JPH075398B2 - Hydrophobic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a hydrophobic material, and more specifically, to a hydrophobic material which can be easily impregnated into a porous material. It relates to reduced hydrophobic materials.

(Prior Art and Its Problems) In the fields of civil engineering, construction and construction, porous materials made of various materials such as gypsum, pottery, porcelain or mortar are widely used.

However, these porous materials easily absorb moisture and moisture in the air, and due to the action of these moisture,
The material softens, expands, or becomes brittle. When such a situation occurs, for example, structures using these materials are in danger of collapsing.

In spite of such problems, these porous materials are rarely subjected to hydrophobic treatment as a countermeasure, and a plate of these materials is slightly laminated with oil-impregnated paper. It was about to be used.

It is an object of the present invention to solve the above problems and to provide a novel hydrophobic material in which a porous material is impregnated with a composition described below and cured to give hydrophobicity.

(Means for Solving the Problems) The material of the present invention is obtained by impregnating a porous material with a ketone solution of a composition comprising a hydroxyl group-containing liquid diene polymer and a polyisocyanate compound, and then adding the composition to the composition. It is characterized by being subjected to a curing treatment.

First, the matrix of the material of the present invention is a porous material, and examples thereof include gypsum, pottery, porcelain, slate, wood, mortar, concrete (hardened material).

The composition in which this porous material is impregnated and cured is a composition in which a hydroxyl group-containing liquid diene polymer and a polyisocyanate compound are essential.

The hydroxyl group-containing liquid diene polymer has a hydroxyl group inside or at the end of the molecular chain and has a number average molecular weight of 300 to 2
5000, preferably 500 to 10,000 liquid diene-based polymers are used. Here, the content of hydroxyl group is usually 0.1 to 10 meq / g,
It is preferably 0.3 to 7 meq / g.

Examples of these liquid diene-based polymers include diene polymers having 4 to 12 carbon atoms, diene copolymers, and copolymers of these diene monomers with α-olefin addition polymerizable monomers having 2 to 22 carbon atoms. There is. Specifically, butadiene homopolymer, isoprene homoprimer, butadiene-
Examples thereof include styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, and butadiene-n-octadecyl acrylate copolymer. These liquid diene polymers can be produced, for example, by reacting a conjugated diene monomer in a liquid reaction medium in the presence of hydrogen peroxide with heating.

The polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule and has a reactive isocyanate group for the hydroxyl group of the hydroxyl group-containing liquid diene polymer. Examples of the polyisocyanate compound include ordinary aromatic, aliphatic and alicyclic compounds, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate and polymethylene polyisocyanate. There are phenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction products,
Among them, MDI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate and the like are preferable.

The mixing ratio of the above two components is not particularly limited, but usually,
Isocyanate group (NCO) of polyisocyanate compound to hydroxyl group (OH) of hydroxyl group-containing liquid diene polymer
The molar ratio of (NCO / OH) is 0.2 to 25, preferably 0.5 to
Should be 15. If the molar ratio is out of the above range, it becomes difficult to cure, which is not preferable.

In the composition according to the present invention, in addition to the above essential components, a polyol compound or a polyamine compound can be added as a reinforcing agent, if desired, and various other additives can be added.

As the polyol compound added as desired, any of a primary polyol, a secondary polyol and a tertiary polyol 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,
There may be mentioned low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon such as N'-bishydroxyisopropyl-2-methylpiperazine and propylene oxide adduct of bisphenol A.

Furthermore, as the polyol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or the like which does not contain a hydroxyl group bonded to secondary carbon can be used. . A diol is usually used as the polyol,
Triol or tetraol may be used, and the molecular weight is
It is in the range of 50 to 500.

The polyamine compound may be diamine, triamine or tetraamine. Further, any of primary polyamine, secondary polyamine, and tertiary polyamine can be used. Examples of the polyamine compound include aliphatic amines such as hexamethylenediamine; 3,3′-dimethyl; alicyclic amines such as 4,4′-diaminodicyclohexylmethane; aromatic amines such as 4,4′-diaminodiphenyl;
Examples thereof include tetramine such as 2,4,6-tri (dimethylaminomethyl) phenol.

When blending these polyol compounds and polyamine compounds, the blending ratio is not particularly limited, usually 1 to 100 parts by weight of the hydroxyl group-containing liquid diene polymer described above polyol compound or polyamine compound
The amount is 1000 parts by weight, preferably 3 to 200 parts by weight.

Further, as other additives to be added if desired, for example, fillers such as mica, graphite, flint, calcium carbonate, and powdered stote can be mentioned.

In addition, a plasticizer such as dioctyl phthalate may be added as a viscosity modifier, a softener such as an aroma-based, naphthene-based or paraffin-based oil may be added, and an alkylphenol resin, a terpene resin or a terpene resin may be used to adjust the adhesive strength and the adhesive strength. Phenol resin, xylene formaldehyde resin,
It is also possible to add tackifying resins such as rosin, hydrogenated rosin, coumarone resins, aliphatic and aromatic petroleum resins. Further, a curing accelerator such as dibutyltin dilaurate, stannous octoate, or polyethylenediamine may be added. Furthermore, an anti-aging agent may be added to improve weather resistance, and a silicon compound or the like may be added as an antifoaming agent.

The composition is obtained by mixing and mixing the above raw materials. Usually, first, the raw materials excluding the polyisocyanate compound among the above raw materials are blended, stirred and mixed at 15 to 120 ° C., preferably 70 to 100 ° C. for 5 to 240 minutes, preferably 30 to 180 minutes, and then this mixture The polyisocyanate compound is added to 0 to 70 ° C, preferably 15 to 50 ° C at 0.
The liquid composition is obtained by stirring and mixing for 5 seconds to 240 minutes, preferably 1 second to 180 minutes.

In the production of the material of the present invention, the composition described above is dissolved in a ketone such as acetone, diethylketone, dipropylketone, methylethylketone, methylpropylketone to form a solution, and this solution is formed into a porous material. Impregnate. When used as such a solution,
Since the increase in viscosity due to the prepolymer produced by the reaction between the hydroxyl group-containing liquid diene polymer and the polyisocyanate compound can be suppressed, the impregnation operation becomes easy and the whole handling becomes easy.

When such a solution is used, it is dissolved in a ketone so that the composition has a concentration of 3 to 80% by weight. Preferably 5
~ 50% by weight.

After impregnating the porous material with the composition, the composition is cured.

The conditions for curing treatment are not particularly limited, but usually 0 to
At 120 ° C., preferably 15 to 70 ° C., it is 0.5 to 168 hours, preferably 1 to 75 hours.

Thus, the hydrophobic material of the present invention is obtained in which the cured material of the above composition is filled in the porous portion of the porous material that is the matrix.

(Examples of the invention) Examples 1 to 4 and Comparative Example 1 Of the indicated components, each component excluding the polyisocyanate compound was blended in the indicated proportions (parts by weight) to give a total of 80
Mix for 1 hour at 0 ° C., then add the indicated amount of polyisocyanate compound thereto, 20 minutes at 20 ° C. for Examples 1-2 and Comparative Example 1 and 20 ° C. for Examples 3 and 4.
A predetermined composition was prepared by mixing and stirring each time.

Acetone and methyl ethyl ketone were added to the respective compositions of Examples 1 to 4 in the indicated amounts (parts by weight) and mixed at 20 ° C. for 1 minute to prepare solutions.

A test piece of porous material made of the indicated material (test piece size: 50 x 50 x 5 mm) is immersed in these compositions or solutions, taken out after 30 seconds, and cured at 25 ° C for 72 hours. did.

After these test pieces were immersed in distilled water for 3 minutes, they were pulled up, water adhering to the surface of each test piece was wiped off, and the water absorption rate (%) was calculated based on the following formula.

The above results are collectively shown in the table.

The water absorptions of the gypsum and mortar cured products without the treatment of the present invention were 30% by weight and 10% by weight, respectively.

(Effect of the Invention) As is clear from the above description, the hydrophobic material of the present invention is
The water absorption rate is significantly reduced, and its industrial value is great as a material used in the fields of civil engineering, construction, and construction.

Claims (1)

[Claims] 1. A method of impregnating a porous material with a ketone solution of a composition comprising a hydroxyl group-containing liquid diene polymer and a polyisocyanate compound, and then subjecting the composition to a curing treatment. Hydrophobic material.