JP2012101857A - Filling/packaging method for moisture curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture curing composition package for preventing a moisture curing composition from being cured internally while the composition is stored in a container and for easily removing even a small amount of a cured material generated by its prevention principle.SOLUTION: In filling a moisture curing composition in a sealed container comprising a container body and a top lid, the moisture curing composition is filled with a gap provided in the container, and a compound with a hydrolyzable silyl group whose viscosity is 0.1-100,000 mPa s is applied on the top face of the composition.

Description

  The present invention relates to a method for filling and packaging a moisture curable composition. More specifically, the present invention relates to a method for filling and packaging a moisture-curable composition that is excellent in product stability and workability even after long-term storage.

  The moisture curable composition reacts with moisture in the air, is polymerized, three-dimensionally cured, exhibits various desired physical properties, and is applied to various uses. Therefore, the packaging container needs to be completely shielded from the outside air in order to suppress curing. As a packaging form of a moisture curable composition generally used, a metal, plastic can or the like having a sealed structure of a cartridge, a film pack, and a can lid is used.

  In a large-capacity packaging form, a can with an aluminum laminated sheet inner bag (Patent Document 1) and a moisture-proof material filled between a coating film and a can wall (Patent Documents 2 to 3) are proposed. Yes.

Japanese Patent Laid-Open No. 10-72059 JP 2004-299777 A JP 2007-284091 A

  In general, metal cans and plastic cans are used for packaging capable of handling large-capacity packaging units. However, in packaging using a can, it is difficult to completely seal it compared to packaging such as cartridges and film packs, and the moisture-curable composition is likely to partially cure. In order to prevent the hardening, the size of the can lid is reduced or a special sealing treatment is applied to improve the sealing performance. Problems such as can handling and filling work occur.

  On the other hand, various attempts have been made such as a method of coating a moisture-proof film on the surface of the moisture-curable composition in the can, a method of putting a hygroscopic material in the void in the can, and a method of enclosing an inert gas in the void. There is nothing perfect.

  In particular, when the area of the can opening is increased in order to ensure workability during construction, it is considered extremely difficult to ensure a complete sealed structure. Patent Document 1 proposes a method of sealing an aluminum laminated sheet inner bag in a container, but this method unavoidably cures a part of the moisture-curable composition. There are problems such as being a waste and difficult to scrape out the moisture-curable composition. When the surface of the moisture curable composition is covered with the moisture proof film, curing proceeds in the gaps of the moisture proof film even if the inside can be used without any problem, which hinders work. The method of putting a hygroscopic material in the gap in the can and the method of sealing the inert gas in the gap can prevent curing to some extent, but due to fluctuations in the pressure in the can due to temperature differences during storage until use, Hard moisture cannot penetrate for a long period of time. In particular, the moisture curable composition used for the sealant is designed to have high thixotropic properties, and therefore must be scraped off with a spatula or the like in order to take out the material from the inside. In that case, when hardened | cured material arises in a can wall etc., there exists a problem that workability | operativity will be impaired remarkably. Further, Patent Documents 2 to 3 propose a method of filling a specific material in a gap between the coating film and the can wall and curing and sealing, but this method avoids the adhesion of the cured product to the can wall. The problem that the filling operation becomes complicated, the step of peeling the coating film when using the moisture-curable composition, and the problem that it is necessary to dispose of the coating film are included.

  The present invention is capable of preventing internal curing during storage of a moisture-curable composition in a container, is easy to fill the container with the moisture-curable composition, and can be used immediately after opening after storage. It is an object of the present invention to provide a method for filling and packaging a composition.

  In order to solve the above problems, as a result of intensive studies, in a method of filling a moisture curable composition in a sealed container composed of a container body and a lid, the container body is filled with a moisture curable composition by providing a gap. The present inventors have found that the above problems can be solved by applying a compound having a hydrolyzable silyl group having a viscosity of 0.1 to 100,000 mPa · s on the upper surface of the moisture-curable composition. That is, the present invention includes the following (1) to (3).

That is, the present invention relates to (1) a method of filling a moisture curable composition in a sealed container composed of a container body and an upper lid part, and providing a moisture curable composition by providing a gap in the sealed container. A method for filling and packaging a moisture-curable composition, wherein a compound having a hydrolyzable silyl group having a viscosity of 0.1 to 100,000 mPa · s is applied to the upper surface of the composition.
(2) The moisture curable composition filling and packaging method according to (1), wherein the compound having a hydrolyzable silyl group contains the same components in the moisture curable composition.
(3) The application amount of the hydrolyzable silyl group compound is 0.01 to 10 cc per 1 L of the void volume of the sealed container after filling with the moisture curable composition, as described in (1) to (2) A method for filling and packaging a moisture curable composition of the present invention.

In the method of filling and packaging the moisture curable composition of the present invention, the filling process at the time of creation is reduced because no film is used when filling the moisture curable composition into a container body having a gap such as a pail can and a drum can. In addition, the formation of cured foreign matter during storage can be suppressed, so that it has storage stability, and further has an effect that it can be opened immediately after storage and used immediately.

It is sectional drawing of the container which shows embodiment of this invention, and is sectional drawing of the container which shows embodiment.

Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of a container showing an embodiment of the present invention. In the present invention, in a method of filling a moisture curable composition 2 in a sealed container composed of a container body 1 and an upper lid portion 5, the moisture curable composition 2 is filled by providing a gap 3 in the sealed container and filling the moisture curable composition 2. A compound 4 having a hydrolyzable silyl group having a viscosity of 0.1 to 100,000 mPa · s is applied to the upper surface of the product 2. By doing in this way, the production | generation of a hardening foreign material can be suppressed, without using a film etc.

  In this case, the hydrolyzable silyl group-containing compound 4 which is substantially the same component as the hydrolyzable silyl group-containing compound substantially contained in the moisture-curable composition 2 is formed on the moisture-curable composition surface. It reacts with the moisture in the sealed container, and the cured part functions as a moisture-proof layer to suppress the progress of internal curing.

The moisture curable composition in the present invention may be any moisture curable composition, but a silicone moisture curable composition and a modified silicone moisture curable composition are particularly preferable.
The viscosity of the moisture curable composition is preferably 1000 mPa · s or more. Particularly preferably, it is 10,000 mP · s or more.

  Silicone moisture curable compositions and modified silicone moisture curable compositions are mainly composed of a polymer having silanol groups or hydrolyzable silyl groups, and plasticizers, fillers, solvents, thixotropic agents as necessary. An imparting agent, an ultraviolet absorber, an antioxidant, a silanol condensation catalyst, a curing accelerator, a curing retarder, an adhesion imparting agent, a dehydrating agent, and other additives can be used.

  A polymer having a silanol group or hydrolyzable silyl group as a main component is a polymer that can be cross-linked by a silanol condensation reaction, and a polymer that forms a siloxane bond by condensation and changes into a resinous or rubbery form. Point to.

  Examples of polymers include organosiloxanes having silanol groups or hydrolyzable silyl groups, polyalkylene oxides having hydrolyzable silyl groups, acrylic polymers having hydrolyzable silyl groups, and hydrolyzable silyl groups. Examples include polyisobutylene polymers. The above polymer having hydrolyzable silyl groups is cured by humidity in the air at room temperature, and the cured product has excellent flexibility, elongation characteristics, transparency, and water tightness. Although there is, it is not limited to this. Examples of the commercially available polyalkylene oxide having a hydrolyzable silyl group include S943S, S911S, MA440, MA447, MA903M (manufactured by Kaneka Corporation) and the like. Examples of commercially available acrylic polymers having hydrolyzable silyl groups include SA100S, SA310S, OR100S (manufactured by Kaneka Corporation), and the like. Examples of commercially available polyisobutylene polymers having hydrolyzable silyl groups include Epion 303S, Epion 505S, and Epion 103S (manufactured by Kaneka Corporation).

  The closed container used in the present invention refers to a combination of the container body 1 and the upper lid part 5. Although it does not specifically limit as the container main body 1, Conventionally well-known various container main bodies, such as a round can, a square can, a Ito can, a pail can, a drum can, etc. whose capacity | capacitance of a container main body is about 100 milliliters-200 liters. Preferably used. As the various upper lid portions 5, conventionally known various upper lid portions 5 such as a cap lid, a double lid, and an open lid are suitably used.

  In order to prevent deformation or breakage of the container body 1 during storage or transportation, the thickness of the wall surface of the container body is not particularly limited, but is preferably about 0.2 mm or more. In addition, a packing portion made of rubber or plastic may be provided inside the upper lid of the sealed container in order to improve airtightness, buffering property, and the like.

  Examples of the container body 1 include commonly used metal types and plastic types. Examples of the plastic include materials such as polyethylene, polypropylene, ethylene vinyl acetate copolymer, polyethylene terephthalate, and polyamide. The container body is preferably a plastic or metal type container body that does not transmit moisture or has very little moisture.

  Examples of the hydrolyzable group in the compound having a hydrolyzable silyl group applied to the upper surface of the moisture curable composition in the present invention include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, and an ethoxyethoxy group. Alkoxy groups such as groups; acyloxy groups such as acetoxy group, propionyloxy group, butylcarbonyloxy group and benzoyloxy group; alkenyl groups such as isopropenyloxy group, isobutenyloxy group and 1-ethyl-2-methylvinyloxy group Oxy group; ketoxime group such as dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group, cyclopentanoxime group, cyclohexanoxime group; N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethyl Amino groups such as amino group, N, N-diethylamino group and N-cyclohexylamino group; amide groups such as N-methylacetamide group, N-ethylacetamide group and N-methylbenzamide group; N, N-dimethylaminooxy group And aminooxy groups such as N, N-diethylaminooxy group.

  Specific examples of the compound having a hydrolyzable silyl group applied to the upper surface of the moisture curable composition include ethyl silicate, propyl silicate, methyltrimethoxysilane, methylethoxysilane, vinyltrimethoxysilane, biltriethoxysilane, methyltris ( Methoxyethoxy) silane, vinyltris (methoxyethoxy) silane, methyltripropenoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, vinyltrimethylethylketoximesilane, methyltrimethylethylketoximesilane, methyltri (butanoxime) silane, vinyltri (butanoxime) Silane, phenyltri (butanoxime) silane, propyltri (butanoxime) silane, tetra (butanoxime) silane, 3,3,3-trifluoropropi (Butanoxime) silane, 3-chloropropyl (butanoxime) silane, methyltri (propanoxime) silane, methyltri (bentanoxime) silane, methyltri (isopentanoxime) silane, vinyl (cyclopentanoxime) silane, methyltri (cyclohexanoxime) Silane etc. and these partial hydrolysis-condensation products are mentioned.

  The selection of the compound having a hydrolyzable silyl group applied to the upper surface of the moisture curable composition in the present invention is the same as the compound having the hydrolyzable silyl group added to the moisture curable composition to be filled in the container. A compound is preferred. For example, when a compound having an alkoxy group is used as a compound having a hydrolyzable silyl group blended in a moisture curable composition filled in a container, hydrolysis applied to the upper surface of the moisture curable composition in the present invention Similarly, a compound having an alkoxy group is also preferably used as the compound having a functional silyl group. Furthermore, when the compound having a ketoxime group is used as the compound having a hydrolyzable silyl group to be blended in the moisture curable composition filled in the container, it is applied to the upper surface of the moisture curable composition in the present invention. Similarly, a compound having a ketoxime group is also preferably used as the compound having a hydrolyzable silyl group. The compound having a hydrolyzable silyl group added to the moisture curable composition filled in the container is different from the compound having a hydrolyzable silyl group applied to the upper surface of the moisture curable composition in the present invention. In such a case, the properties of the cured product of the moisture curable composition after storage may be changed.

  The viscosity at 20 ° C. of the compound having a hydrolyzable silyl group applied to the upper surface of the moisture curable composition in the present invention is preferably 0.1 to 100,000 mPa · s. Particularly preferred is 500 to 50,000 mP · s. When the viscosity is 0.1 mPa · s or less, a compound having a hydrolyzable silyl group tends to flow, and unevenness is likely to occur on the resin surface, so that it partially cures and coats. If the viscosity is 100,000 mPa · s or more, the coating operation becomes difficult. The coating amount of the compound having a hydrolyzable silyl group applied to the upper surface of the moisture curable composition in the present invention is 0.01 to 10 cc per 1 L of the void volume of the sealed container after filling with the moisture curable composition. desirable. Preservation of sealant since the water content in the container body cannot be sufficiently removed when the coating amount of the compound having hydrolyzable silyl group is 0.01 cc or less per 1 L of void volume of the sealed container after filling with the moisture curable composition A decrease in stability will occur. If the application amount of the compound having a hydrolyzable silyl group is 10 cc or more per 1 L of the void volume of the sealed container after filling with the moisture curable composition, the properties of the moisture curable composition are affected.

  Examples of the coating method of the compound having a hydrolyzable silyl group in the present invention include, but are not limited to, spraying, mist, and inkjet.

  In the present invention, after filling the container body with the moisture curable composition, the container body may be stored with the upper lid closed after passing through the step of replacing the air in the container body with an inert gas. Although it does not specifically limit as a kind of inert gas, Nitrogen gas, a carbon dioxide gas, etc. are mentioned, It uses suitably.

Next, based on an Example, it demonstrates concretely.
(Preparation of silicone moisture-curable composition)
100 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 mPa · s blocked at both ends of the molecular chain with hydroxyl groups, 20 parts by weight of vinyltrimethylethylketoxime silane, 150 parts by weight of calcium carbonate powder, 0.3 parts by weight of dibutyltin dioctoate Were mixed under anhydrous conditions to obtain a composition A.

Example 1
After filling a 20L plastic pail can (polypropylene capacity 20 liters, inner diameter 286 mm, inner height outer height 342 mm, Maeda Seisakusho Co., Ltd.) with about 20 kg of the composition A prepared above, the air in the can was replaced with nitrogen gas The resin surface filled with vinyl trimethylethyl ketoxime silane (viscosity 300 mPa · s, molecular weight 317.5) as a compound having a hydrolyzable silyl group was spray-applied to cover the entire resin surface and immediately covered with an upper lid (made of polyethylene). The sample was sealed and an evaluation sample was prepared. The void volume of the sealed container after filling with the moisture curable composition was 5 L.

(Example 2)
An evaluation sample was prepared in the same manner as in Example 1 except that n-octyltriethoxysilane (viscosity 2 mPa · s) was used instead of vinyltrimethylethylketoximesilane covering the entire resin surface filled in Example 1. .

(Example 3)
A sample for evaluation was prepared in the same manner as in Example 1 except that the amount of vinyltrimethylethylketoxime silane covering the entire resin surface filled in Example 1 was changed to 0.05 cc.

Example 4
A sample for evaluation was prepared in the same manner as in Example 1 except that the amount of vinyltrimethylethylketoximesilane coated on the entire resin surface filled in Example 1 was changed to 0.01 cc.

(Example 5)
A sample for evaluation was prepared in the same manner as in Example 1 except that the amount of vinyltrimethylethylketoximesilane covering the entire resin surface filled in Example 1 was changed to 50 cc.

(Example 6)
An evaluation sample was prepared in the same manner as in Example 1 except that the amount of vinyltrimethylethylketoxime silane covering the entire resin surface filled in Example 1 was changed to 100 cc.

(Comparative Example 1)
Instead of applying the vinyltrimethylethylketoxime silane of Example 1 to the resin surface, an evaluation sample was prepared in the same manner as in Example 1 except that an aluminum laminate sheet was placed on the resin surface and a desiccant was set. At this time, it was difficult to cover the aluminum laminate sheet without leaving the entire surface of the moisture-curable composition in the container.

(Comparative Example 2)
A saturated hydrocarbon polymer having a hydrolyzable silyl group instead of vinyltrimethylethylketoxime silane covering the entire resin surface filled in Example 1 (Epion EP505S; manufactured by Kaneka Chemical Co., Ltd., viscosity 120,000 mPa A sample for evaluation was prepared in the same manner as in Example 1 except that s was changed to a molecular weight of about 5,000 to 20,000.
At this time, since it is difficult to apply polyisobutylene having a hydrolyzable silyl group so as to cover the entire surface of the moisture-curable composition in the container, spray application was difficult, so it was dropped. A sample for evaluation was prepared by stretching with a spatula.
An attempt was made to measure the physical properties of a sample for evaluation after storage for 6 months under an atmosphere of 25 ° C.-55% RH.

[test]
The results of evaluating the samples for evaluation obtained in Examples 1 to 6 and Comparative Examples 1 and 2 by the following method were as shown in Table 1.
[Workability during sample preparation]
The difficulty of the work at the time of preparation of the sample for evaluation was evaluated.
[Storage stability]
Each evaluation sample was stored in an atmosphere of 25 ° C.-55% RH for 3 months and 6 months, then opened and the state of occurrence of a cured film on the surface of the moisture curable resin composition was visually observed. The storage stability was determined.
<Evaluation criteria>
○ ………… No cured film △ …… There is a cured film of 10 mm or less in the depth direction from the surface of the moisture curable resin composition × ………… A cured film of 10 mm or more in the depth direction from the surface of the moisture curable resin composition [Opening workability of sample after storage]
Each evaluation sample was stored for 6 months in an atmosphere of 25 ° C.-55% RH, and then the workability at the time of opening the sample was determined according to the following evaluation criteria.
<Evaluation criteria>
○ ...... Can be used immediately after opening.
Δ: After opening, it is necessary to remove the cured film or sheet on the surface.
× ············································································································································································································································ After opening
[Measurement of physical properties]
The initial physical properties of the evaluation sample and the physical properties of the evaluation sample after storage for 6 months in an atmosphere of 25 ° C.-55% RH were measured by the following evaluation methods and are shown in Table 1.
Viscosity was measured at 20 ° C. with an extrusion viscometer conforming to an apparent viscosity measuring apparatus defined in ASTM D-1092.
Rubber properties were molded into a sheet having a thickness of 2 mm and cured for 7 days in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH to obtain a rubber elastic body. The physical properties were measured according to JIS-K-6249.

  In the method of filling and packaging the moisture curable composition of the present invention, when the moisture curable composition is filled into a sealed container having a gap such as a pail can or a drum can, the cured foreign matter that is being stored without using a film or the like is used. Since production is suppressed and storage stability is obtained, it is effective in reducing the number of filling steps and reducing waste of deposits. Since it can be applied to a wider field, it is industrially useful.

DESCRIPTION OF SYMBOLS 1 Container body 2 Moisture curable resin composition 3 Void 4 Compound 5 having hydrolyzable silyl group Upper lid

Claims (3)

In a method of filling a moisture curable composition in a sealed container composed of a container body and an upper lid, a space is provided in the sealed container to fill the moisture curable composition, and the viscosity of the upper surface of the moisture curable composition is 0.00. A method for filling a moisture-curable composition, which comprises applying a compound having a hydrolyzable silyl group of 1 to 100,000 mPa · s. The method for filling and packaging a moisture-curable composition according to claim 1, wherein the compound having the hydrolyzable silyl group contains the same component in the moisture-curable composition. 3. The moisture curing according to claim 1, wherein a coating amount of the compound having a hydrolyzable silyl group is 0.01 to 10 cc per 1 L of the void volume of the sealed container after filling with the moisture curable composition. Filling and packaging method of mold composition.