JP5649191B2 - 2-Cyanoacrylate adhesive composition - Google Patents

Description

The present invention is an invention relating to a 2-cyanoacrylate adhesive composition generally known as an instantaneous adhesive.

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, the cyanoacrylate adhesive has the advantage that it is a single liquid and has a high curing speed at room temperature, but there is a problem of thickening during storage due to moisture in the air. Since cyanoacrylate adhesives are often used in liquid drops, they are often squeezed and are often filled into inexpensive small containers. Generally, containers such as polyethylene containers and aluminum tubes are used. It is taken. (For example, Patent Document 1 and Patent Document 2)

On the other hand, when surface bonding is usually performed using a brush or the like with an adhesive other than a cyanoacrylate adhesive such as an epoxy resin adhesive, glass containers are used as these adhesive containers. Since the surface is alkaline, the storage stability of the cyanoacrylate adhesive tends to deteriorate, so far, a polyolefin brush container has been used. (For example, Patent Document 3) However, since the polyolefin container is light, there is a problem that the container body falls when the brush is put in and out, a problem that the container is difficult to recycle, and the container is opaque and the remaining amount is difficult to understand. For this reason, there has been a demand to use a glass container even in a cyanoacrylate type.

Therefore, the inventors of the present application describe, for example, Patent Document 4, Patent Document 5, and Patent Document 6, as stability improvers for cyanoacrylate adhesive compositions sealed in containers such as polyolefin containers and aluminum tubes. In general, anionic polymerization inhibitors such as inorganic acids, organic acids, acid gases, borohydrofluoric acid, and the like were added, and it was confirmed that the stability to glass containers was improved. It turns out that simply increasing the amount of polymerization inhibitor or changing the combination will not only increase the storage stability, but also decrease the adhesive performance, such as a decrease in the curing rate and coloring and clouding during storage. did.

JP 1997-249238 A JP 2008-101042 A JP-A-10-21970 JP 49-94631 A JP-A-62-100568 Japanese Unexamined Patent Publication No. 03-7786

An object of the present invention is to provide a 2-cyanoacrylate adhesive composition that improves the stability when a glass container is employed as the container of the cyanoacrylate adhesive composition.

In order to solve the above-mentioned problems, the inventors of the present invention focused on the additive of 2-cyanoacrylate adhesive composition and the blending ratio thereof, and as a result of intensive studies, in order to obtain stability in a glass container, By using sulfur dioxide (SO ₂ ) among acid gases as a phase stabilizer and using trifluoromethane sulfonic acid as a liquid phase stabilizer among other sulfonic acids, it is possible to improve the stability of glass. It has been found to show an effect. Specifically, (B) 0.0001 to 0.01 part by weight of sulfur dioxide (SO ₂ ) and (C) trifluoromethanesulfonic acid in an amount of 0.001 to 100 parts by weight of (A) 2-cyanoacrylate. By containing 0001 to 0.01 part by weight, it is possible to provide an adhesive having improved stability with respect to a glass container and having the same ability as a conventional cyanoacrylate adhesive composition. As a result, the present invention has been completed.

According to the cyanoacrylate adhesive composition of the present invention, the stability of a glass container suitable for a brushed container is improved, and at the same time, an adhesive having the same ability as a conventionally known cyanoacrylate adhesive composition is obtained. It can be provided.

Hereinafter, the present invention will be described in detail.
As the (A) 2-cyanoacrylate in the present invention, 2-cyanoacrylate represented by the formula (1) 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.

The amount of (B) sulfur dioxide used in the present invention is 0.001 to 0.01 parts by weight with respect to 100 parts by weight of (A) 2-cyanoacrylate. If the amount is less than 0.001 part by weight, the stability of the glass container, which is the effect of the present application, is lowered. If the amount exceeds 0.01 part by weight, the curing rate is slowed or coloring is not preferable.

The amount of (C) trifluoromethanesulfonic acid used in the present invention is 0.0001 to 0.01 parts by weight, preferably 0.0001, per 100 parts by weight of (A) 2-cyanoacrylate. -0.005 weight part.
If the amount is less than 0.001 part by weight, the stability of the glass container, which is the effect of the present application, is lowered. If the amount exceeds 0.01 part by weight, the curing rate is slowed or coloring is not preferable.

In the 2-cyanoacrylate adhesive of the present invention, it is preferable to blend a quick-curing additive within the range where the effects of the present invention are not inhibited.

Examples of the fast curing additive used as necessary in the present invention include (D) polyalkylene oxide derivatives, calixarenes, crown ethers and the like.

In the present invention, among the (D) polyalkylene oxide derivatives, calixarenes, crown ethers and the like which are fast curing additives used as necessary, the polyalkylene oxide derivative is represented by the formula (2)

（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 (eg 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 crotonate, etc.), polyalkylene glycol diesters (eg, diethylene glycol diacetate, diethylene glycol dipropionate, die Lenglycol 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.

As calixarenes, the following formula (3)

（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。）

(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.)

And calixarenes represented by As such calixarenes, 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] arene, 25,26,27,28-tetra- (2-ethoxy-2-oxoethoxy) -calix [4] allene and the like are listed. The

Examples of crown ethers include 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, dithia-15-crown-5-ether, and benzo-12-crown-5-ether. Benzo-15-crown-5-ether, benzo-18-crown-6-ether, dibenzo-15-crown-5-ether, dibenzo-18-crown-6-ether, dibenzo-24-crown-8-ether Dicyclohexano-18-crown-6-ether, 1,2-naphth-15-crown-5-ether, 1,2-methylbenzo-18-crown-6-ether, and the like.

In the present invention, these fast-curing additives can be used alone or in combination of two or more. Among these fast-curing additives, methoxypolyethylene glycol # 400 methacrylate, methoxypolyethylene glycol # 1000 methacrylate, 25,26,27,28-tetra- (2-ethoxy-2-oxoethoxy) -calix [4] allene, 12-crown-4-ether, 15-crown-5-ether and 18-crown-6-ether are preferred.

In this invention, the usage-amount of the quick hardening additive used as needed is 0.005-5 weight part normally with respect to 100 weight part of 2-cyanoacrylate, Preferably it is 0.01-1 weight part. is there. If the amount is less than 0.005 parts by weight, a sufficient curing rate may not be obtained, and if it exceeds 5 parts by weight, the stability may be lowered.

In addition, the 2-cyanoacrylate adhesive composition of the present invention includes a stabilizer (for example, hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, conventionally used by adding to a 2-cyanoacrylate adhesive). Radical polymerization inhibitors such as catechol and pyrogallol), plasticizers (dimethyl phthalate, diethyl phthalate, diisodecyl phthalate, etc.), thickeners (acrylic ester copolymer elastomer, styrene-butadiene copolymer elastomer, Polyurethane elastomers, chloroprene elastomers, carboxylated acrylonitrile-butadiene copolymer elastomers, polyester elastomers, fluorine elastomers, polyisoprene elastomers, epichlorohydrin elastomers, ethylene 2-propylene copolymer elastomers, ethylene-vinyl acetate copolymer elastomers), colorants, fragrances, solvents, strength improvers, aliphatic polycarboxylic acids, aromatic polycarboxylic acids, etc., depending on the purpose. As long as the stability of the acrylate monomer is not impaired, it can be added and blended as appropriate.
Hereinafter, the present invention will be described in more detail with reference to examples.

(Example)
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

〔Test method〕
<Test 1: Glass stability test>
A glass test tube (inner diameter: 10 mm × height: 65 mm) is immersed in 98% sulfuric acid for 1 day, and 98% sulfuric acid is thoroughly washed with water and dried. After this, 4 g of the adhesive composition is put in a glass test tube and covered with a silicone rubber stopper covered with PE film. In this state, the gelation days of the adhesive composition are measured by exposure to an atmosphere at 82 ° C. The longer the gelation days, the better the stability. The stability in a glass container was evaluated as follows according to the number of days for gelation. ○: 11 days or more, ×: 10 days or less.

<Test 2: Set time>
It measured according to JIS-K6861 using EPDM for the material of the test piece. The curing speed was evaluated as follows according to the set time. ○: Less than 2 seconds, Δ: 2 seconds or more and less than 10 seconds, × 10 seconds or more.

<Test 3: Tensile shear bond strength>
It measured according to JIS-K6861 using EPDM for the material of the test piece. The tensile shear bond strength was evaluated as follows. ○: 1 N / mm ² or more, Δ: less than 1 N / mm ² , 0.1 N / mm ² or more, x: less than 0.1 N / mm ² .

(A) 2-Cyanoacrylate adhesive composition by adding 0.002 part by weight of sulfur dioxide and (C) 0.0003 part by weight of trifluoromethanesulfonic acid to 100 parts by weight of 2-ethylcyanoacrylate Was prepared. Table 2 shows the measurement results of tests 1 to 3 for the obtained adhesive composition.

(Examples 2-11, Comparative Examples 1-10)
A 2-ethylcyanoacrylate adhesive composition was prepared in the same manner as in Example 1 except that each component had the composition shown in Tables 1 and 2. The measurement results of Tests 1 to 3 of the adhesive composition are shown in Table 3.

The meanings of symbols and chemical formulas used in the following table are as follows.
TFMSA; trifluoromethanesulfonic acid, MSA; methanesulphonic acid, PTS; p-toluenesulfonic acid, HBF _4; fluoboric acid, SO _2; sulfur dioxide, HF; hydrogen fluoride, BF _3; boron trifluoride, 18CRE 18-crown-6-ether, 15CRE; 15-crown-5-ether, 12CRE: 12-crown-4-ether, PEG # 400; polyethylene glycol # 400 monomethyl ether monomethacrylate, CA; 25, 26, 27, 28-tetra- (2-ethoxy-2-oxoethoxy) -calix [4] arene.

Claims (2)

(A) 0.001 to 0.01 parts by weight of (B) sulfur dioxide (SO2) and (C) 0.0001 to 0.01 parts by weight of trifluoromethanesulfonic acid with respect to 100 parts by weight of 2-cyanoacrylate. A 2-cyanoacrylate adhesive composition characterized by containing a part.
(D) 0.005-5 parts by weight of at least one compound selected from (D) polyalkylene oxide derivatives, calixarenes, and crown ethers as a fast-curing additive with respect to 100 parts by weight of 2-cyanoacrylate The 2-cyanoacrylate adhesive composition according to claim 1.