JPH0459811A - Polyurethane resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition of moisture-curing one pack type having excellent storage stability, comprising an isocyanate group-containing urethane polymer and a specific amount of bis(dimethylmorpholino) ethyl ether. CONSTITUTION:The objective composition comprising (A) an isocyanate group- containing urethane polymer prepared by reacting a polyol (e.g. polyether polyol) with a polyisocyanate (e.g. 2,4-tolylene diisocyanate) preferably at 50-100 deg.C and (B) 0.05-5wt.%, preferably 0.1-3wt.% based on the component A of bis(dimethylmorpholino) ethyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyurethane resin composition, and particularly to a one-component moisture-curing polyurethane resin composition that has excellent storage stability and quick curing.

(Prior Art) Polyurethane elastomers have conventionally been widely used as sealants, adhesives, primers, paints, waterproofing materials, flooring materials, and the like. Among these, wave-shaped moisture-curing polyurethane resins do not require measuring or mixing before use compared to two-component polyurethane resins, and therefore have the characteristic that there is no unevenness in the development of physical properties due to measurement errors or insufficient mixing. be.

(Problems to be Solved by the Invention) One-component moisture-curable polyurethane resin compositions usually require a long time to cure. Therefore, when curing is desired in a short period of time, organic metal compounds, amine compounds, and the like are used as catalysts to accelerate curing. However, these methods have the problem of reducing the storage stability of the product at the cost of shortening the curing time.

(Means for Solving the Problems) The present inventors have conducted repeated studies to develop a one-component moisture-curable polyurethane resin composition with excellent storage stability and a short curing time, and as a result, they have arrived at the present invention.

That is, the one-component moisture-curable polyurethane resin composition according to the present invention comprises a urethane prepolymer having an isocyanate group obtained by reacting a polyol and a polyisocyanate, and 0.05 to 5% by weight of bis(dimethylmorpholino). ) ethyl 21thyl.

Hereinafter, one aspect of the present invention will be explained in detail.

Examples of polyols used in the production of the isocyanate group-containing urethane prepolymers of the present invention include ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane, and triethanolamine.

Low-molecular polyols such as pentaerythritol and sorbitol; polyether polyols having a structure in which alkylene oxides such as ethylene oxide and propylene oxide are added to water, the above-mentioned low-molecular polyols, and polyamines such as ethylene diamine, diethylene triamine, and tolylene diamine; succinic acid , polyester polyols by reaction of dicarboxylic acids such as maleic acid, sebacic acid, adipic acid, fumaric acid, phthalic acid, and dimer acid with the above-mentioned low molecular weight polyols; ring-opening polymerization of lactones such as γ-butyllactone and ε~caprolactone. polylactone polyol obtained by; polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran; castor oil or its alkylene oxide addition-modified product; polydiene polyol which is a polymer of diene compounds such as butadiene and isoprene and has a hydroxyl group at the terminal or hydrogenated products thereof, and these may be used alone or in combination of two or more.

On the other hand, examples of polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, p-
Aromatic polyisocyanates such as phenylene diisocyanate and polymethylene polyphenylene polyisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate; 3-isocyanatomethyl-3,5°5-trimethylcyclohexyl isocyanate, 4.4
``-Alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate; arylaliphatic polyisocyanates such as xylylene diisocyanate; and carbodiimide-modified or isocyanurate-modified polyisocyanates of these, and these may be used alone or in combination of two or more. used as.

The mixing ratio of the polyol and polyisocyanate to obtain a urethane prepolymer having isocyanate groups is usually 1.2 to 5 equivalents, preferably 1.5 to 3 equivalents of polyisocyanate per equivalent of polyol.

Additionally, this reaction is usually carried out at 30 to 120°C, preferably at 50°C.
This is achieved by heating and stirring at ~100°C.

Bis(dimethylmorpholino)ethyl ether, more precisely bis-4-(2,6-dimethylmorpholino)ethyl ether, used as catalyst in the compositions of the invention is a combination of 2,6-dimethylmorpholine and 2,2' -obtained by reaction with dichlorodiethyl ether.

The amount of bis(dimethylmorpholino)ethyl ether used is usually O, O per 100 parts by weight of the urethane prepolymer.
S to 5 parts by weight, preferably 0.1 to 3 parts by weight.

This composition may also contain stabilizers such as acid chlorides such as benzoyl chloride and sulfonic acids such as methanesulfonic acid, either alone or in combination of two or more.

The amount of stabilizer used varies depending on the type of stabilizer, the type of catalyst, etc., but is usually 1 to 30 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of catalyst.

Furthermore, the composition of the present invention includes deodorants, antioxidants,
Various additives may be used, such as ultraviolet absorbers, colorants such as pigments and dyes, and fillers such as calcium carbonate, titanium dioxide, carbon black, and clay.

In preparing this composition, catalysts, stabilizers, and various additives may be added to the urethane prepolymer, and some of the catalysts, stabilizers, and various additives may be added in advance when producing the urethane prepolymer. Alternatively, the entire amount may be added. A polyurethane resin composition containing a catalyst and various additives is stored in a container that can block moisture. If necessary, the container can be opened, filled, applied or coated in a conventional manner, and cured by reaction with moisture or moisture in the air.

(Examples) Hereinafter, specific aspects of the present invention will be explained using Examples and Comparative Examples, but the present invention is not limited thereto.

In addition, in the examples, all parts represent parts by weight.

(Manufacture of urethane prepolymer composition) 800 parts of dioctyl phthalate, 80 parts of crown talc (manufactured by Matsuzai Sangyo ■)
0 parts and 400 parts of Titanium White R820 (manufactured by Ishihara Sangyo ■) were mixed in a universal mixer, and then dehydrated under reduced pressure at 100°C. When I sampled and measured the moisture content, it was 0.0.
It was 2%. After cooling the dehydrated product to 50°C, 11.2 parts of Isonate 125M (manufactured by MD Kasei ■, diphenylmethane diisocyanate) was added and stirred for 10 minutes. Furthermore, 1000 parts of Takenate L-1072 (manufactured by Takeda Pharmaceutical Co., Ltd., urethane prepolymer) was added and
After mixing for 0 minutes, add 30 parts of Aerosil R972 (Japan Aerosil 14IIIlII and add 2t) and mix for 2 minutes.
A urethane prepolymer composition was obtained. This was used as a reference example.

Example 1 4 parts of bis(dimethylmorpholino)ethyl ether was added to 1017 parts of the above urethane prepolymer composition, mixed in a universal mixer under a nitrogen stream, packed in plastic bags of about 200 g each, and then placed in aluminum-laminated plastic bags. I put it in and heat sealed the opening. This was used as the urethane resin composition of Example 1.

Comparative Examples 1 and 2 - 1.1 parts of bisdimethylaminoethyl ether and 6 parts of dibutyltin dilaurate were blended into 1017 parts of the above urethane prepolymer composition in the same manner as in Example 1, and packed into bags. The urethane resin composition No. 2 was prepared.

(Performance evaluation of each composition) The curability and storage stability of each of the compositions of Reference Example, Example 1, and Comparative Examples 1 and 2 were evaluated by the following methods, and the results are shown in the table.

・Curability: Apply each composition to a thickness of about 3+m+ on a glass plate and heat at 25°C.
The sample was dried at a relative humidity of 50%, and the time required for the sample to stop adhering to the fingertip (touch dry time) was measured and used as a measure of curability.

・Storage stability: For each composition sealed in a plastic bag and for each composition stored in a constant temperature dryer at 40°C for 7 days, the diameter of the cylinder was 3.15+m, and the diameter of part of the cylinder was 25.41m. The sample was placed in a syringe, and the amount extruded in 2 minutes was measured under a load of 5 kg, which was used as a measure of storage stability.

Note that the symbols for the types of compositions in Table 1 have the following meanings.

I: Bis(dimethylmorpholino)ethyl ether ■: Bisdimethylaminoethyl ether ■ Nidibutyltin dilaurate (Effects of the invention) According to the present invention, a liquid-type moisture-curing product that cures quickly upon use and has excellent storage stability. It is a type of polyurethane resin composition that is extremely useful in the production of sealants, adhesives, paints, waterproofing materials, flooring materials, etc.

Patent applicant: Sun-Apro Co., Ltd.

Claims (1)

[Claims] 1. A urethane prepolymer having isocyanate groups obtained by reacting a polyol and a polyisocyanate,
0.05-5% by weight of this bis(dimethylmorpholino)
A polyurethane resin composition consisting of ethyl ether.