JP2003119382A - Polysulfide-based curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing composition suitable as a sealing material having a slight residual tack on the surface of a cured product, good water-resistant adhesion and a slighter change in physical properties after heating. SOLUTION: This curing composition comprises (A) a polysulfide polyether polymer, (B) a urethane prepolymer, (C) a compound having an air-oxidizable unsaturated group, (D) a fatty acid ester and (E) an inorganic filler having the surface treated with a paraffin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition, and in particular, a cured product having less residual tack on the surface of the cured product, excellent water-resistant adhesiveness, and less change in physical properties after heating, and sealing. The present invention relates to a curable composition suitably used as a material.

[0002]

2. Description of the Related Art A curable composition comprising (A) a polysulfide polyether polymer and (B) a urethane prepolymer is used as a polysulfide-based sealing material and has excellent weather resistance and durability. It is a non-contaminating sealing material that does not contaminate the surface of the cured product outdoors. However, the surface tackiness (hereinafter, referred to as residual tack) in the early stage of curing is slowly lost in a state where it is not exposed to sunlight, especially in indoor construction, and dust in the air may be attached to contaminate the surface. In order to improve this, in Japanese Patent Laid-Open No. 2000-344853,
(1) A polymer having two or more thiol groups in the molecule, (2) a compound having two or more isocyanate groups in the molecule, and (3) a compound having an air-oxidizable unsaturated group, Further, by adding (4) a fatty acid ester, a curable composition has been proposed in which the residual tack on the surface of the cured product is small, and the increase in tensile stress and the decrease in elongation due to heating are reduced. However, the obtained curable composition has drawbacks in water-resistant adhesiveness, and is also practically insufficient in terms of retaining physical properties after heating.

[0003]

Problem to be Solved by the Invention Problem to be Solved by the Invention (Objective)
Another object of the present invention is to provide a curable composition suitable as a sealing material, which has less residual tack on the surface of the cured product, has good water-resistant adhesiveness, and has less change in physical properties after heating.

[0004]

As a result of earnest research in view of the above object, the present inventors have added a fatty acid ester to a polysulfide polyether polymer, a urethane prepolymer and a compound having an air-oxidizable unsaturated group, and further, It has been found that the use of the paraffin-treated inorganic filler results in less residual tack, excellent water-resistant adhesion, and less change in physical properties after heating.

The present invention will be described below. Claim 1
Of the invention, (A) polysulfide polyether polymer, (B) urethane prepolymer, (C) compound having an air-oxidizable unsaturated group, (D) fatty acid ester, and (E) surface paraffin-treated inorganic substance A curable composition comprising a filler. It is possible to obtain a curable composition having a small amount of residual tack, an excellent water-resistant adhesive property, and an extremely small change in physical properties after heating, only by combining the configurations of (A) to (E).

The invention of claim 2 is characterized in that the compound (C) having an air-oxidizable unsaturated group is a drying oil. By this technical means, a curable composition having less residual tack can be obtained. The invention of claim 3 is
(C) The compound having an air-oxidizable unsaturated group is tung oil. By this technical means, a curable composition having less residual tack can be obtained.
The invention of claim 4 is characterized in that the fatty acid of the fatty acid ester (D) has 24 to 34 carbon atoms. By this technical means, it is possible to obtain a curable composition having better water-resistant adhesiveness than a fatty acid ester having a small number of carbon atoms. The invention of claim 5 is characterized in that the inorganic filler of the (E) surface paraffin-treated inorganic filler is calcium carbonate. By this technical means, it is possible to obtain a curable composition with less change in physical properties after heating.

The invention of claim 6 is characterized in that the inorganic filler of the (E) surface paraffin-treated inorganic filler is heavy calcium carbonate. By this technical means, it is possible to obtain a curable composition which is more economical than colloidal calcium carbonate and has less change in physical properties after heating. Claim 7
The invention (1) is characterized in that (E) the paraffin of the surface-paraffin-treated inorganic filler is solid paraffin. By this technical means, since the melting point is higher than that of liquid paraffin, a curable composition having less change in physical properties after heating can be obtained. The invention of claim 8 is characterized in that the sealing material comprises the curable composition according to any one of claims 1 to 7. By this technical means, it is possible to obtain a sealing material having little residual tack, excellent water-resistant adhesiveness, and extremely little change in physical properties after heating.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Each constitution of the present invention will be described in detail below. (A) Polysulfide polyether polymer (hereinafter,
Sometimes referred to simply as (A). The number average molecular weight of the polysulfide polyether polymer of the present invention is usually 600 to 200,000, preferably 800 to 50,000. Such a polysulfide polyether polymer is disclosed, for example, in JP-A-4-
As described in Japanese Patent No. 363325, a halogen-terminated prepolymer obtained by adding epihalohydrin to polyoxyalkylene glycol and a polysulfide polymer are mixed with alkali hydrosulfide and // at a weight ratio such as 95/5 to 5/95. Alternatively, it can be produced by a method of reacting with an alkali polysulfide.

(B) Urethane Prepolymer (Hereinafter, May Be Simply Referred to as (B).) The urethane prepolymer of the present invention is a urethane prepolymer obtained by reacting an active hydrogen-containing compound with an organic polyisocyanate compound. preferable. Examples of the organic polyisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate (crude MDI), xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
As the active hydrogen-containing compound, a hydroxyl group-terminated polyester, a polyvalent polyalkylene ether, a hydroxyl group-terminated polyurethane polymer, an acrylic polyol having a hydroxyl group introduced into an acrylic copolymer, a hydroxyl group-terminated polybutadiene, a polyvalent polythioether, a polyacetal, an aliphatic polyol. ,
Diamines, including aromatic, aliphatic and heterocyclic diamines, and the like, and mixtures thereof.

In the present invention, the ratio of (A) / (B) is the molar ratio of the isocyanate group in the compound (B) and the thiol group in the polysulfide polyether polymer (A) (isocyanate group). / Thiol group)
However, it is preferable to mix them so as to be 0.5 to 4.0. When the molar ratio is less than 0.5, the curable composition does not have a sufficiently high molecular weight, which is not preferable, while when it exceeds 4.0, the cured product becomes hard and brittle, which is not preferable.
A more preferable molar ratio is 0.7 to 3.0.

(C) A compound having an air-oxidizable unsaturated group
Compounds Examples of the compound having an air-oxidizable unsaturated group of the present invention include a drying oil. Specifically, mixed triglycerides of unsaturated fatty acids and fats and oils having an iodine value of 130 or more (vegetable oil and fish oil) can be used. Examples of vegetable oils include flaxseed oil, eno oil, tung oil, paulownia oil, deer oil, hemp oil, kaya oil, inugaya oil, walnut oil, nigrum oil,
Poppy oil, sunflower oil, soybean oil, safflower oil, etc. Examples of the fish oil include sardine oil, herring oil, menhaden oil and the like. Other than this, isomerized oil obtained by alkali isomerization of fish oil, dehydrated castor oil obtained by dehydrating castor oil, and the like can be mentioned. Particularly preferred examples are tung oil and eucalyptus oil containing a large amount of conjugated acid type unsaturated fatty acids such as eleostearic acid. In the present invention, the amount of the drying oil added is 0.1 to 30 parts by weight, and more preferably 0.5 to 20 polymerization parts, based on 100 parts by weight of the total of (A) and (B). If the amount added is less than 0.1 parts by weight, the residual tack improvement will be poor, and if it exceeds 30 parts by weight, it is not preferable in terms of economy and odor.

(D) Fatty Acid Ester The fatty acid ester of the present invention includes a fatty acid and a monovalent or divalent fatty acid.
It is possible to use a wax composed of a dihydric alcohol or a fatty acid glycerin ester composed of a fatty acid and glycerin, and the acid group may be a saturated fatty acid and / or an unsaturated fatty acid. Examples of the saturated fatty acid include butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ligrinoseric acid, cerotic acid, montanic acid, and melissic acid. Examples of unsaturated fatty acids include succinic acid, linderic acid, tsuzuic acid, macouic acid, myristooleic acid,
Zomaric acid, petroselinic acid, oleic acid, vaccenic acid, gadoleic acid, whale oil acid, erucic acid, shark oil acid, linoleic acid, hiragoic acid, eleostearic acid, bunicic acid,
Examples thereof include tricosanoic acid, linolenic acid, moloctic acid, parinaric acid, arachidonic acid, sardine acid, hiragashilaic acid and nisinic acid.

Among the above fatty acid esters, the fatty acid acid group is preferably a saturated fatty acid, and more preferably a fatty acid having 24 to 34 carbon atoms. Among them, water-resistant adhesion,
A montanic acid ester wax composed of montanic acid / ethylene glycol, which has little change in physical properties after heating, is particularly preferable. The amount of the fatty acid ester added is 1 to 20 parts by weight, preferably 2.0 to 30 parts by weight, based on 100 parts by weight of the total of (A) and (B). When the addition amount is less than 1 part by weight, the change in physical properties after heating becomes large, and when it exceeds 30 parts by weight, it is not preferable from the viewpoint of economy and physical properties.

(E) Surface Paraffin Treated Inorganic Filler The surface paraffin treated inorganic filler can be produced by mixing the inorganic filler and the surface treating agent paraffin. Examples of the inorganic filler include heavy calcium carbonate produced by mechanically crushing limestone, talc whose main component is hydrous magnesium silicate, and clay containing pyrophyllite as a rough stone. As surface treatment paraffin,
Since solid paraffin has a higher melting point than liquid paraffin, a curable composition with less change in physical properties after heating can be obtained, which is more preferable.

In the present invention, the compounding amount of the surface-paraffin-treated inorganic filler is 10 in total of the above (A) and (B).
15 to 75 parts by weight, preferably 25 to 75 parts by weight
It is 65 parts by weight. If the amount is less than 15 parts, the effect of retaining physical properties after heating is poor, and if it is more than 65 parts, the adhesion of the water-based coating is reduced. -Other compounds In the curable composition of the present invention, silica, from the viewpoints of economy, workability when applying the composition and improvement of physical properties of the composition,
Fillers for hollow microspheres such as zeolite, perlite, ceramic balloons, glass balloons, silica balloons, shirasu balloons, alumina balloons, plastic balloons, phthalates, butylbenzyl phthalate, hydrogenated terphenyls, xylene resins, etc. Plasticizer,
A phosphite compound, an unsaturated alcohol, a tin catalyst, and an amine-based catalyst can be added as additives.

[0016]

EXAMPLES The present invention will now be described in more detail by way of examples. (Example 1) Polysulfide polyether polymer (trade name: Thiokol LP282, manufactured by Toray Thiokol Ltd., mercaptan content 2.0% by weight, viscosity 910)
0 cp / 25 ° C) 60 parts by weight, plasticizer (dioctyl phthalate) 27 parts by weight, and tin catalyst (trade name: SCAT4A
0.3 parts by weight of Sankyo Machine Gosei Co., Ltd., 0.9 parts by weight of oleyl alcohol (product name: Angkor 90N Shin Nihon Rika Co., Ltd.), and phosphite ester (product name: JP333E) 0.9 part by weight of Johoku Chemical Industry Co., Ltd., 9 parts by weight of xylene resin (trade name: Nikanol LLL Mitsubishi Gas Chemical Co., Ltd.), and colloidal calcium carbonate (trade name: Neolite SP-T Takehara Chemical Industry) 90 parts by weight (manufactured by K.K.) were uniformly mixed.

Next, to 188 parts by weight of this mixture, 50 parts by weight of surface-paraffin-treated heavy calcium carbonate (trade name: MC coat P1 (average particle size of about 10 μm) manufactured by Maruo Calcium Co., Ltd.) and polypropylene glycol and xylene diisocyanate were added. Urethane prepolymer (isocyanate content 4.2% by weight) obtained by adding 4
0 parts by weight, tung oil 3 parts by weight, and 5.0 parts by weight of montanic acid ester wax (hereinafter abbreviated as montanic acid ester) composed of montanic acid / ethylene grill coal were mixed to prepare a curable composition. Prepared. (Example 2) As a surface paraffin-treated inorganic filler,
Surface paraffin-treated heavy calcium carbonate with a smaller particle size (trade name: MC coat P10 (average particle size of about 7μ
m) Example 1 except using Maruo Calcium Co., Ltd.)
A curable composition was prepared in the same manner as in. (Example 3) As a surface paraffin-treated inorganic filler,
Surface-paraffin-treated heavy calcium carbonate with a smaller particle size (trade name: MC coat P20 (average particle size of about 3 μ
m) Example 1 except using Maruo Calcium Co., Ltd.)
A curable composition was prepared in the same manner as in.

Comparative Example 1 A curable composition was prepared in the same manner as in Example 3 except that montanic acid ester was not used. (Comparative Example 2) Surface paraffin-treated heavy calcium carbonate (trade name: MC coat P1 (average particle size: about 10 μm)
Example 1 except that saturated calcium carbonate treated with saturated fatty acid (trade name: Ncc # 45 (average particle diameter of about 4.4 μm) manufactured by Nitto Koka Kogyo Co., Ltd.) was used in place of Maruo Calcium Co., Ltd. A curable composition was prepared in the same manner as in. (Comparative Example 3) Instead of surface-paraffin-treated heavy calcium carbonate (trade name: MC coat P1 (average particle size: about 10 μm)), untreated heavy calcium carbonate (trade name: NS40)
0 (Average particle size: 1.7 μm) Nitto Koka Kogyo Co., Ltd.
A curable composition was prepared in the same manner as in Example 1 except that (Comparative Example 4) A curable composition was prepared in the same manner as in Example 3 except that (C) tung oil was not used.

With respect to the curable compositions of Examples 1 to 3 and Comparative Examples 1 to 4, the following tests 1 to 3 were conducted. The results are shown in Tables 1 and 2. Surface Tack A sheet having a thickness of 10 mm was prepared from the curable compositions of Examples and Comparative Examples, and the state of the surface tack after 23 days at 23 ° C. was examined by touch with a finger. The case where the tack was not felt at all was marked as ◎, the tack which was hardly felt was marked as ○, the tack which was felt a little was marked as △, and the tack which was greatly felt was marked as ×.

Tensile Adhesiveness The adherend was made of anodized aluminum, and "Bond Seal Primer # 9, manufactured by Konishi Co., Ltd." was used as a primer. In order to prevent bubbles from entering the space of 12 × 12 × 50 mm, which is formed by combining the curable compositions of Examples and Comparative Examples with two adherends of alumite aluminum (50 × 50 mm) and two spacers. It filled and created the H type test body. Next, a tensile adhesion test was performed on this H-type test body in accordance with JIS A 1439. The adhesiveness of the H-shaped test body after curing, after water immersion and after heating was measured by performing a tensile adhesion test at 23 ° C. after placing it under the following test conditions. <Test conditions>"Adhesion after curing": 23 ° C 7 days + 50 ° C 7 days "Adhesion after immersion in water": After curing (23 ° C 7 days + 50 ° C 7
Sun) + 23 ° C in water 7 days "Adhesion after heating": After curing (23 ° C 7 days + 50 ° C 7 days)
+ 90 ° C. 14 days Tensile adhesion (abbreviated as “adhesion” in the table)
The state of destruction was indicated by ◯ for cohesive failure of the curable composition, Δ for thin layer cohesive failure, and x for interface failure.

After curing → elongation at maximum load after heating
The retention rate of elongation at maximum load after heating (23 ° C 7 days + 50 ° C 7 days) to 90 ° C 14 days after curing is calculated by the following formula, and 80% or more is ○, 60 to 80% Less than △, 60%
Less than was designated as x.

[0022]

[Table 1]

[0023]

[Table 2]

From the results of Table 1 and Table 2, Examples 1 to 3 are
Compared to Comparative Examples 1 to 4, less residual tack was present, and adhesiveness after curing / adhesiveness after immersion in water (corresponding to waterproof adhesiveness) /
It can be seen that the adhesiveness after heating is excellent and the retention of elongation after heating is large (the change in physical properties after heating is small), and that it is particularly suitable as a sealing material.

[0025]

EFFECT OF THE INVENTION According to the present invention, it is possible to provide a curable composition having less residual tack on the surface of a cured product, good water-resistant adhesiveness, and little change in physical properties after heating. Since the problem of surface tackiness in the early stage of curing in indoor construction is solved, it can make a special contribution in the field of sealing materials.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 3/10 C09K 3/10 DF QZ (72) Inventor Tsutomu Nanami 5-3 Nishibori, Saitama City Saitama Prefecture −35 Konishi Co., Ltd. Urawa Research Institute (72) Inventor Rieko Fuji 5-3-35 Nishibori Saitama City Saitama Prefecture F Term (reference) 4U017 AA04 AA25 AA31 AA39 AB03 AB14 AC11 AC17 AD05 AE03 4J002 AE053 AE054 CK03X CK04X CK05X CN01W DE207 DE237 DJ037 DJ047 EH036 EH046 EH076 FB267 FD010 FD017 FD020 FD14X FD150 GJ02 4J034 BA03 CA01 CA15 CB02 HC63 HC06 HC06 HC06 HA02 HA06 HA22 HA06 HA22 HA01 HA22 HA01 DP22 HC67 HC71 HC73 JA42 JA43 MA01 MA04 MA12 MA26 RA08

Claims (8)

[Claims] 1. A polysulfide polyether polymer (A), a urethane prepolymer (B), an air-oxidizable unsaturated group-containing compound (C), a fatty acid ester (D), and a surface paraffin treatment (E). A curable composition comprising an inorganic filler. 2. The curable composition according to claim 1, wherein the compound (C) having an air-oxidizable unsaturated group is a drying oil. 3. The curable composition according to claim 1, wherein the compound (C) having an air-oxidizable unsaturated group is tung oil. 4. The curable composition according to claim 1, wherein the fatty acid of the fatty acid ester (D) has 24 to 34 carbon atoms. 5. The curable composition according to claim 1, wherein the inorganic filler of the (E) surface-paraffin-treated inorganic filler is calcium carbonate. 6. The curable composition according to claim 1, wherein the inorganic filler of the (E) surface-paraffin-treated inorganic filler is ground calcium carbonate. 7. The curable composition according to claim 1, wherein (E) the paraffin of the surface paraffin-treated inorganic filler is solid paraffin. 8. A sealing material comprising the curable composition according to claim 1.