JPH0535101B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a water-permeable tile, and more particularly to a water-permeable tile that can be manufactured without the need for a drying process prior to forming and firing steps. [Prior Art and Problems to be Solved by the Invention] Water-permeable tiles installed on poolsides and park pavements have traditionally been made of clay, polyvinyl alcohol,
It has been common practice to mix resins that are easily soluble in water or organic solvents, such as polyvinyl acetate, in the form of a resin solution, and then to manufacture it by molding and baking it. However, when using such a resin solution, it is necessary to remove water and organic solvents prior to the molding and firing process in order to ensure good moldability and improve the efficiency of the firing process. They had no choice but to use sun drying or other drying treatments. Furthermore, conventional water permeable tiles have had the disadvantage that a relatively large amount of resin must be blended in order to obtain excellent water permeability. The present invention solves these conventional problems and aims to provide a water-permeable tile that, firstly, does not require a drying process prior to molding and firing, and secondly, has excellent water permeability with a small amount of additives. . [Means for Solving the Problem] As a result of intensive research to achieve the above object, the present inventor found that when a hydroxyl group-containing liquid diene polymer and a polyisocyanate compound are used as substances to be added to clay, clay and Only a very small amount of water can be used when compounding, so molding,
The present invention was completed by discovering that a drying step prior to firing is unnecessary. That is, the water-permeable tile of the present invention is characterized by being formed from a molded and fired clay composition comprising clay, a hydroxyl group-containing liquid diene polymer, and a polyisocyanate compound. [Specific Description] The water-permeable tile of the present invention is obtained by molding and firing a clay composition having the above-mentioned three components as essential components. The type is not particularly limited, such as china clay, kaolin,
Examples include bentonite, Kibushi clay, and Gairome clay. The second component, the hydroxyl group-containing liquid diene polymer, has a hydroxyl group in the molecule or at the end of the molecule and has a number average molecular weight of 300 to 25,000;
Preferably, a liquid diene polymer having a molecular weight of 500 to 10,000 is used. Here, the content of hydroxyl groups is usually 0.1~
10 meq/g, preferably 0.3 to 7 meq/g. These liquid diene polymers have a carbon number of 4
-12 diene polymers, diene copolymers, and copolymers of these diene monomers with α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. Specifically, butadiene homopolymer, isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer,
Examples include butadiene-2-ethylhexyl acrylate copolymer and butadiene-n-octadecyl acrylate copolymer.
These liquid diene polymers can be produced, for example, by subjecting a conjugated diene monomer to a heating reaction in a liquid reaction medium in the presence of hydrogen peroxide. In addition, the polyisocyanate compound as the third component is an organic compound having two or more isocyanate groups in one molecule, and is an organic compound having reactive isocyanate groups with respect to the hydroxyl groups of the hydroxyl group-containing liquid diene polymer. It is something that you have.
Examples of polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate. , polymethylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, addition reaction product of polypropylene glycol and tolylene diisocyanate, etc. MDI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate, etc. are preferred. The amounts of these three essential components are not particularly limited, but usually the hydroxyl group-containing liquid diene polymer and the polyisocyanate compound are each 5 to 50 parts by weight per 1000 parts by weight of the clay.
Further, it is preferably about 10 to 30 parts by weight. In addition, the ratio of the isocyanate groups in the polyisocyanate to the hydroxyl groups contained in the hydroxyl group-containing liquid diene polymer (NCO/OH) is 0.2 to 25,
Furthermore, it is preferable to set the blending amount of both to be 0.5 to 15. In addition to the above-mentioned three essential components, the clay composition of the present invention may contain a polyol compound, a polyamine compound, and other additives, if necessary. First, there are no particular limitations on the polyol compound, and any of primary polyols, secondary polyols, and tertiary polyols may be used. Specifically, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-
Butanediol, 2,3-butanediol, 1,
2-pentanediol, 2,3-pentanediol, 2,5-hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin,
N,N-bis-2-hydroxypropylaniline, N,N'-bishydroxyisopropyl-2
- low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon, such as methylpiperazine, propylene oxide adduct of bisphenol A; Furthermore, as a polyol, ethylene glycol containing no hydroxyl group bonded to a secondary carbon, 1,3
-Propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. can also be used. Diols are usually used as polyols, but triols and tetraols may also be used, and their molecular weights range from 50 to 500. The polyamine compound may be any of diamine, triamine, and tetraamine. Furthermore, 1
Any of class polyamine, secondary polyamine, and tertiary polyamine can be used. Examples of polyamine compounds include aliphatic amines such as hexamethylene diamine; alicyclic amines such as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane;
Aromatic amines such as 4,4'-diaminodiphenyl;
Examples include tetramines such as 2,4,6-tri(dimethylaminomethyl)phenol. The blending amount of these polyol compounds or polyamine compounds is, for example, 1 to 1 to 100 parts by weight of the above-mentioned hydroxyl group-containing liquid diene polymer.
It is preferably about 1000 parts by weight, more preferably about 3 to 200 parts by weight. Other additives include fillers such as mica, graphite, vermiculite, calcium carbonate, and slate powder. Furthermore, plasticizers such as dioctyl phthalate are added as clay conditioners, and softeners such as aromatic, naphthenic, and paraffinic oils are added.
Tackifying resins such as alkyl phenol resins, terpene resins, terpene phenol resins, xylene formaldehyde resins, rosins, hydrogenated rosins, chroman resins, aliphatic and aromatic petroleum resins may be added to adjust adhesive strength and adhesive strength. can.
Further, curing accelerators such as dibutyltin dilaurate, stannous octoate, polyethylene diamine, etc. can also be added. Furthermore, an anti-aging agent can be added to improve weather resistance, and a silicon compound or the like can be added as an antifoaming agent. The water-permeable tile of the present invention can be manufactured, for example, as follows. First, a clay composition is prepared by blending and mixing the above-mentioned essential components and, if necessary, additional components in predetermined amounts. Next, the obtained clay composition is molded into a predetermined shape and then fired. At this time, the firing temperature is 800~1500℃, furthermore, 1000~
Preferably, the temperature is set at 1300°C. Furthermore, no drying step is required prior to molding and firing. [Example] Examples 1 and 2 The components shown except for the clay and the polyisocyanate compound were stirred and mixed at 80°C for 3 hours, and then the polyisocyanate compound was added at 20°C and mixed for 1 minute. A clay composition was prepared by further adding clay and stirring and mixing. After that, this clay composition was 300mm long and 300mm wide.
Pour into a mold with a depth of 50 mm and hold at 80°C for 1 hour to harden.
A water-permeable tile was obtained by firing at ℃ for 5 hours. Next, the water permeability test as described below was conducted using the obtained water permeable tiles. That is, a test piece with a diameter of 50 mm was cut out from this tile, and this was fixed in a predetermined position in a glass funnel with the same inner diameter.
100ml of water was poured from above and the time (in seconds) until all the water had passed through the tile was measured and the results are shown in the table. Comparative Example Same as the above example except that a clay composition was prepared by stirring and mixing clay and water at the indicated ratio, then adding and mixing polyvinyl acetate, and drying in the sun for 72 hours before firing. A similar water permeability test was carried out using the same method, and the results are shown in the table.

【table】

[Table] [Effects of the Invention] As is clear from the above description, the water-permeable tile of the present invention contains specific components, namely, a hydroxyl group-containing liquid diene polymer and a polyester, in the clay composition that is its raw material. Contains isocyanate compounds, which react with the moisture contained in the clay to generate _CO2 and foam, so even if the amount of these compounds is extremely small, it is possible to obtain good water permeability. can. Furthermore, the amount of water added can be significantly reduced compared to conventional products, and as a result, a drying step prior to molding or firing is no longer necessary, which is advantageous in terms of the manufacturing process. Therefore, its industrial value is high in the field of tile construction for poolsides, park pavements, etc.

Claims (1)

[Claims] 1. A water-permeable tile comprising a molded and fired body of a clay composition comprising clay, a hydroxyl group-containing liquid diene polymer, and a polyisocyanate compound.