JP5794236B2 - Curable composition - Google Patents

Description

  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.

  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.

  Anaerobic curable compositions have rapid curability at room temperature and have stable physical properties even after curing, so 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).

Japanese Unexamined Patent Publication No. 2003-119208

  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.

  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.

  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.

  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.

According to the present invention (meth) acrylic curable composition, (a) (b) component 0.05 to 5 parts by weight per 100 parts by weight of component, (c) component 0.001 parts by weight It is.

Further, in the (meth) acrylic curable composition, (b) component are those containing ethylenediamine derivatives not a metal salt, (c) component Ru der those containing anionic surfactants.
Further, in the embodiment of the present invention, the component (c) includes an anionic surfactant having a linear alkyl group having 10 or more carbon atoms, or the (meth) acrylic curable composition has anaerobic curability. It is particularly preferable to have one or more configurations.

  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.

  Various acrylic acid derivatives can be used as the (a) (meth) acrylic acid ester monomer or oligomer containing one or more hydroxyl groups in the molecule used in the present invention. 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.

  In addition to the component (a), other (meth) acrylic acid ester monomers or oligomers may be used. 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.

  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.

  As the chelating agent compound (b) 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 this 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.

  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.

  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.

  The (c) surfactant used in the present invention functions as a deterioration inhibiting component under 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.

  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.

  The amount of 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 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.

  In the present invention, any 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.

  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.

  As said (d) organic peroxide, what was used in order to harden an anaerobic curable composition conventionally 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. In addition, it is preferable that the addition amount of (d) organic peroxide is 0.1-10 weight part with respect to 100 weight part of said (a) component. 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-benzoxulfimide is so-called saccharin, and the preferred amount thereof is 0.1 to 25 parts by weight per 100 parts by weight of the component (a).

  Moreover, in this invention, it can use arbitrarily in the range which does not inhibit the effect | action of this invention also about components other than (a)-(e) shown above. 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.

  Furthermore, the curable composition of the present invention may be not only anaerobically 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-dimethylaminophene) 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, p, p'-dichlorobenzyl, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, etc. Thioxanthone compounds, and 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.

  Hereinafter, the effects of the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

  The (meth) acrylic curable compositions according to Examples 1 to 7 and Reference Examples 1 to 6 and Comparative Examples 1 to 3 were prepared according to the addition amount 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) 2-hydroxyethyl methacrylate (product of Nippon Shokubai Co., Ltd., trade name HEMA) as component (a), ethylenediaminetetraacetic acid (product of Dojin Chemical Laboratory, trade name 4H), ethylenediaminetetraacetic acid Disodium salt (product of Dojindo Laboratories, 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 which is a nonionic surfactant (product of Kao Corporation, trade name Emanon 1112), and o-benzoixsulfimide (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) acrylic For the purpose of adjusting the properties of the cured product of the curable composition, 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) was used as a photopolymerization initiator which is an optional additional component, and dodecanethiol (product of Tokyo Chemical Industry Co., Ltd.) was used as a polymerization accelerator. .

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 an 80 ° C. thermostat and gel until gelation, and the storage stability was evaluated. 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.

  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.

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.

  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 (3)

(A) containing one or more hydroxyl groups in the molecule (meth) per 100 parts by weight of acrylic acid ester monomer or oligomer, 0.05 to 5 weight chelating compound containing ethylenediamine derivative is not a (b) a metal salt parts, and (c) an anionic surfactant surfactant comprises an active agent containing 0.001 parts by weight (meth) acrylic curable composition. The (meth) acrylic curable composition according to claim 1 , wherein the component (c) includes an anionic surfactant having a linear alkyl group having 10 or more carbon atoms. The (meth) acrylic curable composition having anaerobic curable claim 1 or according to 2 (meth) acrylic curable composition.