JPH0725967A - Hydrophilic one-pack type polyurethane composition, waterproof material, wall covering material and water-swelling sealing material - Google Patents

Abstract

PURPOSE:To provide a hydrophilic one-pack type polyurethane composition which has excellent characteristics, for example, shows extremely high curing rate, when it is used in the air, lowered reduction in hardness after swelling despite of large swelling, when it is soaked in water, good shape retention after swelling and low solubility in water and high resistance to hydrolysis, when it is exposed to high temperature. CONSTITUTION:A hydrophilic one-pack type polyurethane composition, a waterproof material, wall covering material, ornamental covering material therefrom and water-swelling sealing. The composition is composed of (a) hydrophilic urethane prepolymer of 1 to 20wt.% terminal isocyanate group content, resulting from the reaction of a polyether-polyol containing more than 10-wt.% of oxyethylene groups in the oxyalkyl chains with an organic poly-isocyanate and (b) a blocked amine which substantially does not react with isocyanate but forms a primary or secondary amine by its reaction with water.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a hydrophilic one-pack type polyurethane composition, a waterproof material, a wall material, a floor paving material and a water-swellable sheet.
It concerns ring materials.

[0002]

Conventionally, water-swellable polyurethane compositions have a hydrophilic group such as a sulfonic acid group, a carboxyl group or a polyoxyethylene group, and are used as a waterproof material, a sealing material, a caulking material in civil engineering and construction work, As a sealant,
A moisture-curable polyurethane composition having a polyoxyalkylene chain is used as an adhesive, a waterproof material and the like.

However, the water-swellable polyurethane composition is insufficient in water-swellability because it has a sulfonic acid group, a carboxyl group and the like. Further, in order to secure water swelling property, the content of polyoxyethylene chain in the polyether polyol is very high and the hydroxyl group equivalent is 1000.
Since the hardness is large as described above, the hardness after swelling in water of the polyurethane resin is low in spite of the large swelling rate, and the shape retention after swelling in water is poor, and especially the solubility in water is high at high temperature, which means that the polyurethane easily dissolves. There was a problem. On the other hand, in the above-mentioned moisture-curable polyurethane composition, the curing is slow, and particularly when thickly applied, the surface is cured but the lower layer is slowly cured, and there is a problem that the coating film falls off when coating the wall surface and the like. It was

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and its object is to achieve an extremely high curing rate when used in air.
In addition, it has excellent properties such as a small decrease in hardness after water swelling, a good shape retention after water swelling, low solubility even at high temperatures and no hydrolysis, even though the water swelling rate is large when immersed in water. One object is to provide a one-component type polyurethane composition.

[0005]

The present inventors have arrived at the present invention as a result of earnest research to solve the above problems. That is, the present invention provides (a) a terminal isocyanate group content of 1 to 20% by weight obtained by reacting an organic polyisocyanate compound with a polyether polyol containing 10% by weight or more of an oxyethylene chain in an oxyalkylene chain.
The hydrophilic urethane prepolymer of (2) is blended with a block amine compound which does not substantially react with (b) isocyanate groups and produces a primary or secondary amino group due to water. -Type polyurethane composition, waterproof material, wall material or floor pavement material, and polyethylene material comprising the hydrophilic one-pack type polyurethane composition in which the oxyethylene chain content in the oxyalkylene chain of the polyether polyol is 10 to 50% by weight. -A water-swellable sheath comprising the hydrophilic one-pack type polyurethane composition in which the oxyethylene chain content in the oxyalkylene chain of the terpolyol is 40% by weight or more.
A ring material, and a water-swellable sealing material obtained by molding the hydrophilic one-pack type polyurethane composition having an oxyethylene chain content of 40% by weight or more in an oxyalkylene chain of a polyether polyol. .

Examples of the polyether polyol used in the urethane prepolymer include ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, glycerin, trimethylolpropane, triethanolamine and diglycerin. , Pentaerythritol, sorbitol, sucrose, etc., alone or in mixture, ethylene oxide (hereinafter also referred to as EO) alone or ethylene oxide together with propylene oxide (hereinafter also referred to as PO), butylene oxide (hereinafter also referred to as BO), etc. are known. 1 oxyethylene chain in the oxyalkylene chain obtained by addition polymerization by the method
Contains 0% by weight or more and has a molecular weight of 300 to 100,000.
And a polyether polyol which is

When the oxyethylene chain content of the polyether polyol is 10 to 50% by weight, the resulting hydrophilic one-pack type polyurethane composition is most suitable as a waterproof material, a wall material or a floor paving material. When the oxyethylene chain content is 40% by weight or more, it is most suitable as a water-swellable sealing material. Further, other polyols may be appropriately used in combination with these polyether polyols as long as the resulting hydrophilic urethane prepolymer retains hydrophilicity.

Examples of the organic polyisocyanate compound reacted with the polyether polyol include diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, liquid diphenylmethane diisocyanate, tolylene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and hydrogenated xylylene. Diisocyanate,
Examples thereof include tetramethylxylylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like, or burettes, isocyanurates, or carbodiimide-modified products.

The reaction ratio between the polyether polyol and the organic polyisocyanate compound is such that the content of terminal NCO groups in the resulting hydrophilic urethane prepolymer is 1 to 20% by weight,
The ratio is preferably 1.5 to 7.0% by weight. N
When the CO group content is 1.0 terminal, the viscosity of the prepolymer is high and handling is difficult. When the CO group content is 20% by weight or more, the hardness of the cured urethane resin is high and it becomes a molloy.

Next, as a block amine compound (hereinafter also referred to as a block amine compound) which does not substantially react with an isocyanate group and produces a primary or secondary amino group by moisture, for example, aldimine, ketimine and enamine. , Oxazolidine and the like, and specifically, a compound having at least one primary or secondary amino group and having active hydrogen such as primary or secondary amino group and hydroxyl group (hereinafter , A compound (A)) with an aldehyde or a ketone, and further with two ketimines or oxazolidines in the molecule obtained by reacting the above-mentioned organic polyisocyanate compound with a ketimine alcohol or an oxazolidine alcohol which is also the condensate. The compound etc. which have the above are mentioned.

A typical example of the compound (A) is a compound having a primary amino group and a hydroxyl group,
Compound having primary amino group and hydroxyl group, compound having primary amino group and secondary amino group, compound having primary amino group, secondary amino group and hydroxyl group, two first A compound having a secondary amino group, a compound having two secondary amino groups, a compound having a secondary amino group and two hydroxyl groups, and the like,

Specifically, for example, 2- (2-aminoethoxy) ethanol, N- (2-aminoethyl) piperazine, ω-hydroxyhexylamine, N-methyl-1,
6-hexanediamine, diethylenetriamine, N-
Polyamide obtained from (2-hydroxyethyl) ethylenediamine, 3-aminoethylpiperidine, N- (2-hydroxyethyl) piperazine, various oils and fats (for example, dimer acid tall oil fatty acid) and anhydrous piperazine, 1-
Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, N- (methylaminoethyl) piperazine, aniline, toluidine, xylidine, isophoronediamine, diaminocyclohexane, diaminodiphenylmethane, xylylenediamine, diaminobenzene, diaminomethylnorbornene , Diaminomethylbicycloheptane, ethanolamine, diethanolamine, dipropanolamine, hexanolamine and the like.

Examples of aldehydes or ketones include acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde,
Examples thereof include triethylacetaldehyde, valeraldehyde, acrolein, crotonaldehyde, furfural, benzaldehyde, acetone, methylethylketone, methylisobutylketone, diethylketone, diisobutylketone, methylheptenone, cyclohexanone, trimethylcyclohexanone, isophorone and acetophenone. The reaction of these compounds (A) with aldehydes or ketones is carried out under known reaction conditions.

The blending amount of the above urethane prepolymer and the above block amine compound depends on the N of the urethane prepolymer.
The amine equivalent ratio of the block amine compound to the CO equivalent is NCO / amine = 1 / 0.2 to 4.0, preferably 1.
/0.5 to 1.5, and when it is out of the above range, the shape stability is deteriorated and the mechanical properties of the cured product are poor.

If necessary, the hydrophilic one-pack type polyurethane composition is provided with a solvent, a catalyst, a viscosity reducing agent, a plasticizer, a pigment, a colorant, a filler, a stabilizer, a flame retardant, and a thixotropic property. Agents, surfactants, inorganic fillers, and other urethane resins, epoxy resins, acrylic resins, ethylene-propylene rubber, ethylene-propylene-diene rubber, chloroprene rubber, nitrile-butadiene rubber, styrene-butadiene rubber, natural rubber, etc. You may use it together.

The hydrophilic one-pack type polyurethane composition thus obtained was used as a waterproof material, a wall material, and a floor paving material in a roller or layer.
Extruder, by filling or coating directly into the gap with a caulking gun, spatula, spatula, trowel, etc. as a sealing material with a ki, trowel or spray and hardening it at room temperature or before heating , A press, and an injection molding machine are used to form a tape-shaped, plate-shaped, or tubular molded product, and the gap is filled.

[0017]

The function of the hydrophilic one-pack type polyurethane composition of the present invention is as follows:
Since it contains a block amine compound as an essential component,
The moisture in the air or the moisture in the substrate is absorbed and penetrated, the hydrolysis of the block amine is promoted, primary or secondary amine is produced, and it acts as a cross-linking agent for the urethane prepolymer in the composition, thus curing. The urethane resin obtained in this manner has no blistering due to carbon dioxide gas as compared with the case where no block amine compound is added, and the water resistance,
It has excellent heat resistance, weather resistance, etc., and has an extremely fast curing rate in air as compared with a non-hydrophilic one-component polyurethane composition.

Further, when they are used as a sealing material, the water-stopping effect in the field of civil engineering and construction is extremely good, and unlike conventional ones, the hardness after water swelling is high and the solubility at high temperatures is low, In addition, since the water swelling property is sufficiently ensured, it can be used after being formed into various shapes depending on the shape of the target gap or joint.

[0019]

The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
In addition, the part in an Example shows a weight part.

Example 1. NCO / OH equivalent ratio of 100 parts of polyoxypropylene polyoxyethylene triol (oxyethylene chain content 20% by weight and molecular weight 3000) and 27.5 parts of hydrogenated diphenylmethane diisocyanate =
A hydrophilic urethane prepolymer having an NCO group content of 3.6% by weight was obtained by reacting with 2.1.

Ketimine alcohol 3 obtained by reacting 100 parts of this hydrophilic urethane prepolymer with 1 part of an ultraviolet absorber and equimolar reaction of hexanolamine and cyclohexanone
Bulleted hexamethylene diisocyanate 1
A hydrophilic one-pack type polyurethane composition was obtained by blending 31.5 parts of the blocked amine compound obtained from Mole. In addition,
At this time, the NCO to amine equivalent ratio of the hydrophilic one-pack type urethane prepolymer to the block amine compound is 1/1.

Next, this hydrophilic one-pack type urethane prepolymer was applied at a rate of 1.0 kg / m ² to a veranda made of concrete having a gradient of 1/10 which had been previously subjected to urethane primer treatment. Air temperature during construction is 27 ° C, humidity is 65% (R
Although it was H), the coating film hardened after 10 hours and the surface had no abnormalities and clear coating of concrete was possible. Even one year after the coating, there was no abnormality in the coating film. I was not able to admit.

Comparative Example 1. Polyoxypropylene trio
Of 100 parts (molecular weight 3000) and 27.5 parts of hydrogenated diphenylmethane diisocyanate are NCO / OH equivalent ratio =
100 parts of the hydrophilic urethane prepolymer having an NCO group content of 3.6% by weight obtained by the reaction of 2.1 with an ultraviolet absorber 1
Parts, 3 moles of ketimine alcohol obtained by reacting equimolar amounts of hexanolamine and cyclohexanone, and 31.5 parts of a block amine compound obtained from 1 mole of buretted hexamethylene diisocyanate to prepare a one-component polyurethane composition. I got a thing. This was concretely coated in the same manner as in Example 1. The surface of the coated object was cured, but the curing of the back surface in contact with concrete was slow, and the coating film slipped and fell from the upper part of the veranda to the lower part.

Comparative Example 2. In Example 1, 31.5 parts of a block amine compound obtained by reacting 3 moles of ketimine alcohol obtained by reacting hexanolamine and cyclohexanone in an equimolar amount and 1 mole of buretted hexamethylene diisocyanate was not used. Was performed in the same manner as in Example 1. The surface of the coated object was cured, but the curing of the back surface in contact with concrete was slow, and the coating film slipped and fell from the upper part of the veranda to the lower part.

Example 2. EO and P in ethylene glycol
O (EO / PO = 80/20) mixture was added to obtain oxyethylene chain content 80% by weight and molecular weight 3000
Polyether glycol 100 parts, glycerin PO
30 parts of a polyether triol having a molecular weight of 5,000 and diphenylmethane diisocyanate 23.
Add 4 parts (NCO / OH equivalent ratio = 2.2) and add 100 ° C.
At room temperature for 3 hours to obtain a hydrophilic urethane prepolymer having an NCO group content of 2.8% by weight.

To 100 parts of this hydrophilic urethane prepolymer, 20 parts of a block amine compound obtained from 2 mol of a ketimine alcohol obtained by reacting equimolar amounts of hexanolamine and cyclohexanone and 1 mol of 2,4-tolylene diisocyanate is blended. Thus, a water-swellable polyurethane composition was obtained. At this time, the NCO to amine equivalent ratio of the hydrophilic urethane prepolymer to the block amine compound was 1/1.
Is.

Example 3. Glycerin with EO and PO EO
80 parts of polyether triol having an oxyethylene chain content of 75% by weight and a molecular weight of 5000 obtained by adding a mixture of 75/25 in a weight ratio of / PO and ethylene glycol.
20 parts of a polyether glycol having a molecular weight of 400 obtained by adding O and 2,4-tolylene diisocyanate 23.
Add 2 parts (NCO / OH equivalent ratio = 1.80) and add 100
The reaction was conducted at 8 ° C. for 8 hours to obtain a hydrophilic urethane prepolymer having an NCO group content of 4.0% by weight.

100 parts of this hydrophilic urethane prepolymer was mixed with 13.8 parts of dialdimine obtained by the equivalent reaction of diaminomethylbicycloheptane and triethylacetaldehyde as a block amine compound and 20 parts of xylene to obtain a water-swellable polyurethane composition. It was The NCO to amine equivalent ratio of the hydrophilic urethane prepolymer to the block amine compound at this time was 1/1.

Example 4. EO and P in ethylene glycol
A mixture of O and EO / PO in a weight ratio of 70/30 was added to obtain an oxyethylene chain content of 70% by weight and a molecular weight of 40.
E to 90 parts of polyether glycol of 00 and glycerin
A mixture of O and PO at a EO / PO weight ratio of 10/90 was added to obtain 10 parts by weight of oxyethylene chain and a molecular weight of 800, and 10 parts of polyether triol and 13 parts of 2,4-tolylene diisocyanate (NCO / OH equivalent ratio =
1.80) was added and reacted at 100 ° C. for 8 hours to obtain NCO
A hydrophilic urethane prepolymer having a group content of 2.5% by weight was obtained.

2- (2-Ethyl-1,3-oxazolidin-3-yl) obtained by reacting 100 parts of this hydrophilic urethane prepolymer with diethanolamine as a block amine compound and propionaldehyde at a molar ratio of 1: 1. ) -Ethanol (2 mol) was mixed with 2.4 parts of a bisoxazolidine compound obtained by reacting 1 mol of 2,4-tolylene diisocyanate to obtain a water-swellable polyurethane composition. The NCO to amine equivalent ratio of the hydrophilic urethane prepolymer to the block amine compound at this time was 1 / 1.3.

Comparative Example 3. EO and P in ethylene glycol
A mixture of O and EO / PO in a weight ratio of 80/20 was added to obtain an oxyethylene chain content of 80% by weight and a molecular weight of 30.
100 parts of polyether glycol of 00 and glycerin, and a mixture of EO and PO of 80/20 by weight ratio of EO / PO were added to 33 parts of polyether triol having an oxyethylene chain content of 80% by weight and a molecular weight of 3000. Four
16 parts of tolylene diisocyanate (NCO / OH equivalent ratio = 1.80) was added and reacted at 100 ° C. for 8 hours to give N.
A urethane prepolymer having a CO group content of 2.3% by weight was obtained.

Comparative Example 4. Ethylene glycol EO and PO
Of EO / PO at a weight ratio of 10/90 was added to obtain an oxyethylene chain content of 10% by weight and a molecular weight of 300.
100 parts of 0 polyether polyether glycol and 5 parts of polyether triol having a molecular weight of 500 obtained by adding PO to glycerin and 2,4-tolylene diisocyanate 1
Add 5.4 parts (NCO / OH equivalent ratio = 1.80) and add 1
The reaction was carried out at 00 ° C for 8 hours to obtain a urethane prepolymer having an NCO group content of 2.8% by weight.

The urethane compositions obtained in Examples 2 to 4 and Comparative Examples 3 to 4 described above were coated on a release paper to give a length of 50.
A molded body having a size of 20 mm, a width of 20 mm, and a thickness of 3 mm was prepared, and was aged at room temperature (humidity 65% (RH) at 20 ° C.) for 7 days, and then immersed in water at 20 ° C. for 7 days. The results are shown in Table 1.

[0034]

[Table 1]

However, in the table, the swelling rate, hardness before and after swelling, and shape retention were evaluated as follows. Swelling rate: [(length after dipping-length before dipping) / length before dipping] × 100 = swelling rate (%). Hardness before and after swelling: Measured according to JIS K 6301. Shape retention: After being immersed in water or warm water, a change in shape due to dissolution of the surface of the molded body taken out was visually judged.
Shape change x, no shape change o. same as below.

Similarly, the urethane compositions obtained in Examples 2 to 4 and Comparative Examples 3 to 4 were coated on a release paper to give a length of 50.
A molded body having a size of 20 mm, a width of 20 mm, and a thickness of 3 mm was prepared, and was aged at room temperature (humidity 65% (RH) at 20 ° C.) for 7 days, and then immersed in warm water at 80 ° C. for 7 days. The results are shown in Table 2.

[0037]

[Table 2]

[0038]

EFFECTS OF THE INVENTION The hydrophilic one-pack type polyurethane composition of the present invention has a fast curing rate when applied in the atmosphere, and has a high water swelling property, but has a small decrease in hardness after water swelling. It also has good shape retention afterwards, has low temperature solubility and does not hydrolyze.
Most suitable as wall material, floor paving material and water swellable sealing material.

Claims (4)

[Claims] (A) A terminal polyol containing 1 to 20% by weight of a terminal isocyanate group obtained by reacting a polyether polyol having an oxyethylene chain in the oxyalkylene chain of 10% by weight or more with an organic polyisocyanate compound. A hydrophilic one-pack type comprising a hydrophilic urethane prepolymer and a block amine compound which does not substantially react with (b) isocyanate group and produces a primary or secondary amino group by moisture. Polyurethane composition. 2. The content of oxyethylene chain in the oxyalkylene chain of the polyether polyol is 10 to 50% by weight.
The waterproof material, wall material or floor paving material comprising the hydrophilic one-pack type polyurethane composition according to claim 1. 3. A water-swellable sealing material comprising a hydrophilic one-pack type polyurethane composition according to claim 1, wherein the oxyethylene chain content of the oxyalkylene chain of the polyether polyol is 40% by weight or more. 4. A water-swellable silicone composition obtained by molding a hydrophilic one-pack type polyurethane composition according to claim 1, wherein the oxyethylene chain content of the oxyalkylene chain of the polyether polyol is 40% by weight or more. -Ring material.