WO2012073684A1 - Curable composition - Google Patents

Curable composition Download PDF

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Publication number
WO2012073684A1
WO2012073684A1 PCT/JP2011/076216 JP2011076216W WO2012073684A1 WO 2012073684 A1 WO2012073684 A1 WO 2012073684A1 JP 2011076216 W JP2011076216 W JP 2011076216W WO 2012073684 A1 WO2012073684 A1 WO 2012073684A1
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Prior art keywords
meth
acrylate
curable composition
component
acrylic
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PCT/JP2011/076216
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French (fr)
Japanese (ja)
Inventor
光浩 金田
金子　哲
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株式会社スリーボンド
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Priority to CN201180058270.2A priority Critical patent/CN103237821B/en
Priority to JP2012546759A priority patent/JP5794236B2/en
Priority to KR1020137014198A priority patent/KR101803595B1/en
Publication of WO2012073684A1 publication Critical patent/WO2012073684A1/en

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    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof

Definitions

  • the present invention relates to a curable composition
  • a curable composition comprising a (meth) acryl functional compound as a main component, which is suitable for adhesion and sealing applications, and retains storability in an uncured state while curing after a curing reaction.
  • the moisture resistance strength of the object can be improved.
  • the curable composition having a (meth) acrylic functional group is cured by a polymerization reaction of the (meth) acrylic functional group.
  • the anaerobic curable composition is mainly composed of a (meth) acrylic acid ester monomer as air. Or, while in contact with oxygen (hereinafter simply referred to as air), it does not gel for a long time and remains stable in a liquid state, and has the property of rapidly curing when air is shut off or eliminated.
  • air oxygen
  • the curable composition is used for bonding screws, bolts, etc., fixing, fixing fitting parts, bonding between flange surfaces, sealing, filling of burrows generated in cast parts, etc. I came.
  • Anaerobic curable compositions have rapid curing properties at room temperature and have stable physical properties even after curing, so that their use in electrical and electronic parts has increased in recent years.
  • anaerobic curable compounds used in combination with a curing accelerator are used for adhesion between a bearing and its shaft, fitting adhesion at the peripheral portion, and the like (for example, Patent Document 1).
  • the conventional (meth) acrylic curable composition particularly the anaerobic curable composition, has a problem particularly in use under a high temperature and high humidity environment.
  • the solution has not been realized.
  • the adhesive composition can provide a material that can be used as an adhesive, a sealant, a filler and the like particularly suitable for use in a high temperature and high humidity environment.
  • the (meth) acrylic curable composition in the (meth) acrylic curable composition, 0.05 to 5 parts by weight of the component (b) and 0.1 part of the component (c) are added to 100 parts by weight of the component (a). 001 to 3 parts by weight.
  • the component (b) includes an ethylenediamine derivative that is not a metal salt, or the component (c) includes an anionic surfactant, and the component (c).
  • the component contains an anionic surfactant having a straight chain alkyl group having 10 or more carbon atoms, or the (meth) acrylic curable composition has anaerobic curability. It is particularly preferable to have a configuration.
  • the (meth) acrylic curable composition of the present invention can prevent a decrease in strength even when used in a high-temperature and high-humidity environment while ensuring initial adhesiveness, and particularly requires moisture resistance strength. It can be suitably used as an adhesive or seal material for the intended use.
  • acrylic acid ester monomer or oligomer containing one or more hydroxyl groups in the molecule used in the present invention various acrylic acid derivatives can be used.
  • examples of such substances include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-butanediol ( (Meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone modified 2-hydroxy Ethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, and the like can be used.
  • (meth) acrylic acid ester monomers or oligomers may be used in combination with the component (a).
  • the (meth) acrylic acid ester monomer or oligomer can be arbitrarily selected as long as it does not impair the characteristics of the present invention.
  • acrylic acid ester monomers or oligomers may be used alone or in combination with the component (a) for the purpose of adjusting the viscosity of the curable composition of the present invention or adjusting the properties of the cured product.
  • component (a) for the purpose of adjusting the viscosity of the curable composition of the present invention or adjusting the properties of the cured product.
  • the (b) chelating agent compound that is not a metal salt used in the present invention a compound having a so-called chelating ability can be suitably used.
  • the chelating agent include ethylenediamine, diethylenetriamine, triethylenetetramine, ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, cyclohexane-1,2-diaminetetraacetic acid, iminodiacetic acid, nitrotriacetic acid, bipyridine, phenanthroline, Known substances such as porphyrin, phthalocyanine, terpyridine, crown ether, cyclodextrin and the like can be used.
  • an ethylenediamine derivative that is not a metal salt can be particularly preferably used.
  • the amount of component (b) added is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of component (a). If it exceeds 5 parts by weight, there will be a problem in curability, and if it is less than 0.05 part by weight, it may not be possible to exhibit suitable storage properties.
  • the component (b) is used as a storage stability improving component, but conventionally known chelating agents, particularly ethylenediamine derivatives, are known as storage stability improving components for acrylic curable compositions. In most cases, it is used as a metal salt such as a sodium salt. In the present invention, the mechanism of action is unknown, but when an ethylenediamine derivative that has become a metal salt is used as a storage stability improving component, the adhesive strength is significantly reduced when a moisture resistance deterioration test is performed on the curable composition. Therefore, it is preferable to use a non-metal salt.
  • the surfactant used in the present invention functions as a deterioration inhibiting component in a high temperature and high humidity environment.
  • a nonionic surfactant e.g., sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester.
  • Polyoxyethylene glycerin fatty acid ester Polyoxyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxy Ethylene castor oil, polyoxyethylene lanolin, polyoxyethylene Roh phosphorus alcohol ether, polyoxyethylene lanolin fatty acid esters, polyoxyethylene-polyoxypropylene-proc polymers, sucrose fatty acid esters, polyoxyethylene alkylphenyl formaldehyde condensates and the like.
  • (ii) include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether acetates, alkyl sulfonates, ⁇ -olefin sulfonates, alkyl phosphates, polyoxyethylene alkyls. An ether phosphate etc. are mentioned.
  • Specific examples of (iii) include alkyl carboxy betaines, alkyl dimethyl amine oxides, monoamino monocarboxylic acids, diamino monocarboxylic acids, polyamino monocarboxylic acids, glycine derivatives, lecithin and the like.
  • the amount of the component (c) added is preferably 0.001 to 3 parts by weight, more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the component (a). If the amount exceeds 3 parts by weight, the affinity with moisture becomes excessive, causing a problem in moisture resistance, and if it is less than 0.001 part by weight, it may not be possible to exhibit suitable moisture resistance stability. Even if the component (b) functions as a surfactant, it is preferable to add the component (c) separately from this.
  • an optional component (c) can be used, but (ii) an anionic surfactant is preferably included in order to improve storage stability.
  • an anionic surfactant having a linear alkyl group having 10 or more carbon atoms such as sodium stearate and sodium dodecyl sulfate.
  • the (meth) acrylic curable composition is preferably anaerobic curable composition, and therefore a component for imparting anaerobic curable property to the composition can be further added.
  • a component for example, a combination containing (d) an organic peroxide and (e) o-benzoixsulfimide can be further added.
  • (d) organic peroxide those which have been used for curing anaerobic curable compositions can be used.
  • examples of such substances include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, Peroxyketals such as n-butyl-4,4-bis (t-butylperoxy) valerate and 2,2-bis (t-butylperoxy) butane; t-butyl hydroperoxide, cumene hydroperoxide, Diis
  • the amount of (d) organic peroxide added is preferably 0.1 to 10 parts by weight per 100 parts by weight of component (a). If it exceeds 10 parts by weight, the storage stability of the curable composition is lowered, and if it is less than 0.1 part by weight, the reaction of the curable composition is insufficient.
  • the (e) o-benzoixsulfimide is so-called saccharin, and the preferred addition amount is 0.1 to 25 parts by weight with respect to 100 parts by weight of the component (a).
  • components other than (a) to (e) shown above can be optionally used as long as the action of the present invention is not inhibited.
  • polymerization promoting components such as amine compounds, mercaptan compounds, hydrazine derivatives, storage stability improving components such as quinone compounds, fillers, thixotropic agents, plasticizers, colorants, thickeners, etc.
  • the amount can be appropriately adjusted and added according to the characteristics required.
  • the curable composition of the present invention may be not only anaerobic curable but also curable by actinic light irradiation, or may have both the anaerobic curable property and the photocurable property.
  • a photopolymerization initiator examples include benzophenone, acetophenone, propiophenone, xanthol, and fluorin.
  • Thioxanthone compounds 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,6-dichloro) -Benzoyl) -4'-n- Acylphosphine oxides such as propylphenylphosphine oxide and bis (2,6-dimethylbenzoyl) diphenylphosphine oxide can be used.
  • 2-hydroxyethyl methacrylate product of Nippon Shokubai Co., Ltd., trade name HEMA
  • component (a) 2-hydroxyethyl methacrylate (product of Nippon Shokubai Co., Ltd., trade name HEMA) as component (a), ethylenediaminetetraacetic acid (product of Dojindo Laboratories, trade name 4H), ethylenediaminetetraacetic acid Disodium salt (product of Dojin Chemical Laboratory, trade name EDTA 2NA), anionic surfactant sodium dodecyl sulfate (product of Wako Pure Chemical Industries) as component (c), sodium stearate (product of Wako Pure Chemical Industries) Product), polyethylene glycol monolaurate (a product of Kao Corporation, trade name Emanon 1112), a nonionic surfactant, and o-benzoxlufimide (a product of Daiwa Kasei Co., trade name: Saccharin B-1) as a curing agent component ,
  • the prepared curable composition sample was prepared on a test plate (material: electroless Ni-plated steel plate, dimensions: 1.6 ⁇ 25 ⁇ 100 mm) on a chip test piece (material: electroless Ni-plated magnet, dimensions: 1.3). ⁇ 2.3 ⁇ 4.1 mm) was installed and applied by infiltrating with a dropper from the side surface of the chip test piece. By irradiating ultraviolet rays under the condition of 30 kJ / m 2 from the upper part with a high pressure mercury lamp, the curable composition sample protruding from the side part is cured, and then cured at a temperature of 25 ° C. for 24 hours. Evaluation was performed as a test piece for evaluation.
  • the adhesive strength evaluation was carried out using the test piece prepared by the above method as an initial adhesive strength evaluation test piece, and a test piece for standing for 72 hours at a temperature of 85 ° C. and a humidity of 85% RH for 72 hours. This was carried out by measuring the chip adhesive strength with a chip strength tester (manufactured by Shinpo Co., Ltd .; digital force gauge FGC-200, extrusion speed 6 mm / min). The chip adhesive strength was calculated from a value obtained by dividing the strength when the chip test piece was removed by the adhesion area of the chip test piece.
  • each curable composition was taken in a 5 g test tube and allowed to stand in a constant temperature bath at 80 ° C., and the time until gelation was evaluated as storage stability. Evaluation was made by judging that the gel did not gel within 2 hours, ⁇ when gelled within 30 minutes to 1 hour, and x when gelled within 30 minutes. The gelation state of each curable composition was visually evaluated. Each evaluation result is shown in each table.
  • the curable composition containing the constitutions (a), (b) and (c) of the present invention has an initial adhesive strength without reducing the amount of hydrophilic (meth) acrylic monomer added. Curability with good strength and small decrease in strength under high temperature and high humidity environment (almost half change in bond strength value, bond strength value after humidity resistance test is 40 N / m or more), and excellent storage stability It is a composition.
  • the constitution (b) of the present invention is a metal salt
  • the initial adhesive strength is good, but the adhesive strength after the moisture resistance test is remarkably reduced, and the storage stability is sufficient. It wasn't.
  • the (meth) acrylic curable composition of the present invention gives a cured product having good moisture resistance, and can be suitably used in applications such as adhesion, sealing, and potting of various members that are particularly required to have moisture resistance. It is possible.

Abstract

The present invention relates to a curable (meth)acrylic composition comprising (a) a (meth)acrylic acid ester monomer or oligomer containing at least one hydroxyl group in the molecule, (b) a chelating compound that is not a metal salt, and (c) a surfactant.

Description

硬化性組成物Curable composition
　本発明は接着、封止用途に好適な、（メタ）アクリル官能性化合物を主成分としてなる硬化性組成物に関するものであり、未硬化の状態では保存性を保持しつつ、硬化反応後における硬化物の耐湿強度を向上させることができるというものである。 The present invention relates to a curable composition comprising a (meth) acryl functional compound as a main component, which is suitable for adhesion and sealing applications, and retains storability in an uncured state while curing after a curing reaction. The moisture resistance strength of the object can be improved.
　（メタ）アクリル官能基を有する硬化性組成物は、（メタ）アクリル官能基の重合反応により硬化するものであるが、特に嫌気硬化性組成物は（メタ）アクリル酸エステルモノマーを主成分として空気または酸素（以下、単に空気という）と接触している間は長期間ゲル化せずに液状状態で安定に保たれ、空気が遮断もしくは排除されると急速に硬化する性質を有するものであって、このような性質を利用して前記硬化性組成物はネジ、ボルト等の接着、固定、嵌め合い部品の固着、フランジ面間の接着、シール、鋳造部品に生じる巣孔の充填等に使用されてきた。 The curable composition having a (meth) acrylic functional group is cured by a polymerization reaction of the (meth) acrylic functional group. In particular, the anaerobic curable composition is mainly composed of a (meth) acrylic acid ester monomer as air. Or, while in contact with oxygen (hereinafter simply referred to as air), it does not gel for a long time and remains stable in a liquid state, and has the property of rapidly curing when air is shut off or eliminated. By utilizing such properties, the curable composition is used for bonding screws, bolts, etc., fixing, fixing fitting parts, bonding between flange surfaces, sealing, filling of burrows generated in cast parts, etc. I came.
　嫌気硬化性組成物は常温において速硬化性を有し、硬化後も安定した物性を有するため、電気電子部品などへの利用が近年増大してきている。特にモーター分野において、その生産性からベアリングとそのシャフトの接着やその周辺箇所の嵌め合い接着等に硬化促進剤と併用した嫌気硬化性成物が使用されている（特許文献１など）。 Anaerobic curable compositions have rapid curing properties at room temperature and have stable physical properties even after curing, so that their use in electrical and electronic parts has increased in recent years. In particular, in the motor field, anaerobic curable compounds used in combination with a curing accelerator are used for adhesion between a bearing and its shaft, fitting adhesion at the peripheral portion, and the like (for example, Patent Document 1).
日本国特開２００３－１１９２０８号公報Japanese Unexamined Patent Publication No. 2003-119208
　嫌気硬化性組成物は前記のような特徴が知られている一方で、高温高湿環境下での使用においては、硬化物が吸湿することにより膨潤してしまったり、金属等の被着体表面に状態変化をもたらすことにより接着強度が著しく低下してしまうという問題があった。この問題を解決するために、組成物中に含まれる親水性（メタ）アクリルモノマー等の親水性物質を低減させる必要があるが、親水性（メタ）アクリルモノマーを低減させると組成物の初期接着強度が著しく低下するという別の問題が生じてしまうものであった。 While anaerobic curable compositions are known for their characteristics as described above, when used in a high-temperature and high-humidity environment, the cured product may swell due to moisture absorption, or the surface of an adherend such as metal. There is a problem that the adhesive strength is remarkably lowered by causing a change in state. In order to solve this problem, it is necessary to reduce hydrophilic substances such as hydrophilic (meth) acrylic monomers contained in the composition. However, if the hydrophilic (meth) acrylic monomer is reduced, the initial adhesion of the composition is reduced. Another problem was that the strength was significantly reduced.
　あるいは、ガラス転移点（Ｔｇ）の高い（メタ）アクリルモノマーを用いることにより吸水率低減を図ったり、カップリング剤を添加することにより密着性改善を図ることも考えられるが、これらの対策では初期接着強度が低下したり、保存安定性が悪化するというような別の問題が生じてしまう。 Alternatively, it is conceivable to reduce the water absorption rate by using a (meth) acrylic monomer having a high glass transition point (Tg) or to improve the adhesion by adding a coupling agent. Another problem arises that the adhesive strength is lowered and the storage stability is deteriorated.
　斯様に従来の（メタ）アクリル系硬化性組成物、特に嫌気硬化性組成物は、特に高温高湿環境下での使用に於いて問題を有するものであったが、これら問題に対する根本的な解決は実現できていない。 Thus, the conventional (meth) acrylic curable composition, particularly the anaerobic curable composition, has a problem particularly in use under a high temperature and high humidity environment. The solution has not been realized.
　本発明者らは、上述した従来の問題点を克服すべく鋭意検討した結果、以下の構成の硬化性組成物によりこれを達成することが出来た。すなわち（ａ）分子中に１つ以上の水酸基を含有する（メタ）アクリル酸エステルモノマーまたはオリゴマー、（ｂ）金属塩でないキレート化剤化合物、（ｃ）界面活性剤を含む（メタ）アクリル系硬化性組成物により、高温高湿環境下での使用に特に好適な接着剤、シール剤、充填剤等として用いることができる材料を提供できる。 As a result of intensive studies to overcome the above-described conventional problems, the present inventors have been able to achieve this with a curable composition having the following configuration. (A) (meth) acrylic acid ester monomer or oligomer containing one or more hydroxyl groups in the molecule, (b) a chelating agent compound that is not a metal salt, (c) a (meth) acrylic curing containing a surfactant The adhesive composition can provide a material that can be used as an adhesive, a sealant, a filler and the like particularly suitable for use in a high temperature and high humidity environment.
　本発明のより好ましい形態は、前記（メタ）アクリル系硬化性組成物において、（ａ）成分１００重量部に対して（ｂ）成分が０．０５～５重量部、（ｃ）成分が０．００１～３重量部とすることである。 In a more preferred embodiment of the present invention, in the (meth) acrylic curable composition, 0.05 to 5 parts by weight of the component (b) and 0.1 part of the component (c) are added to 100 parts by weight of the component (a). 001 to 3 parts by weight.
　また、前記（メタ）アクリル系硬化性組成物において、（ｂ）成分が金属塩でないエチレンジアミン誘導体を含むものであること、あるいは（ｃ）成分がアニオン系界面活性剤を含むものであること、さらに前記（ｃ）成分が炭素数１０以上の直鎖アルキル基を有するアニオン系界面活性剤を含むものであること、あるいは（メタ）アクリル系硬化性組成物が嫌気硬化性を有するものであることのいずれか一つ以上の構成を有することが特に好ましい。 In the (meth) acrylic curable composition, the component (b) includes an ethylenediamine derivative that is not a metal salt, or the component (c) includes an anionic surfactant, and the component (c). The component contains an anionic surfactant having a straight chain alkyl group having 10 or more carbon atoms, or the (meth) acrylic curable composition has anaerobic curability. It is particularly preferable to have a configuration.
　本発明の（メタ）アクリル系硬化性組成物は、初期接着性を確保した上で、高温高湿環境下で使用しても強度低下を抑えることができるものであって、特に耐湿強度が求められる用途での接着、シール材料として好適に用いることができるものである。 The (meth) acrylic curable composition of the present invention can prevent a decrease in strength even when used in a high-temperature and high-humidity environment while ensuring initial adhesiveness, and particularly requires moisture resistance strength. It can be suitably used as an adhesive or seal material for the intended use.
　本発明に使用される（ａ）分子中に１つ以上の水酸基を含有する（メタ）アクリル酸エステルモノマーまたはオリゴマーとしては、各種のアクリル酸誘導体を使用することができる。当該物質の例としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、１，４－ブタンジオール（メタ）アクリレート、２－ヒドロキシエチルアクリロイルホスフェート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシプロピルフタレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、カプロラクトン変性２－ヒドロキシエチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、グリセリンジ（メタ）アクリレート等を使用することができるが、中でも特に２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレートを好適に使用することができる。 As the (meth) acrylic acid ester monomer or oligomer containing one or more hydroxyl groups in the molecule used in the present invention, various acrylic acid derivatives can be used. Examples of such substances include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-butanediol ( (Meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone modified 2-hydroxy Ethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, and the like can be used. Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate can be preferably used.
　また、前記（ａ）成分と併せてその他の（メタ）アクリル酸エステルモノマーまたはオリゴマーを用いてもよい。当該（メタ）アクリル酸エステルモノマーまたはオリゴマーとしては、本発明の特性を損なわないものであれば随意に選択できるが、たとえばメチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート 、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールポリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシテトラエチレングリコール（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、ノニルフェノキシテトラエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ブトキシトリエチレングリコール（メタ）アクリレート、２－エチルヘキシルポリエチレングリコール（メタ）アクリレート、ノニルフェニルポリプロピレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、グリシジル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、モルホリノ（メタ）アクリレート、エチレンオキサイド（ＥＯ）変性リン酸（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、ＥＯ変性ビスフェノールＡジ（メタ）アクリレート、アルコキシ変性ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＦジ（メタ）アクリレート、ＥＯ変性ビスフェノールＦジ（メタ）アクリレート、アルコキシ変性ビスフェノールＦジ（メタ）アクリレート、ＥＣＨ変性ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＳジ（メタ）アクリレート、ＥＯ変性ビスフェノールＳジ（メタ）アクリレート、アルコキシ変性ビスフェノールＳジ（メタ）アクリレート、ＥＣＨ変性ビスフェノールＳジ（メタ）アクリレート等が挙げられる。なお、（メタ）アクリルとはアクリルとメタクリルを総称したものである。 Further, other (meth) acrylic acid ester monomers or oligomers may be used in combination with the component (a). The (meth) acrylic acid ester monomer or oligomer can be arbitrarily selected as long as it does not impair the characteristics of the present invention. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, dipentaerythritol poly (meth) Acrylate, tetramethylolmethane tetra (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate , Phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxytetraethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxy Ethyl (meth) acrylate, butoxytriethylene glycol (me Acrylate), 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenyl polypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, polypropylene glycol di (meth) Acrylate, morpholino (meth) acrylate, ethylene oxide (EO) modified phosphoric acid (meth) acrylate, bisphenol A di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, alkoxy modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, alkoxy modified bisphenol F di (meth) Chryrate, ECH modified bisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, EO modified bisphenol S di (meth) acrylate, alkoxy modified bisphenol S di (meth) acrylate, ECH modified bisphenol S di (meth) acrylate, etc. Is mentioned. (Meth) acrylic is a generic term for acrylic and methacrylic.
　これら（メタ）アクリル酸エステルモノマーまたはオリゴマーは、本発明の硬化性組成物の粘度の調整、あるいはその硬化物の特性を調整する目的で、単独あるいは複数を前記（ａ）成分と併せて用いることができるが、単独で所望の性能を出すことが困難である場合、必要に応じて複数を混合して使用することが好ましい。 These (meth) acrylic acid ester monomers or oligomers may be used alone or in combination with the component (a) for the purpose of adjusting the viscosity of the curable composition of the present invention or adjusting the properties of the cured product. However, when it is difficult to achieve desired performance alone, it is preferable to use a mixture of a plurality of them as necessary.
　本発明に使用される（ｂ）金属塩でないキレート化剤化合物としては、いわゆるキレート能を有する化合物が好適に用いることができる。このキレート化剤としては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、エチレジアミン四酢酸、エチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、シクロヘキサン－１，２－ジアミン四酢酸、イミノジ酢酸、ニトロトリ酢酸、ビピリジン、フェナントロリン、ポルフィリン、フタロシアニン、ターピリジン、クラウンエーテル、シクロデキストリンなどの公知の物質を用いることができるが、本発明においては金属塩でないエチレンジアミン誘導体が特に好適に用いることができる。 As the (b) chelating agent compound that is not a metal salt used in the present invention, a compound having a so-called chelating ability can be suitably used. Examples of the chelating agent include ethylenediamine, diethylenetriamine, triethylenetetramine, ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, cyclohexane-1,2-diaminetetraacetic acid, iminodiacetic acid, nitrotriacetic acid, bipyridine, phenanthroline, Known substances such as porphyrin, phthalocyanine, terpyridine, crown ether, cyclodextrin and the like can be used. In the present invention, an ethylenediamine derivative that is not a metal salt can be particularly preferably used.
　（ｂ）成分の添加量は、前記（ａ）成分１００重量部に対して０．０５～５重量部にあることが好ましく、より望ましくは０．１～３重量部である。５重量部を越えると硬化性に問題が生じ、また０．０５重量部未満であると好適な保存性を発揮することができなくなる虞がある。 The amount of component (b) added is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of component (a). If it exceeds 5 parts by weight, there will be a problem in curability, and if it is less than 0.05 part by weight, it may not be possible to exhibit suitable storage properties.
　なお本発明において（ｂ）成分は保存安定性向上成分として用いられるものであるが、従来知られているアクリル系硬化性組成物用の保存安定性向上成分としてのキレート化剤、特にエチレンジアミン誘導体は、ナトリウム塩などの金属塩として供される場合が殆どであった。本発明において、作用機序は不明であるが、保存安定性向上成分として金属塩となったエチレンジアミン誘導体を用いると、硬化性組成物の耐湿劣化試験を行った際に著しく接着強度が低下してしまうため、金属塩でないものを使用することが好ましい。 In the present invention, the component (b) is used as a storage stability improving component, but conventionally known chelating agents, particularly ethylenediamine derivatives, are known as storage stability improving components for acrylic curable compositions. In most cases, it is used as a metal salt such as a sodium salt. In the present invention, the mechanism of action is unknown, but when an ethylenediamine derivative that has become a metal salt is used as a storage stability improving component, the adhesive strength is significantly reduced when a moisture resistance deterioration test is performed on the curable composition. Therefore, it is preferable to use a non-metal salt.
　本発明に使用される（ｃ）界面活性剤は、高温高湿環境下での劣化抑制成分として機能するものである。該（ｃ）成分としては、（ｉ）非イオン系界面活性剤、（ｉｉ）アニオン系界面活性剤、（ｉｉｉ）両性界面活性剤を用いることができる。（ｉ）の具体例としては、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、デカグリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、プロピレングリコール脂肪酸エステル、ペンタエリスリトール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビット脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレングリコール脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンフィトステロール、ポリオキシエチレンフィトスタノール、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンヒマシ油、ポリオキシエチレンラノリン、ポリオキシエチレンラノリンアルコールエーテル、ポリオキシエチレンラノリン脂肪酸エステル、ポリオキシエチレン・ポリオキシプロピレン・プロックポリマー、蔗糖脂肪酸エステル、ポリオキシエチレンアルキルフェニルホルムアルデヒド縮合物などが挙げられる。 (C) The surfactant used in the present invention functions as a deterioration inhibiting component in a high temperature and high humidity environment. As the component (c), (i) a nonionic surfactant, (ii) an anionic surfactant, and (iii) an amphoteric surfactant can be used. Specific examples of (i) include sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester. , Polyoxyethylene glycerin fatty acid ester, polyoxyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxy Ethylene castor oil, polyoxyethylene lanolin, polyoxyethylene Roh phosphorus alcohol ether, polyoxyethylene lanolin fatty acid esters, polyoxyethylene-polyoxypropylene-proc polymers, sucrose fatty acid esters, polyoxyethylene alkylphenyl formaldehyde condensates and the like.
　（ｉｉ）の具体例としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、アルキルスルホン酸塩、α－オレフインスルホン酸塩、アルキルリン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩等が挙げられる。（ｉｉｉ）の具体例としては、アルキルカルボキシベタイン、アルキルジメチルアミンオキシド、モノアミノモノカルボン酸、ジアミノモノカルボン酸、ポリアミノモノカルボン酸、グリシン誘導体、レシチン等が挙げられる。 Specific examples of (ii) include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether acetates, alkyl sulfonates, α-olefin sulfonates, alkyl phosphates, polyoxyethylene alkyls. An ether phosphate etc. are mentioned. Specific examples of (iii) include alkyl carboxy betaines, alkyl dimethyl amine oxides, monoamino monocarboxylic acids, diamino monocarboxylic acids, polyamino monocarboxylic acids, glycine derivatives, lecithin and the like.
　（ｃ）成分の添加量は、前記（ａ）成分１００重量部に対して０．００１～３重量部にあることが好ましく、より望ましくは０．０１～２重量部である。３重量部を越えると湿分との親和性が過剰となって耐湿性に問題が生じ、また０．００１重量部未満であると好適な耐湿安定性を発揮することができなくなる虞がある。なお、前記（ｂ）成分が界面活性剤として働くものであったとしても、これとは別に（ｃ）成分を添加することが好ましい。 The amount of the component (c) added is preferably 0.001 to 3 parts by weight, more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the component (a). If the amount exceeds 3 parts by weight, the affinity with moisture becomes excessive, causing a problem in moisture resistance, and if it is less than 0.001 part by weight, it may not be possible to exhibit suitable moisture resistance stability. Even if the component (b) functions as a surfactant, it is preferable to add the component (c) separately from this.
　本発明において（ｃ）成分には随意のものを用いることができるが、保存安定性が向上するため、（ｉｉ）アニオン系界面活性剤を含むことが好ましい。中でも、ステアリン酸ナトリウムやドデシル硫酸ナトリウムのような、炭素数１０以上の直鎖アルキル基を有するアニオン系界面活性剤を含むことが好ましい。 In the present invention, an optional component (c) can be used, but (ii) an anionic surfactant is preferably included in order to improve storage stability. Among these, it is preferable to include an anionic surfactant having a linear alkyl group having 10 or more carbon atoms, such as sodium stearate and sodium dodecyl sulfate.
　本発明においては、前記（メタ）アクリル系硬化性組成物は嫌気硬化性を有するものであることが好ましく、従って当該組成物に嫌気硬化性を与える為の成分を更に加えることができる。このような成分として、例えば（ｄ）有機過酸化物、及び（ｅ）ｏ－ベンゾイックスルフィミドを含む組合せを更に加えることができる。 In the present invention, the (meth) acrylic curable composition is preferably anaerobic curable composition, and therefore a component for imparting anaerobic curable property to the composition can be further added. As such a component, for example, a combination containing (d) an organic peroxide and (e) o-benzoixsulfimide can be further added.
　前記（ｄ）有機過酸化物としては、従前より嫌気硬化性組成物を硬化させる為に用いられていたものを使用することができる。このような物質の例としては、例えばメチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、３，３，５－トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、メチルアセトアセテートパーオキサイド、アセチルアセトンパーオキサイド等のケトンパーオキサイド類；１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）シクロヘキサン、２，２－ビス（ｔ－ブチルパーオキシ）オクタン、ｎ－ブチル－４，４－ビス（ｔ－ブチルパーオキシ）バレレート、２，２－ビス（ｔ－ブチルパーオキシ）ブタン等のパーオキシケタール類；ｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、ｐ－メタンハイドロパーオキサイド、２，５－ジメチルヘキサン－２，５－ジハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド等のハイドロパーオキサイド類；ジｔ－ブチルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ジクミルパーオキサイド、α，α’－ビス（ｔ－ブチルパーオキシ－ｍ－イソプロピル）ベンゼン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキシン－３等のジアルキルパーオキサイド類；アセチルパーオキサイド、イソブチリルパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、３，５，５－トリメチルヘキサノイルパーオキサイド、サクシニックアシッドパーオキサイド、ベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド、ｍ－トルオイルパーオキサイド等のジアシルパーオキサイド類；ジイソプロピルパーオキシジカーボネート、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ（ｎ－プロピル）パーオキシジカーボネート、ビス－（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジミリスチルパーオキシジカーボネート、ジ（２－エトキシエチル）パーオキシジカーボネート、ジメトキシイソプロピルパーオキシジカーボネート、ジ（３－メチル－３－メトキシブチル）パーオキシジカルボネート、ジアリルパーオキシジカーボネート等のパーオキシジカーボネート類；ｔ－ブチルパーオキシアセテート、ｔ－ブチルパーオキシイソブチレート、ｔ－ブチルパーオキシピバレート、ｔ－ブチルパーオキシネオデカノエート、クミルパーオキシネオデカノエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ｔ－ブチルパーオキシラウレート、ｔ－ブチルパーオキシベンゾエート、ジ（ｔ－ブチル）パーオキシイソフタレート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔ－ブチルパーオキシマレイックアシッド、ｔ－ブチルパーオキシイソプロピルカーボネート、クミルパーオキシオクトエート、ｔ－ヘキシルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシネオヘキサノエート、ｔ－ヘキシルパーオキシネオヘキサノエート、クミルパーオキシネオヘキサノエート等のパーオキシエステル類；およびアセチルシクロヘキシルスルホニルパーオキシド、ｔ－ブチルパーオキシアリルカーボネート等の有機過酸化物を単独で、或いは二種以上の混合物として用いることができる。なお（ｄ）有機過酸化物の添加量は、前記（ａ）成分１００重量部に対して０．１～１０重量部であることが好ましい。１０重量部を越えると前記硬化性組成物の保存安定性が低下し、０．１重量部未満であると前記硬化性組成物の反応を生じさせるのに不十分となる。 As the (d) organic peroxide, those which have been used for curing anaerobic curable compositions can be used. Examples of such substances include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, Peroxyketals such as n-butyl-4,4-bis (t-butylperoxy) valerate and 2,2-bis (t-butylperoxy) butane; t-butyl hydroperoxide, cumene hydroperoxide, Diisopropyl Hydroperoxides such as benzene hydroperoxide, p-methane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide; t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t Dibutyl peroxides such as -butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, deca Noyl peroxide, lauroyl peroxide, 3,5,5-to Diacyl peroxides such as methylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide; diisopropyl peroxydicarbonate, di (2-ethylhexyl) Peroxydicarbonate, di (n-propyl) peroxydicarbonate, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, Peroxydicarbonates such as dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, diallylperoxydicarbonate; t-butyl Peroxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylhexano Ate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di (t-butyl) peroxyisophthalate, 2,5-dimethyl -2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctoate, t-hexylperoxyneodecanoate, t-hexylper Oxypivalate, t-butylperoxyneohexanoe Peroxyesters such as tert-hexylperoxyneohexanoate and cumylperoxyneohexanoate; and organic peroxides such as acetylcyclohexylsulfonylperoxide and t-butylperoxyallylcarbonate, Or it can use as a mixture of 2 or more types. The amount of (d) organic peroxide added is preferably 0.1 to 10 parts by weight per 100 parts by weight of component (a). If it exceeds 10 parts by weight, the storage stability of the curable composition is lowered, and if it is less than 0.1 part by weight, the reaction of the curable composition is insufficient.
　前記（ｅ）ｏ-ベンゾイックスルフィミドはいわゆるサッカリンであり、その好適な添加量は（ａ）成分１００重量部に対して０．１～２５重量部である。 The (e) o-benzoixsulfimide is so-called saccharin, and the preferred addition amount is 0.1 to 25 parts by weight with respect to 100 parts by weight of the component (a).
　また本発明においては、上記に示される（ａ）～（ｅ）以外の成分についても本発明の作用を阻害しない範囲で随意に使用することができる。たとえば、アミン化合物類やメルカプタン化合物類、ヒドラジン誘導体類のような重合促進成分、キノン化合物類のような保存安定性向上成分、充填剤、チクソトロピー性付与剤、可塑剤、着色剤、増粘剤などを求める特性に応じた量を適宜調整し添加できる。 In the present invention, components other than (a) to (e) shown above can be optionally used as long as the action of the present invention is not inhibited. For example, polymerization promoting components such as amine compounds, mercaptan compounds, hydrazine derivatives, storage stability improving components such as quinone compounds, fillers, thixotropic agents, plasticizers, colorants, thickeners, etc. The amount can be appropriately adjusted and added according to the characteristics required.
　さらに本発明の硬化性組成物は、嫌気硬化性のみならず、活性光照射により硬化するものであってもよく、また前記嫌気硬化性と光硬化性を併せ持つものでもよい。光硬化性を付与するためには、硬化性組成物中に光重合開始剤を添加することで達成されるが、光重合開始剤としては、例えばベンゾフェノン、アセトフェノン、プロピオフェノン、キサントール、フルオレイン、ベンズアルデヒド、アンスラキノン、トリフェニルアミン、カルバゾール、３－メチルアセトフェノン、４－メチルアセトフェノン、３－ペンチルアセトフェノン、４－メトキシアセトフェノン、３－ブロモアセトフェノン、ｐ－ジアセチルベンゼン、３－メトキシベンゾフェノン、４－アリルアセトフェノン、４－クロロ－４－ベンジルベンゾフェノン、３－クロロキサントーン、３，９－ジクロロキサントーン、３－クロロ８－ノニルキサントーン、ベンゾイル、ベンゾインメチルエーテル、ビス（４－ジメチルアミノフェニル）ケトン、ベンジルメトキシケタール、２－クロロチオキサトーン、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ベンジル、カンファーキノン、３－ケトクマリン、アンスラキノン、α－ナフチル、アセナフセン、ｐ，ｐ’－ジメトキシベンジル、ｐ，ｐ’－ジクロロベンジルなどのカルボニル系化合物、及びに２－クロロチオキサンソン、２－メチルチオキサンソン、２，４－ジエチルチオキサンソン、２，４－ジメチルチオキサンソンなどのチオキサンソン系化合物、及びに２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド、ビス（２，６－ジクロロ－ベンゾイル）－４’－ｎ－プロピルフェニルフォスフィンオキサイド、ビス（２，６－ジメチルベンゾイル）ジフェニルフォスフィンオキサイドなどのアシルフォスフィンオキサイド類等を用いることが出来る。 Further, the curable composition of the present invention may be not only anaerobic curable but also curable by actinic light irradiation, or may have both the anaerobic curable property and the photocurable property. In order to impart photocurability, it is achieved by adding a photopolymerization initiator to the curable composition. Examples of the photopolymerization initiator include benzophenone, acetophenone, propiophenone, xanthol, and fluorin. , Benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-allyl Acetophenone, 4-chloro-4-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, bis (4-dimethylaminophen E) Ketone, benzylmethoxy ketal, 2-chlorothioxatone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyl, camphorquinone, 3-ketocoumarin, anthraquinone, α-naphthyl, acenaphthene, p, p ′ -Carbonyl compounds such as dimethoxybenzyl and p, p'-dichlorobenzyl, and 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, etc. Thioxanthone compounds, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,6-dichloro) -Benzoyl) -4'-n- Acylphosphine oxides such as propylphenylphosphine oxide and bis (2,6-dimethylbenzoyl) diphenylphosphine oxide can be used.
　以下、実施例により本発明の効果を詳細に説明するが、本発明はこれら実施例により限定されるものではない。 Hereinafter, the effects of the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
　実施例１～７並びに参考例１～６、比較例１～３に係る(メタ)アクリル硬化性組成物は、以下の成分を表１，２中に示す添加量比により調製した。なお表中に記載の数値は各成分の添加重量部である。 The (meth) acrylic curable compositions according to Examples 1 to 7, Reference Examples 1 to 6, and Comparative Examples 1 to 3 were prepared according to the addition ratios shown in Tables 1 and 2 below. In addition, the numerical value described in a table | surface is the addition weight part of each component.
　（ａ）成分として２－ヒドロキシエチルメタクリレート（日本触媒社製品、商品名ＨＥＭＡ）、（ｂ）成分及びその比較成分としてエチレンジアミン四酢酸（同仁化学研究所社製品、商品名４Ｈ）、エチレンジアミン四酢酸・２ナトリウム塩（同仁化学研究所社製品、商品名ＥＤＴＡ　２ＮＡ）、（ｃ）成分としてアニオン系界面活性剤であるドデシル硫酸ナトリウム（和光純薬工業社製品）、ステアリン酸ナトリウム（和光純薬工業社製品）、非イオン系界面活性剤であるポリエチレングリコールモノラウレート（花王社製品、商品名エマノーン１１１２）、硬化剤成分としてｏ－ベンゾイックスルフィミド（大和化成社製品、商品名サッカリンＢ－１）、クメンハイドロパーオキサイド（日本油脂社製品、パークミルＨ）、(メタ)アクリル硬化性組成物の硬化物特性を調整する目的で、（ａ）以外のアクリル酸エステルオリゴマーとして、ビスフェノールＡ型エポキシ樹脂のアクリル変性物（新中村化学工業社製品、商品名；ＮＫエステルＥＨ１０１０及びＮＫエステルＢＰＥ－８０Ｎ）、その他任意添加成分である光重合開始剤として１－ヒドロキシシクロヘキシルフェニルケトン（チバジャパン社製品、商品名Ｉｒｇａｃｕｒｅ１８４）、重合促進剤としてドデカンチオール（東京化成工業社製品）を用いた。 2-hydroxyethyl methacrylate (product of Nippon Shokubai Co., Ltd., trade name HEMA) as component (a), ethylenediaminetetraacetic acid (product of Dojindo Laboratories, trade name 4H), ethylenediaminetetraacetic acid Disodium salt (product of Dojin Chemical Laboratory, trade name EDTA 2NA), anionic surfactant sodium dodecyl sulfate (product of Wako Pure Chemical Industries) as component (c), sodium stearate (product of Wako Pure Chemical Industries) Product), polyethylene glycol monolaurate (a product of Kao Corporation, trade name Emanon 1112), a nonionic surfactant, and o-benzoxlufimide (a product of Daiwa Kasei Co., trade name: Saccharin B-1) as a curing agent component , Cumene hydroperoxide (Nippon Yushi Co., Ltd., Park Mill H), (Meth) Aqua As an acrylic ester oligomer other than (a), an acrylic modified product of bisphenol A type epoxy resin (product of Shin-Nakamura Chemical Co., Ltd., trade name; NK ester EH1010 and NK ester BPE-80N), 1-hydroxycyclohexyl phenyl ketone (product of Ciba Japan, trade name Irgacure 184) as a photopolymerization initiator which is an optional additional component, and dodecanethiol (product of Tokyo Chemical Industry Co., Ltd.) as a polymerization accelerator It was.
　調製した硬化性組成物試料は、試験板（材質；無電解Ｎｉメッキ鋼板、寸法；１．６×２５×１００ｍｍ）上にチップ試験片（材質；無電解Ｎｉメッキ製マグネット、寸法；１．３×２．３×４．１ｍｍ）を設置し、該チップ試験片の側面部からスポイトで浸透させ塗布した。この上部から高圧水銀灯により３０ｋＪ／ｍ２条件の紫外線を照射することで、側部からはみ出した硬化性組成物試料を硬化させた後、温度２５℃にし、２４時間養生硬化し、これを接着強度評価用試験片として評価を行った。該接着強度評価は、前記方法により作成した試験片を初期接着強度評価用試験片、及びこれをさらに温度８５℃、湿度８５％ＲＨの条件下で７２時間静置したものを耐湿強度評価用試験片とし、これをチップ強度試験器（シンポ社製；デジタルフォースゲージＦＧＣ－２００、押し出し速度６ｍｍ／ｍｉｎ）にてチップ接着強度の測定を行うことにより実施した。なお前記チップ接着強度は、チップ試験片が脱落した時の強度をチップ試験片の接着面積で除した値により算出した。 The prepared curable composition sample was prepared on a test plate (material: electroless Ni-plated steel plate, dimensions: 1.6 × 25 × 100 mm) on a chip test piece (material: electroless Ni-plated magnet, dimensions: 1.3). × 2.3 × 4.1 mm) was installed and applied by infiltrating with a dropper from the side surface of the chip test piece. By irradiating ultraviolet rays under the condition of 30 kJ / m 2 from the upper part with a high pressure mercury lamp, the curable composition sample protruding from the side part is cured, and then cured at a temperature of 25 ° C. for 24 hours. Evaluation was performed as a test piece for evaluation. The adhesive strength evaluation was carried out using the test piece prepared by the above method as an initial adhesive strength evaluation test piece, and a test piece for standing for 72 hours at a temperature of 85 ° C. and a humidity of 85% RH for 72 hours. This was carried out by measuring the chip adhesive strength with a chip strength tester (manufactured by Shinpo Co., Ltd .; digital force gauge FGC-200, extrusion speed 6 mm / min). The chip adhesive strength was calculated from a value obtained by dividing the strength when the chip test piece was removed by the adhesion area of the chip test piece.
　また、各硬化性組成物を５ｇ試験管に取り、８０℃の恒温槽内で静置してゲル化するまでの時間で以て保存安定性の評価とした。２時間以内にゲル化しないものを○、３０分～１時間でゲル化したものを△、３０分以内にゲル化したものを×と判定して評価を行った。なお、各硬化性組成物のゲル化の状態は目視にて評価した。それぞれの評価結果は各表中に示す。 Further, each curable composition was taken in a 5 g test tube and allowed to stand in a constant temperature bath at 80 ° C., and the time until gelation was evaluated as storage stability. Evaluation was made by judging that the gel did not gel within 2 hours, Δ when gelled within 30 minutes to 1 hour, and x when gelled within 30 minutes. The gelation state of each curable composition was visually evaluated. Each evaluation result is shown in each table.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上表に記載した通り、本発明の構成（ａ）、（ｂ）、（ｃ）を含む硬化性組成物は、親水性（メタ）アクリルモノマーの添加量を低減させることなく、初期接着強度が良好で、かつ高温高湿環境下での強度低下が小さく（概ね接着強度値変化が半減程度、かつ耐湿試験後の接着強度値が４０Ｎ／ｍ以上）、さらに保存安定性にも優れた硬化性組成物である。他方で本発明の構成（ｂ）が金属塩となっているものにおいては、初期接着強度こそ良好であるものの、耐湿試験後の接着強度は著しく低減してしまい、また保存安定性も十分なものではなかった。（ｃ）を含まないものも前記（ｂ）が金属塩のものと同様の傾向であり、また各添加成分の添加量比を好適範囲外としたものにおいても、耐湿試験後の接着強度は著しく低減してしまい、いずれも４０Ｎ／ｍを下回ってしまうものとなった。さらに（ｃ）を非イオン系界面活性剤としたものは、保存安定性に難があるものであった。 As described in the above table, the curable composition containing the constitutions (a), (b) and (c) of the present invention has an initial adhesive strength without reducing the amount of hydrophilic (meth) acrylic monomer added. Curability with good strength and small decrease in strength under high temperature and high humidity environment (almost half change in bond strength value, bond strength value after humidity resistance test is 40 N / m or more), and excellent storage stability It is a composition. On the other hand, in the case where the constitution (b) of the present invention is a metal salt, the initial adhesive strength is good, but the adhesive strength after the moisture resistance test is remarkably reduced, and the storage stability is sufficient. It wasn't. In the case where (c) is not included, the above-mentioned tendency is similar to that in the case where (b) is a metal salt. All of them were reduced below 40 N / m. Furthermore, those using (c) as a nonionic surfactant have difficulty in storage stability.
　本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の範囲と精神を逸脱することなく、様々な修正や変更を加えることができることは、当業者にとって明らかである。
　本出願は、２０１０年１２月３日出願の日本特許出願２０１０－２６９８５５に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope and spirit of the invention.
This application is based on Japanese Patent Application No. 2010-269855 filed on Dec. 3, 2010, the contents of which are incorporated herein by reference.
　本発明の(メタ)アクリル硬化性組成物は、耐湿強度が良好な硬化物を与えるものであり、特に耐湿強度が求められる各種部材の接着、シール、ポッティング等の用途において好適に使用することが出来るものである。 The (meth) acrylic curable composition of the present invention gives a cured product having good moisture resistance, and can be suitably used in applications such as adhesion, sealing, and potting of various members that are particularly required to have moisture resistance. It is possible.

Claims (6)

  1. 　（ａ）分子中に１つ以上の水酸基を含有する（メタ）アクリル酸エステルモノマーまたはオリゴマー、（ｂ）金属塩でないキレート化剤化合物、（ｃ）界面活性剤を含む（メタ）アクリル系硬化性組成物。 (A) (meth) acrylic acid ester monomer or oligomer containing one or more hydroxyl groups in the molecule, (b) a chelating agent compound that is not a metal salt, (c) a (meth) acrylic curable composition containing a surfactant Composition.
  2. 　前記（ａ）成分１００重量部に対して、前記（ｂ）成分が０．０５～５重量部、前記（ｃ）成分が０．００１～３重量部である、請求項１に記載の（メタ）アクリル系硬化性組成物。 The (meta) component according to claim 1, wherein the component (b) is 0.05 to 5 parts by weight and the component (c) is 0.001 to 3 parts by weight with respect to 100 parts by weight of the component (a). ) Acrylic curable composition.
  3. 　前記（ｂ）成分が金属塩でないエチレンジアミン誘導体を含む、請求項１または２に記載の（メタ）アクリル系硬化性組成物。 The (meth) acrylic curable composition according to claim 1 or 2, wherein the component (b) contains an ethylenediamine derivative that is not a metal salt.
  4. 　前記（ｃ）成分がアニオン系界面活性剤を含む、請求項１～３のいずれか１項に記載の（メタ）アクリル系硬化性組成物。 The (meth) acrylic curable composition according to any one of claims 1 to 3, wherein the component (c) contains an anionic surfactant.
  5. 　前記（ｃ）成分が炭素数１０以上の直鎖アルキル基を有するアニオン系界面活性剤を含む、請求項４に記載の（メタ）アクリル系硬化性組成物。 The (meth) acrylic curable composition according to claim 4, wherein the component (c) includes an anionic surfactant having a linear alkyl group having 10 or more carbon atoms.
  6. 　前記（メタ）アクリル系硬化性組成物が嫌気硬化性を有する、請求項１～５のいずれか１項に記載の（メタ）アクリル硬化性組成物。 The (meth) acrylic curable composition according to any one of claims 1 to 5, wherein the (meth) acrylic curable composition has anaerobic curability.
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