JPH0147503B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a colored α-cyanoacrylate adhesive composition which has particularly excellent storage stability. α-Cyanoacrylate is a colorless and transparent liquid with particularly strong anionic polymerizability and quickly polymerizes on solid surfaces, so it can be used as a room temperature curing instant adhesive for a wide range of materials, from metals, inorganic materials, plastics, rubber to living organisms. It is well known that it is used for adhesion. The adhesive performance of adhesives whose main component is α-cyanoacrylate is also affected by the amount of application, so it is necessary to optimize the amount of application during work, and as work becomes automated, In order to more accurately manage work, there has been a strong demand for products to be colored to make them easier to identify. In the past, various studies have been conducted to meet this demand. For example, in Japanese Patent Publication No. 1983-35250, a method using azo dyes, anthraquinone dyes, phthalocyanine dyes, azine dyes, and other oil-soluble dyes that are not alcohol soluble has been proposed. The α-cyanoacrylate composition prepared by this method was considered to be practically necessary when the storage stability test required by JIS-K-6861 (α-cyanoacrylate adhesive test method) was applied. It was a well-known fact that it did not have the storage stability that was expected. For this reason, JP-A-55-
In 98268, oil-soluble dyes are washed with specific acids and
It has been proposed again to remove the base and use it for coloring. As a similar treatment, Japanese Patent Publication No. 53-37260 proposes a method in which a base such as a basic dye is treated with an acid and used as a coloring agent. The method of treating these dyes or dye bases with acid for coloring is as follows:
Since the reaction between the dye and the acid occurs during the treatment process, the color tone tends to change, and the acids used in the treatment remain, which tends to cause delays in performance, particularly curing speed. Coloring with a dye-based compound has the advantage that the compound can be selected from a wide range of areas and it is easy to set a wide range of color tones, so there is no need for acid treatment, which is highly concerned about uneven color tone and residual contamination of the processing agent. However, unless we consider a new coloring agent that dissolves well in α-cyanoacrylate and does not impair storage stability or adhesive performance, it will be difficult to bring α-cyanoacrylate with good color reproducibility and quality to the market. However, as a result of investigation, it was discovered that it is possible to color α-cyanoacrylate without acid treatment, which tends to cause quality fluctuations when a compound with a specific structure is used, leading to the present invention. Thus, the present invention provides an α-cyanoacrylate adhesive composition which is colored by adding a compound having a skeleton of violanthrone, isoviolanthrone, anthoanthrone, indigo, or a phenylthioglycolic acid condensate to α-cyanoacrylate. It provides: To explain further, the formula [In the formula, R is alkyl, aralkyl, aryl,
α- represented by alkenyl, cycloalkyl, etc.
As understood from its molecular structure, cyanoacrylate has strong anionic polymerizability, and is highly polymerizable in water, -OH groups, -
Polymerization is easily initiated by NH groups and other basic groups. The same applies to groups in dye molecules, and compounds with such groups cannot coexist stably with α-cyanoacrylate as they are, so treatment such as the methods of the previously proposed inventions is required. This is what happens. Therefore, as a result of examining the correlation between the anionic polymerizability of α-cyanoacrylate and the structure of the dye, we found that either it develops color in terms of its molecular structure and does not contain an anionic polymerizable active group, or that it contains hydrogen bonds or steric groups even though it is contained in the molecular formula. It has been found that a colored α-cyanoacrylate adhesive composition of stable and preferable quality can be obtained by selecting compounds that do not exhibit anionic polymerization activity due to their structure, such as effects, and are vat dyes that can be used as coloring agents. It was. As a result of further investigation based on this, (A) Colorant compounds that are vat dyes that develop color based on their molecular structure and do not contain anionic active groups include violanthrone, isoviolanthrone, anthoanthrone, and phenylthioglycolic acid condensates. or compounds having these skeletons, i.e., derivatives thereof substituted with halogen groups, alkoxy groups, sulfone groups, etc.; It has been found that indigo or its derivative compounds substituted with the above-mentioned groups using indigo as a backbone are suitable as vat dye compounds not shown. Specific examples of dyes belonging to the former (A) include:
For example CI Vat Blue20, 18, 19, Vat
Green1, Vat Violet1, 9, Vat Orange1,
2, 3, Vat Yellow4, Vat Red1, 2, Vat
Examples of dyes belonging to the latter category (B) include Vat Blue 1, 3, 5, and 41. Examples of these dye compounds are as follows. Dyes belonging to (A) (a) Compounds having a violanthrone skeleton Vat Blue18 (CI59815) shown in or Vat Blue19 (CI59805) with a similar skeleton Vat Blue20 (CI59800) Vat Green1 (CI59825) (b) Compound with isoviolanthrone skeleton Vat Violet1 (CI60010) shown by or Vat Violet9 (CI60005) having the same skeleton as this (c) Compounds having an anthrone skeleton Vat Orange3 (CI59300) shown in or Vat Orange1 (CI68705) having the same skeleton as this,
Vat Yellow4 (CI59100) (d) Compound having a phenylthioglycolic acid condensate skeleton Vat Red1 (CI73360) shown in or Vat Red2 (CI73365) having the same skeleton, Vat
Violet2 (CI73385) Dye belonging to (B) Vat Blue1 (Indigo, CI=73000) indicated by
Or Vat Blue3 (C.
I.73055), Vat Blue5 (CI73065), Vat Blue41
(CI73040) Even with vat dye compounds having the same skeleton as above,
Compounds with groups having anionic polymerization activity,
Compounds in which the NH group is not inactivated by hydrogen bonding or the like cannot be applied to the purpose of the present invention. For example, as an example of the former (A), the VAT of CI59826
Green1 and CI59850 Vat Green9, CI59301
Vat Orange3, as an example of the latter (B), CI73001
Vat Blue1 etc. can be mentioned. Examples of α-cyanoacrylates that can be colored with these compounds and used as adhesive compositions include alkyl phenyls such as methyl, ethyl, propyl, butyl, hexyl, and octyl, aryl such as chlorophenyl, allyl, and propargyl. Compounds having ester groups such as alkenyl, chloroethyl, perchloroethyl, methoxyethyl, ethoxyethyl, and tetrahydrofurfuryl can be used. This α-cyanoacrylate is used in combination with additives such as stabilizers, plasticizers, and thickeners used in ordinary adhesives, as well as improvers for heat resistance, water resistance, impact resistance, and whitening resistance. I can do things. The colored composition according to the present invention has good storage stability because the colorant does not have a functional group that promotes polymerization of α-cyanoacrylate, and there is no need for acid treatment, so It is practically useful because it does not cause deterioration in quality such as delay in curing speed. Examples of the present invention are shown below. Example 1 0.2 parts of Indico [Vat Blue 1 (CI73000) dried in a desiccator] was added to 100 parts of ethyl-α-cyanoacrylate prepared by adding 3 parts of trioctyl pyromellitate to 20 ppm of sulfur dioxide gas and 200 ppm of hydroquinone, and the mixture was shaken. When stirred, it turned dark blue. When this colored adhesive was tested in accordance with JIS-K-6861, it had physical properties as shown in Table 1 below, and there was no deterioration in stability or quality due to coloring.
In addition, when one drop (approximately 0.015 cc) was dropped on copper, steel, etc., the discrimination was good. Comparative Example 1 shows a composition in which Indico is not added.

【table】

[Table] Example 2 20ppm SO ₂ , 300ppm hydroquinone and 4
100 parts citrate tributyl acetate, 1 part tetraethylene glycol dioctoate
of methyl-α-cyanoacrylate and 0.2 parts of violanthrone bromide (CIVat) as a dye.
Orange2 CI59705) was added and stirred for 1 hour to obtain a reddish-orange composition. The physical properties and storage stability of this colored composition are as follows:
As shown in Table 3, the results were good. Example 3 10ppm SO ₂ , 100ppm hydroquinone and 2
0.1 part of isoviolanthrone (CIVat Violet1 CI60010) as a dye was added to ethyl-α-cyanoacrylate containing 1 part of tetrabutyl pyromellitate and 1 part of tricresyl phosphate,
After shaking for 1 hour, a purple composition was obtained. The physical properties and storage stability of this composition were as shown in Tables 2 and 3 and were good. Example 4 In Example 2, instead of violanthrone,
0.2 parts of Vat Yellow 4 (CI59100) was added and treated in the same manner to obtain a yellow composition. The physical properties and storage stability of this composition were as shown in Tables 2 and 3 and were good. Example 5 In Example 1, use Vat instead of Injico.
0.2 parts of Red1 (CI73360) was added and treated in the same manner to obtain a red colored composition. The physical properties and storage stability of this composition were as shown in Tables 2 and 3 and were good.

【table】

[Table] Comparative Examples 2 and 3 in Tables 2 and 3 show cases in which the dyes in Examples 2 and 3 were not used. Comparative Example 4 When preparation was made in the same manner as in Example 1 using Vat Blue 1 of CI73001, the composition thickened and polymerized after 2 days (though a deep blue color was obtained). Comparative Example 5 In Example 4, Vat Yellow4 was replaced with Vat
When similarly prepared using Orange3 (CI59301), a reddish-orange coloring was obtained, but the composition polymerized after 3 days.

Claims (1)

[Claims] 1 α-cyanoacrylate with violanthrone,
An α-cyanoacrylate adhesive composition colored by adding a compound having a skeleton of isoviolanthrone, anthoanthrone, indigo, or a phenylthioglycolic acid condensate.