JPH05230182A - Sealing material composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition suitable for sealing gaps of articles such as glass, having excellent adhesiveness, storage stability, heat resistance and weather resistance, reacting with humidity in atmosphere and curing at room temperature, comprising a specific polymer and a ketimine compound in a specific ratio. CONSTITUTION:(A) 100 pts.wt. polymer which contains epoxy group at an end, has 5,000-30,000 number-average molecular weight and comprises a main chain consisting essentiailly of a polyether is blended with (B) 0.2-50 pts.wt. ketimine such as 1,2-ethylenebis(isopentylidenimine) to give the objective composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealant composition, and more specifically, it has the property of reacting with atmospheric moisture to cure into a rubber at room temperature, and is particularly excellent in adhesiveness and physical properties after curing. The present invention relates to a composition, which is suitable for use in various kinds of sealing such as gap sealing, sealing, and surface coating of articles.

[0002]

2. Description of the Related Art As a sealing material composition which has a property of curing at room temperature and is used for various sealing applications such as gap sealing, sealing and surface coating of articles, for example, polyurethane-based compositions, silicone-based compositions, Modified silicone-based compositions, polysulfide-based compositions, and the like exist (see Adhesive Handbook, Second Edition, p453 to 460). By the way, the polyurethane-based sealing material composition has the drawbacks that it has poor heat resistance and weather resistance after curing, and that it tends to be foamed to contain bubbles during curing. Further, although the silicone composition has good heat resistance and weather resistance after curing, it has poor surface coating properties, dust is likely to adhere to it due to static electricity, and is easily contaminated when used as a stone sealing material. There are drawbacks. On the other hand, the modified silicone-based composition can compensate for the above-mentioned drawbacks of the polyurethane-based composition and the silicone-based composition, but since the adhesiveness is insufficient, after the primer treatment is performed, Often has to be used. Further, in the polysulfide-based composition, a peroxide such as lead peroxide, calcium peroxide, or barium peroxide is usually added to the composition, but it is toxic and has poor storage stability and heat resistance after curing. sex,
There was a drawback that the weather resistance was not sufficient.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the drawbacks of the above-mentioned conventional sealing material compositions, has excellent adhesiveness, has excellent heat resistance and weather resistance after curing, and reacts with moisture in the atmosphere. An object of the present invention is to provide a sealant composition having the property of being cured like a rubber at room temperature.

[0004]

The sealant composition according to the present invention has a number-average molecular weight of from 5,000 to 5,000, in which the main chain is essentially polyether and has epoxy groups at the ends.
The composition contains 100 parts by weight of a polymer of 30,000 and 0.2 to 50 parts by weight of a ketimine compound, and by using such a composition, adhesiveness and physical properties after curing are excellent, and the composition is cured at room temperature. It has the property to do.

As the polyether polymer in the present invention, for example, one having a polyalkylene glycol as a main chain is used, but one having a polypropylene glycol as a main chain is suitable. Also, the terminal epoxy group is
For example, it can be easily introduced by reacting polyalkylene glycol and epichlorohydrin in an alkaline solution.

The polyether polymer used in the present invention has a number average molecular weight in the range of 5,000 to 30,000. This is because if the number average molecular weight is less than 5,000, it tends to be brittle after curing, and if it is more than 30,000, the viscosity tends to be too high and the sealing workability tends to deteriorate. The preferred number average molecular weight range is 8,000 to 24,
It is 000.

The sealant composition of the present invention contains the above polyether polymer and a ketimine compound. The ketimine compound is a stable compound in the absence of water and does not react with the epoxy group in the polyether polymer. However, in the presence of moisture, primary amines are produced by, for example, contact with moisture in the atmosphere, and thus have a function of reacting with epoxy groups to cure the polyether polymer. Examples of such ketimine compounds include 1,2-ethylenebis (isopentylideneimine), 1,2-hexylenebis (isopentylideneimine), 1,2-propylenebis (isopentylideneimine), p, p′-biphenylene bis (isopentylideneimine), 1,2-ethylenebis (isopropylideneimine), 1,3-propylenebis (isopropylideneimine), p-phenylenebis (isopentylideneimine), 2,5 , 8-Triaza-
1,8-nonadiene, 2,10-dimethyl-3,6,9
-Triaza-2,9-undecadiene, 2,10-diphenyl-3,6,9-triaza-2,9-undecadiene, 3,11-dimethyl-4,7,10-triaza-
3,10-tridecadiene, 3,11-diethyl-4,
7,10-triaza-3,10-tridecadiene, 2,
4,12,14-Tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2,4,20,22
-Tetramethyl-5,12,19-triaza-4,19
-Trieicosadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 9- (3-butoxy-2-hydroxypropyl) -5. 13-dimethyl-6,9,12-triaza-5,12-heptadecadiene and the like can be mentioned.

The amount of the ketimine compound used is 0.2 to 50 parts by weight based on 100 parts by weight of the polyether polymer. If the amount used is less than 0.2 parts by weight, the reaction will not be completed and will be in an uncured state, resulting in lack of practicality as a sealing material. If the amount used is more than 50 parts by weight, storage stability will decrease. Because. The suitable amount of the ketimine compound used is 0.3 to 20 parts by weight.

In the sealing material composition of the present invention, various fillers can be added if necessary. As the filler, for example, calcium carbonate, magnesium carbonate, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, titanium oxide, clay, talc, carbon black and the like are used. These fillers may be used alone or in combination of two or more.

Further, in the sealing material composition of the present invention, the elongation property after curing can be improved or the modulus can be lowered by adding a plasticizer. Examples of the plasticizer include tributyl phosphate, tricresyl phosphate and other phosphoric acid esters, dioctyl phthalate and other phthalic acid esters, glycerin monooleic acid ester and other aliphatic monobasic acid esters, dibutyl adipate, dioctyl adipate and other aliphatic esters. A dibasic acid ester or the like is used. These plasticizers may be used alone or in combination of two or more.

Further, in the sealing material composition of the present invention, the storage stability can be improved by adding a dehydrating agent. Examples of the dehydrating agent include hydrolyzable silicon compounds such as vinyltrimethoxysilane and tetraethoxysilane, isocyanate compounds such as tetramethylxylene diisocyanate, and orthoformate esters such as ethyl orthoformate. In the sealing material composition according to the present invention, a resin such as an epoxy resin or a phenol resin may be used for modification, or a pigment, an ultraviolet absorber, an antioxidant or the like may be used.

[0012]

As described above, in the sealant composition of the present invention, the ketimine compound reacts with atmospheric moisture to form a primary amine, which reacts with the terminal epoxy group of the polyether polymer. Acts as a curing agent. Further, it has a high curing rate in the presence of atmospheric humidity and is excellent in storage stability. The number average molecular weight is 5,000.
Since it is ˜30,000, it does not become brittle after curing, and the viscosity is also suitable for sealing workability.

[0013]

EXAMPLES The present invention will be described in more detail by way of examples. In the examples, "parts" means "parts by weight". (Example 1) In a reactor, 100 parts of polypropylene glycol having a number average molecular weight of 10,000 and 18.5 parts of epichlorohydrin were added, and heated to 120 ° C with stirring and refluxed. To this, 4.5 parts of a 40 wt% NaOH aqueous solution was added dropwise over about 3 hours. Of the water and epichlorohydrin distilled during the reaction, only epichlorohydrin was returned to the reactor. After the addition of the aqueous NaOH solution was completed, excess epichlorohydrin was recovered under reduced pressure, and then NaCl and residual alkali were removed using toluene and water. Further, toluene was removed by heating under reduced pressure.
By this reaction, polypropylene glycol diglycidyl ether having an epoxy group at the terminal was obtained, and its epoxy equivalent was 6,250 and the number average molecular weight was 11,000.
Met.

To 100 parts of the polypropylene glycol diglycidyl ether thus obtained, 5 parts of a ketimine compound (trade name H-3 manufactured by Yuka Shell Epoxy Co., Ltd.) was added. Furthermore, 100 parts of calcium carbonate as a filler,
30 parts of dioctyl phthalate as a plasticizer and 3 parts of vinyltrimethoxysilane as a dehydrating agent were mixed, and these were mixed with a three-roll to obtain a uniform composition.

The dumbbell physical properties, storage stability, adhesiveness, and heat resistance of the composition thus obtained were evaluated and the results are shown in Table 1. The evaluation test method was as follows.

A No. 3 dumbbell test piece having a thickness of 2 mm was prepared from the dumbbell physical composition,
After leaving it for 1 week under the conditions of temperature 23 ° C and relative humidity 50%,
Physical properties of No. 3 dumbbell were measured according to JIS K 6301. The pulling speed at this time was 50 mm / min.

The storage-stable composition was sealed at 50 ° C., and the viscosity change after standing for 5 days was measured. The criteria for judgment are as follows. ◯: Viscosity increase is 2 times or less ×: Viscosity increase is more than 2 times

The adhesive composition is applied to a test plate so as to have a thickness of 2 mm and a width of 2.5 mm, left for 1 week at a temperature of 23 ° C. and a relative humidity of 50%, and then manually peeled in a direction of 180 °. And evaluated. The criteria for judgment are as follows. ○: Cohesive failure occurred ×: Interface failure occurred

The heat resistant composition is applied to a test plate and the temperature is 23 ° C. and the relative humidity is 50%.
After curing for 1 week under the conditions of,
It was left for 4 hours and evaluated for appearance and touch. The criteria are as follows. ○: Change is observed, but rubber elasticity is retained ×: Melting

As is clear from the following test results, this composition has excellent storage stability, excellent extensibility even after curing, excellent heat resistance, and adhesion to glass, metal and resin. Since it is also excellent, it was suitable for use as a sealing material for gap sealing, sealing, surface coating and the like of articles made of these materials.

Example 2 The compounding amount of the ketimine compound was 1
A composition was obtained in the same manner as in Example 1 except that 0 part was used. An evaluation test was conducted in the same manner as in Example 1. The results are also shown in the column of Example 2 in Table 1. As is clear from the test results below, this composition was suitable for use as a sealant.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that the amount of the ketimine compound was 0.1 part. An evaluation test was conducted in the same manner as in Example 1. The results are also shown in the column of Comparative Example 1 in Table 1. As in the test results below, the curing was insufficient and the dumbbell physical properties could not be measured, and the adhesiveness and weather resistance were also unmeasurable.

(Comparative Example 2) The compounding amount of the ketimine compound was 7
A composition was obtained in the same manner as in Example 1 except that 0 part was used. An evaluation test was conducted in the same manner as in Example 1. The results are also shown in the column of Comparative Example 2 in Table 1. As in the test results below, this composition had poor storage stability.

(Comparative Example 3) Polypropylene glycol diglycidyl ether having an epoxy equivalent of 1,780,
A composition having a number average molecular weight of 4,000 (Nagase Kasei Co., Ltd., trade name Denacol EX-4000) was used, and the composition was the same as in Example 1 except that the amount of the ketimine compound was 10 parts. Obtained. An evaluation test was conducted in the same manner as in Example 1. The results are also shown in the column of Comparative Example 3 in Table 1. As in the test results below, this composition had poor elongation properties.

(Comparative Example 4) A polypropylene glycol diglycidyl ether was used in place of a number average molecular weight of 7,50.
0 modified silicone polymer (Kanefuchi Chemical Co., Ltd., trade name M
A composition was obtained in the same manner as in Example 1 except that S polymer 20A) was used and 3 parts of the tin catalyst was blended without using the ketimine compound. An evaluation test was conducted in the same manner as in Example 1. The results are also shown in the column of Comparative Example 4 in Table 1. As shown in the test results below, this composition had poor adhesion to glass plates and polycarbonate plates, and also had insufficient weather resistance.

[0026]

[Table 1]

The components (A) (B) (C) used in Table 1 are as follows. (A) Polypropylene glycol diglycidyl ether (epoxy equivalent 6,250, number average molecular weight 11,0
00) (B) Polypropylene glycol diglycidyl ether (epoxy equivalent: 1,780, number average molecular weight: 4,000)
0) (C) Modified silicone polymer (number average molecular weight 7,5
00)

[0028]

The sealant composition of the present invention is excellent in storage stability and has the property of reacting with atmospheric humidity to cure into a rubber at room temperature when used, and has adhesiveness with glass, metal and resin. Excellent in heat resistance and weather resistance after curing. Therefore, it is suitable for use as a sealing material for gap sealing, sealing, surface coating, etc. of articles made of materials such as glass, metal and resin.

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Claims (1)

[Claims] 1. A number-average molecular weight of 5,000 to 3 whose main chain is essentially polyether and has an epoxy group at the terminal.
A sealant composition comprising 100 parts by weight of a polymer of 20,000 and 0.2 to 50 parts by weight of a ketimine compound.