JPS60219217A - Production of epoxyurethane resin - Google Patents

Abstract

PURPOSE:To obtain an epoxyurethane resin excellent in impact and chemical resistances, by reacting a specified urethane prepolymer with 1,2-epoxyalcohol. CONSTITUTION:The following isocyanato group-terminated urethane prepolymer is reacted with a 1,2-epoxyalcohol. The urethane prepolymer used is one obtained by reacting a polyhydroxy compound containing 10-95wt% polycaprolactone-polyol with a polyisocyanate compound. Said polycaprolactone-polyol can be synthesized by polymerizing by ring opening epsilon-caprolactone and a polyalcohol in the presence of a catalyst. In the production of said urethane prepolymer, the reaction is carried out at a temperature in the range of 20-140 deg.C. This reaction may be carried out in the absence or presence of a solvent.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing an epoxy urethane resin having excellent impact resistance and chemical resistance. It is a resin that has an epoxy group in it, and was proposed as a resin that gives flexibility to epoxy resin. By appropriately selecting the structure of the epoxy resin, the structure and content of the urethane, and the modification method used in the epoxy urethane resin, it is possible to set the quality of a wide range of products using EiJ's ability to create hard and strong resins. It is possible to obtain rubber-like cured products with high elasticity. With these features, paints, adhesives,
It is attracting wide attention as a material for molding materials, casting resins, etc.

Epoxy urethane resin is usually a urethane prepolymer synthesized from polyol and polyinner inert.
-Synthesized by reacting epoxy alcohol.

(Prior art and its drawbacks) However, among these polyols, epoxy urethane resins synthesized using known polyester polyols are not practical in fields where impact resistance and chemical resistance are required. No satisfactory epoxy urethane resin was obtained. Therefore, in the case of an epoxy urethane resin obtained using a polycaprolactone-based polyester polyol that has improved these drawbacks, water resistance is improved without impairing impact resistance, but chemical resistance is not improved.

(Structure of the present invention) Therefore, the inventors of the present invention diligently overlapped the sides, and by using polycaprolact/polyol in combination with other polyol components, it was possible to achieve this without impairing the 4 impact properties and water resistance. The inventors have discovered that a urethane epoxy resin with excellent chemical resistance can be obtained, and have arrived at the present invention.

That is, the present invention uses polycaprolactone polyol in an amount of 10 to
1.2 to the urethane polymer (containing terminal incyanate groups) obtained by reacting a polyhydroquine compound containing 95% by weight with a polyisocyanate compound.
-Regarding a method for producing an epoxy/urethane resin obtained by reacting an epoxy alcohol.

The polycaprolact/polyol in the present invention is 10 to
A polyhuman oxygen compound containing 95% by weight is a polyether polyol represented by polyethylene glycol, polypropylene glycol, polytetramethylene glycol, synthesized from ethylene glycol and adipic acid,
Polyhydric alcohol-polybasic acid polyester polyol represented by polyester synthesized from 1,6-hexanediol and adipic acid, polybutadienodiol with hydroxyfluorized polybutanene terminal, polyhydric alcohol and ether/carbonate or Polycarbonate diols synthesized from phosge/, castor/long chain carboxylic acids with hydroxyl groups such as oil, chryseri/esters, etc. - polyol compounds not made from lactones 5
~90% by weight and polycaprolact/polyol 10~
95% by weight of 6-caprolactone, or a polyol compound obtained by ring-opening addition polymerization of ε-caprolactone to a polyol compound not made from the above-mentioned 6-caprolactone so that the caprolactone component becomes 10 to 95% by weight.

Here, polycaprolact/polyol can be synthesized by ring-opening addition polymerization of ε-caprolact/polyhydric alcohol in the presence of a catalyst.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,4-hexanediol, nemepentel glycol, and the like. This polyhydric alcohol has ε-
A reaction that adds caprolactone to a polyol compound that is not made from caprolactone as a raw material.
The reaction for adding can be carried out under similar reaction conditions.

Catalysts include titanium compounds such as tetraphthyl titanate and tetrapropyl titanate, zinc chloride, tin octylate, dibnaltin oxide, stannous chloride, stannous chloride, stannous iodide, etc. 0.0
It is preferable to use 1 to 50 ppm, preferably 01 to 10 ppm.

Usually, polyhydric alcohol, polyol compound, ε-caprolactone, and the above catalyst are simultaneously charged in a reactor and reacted to synthesize polycaprolactone/polyol or caprolactone-containing 9-ol.

The reaction temperature is 130°C ~ 2406C1 Yoshiashikake 140
~230°C. Also, passing an inert gas such as a phonetic gas during the reaction gives good results on the hue of the resin, etc.

The average molecular weight can be adjusted by changing the number of moles of ε-kacapracto added to the polyhydric alcohol or polyol compound.

The average molecular weight in the present invention is a value calculated by the following formula.

The hydroxyl value is measured according to J, IS K-1557, 64.

The polycaprolact/polyol used in the present invention is 10 to
The average molecular weight of the polyhydroxy compound containing 95% by weight is 5
It is preferable to use one with a value of 00 to 5000.1. stomach.

A urethane/prepolymer is obtained by reacting the polyhydroxy compound thus obtained with a polyisocyanate compound. At this time, one hydroxyl group and 1.1 to 5 incyanate groups of the polyhydroxy compound are added.
0 equivalents, preferably 1.2 to 20 equivalents are reacted. If the ratio is less than 1.1, the molecular weight of the urethane prepolymer produced becomes too large and the viscosity increases, resulting in a urethane epoxy resin that cannot be handled normally. Sota 5, 0
If the coulometric amount is higher than that, the average molecular weight of the urethane prepolymer produced tends to be low, and the resulting epoxy urethane resin is not only strong in strength but also poor in flexibility.

As the bolyinite compound, g4-trile/
diinaneanate, 2.6-tosole/') insi7ne-
), 4.4'-diphenylmethane isocyanate, 1
, 5-naphthalene diisocyanate, xylyle/diisocyanate, hexamethylene diisocyanate, diphenyl ether diisocyanate, inholo/diisocyanate, and various other isocyanate compounds commonly used in bosoureta/manufacturing can be used.

When producing the urethane prepolymer of the present invention, 20
The reaction is carried out in a temperature range of 0C to 140C, preferably 50C to 1200C. The reaction can be carried out without a solvent or in a solvent. As the solvent, one that is inert to incyanate is used. For example, toluene/, xylene, ethyl acetate, butyl acetate,
Methyl ethyl keto/, dimethylformamide, tetrahydrofurano, etc. are used.

The reaction between the polyhydroquine compound and the polyincyanate compound proceeds satisfactorily even without a catalyst, but the reaction proceeds more rapidly in the presence of a catalyst commonly used in urethanization reactions, such as butyltin laurate and diethylaminoethanol.

The urethane prepolymer thus obtained and 1.2-
Epoxy urethane resin is obtained by reacting with epoxy alcohol.

1.2-modified alcohols include glycidol and its derivatives, glycidyl ethers of diols synthesized from shrimp chlorhydride/and diols, such as ethylene glycol monoglycidyl/p ether, buta/diol monoglycidyl ether, Examples include hexanediol monoglycidyl ether.

The reaction ratio of the urethane prepolymer and 1,2-epoxy alcohol is such that the hydroxyl group of the 1,2-epoxy alcohol is used in an amount greater than the required amount per isocyanate group of the urethane prepolymer, preferably 10 to 12. be. The reaction between the urethane prepolymer and the 1.2-epoxy alcohol can be carried out under substantially the same conditions as the synthesis reaction of the urethane prepolymer. That is, for reaction-wet hair, 200C to 140°C1IL<H3O00 to 12
At 0'Cf, the reaction can be carried out without a solvent or in the presence of a solvent.

Similar solvents can also be used.

The reaction can usually be carried out without a catalyst, but it is not recommended to use a catalyst.

The epoxy urethane resin of the present invention obtained as described above contains commonly used epoxy curing agents, dyes, pigments, etc.
Adhesives, paints,
It can be used as a sealant, casting resin, etc.

The present invention will be further explained in detail with reference to examples below.

Synthesis Example-1 265 parts of ethylene glycol, 173 parts of ε-caprolactone in a flask equipped with a nitrogen inlet tube, a thermometer, and a stirring device
5i1, 002 parts of tetrabutyl titanate, prepared 1
When ring-opening addition polymerization was carried out at 70-1800c for 6 hours, the acid value was 0.2KOHm9/&, and the hydroxyl value was 136.8KOH~
/g of polycaprolactone polyol was obtained.

Example-1 373.4 parts of polycaprolactone obtained in Synthesis Example-1 and molecule 1 were placed in a flask equipped with a nitrogen inlet tube, a thermometer, and a stirring device.
zooo polycarbonate polyol (Sumitomo Bayer AG, Desmaux: /-2020E) 177.2 parts,
1224 parts of bexamethele/diisocyanate and 05 parts of diptyltin laurate were charged and reacted at 70-90'C for 4 hours, then 27.0 parts of glycidol was further added and reacted at 70-90'C for another 4 hours. An epoxy urethane resin having an equivalent weight of 1,600 and an average molecular weight of 3,845 was obtained.

Example 2 7424.9 parts of polycaprolact obtained in Synthesis Example 1 and polytetramethidi/glycol (Mitsubishi Gas Chemical Co., Ltd., PTMG) were placed in a flask equipped with a nitrogen inlet tube, a thermometer, and a stirring device.
-2,000) 113.1 parts, 2,4-tolylene diisocyanate 133.5 parts, dibutyltin laurate 0
After adding 5 parts of glycidol and reacting at 70 to 90°C for 4 hours, 284 parts of glycidol was added and the mixture was heated at 70 to 90°C.
When the reaction was further carried out for 4 hours, the epoxy equivalent was 1.6.
40, and an epoxy urethane resin having an average molecular weight of 3.649 was obtained.

Claims (1)

[Claims] 1,2-epoxy alcohol is added to a urethane prepolymer (containing a terminal in-7-atom group) obtained by reacting a polyhydroxy compound containing 10 to 95% by weight of borocafluoract/polyol with a polyyne/anate compound. Manufacturing method of epoxy urethane resin that involves reaction 0