JPH09194717A - Polyurethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture-curing one-pack polyurethane resin composition, more particularly a moisture-curing one-pack polyurethane resin composition having excellent storage stability and curability. SOLUTION: This polyurethane resin composition contains (a) 100 pts.wt. of a urethane prepolymer having isocyanato group on the molecular terminal, (b) 5-300 pts.wt. of calcium carbonate treated with an organic acid or an organic acid ester and having a BET specific surface area of >=3m<2> /g and (c) 0.1-30 pts.wt. of an organopolysiloxane containing at least one structure of the formula (R<1> is methyl, ethyl or phenyl; R<2> is a 1-30C hydrocarbon group; (n) is recurring number) in one molecule.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a one-pack type moisture-curable polyurethane resin composition. More specifically, it relates to a one-pack moisture-curable polyurethane resin composition having excellent storage stability and good curability.

[0002]

2. Description of the Related Art Conventionally, various polyurethane resin compositions have been widely used as sealing agents, adhesives, primers, paints, waterproof materials, floor materials and the like. As such a polyurethane resin composition, a two-pack type resin composition composed of a polyol compound and an isocyanate group compound and a one-pack type resin composition which is cured by moisture in the air are known. However, in recent years, the use of the one-pack type moisture-curable polyurethane resin composition has been expanding in view of the fact that it is not necessary to adjust the composition of the composition in the field construction and is easy to handle. In most cases, a basic filler is used as a filler in the one-pack type moisture-curable polyurethane resin composition, and among them, calcium carbonate is widely used. In most cases, calcium carbonate that has been surface-treated with a fatty acid, a resin acid, or a fatty acid ester is used, but one treated with a fatty acid or a resin acid has very poor storage stability and is a one-pack type moisture-curable polyurethane. Not used in any resin. Further, it is difficult to obtain satisfactory storage stability even when calcium carbonate surface-treated with a fatty acid ester is used. Here, the resin acid is a general term for organic acids existing as free or as an ester in a natural resin.

[0003]

One of the factors that greatly affects the storage stability of a one-pack type moisture-curable polyurethane composition is water adsorbed on a filler or the like incorporated in the composition. . That is, since the curing reaction proceeds during storage due to the presence of this moisture, good storage stability cannot be obtained. Therefore, it is fundamentally impossible to obtain excellent storage stability without solving this moisture problem.

[0004]

An object of the present invention is to solve the problems of the above-mentioned technique, and to solve the problem of deterioration of storage stability due to water adsorbed on fillers,
It is an object of the present invention to provide a one-pack type moisture-curable polyurethane resin composition having excellent storage stability and good curability that cures in a short time. That is, the object of the present invention is (a)
With respect to 100 parts by weight of the urethane prepolymer having an isocyanate group at the terminal, (b) 5 to 300 parts by weight of calcium carbonate having a BET specific surface area of 3 m ² / g or more, which has been treated with an organic acid or an organic acid ester, and (c) the following formula ( There is provided a polyurethane resin composition containing 0.1 to 30 parts by weight of an organopolysiloxane having at least one structure 1) in the molecule.

Embedded image Here, in the formula (1), R ¹ is either a methyl group, an ethyl group or a phenyl group, but the same or different groups may be mixed in the molecule. Further, R ² has 1 to 30 carbon atoms.
Represents a hydrocarbon group, and the same or different groups may be mixed in the molecule. n represents repetition. Hereinafter, the polyurethane resin composition of the present invention will be described in detail. The present invention is a one-component moisture-curable polyurethane resin composition (hereinafter referred to as a urethane composition), which comprises a urethane prepolymer having a terminal isocyanate group, calcium carbonate treated with an organic acid or an organic acid ester, and a predetermined amount. It contains an organopolysiloxane represented by the chemical formula of as an essential component. The urethane prepolymer (a) blended in the urethane composition of the present invention is the same as in a normal one-pack type polyurethane resin composition, and the polyol compound and the excess polyisocyanate compound (that is, the excess NCO relative to the OH group). Group) and generally contains 0.5 to 5% by weight of isocyanate groups at the molecular ends. As the polyisocyanate compound for producing such a urethane prepolymer, various kinds of compounds similar to the ordinary one-pack type polyurethane resin composition are exemplified, and specifically, 2,4-tolylene diisocyanate and 2,6-trilene isocyanate are exemplified. Aromatic polyisocyanates such as diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate, etc. Alicyclic polyisocyanates; arylaliphatic polyisocyanates such as xylylene diisocyanate; carbodiimide-modified or isocyanurate-modified polyisocyanates of the above polyisocyanates Sulfonate; and the like are preferably exemplified, is used as one kind of them or two or more thereof.

On the other hand, the polyol compound used in the present invention is the same as a usual one-pack type polyurethane resin composition.
These are polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. Specifically, as the polyether polyol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin,
1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1,4-
At least one selected from polyhydric alcohols such as butanediol, 4,4′-dihydroxyphenylpropane, 4,4′-dihydroxyphenylmethane and pentaerythritol, and propylene oxide, ethylene oxide, butylene oxide, styrene oxide, etc. A polyol obtained by adding at least one selected;
Suitable examples thereof include polyoxytetramethylene oxide;

Further, as the polyester polyol,
At least one selected from ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, or other low molecular weight polyol, and glutaric acid, adipine Acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, or a condensation polymer with at least one selected from other low-molecular-weight carboxylic acids and oligomeric acids; such as propionlactone and valerolactone Suitable examples are ring-opening polymers.

Further, other polyols include polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, acrylic polyol, etc., ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, etc. The low molecular weight polyols are also suitable examples.

The mixing ratio of the polyol compound and the polyisocyanate compound in obtaining the urethane prepolymer having a terminal isocyanate group consisting of the polyol compound and the excess polyisocyanate compound is usually 1 equivalent of the polyol compound (OH equivalent). ), The polyisocyanate compound is 1.2 to 5 equivalents (NCO equivalent), preferably 1.5 to 3 equivalents.

Further, in the production of this urethane prepolymer, as in the case of a normal urethane prepolymer, both compounds are mixed in a predetermined amount ratio, and usually 30 to 120 ° C., preferably 5
It is performed by heating and stirring at 0 to 100 ° C.

Blended with the urethane composition of the present invention,
As the (b) calcium carbonate treated with an organic acid or an organic acid ester, a BET specific surface area of 3 m ² / g or more is preferably exemplified. Specific surface area by BET method is 3m
If it is less than ² / g, the water adsorbed on the calcium carbonate can be easily removed, and the storage stability is not so affected. The calcium carbonate may be either precipitated calcium carbonate or ground calcium carbonate.

As the organic acid used for the surface treatment, as disclosed in JP-B-60-231744, caprylic acid having 8 or more carbon atoms, lauric acid, myristic acid,
Saturated fatty acids such as palmitic acid, stearic acid and arachidic acid, unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid and ricinoleic acid, alicyclic carboxylic acids such as naphthenic acid, resin acids such as apietic acid and the like. Examples thereof include salts such as sodium, potassium and ammonium. Further, as the organic acid ester, methyl of the above organic acid,
Not only esters produced from monohydric alcohols such as ethyl, propyl, butyl and octyl, but also fatty acid esters produced from polyhydric alcohols such as glycerin are sufficiently effective. Specifically, as disclosed in JP-A-2-38309, stearic acid stearate, stearic acid laurate, palmitic acid stearate, palmitic acid laurate, palmitic acid glyceride and the like can be mentioned.

In the urethane composition of the present invention, the compounding amount of such calcium carbonate is 5 to 300 parts by weight based on 100 parts by weight of the urethane prepolymer. If the blending amount of calcium carbonate is less than 5 parts by weight, the effect of improving the physical properties of the cured product and the addition effect of the basic filler as an extender cannot be obtained. Conversely, if blending exceeds 300 parts by weight, the modulus, This is because problems such as the inability to obtain a cured product having satisfactory physical properties in terms of elongation and strength occur. In the urethane composition of the present invention, the blending amount of calcium carbonate is preferably urethane prepolymer 1
It is about 50 to 200 parts by weight with respect to 00 parts by weight.
By setting the blending amount of calcium carbonate within the above range,
Preferable results are obtained in terms of elongation, modulus and strength of the cured product.

The urethane composition of the present invention contains, in addition to the urethane prepolymer and calcium carbonate having a BET specific surface area of 3 m ² / g or more treated with an organic acid or an organic acid ester, 100 parts by weight of the urethane prepolymer ( c) 0.1 to 30 parts by weight of an organopolysiloxane having at least one structure represented by the following formula (1) in the molecule is contained.

Embedded image (R ¹ represents a methyl group, an ethyl group or a phenyl group, R ² represents a hydrocarbon group having 1 to 30 carbon atoms, and n represents a repetition.)

The polysiloxane is more easily hydrolyzed to carboxylic acids and silanols than the isocyanate groups of the urethane prepolymer. Therefore, by blending the above-mentioned polysiloxane in the urethane composition, it is possible to prevent the curing reaction of the urethane prepolymer due to the water adsorbed to the filler, etc., without adversely affecting the curing time at the time of construction and to stabilize the storage. A urethane composition having excellent properties can be realized.

In the polysiloxane represented by the above formula, R ¹ is specifically a methyl group, an ethyl group,
Examples thereof include a phenyl group, and the same or different groups may be mixed in the molecule. In the polysiloxane represented by the above formula, R ² is a hydrocarbon group having 1 to 30 carbon atoms, and the same or different groups may be mixed in the molecule. Specifically, a methyl group, a propyl group, a butyl group, a stearyl group, an octyl group, a lauryl group, a palmityl group, an eicosyl group, a hexacosyl group, a phenyl group, a benzyl group, a carboxylic acid described below used for the synthesis of polysiloxane. Examples of the hydrocarbon group contained in are. Particularly, from the viewpoint of odor and stability of carboxylic acid, hydrocarbon groups having 6 to 21 carbon atoms such as stearyl group, palmityl group, lauryl group, octyl group, eicosyl group, phenyl group, benzyl group and the like are particularly preferable.

In the polysiloxane represented by the above formula, the repeating unit n is an integer of 1 or more, but preferably about 10% or more based on all siloxane units.
Preferably n is 1-50.

In addition to the polysiloxane unit represented by the above formula,

Embedded image It goes without saying that such repeating units may be randomly arranged, block-wise arranged, or a mixture of both. Such polysiloxanes include Group VIII transition metals Pt, Rh, I
Using a simple substance of r, Pd, or Ni, or a chloride or olefin complex thereof as a catalyst, a polyhydrogensiloxane having a corresponding acyloxyalkyl group of hydrogen is reacted with a carboxylic acid to form a silyl ester group. It can be synthesized by

As the polyhydrogen siloxane,

Embedded image One or a combination of two or more thereof is preferably exemplified.

On the other hand, as the carboxylic acid, acetic acid, butyric acid,
Caproic acid, caprylic acid, pelargonic acid, capric acid,
Straight chain saturated fatty acids such as undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, or melicinic acid; caproic acid, oleic acid, cetoleic acid, sorbin Unsaturated fatty acids such as acid, linoleic acid, or linoleic acid; aromatic carboxylic acids such as benzoic acid, phenylacetic acid, 3-phenoxyundecanoic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, or benzophenonetetracarboxylic acid An acid; an alicyclic carboxylic acid such as tetrahydrophthalic acid or nadic acid, and one kind or a combination of two or more kinds of other carboxylic acids are exemplified. The carboxylic acid is not particularly limited,
It is preferable that the carbon number is 8 or more.

In the urethane composition of the present invention, the amount of such polysiloxane compounded is 0.1 to 30 parts by weight based on 100 parts by weight of the above-mentioned urethane prepolymer. If the amount of the polysiloxane is less than 0.1 part by weight,
The effect of the polysiloxane cannot be obtained, and good storage stability cannot be obtained. On the contrary, when the polysiloxane exceeds 30 parts by weight, the curing time of the urethane composition becomes long. , Because it causes a problem in practical use. The amount of polysiloxane compounded is preferably 0.5 to 100 parts by weight of the urethane prepolymer.
20 parts by weight, more preferably 1 to 10 parts by weight. Thereby, favorable results are obtained in terms of storage stability, curability and the like. Since such polysiloxane is crystalline in some cases, it may be swollen in toluene, xylene or the like before use. The urethane composition of the present invention further comprises
Various additives to be added to a known one-pack type urethane composition as required, specifically, plasticizers such as dioctyl phthalate, antioxidants, ultraviolet absorbers, coloring agents such as pigments and dyes, titanium dioxide A filler such as carbon black or clay, a curing catalyst (curing accelerator) such as an organometallic compound or an amine may be added. The amount of these additives blended is appropriately determined according to the application of the urethane composition of the present invention.

The method for preparing the urethane composition of the present invention is not particularly limited, and may be the same as a usual one-pack type urethane composition. For example, a method of sufficiently kneading each component under reduced pressure and uniformly dispersing the components is exemplified.

The urethane composition of the present invention may be further modified or improved within a range not impairing the characteristics of the composition of the present invention.

[0023]

The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to the following embodiments. (Synthesis of urethane prepolymer) Number average molecular weight 3000
850g polypropylene glycol, number average molecular weight 3
5,000 polypropylene triol (150 g) and dioctyl phthalate (300 g) were further mixed, and diphenylmethane diisocyanate (124 g) was added, and the mixture was stirred and reacted at 80 ° C. for 10 hours to give isocyanate groups of 0.
A urethane prepolymer containing 75% was synthesized.

(Synthesis of Polysiloxane) <a. Synthesis of Polysiloxane I> Stearic Acid 450g
Was dried under reduced pressure at 90 ° C. for 1 hour, and then 150 g of polyhydrogensiloxane KF9901 (produced by Shin-Etsu Chemical Co., Ltd.)
Then, 0.1 ml of a 1% isopropyl chloroplatinate solution was added, and the mixture was reacted at 90 ° C. for 6 hours to synthesize polysiloxane I represented by the following formula.

[Chemical 6] <B. Synthesis of Polysiloxane II> Stearic Acid 450
After being dried under reduced pressure at 90 ° C. for 1 hour, 100 g of polyhydrogensiloxane KF99 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.1 ml of a 1% isopropyl chloroplatinate solution were added, and reacted at 90 ° C. for 6 hours to give the following: A polysiloxane II represented by the formula was synthesized.

Embedded image

Various urethane carbonates shown in Table 1 below were produced by adding and kneading various calcium carbonates to the urethane prepolymer synthesized above, polysiloxane I or II. The viscosity of each urethane composition obtained was measured by a B-type viscometer immediately after kneading, 1 day after kneading at 20 ° C., and after storage at 70 ° C. for a day. Further, the urethane composition was applied on a glass plate, and the time until polyethylene terephthalate stopped adhering to the urethane composition was measured under the conditions of 20 ° C. and 65% relative humidity, and the tack free time was measured. The results are shown in the table below.

[0026]

[Table 1]

In the table, the compositional component amounts are parts by weight. The description in the table is as follows. The specific surface area of all calcium carbonate measured by the BET method was 3 m ² / g or more. Calcium carbonate A; Calfine 200 (fatty acid treatment;
Maruo Calcium Co., Ltd.) Calcium carbonate B; MC-5 (fatty acid, resin acid treatment; Maruo Calcium Co., Ltd.) Calcium carbonate C; Shirahama CC (fatty acid treatment; Shiraishi Calcium Co.) Calcium carbonate D; Gelton 50 (fatty acid treatment; Shiraishi) Calcium Co., Ltd.) Calcium Carbonate E; Shiro Gloss DD (fatty acid treatment; Shiraishi Calcium Co.) Calcium Carbonate F; Sealets 200 (fatty acid ester treatment; Maruo Calcium Co.)

[0028]

EFFECTS OF THE INVENTION According to the present invention, the problem of deterioration of storage stability due to moisture adsorbed on a filler or the like is solved, storage stability is excellent, and good curability that cures in a short time is achieved. A one-pack type moisture curable polyurethane resin composition can be obtained.

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[Procedure amendment]

[Submission date] March 4, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

In the polysiloxane represented by the above formula, R ¹ is specifically a methyl group, an ethyl group,
Examples thereof include a phenyl group, and the same or different groups may be mixed in the molecule. In the polysiloxane represented by the above formula, R ² is a hydrocarbon group having 1 to 30 carbon atoms, and the same or different groups may be mixed in the molecule. Specifically, a methyl group, a propyl group, a butyl group, a stearyl group, an octyl group, a lauryl group, a palmityl group, an eicosyl group, a hexacosyl group, a phenyl group, a benzyl group, a carboxylic acid described below used for the synthesis of polysiloxane. Examples of the hydrocarbon group contained in are. Particularly, from the viewpoint of odor and stability of carboxylic acid, hydrocarbon groups having 7 or more carbon atoms such as stearyl group, palmityl group, lauryl group, octyl group, eicosyl group, phenyl group and benzyl group are particularly preferable.

Claims (1)

[Claims] 1. A calcium carbonate having a specific surface area of 3 m ² / g or more as measured by the BET method in which (a) 100 parts by weight of a urethane prepolymer having an isocyanate group is treated with (b) an organic acid or an organic acid ester. 5-300
Parts by weight, and (c) 0.1 to 3 organopolysiloxane having at least one structure represented by the following formula (1) in the molecule.
A polyurethane resin composition containing 0 parts by weight. Embedded image (R ¹ represents a methyl group, an ethyl group or a phenyl group, R ² represents a hydrocarbon group having 1 to 30 carbon atoms, and n represents a repetition.)