JPH07228861A - Sealing material composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a modified polysulfide polymer, a curing catalyst and a polyoxyalkylene monoether without causing the bleed and migration of a plasticizer to the surface of a cured product and a coating, excellent in stability of physical properties of products and useful for construction, etc. CONSTITUTION:This composition contains (A) a modified polysulfide polymer, (B) a curing catalyst and (C) a polyoxyalkylene monoether. Furthermore, e.g. a compound expressed by formula I [R<1> to R<4> each is a bivalent organic group, etc.; (n) is a positive number] is preferably used as the component (A) and, e.g. a compound expressed by formula II [R<5> and R<6> each is H or a 1-18C hydrocarbon; (x) is 1-4; M<1> is a group VIIb or VIII metal of the Periodic Table], especially a mixture of equal amounts of ferric dimethyldithiocarbamate with zinc dibutyldithiocabamate is preferably used as the component (B). For example, a compound expressed by formula III [R<11> is a 2-4C alkylene; R<12> is a l-8C alkyl, a 2-8C alkenyl, etc.; (n) is an integer within the range so as to provide 500-5000 molecular weight], especially polyoxypropylene monomethyl ether is preferably used as the component (C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component oxygen-curable sealant composition containing a modified polysulfide polymer, which is useful for construction / civil engineering, ships, automobiles, etc., and more specifically, a plasticizer. The present invention relates to a sealant composition having no bleeding on the surface of a cured product and transfer to a coating material and having excellent stability of physical properties.

[0002]

2. Description of the Related Art In the fields of construction / civil engineering, ships, automobiles and the like, various types of sealing materials are used for filling and sealing joints and cracks for the purpose of watertightness and airtightness. Of these, the moisture-curing type and the dry-curing type are mainly known as one-component type sealing materials, but the oxygen-curing type containing a modified polysulfide polymer is a newly developed sealing material and has been rapidly developed in recent years. This is a growing field. Such a modified polysulfide-based sealing material is disclosed, for example, in JP-A-62-13106.
No. 1, JP-A-4-266987, and JP-A-4-26687.
It is disclosed in Japanese Patent No. 266986.

Conventionally, in order to improve the workability at the time of construction and to control the rubber physical properties of the cured product obtained, this type of sealing material is generally made of a phthalate ester such as dioctyl phthalate, or dioctyl adipate. A fatty acid ester plasticizer is blended. However, it has been pointed out that the sealing material containing the above-mentioned plasticizer has problems such as the plasticizer bleeding and stickiness on the surface of the cured product, the plasticizer migrating to the paint when the paint is overcoated, and contaminating. It was In order to solve this problem, the present inventors have proposed to use polypropylene glycol or polyethylene glycol as a plasticizer (Japanese Patent Application No. 3-329120).

[0004]

However, when polypropylene glycol or polyethylene glycol is used as a plasticizer, bleeding of the plasticizer, migration of the plasticizer to the paint, and the like have been solved, but this plasticizer has both its molecular structure. Since it has a hydroxyl group at the terminal, there is a problem in that the physical properties of the product are not stable due to interactions such as hydrogen bonds between the polymer and other compounds and between the plasticizers. The present invention has been made in view of the above problems, and an object thereof is a sealant having no bleeding on the surface of a cured product of a plasticizer, migration to a coating material, and the stability of product physical properties. To provide a composition.

[0005]

The sealant composition of the present invention is characterized by containing a modified polysulfide polymer, a curing catalyst for the same, and a polyoxyalkylene monoether, whereby the above object is achieved.

The modified polysulfide polymer used in the present invention may be a modified polysulfide polymer conventionally used in modified polysulfide-based sealing material compositions. For example, a mercapto group (--SH group) capable of being crosslinked at the molecular end may be used. It has at least one and has a polyether urethane bond in the main chain, and examples thereof include those represented by the following general formula (I).

[0007]

[Chemical 1]

In the formula, R ¹ , R ² , R ³ and R ⁴ independently represent a divalent organic group, and n represents a positive number.
Examples of commercially available modified polysulfide polymers represented by the above general formula (I) include "Permapol P-500" and "Permapol P-96" manufactured by Nippon Shokubai Co., Ltd.
5 "(each having a molecular weight of about 10,000 to 20,000).

As the curing catalyst for the modified polysulfide polymer, those conventionally used as a curing catalyst for curing the modified polysulfide polymer are suitable, and are represented by, for example, the following general formulas (II) to (V). There are things.

[0010]

[Chemical 2]

In the formula (II), R ⁵ and R ⁶ are independently hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, x is an integer of 1 to 4, M ¹ is a group VIIb or VIII of the periodic table. Indicates a group metal.

[0012]

[Chemical 3]

In the formula (III), R ⁷ is a divalent hydrocarbon group having 1 to 18 carbon atoms, x is an integer of 1 to 4, and M ¹ is VI in the periodic table.
Indicates a Group Ib or Group VIII metal.

[0014]

[Chemical 4]

In the formula (IV), R ⁸ and R ⁹ are independently hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, and M ² is Ia in the periodic table.
Group Ib group, IIa group, IIb group, IIIa group, IVa group, VIa group or VIb group metal, y represents an integer of 1 to 4.

[0016]

[Chemical 5]

In the formula (V), R ¹⁰ is 2 having 1 to 18 carbon atoms.
Valent hydrocarbon group, M ² is Ia group, Ib group, IIa of the periodic table
Group IIb group, IIIa group, IVa group, VIa group or VIb group metal, y is an integer of 1 to 4.

As the curing catalyst, it is preferable to use one or more kinds represented by the formulas (II) and (III) and one or more kinds represented by the formulas (IV) and (V) in combination. Particularly, an equal mixture of ferric dimethyldithiocarbamate and zinc dibutyldithiocarbamate is preferable.

If the amount of the curing catalyst added is small, the curing speed will be slow, and if it is large, the cured physical properties may be deteriorated. Therefore, the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the modified polysulfide polymer is recommended. preferable.

The polyoxyalkylene monoether used in the present invention is a compound represented by the following general formula (VI). R ¹² O (R ¹¹ O) _n H ... (VI)

In the formula (VI), R ¹¹ represents an alkylene group having 2 to 4 carbon atoms, and R ¹² represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a phenyl group or a phenyl ring. Represents a phenyl group or a benzyl group having an alkyl group having 1 to 9 carbon atoms as a substituent, and n represents an integer in the range where the molecular weight of the compound of the general formula (VI) is 500 to 5000. As the alkylene group, not only one kind but also two or more kinds of alkylene groups may be bonded. When two or more kinds of alkylene groups are bonded, the bonding state may be block or random. As the alkylene group, a propylene group that is liquid at room temperature even if it has a high molecular weight and is also a main chain of the modified polysulfide polymer is preferable.

Specific examples of the compound represented by the general formula (VI) include polyoxypropylene monomethyl ether polyoxypropylene monoethyl ether polyoxypropylene mono n-propyl ether polyoxypropylene monoisopropyl ether polyoxypropylene mono n-. Butyl ether Polyoxypropylene monoisobutyl ether Polyoxypropylene mono t-butyl ether Polyoxypropylene mono n-amyl ether Polyoxypropylene monoisoamyl ether Polyoxypropylene mono n-hexyl ether Polyoxypropylene mono-2-ethylhexyl ether Polyoxypropylene monoallyl ether Polyoxypropylene monophenyl ether Polyoxypropylene monocresyl ether Polyoxypro Ren monooctyl ether polyoxypropylene monobutyl nonylphenyl ether polyoxypropylene monobenzyl ethers. Among these, polyoxypropylene mono C _1-7 alkyl ether, polyoxypropylene monophenyl ether and polyoxypropylene monocresyl ether are particularly preferable.

When the average molecular weight of the polyoxyalkylene monoether used in the present invention is small, tackiness is likely to occur on the surface of the cured product, and when it is large, the viscosity of the composition is high and the workability is deteriorated. 5000 is preferred and about 1000 to 3000 is particularly preferred.

When the amount of the polyoxyalkylene monoether added is small, the plasticizing effect of the cured product decreases, and when it is large, bleeding easily occurs on the surface of the cured product. Therefore, 30 to 100 parts by weight of the modified polysulfide polymer is added.
120 parts by weight is preferable, and 50 to 90 parts by weight is particularly preferable.

The polyoxyalkylene monoethers may be used alone or in combination of two or more.

Polyoxyalkylene monoethers can be produced by various methods, but a method in which a monohydric alcohol and an alkylene oxide are subjected to an addition reaction with an alkali or an acid as a catalyst is general.

Examples of the above-mentioned monohydric alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n.
-Axyl alcohol, 2-ethylhexyl alcohol, aliphatic alcohols such as allyl alcohol, aromatic alcohols such as phenol, cresol, octylphenol, nonylphenol, benzyl alcohol, and the like, and examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene. Oxide may be mentioned.

The sealant composition of the present invention also comprises
If necessary, an antioxidant, an adhesiveness-imparting agent, a UV absorber, a glass balloon, a pigment (for example, titanium oxide), other fillers (for example, calcium carbonate), a fragrance, a solvent (for example, xylene), etc. It may be included.

The sealant composition of the present invention comprises a modified polysulfide polymer, a curing catalyst, a polyoxyalkylene monoether and, if necessary, a predetermined amount of a filler, a solvent and the like, and kneading them with a roll, a planetary mixer or the like. Obtained by

Since the sealing material composition of the present invention is cured by contact with oxygen in the air, it is filled in a cartridge or the like and stored after being shielded from oxygen in the air.

[0031]

Function: -O at both ends of polyalkylene glycol molecule
By substituting the hydrogen of the --OH group on one side of the H group with another compound, the adverse effect of the hydrogen bond etc. exerted by the hydroxyl group is halved and the interaction between the formulations is suppressed, so that the sealing material composition with stable product properties The thing is obtained.

[0032]

EXAMPLES Examples and comparative examples of the present invention will be shown below. Example 1 100 parts by weight of a modified polysulfide polymer (“Permapol P-500” manufactured by Nippon Shokubai Co., Ltd.), ferric dimethyldithiocarbamate (“Nocceler TTFE” manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) and dibutyldithiocarbamate as a curing catalyst. 0.6 parts by weight of an equal mixture of zinc (“Sanceler BZ” manufactured by Sanshin Chemical Industry Co., Ltd.), polyoxypropylene mono-n-
Butyl ether (average molecular weight: about 3000) 60 parts by weight, calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., heavy calcium carbonate) 120 parts by weight, titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd.) 20
One part by weight and 15 parts by weight of xylene were kneaded in a planetary mixer for about 60 minutes and then degassed in vacuum to obtain a sealant composition.

Examples 2 and 3 and Comparative Example 1 Instead of polyoxypropylene mono-n-butyl ether in Example 1, polyoxypropylene monophenyl ether (average molecular weight: about 3000) (Example 2),
Polyoxypropylene monocresyl ether (average molecular weight: about 3000) (Example 3) or polypropylene glycol (manufactured by Mitsui Toatsu Chemicals, Inc., "Diol-300").
0 ”) (Comparative Example 1) was used, and a sealing material composition was obtained in the same manner as in Example 1.

Performance Evaluation of Sealing Material Compositions The sealing material compositions of Examples 1 to 3 and Comparative Example 1 were evaluated for stability of viscosity with time, workability after curing and paint stain resistance, and the results are shown in Table 1. Shown in 1. Viscosity stability After the sealing material composition is manufactured, it is stored in a standard state (20 ° C., relative humidity 65%) for 2 months, 4 months and 6 months, and in the above standard state, a rotor N is used with a BS type viscometer.
o. 7, the viscosity was measured under the condition of 10 rpm. Workability 6 in the above standard condition (20 ° C, relative humidity 65%) after manufacturing
After storage for 6 months, the workability when the sealant composition was spread on a flat plate with a spatula was tested by 5 arbitrary testers in a standard state, and the results were evaluated in the following 5 stages. ,
The average value was calculated. 1: Very light 2: Light 3: Normal 4: Heavy 5:
A very heavy paint-staining sealant composition was applied to a thickness of about 2 mm and allowed to cure for 48 hours in the standard state, after which the paint ("DA" manufactured by Nippon Paint Co., Ltd.
N Uni SH Ceramic White ") was applied and left for 7 days in the standard state, and then the stain state of the paint was evaluated by touch with a finger.

[0035]

[Table 1]

From Table 1, it is clear that the sealing material composition using polyoxyalkylene monoether as the plasticizer does not cause the plasticizer to migrate to the coating material and is excellent in the stability of the physical properties of the product. is there.

[0037]

The composition of the sealing material composition of the present invention is as described above, and since it contains the modified polysulfide polymer, the curing catalyst and the polyoxyalkylene monoether, bleeding of the plasticizer to the surface of the cured product, There is no transfer to paint and the stability of product properties is excellent.

Claims (1)

[Claims] 1. A sealant composition comprising a modified polysulfide polymer, a curing catalyst thereof and a polyoxyalkylene monoether.