JP2016011366A - Colored 2-cyanoacrylate-based adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a 2-cyanoacrylate-based adhesive composition capable of eliminating glossiness of an adhesive cured product while inhibiting white turbidness of the cured product itself in conducting adhesion or potting by using the 2-cyanoacrylate-based adhesive composition.SOLUTION: There is provided a colored 2-cyanoacrylate-based adhesive composition containing 2-cyano acrylic acid ester (a) and a coloring agent (b), where the coloring agent (b) is 0.0025 to 10 mass% when the 2-cyanoacrylate-based adhesive composition is 100 pts.mass, a brightness Lof a cured product where the 2-cyanoacrylate-based adhesive composition is deposited on an ethylene-propylene-diene rubber with a thickness of 100 μm is 20 or less and the brightness of the cured product with an incident angle 60° is 70 or less.

Description

  The present invention relates to a colored 2-cyanoacrylate adhesive composition containing 2-cyanoacrylate and a colorant.

The 2-cyanoacrylate adhesive composition is polymerized by a weak anion such as a slight amount of water adhering to the adherend surface due to the unique anionic polymerizability of the main component 2-cyanoacrylate. Various materials can be firmly bonded in a short time. Therefore, it is used as a so-called instantaneous adhesive in a wide range of fields such as industrial use, medical use and home use. For example, Patent Documents 1 and 2 describe 2-cyanoacrylate-based adhesive compositions containing various curing accelerators, which are difficult to obtain such as ethylene-propylene-diene rubber (hereinafter abbreviated as “EPDM”). It is disclosed that it is suitable for bonding adhesive materials.
On the other hand, it has also been proposed to color the 2-cyanoacrylate-based adhesive composition in order to identify the bonding location and the coating amount in the bonding process and improve productivity. For example, Patent Document 3 discloses a colored adhesive composition obtained by dissolving an oil-soluble dye washed with a specific acid. Patent Document 4 discloses a colored cyanoacrylate adhesive composition containing a vat dye that does not have a group exhibiting an anionic polymerization promoting effect. Patent Document 5 discloses a cyanoacrylate adhesive composition colored with an azo dye pigment not containing a metal atom. Further, Patent Document 6 discloses a 2-cyanoacrylate-based adhesive composition obtained by blending a synthetic resin expanded hollow microsphere insoluble in 2-cyanoacrylate and a colorant.

JP 2001-164199 A JP 2008-184527 A JP 55-98268 A JP-A-57-53577 JP-A-2-202567 Japanese Patent Laid-Open No. 4-63885

  However, in the 2-cyanoacrylate-based adhesive composition described in Patent Documents 1 and 2 above, although the adhesion rate to black rubber such as EPDM is improved, the adhesive cured product itself becomes clouded, and the adhesive portion There is a problem that it looks bad.

  Moreover, the colored 2-cyanoacrylate-based adhesive composition described in Patent Documents 3 to 5 is used for identifying an adhesive portion, and prevents whitening in a black adherend, The gloss of the cured adhesive cannot be erased. Furthermore, the 2-cyanoacrylate-based adhesive composition described in Patent Document 6 can obtain a black composition, but because it thickens by the addition of synthetic resin hollow microspheres, a low-viscosity product is required. It is unsuitable for doing. Moreover, when a hardening accelerator is added to this composition, sufficient whitening prevention may not be performed.

  The present invention has been made in view of the above problems, and when performing adhesion and potting using a 2-cyanoacrylate adhesive composition, the adhesive cured product itself is prevented from being clouded and cured. An object of the present invention is to provide a 2-cyanoacrylate-based adhesive composition that can erase the gloss of an object.

The inventors of the present invention are 2-cyanoacrylate adhesive compositions containing a predetermined amount of 2-cyanoacrylate and a colorant, and the lightness L ^* and glossiness of the cured product of the adhesive composition are in a specific range. In this case, it was found that the gloss of the cured adhesive was not clouded and the gloss could be erased, and the present invention was completed.

That is, the present invention is as follows.
1.2-cyanoacrylate-based adhesive composition containing a 2-cyanoacrylate (a) and a colorant (b), the 2-cyanoacrylate (a) being 100 parts by mass In this case, the colorant (b) is 0.0025 to 10% by mass, and the cured product obtained by forming the 2-cyanoacrylate adhesive composition on an ethylene-propylene-diene rubber with a thickness of 100 μm. A colored 2-cyanoacrylate adhesive composition characterized by having a lightness L ^* of 20 or less and the gloss of the cured product having an incident angle of 60 ° is 70 or less.
2. The colored 2-cyanoacrylate adhesive composition according to the above 1, wherein the colorant (b) is an oil-soluble black dye or a mixture of complementary oil-soluble dyes.
3. The coloring according to 1 or 2 above, wherein the curing accelerator (c) is further contained, and when the 2-cyanoacrylic acid ester (a) is 100 parts by mass, the curing accelerator (c) is 10 to 20000 ppm. 2-cyanoacrylate-based adhesive composition.
4). The colored accelerator according to 3 above, wherein the curing accelerator (c) is at least one selected from the group consisting of polyalkylene oxides, crown ethers, and an onium salt represented by the following general formula (1). 2-Cyanoacrylate adhesive composition.
C ⁺ A ^- (1)
[Wherein C ⁺ is an onium cation. A ⁻ is a sulfonate anion represented by R ¹ SO ₃ ^— (R ¹ is an alkyl group, a C 1-10 perfluoroalkyl group, a cycloalkyl group, a vinyl group, an aryl group, a perfluoroaryl group, an aralkyl group. , or a halogen atom), or (R ² SO _{2) 2} N ^- bis (substituted sulfonyl) imide anion represented by (R ² is an alkyl group, a perfluoroalkyl group having 1 to 10 carbon atoms, aryl Group or halogen atom). ]

The colored 2-cyanoacrylate adhesive composition according to the present invention contains a predetermined amount of 2-cyanoacrylate and a colorant, and has a lightness L ^* and a glossiness of a cured product formed on EPDM. It is a specific range. Therefore, there is an effect that the gloss of the adhesive cured product itself can be erased without being clouded. When the 2-cyanoacrylate adhesive composition of the present invention is used, even if it is a black adherend such as EPDM, the adhesion portion is not noticeable, and the appearance of the adherend is not impaired.
Even when the 2-cyanoacrylate-based adhesive composition further contains a curing accelerator, the adhesive cured product does not cause white turbidity or gloss, and the curability can be improved.

  An embodiment of the present invention will be described as follows, but the present invention is not limited to this.

The 2-cyanoacrylate adhesive composition according to the present invention (hereinafter also simply referred to as “adhesive composition”) contains a predetermined amount of 2-cyanoacrylate (a) and a colorant (b), and EPDM. Further, the lightness L ^* and glossiness of the cured product formed into a film with a thickness of 100 μm are in a specific range. Each component of the adhesive composition according to the present invention will be specifically described.

  As the “2-cyanoacrylate ester (a)”, 2-cyanoacrylate esters generally used in 2-cyanoacrylate adhesive compositions can be used without any particular limitation. Examples of the 2-cyanoacrylic acid ester include methyl, ethyl, chloroethyl, n-propyl, i-propyl, allyl, propargyl, n-butyl, i-butyl, n-pentyl, n-hexyl of 2-cyanoacrylic acid, Cyclohexyl, phenyl, tetrahydrofurfuryl, heptyl, 2-ethylhexyl, n-octyl, 2-octyl, n-nonyl, oxononyl, n-decyl, n-dodecyl, methoxyethyl, methoxypropyl, methoxyisopropyl, methoxybutyl, ethoxyethyl , Ethoxypropyl, ethoxyisopropyl, propoxymethyl, propoxyethyl, isopropoxyethyl, propoxypropyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxyisopropyl, butoxybutyl, 2,2,2-trif Oroechiru and esters, such as hexafluoro isopropyl. These 2-cyanoacrylic acid esters may be used alone or in combination of two or more. Of these 2-cyanoacrylic acid esters, 2-cyanoacrylic acid esters having an alkyl group having 3 or less carbon atoms are preferred because of their excellent adhesion to hard-to-adhere materials such as EPDM. More preferred is ethyl.

The 2-cyanoacrylate adhesive composition of the present invention contains “colorant (b)”. This colorant colors the adhesive composition, and any colorant can be used as long as the lightness L ^* and glossiness of the cured product fall within the scope of the present invention. The colorant (b) is preferably a dark dye or pigment, or a mixture of a dye or pigment having a complementary color relationship such as red and blue-green, purple and yellow-green, or yellow and blue-violet.

  Examples of pigments that can be used in the present invention include aluminum lake, monoazo, diazo, azine, anthraquinone, and inorganic pigments.

  Examples of the aluminum lake pigment include C.I. I. Acid Yellow 23, C.I. I. Acid Red 27, C.I. I. Food Red 14, and C.I. I. Food Blue 1 etc. are mentioned. Examples of monoazo pigments include C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 167, and C.I. I. Pigment Red 22 or the like. Examples of diazo pigments include C.I. I. Pigment Orange 13, C.I. I. Pigment Yellow 63, and C.I. I. Pigment Orange 16 and the like. Examples of azine pigments include C.I. I. Pigment Black 1 and the like, and examples of the anthraquinone pigment include C.I. I. Pigment Black 20, and C.I. I. Pigment Black 31 and the like. Here, “CI” is an abbreviation for Color Index Generic Name.

  Examples of the inorganic pigment include C.I. I. Pigment Black 7, C.I. I. Pigment Black 10, C.I. I. Pigment Black 11, C.I. I. Pigment Blue 27, and C.I. I. Pigment Blue 29 and the like.

  Examples of the dye that can be used in the present invention include monoazo dyes, diazo dyes, xanthene dyes, azine dyes, anthraquinone dyes, indigoid dyes, perinone dyes, methine dyes, and mixed dyes thereof. It is done.

  Examples of the monoazo dye include C.I. I. Solvent Yellow 14 and the like, and diazo dyes include C.I. I. Solvent Black 3 etc. are mentioned. Examples of xanthene dyes include C.I. I. Acid Red 50, and C.I. I. Acid Red 52 and the like, and examples of azine dyes include C.I. I. Solvent Black 5, and C.I. I. Solvent Black 7 etc. are mentioned.

  Examples of the anthraquinone dyes include C.I. I. Disperse Red 9, C.I. I. Disperse Red 60, C.I. I. Solvent Green 3, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 105, C.I. I. Solvent Violet 12, C.I. I. Solvent Violet 13, C.I. I. Vat Blue 18, C.I. I. Vat Blue 19, C.I. I. Vat Blue 20, C.I. I. Vat Green 1, C.I. I. Vat Violet 1, C.I. I. Vat Violet 9, C.I. I. Vat Orange 1, C.I. I. Vat Orange 3, and C.I. I. Vat Yellow 4 etc. are mentioned.

Examples of the indigoid dyes include C.I. I. Food Blue 1, C.I. I. Vat Red 1, C.I. I. Vat Red 1, C.I. I. Vat Violet 2, C.I. I. Vat Blue 1, C.I. I. Vat Blue 3, C.I. I. Vat Blue 5, and C.I. I. Vat Blue 14 etc. are mentioned.
These pigments and dyes may be used alone or in combination of two or more.

  Among the colorants, an oil-soluble black dye or a mixture of oil-soluble dyes having a complementary color relationship is preferable because the adhesion portion is not noticeable on the black adherend. Such dyes are commercially available. For example, Nippon Kayaku Co., Ltd. registered trademark “Kayaset”, Sanyo Dye Co., Ltd. registered trademark “SOPROTONER”, Orient Chemical Industry Co., Ltd. registered trademark “NUBIAN”, Dainichi Seika Kogyo Co., Ltd. registered trademark “Seika” "First", Hodogaya Chemicals registered trademark "AIZEN", Sumika Chemtex registered trademark "Spirit", etc. can be used.

  In order to improve the storage stability of the adhesive composition, the colorant is preferably washed with an organic acid in advance and then added to the 2-cyanoacrylic acid ester. As a cleaning method using an organic acid, for example, known methods described in Patent Document 3 (Japanese Patent Laid-Open No. 55-98268) and Patent Document 5 (Japanese Patent Laid-Open No. 2-202567) can be used.

  Content of a coloring agent (b) is 0.0025-10 mass% when 2-cyano acrylate ester (a) is 100 mass parts. The content of the colorant is preferably 0.005 to 5% by mass, and more preferably 0.005 to 3% by mass. When the content of the colorant is less than 0.0025% by mass, the coloring effect is insufficient and the effect of the present invention cannot be obtained. On the other hand, when content of a coloring agent exceeds 10 mass%, the storage stability of an adhesive composition may fall.

The 2-cyanoacrylate-based adhesive composition of the present invention has a lightness L ^* of a cured product formed to a thickness of 100 μm on EPDM of 20 or less and a glossiness of the cured product having an incident angle of 60 °. Is 70 or less.

When the lightness L ^{* of the} cured product exceeds 20, the cured adhesive product itself may become cloudy and impair the appearance of the adherend. The brightness L ^{* of the} cured product can be adjusted by the type and addition amount of the colorant and the type and addition amount of the curing accelerator described later.

The gloss of the cured product having an incident angle of 60 ° is preferably 60 or less, and more preferably 40 or less. When this glossiness exceeds 70, even if the cured product itself does not become cloudy, it has gloss (shine) and the bonded portion becomes noticeable. Glossiness can be adjusted by the kind and addition amount of a coloring agent, and the kind and addition amount of the hardening accelerator mentioned later similarly to the said lightness L ^* .

  The 2-cyanoacrylate adhesive composition of the present invention can further contain a curing accelerator (c). In general, when the adhesive composition contains a curing accelerator, it cures quickly and cures before the adhesive composition volatilizes, so that the whitening phenomenon around the adhesive portion can be suppressed. By containing a curing accelerator, white turbidity of the cured product tends to occur. Even when the adhesive composition of the present invention contains a curing accelerator, the turbidity of the cured product does not occur and the gloss can be erased.

Any curing accelerator can be used as long as it promotes anionic polymerization of the 2-cyanoacrylate adhesive composition. Examples of the curing accelerator include polyether compounds, calix allenes, thiacalix allenes, pyrogallol allenes, and onium salts, but the adhesive cured product has no white turbidity and the gloss can be erased. , Polyether compounds, and onium salts of the following general formula (1) are preferred.
C ⁺ A ^- (1)
[Wherein C ⁺ is an onium cation. A ⁻ is a sulfonate anion represented by R ¹ SO ₃ ^— (R ¹ is an alkyl group, a C 1-10 perfluoroalkyl group, a cycloalkyl group, a vinyl group, an aryl group, a perfluoroaryl group, an aralkyl group. , or a halogen atom), or (R ² SO _{2) 2} N ^- bis (substituted sulfonyl) imide anion represented by (R ² is an alkyl group, a perfluoroalkyl group having 1 to 10 carbon atoms, aryl Group or halogen atom). ]

  The polyether compound is a chain or cyclic compound having a plurality of ether partial structures as a skeleton. Examples of the polyether compound include polyalkylene oxides, crown ethers, silacrown ethers, and cyclodextrins. Among these, polyalkylene oxides, crown ethers, and silacrown ethers are preferable, and crown ethers are more preferable because they exhibit an excellent adhesion rate and are excellent in storage stability.

  The polyalkylene oxides are polyalkylene oxides and derivatives thereof, such as, for example, JP-B-60-37836, JP-B-1-43790, JP-A-63-128088, JP-A-3-167279, US Examples thereof include those disclosed in Japanese Patent No. 4386193 and US Pat. No. 4,424,327. Specifically, (1) polyalkylene oxides such as diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol, (2) polyethylene glycol monoalkyl ester, polyethylene glycol dialkyl ester, polypropylene glycol dialkyl ester, diethylene glycol monoalkyl ether, diethylene glycol And polyalkylene oxide derivatives such as dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

  Examples of crown ethers include those disclosed in Japanese Patent Publication No. 55-2238, Japanese Patent Laid-Open No. 3-167279, and the like. Specifically, 12-crown-4, 15-crown-5, 18-crown-6, benzo-12-crown-4, benzo-15-crown-5, benzo-18-crown-6, dibenzo-18 -Crown-6, dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-24 -Crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphth-15-crown-5, 3,4,5-naphthyl-16-crown-5 1,2-methylbenzo-18-crown-6, 1,2-tert-butyl-18-crown-6, 1,2-vinylbenzo-15-crown Etc. The. Examples of silacrown ethers include those disclosed in JP-A-60-168775. Specific examples include dimethylsila-11-crown-4, dimethylsila-14-crown-5, and dimethylsila-17-crown-6.

  The cation of the onium salt includes a quaternary ammonium cation, a quaternary phosphonium cation, an imidazolium cation, a pyridinium cation represented by the following general formula (2), and a tertiary sulfonium cation represented by the general formula (3). Is mentioned.

［式中、Ｒ³〜Ｒ⁶は、それぞれ独立して、炭素数１〜２０の非置換若しくは置換のアルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基又はアルキニル基である；あるいは、Ｒ³〜Ｒ⁶の一部又は全部が、Ａで示される原子と一緒になって、非置換又は置換の３〜１０員環（ここで、該環はＯ、Ｓ等のヘテロ原子を含んでいてもよい）を形成し、該環の形成に関与していないＲ³〜Ｒ⁶は、前記で定義したとおりである；そしてＡは、窒素原子又はリン原子を表す。なお、上記置換のアルキル基の具体例としては、例えば、アルコキシ基及びアルカノイル基が挙げられる。また、Ｒ³〜Ｒ⁶の一部が環を形成する場合、通常、Ｒ³〜Ｒ⁶のうちの２又は３つが環を形成する。Ｒ³〜Ｒ⁶の２つが環を形成する式（２）化合物の具体例としては、ピペリジニウムカチオン、モルホリニウムカチオン、ピロリジニウムカチオンなどが挙げられる。］

[Wherein, R ^{3 to} R ⁶ are each independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or an alkynyl group; A part or all of R ^{3 to} R ⁶ together with the atom represented by A is an unsubstituted or substituted 3- to 10-membered ring (wherein the ring contains a heteroatom such as O and S). And R ^{3 to} R ⁶ that are not involved in the formation of the ring are as defined above; and A represents a nitrogen atom or a phosphorus atom. Specific examples of the substituted alkyl group include an alkoxy group and an alkanoyl group. When a part of R ^{3 to} R ⁶ forms a ring, usually two or three of R ^{3 to} R ⁶ form a ring. Specific examples of the compound of the formula (2) in which two of R ^{3 to} R ⁶ form a ring include a piperidinium cation, a morpholinium cation, and a pyrrolidinium cation. ]

［式中、Ｒ⁷〜Ｒ⁹は、それぞれ独立して、炭素数１〜２０の非置換若しくは置換のアルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基又はアルキニル基である；あるいは、Ｒ⁷〜Ｒ⁹の一部又は全部が、硫黄原子と一緒になって、非置換又は置換の３〜１０員環（ここで、該環はＯ、Ｓ等のヘテロ原子を含んでいてもよい）を形成し、該環の形成に関与していないＲ⁷〜Ｒ⁹は、前記で定義したとおりである。なお、上記置換のアルキル基の具体例 としては、例えば、アルコキシ基及びアルカノイル基が挙げられる。］

[Wherein R ^{7 to} R ⁹ are each independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or an alkynyl group; A part or all of R ^{7 to} R ⁹ together with a sulfur atom is an unsubstituted or substituted 3- to 10-membered ring (wherein the ring may contain a heteroatom such as O and S). R ^{7 to} R ⁹ which are not involved in the formation of the ring are as defined above. Specific examples of the substituted alkyl group include an alkoxy group and an alkanoyl group. ]

  Specific examples of the quaternary ammonium cation include tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, tetra-n-butylammonium, trimethyl-n-propylammonium, isopropyltrimethylammonium, n- Butyltrimethylammonium, isobutyltrimethylammonium, t-butyltrimethylammonium, n-hexyltrimethylammonium, dimethyldi-n-propylammonium, diisopropyldimethylammonium, isopropyldimethyl-n-propylammonium, methyltri-n-propylammonium, triisopropylmethylammonium Isopropylmethyldi-n-propylammo , Methyl-n-propyldiisopropylammonium, triethyl-n-propylammonium, triethylisopropylammonium, n-butyltriethylammonium, triethylisobutylammonium, t-butyltriethylammonium, di-n-butyldimethylammonium, diisobutyldimethylammonium, di -T-butyldimethylammonium, n-butylethyldimethylammonium, isobutylethyldimethylammonium, t-butylethyldimethylammonium, n-butylisobutyldimethylammonium, n-butyl-t-butyldimethylammonium, t-butylisobutyldimethylammonium, Diethyldi-n-propylammonium, diethyldiisopropylammonium, diethyliso Propyl-n-propylammonium, ethyltri-n-propylammonium, ethyltriisopropylammonium, ethylisopropyldi-n-propylammonium, ethyldiisopropyl-n-propylammonium, diethylmethyl-n-propylammonium, ethyldimethyl-n-propyl Ammonium, ethylmethyldi-n-propylammonium, diethylisopropylmethylammonium, ethylisopropyldimethylammonium, ethyldiisopropylmethylammonium, ethylmethyl-n-propylisopropylammonium, tetra-n-propylammonium, tetraisopropylammonium, triisopropyl-n-propyl Ammonium, diisopropyldi-n-propylammonium, isopropyl Rutri-n-propylammonium, butyltrimethylammonium, trimethylpentylammonium, hexyltrimethylammonium, heptyltrimethylammonium, trimethyloctylammonium, trimethylnonylammonium, decyltrimethylammonium, trimethylundecylammonium, dodecyltrimethylammonium, didecyldimethylammonium, di Lauryldimethylammonium, dimethyldistyrylammonium, dimethyldioctadecylammonium, dimethyldioctylammonium, dimethyldipalmitylammonium, ethylhexadecyldimethylammonium, hexyldimethyloctylammonium, dodecyl (ferrocenylmethyl) dimethylammonium, N-methylhomaroto Bini Tetraalkylammonium cations such as benzyltrimethylammonium, benzyltributylammonium, benzyldodecyldimethylammonium and the like; aromatic-substituted ammonium cations such as trimethylphenylammonium and tetraphenylammonium; pyrrolidinium (for example, 1 , 1-dimethylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium, 1,1-diethylpyrrolidinium, 1,1-tetramethylenepyrrolidinium, 1-butyl-1-methylpyrrolidinium), Piperidinium (eg, 1,1-dimethylpiperidinium, 1-ethyl-1-methylpiperidinium, 1,1-diethylpiperidinium, 1-butyl-1-methylpiperidinium), morpholinium (E.g., 1,1-dimethyl morpholinium, 1-ethyl-1-methyl-morpholinium, 1,1-diethyl morpholinium) aliphatic cyclic ammonium cation or the like, and the like.

  Specific examples of the quaternary phosphonium cation include cations such as tetramethylphosphonium, triethylmethylphosphonium, and tetraethylphosphonium.

  Specific examples of the imidazolium cation include 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1 -Methyl-3-n-octylimidazolium, 1-hexyl-3-methylimidazolium, 1,3-diethylimidazolium, 1,2-diethyl-3-methylimidazolium, 1,3-diethyl-2-methyl Imidazolium, 1,2-dimethyl-3-n-propylimidazolium, 1-n-butyl-3-methylimidazolium, 1-n-butyl-2,3-methylimidazolium, 1,2,4-trimethyl -3-n-propylimidazolium, 1,2,3,4-tetramethylimidazolium, 1,2,3,4,5-pentamethyl Midazolium, 2-ethyl-1,3-dimethylimidazolium, 1,3-dimethyl-2-n-propylimidazolium, 1,3-dimethyl-2-n-pentylimidazolium, 2-n-heptyl-1, 3-dimethyl-imidazolium, 1,3,4-trimethylimidazolium, 2-ethyl-1,3,4-trimethylimidazolium, 1,3-dimethylbenzimidazolium, 3-methyl-1-phenylimidazolium, 1-benzyl-3-methylimidazolium, 2,3-dimethyl-1-phenylimidazolium, 1-benzyl-2,3-dimethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 2-benzyl- 1,3-dimethylimidazolium, 1,3-dimethyl-2-n-undecylimidazolium, 1,3-dimethyl It includes cations such as Le -2-n-heptadecyl imidazolium.

  Examples of the pyridinium cation include cations such as 1-methylpyridinium, 1-ethylpyridinium, 1-n-propylpyridinium, 1-isopropylpyridinium, 1-n-butylpyridinium, 1-n-butyl-3-methylpyridinium .

  Specific examples of the tertiary sulfonium cation represented by the general formula (3) include cations such as trimethylsulfonium, triethylsulfonium, tripropylsulfonium, and triphenylsulfonium.

  Among the above cations, quaternary ammonium cations, imidazolium cations, or pyridinium cations from the standpoints of excellent solubility in 2-cyanoacrylic acid esters and a balance between curing acceleration ability and storage stability of the adhesive composition Is more preferable.

Next, the anion of the onium salt is a sulfonate anion represented by R ¹ SO ₃ ^— (R ¹ is an alkyl group, a C 1-10 perfluoroalkyl group, a cycloalkyl group, a vinyl group, an aryl group, A perfluoroaryl group, an aralkyl group, or a halogen atom), or a bis (substituted sulfonyl) imide anion represented by (R ² SO ₂ ) ₂ N ^— (R ² is an alkyl group having 1 to 10 carbon atoms) A perfluoroalkyl group, an aryl group, or a halogen atom. The number of carbon atoms in the alkyl group of R ¹ and R ² are preferably 1 to 15.

Specific examples of the sulfonic acid anion represented by R ¹ SO ₃ ^— include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, dodecanesulfonic acid, and vinylsulfonic acid. And anions such as benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, 10-camphorsulfonic acid, pentafluorobenzenesulfonic acid, fluorinated sulfonic acid, chlorosulfonic acid, and brominated sulfonic acid. Examples of the C1-C10 perfluoroalkylsulfonic acid anion include anions of trifluoromethanesulfonic acid, hexafluoroethanesulfonic acid, perfluorooctanesulfonic acid, and the like.

Specific examples of the bis (substituted sulfonyl) imide anion represented by (R ² SO ₂ ) ₂ N ⁻ include bis (methanesulfonyl) imide anion, bis (ethanesulfonyl) imide anion, and bis (propanesulfonyl). Examples thereof include an imide anion, a bis (trifluoromethanesulfonyl) imide anion, a bis (pentafluoroethanesulfonyl) imide anion, a bis (heptafluoropropanesulfonyl) imide anion, and a bis (nonafluorobutanesulfonyl) imide anion.

  Among these anions, a perfluoroalkane has an excellent adhesion rate to thermoplastic elastomers with low polarity, is excellent in storage stability of the adhesive composition, and has a good appearance of the cured product. Sulfonate anions and bis (perfluoroalkanesulfonyl) imide anions are preferred. The number of carbon atoms of the perfluoroalkyl group in the anion is preferably 1 to 8 from the viewpoint of the solubility of the corresponding onium salt in 2-cyanoacrylate and the appearance of the cured adhesive product. It is more preferable that

The onium salt used in the present invention is not particularly limited as long as it is a combination of the above cation and anion. Specific examples of onium salts include tetra-n-butylammonium methanesulfonate, methyltri-n-octylammonium methanesulfonate, 1-ethyl-3-methylimidazolium methanesulfonate, and 1-ethyl-2,3-dimethylimidazolium methane. Sulfonate, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-2,3-dimethylimidazolium methanesulfonate, 1-ethyl-1-methylpiperidinium methanesulfonate, 1-butyl-1-methylpiperidi Nium methanesulfonate, 1-ethyl-1-methylpyrrolidinium methanesulfonate, 1-butyl-1-methylpyrrolidinium methanesulfonate, 1-methyl-1-propylpyrrolidinium methanesulfonate, 1-ethylpyridine Nium methanesulfonate, 1-ethyl-3-methylpyridinium methanesulfonate, 1-butyl-3-methylpyridinium methanesulfonate, tetraethylphosphonium methanesulfonate, tetraethylphosphonium methanesulfonate, tetraethylammonium trifluoromethanesulfonate, tetra-n-butylammonium trifluoromethane Sulfonate, methyltri-n-octylammonium trifluoromethanesulfonate, amyltriethylammonium trifluoromethanesulfonate, cyclohexyltrimethylammonium trifluoromethanesulfonate, benzyltributylammonium trifluoromethanesulfonate, benzyldodecyldimethylammonium trifluoromethanesulfonate Didecyldimethylammonium trifluoromethanesulfonate, dilauryldimethylammonium trifluoromethanesulfonate, hexyldimethyloctylammonium trifluoromethanesulfonate, dodecyl (ferrocenylmethyl) dimethylammonium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-methyl-3-n -Octylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium Mutrifluoromethanesulfonate, 2-ethyl-1,3-dimethylimidazolium trifluoromethanesulfonate, 1,3-dimethyl-2-n-propylimidazolium trifluoromethanesulfonate, 1,3-dimethyl-2-n-pentylimidazolium Trifluoromethanesulfonate, 1,3-dimethyl-2-n-heptylimidazolium trifluoromethanesulfonate, 1-ethyl-1-methylpiperidinium trifluoromethanesulfonate, 1-butyl-1-methylpiperidinium trifluoromethanesulfonate, 1 -Ethyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-methyl-1-propylpyrrolidinium trifluoro L-methanesulfonate, 1-ethylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-4-methylpyridinium trifluoromethanesulfonate, 1-butyl Pyridinium trifluoromethanesulfonate, 1-butyl-4-methylpyridinium trifluoromethanesulfonate, tetramethylphosphonium trifluoromethanesulfonate, triethylmethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoromethanesulfonate, tetra-n-butylammonium p-toluenesulfonate, methyltri- n-octylammonium p-to Ensulfonate, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-ethyl-2,3-dimethylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium p-toluenesulfonate, 1-butyl -2,3-dimethylimidazolium p-toluenesulfonate, 1-ethyl-1-methylpiperidinium p-toluenesulfonate, 1-butyl-1-methylpiperidinium p-toluenesulfonate, 1-ethyl-1-methyl Pyrrolidinium p-toluenesulfonate, 1-butyl-1-methylpyrrolidinium p-toluenesulfonate, 1-methyl-1-propylpyrrolidinium p-toluenesulfonate, 1-ethylpyridinium p-toluenesulfonate, 1-ethyl -3-methylpyridi Nium p-toluenesulfonate, 1-butyl-3-methylpyridinium p-toluenesulfonate, tetraethylphosphonium p-toluenesulfonate, tetraethylammonium bis (trifluoromethanesulfonyl) imide, tetra-n-butylammonium bis (trifluoromethanesulfonyl) imide, Methyltri-n-octylammonium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-2,3-dimethylimidazolium bis (trifluoro Romethanesulfonyl) imide, 1-ethyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-methylpyrrolidi Nitrobis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethylpyridinium bis (Trifluoromethanesulfonyl) imide, 1-ethyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, and triethyl Sulfonium bis (trifluoromethanesulfonyl) imide, and the like.
These hardening accelerators may use only 1 type and may use 2 or more types together.

  The content of the curing accelerator (c) in the adhesive composition is preferably 10 to 20000 ppm, more preferably 25 to 15000 ppm with respect to 100 parts by mass of the 2-cyanoacrylate ester (a). Preferably, it is 50-10000 ppm. When the content is less than 10 ppm, the effect as a curing accelerator is not sufficiently exhibited. On the other hand, when it exceeds 20000 ppm, the storage stability of the adhesive composition may deteriorate.

  In the adhesive composition of the present invention, in addition to the above curing accelerator, a stabilizer, a plasticizer, and a thickener that are conventionally used by blending with an adhesive composition containing 2-cyanoacrylate ester. Depending on the purpose, particles, colorants, fragrances, solvents, strength improvers, etc. can be blended in appropriate amounts within a range that does not impair the curability, adhesive strength, and appearance of the cured product. .

Stabilizers include (1) aliphatic sulfonic acids such as sulfur dioxide and methanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, trifluoride such as boron trifluoride methanol and boron trifluoride diethyl ether. Examples include anionic polymerization inhibitors such as boron complexes, HBF ₄ , and trialkyl borates, and (2) radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, catechol, and pyrogallol. These stabilizers may be used alone or in combination of two or more.

  Plasticizers include triethyl acetyl citrate, tributyl acetyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, phthalate Diheptyl acid, dioctyl phthalate, bis (2-ethylhexyl) phthalate, diisononyl phthalate, diisotridecyl phthalate, dipentadecyl phthalate, dioctyl terephthalate, diisononyl isophthalate, decyl toluate, bis (2-ethylhexyl) camphorate, 2 -Ethylhexyl cyclohexyl carboxylate, diisobutyl fumarate, diisobutyl maleate, triglyceride caproate, 2-ethylhexyl benzoate, dipropylene glycol di Nzoeto, and the like. Among these, tributyl acetyl citrate, dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate, and dipropylene glycol have good compatibility with 2-cyanoacrylate and high plasticization efficiency. Dibenzoate is preferred. These plasticizers may be used alone or in combination of two or more.

  Thickeners include polymethyl methacrylate, copolymers of methyl methacrylate and acrylic esters, copolymers of methyl methacrylate and other methacrylate esters, acrylic rubber, polyvinyl chloride, polystyrene, cellulose esters , Polyalkyl-2-cyanoacrylic acid ester and ethylene-vinyl acetate copolymer. These thickeners may be used alone or in combination of two or more.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, parts and% are based on mass unless otherwise specified.

1. Evaluation method (1) Brightness L ^{* of the} cured product
A colored adhesive composition was applied to an EPDM plate having a length of 50 mm, a width of 50 mm, and a thickness of 3 mm so as to have a thickness of 100 μm, and was left to cure in an environment of 23 ° C. and 60% RH for 3 days. . The lightness L ^* of this cured product was measured using a color difference meter according to JIS Z 8722 “Color measurement method—reflection and transmission object color”. The EPDM and color / color difference meter used are as follows.
Black EPDM plate: EPDM-5065 manufactured by Chukyo Rubber Co., Ltd.
Measuring device: CR-400 manufactured by Konica Minolta

(2) Glossiness of cured product A cured product of the adhesive composition was prepared on an EPDM plate in the same manner as (1) above, and the incident angle was 60 ° according to JIS Z 8741 “Specular Glossiness—Measurement Method”. Gloss was measured.
Measuring device: GM-268 manufactured by Konica Minolta

(3) Appearance of the cured product A few drops (about 20 mg) of the colored adhesive composition was dropped on the EPDM plate used in (1) above, and allowed to cure for 3 days in an environment of 23 ° C. and 60% RH. It was. The appearance of this cured product was visually observed.
<Evaluation criteria>
3: The cured product is not noticeable 2: The cured product is not noticeable 1: The cured product is cloudy or the cured product is glossy

2. Washing of colorant While stirring 50 g of a methanol solution containing 1% methanesulfonic acid, 5 g of a colorant was gradually added. After the addition was complete, the mixture was further stirred for 5 minutes and filtered off. This was dried under reduced pressure at 50 ° C. for 24 hours to obtain a washed colorant.
In addition, the commercial item was used for the coloring agent which does not wash | clean.

3.2 Production of 2-cyanoacrylate adhesive composition, Example 1
Oil-soluble black dye (Nippon Kayaku Co., Ltd., trade name “Kayaset Black A-N” in which 20 ppm of sulfur dioxide and 1000 ppm of hydroquinone are blended with 100 parts by mass of ethyl 2-cyanoacrylate, and perinone and anthraquinone are mixed therein. ”) 0.025% was added, and the mixture was stirred and mixed at room temperature (15 to 30 ° C.) for 60 minutes to produce an adhesive composition. Using the obtained adhesive composition, the lightness L ^* , glossiness and appearance of the cured product were evaluated. The results are shown in Table 3.

-Examples 2-12
It was manufactured in the same manner as in Example 1 except that the colorant and the curing accelerator to be blended in the adhesive composition were changed as shown in Table 1. The evaluation results are as shown in Table 3.

The following colorants and curing accelerators described in Tables 1 and 2 were used.
Kayset Black A-N, Kayase Black B, Kayase Black G, Kayase Red A-BR, Kayase Violet A-R: Kayset Yellow AG-Made by Mitsubishi Kagaku Co., Ltd. Product name SOPROTONER BLUE Carbon Black # 2600: Mitsubishi Chemical Corporation trade name 15-Crown-5: Nippon Soda Co., Ltd. trade name "Crown Ether O-15"
18-Crown-5: Reagent Methyltri (n-octyl) ammonium bis (trifluoromethanesulfonyl) imide manufactured by Kishida Chemical Co., Ltd. Reagent 1-ethyl-3-methylimidazolium trifluoromethanesulfonate manufactured by Tokyo Chemical Industry Co., Ltd. Manufactured reagent 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide: manufactured by Tokyo Chemical Industry Co., Ltd. Reagent methoxypolyethylene glycol # 400 methacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd. Trade name “M-90G”
4-tert-butylcalix [4] arene-O, O ′, O ″, O ′ ″-tetraethyl tetraacetate: trade name “CALIXB4-EA” manufactured by Sugai Chemical Industry Co., Ltd.

・ Comparative Examples 1-6
It was manufactured in the same manner as in Example 1 except that the colorant and the curing accelerator to be blended in the adhesive composition were changed as shown in Table 2. The evaluation results are as shown in Table 3.

According to the result of Table 3, since the adhesive composition of Examples 1-12 has the brightness L ^* and glossiness of hardened | cured material within the range of this invention, hardened | cured material does not have cloudiness and glossiness, and EPDM It was hardly noticeable above. On the other hand, the adhesive composition not containing the colorant of the present invention (Comparative Examples 1 to 3) has a lightness L ^* or glossiness of the cured product outside the range of the present invention. The cured product remained glossy. Further, even in an adhesive composition containing a colorant and a curing accelerator (Comparative Examples 4 to 6), when the lightness L ^* and glossiness of the cured product are not within the scope of the present invention, the cured product becomes cloudy, The cured product remained glossy.

  The colored 2-cyanoacrylate adhesive composition of the present invention can be used as a so-called instantaneous adhesive in a wide range of products such as industrial, medical and household use. In particular, it is useful for applications where the appearance of the bonded portion is required in addition to the conventionally required bonding speed, such as when bonding a black adherend such as EPDM.

Claims (4)

A 2-cyanoacrylate adhesive composition containing 2-cyanoacrylate (a) and a colorant (b),
When the 2-cyanoacrylic acid ester (a) is 100 parts by mass, the colorant (b) is 0.0025 to 10% by mass,
The cured product obtained by depositing the 2-cyanoacrylate adhesive composition on ethylene-propylene-diene rubber with a thickness of 100 μm has a lightness L ^* of 20 or less and an incident angle of 60 °. A colored 2-cyanoacrylate adhesive composition having a glossiness of 70 or less.   The colored 2-cyanoacrylate adhesive composition according to claim 1, wherein the colorant (b) is an oil-soluble black dye or a mixture of oil-soluble dyes having a complementary color relationship.   The curing accelerator (c) is 10 to 20000 ppm when it further contains a curing accelerator (c) and the 2-cyanoacrylic acid ester (a) is 100 parts by mass. Colored 2-cyanoacrylate adhesive composition. The coloring according to claim 3, wherein the curing accelerator (c) is at least one selected from the group consisting of polyalkylene oxides, crown ethers, and an onium salt represented by the following general formula (1). 2-cyanoacrylate-based adhesive composition.
C ⁺ A ^- (1)
[Wherein C ⁺ is an onium cation. A ⁻ is a sulfonate anion represented by R ¹ SO ₃ ^— (R ¹ is an alkyl group, a C 1-10 perfluoroalkyl group, a cycloalkyl group, a vinyl group, an aryl group, a perfluoroaryl group, an aralkyl group. , or a halogen atom), or (R ² SO _{2) 2} N ^- bis (substituted sulfonyl) imide anion represented by (R ² is an alkyl group, a perfluoroalkyl group having 1 to 10 carbon atoms, aryl Group or halogen atom). ]