JPS6397620A - Protective material - Google Patents

Abstract

PURPOSE:To obtain a protective material which is excellent in thermal aging resistance and which, when applied to a building, is suitable to improve its water resistance, weathering resistance, damage resistance and corrosion resistance, by mixing a hydrogenation product of an isocyanate-containing. CONSTITUTION:A hydrogenated liquid polyisoprene (a) obtained by hydrogenating liquid polyisoprene having internal or terminal OH groups and a number- average MW of 300-25,000 in the presence of a hydrogenation catalyst is reacted with a polyisocyanate compound (b) to obtain a hydrogenated isocyanate-containing liquid polyisoprene (A). Component A is mixed with a polyol compound (B) [e.g., N,N-bis(2-hydroxypropyl)aniline] and/or a polyamine compound (e.g., 3,3'-dichloro-4,4'-diaminodiphenylmethane) and, optionally, 20-2,000wt%, based on component A, bitumen (e.g., straight asphalt).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a protective material that has excellent heat aging resistance, and more specifically, for use in buildings made of cement, mortar, concrete, metal, wood, etc. By coating, spraying, impregnating and curing, or forming into a sheet and applying to buildings, etc., waterproofing, weatherproofing,
The present invention relates to a protective material that can provide damage resistance, corrosion protection, etc.

[Prior art and its problems] In general, in order to make various buildings waterproof, weather resistant, anti-corrosive, etc., it is necessary to apply or impregnate the building and harden it, or to cover the building with a sheet. Protective materials are used to protect the structure.

As this protective material, a protective material mainly composed of liquid polybutadiene having a hydroxyl group and a polyisocyanate compound has been known and has been widely used in various buildings.

However, due to the presence of unsaturated double bonds in each molecule, this conventional protective material is inferior in terms of weather resistance and heat aging resistance due to the wood quality, and is susceptible to aging or heat history. This has the disadvantage that its performance deteriorates.

In order to solve this problem, it has been proposed to use a hydride of liquid polybutadiene instead of using liquid polybutadiene, and it has been found that when this method is adopted, weather resistance is improved to some extent.

However, when polybutadiene, the precursor of this hydride, contains a large amount of 1,4-addition type skeleton, the hydride tends to become solid and difficult to handle near room temperature. Furthermore, in the case of polybutadiene containing a large amount of 1,2-addition type skeleton, the average number of functional groups (OH) is small, so that the heat aging resistance cannot be improved.

[Means for Solving the Problems] The structure of the first invention for solving the above problems includes containing a hydride of liquid polyisoprene having an isocyanate group and a polyol compound and/or a polyamine compound. The second invention is a protective material characterized by containing a hydride of liquid polyisoprene having an isocyanate group, a polyol compound and/or a polyamine compound, and a bituminous substance.

As the liquid polyimbrene having an isocyanate group in the present invention, a liquid polyisoprene having a hydroxyl group within one molecule or at the end of the molecule and having a number average molecular weight of 300 to 25,000, preferably 500 to 10,000 is used as a raw material. Here, the content of hydroxyl groups is usually 0.1 to 10
Q/g per rs, preferably 0.3 to 7 m equivalent/g.

This liquid polyisoprene having hydroxyl groups can be produced, for example, by subjecting isoprene to a heating reaction in the presence of hydrogen peroxide in a liquid reaction medium.
By hydrogenating 7 in the presence of a hydrogenation catalyst such as Ni, Co, Fe, Pt, Ru, etc., a hydride of liquid polyisoprene having hydroxyl groups is obtained.

By reacting this hydride with a polyisocyanate compound, a hydride of liquid polyisoprene having isocyanate groups can be obtained.

The polyisocyanate compound referred to herein is an organic compound having two or more isocyanate groups in one molecule.

Examples of polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diincyanate) (M
DI), liquid modified diphenylmethane diisocyanate,
Polymethylene polyphenylisocyanate, xylylene diisocyanate, cyclohexyl diisocyanate,
Examples include cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction product, etc.
Particularly preferred are MITI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate, and the like.

As the polyol compound, any of primary polyol, secondary polyol, and 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-
Bentanediol, 2,3-hentanediol, 2,5
-hexanediol, 2.4-hexanediol, 2-
At least one of ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N,N-bis-2-hydroxypropylaniline, N,N'-bishydroxyisopropyl-2-methylbiperazine, propylene oxide adduct of bisphenol A, etc. Examples include low molecular weight polyols containing hydroxyl groups bonded to two secondary carbons.

Furthermore, as a polyol, secondary R'J? It is also possible to use ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-bentanediol, 1,8-hexanediol, etc., which do not contain a hydroxyl group bonded to. Diols are usually used as polyols, but triols and tetraols may also be used.

Further, the polyamine compound used together with or in place of the polyol described above may be any of diamines, triamines, and tetraamines, and furthermore, any of primary polyamines, secondary polyamines, and tertiary polyamines may be used. Examples of the boiamine compound include aliphatic amines such as hexamethylene diamine; 3,3'
Alicyclic amines such as -dimethyl-4,4'-diaminodicyclohexylmethane; aromatic amines such as 4,4'-diaminodiphenyl; tetramines such as 2,4.6-)s(dimethylaminomethyl)phenol; can be mentioned.

In the second invention, in addition to the hydroxide of liquid polyisoprene having an isocyanate group, a polyol compound and/or a polyamine compound, a bituminous substance is further mixed and used.

Examples of the bituminous materials include petroleum asphalts such as straight asphalt, blown asphalt, semi-prone asphalt, and solvent source asphalt: petroleum pilates, coal pitch, coal tar, heavy oil, and the like. The amount of this bituminous substance used is usually 20 to 2000 parts by weight, preferably 50 parts by weight, per 100 ffl parts of the liquid polyisoprene hydroxide having isocyanate groups.
~500 parts by weight.

The incorporation of the bituminous material further improves at least the elongation of the protective material.

Other additives can be added to the protective materials according to the first invention and the second invention as necessary.

Examples of the additives include mica, graphite,
Fillers include vermiculite, calcium carbonate, and slate powder.

Furthermore, this protective material can contain plasticizers such as dioctyl phthalate as a viscosity modifier, softeners such as aromatic, naphthenic, and paraffin oils, and can be used to adjust adhesive strength and adhesive strength. Tackifying resins such as alkyl phenolic resins, terpene resins, terpene phenolic resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic and aromatic petroleum resins may also be included. It is also possible to contain a curing accelerator such as tin octoate and polyethylene diamine. Furthermore, an anti-aging agent may be contained in order to improve weather resistance, and a silicon compound or the like may be contained as an antifoaming agent.

No matter what kind of additives are added, the amount of liquid polyisoprene hydride having isocyanate groups (abbreviated as NCo), polyol compound (abbreviated as OH) and/or polyamine compound (abbreviated as N) is as follows: In molar ratio (
on crystal an/xea N)/MCO=0.01~10
．． 0, preferably in the range of 0.1 to 5.0.

There are no particular restrictions on the conditions for curing the adhesive material constructed as described above, but it is usually at 0 to 120°C, preferably 15 to 70°C for 0.5 to 75 hours, preferably 1 to 72 hours.

Suitable objects to which the protective material constructed according to the present invention can be used include various buildings made of cement, mortar, concrete, concrete, wood, etc.

[Effect of the invention] As fully explained by the results of the examples, the protective material according to the invention has sufficient weather resistance, and
It is a protective material with excellent heat aging resistance, as its properties do not decrease significantly even when subjected to heat history.

[Example] Hereinafter, the structure and effects of the present invention will be explained in more detail by showing some specific examples.

(Production Example 1) (Production of liquid polyisoprene hydride containing isocyanate) 200 g of isoprene was placed in a 11 stainless steel pressure-resistant reaction vessel.
Take and add hydrogen peroxide solution IB with a C degree of 501rr amount%.
g, secondary butyl alcohol too as solvent
g was added, the mixture was covered with a lid, the temperature was set at 120°C, and the reaction was allowed to proceed for 2 hours. The pressure inside the container showed a maximum of 8Kg/c+s2G.

After that, the contents were transferred to a separating funnel, 600 g of wood was added, shaken, and left to stand for 3 hours to separate the oil layer.
By removing the solvent, unreacted monomers, and low point components at 100° C. for 2 hours, liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained in a yield of 88% by weight.

The number average molecular weight of this product is 2150, and the hydroxyl group content is 0.
98 m equivalent was 7 g, and the viscosity was 56 poise/30°C.

Liquid polyisoprene 100 having hydroxyl groups as described above
g was placed in a pressure-resistant reaction vessel made of Ti stainless steel, and 10 g of 5% by weight ruthenium black (Ru-C) was added as a hydrogenation catalyst.
, add 100 g of Sansan to the cyclo as a solvent, and add 50 g of
It was filled with hydrogen to form a 2G kg/c layer and reacted at 140° C. for 5 hours.

After the reaction, the contents were taken out and the catalyst was removed using a membrane filter with 0.45 μm pores, and the solvent was distilled off at 110°C for 2 hours to obtain liquid polyisoprene having hydroxyl groups. The hydride of was obtained.

The number average molecular weight of this product was 2210, the water N group content was 0.94 ra equivalent/g, the iodine number was 1 or less, and the viscosity was 383 voids/30°C.

50 g of this hydride was placed in a 300 tnl separable flask, 15-8 g of tolylene diene cyanide was added thereto, and the mixture was stirred for 2 hours while heating to 25°C without a solvent.
Next, by reacting at 70°C for 4 hours, a liquid polyisoprene having incyane B& at the end of the molecular chain, which has an isocyanate group content of 8.93% by weight and a viscosity of 573 voids/30°C, was prepared. A hydride was obtained.

(Production Example 2) 1,4-addition type liquid polybutadiene having a hydroxyl group at the end of the molecular chain [R-45HT manufactured by Idemitsu Arco ■, number average molecular weight 2800, hydroxyl group content 0.821/71/g,
50 voids/30°C, 1,4-adduct content 80 mol%
, 1.2-adduct content - 120 mol %] using 100 g of ruthenium black catalyst (RuJl:, ruthenium-containing b
15% by weight) was charged into a reaction vessel similar to that used in Example 1 together with cyclohexane, and 50Kg/c
React at 140° C. for 4.5 hours under hydrogen pressure in layer 2G,
After that, the contents were taken out, toluene at 500°C was added thereto, the catalyst was separated using a membrane filter with pores of 0.45 #Lm, and the mixture was heated at 2 mmHg and 110°C.
The solvent was removed for 2 hours under these conditions.

The number average molecular weight of the hydride thus obtained was 2920.
, the hydroxyl group content is 0.80 m equivalent 7 g,
Its appearance was a waxy solid.

(Production Example 3) In place of the starting material in Production Example 2, 1,2-addition type liquid polybutadiene having a hydroxyl group in one molecular chain [Japan +
,I; i! (2) A hydride was obtained by repeating Example 3, except that Nl5SOPHG-2000, number average molecular weight 2000, hydroxyl group content 0.85-equivalent/g, viscosity 1330 voids/3G°C] was used.

This hydride has a number average molecular weight of 2080,
The hydroxyl group content was 0.84 m equivalent 7 g, and the liquid had such a high viscosity that measurement was unbalanced at 30° C. using a B-type viscometer.

(Example 1.2, Comparative Examples 1 and 2) Each component shown in the following table was collected separately in a container and stirred and mixed at 23°C for 3 minutes, and then placed on a 7g thick mortar plate. It was applied to a thickness of 3 mm.

Then, a curing treatment was performed for 48 hours at 23° C. and 60% humidity. Thereafter, a weather resistance test and a heat aging resistance test were conducted, and the condition was observed. Next, the cured product was peeled off from the mortar plate using a cutter knife. The physical properties of this cured product were measured in accordance with JIS K2SO3.

The results are shown in Table 1.

(Examples 3 and 4, Comparative Example 3.4) In the above Example 1.2 and Comparative Examples 1 and 2, 150
It was carried out in the same manner as in Example 1.2 and Comparative Example 1.2, except that asphalt heated to .degree. C. was blended.

The results are shown in Table 1.

In addition, the weather resistance test and the heat aging resistance test were conducted as follows.

(Weather resistance test) Using a Canon weathering tester and a xenon lamp tester, the black panel temperature was 45℃ and the humidity was 6.
The coated surface was irradiated for 1000 hours under 0% conditions with the coated surface facing the lamp side. One cycle was 120 minutes, during which time water was sprayed for 18 minutes.

(Heat aging resistance test) Using a gear type heat aging tester, place the coated surface facing upward.
Physical properties were measured after 188 hours at a temperature of 20°C.

tl Manufactured by Idemitsu Kosan Co., Ltd.; 60/80 Straight Asphalt Zero 2 Manufactured by M.D. Kasei Co., Ltd.; Isonol C-1
00, OH-containing 2719.80℃ equivalent m/gY&3 manufactured by Ihara Chemical Co., Ltd.; Iharakyuamine MT, amine-containing i 7.50 m equivalent r; Ni/g book 4 manufactured by Nippon Polyurethane Co., Ltd.: liquid modified, Millionate MTL, N CO containing m29. III Amount % 5 Manufactured by Idemitsu Kosan Co., Ltd.: Aromatic process oil A C-12 t6 Because the solids did not dissolve during blending, it was heated to 50°C, but a composition that was easy to coat was not obtained.

tl Sagging was significant, and a sample for measuring physical properties could not be prepared.

Claims (2)

[Claims] (1) A protective material characterized by containing a hydride of liquid polyisoprene having an isocyanate group, and a polyol compound and/or a polyamine compound. (2) A protective material containing a hydride of liquid polyisoprene having an isocyanate group, a polyol compound and/or a polyamine compound, and a bituminous substance.