JPS6233144B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a container made of a special material for containing an adhesive, such as an α-cyanoacrylate adhesive, which can polymerize and bond extremely quickly in the presence of anions. The purpose of this day is to prevent clogging of the discharge section, especially near the tip of the discharge section, due to polymerization and solidification of the α-cyanoacrylate adhesive, and to prevent the sealing attachment from sticking due to the adhesive flowing out from the discharge section. In addition to preventing
The purpose is to prevent the formation of a whitening film due to polymerization and solidification of the adhesive on the outer circumferential surface of the container, particularly on the outer circumferential surface of the discharge portion.

Due to the unique anionic polymerizability of the α-cyanoacrylate monomer, which is the main component, α-cyanoacrylate adhesives initiate polymerization using a weak anionic polymerization catalyst such as water that slightly adheres to the surface of the adherend. It is used as an instant adhesive for industrial, medical, and even household use because it firmly bonds almost all materials in seconds or minutes, except for some inert materials such as polyethylene, polypropylene, and Teflon. It is widely used in Conventionally, this α−
As a container for cyanoacrylate adhesive, a container is used, which consists of a container body consisting of an adhesive storage part and an adhesive discharge part, and an attachment for sealing the discharge part, such as a cap, and the material of the container is α.
- A limited number of materials are used, such as polyethylene, polypropylene, Teflon, and aluminum, tin, lead, etc., which are inert to cyanoacrylate monomers.

However, polyethylene, polypropylene,
Even if containers made of materials inert to α-cyanoacrylate monomers, such as Teflon, are used, the following problems still remain in this industry, and we are struggling to resolve them. This is the actual situation. That is, when the discharge part of the adhesive container, for example, the vicinity of the tip of the nozzle, comes into contact with the outside air, the α-cyanoacrylate monomer will quickly polymerize and solidify due to the moisture contained therein, causing the nozzle to become clogged. .

The α-cyanoacrylate adhesive that flowed out of the nozzle polymerized and solidified on the outer peripheral wall of the nozzle, forming a whitened film that impairs the aesthetic appearance and impairs the fit of the cap, making it impossible to seal it. As polymerization and solidification progress, the nozzle becomes clogged and the cap becomes unable to fit, resulting in a repeating vicious cycle.

If the cap is placed on the cap while the adhesive is flowing out from the nozzle, the adhesive will adhere to the inner peripheral wall of the cap, polymerize and solidify, making it difficult to remove the cap.

As a result of continuing research to solve these conventional problems, the present inventors have discovered that the above problems can be solved all at once by using an organic synthetic resin made of a special material. The present invention has been completed.

The gist of the present invention is a container consisting of a container body comprising an α-cyanoacrylate adhesive storage section and a discharge section provided following the storage section, and an attachment for sealing the discharge section. , an α-cyanoacrylate adhesive container in which at least a portion of the container is formed of an organic synthetic resin that retains acidic groups in its structure.

In the container of the present invention, at least a part of which is formed from an organic synthetic resin (hereinafter referred to as acidic resin) that retains acidic groups in its structure, a specific example of which is shown in the drawings. explain.

In A of FIGS. 1 and 2, 1 is an adhesive storage section, and 2 is a discharge section provided following the storage section. In Figure 1, adhesive storage section 1 and discharge section 2 are shown.
An adhesive filling port 4 is provided at the bottom of the adhesive storage portion 1, and a closing lid 5 is screwed onto the adhesive filling port 4. On the other hand, FIG. 2 shows a case where the adhesive storage section 1 and the discharge section 2 are formed separately and are screwed together. Note that 3 is an adhesive discharge port.

In the present invention, at least one component of the attachment 6 that seals the adhesive storage section 1, the discharge section 2, and the discharge section 2 shown by B in FIGS. 1 and 2 is made of acidic resin. It is something that 9 is a rough surface portion that prevents slipping.

FIG. 1C shows another example of an accessory in which a needle is provided under an umbrella-shaped lid 8, with which the discharge port 3 can be sealed.

As another embodiment of the discharge section of the present invention, it is also possible to form it into a felt pen shape as shown in FIG. 3A.

That is, as shown in FIG. 3A, the felt core 2'' is fixed through the discharge part 2' which can be screwed onto the adhesive storage part 1, and the felt core 2'' alone or the felt core 2'' and the discharge part 2' are made of acidic resin. If only the felt core is made of acidic resin, the discharge part 2' may be made of polyethylene, polypropylene, etc. It can be easily manufactured by this method.

Of course, the sealing attachment 6 shown in FIG. 3B may be made of acidic resin, and the adhesive storage portion 1 may be made of acidic resin. 10 is a desiccant, which can further prevent the tip of the felt core 2'' from solidifying.

In particular, in the present invention, the discharge section 2 or FIG.
It is preferable that the discharge portion 2', the felt core 2'', the sealing attachment 6, etc. shown in 2 are formed of acidic resin.

Because of the acidic atmosphere created by the acidic groups in the portion formed of the acidic resin, anionic polymerization of the α-cyanoacrylate monomer is suppressed, and solidification on the outer surface of the container does not occur. Therefore, the discharge section,
In particular, it can prevent clogging near the tip of the discharge part, prevent the sealing attachment from sticking due to adhesive leakage, and form a whitening film due to polymerization and solidification of the adhesive on the outer circumferential surface of the container. can be prevented.

In the present invention, usable acidic resins include, for example, sulfonated polyethylene, sulfonated polypropylene, sulfonated fluororesin, sulfonated polystyrene, chlorosulfonated polyethylene, chlorosulfonated polystyrene, carboxylated polyethylene, and carboxylated polypropylene. , carboxylated fluororesin, polyacrylic acid copolymer, sulfonated polyethylene, phosphonated polypropylene, phosphonated polystyrene, etc. are preferably used.

If the above acidic resin is not used for manufacturing the adhesive storage section, polyethylene, polypropylene, fluororesin, etc. may be used.

As the above-mentioned acidic resin, commonly available commercially available ones can be used. For example, Mitsui Petrochemical's Admer, Dupont's Hypalon, Surlyn,
Nafion etc.

The above acidic resin can also be produced by a commonly known method.

For example, a method of copolymerizing monomers having groups such as sulfonic acid, carboxylic acid, and phosphoric acid, or polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polycarbonate, ABS,
polyacetal, polyamide, acrylic resin,
It can be manufactured by, for example, performing the following treatment before or after molding the discharge part, storage part, and sealing attachment with fluororesin, phenolic resin, polyester resin, or the like.

Method of irradiation with light in SO ₂ /Cl ₂ mixed gas, method of treatment with PCl ₃ /O ₂ , method of irradiating thiocarbonyl with ultraviolet rays in the presence of carbon sulfide to introduce a mercapto group, and then sulfonation, Methods include treatment with sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, etc., and methods of introducing acidic groups through plasma treatment.

The present invention will be further specifically explained below with reference to Reference Examples and Examples.

Reference example 1 Polyethylene powder (number average molecular weight 1.4×10 ⁴ )
It was dissolved in phosphorus trichloride heated to 78°C, a small amount of azobisisobutyronitrile was added, and a chlorophosphonation reaction was carried out for 4 hours while blowing dry oxygen gas. The reaction product was poured into finely ground water for hydrolysis, washed with water, and vacuum dried to obtain phosphonated polyethylene. This was sandwiched between Teflon sheets and press-molded at 170°C and 350 kgf/cm ² to form a film. Maintaining a clearance of 0.2 mm between these two films, α-cyanoacrylate adhesive was injected between them, and after leaving it at 23℃ for 24 hours, the two films were peeled off and the α-cyanoacrylate adhesive was injected. No solidification was observed. As a comparative example, in a polyethylene film that was not phosphonated, the α-cyanoacrylate adhesive was solidified between the films.

Reference Example 2 Solution polymerization was carried out using azobisisobutyronitrile and perfluorovinyl ether having a terminal carboxylic acid ester and tetrafluoroethylene as a catalyst. The obtained copolymer was press-molded into a film, and then hydrolyzed to obtain a carboxylated Teflon film. After washing this film with hot water and vacuum drying, the same test as in Example 1 was conducted, but no solidification of the α-cyanoacrylate adhesive was observed. Further, no whitening phenomenon caused by polymerization of monomer vapor near the α-cyanoacrylate adhesive was observed at all (whitening phenomenon was observed in the case of polyethylene film).

Example 1 A composite nozzle made of Admar QB-010 (manufactured by Mitsui Petrochemicals) and nylon-6 was heated to 230°C from the first extruder and nylon at 250°C from the second extruder using a two-layer molding machine. Extrusion with die (230℃)
Both resins were combined and molded. The wall thickness ratio of the outer layer of nylon and the inner layer of Admer was set to 1/9.

Attach this nozzle to a polyethylene container filled with α-cyanoacrylate adhesive,
Although various tests were conducted, no polymerization or solidification of the α-cyanoacrylate adhesive was observed at the nozzle portion, and the adhesive could be discharged at any time.

Furthermore, there was no deterioration in set time or gelation of the α-cyanoacrylate adhesive during long-term storage compared to the case of ordinary polyethylene containers and nozzles.

Example 2 Sulfonated Teflon (DuPont Nafion)
120) The film was subjected to an adhesion test using a cyanoacrylate adhesive in the same manner as in Example 1, but no solidification of the adhesive was observed. This film was cut into pieces as thin as possible, and a brush-like (felt core) adhesive application area was created by cutting the film into pieces as thin as possible, which were then fitted and fixed into the nozzle part of a polyethylene container. Fill this container with α-cyanoacrylate adhesive,
We conducted repeated adhesion tests and found that the cyanoacrylate adhesive did not polymerize or solidify at the brush-like application area, and its storage stability in terms of set time and gelation was significantly lower than that of conventional containers. Nakatsuta.

This coatable cyanoacrylate adhesive container facilitates coating work over a wide area, significantly improving workability. Furthermore, the degree of freedom in the structure and design of containers, which was previously limited by the instant adhesive properties of α-cyanoacrylate monomers, has been dramatically increased.

Example 3 The cap portion of an α-cyanoacrylate adhesive container was manufactured from sulfonated polystyrene. Specifically, a styrene monomer containing 4% divinylbenzene was subjected to suspension polymerization using benzoyl peroxide as a catalyst, and the resulting polymer was molded to form a cap for an α-cyanoacrylate adhesive container. Next, this was immersed in chlorosulfonic acid for 60 minutes at room temperature to sulfonate the surface, washed with water and dried. A polyethylene container with a nozzle was filled with α-cyanoacrylate adhesive, the nozzle was opened, and the container was stored at room temperature with this cap or a cap made of polyethylene attached. After one month, no whitening phenomenon was observed on the inside of the cap in the example, whereas in the comparative example made of polyethylene, the whitening phenomenon caused by the polymerization of cyanoacrylate monomer vapor was significant and the appearance was impaired. .

[Brief explanation of the drawing]

1, 2, and 3 are cross-sectional views showing an example of the container of the present invention, where A shows an example of the container body consisting of an adhesive storage part and a discharge port, and B and C show the discharge part. An example of a sealing attachment is shown. 1... Adhesive storage section, 2, 2' and 2''... Discharge section, 3... Discharge port, 4... Adhesive filling port, 5...
Closing lid, 6... Sealing attachment, 7... Needle, 8...
Umbrella-shaped lid, 9... Rough surface portion, 10... Desiccant.

Claims (1)

[Scope of Claims] 1. A container consisting of a container body comprising an α-cyanoacrylate adhesive storage part and a discharge part provided following the storage part, and an attachment for sealing the discharge part, the container comprising: 1. A container for an α-cyanoacrylate adhesive, at least a part of which is made of an organic synthetic resin that retains acidic groups in its structure. 2. The container according to claim 1, wherein the discharge portion of the container body is formed of an organic synthetic resin that retains acidic groups in its structure. 3. The discharge part of the container main body is constructed by penetrating and fixing a felt-like core to its discharge port, and the discharge part and/or the felt-like core are made of organic synthetic resin that retains acidic groups in its structure. A container according to claim 1, which is formed by: 4. The container according to claim 1, 2, or 3, wherein the sealing attachment is formed of an organic synthetic resin that retains acidic groups in its structure.