JP2006273915A - Waterproofer, pavement material and base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a waterproofer, a pavement material and a base material having the same functions as those of conventional cured products without using materials suspicious to have environmental hormone activities. <P>SOLUTION: The waterproofer, the pavement material and the base material comprise a compound comprising a terminal isocyanate group-having urethane prepolymer prepared by reacting a polyol with a polyisocyanate, an inorganic filler and a two-component curing urethane composition containing an alkylmonocarboxylic acid-modified higher fatty acid ester and have 1,000-12,000mPa s viscosity at 25°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a waterproof material, a pavement material, and a flooring material. More specifically, the present invention relates to a two-component curable urethane composition comprising a high-safety and low-risk alkyl monocarboxylic acid-modified hydroxyl group-containing higher fatty acid ester. It relates to waterproofing material, paving material and flooring.

Urethane curable compositions are widely used as waterproofing materials, pavement materials, flooring materials, and sealing materials.
The two-component curable urethane composition is mainly composed of a urethane prepolymer having an isocyanate group at the terminal, which is a main component (such as TDI), and a curing agent containing an active hydrogen compound, and generally includes a plasticizer and a catalyst. , Fillers, pigments and the like are blended. In this case, reduce the viscosity of the curing agent,
Plasticizers are used to dissolve solid amines.
In general, dioctyl phthalate (DOP), for reducing viscosity and dissolving solid amines,
Phthalic acid ester compounds such as dibutyl phthalate (DBP) have been widely used. However, these have been suspected of environmental hormone action in recent years.
Therefore, in recent years, instead of the phthalate ester compound, it is replaced with a trimellitic acid compound (see, for example, Patent Document 1), or a monocarboxylic acid composed of a mixture of an unsaturated fatty acid having 10 to 24 carbon atoms and a saturated fatty acid. And a plasticizer (for example, see Patent Document 2) containing an ester of a monool having 1 to 10 carbon atoms.
Since trimellitic acid compounds have a structure similar to phthalate esters, there is a possibility that environmental hormone action will be observed in the future. In addition, coconut oil fatty acid methyl ester, soybean oil fatty acid methyl ester, methyl oleate and the like, which are esters of monocarboxylic acids and monools having 1 to 10 carbon atoms, are easily decomposed and have problems such as shrinkage and odor.
JP 2003-96153 A JP 2002-348463 A

In recent years, there has been an increasing demand for the use of environmentally and highly safe materials in all industrial fields, and it has become important to consider the selection of materials used and production methods from the perspective of maintaining safety for the human body and protecting the global environment. ing.
Therefore, it is desired to use materials that are friendly to the human body and the global environment as materials for use in polyurethane waterproofing materials, pavement materials, and flooring materials.
An object of the present invention is to provide a waterproof material, a pavement material, and a floor material having the same performance as that of a conventional cured product without using any substance suspected of having an action of environmental hormones.

As a result of intensive studies on the above problems, the present inventors have found that when an alkyl monocarboxylic acid-modified higher fatty acid ester is used, a composition having the same performance as a conventional cured product can be obtained without using a substance suspected of having an environmental hormone action. In order to discover what can be obtained, the present invention has been completed.
That is, the present invention is a two-component curable type containing a terminal isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate, a compound having active hydrogen, an inorganic filler, and an alkyl monocarboxylic acid-modified higher fatty acid ester. The present invention provides a waterproof material, a paving material and a flooring material comprising a urethane composition and having a viscosity at 25 ° C. of 1,000 to 12,000 mPa · s.

The waterproof material, pavement material and flooring material comprising the two-component curable urethane composition of the present invention should obtain a cured product having excellent hardness, tensile strength, tear strength, etc. without using a substance suspected of having an environmental hormone action. Can do.

  The present invention will be described in detail below.

The waterproofing material, pavement material and flooring material of the present invention are 1) high in safety (does not contain substances suspected of environmental hormones), 2) high in safety (Class 4 and 4 of the Fire Service Act) 3) High polarity, high solubility in urethane and solid amines, low bleed, 4) low odor, 5) low viscosity, easy operation, etc.

The terminal isocyanate group-containing urethane prepolymer used in the present invention can be obtained by reacting a polyol and a polyisocyanate.
Examples of the polyol used in the above urethane prepolymer include polyester polyols, polyether polyols, polyester polyamide polyols, polycarbonate polyols, polycaprolactone polyester polyols, polybutadiene polyols, polypentadiene polyols, castor oil-based polyols, It is selected from low molecular weight diols, trimethylolpropane, glycerin, sorbitol, mannitol, dulcitol and the like. Polyether polyols are preferable, and those having a number average molecular weight of about 200 to 10,000 are preferable.
Such polyether polyols include low molecular weight diol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, pentaerythritol,
Ethylenediamine, tolylenediamine, diphenylmethanediamine, tetramethylolcyclohexane, methylglucoside, 2,2,6,6-tetrakis (hydroxylmethyl)
Examples include those obtained by addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide using cyclohexanol, diethylenetriamine, sorbitol, mannitol, sucrose and the like as starting materials, such as polyoxypropylene diol.

  Such low molecular weight diols are those having a molecular weight of less than 200, such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, bisphenol A. Etc.

Examples of the polyisocyanate used in the urethane prepolymer include 2,4-tolylene diisocyanate (abbreviated as TDI), 65 / 35-TDI, 80 / 20-TDI, 4,4′-MDI, and 2,2 '-MDI alone or as a mixture and carbodiimide-modified MDI, dianisidine isocyanate, toridene diisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyisocyanate, hydrogenated MDI, water Aromatic diisocyanates such as additive TDI and alicyclic diisocyanates.
The said urethane prepolymer can be obtained by making it react so that the equivalent ratio of the isocyanate group in polyisocyanate and the hydroxyl group in a polyol may become NCO / OH = 0.5-1.5.

  Regarding the terminal isocyanate group-containing urethane prepolymer obtained from the above-mentioned polyisocyanate compound and polyol, the viscosity at 25 ° C. is preferably 1,000 to 8,000 mPa · s, more preferably 1500 to 6,000 mPa · s. It is. Further, the isocyanate content is 2 to 20%, preferably 5 to 15%.

Examples of the compound having active hydrogen used in the present invention include single-chain glycols such as ethylene glycol and propylene glycol, long-chain polyols having a molecular weight of 200 to 5,000, and polyamines. The compound having active hydrogen is used as a curing agent for the terminal isocyanate group-containing urethane prepolymer as the main agent.
The viscosity at 25 ° C. of the compound having active hydrogen is 1,500 to 40,000 mPa · s.
It is. Among these, when used for flooring, it is preferably 1,500 to 6,000 mPa · s, and when used for waterproofing and pavement, it is preferably 3,000 to 20,000 mPa · s.

The ratio of the urethane prepolymer and the compound having active hydrogen varies depending on the waterproofing material, the paving material or the flooring material, but is preferably 1: 1 to 3 in weight ratio.

Examples of the inorganic filler used in the present invention include calcium carbonate, clay, talc, titanium white, carbon black, zeolite, titanium dioxide, and bengara.
The inorganic filler is preferably used in an amount of 20 to 60 parts by weight with respect to 100 parts by weight of the compound having active hydrogen.

  The alkyl monocarboxylic acid-modified higher fatty acid ester used in the present invention is obtained by reacting a higher fatty acid ester having a functional group that reacts with a carboxyl group and an alkyl monocarboxylic acid.

As the higher fatty acid having a functional group that reacts with a carboxyl group, those having an alkyl group having 10 to 25 carbon atoms are preferable. Examples of the higher fatty acid having an alkyl group having 10 to 25 carbon atoms and having a functional group that reacts with a carboxyl group include dimorphecolic acid, coriclic acid, and kamlolenic acid. Acid), licanoic acid, uniperic acid (Juniperic acid), ricinoleic acid, densipolic acid (Densipolic acid), higher fatty acids having a hydroxyl group such as α-oxylinolenic acid, vernolic acid (Coronaric acid), etc. Higher fatty acid having an epoxy group, and ricinoleic acid containing a hydroxyl group is preferred.
The higher fatty acid ester used in the present invention is obtained by reacting such higher fatty acid with alcohol.
Examples of the alcohol include methanol, ethanol, propanol, decanol and the like. Among these, methanol is preferable in terms of viscosity.
The alkyl monocarboxylic acid is preferably a carboxylic acid having an alkyl group having 1 to 10 carbon atoms, such as formic acid, acetic acid, propionic acid, caproic acid, capric acid and the like. Of these, acetic acid is preferred in terms of viscosity and stability.
From the above, ricinoleic acid acetyl methyl ester is particularly preferable as the alkyl monocarboxylic acid-modified higher fatty acid ester.

The amount of the alkyl monocarboxylic acid-modified higher fatty acid ester used is preferably 1 to 60 parts by weight, particularly preferably 3 to 50 parts by weight, based on 100 parts by weight of the urethane curable composition. When the amount of the alkyl monocarboxylic acid-modified higher fatty acid ester used is 1 to 60 parts by weight, the viscosity reducing effect and the solubility in solid amine are good.
As a method for adding to the urethane curable composition, for example, it may be added in advance as a raw material of the urethane curable composition, or may be added to the curable composition immediately before attempting to cure.

The waterproofing material, paving material and flooring material comprising the two-component curable urethane composition of the present invention can be used depending on the application.
Add primary plasticizers such as dioctyl phthalate (DOP) and dioctyl adipate (DOA) as necessary, pigments, solvents such as toluene, xylene, terpenes, aliphatic hydrocarbons, high-boiling esters, and other catalysts. Also good.

The two-component curable urethane composition of the present invention includes, for example, a curing agent composed of a main component composed of a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyisocyanate and a polyol and an active hydrogen compound, and an alkyl monocarboxylic acid modified. It can be obtained by mixing a higher fatty acid ester and an inorganic filler at room temperature.
Examples of such a mixing method include a method of mixing with a high-speed stirrer equipped with a stirrer.

The viscosity at 25 ° C. of the waterproof material, paving material and flooring material comprising the two-component curable urethane composition of the present invention is 1,000 to 12,000 mPa · s, preferably 2,000 to 8,000 m.
Pa · s. If the viscosity is within this range, a waterproof material, a paving material and a flooring material excellent in paintability and leveling properties can be obtained.
Under the present circumstances, it can use for each use by adjusting the equivalent ratio of the isocyanate group of a urethane prepolymer, and the active hydrogen of an active hydrogen compound, and making it moderate hardness.

The waterproof material is applied to a waterproof base made of concrete, mortar, etc., and a waterproof waterproof material or the like that forms a waterproof layer having a predetermined thickness at room temperature, and the hardness is adjusted to a JISA hardness of 45 to 55. Used.
The paving material is used after adjusting to a JISA hardness of 55 to 70. The flooring is adjusted to a JISA hardness of 80 to 100.
These materials are usually used by being applied to a substrate to a thickness of 1 to 7 mm.

The present invention will be described in detail with reference to examples. The present invention is not limited to these examples. In the text, “parts” and “%” are based on weight unless otherwise specified.
Reference Example First, for the alkyl monocarboxylic acid-modified higher fatty acid ester and other compounds used in the present invention, comparative experiments were conducted on the solubility, flash point and odor of solid amines.
1) Solubility of solid amine 4,4′-diamino-3,3′-dichlorodiphenylmethane (MBOCA; solid amine) was directly dissolved in higher fatty acid ester at about 120 ° C., and the MBOCA solution was dissolved in a refrigerator at 5 ° C. 3 It preserve | saved for months and confirmed whether MBOCA precipitated. The amount of MBOCA was blended so as to be 10, 15, 20, 25 and 30% of Table-1.
As higher fatty acid esters, ricinoleic acid acetyl methyl ester, soybean oil fatty acid methyl ester, coconut oil fatty acid methyl ester, and ricinoleic acid methyl ester were used. Dioctyl phthalate (DOP) was used as the plasticizer.

注） ○：ＭＢＯＣＡの析出無し
×：ＭＢＯＣＡの析出有り
２）引火点
リシノール酸アセチルメチルエステル、大豆油脂肪酸メチルエステル、糠油脂肪酸メチ
ルエステル、リシノール酸メチルエステル及びジオクチルフタレートについて、引火点を
クリーブランド開放式測定法で測定した。

Note) ○: No MBOCA precipitation ×: MBOCA precipitation 2) Flash point For ricinoleic acid acetyl methyl ester, soybean oil fatty acid methyl ester, coconut oil fatty acid methyl ester, ricinoleic acid methyl ester and dioctyl phthalate, the flash point is Cleveland open type It was measured by the measurement method.

注） ○：引火点２００℃以上
△：引火点７０℃〜２００℃未満
×：引火点７０℃未満
３）臭気
表中の材料５０ｇを、１００ｃｃのガラス瓶に取り、ガラス瓶の口に鼻をあてて臭いを
かいだ臭気を評価した。評価結果は５人による評価の平均である。

Note) ○: Flash point of 200 ° C or higher △: Flash point of 70 ° C to less than 200 ° C ×: Flash point of less than 70 ° C 3) Odor Take 50g of the material in the table into a 100cc glass bottle and put the nose on the mouth of the glass bottle. The smell of smell was evaluated. The evaluation result is an average of evaluations by five people.

注） ◎：臭気まったく無し
○：臭気ややあり
△：臭気強い
×：異臭な臭気

Note) ◎: No odor ○: Slight odor △: Strong odor ×: Offensive odor

Example 1
Hyprox DP-2000 (polyoxypropylene glycol having a number average molecular weight of 2,000, manufactured by Dainippon Ink & Chemicals, Inc.) 500 parts in a 2 L flask, Hyprox TG-3000 (polyoxypropylene glycol having a number average molecular weight of 3,000) , Manufactured by Dainippon Ink & Chemicals, Inc.) was added with 174 parts of tolylene diisocyanate having an isomer ratio of 2,4- / 2,6- = 80/20, and the reaction was continued at 80 ° C. for 6 hours. .
The viscosity of the obtained urethane prepolymer was 7,700 mPa · s at 25 ° C., and the amount of free isocyanate was 3.5%. This urethane prepolymer is referred to as urethane prepolymer (I-1).
Pandex OD-X-825 (polyoxypropylene glycol with a number average molecular weight of 3,200, manufactured by Dainippon Ink & Chemicals, Inc.) and Rick Sizer C-101 (ricinoleic acid acetyl methyl ester, manufactured by Ito Seiyaku Co., Ltd.) 6 parts of MBOCA was dissolved in 35 parts of the mixture by heating. Furthermore, a total of 200 parts including 108 parts of calcium carbonate (manufactured by Nitto Flour Chemical Co., Ltd., NS-200), 5 parts of pigment chromium oxide green, 4 parts of 24% lead octylate solution, 1 part of stabilizer and 1 part of antifoaming agent. Was kneaded with a planetary mixer to obtain a curing agent having a green color and a viscosity of 10,000 mPa · s. This curing agent is hereinafter referred to as curing agent (II-1).
50 parts of urethane prepolymer (I-1) and 100 parts of curing agent (II-1) were placed in a beaker and stirred and mixed uniformly. The viscosity of the obtained mixture at 25 ° C. was 8,000 mPa · s.
This mixture was applied smoothly on a horizontal plate treated with a release agent to a thickness of 2 mm, and cured at room temperature for 7 days.
Example 2
In a 2 L flask, 810 parts of Hyprox DP-2000, 7 parts of Hyprox RT-400 (polyoxypropylene glycol having a number average molecular weight of 400, manufactured by Dainippon Ink & Chemicals, Inc.), 2,4- / 2,6- = 180 parts of tolylene diisocyanate having an isomer ratio of 80/20 was added, and the reaction was continued at 80 ° C. for 6 hours. And 3% of Rick Sizer C-101 was mixed, the viscosity of the obtained urethane prepolymer was 4,800 mPa · s at 25 ° C., and the amount of free isocyanate was 5.0%.
12 parts of MBOCA was heated and dissolved in a mixture of 31 parts of Pandex OD-X-825 and 28 parts of Rick Sizer C-101. Furthermore, 119 parts of calcium carbonate (manufactured by Nitto Flourishing Co., Ltd., NS-200), 5 parts of pigment chromium oxide green, 3 parts of 24% lead octylate solution, 1 part of stabilizer, 1 part of antifoaming agent, total 200 parts. Was kneaded with a planetary mixer to obtain a curing agent having a green color and a viscosity of 8,000 mPa · s. This curing agent is hereinafter referred to as curing agent (II-2).
50 parts of urethane prepolymer (I-2) and 100 parts of curing agent (II-2) were placed in a beaker and uniformly stirred and mixed. The viscosity of the obtained mixture at 25 ° C. was 6,000 mPa · s. This mixture was applied smoothly on a horizontal plate treated with a release agent to a thickness of 2 mm, and cured at room temperature for 7 days.
Example 3
To a 2 L flask, 286 parts of tolylene diisocyanate having an isomer ratio of 2,4- / 2,6- = 80/20 was added to 1000 parts of Hyprox TG-3000, and the reaction was continued at 80 ° C. for 6 hours. The viscosity of the obtained urethane prepolymer was 3,800 mPa · s at 25 ° C., and the amount of free isocyanate was 7.5%.
150 parts of MBOCA was dissolved by heating in a mixture of 400 parts of Hyprox TG-3000 and 80 parts of Rick Sizer C-101. Furthermore, 327 parts of calcium carbonate (manufactured by Nitto Flourishing Co., Ltd., NS-200), 30 parts of pigment chrome oxide green, 3 parts of 24% lead octylate solution, 9 parts of stabilizer, and 1 part of antifoaming agent total 1000 parts. Was kneaded with a planetary mixer to obtain a curing agent having a green color and a viscosity of 5,400 mPa · s. This curing agent is hereinafter referred to as curing agent (II-3).
50 parts of urethane prepolymer (I-2) and 100 parts of curing agent (II-3) were placed in a beaker and uniformly stirred and mixed. The viscosity of the obtained mixture at 25 ° C. was 4,500 mPa · s. This mixture was applied smoothly on a horizontal plate treated with a release agent to a thickness of 2 mm, and cured at room temperature for 7 days.
Comparative Example 1
6 parts of MBOCA was heated and dissolved in a mixture of 40 parts of Pandex OD-X-825 and 35 parts of dioctyl phthalate. Furthermore, a total of 200 parts including 108 parts of calcium carbonate (manufactured by Nitto Flour Chemical Co., Ltd., NS-200), 5 parts of pigment chromium oxide green, 4 parts of 24% lead octylate solution, 1 part of stabilizer and 1 part of antifoaming agent. Was kneaded with a planetary mixer to obtain a curing agent having a green color and a viscosity of 14,000 mPa · s. This curing agent is referred to as curing agent (II-4).
17) (Production of cured coating film) 50 parts of urethane prepolymer (I-1) and 100 parts of curing agent (II-4) were placed in a beaker and uniformly stirred and mixed.
This mixture was applied smoothly on a horizontal plate treated with a release agent to a thickness of 2 mm, and cured at room temperature for 7 days.
Comparative Example 2
6 parts of MBOCA was heated and dissolved in a mixture of 40 parts of Pandex OD-X-825 and 35 parts of TOENOL # 3120 (soybean oil fatty acid methyl ester, manufactured by Toei Chemical Co., Ltd.). Furthermore, a total of 200 parts including 108 parts of calcium carbonate (manufactured by Nitto Flour Chemical Co., Ltd., NS-200), 5 parts of pigment chromium oxide green, 4 parts of 24% lead octylate solution, 1 part of stabilizer and 1 part of antifoaming agent. Were kneaded with a planetary mixer to obtain a curing agent having a green color and a viscosity of 9,500 mPa · s. This curing agent is hereinafter referred to as curing agent (II-5).
50 parts of urethane prepolymer (I-1) and 100 parts of curing agent (II-5) were placed in a beaker and stirred and mixed uniformly. The viscosity of the obtained mixture at 25 ° C. was 11,000 mPa · s.
This mixture was applied smoothly on a horizontal plate treated with a release agent to a thickness of 2 mm, and cured at room temperature for 7 days.
Comparative Example 3
6 parts of MBOCA was heated and dissolved in a mixture of 40 parts of Pandex OD-X-825 and 35 parts of TOENOL # 3110 (rice bran oil fatty acid methyl ester, manufactured by Toei Chemical Co., Ltd.). Furthermore, a total of 200 parts including 108 parts of calcium carbonate (manufactured by Nitto Flour Chemical Co., Ltd., NS-200), 5 parts of pigment chromium oxide green, 4 parts of 24% lead octylate solution, 1 part of stabilizer and 1 part of antifoaming agent. Were kneaded with a planetary mixer to obtain a curing agent having a green color and a viscosity of 9,000 mPa · s. This curing agent is hereinafter referred to as curing agent (II-6).
50 parts of urethane prepolymer (I-1) and 100 parts of curing agent (II-6) were placed in a beaker and uniformly stirred and mixed. The viscosity of the obtained mixture at 25 ° C. was 10,000 mPa · s.
This mixture was applied smoothly on a horizontal plate treated with a release agent to a thickness of 2 mm, and cured at room temperature for 7 days.
Comparative Example 4
6 parts of MBOCA was heated and dissolved in a mixture of 40 parts of Pandex OD-X-825 and 35 parts of CO-FA methyl ester (ricinol oil fatty acid methyl ester, manufactured by Ito Seiyaku Co., Ltd.). Furthermore, a total of 200 parts including 108 parts of calcium carbonate (manufactured by Nitto Flour Chemical Co., Ltd., NS-200), 5 parts of pigment chromium oxide green, 4 parts of 24% lead octylate solution, 1 part of stabilizer and 1 part of antifoaming agent. Was kneaded with a planetary mixer to obtain a curing agent having a green color and a viscosity of 11,000 mPa · s. This curing agent is hereinafter referred to as curing agent (II-7).
50 parts of urethane prepolymer (I-1) and 100 parts of curing agent (II-7) were placed in a beaker and stirred and mixed uniformly.
This mixture was applied smoothly on a horizontal plate treated with a release agent to a thickness of 2 mm, and cured at room temperature for 7 days.
<Measurement method>
About the hardened | cured material obtained in said Example 1, 2, 3 and Comparative Examples 1, 2, 3, and 4, performance was evaluated with the following method.
Hardness: Measured according to JIS K-6254 method.
Tensile strength and elongation at break; measured according to JIS K-6251.
Tear strength: measured according to JIS K-6252.

Claims (4)

It consists of a two-component curable urethane composition containing a terminal isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate, a compound having active hydrogen, an inorganic filler, and an alkyl monocarboxylic acid-modified higher fatty acid ester, 2
A waterproof material, a paving material and a flooring material having a viscosity at 5 ° C. of 1,000 to 12,000 mPa · s. The waterproof material, pavement material and flooring material according to claim 1, wherein the alkyl monocarboxylic acid is a carboxylic acid having an alkyl group having 1 to 10 carbon atoms. The waterproof material, pavement material and flooring material according to claim 1 or 2, wherein the higher fatty acid is a higher fatty acid having an alkyl group having 10 to 25 carbon atoms. The waterproofing material, paving material and flooring material according to claim 3, wherein the higher fatty acid having an alkyl group having 10 to 25 carbon atoms is ricinoleic acid.