JPH05331421A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide the cyanoacrylate adhesive composition weakened in the adhesive force to skins. CONSTITUTION:The cyanoacrylate adhesive composition is characterized by containing an aliphatic alcohol having an aliphatic group containing >= six carbon atoms directly bonded to each other in an amount of 10-40wt.% in the composition. The adhesive composition reduces the troubles of skin adhesion in adhesion works, can widely be utilized in further more uses than those of conventional adhesive compositions, and can safely be handled for adhesion in various industrial fields, medical treatment fields, leisure fields, and further the fields of general homes and school children, e.g. the adhesion of stationeries by the school children.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyanoacrylate adhesive composition having a weakened adhesive force to the skin, which is used in various industries and medical treatments which utilize a cyanoacrylate adhesive which is an instant adhesive. Field, leisure field,
Furthermore, it is widely used in general households.

[0002]

2. Description of the Related Art A cyanoacrylate-based adhesive containing 2-cyanoacrylate as a main component is easily anionically polymerized and rapidly cured due to the presence of a small amount of water and a basic substance. Since it has such a property, it is widely used as an instant adhesive in various industries, medical fields, leisure fields, and general households.

However, the 2-cyanoacrylate adhesive has the convenient property of instantly adhering glass, metal, plastic, wood, fabric, paper, etc., but if the method of using the adhesive is wrong, Adhesion problems may occur in which the skin of the person who handles it or the skin or the adherend also adheres.

This is because the surface of human skin contains a large amount of basic substances contained in water, sweat, etc. that accelerate the anionic polymerization of the 2-cyanoacrylate adhesive.
This happens especially because the skin is easily adhered.

Since the skin adhered by the 2-cyanoacrylate adhesive adheres to the skin or the adherend other than the skin with a very strong strength, the adhered skin should be forcibly peeled off. This may cause serious damage to skin and subcutaneous tissue.

From the above background, there is a strong demand for an instant adhesive that reduces the trouble of adhering the skin during the adhering work and can be handled more easily and safely than conventional instant adhesives.

[0007]

SUMMARY OF THE INVENTION The present invention has a low adhesion rate to the skin, but has a high adhesion rate to adherends other than the skin, such as wood, plastic, rubber, metal and ceramics. It is an object to provide an instant adhesive.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a cyanoacrylate-based adhesive composition containing one or more specific alcohols can be applied to the skin. Although it has a slow adhesion speed to, it has been found that materials other than the skin such as wood, plastic, rubber, metal, and ceramic are instantaneously bonded,
The present invention has been completed.

That is, the present invention is characterized in that the composition contains 10 to 40% by weight of an aliphatic alcohol having an aliphatic group in which 6 or more carbon atoms are directly bonded to each other. The present invention relates to an acrylate adhesive composition.

The adhesive composition of the present invention will be described below. The main component of the cyanoacrylate-based adhesive is 2-cyanoacrylate, and various 2-cyanoacrylates are used as the main component in the present invention as well as the conventional ones. Specifically, methyl 2-cyanoacrylate is used. ,
Ethyl, chloroethyl, n-propyl, i-propyl,
Allyl, propargyl, n-butyl, i-butyl, n-pentyl, n-hexyl, cyclohexyl, phenyl, tetrahydrofurfuryl, heptyl, 2-ethylhexyl, n-octyl, n-nonyl, oxononyl, n-decyl, n- Dodecyl, 2-ethoxyethyl, 3-methoxybutyl, 2-ethoxy-2-ethoxyethyl, butoxy-ethoxy-ethyl, 2,2,2-trifluoroethyl,
An ester such as hexafluoroisopropyl is used as the main component of the composition of the present invention.

Specific examples of the aliphatic alcohol having an aliphatic group in which 6 or more carbon atoms are directly bonded to each other used in the present invention include the following.

That is, n-hexyl alcohol, n-
Octyl alcohol, n-nonyl alcohol, 2-nonyl alcohol, decyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, β-citronellol, 9-decen-1-ol, 1,
1-dimethyl-5-methyl-6-hepten-1-ol, dihydromyrcenol, geraniol, 1,5-dimethyl-
Specific examples include monohydric alcohols such as 1-vinyl-4-hexen-1-ol and ω-undecenyl alcohol,
Although these are preferable for the present invention, they are not limited to these.

The alcohol used in the present invention is an aliphatic alcohol having an aliphatic group in which 6 or more carbon atoms are directly bonded to each other in the molecule, and all of the aliphatic groups in the molecule are directly bonded to each other. When the number of bonded carbon atoms is 5 or less, the speed of adhesion to the skin increases,
It cannot be used in the present invention because troubles occur during the bonding work.

On the contrary, when there is an aliphatic group in the molecule of which 16 or more carbon atoms are linked, the solubility in cyanoacrylate becomes poor. Therefore, preferred aliphatic alcohols for the present invention are those having 15 or less carbon atoms directly bonded to each other in the aliphatic group, and particularly preferred aliphatic alcohols are directly bonded to each other in the aliphatic group. It has 8 to 15 carbon atoms.

As the aliphatic group, a hydrocarbon group (straight chain or branched polymethylene or polyolefin) is preferable, as is clear from the examples of the specific compounds described above.

If the amount of the aliphatic alcohol compounded in the adhesive composition is too small, sufficient skin-difficulty adhesion cannot be obtained, and if it is too large, the adhesion speed to the adherend other than the skin becomes slow. It is necessary to add 10 to 40% by weight, preferably 15 to 30% by weight in the cyanoacrylate adhesive composition.

When the composition of the present invention is used in combination with an anionic polymerization accelerator, the effect intended by the present invention can be further exhibited. Examples of the anionic polymerization accelerator used in combination include the following.

The polyoxyalkylene oxide or its derivative is first mentioned, and it is already known in Japanese Patent Publication No. 60-37836, Japanese Patent Publication No. 60-26513, Japanese Patent Publication No. 1-43790, Japanese Patent Publication No. 63-128088, Japanese Patent Publication No. 3-167279 and the like. All of the above can be used in the present invention. Specific examples thereof include the following.

[Polyalkylene oxide] diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, poly 1,3-propylene glycol, polytrimethylene oxide, polytetramethylene oxide, polyepichlorohydrin, poly 3,3- Bis (chloromethyl) butylene oxide, polytetramethylene ether glycol, poly-1,3-dioxolane, poly-2,2-bis (chloromethyl) propylene oxide, ethylene oxide-propylene oxide block polymer, diglycerin, triglycerin, tetraglycerin And the like, such as polyglycerin, formaldehyde condensate, acetaldehyde condensate, and trioxane polymer. Various polyalkylene oxides commercially available as polyether type urethane curing polyols can also be used in the present invention.

[Polyalkylene Oxide Derivative] The polyalkylene oxide derivative is represented by an ester of the above polyalkylene oxide and an acid and an ether of a hydroxy group-containing compound, and those are preferable. , Not particularly limited thereto, those having various substituents at the terminal of the molecule, those having other bonding moieties inside the polyalkylene oxide, etc., the polyalkylene oxide structure inside the molecule If it has the following, the effect intended by the present invention can be better exhibited.

As the acid capable of forming the ester, acetic acid,
Propionic acid, butyric acid, isobutyric acid, pivalic acid, pentanoic acid, n-hexanoic acid, 2-methyl-pentanoic acid, n-octanoic acid, n-decanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, cyclohexylcarboxylic acid Acid, cyclopentylcarboxylic acid, cyclopropylcarboxylic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, naphthenic acid, benzoic acid, β-naphthylcarboxylic acid, p-toluenecarboxylic acid, furancarboxylic acid, p-chlorobenzoic acid , Monochloroacetic acid, cyanoacetic acid, glycolic acid, lactic acid, phenyloxypropionic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, butanetetracarboxylic acid, aconitic acid, propane-1,2,3-tricarboxylic acid, citric acid , Orthophthalic acid, isophthalic acid Acids such as trimellitic acid and pyromellitic acid can be mentioned.

Hydroxy group-containing compounds which can form ethers include methanol, ethanol, propanol, isobutanol, hexanol, cyclohexanol, 2-ethyloctanol, decanol, lauryl alcohol, cesyl alcohol, stearyl alcohol,
Oleyl alcohol, phenol, α-naphthol, β
-Naphthol, cresol, t-butylphenol, octylphenol, nonylphenol, p-chlorophenol, resole, bisphenol A, 2-chloroethanol, ethylene cyanohydrin, trifluoroethanol, benzyl alcohol, 1,4-butanediol,
1,6-hexanediol, glycerin, sorbitol,
Examples thereof include hydroxy group-containing compounds such as hydrogenated bisphenol A and trimethylolpropane.

Specific examples of the ether as the polyalkylene oxide derivative include diethylene glycol monoalkyl ether (where alkyl is, for example, methyl, ethyl, propyl, butyl, etc.), diethylene glycol dialkyl ether (where alkyl is, for example, methyl,
Ethyl, propyl, butyl, etc.), polyethylene glycol monoalkyl ether (as alkyl, for example, methyl, ethyl, propyl, butyl, lauryl, cesyl,
Stearyl, oleyl, etc.), polypropylene glycol monoalkyl ether (eg alkyl is methyl, ethyl, propyl, butyl, lauryl, cesyl, stearyl, oleyl, perfluoroalkyl etc.), polyethylene glycol monoaryl ether (eg aryl is octyl). Phenyl, nonylphenyl, etc.), polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, polyethylene glycol diaryl ether and the like.

Specific examples of the ester as the polyalkylene oxide derivative include polyethylene glycol monoalkyl ester (eg, acetate, trifluoroacetate, laurate, stearate, oleate,
Ester such as methacrylate), polyethylene glycol diester, polypropylene glycol diester,
Bisphenol A-polyalkylene oxide adduct (for alkylene, for example, ethylene, propylene and the like below), hydrogenated bisphenol A-polyalkylene oxide adduct, trimethylolpropane-polyalkylene oxide adduct, glycerin-polyalkylene oxide adduct, Polyoxyethylene sorbitan ester, tetraoleic acid-polyoxyethylene sorbit, adipic acid-polyalkylene oxide adduct, trimellitic acid-polyalkylene oxide adduct, isocyanate compound-polyalkylene oxide adduct,
Examples thereof include phosphoric acid-polyalkylene oxide adducts, silicic acid-polyalkylene oxide adducts, (polyoxyalkylene) polysilarates, (polyoxyalkylene) polyesters, (polyoxyalkylene) polyphosphates and the like.

Examples of the second anionic polymerization accelerator include crown ethers and their derivatives.
All of those already publicized in JP-A-2238, JP-A-3-167279 and the like can be used. Specific examples thereof include the following.

[Crown ether] 15-crown-5,
18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5, dibenzo-24-crown-8,
Dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, Cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-
Naphthyl-16-crown-5,1,2-methylbenzo-18
-Crown-6, 1,2-methylbenzo-5,6-methylbenzo-18-crown-6, 1,2-tert-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5,
1,2-Vinylbenzo-18-crown-6,1,2-tert-
Butylcyclohexyl-18-crown-6, 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7 and the like.

Examples of the third anionic polymerization accelerator include silacrown and its derivatives.
All of those already known in 1034, JP-A-60-168775 and the like can be used. Specific examples thereof include the following.

[Sila Crown Compound] Dimethyl Sila-11
-Crown-4, dimethylsila-14-crown-5, dimethylsila-17-crown-6 and the like can be mentioned.

Examples of the fourth anionic polymerization accelerator include calixarene derivatives, which are disclosed in JP-A-60-17948.
2, JP-A-62-235379, JP-A-63-8815
Any of those already publicized as 2 etc. can be used. Specific examples thereof include compounds represented by Formula 1 and Formula 2.

[0030]

[Formula 1]

In the formula 1, R ¹ represents alkyl, alkoxy, substituted alkyl or substituted alkoxy, R ² represents H or alkyl, and n represents 4, 6 or 8.

[0032]

[Formula 2]

In equation 2, m and n are both integers, and m + n
= 4, 6, or 8 and an integer satisfying n ≧ 1/2 (m + n). R ⁵ is aryl, hydrocarbyl aryl, aryloxy, hydrocarbyl aryloxy, substituted aryl,
Substituted hydrocarbyl aryl, substituted aryloxy, or substituted hydrocarbyl aryloxy, where R ⁴ is aryl, hydrocarbyl aryl, substituted aryl or substituted hydrocarbyl aryl, R ⁵ is hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyl, or substituted hydrocarbyloxy. Is. R ⁴ is H, hydrocarbyl,
Aryl, hydrocarbyl aryl, substituted hydrocarbyl, substituted aryl, or substituted hydrocarbyl aryl. R ³ is H, hydrocarbyl, or substituted hydrocarbyl.

Examples of the fifth anionic polymerization accelerator include cyclic sulfur compounds, and any of those already known in JP-A-59-64681 can be used. The compound is a cyclic compound having a polysulfide bond and an ether bond in the molecule and is represented by Formula 3.

[0035]

[Formula 3]

In the formula 3, R ⁶ and R ⁷ represent a hydrocarbon chain having 2 to 6 carbon atoms, m is 2 to 4 and n is an integer of 1 to 3.

The amount of the anionic polymerization accelerator added is preferably 1 with respect to the cyanoacrylate adhesive composition.
It is 0 to 100,000 ppm, more preferably 30 to 10,000 ppm.

It is known that when an anionic polymerization accelerator is added to a cyanoacrylate-based adhesive, the adhesion speed of the cyanoacrylate-based adhesive to the adherend is increased, but the present inventors have found that 2-cyanoacrylate and When an anionic polymerization accelerator is added to the cyanoacrylate-based adhesive composition consisting of the chain alcohol, the effect of shortening the adhesion speed to the adherend material such as wood, plastic, rubber, metal, ceramics other than the skin is very great. Although excellent, the effect of shortening the adhesion speed to the skin is extremely short, and by applying this phenomenon to the present invention, a better adhesive can be obtained.

When the content of the anionic polymerization accelerator in the composition of the present invention is less than 10 ppm, it is difficult to obtain sufficient rapid curing property. On the other hand, when it exceeds 100,000 ppm, the rapid curing property does not increase so much. The strength and storage stability are significantly reduced.

Like the conventional products, it is preferable to add, for example, a trace amount of hydroquinone and sulfurous acid gas as a polymerization inhibitor to the cyanoacrylate adhesive composition of the present invention in order to improve storage stability. Further, 2-cyanoacrylate is originally a colorless and transparent low-viscosity liquid, but as a thickener therefor, for example, polymethylmethacrylate, acrylic rubber, cellulose derivative, silica or the like is dissolved or dispersed to make it viscous. It can be said that it is a liquid or a liquid having a thixotropic property, or it is colored with a specific dye.

[0041]

The reason for the cyanoacrylate-based adhesive obtained from the composition of the present invention has not been clarified yet, but it can be applied to materials other than the skin such as wood, plastic, rubber, metal and ceramics. , Shows excellent instantaneous adhesion, but does not show instantaneous adhesion to the skin,
It shows a very specific behavior.

[0042]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples 1 to 15 Adhesion tests were conducted using various adherends shown in Table 1 and human fingers shown in Table 2 using the adhesives having the compositions shown in Tables 3 and 4.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

Decanol, tridecanol, oxochol 1213, oxochol 1215 in Tables 3 and 4
Used one manufactured by Kyowa Hakko Kogyo Co., Ltd. In addition, calixarene # 1 in the accelerator is 37,38,39,40,41,42-
Hexa- (2-oxo-2-ethoxy) -ethoxycalix [6] arene, wherein calixarene # 2 is a compound represented by formula 4 and the cyclic sulfur compound is a compound represented by formula 5.

[0049]

[Formula 4]

[0050]

[Formula 5]

The evaluation test method was as follows. Set time measuring method: (hard vinyl chloride) Hard vinyl chloride according to JISK6849
The time for reaching the adhesive strength of 3 kg or more with the adhesive was set as the set time. (Balsa, chloroprene rubber) Test piece is JISK685
In accordance with 0, the set time was defined as the time required for sticking with an adhesive and lightly pulling the test piece in the long axis direction by hand until it did not come off. (Finger) Apply adhesive on the index finger, press the thumb lightly, spread it out thinly, and set the time t at which the index finger and thumb are peeled off by themselves for t ≤ 1 second, 1 second <t ≤ 1 within the range where no pain is felt.
5 seconds, 15 seconds <t ≦ 30 seconds, 30 seconds <t ≦ 60 seconds, 60
The measurement was performed in 5 steps of seconds <t. The measurement environment is temperature = 23 ℃,
Humidity = 60% RH. The test results are shown in Table 5.

[0052]

[Table 5]

Comparative Examples 1 to 6 Table 7 shows the results of the same tests as in Examples using the adhesives having the compositions shown in Table 6.

[0054]

[Table 6]

[0055]

[Table 7]

[0056]

EFFECTS OF THE INVENTION The cyanoacrylate adhesive composition of the present invention can be used for other than skin, such as wood, plastic, rubber,
It has excellent instantaneous adhesiveness to adherends such as metals and ceramics, but does not exhibit instantaneous adhesiveness to the skin, and reduces skin adhesion problems during adhesive work. The instant adhesive according to the present invention is widely used in many more applications than conventional ones, and can be safely used in various industrial fields, medical fields, leisure fields, and bonding of stationery materials for general households and school children. It has an excellent effect that it can be handled.

Claims (1)

[Claims] 1. A cyanoacrylate adhesive characterized in that the composition contains 10 to 40% by weight of an aliphatic alcohol having an aliphatic group in which 6 or more carbon atoms are directly bonded to each other. Composition.