JPH0261993B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful caulking or sealing material, and more particularly to a caulking or sealing material comprising a specific fatty acid-modified vinyl copolymer as an essential resin component. In recent years, many base resins have been developed and put into practical use for these caulking and sealing materials. Among them, polymerized oils and alkyds have been used for the longest time, but they themselves are inexpensive. Moreover, it continues to be used in large quantities even today because it has the advantage of being extremely easy to handle. However, these caulking or sealing materials based on polymerized oils or alkyds have fatal flaws such as being prone to cracking when drying and having poor weather resistance. Improvements in these points are desired. However, as a result of intensive research in view of the above-mentioned actual situation, the present inventors found that when a specific (β-methyl)glycidyl group-containing vinyl copolymer modified with a drying oil fatty acid was used, the The present invention was completed by discovering that it is possible to obtain a caulking or sealing material that does not cause cracks and has excellent weather resistance. That is, in the present invention, 100 parts by weight of the (β-methyl)glycidyl group-containing vinyl copolymer has an iodine value.
The present invention provides a caulking material or a sealing material comprising as an essential resin component a fatty acid-modified vinyl copolymer obtained by addition-reacting 3 to 200 parts by weight of drying oil fatty acids of 100 to 200%. Here, the (β-methyl)glycidyl group-containing vinyl copolymer mentioned above refers to (β-methyl) glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, diglycidyl fumarate, etc. A vinyl monomer containing a glycidyl group, styrene, t-butylstyrene, an alkyl (meth)acrylate or dialkyl fumarate, dialkyl maleate or itaconate having an alkyl group of _C1 to _C22 ,
Representative examples include β-hydroxyethyl (meth)acrylate or β-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate, acrylamide or butoxyethyl acrylamide, acrylonitrile, vinyl chloride or vinyl acetate. As an example, it refers to a copolymer obtained from other vinyl monomers that do not contain (β-methyl) glycidyl groups. The ratio of glycidyl group-containing vinyl monomer to other vinyl monomers not containing (β-methyl)glycidyl group is 3.
A suitable range is 97:97-3, preferably 5-50:95-50 (weight ratio). On the other hand, typical drying oil fatty acids mentioned above include fatty acids of natural oils such as rice sugar oil, cottonseed oil, soybean oil, dehydrated castor oil, safflower oil, tall oil, or Chinese tung oil, or "PAMOLYN". Synthetic drying oil fatty acids such as ``200 and 300'' (products of Hercules Co., Ltd., USA) have an iodine value within a specific range of 100 to 200, and these can be used alone or in a mixture in any proportion. Can be done. The caulking material of the present invention has as an essential base resin component a modified copolymer obtained by addition-reacting the vinyl copolymer and fatty acid as described above. ) in the glycidyl group-containing vinyl copolymer (β
-Methyl)glycidyl group and the carboxyl group in the drying oil fatty acid, and the ratio of these two raw materials is 100 parts by weight of the copolymer to A suitable proportion is 3 to 200 parts by weight, preferably 5 to 100 parts by weight. Both the method for preparing such a modified copolymer and the method for preparing the (β-methyl)glycidyl group-containing vinyl copolymer used to obtain the modified copolymer are based on known and commonly used methods. Means such as bulk polymerization, solution polymerization, or suspension polymerization can be employed as they are, but among these known and commonly used means, reaction in a solvent can be said to be the easiest. That is, to prepare the vinyl copolymer containing (β-methyl)glycidyl group, first, an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide or t-butyl perhexoate is used. The (β-methyl)glycidyl group-containing vinyl monomer as described above and another vinyl monomer containing no (β-methyl)glycidyl group may be polymerized in the presence of a polymerization initiator such as the above. Next, in order to prepare a fatty acid-modified vinyl copolymer by an addition reaction between the (β-methyl)glycidyl group-containing vinyl copolymer obtained in this way and the above-mentioned drying oil fatty acid, a compound such as imidazole or triphenylphosphone, etc. The copolymer and the fatty acid are heated at 50 to 250°C in the presence or absence of a catalyst.
It is sufficient to heat it within a certain range. The modified copolymer thus obtained remains as it is;
Alternatively, once the solvent has been removed, if necessary,
Furthermore, various dryer components such as cobalt naphthenate or lead naphthenate can be added to make a caulking material or a sealing material by a conventional method. However, when referring to a caulking material in the present invention, the term "caulking material" also includes a sealing material. It is sometimes used in a different form. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, where all "parts" are "parts by weight" unless otherwise specified. Examples 1 to 6 and Comparative Example 1 A flask was charged with 100 parts of xylene, nitrogen gas was blown into the flask, the temperature was raised to 110°C with stirring, and then various vinyl monomers and polymerization initiators as shown in Table 1 were added thereto. A mixture consisting of the above was added dropwise over 1 hour, and then kept at the same temperature for 5 hours, and then 2-methylimidazole and fatty acids as shown in Table 2 were added and kept at the same temperature for 10 hours. Then in each case the respective acid value was 2 mg.
When it was confirmed that the concentration was below KOH/g,
The solvent was removed under conditions of 200°C and 1 mmHg to obtain various fatty acid-modified vinyl copolymers. Thereafter, each of the copolymers thus obtained was used to prepare a caulking material according to the formulation shown in Table 2, and then each of these was individually placed on a metal plate.
It was rolled out to a thickness of cm. For each caulking material treated board, the condition of the treated surface after one week and after being exposed outdoors (Nichinan Coast, Miyazaki Prefecture) for 6 months was observed.

[Table] * Each number in the table is the preparation amount of each raw material compound.
It means a number.

【table】

[Table] * Each number in the table means the number of parts mixed.
Note 1) Linseed oil fatty acid modified alkyd resin manufactured by Dainippon Ink and Chemicals Co., Ltd.; oil length 80.

Claims (1)

[Claims] 1. Obtained as an essential resin component by adding 3 to 200 parts by weight of a drying oil fatty acid having an iodine value of 100 to 200 to 100 parts by weight of a vinyl copolymer containing glycidyl groups and/or β-methylglycidyl groups. A caulking material containing a fatty acid-modified vinyl copolymer.