JPS61106617A - Novel urethane oligomer - Google Patents

Abstract

PURPOSE:A radical-polymerizable urethane oligomer, prepared by reacting an isocyanate-terminated prepolymer obtained by reacting a polyisocyanate with a specified polyalcohol with a hydroxyl group-containing unsaturated compound. CONSTITUTION:A polyalcohol containing 5-50wt% thiodiglycol is used. Namely, a polyisocyanate (e.g., tolylene diisocyanate) is reacted with a polyalcohol (other than a thiodiglycol), e.g., ethylene glycol, and reacted with a thiodiglycol (total OH/NCO molar ratio <1). The obtained isocyanate-terminated oligomer is reacted with a hydroxyl group-containing unsaturated compound (e.g., 2- hydroxyethyl acrylate) (OH/NCO molar ratio >=1) to obtain a urethaen oligomer (of a MW of about 1,000-5,000). Said oligomer forms a cured product excellent in hardness and adhesion to the surface of iron by heating or irradiation with UV in the presence of a radical polymerization initiator.

Description

[Detailed description of the invention] A87. INDUSTRIAL APPLICATION FIELD The present invention relates to a novel urethane oligomer that can be homopolymerized or copolymerized with a suitable reactive monomer in the presence of a radical polymerization initiator, by heat, ultraviolet light, or by electron beam irradiation. It is used in paints, inks, adhesives, yeast immobilization, and dental filling materials, and also takes advantage of its unique property of curing with ultraviolet light.
The present invention relates to radically polymerizable urethane oligomers that are useful for printing plate materials, photoresists, resist inks for printed wiring, and the like.

B. Prior Art Radically polymerizable urethane 11 sesame is often used as an ultraviolet curable bleed polymer.

Therefore, to explain this field, first, an ultraviolet curable resin is a resin that changes from a liquid state to a solid state when exposed to ultraviolet light, and is composed of a sesame-reactive diluent and a photopolymerization initiator. The mainstream of the above oligomers is the ac-11-based 11 sesame, and these ac-11-based oligomers can be roughly divided into three types: the 11-ester ester 11-rate type, the epoxy acrylate type, and the urethane acrylate type. The most suitable oil sesame is selected and used from among these according to various uses.

This urethane acrylate type HA, Special Publication No. 48-4170
8. As pointed out in Special Publication No. 55-8013, etc.
It has good air curability, and the cured product is strong and has excellent adhesion, and the reactivity of the isocyanate makes it possible to produce a moderate amount of urethane oligomer, so it is viewed as a promising product.

C9 Problems to be Solved by the Invention As mentioned above, when producing urethane oligomers, the reactivity of incyanate allows for various molecular designs, and although it has many possibilities, it is difficult to actually The current situation is that no one with sufficiently satisfactory performance has been obtained.

Friendly Means to Solve the D0 Problem In view of the above situation, the inventors of the present invention have made extensive studies and have produced terminal incyanate prevo] 1-mer by the reaction of polyhydric incyanate and polyhydric alcohol. Reacting a prepolymer with a hydroxyl group-containing unsaturated compound)
-1c>, and as a part of the above polyhydric alcohol, thiodig1) Call (1) HOCHOH/C0-CH,CH-OH......(
The present invention has been accomplished by discovering that a urethane oligomer containing 1) in an amount of 5% to 50% by weight based on the total polyhydric alcohol produces a cured product with excellent hardness and adhesion to iron surfaces. reached.

80 Effects The polyvalent incyanates in the present invention include tolylene diisocyanate, hydrogenated tolidine diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, xylene diisocyanate, bis(incyanate methyl)cyclohexane, naphthalene diisocyanate, tolidine diisocyanate, and phenylene. Diisocyanate, hexamethylene diisocyanate, 11 methylhexamethylene diisocyanate, 1
1 Jin diisocyanate, inpropylidene bis(cyclohexyl isocyanate), inphorone diinocyanate, etc., or adducts thereof with water, trimethylolpropane, etc.

means a compound.

[Polyhydric alcohol is ethylene di-11 alcohol, 1゜6
-Hexanediol, diethylene 11col, Bot 1
polyhydric alcohols having three or more terminal alcoholic hydroxyl groups such as trimethylolpropane and pentaerythritol; It means terminal hydroxyl group-containing 11 esters, castor oil, hydroxyl group-containing butadiene, etc. obtained by reacting glycols with dicarboxylic compounds such as phthalate and terephthalate.

Furthermore, hydroxyl group-containing unsaturated compounds include, for example, hydroxyl group-containing (meth)acrylates such as 2-hydroxydiethyl acrylate and 2-hydroxyethyl methacrylate, lower unsaturated compounds such as ac-11 alcohol, and 4-hydroxybutene. Means alcohol, etc.

Next, an example of the manufacturing method of the present invention will be shown.

First, polyhydric alcohol and polyhydric incyanate are reacted, and after the reaction, thioglycol (HOCs H45C-
H40H) at a ratio of total hydroxyl groups per incyanate group (OH/NC0) <1 C mol 1 mol],
The terminal isocyanate II sesmer is completely prepared. The amount of thioglycol separated here is 5 times i based on the total alcohol.
t% or more and 50% by weight or less. If thioglycol is added less than 5% by weight, the physical properties obtained by adding thioglycol will not be exhibited, and if more than 50% by weight is added, an insoluble and infusible solid will be obtained, which will be disadvantageous in terms of production or handling. Next, the above terminal incyanate No. 11 sesame is added to the hydroxyl group-containing unsaturated compound and the ratio of hydroxyl group per incyanate group (OH/NC0)≧
1 part to obtain a urethane oligomer.

The molecular weight of the urethane No. 11 sesame of the present invention is not particularly limited, but is preferably 1000 or more and 5000 or less. This is because those with an average molecular weight of less than 1,000 are difficult to make due to limitations in the molecular structure, and the reason why the average molecular weight is less than 500 is because if it is higher than that, it will be difficult to dissolve in tsummer etc. due to reactivity, or it will dissolve. This is because even if it is used, it has problems such as high viscosity, which is undesirable for work.

The above reaction temperature is preferably 50°C or lower. Furthermore, dibutyltin dilaurate, lead naphthenate, etc. may be added as a catalyst. As a polymerization inhibitor, for example, a trace amount of s-hydroquinone, p-benzoquinone, p-cresol, etc. may be added. The reaction can be carried out in the absence of a solvent or in a solvent with strong WI binding properties, such as tetrahydrofuran, dimethylformamide, etc.

Fo, Example The present invention will be explained below with reference to Examples.

[Example-1] Tolylene diisocyanate 174f (1 mol), diethylene glycol 42, 4fC0.4 mol], dibutyltin dilaurate 0.2f, tetrahydro 7ran in an IL 4 flask equipped with a thermometer, cooling tube, and stirring device. 3
After adding 0.005 g of Th and reacting at 50°C for 4 hours, Thiodig 11 call (Toyo Kasei Kogyo ■) 42.7 fC0.35 mol) was added, 96 wt.
React at 0℃ for 4 hours. After the reaction, 2-hydroxyne monoether 0-02fk was added to this solution and reacted at 40°C for 6 hours.
'T, north. Tetrahydrofuran was distilled off using an evaporator (after that, the mixture was further dried under reduced pressure at 40°C overnight to completely remove the solvent, and a solid pale yellow substance (named Compound 1) was obtained.

The characteristic peaks of the IR spectrum of this compound (1) are shown.

3330σ-' N-H 15303-' C-N 650cm-" CS (The peak around 2270 as-" due to the isocyanate group has completely disappeared'fc) Also, Kölpermeation Chromadog 57CGPC) This The average molecular weight (value using a polystyrene calibration curve) is 1200.

[Comparative Example-1] Thioglycol 42.7r (0,35
.

mole) t-diethylene 11col 37.1f (0,3
A thioglycol-free diurethane oligomer was obtained in exactly the same manner except that the concentration was changed to 5 mol). (Comparative compound, named ■) A compound produced in the same manner as Example 1 and its average molecular weight calculated from CGPC] is shown. (The names of the working compounds and comparative compounds have the same meanings as above. Comparative compounds are indicated by the numbers of the corresponding working compounds and are compared.) The IR spectra of working compounds 2 to 18 in Table 1 are the same as that of working compound 1. It showed similar peaks.

TDI-)IJ Range Inocyanate IP
DI...Inphoron diisocyanate MD
I-・diphenylmethane diincyanate DEC-・diethylene 11 call (average molecule i-1' 000) HEA...2-hydroxyethyl 1
Ruto HEMA...2-Hydroxyethyl methacrylate At-OH...A11 alcohol G0 Effect of the invention Compounds 1, 4, 7, 10, 13, Comparative compounds 1, 4
Regarding ゜7.10.13, an ultraviolet curable resin was manufactured with the formulation shown in Table 2. Apply this resin on a steel plate and
A coating film was obtained by standing still for 10 seconds and exposed directly under a 10 cm high-pressure mercury lamp with an output of 0 W/cm, and the physical property test results of the obtained coating film are shown in Table 3.

Table 2 Parts by weight Urethane Eleventh Sesame - 50 parts II Methylolpropane triacrylate 20 parts Tetrahydrofur 7-lyl acrylate 24 parts 0
-Methyl benzoylbenzoate 6 parts Table 30
From the results, it was found that urethane No. 11 sesame containing Thiodig 11 call as a raw material, urethane no.
) It has been shown that it is much better than sesame in terms of hardness and adhesion to steel surfaces.

Procedural amendment transfer January 16, 1985

Claims (1)

[Scope of Claims] A urethane oligomer obtained by producing a terminal isocyanate prepolymer by reacting a polyhydric isocyanate and a polyhydric alcohol, and reacting the prepolymer with a hydroxyl group-containing unsaturated compound, wherein the polyhydric alcohol Thiodiglycol (I
) HOCH_2CH_2-S-CH_2CH_2OH・・
...(I) 5% by weight based on the total polyhydric alcohol
A urethane oligomer containing 50% by weight or more.