JP2013136652A - 2-cyanoacrylate adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a 2-cyanoacrylate adhesive composition having a satisfactory performance in an adherend in a high temperature state.SOLUTION: The 2-cyanoacrylate adhesive composition contains, with respect to (A) 100 pts.wt. of 2-cyanoacrylate, (B) 1 to 10 pts.wt. of a polymethacrylate ester having a weight-average molecular weight of 300,000 to 800,000, (C) 0.005 to 1 pt.wt. of at least one selected from polyhydric alcohols, polyalkylene oxide derivatives, calixarene compounds and crown ethers, and (D) 0.005 to 0.2 pt.wt. of a compound represented by formula (1) wherein Ris a methyl group or an ethyl group; and n is an integer of 2 or 3, and m is an integer of 0 to 3, wherein the viscosity at 25°C of the adhesive composition is 30 to 300 mPa-s.

Description

The present invention relates to a 2-cyanoacrylate adhesive composition that favorably adheres an adherend in a high temperature state.

The cyanoacrylate adhesive composition mainly composed of 2-cyanoacrylate is polymerized and cured in a short time by anion species such as the surface of the adherend and moisture in the air due to its high anionic polymerizability, thereby bonding various materials. As an instant adhesive, it is widely used in various industries such as electronics, electricity and automobiles, leisure field and general households. However, these 2-cyanoacrylate adhesive compositions are usually used at room temperature, and adhere to an adherend in a high temperature state exceeding 100 ° C., for example, by volatilizing the adhesive when applied. Not suitable for.

On the other hand, when trying to bond a rubber member with a cyanoacrylate adhesive immediately after molding in an automobile parts factory or the like, the surface temperature of the rubber member may exceed 100 ° C. It turned out to be difficult to bond with the agent. Although cyanoacrylate compositions with improved heat resistance (for example, Patent Document 1) have been known so far, all have heat resistance after a curing reaction, and the adherend is heated to a high temperature during bonding (before curing). In this case, a cyanoacrylate composition that exhibits satisfactory adhesion performance has not been known.

JP 2010-285562 A

The object of the present invention is to provide a 2-cyanoacrylate-based adhesive composition that has these problems that conventional 2-cyanoacrylate-based adhesives have, that is, satisfactory adhesive performance even on a high-temperature adherend. It is to provide.

In view of the above problems, the inventors have completed the present invention by adding a specific additive at a specific ratio to 2-cyanoacrylate and further adjusting the viscosity of the adhesive composition to a constant value. I let you.

That is, the present invention provides the following (1) to (2).
(1) (A) 1 to 10 parts by weight of a copolymer of polymethacrylic acid ester and / or polyacrylic acid ester having a weight average molecular weight of 300 to 800,000 with respect to 100 parts by weight of 2-cyanoacrylate , (C) 0.005 to 1 part by weight of at least one selected from the group selected from polyhydric alcohols, polyalkylene oxide derivatives, calixarene compounds and crown ethers, and (D) Formula (1)

（式中Ｒ１はメチル基またはエチル基、ｎ＝２〜３、ｍ＝０〜３の整数を表す。）
で表される化合物を０．００５〜０．２重量部含むことを特徴とする２―シアノアクリレート系接着剤組成物であって、前記接着剤組成物の２５℃における粘度が３０〜３００mPa・sであることを特徴とする２−シアノアクリレート系接着剤組成物。
（２）上記の２−シアノアクリレート系接着剤組成物を用いて、表面温度が１００〜２５０℃の被着体を接着することを特徴とする高温被着体の接着方法。

(In the formula, R1 represents an integer of methyl group or ethyl group, n = 2 to 3, m = 0 to 3)
The cyanoacrylate-based adhesive composition is characterized by containing 0.005 to 0.2 parts by weight of a compound represented by the formula: wherein the adhesive composition has a viscosity at 25 ° C. of 30 to 300 mPa · s. A 2-cyanoacrylate-based adhesive composition characterized by:
(2) A method for adhering a high-temperature adherend, characterized in that an adherend having a surface temperature of 100 to 250 ° C. is adhered using the above-described 2-cyanoacrylate adhesive composition.

In the present invention, a specific additive is added at a specific ratio with respect to 2-cyanoacrylate, and the viscosity of the adhesive composition is adjusted to a certain value, so that it can be satisfied even in a high-temperature adherend. The present invention provides a 2-cyanoacrylate adhesive composition having adhesive performance.

Hereinafter, the present invention will be described in detail.
As the (A) 2-cyanoacrylate in the present invention, 2-cyanoacrylate represented by the formula (2) is preferably used.

（式中Ｒは炭素数１〜１６の置換基を有していてもよい飽和または不飽和の脂肪族もしくは脂環族基又は芳香族基を示す。）

(In the formula, R represents a saturated or unsaturated aliphatic or alicyclic group or aromatic group which may have a substituent having 1 to 16 carbon atoms.)

Specific examples of (A) 2-cyanoacrylate in the present invention include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, octyl, neopentyl, cyclohexyl of 2-cyanoacrylic acid. , Ethylhexyl, dodecyl, allyl, methoxyethyl, ethoxyethyl, methoxypropyl, benzyl, phenyl, chloroethyl, tetrahydrofurfuryl and the like. Moreover, these 2-cyanoacrylates can be used 1 type or in mixture of 2 or more types. Of these, the most preferred is ethyl-2-cyanoacrylate.

In the present invention, (B) polymethacrylic acid ester and / or polyacrylic acid ester having a weight average molecular weight of 300 to 800,000, specifically, as the methacrylic acid ester, methyl methacrylate, ethyl methacrylate, methacrylic acid Acid-n-propyl, methacrylate-iso-propyl, methacrylate-n-butyl, methacrylate-iso-butyl, methacrylate-n-hexyl, methacrylate-n-heptyl, methacrylate-n-octyl, methacrylic acid 2-ethylhexyl, nonyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, ethoxyethyl methacrylate, ethoxypropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, Examples thereof include allyl methacrylate, tetrahydrofurfuryl methacrylate, and the like. As the acrylic ester, specifically, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, acrylic acid-iso-propyl, acrylic acid- n-butyl, acrylic acid-iso-butyl, acrylic acid-n-hexyl, acrylic acid-n-heptyl, acrylic acid-n-octyl, acrylic acid-2-ethylhexyl, nonyl acrylate, methoxyethyl acrylate, acrylic acid Examples include methoxypropyl, ethoxyethyl acrylate, ethoxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, and the like. Is a homopolymer of the above monomers such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate and the like, and a copolymer, terpolymer, tetramer, etc. comprising at least two different structures in the monomers The copolymer of these is mentioned. Moreover, what mixed 2 or more types of copolymers, such as these copolymers, a terpolymer, and a tetramer, may be used. Among these, methyl methacrylate and methyl acrylate are preferable in order to exhibit the effects of the present invention.

The acrylic resin is added to adjust the viscosity of the adhesive composition of the present invention, and the addition amount varies depending on the acrylic resin to be added, but is usually 1 to 10 parts by weight. If the amount is less than 1 part by weight, a sufficient thickening effect cannot be obtained, and volatilization tends to occur with respect to the high-temperature adherend.
The acrylic resin having a weight average molecular weight of 300 to 800,000 is used. If the weight average molecular weight is less than 300,000, the blending amount increases, so that the curing rate is slowed. If it exceeds 800,000, the adhesive composition tends to be stringed and workability is deteriorated.

The viscosity range at 25 ° C. of the 2-cyanoacrylate adhesive composition in the present invention is 30 to 300 mPa · s, preferably 50 to 200 mPa · s. When the viscosity is less than 30 mPa · s, the adhesive composition tends to volatilize when applied to a high-temperature adherend, and when it exceeds 300 mPa · s, the curing rate of the adhesive composition becomes slow, which is not preferable.

Examples of the compound group (C) in the present invention include polyhydric alcohols, polyalkylene oxide derivatives, calixarene compounds, and crown ethers.

Specific examples of the polyhydric alcohols among the compound group (C) include, for example, ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, octamethylene glycol, polybutadiene diol, chloropropylene glycol, and 3-methylpentanediol. 2,2-diethylpropanediol, 2-ethyl-1,4-butanediol, glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 2,5-hexanediol, etc. These derivatives include alkyl, alkenyl, aryl, and aralkyl ethers or esters thereof, such as methyl cellosolve, ethyl cellosolve, ethylene glycol-n-butyl. Ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, propylene glycol methyl ether, tetramethylene glycol propyl ether, ethylene glycol diethyl ether, ethylene glycol acetate, ethylene glycol monolaurate, ethylene glycol monostearate, ethylene glycol distearate , Ethyl cellosolve stearate, glycerin monolaurate, glycerin monostearate, sorbitan monolaurate, cellosolve acrylate, cellosolve methacrylate, cellosolve crotonate and the like, but are not limited thereto.

Of the compound group (C), the polyalkylene oxide derivative is represented by the formula (3)

（式中、Ｘ４ およびＸ５ は、それぞれ独立に水素原子、ハロゲン原子、水酸基、置換若しくは非置換のアルキル、アルケニル、アリール又はアラルキル基を示す。ｐは１以上の整数、ｑは２以上の整数を示し、末端は環形成されていてもよい。）
なる繰り返し単位を有する化合物から選ばれた１種以上が挙げられる。

(Wherein X4 and X5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl, alkenyl, aryl or aralkyl group. P is an integer of 1 or more, and q is an integer of 2 or more. And the terminal may be ring-formed.)
1 type or more chosen from the compound which has the repeating unit which becomes.

Specific examples of the polyalkylene oxide derivative include, but are not limited to, the following compounds.

  Formaldehyde condensate, acetaldehyde condensate, trioxane polymer, polyalkylene glycol (for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (400, 1000, etc.), dipropylene glycol, polypropylene glycol, polytetramethylene oxide, poly-3 , 3-bis (chloromethyl) butylene oxide, poly 1,3-dioxolane, ethylene oxide-propylene oxide block polymer, etc.)

Polyalkylene glycol monoethers (eg methyl carbitol, carbitol, diethylene glycol-n-butyl ether, diethylene glycol phenyl ether, diethylene glycol benzyl ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, polyethylene glycol methyl ether, polyethylene glycol propyl ether Polyethylene glycol lauryl ether, polyethylene glycol stearyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol allyl ether, etc.), polyalkylene glycol diethers (eg, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, triethylene glycol) Lumpur dimethyl ether, tetraethylene glycol distearyl ether, polyethylene glycol dimethyl ether.)

Polyalkylene glycol monoesters (eg, diethylene glycol monopropionate, tetraethylene glycol monoacetate, tripropylene glycol mono-n-
Butyrate, polyethylene glycol monoacetate, polyethylene glycol monopropionate, polyethylene glycol laurate, polyethylene glycol sebacate, polyethylene glycol stearate, polyethylene glycol oleate, polyoxyethylene sorbitan monolaurate, diethylene glycol acrylate, diethylene glycol methacrylate, diethylene glycol croto Nate etc. ), Polyalkylene glycol diesters (eg, diethylene glycol diacetate, diethylene glycol dipropionate, diethylene glycol diacrylate, diethylene glycol distearate, diethylene glycol dimethacrylate, tetraethylene glycol dicrotonate, polyethylene glycol diacetate, polyethylene glycol di-n-butyrate) , Polyethylene glycol diurarate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dicrotonate, polyethylene glycol di-2-cyanoacrylate, polyethylene glycol stearyl-methacrylate, polyethylene glycol lauryl-acrylate, etc.).

Polyalkylene glycol monoether monoester (for example, methyl carbitol, carbitol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, tetraoxyethylene glycol monomethyl ether, polyoxyethylene glycol monolauryl Ethers, acrylates, methacrylates, crotonates, or 2-cyanoacrylates of glycol monoether compounds such as polyoxyethylene glycol monononylphenyl ether), other bisphenol A-polyalkylene oxide adducts, trimethylolpropane-polyalkylene oxide additions Glycerin-polyalkylene oxide Addendum, adipic acid - polyalkylene oxide adducts, trimellitic acid - polyalkylene oxide adducts and the like.

Of the compound group (C), specific examples of the crown ethers include 18-crown-6-ether, 15-crown-5-ether, dithio-15-crown ether, dibenzo-18-crown-6. Ether, dicyclohexyl-18-crown-6-ether, 1,2-naphth-15-crown-5-ether, 1,2-methylbenzo-18-crown-6-ether, etc. can also be used. An agent may use 1 type (s) or 2 or more types.

In the compound group (C), as the calixarene compound, a conventionally known calixarene compound can be used, and specifically, a calixarene compound represented by the formula (4) can be given.

（式中、Ｒ４は水素原子、更に置換されていてもよいアルキル基および置換されていてもよいアルコキシ基であり、Ｒ５は水素原子又は置換されていてもよいアルキル基である。また、ｙは４，６又は８である。）
このようなカリックスアレン化合物としては、具体的には、５,１１，１７，２３，２９，３５ −ヘキサ−ｔｅｒｔ−ブチル−３７，３８，３９，４０，４１，４２−ヘキサヒドロオキシカリックス〔６〕アレン、３７，３８，３９，４０，４１，４２−ヘキサヒドロオキシカリックス〔６〕アレン、或いは例えば特開昭６０−１７９４８２号公報に記載されている ３７，３８，３９，４０，４１，４２−ヘキサ−（２−エトキシ−２−オキソエトキシ）−カリックス〔６〕アレン、 ２５，２６，２７，２８−テトラ−（２−エトキシ−２−オキソエトキシ）−カリックス〔４〕アレン等が好ましく用いられる。

(Wherein R4 is a hydrogen atom, an optionally substituted alkyl group and an optionally substituted alkoxy group, R5 is a hydrogen atom or an optionally substituted alkyl group, and y is 4, 6 or 8.)
As such calixarene compounds, specifically, 5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41,42-hexahydroxycalix [6 ] Allene, 37,38,39,40,41,42-hexahydroxycalix [6] allene, or 37,38,39,40,41,42 described in, for example, JP-A-60-179482 -Hexa- (2-ethoxy-2-oxoethoxy) -calix [6] allene, 25,26,27,28-tetra- (2-ethoxy-2-oxoethoxy) -calix [4] allene and the like are preferably used It is done.

The compound group (C) enumerated above can be used by mixing two or more kinds as necessary. Among these, polyethylene glycol methacrylate, 18-crown-6 is used in order to exhibit the effects of the present invention. -Ether and 15-crown-5-ether are preferred.

The usage-amount of the compound group (C) in this invention is 0.005-1 weight part with respect to 100 weight part of 2-cyanoacrylate, Preferably it is 0.01-0.5 weight part. When the amount used is less than 0.005 parts by weight, a sufficient curing rate cannot be obtained, and when the amount used exceeds 1 part by weight, the storage stability tends to decrease.

(D) Formula (1) used in the present invention

（式中Ｒ１はメチル基またはエチル基、ｎ＝２〜３、ｍ＝０〜３の整数を表す。）
で表される化合物としては、具体的には、ピロガロール、１，２，４−トリヒドロキシベンゼン、１，２，５−トリヒドロキシベンゼン、５−メチルピロガロール、５−エチルピロガロールが挙げられる。これらの中でもピロガロールが好ましい。これらは必要により１種または２種以上の混合物として用いられる。

(In the formula, R1 represents an integer of methyl group or ethyl group, n = 2 to 3, m = 0 to 3)
Specific examples of the compound represented by the formula include pyrogallol, 1,2,4-trihydroxybenzene, 1,2,5-trihydroxybenzene, 5-methyl pyrogallol, and 5-ethyl pyrogallol. Of these, pyrogallol is preferred. These may be used as one or a mixture of two or more if necessary.

The amount of the compound represented by the chemical formula (1) in the present invention is 0.005-0.2 parts by weight, preferably 0.01-0. 1. When the addition amount is less than 0.005 parts by weight, fast curability and sufficient adhesive strength cannot be obtained, and when it is more than 0.2 parts by weight, the stability of the cyanoacrylate composition tends to decrease.

Further, the ethyl-2-cyanoacrylate adhesive composition of the present invention includes a stabilizer (for example, sulfur dioxide, methanesulfonic acid, p- Anionic polymerization inhibitors such as toluenesulfonic acid, boron trifluoride diethyl ether, HBF ₄ , trialkylborate, etc., radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and t-butylcatechol), plasticizers (dimethyl phthalate) , Diethyl phthalate, diisodecyl phthalate, tributyl acetyl citrate, etc.), colorant, fragrance, solvent, strength improver, aliphatic polycarboxylic acid, aromatic polycarboxylic acid, etc., depending on the purpose, 2-cyanoacrylate Appropriately added and used as long as the curing rate and stability of the monomer are not impaired Door can be.

Hereinafter, the present invention will be described in more detail with reference to examples.

〔Test method〕
[Method of measuring weight average molecular weight of polymethacrylic acid ester and / or polyacrylic acid ester copolymer]
The weight average molecular weight of the copolymer of polymethacrylic acid ester and / or polyacrylic acid ester was measured by the following method.
Measurement method: Gel permeation chromatography (GPC)
GPC device: Model “HLC-8220” manufactured by Tosoh Corporation
Column: “TSKgel SuperHZ-4000”, “TSKgel SuperHZ-2500”, and “TSKgel SuperHZ-1000” manufactured by Tosoh Corp. Connected mobile phase: Tetrahydrofuran Measurement temperature: 40 ° C.
In addition, the value of molecular weight is a polystyrene conversion value analyzed under the above conditions.
[Measurement method of viscosity]
It measured by the method according to JIS K-6833-6.3 "viscosity measuring method".
Unit (mPa · s)
[How to check for volatilization]
An EPDM test piece (2 × 25 × 50 mm) was heated in an oven at 200 ° C. for 1 hour, and a drop of adhesive was applied on the test piece immediately after removal, and the presence or absence of volatilization was visually confirmed.
Adhesive does not volatilize ... ○, adhesive volatilizes ... ×
[Measurement method of set time]
EPDM test pieces (2 × 25 × 50 mm) were heated in an oven at 200 ° C. for 1 hour, and the time until the test pieces immediately after being taken out were stuck together with an adhesive was measured.
Set time 1 second or less ○, Set time 2 seconds or less △, Set time 3 seconds or more ×
[Measurement method of tensile shear bond strength]
EPDM test pieces (2 × 25 × 50 mm) were heated in an oven at 200 ° C. for 1 hour, the test pieces immediately after being taken out were pasted together with an adhesive, and after curing at room temperature for 24 hours, the tensile shear bond strength was measured. .
Tensile speed: 200 mm / min

[Examples 1-7, Comparative Examples 1-7]
(A) A 2-cyanoacrylate adhesive composition was prepared by adding the components (B), (C), and (D) shown in the table to 100 parts by weight of 2-ethylcyanoacrylate, and the viscosity was measured. The presence or absence of volatilization was confirmed, the set time was measured, and the tensile shear bond strength was measured.

＊：材料破断

*: Material breakage

＊：材料破断
―：測定不可

*: Material rupture-: Cannot be measured

Claims (2)

(A) 1-10 parts by weight of (B) a copolymer of polymethacrylic acid ester and / or polyacrylic acid ester having a weight average molecular weight of 300-800,000 with respect to 100 parts by weight of 2-cyanoacrylate, (C ) 0.005 to 1 part by weight of at least one selected from the group selected from polyhydric alcohols, polyalkylene oxide derivatives, calixarene compounds and crown ethers, and (D)

(1)
(In the formula, R1 represents an integer of methyl group or ethyl group, n = 2 to 3, m = 0 to 3)
The cyanoacrylate-based adhesive composition is characterized by containing 0.005 to 0.2 parts by weight of a compound represented by the formula: wherein the adhesive composition has a viscosity at 25 ° C. of 30 to 300 mPa · s. A 2-cyanoacrylate-based adhesive composition characterized by: A method for adhering a high-temperature adherend comprising adhering an adherend having a surface temperature of 100 to 250 ° C., using the 2-cyanoacrylate adhesive composition according to claim 1.