mass or more, the holding power of the cured product is improved, and when it is 10 parts by mass or less, the adhesive strength of the cured product is maintained.
  • the component (B) needs to be a macromonomer having a (meth) acryloyl group at one end.
  • a macromonomer having a (meth) acryloyl group in the middle of the main chain other than the terminal and a (meth) acryloyl group at both ends is used, the resulting cured product cannot be balanced in adhesive force and cohesive strength.
  • hardenability by active energy ray irradiation is more preferable.
  • the present composition needs to add a photopolymerization initiator (C) (hereinafter also referred to as “C component”) for the purpose of curing with active energy rays such as ultraviolet rays and visible light.
  • C component a photopolymerization initiator
  • Component (C) includes benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methyl Vinyl) phenyl] propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methylpropan-1-one, 2-methyl-1 -[4- (methylthio)] phenyl] -2-morpholinopropan-1-one, 2- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethyla
  • the compounding ratio of the component (C) is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).
  • the composition can be cured with an appropriate amount of ultraviolet light or visible light, and the productivity can be improved. By doing this, it is possible to increase the retention of the cured product and to have excellent weather resistance and transparency.
  • composition of the present invention may contain other components described later as required.
  • specific examples include inorganic materials, leveling agents, silane coupling agents, polymerization inhibitors or / and antioxidants, light resistance improvers, organic solvents and / or water.
  • these components will be described.
  • the composition of the present invention can be added as a photopolymerization initiation assistant.
  • the photopolymerization initiation assistant include aliphatic amines and aromatic amines such as diethylaminophenone, dimethylaminobenzoic acid ethyl, and dimethylaminobenzoic acid isoacyl.
  • the blending ratio of the photopolymerization initiation assistant is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, based on 100 parts by weight of the solid content of the composition.
  • Leveling agent examples include silicone compounds and fluorine compounds.
  • the blending ratio of the leveling agent is preferably 0.5% by weight or less with respect to 100 parts by weight of the solid content of the composition because the adverse effect on the adhesive performance is small.
  • a silane coupling agent can also be added for the purpose of improving the adhesion performance to inorganic substances such as glass, metal and metal oxide.
  • a silane coupling agent is a compound having one or more alkoxysilyl groups and one or more organic functional groups in one molecule. Examples of the organic functional groups include (meth) acryloyl groups, epoxy groups, amino groups, and thiols. Group is preferred, more preferably a (meth) acryloyl group.
  • the blending ratio of the silane coupling agent is preferably 5% by weight or less with respect to 100 parts by weight of the solid content of the composition from the viewpoint of reducing outgas.
  • the composition of the present invention may be added with a polymerization inhibitor or / and an antioxidant to preserve the stability of the composition of the present invention and the photocurable filled resin sheet. It is possible to improve the properties.
  • a polymerization inhibitor hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants are preferable, but sulfur secondary antioxidants, phosphorus secondary antioxidants are preferable. Subsequent antioxidants, clopene antioxidants and the like can also be added.
  • the total blending ratio of these polymerization inhibitors and / or antioxidants is preferably 0.001 to 3% by weight, more preferably 0.01 to 0.00%, based on 100 parts by weight of the solid content of the composition. 5% by weight.
  • Light resistance improver An ultraviolet absorber or a light stabilizer can be added to the composition of the present invention depending on the application.
  • the blending ratio of the light resistance improver is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, based on 100 parts by weight of the solid content of the composition.
  • Organic solvent The composition of the present invention preferably contains no organic solvent from the viewpoint of productivity and environment, but may contain an organic solvent for the purpose of improving coating properties.
  • organic solvent for example, the organic solvent described above in connection with the production of the component (B) can be used.
  • the composition of the present invention can be obtained by mixing the above-described raw materials at room temperature or under heating by a conventionally known method.
  • the viscosity of the composition is not particularly limited, but it is preferably 200 to 20,000 mPas at 25 ° C. When the viscosity is within this range, smooth coating is possible.
  • the glass transition temperature (Tg) of the cured product obtained by active energy ray irradiation is ⁇ 20 ° C. or lower, preferably ⁇ 30 ° C. or lower, more preferably ⁇ 40 ° C. or lower. It is. By setting the Tg to ⁇ 20 ° C. or less, good adhesiveness can be exhibited.
  • the Tg of the pressure-sensitive adhesive composition is also measured by the midpoint of the endothermic peak detected by the differential scanning calorimeter, as in the case of the component (B).
  • the pressure-sensitive adhesive composition of the present invention can be applied to substrates such as various films such as paper, various plastics, metals, inorganic materials, and wood, or molded articles. Moreover, it can be used also for the application (bonding) of various members, such as a film and a glass plate.
  • the plastic include polyethylene terephthalate, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polycarbonate resin, epoxy resin, and polyurethane resin.
  • the inorganic material include mortar, concrete, and glass.
  • the method for applying the composition of the present invention to the substrate may be in accordance with conventional methods, and examples thereof include bar coating, roll coating, spin coating, dip coating, gravure coating, die coating, flow coating, and spray coating.
  • the film thickness of the pressure-sensitive adhesive composition with respect to the substrate may be appropriately set depending on the purpose, but is about 5 to 100 ⁇ m in the state after irradiation with active energy rays.
  • Examples of the active energy rays for curing the composition of the present invention include electron beams, ultraviolet rays, visible rays, and X-rays, but ultraviolet rays are preferred because inexpensive devices can be used.
  • Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED. Irradiation conditions should be appropriately set according to the type and composition of the active energy ray, but are preferably 0.1 to 200 mW / cm 2 and more preferably 0.5 to 100 mW / cm 2 in terms of irradiation intensity. . Further, preferably 10 ⁇ 5000mJ / cm 2 as irradiation energy, more preferably 100 ⁇ 2000mJ / cm 2.
  • an electron beam (EB) irradiation device that can be used, such as a Cockloft-Waltsin type, a bandegraph type, and a resonance transformer type device.
  • the electron beam preferably has an energy of 50 to 1,000 eV, more preferably 100 to 300 eV.
  • the pressure-sensitive adhesive product of the present invention can include a cured product of the active energy ray-curable pressure-sensitive adhesive composition of the present invention.
  • the pressure-sensitive adhesive product may be any product as long as the cured product of the present invention is held in a state of exhibiting adhesiveness, and the form thereof is not particularly limited.
  • an adhesive product comprises one or more substrates and a cured product of the present invention held against at least a portion thereof.
  • the cured product is provided as an adhesive site or an adhesive layer.
  • the substrate is not particularly limited, and includes all substrates, parts, and products that are useful to have adhesiveness. Further, the material of the base material is not particularly limited as described above.
  • the adhesive product may include a cured product on at least a part of a base material such as a sheet or film of a known material.
  • a well-known adhesive tape and film are mentioned typically.
  • cured material may be provided with respect to components of various shapes. Typical examples of this form include various parts having an adhesive layer, and examples thereof include an optical film, a surface protective film, and a foam having an adhesive layer.
  • a part or a product in which a surface protective film or an optical film is fixed to an adherend as an adherend through an adhesive layer can be mentioned.
  • Such an adhesive product is not particularly limited besides an electronic material and an optical material.
  • the thickness of the cured product in the pressure-sensitive adhesive product is not particularly limited and is appropriately set according to the purpose, and can be set to 5 to 100 ⁇ m, for example.
  • the method for producing a pressure-sensitive adhesive product of the present invention includes a step of supplying the active energy ray-curable pressure-sensitive adhesive composition of the present invention to one or two or more substrates, and curing by irradiating the composition with active energy rays. And a step of exerting adhesiveness.
  • the supplying step can be performed by supplying the composition to the base material according to a conventional method, and the sticking performance step is also performed by adopting various conditions as described above. Can do.
  • part means part by mass.
  • Macromonomers B2 to B8 and polymers P1 and P4 to 7 were obtained in the same manner as in Production Example 1, except that the monomers, chain transfer agent and modifier were used as shown in Tables 1 and 2.
  • the polymers P6 and P7 are macromonomers obtained by introducing an average of 4 and 1 acryloyl group per molecule, respectively, in the middle of the molecular chain of the polymer.
  • Tables 1 and 2 show physical property values of the macromonomers B2 to B8 and the polymers P1 and P4 to 7.
  • MMA methyl methacrylate St: styrene EA: ethyl acrylate AN: acrylonitrile MAA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate MPA: 3-mercaptopropionic acid MTG: 2-mercaptoethanol DM: n-dodecyl mercaptan MOI: methacryl 2-isocyanatoethyl acid ("Karenz MOI” manufactured by Showa Denko) AOI: 2-isocyanatoethyl acrylate ("Karenz AOI” manufactured by Showa Denko) GMA: glycidyl methacrylate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (“4HBAGE” manufactured by Nippon Kasei) TMI: Dimethyl metaisopropenyl benzyl isocyanate (Mitsui Cytec's “TMI”
  • Examples 1 to 13 and Comparative Examples 1 to 13 The active energy ray-curable resin composition was obtained by blending (A) component, (B) component, photoinitiator (C), and other components in the proportions shown in Table 3 and mixing them uniformly. Various performances of the obtained compositions were evaluated by the evaluation methods described below, and the results are shown in Table 3.
  • each composition was applied to a 50 ⁇ m PET film (“Lumirror T-60 # 50” manufactured by Toray) so that the film thickness was 25 ⁇ m. Thereafter, ultraviolet rays were irradiated using an ultraviolet irradiation device (ECS-401GX, manufactured by Eye Graphics Co., Ltd.) under the following conditions until the integrated light amount reached 1000 mJ / cm 2 to obtain a cured pressure-sensitive adhesive layer. Thereafter, a 38 ⁇ m release PET film (“Therapy BK” manufactured by Toray Film Processing Co., Ltd.) was applied to the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet used for the test. UV irradiation conditions: 80W / cm condensing type high pressure mercury lamp lamp height 10cm The conveyor speed is adjusted so that the irradiation amount per pass is 100 mJ / cm 2 .
  • the YI value of the pressure-sensitive adhesive sheet was measured using a high-speed integrating sphere type spectral transmittance measuring instrument [SPECTROTOPOMETER DOT-3C manufactured by Murakami Color Research Laboratory Co., Ltd.]. The measured value was a blank made of two layers of Lumirror T-60 # 50 and Therapy BK.
  • Adhesive strength The pressure-sensitive adhesive sheet was cut to a width of 25 mm, and the release PET film was peeled off and attached to a BA-treated SUS304 plate, and a test piece was prepared by pressure bonding with a load of 2 kg ⁇ 1 with an automatic roller device. . Using this test piece, under the conditions of 23 ° C. and 50% RH, the 180 ° peel strength was measured according to the method described in JIS Z 0237, and the obtained value was taken as the adhesive strength.
  • the pressure-sensitive adhesive sheet is cut to a width of 25 mm, and the release PET film is peeled off and bonded to a BA-treated SUS304 plate so that the bonding area is 25 mm ⁇ 25 mm.
  • a test piece was prepared by pressure bonding with a load of 2 kg ⁇ 1. Under the conditions of 23 ° C. and 50% RH, the holding power of this test piece was measured according to the method described in JIS Z 0237. Note that the load was 1 kg, the time until peeling off after the load was applied was measured, and the holding time [hr] was taken as the holding force. In addition, when it hold
  • the pressure-sensitive adhesive sheet was cut to a width of 25 mm, and the release PET film was peeled off and bonded onto an aluminum plate, and then left for 48 hours in a high-temperature and high-humidity condition of 60 ° C. ⁇ 90% RH. . Then, the sample was peeled off from the aluminum plate, the surface was visually confirmed, and evaluated according to the following criteria. ⁇ : No discoloration was observed on the aluminum foil surface. X: Discoloration was confirmed on the surface of the aluminum foil.
  • Examples 1 to 13 are experimental examples of an active energy ray-curable pressure-sensitive adhesive composition that satisfies the requirements defined in the present invention, and have good curability.
  • the resulting pressure-sensitive adhesive sheet has adhesive strength and cohesive strength. At a high level, little coloring, and metal corrosion was suppressed. From the comparison of Examples 1 and 8, it can be seen that the use of a macromonomer having an acryloyl group as a terminal polymerizable functional group is superior in terms of curability to that of a methacryloyl group.
  • Comparative Examples 1 and 8 to 11 are those in which the component (B) does not satisfy the requirements defined in the present invention or the pressure-sensitive adhesive composition in which the component (B) itself is not used, but the balance of the adhesive performance. It was inferior to. Moreover, since Comparative Example 2, 3, 5 and 12 use the compound which has an acid group for the raw material of (A) component or (B) component, metal corrosion was recognized. In Comparative Example 4, since the polymerizable functional group of the component (B) was not a (meth) acryloyl group, the curability by irradiation with active energy was inferior.
  • Comparative Examples 6 and 7 are examples in which a polymer having an acryloyl group in the middle of the molecular chain, not at the end, was used as the component (B).
  • a polymer having one acryloyl group on average was used, but turbidity occurred in the obtained coating film. This is presumably due to the influence of a polymer having no functional group.
  • Comparative Example 6 had four acryloyl groups on average, the effect of the polymer having no functional group was small, and although the coating film was not turbid, the adhesive strength was insufficient.
  • Comparative Example 13 since the glass transition temperature of the cured product exceeded ⁇ 20 ° C., the adhesive strength was insufficient.
  • the active energy ray-curable pressure-sensitive adhesive composition of the present invention When the active energy ray-curable pressure-sensitive adhesive composition of the present invention is used, it is possible to obtain a pressure-sensitive adhesive that is excellent in adhesive strength and cohesive strength, has less turbidity and coloring of the cured product, and can suppress metal corrosion. For this reason, it can utilize as various adhesive products including the field

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Abstract

L'invention porte sur une composition adhésive durcissable par des rayons d'énergie active, qui contient un monomère à base de vinyle (A) n'ayant pas de groupe acide, un macromonomère (B) ayant un groupe (méth)acryloyle à une extrémité et un initiateur de photopolymérisation (C) et qui est caractérisée en ce que le constituant (B) a une température de transition vitreuse supérieure ou égale à 30 °C et est obtenu sans utiliser une matière première ayant un groupe acide dans le procédé de production et en ce que la température de transition vitreuse d'un adhésif après durcissement est inférieure ou égale à -20 °C.
PCT/JP2014/074611 2013-09-19 2014-09-18 Composition adhésive durcissable par des rayons d'énergie active WO2015041266A1 (fr)

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WO2018152076A1 (fr) * 2017-02-17 2018-08-23 3M Innovative Properties Company Composition de copolymère au (méth) acrylate physiquement réticulable
JP2022515643A (ja) * 2018-12-28 2022-02-21 サン－ゴバン パフォーマンス プラスティックス コーポレイション 接着剤組成物およびそれを形成する方法

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JP2000248242A (ja) * 1999-03-02 2000-09-12 Sliontec Corp 無基材感圧性両面接着テープ・シート及びその製造方法
JP2011052131A (ja) * 2009-09-02 2011-03-17 Nippon Shokubai Co Ltd 溶剤型再剥離用粘着剤組成物および再剥離用粘着製品
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WO2018152076A1 (fr) * 2017-02-17 2018-08-23 3M Innovative Properties Company Composition de copolymère au (méth) acrylate physiquement réticulable
JP2022515643A (ja) * 2018-12-28 2022-02-21 サン－ゴバン パフォーマンス プラスティックス コーポレイション 接着剤組成物およびそれを形成する方法
JP7275283B2 (ja) 2018-12-28 2023-05-17 サン－ゴバン パフォーマンス プラスティックス コーポレイション 接着剤組成物およびそれを形成する方法

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