JPS62115012A - Photocurable resin composition - Google Patents

Abstract

PURPOSE:To improve the hardness, adhesion, flexibility, etc., of a cured product, by using a specified urethane oligomer as a base resin used in a photocurable resin composition containing a base resin, a reactive diluent, a photopolymerization initiator, etc. CONSTITUTION:A polyisocyanate (A) (e.g., 2,4-tolylene diisocyanate) is reacted with a spiroglycol (B) of formula I and a polycaprolactone (meth)acrylate (C) of formula II (wherein R1 is H or CH3 and n is 1-10) to produce a urethane oligomer. The obtained urethane oligomer is used as part or the whole of the base resin, and mixed with a reactive diluent (e.g., trifluoromethylolpropane triacrylate) and a photopolymerization initiator (e.g., benzophenone) or the like to obtain the purpose photocurable resin composition. This composition can be suitably used for paints, photoresists, etc.

Description

[Detailed description of the invention] A. Industrial application field The composition of the present invention can be used as a paint, ink, or adhesive.

The present invention relates to a photocurable resin composition that is used for yeast immobilization, dental filling materials, etc., and is also useful for printing plate materials, photoresists, resist inks for printed wiring, etc. due to its property of curing with light.

B. Prior art A photocurable resin is a resin that changes from liquid to solid upon irradiation with light, and is usually composed of a reactive oligomer, a reactive diluent, and a photopolymerization initiator. The mainstream of these reactive oligomers is acrylic oligomers.

Acrylic oligomers include polyester acrylate types, epoxy acrylate types, urethane acrylate types, etc., and oligomers that suit the function and purpose are used as appropriate.

Among them, the urethane acrylate type is
08. As pointed out in Japanese Patent Publication No. 55-8013, it has better air curability than other oligomers, forms a tough coating film, and has excellent adhesion to iron and glass. It is viewed as promising in the future because it is expected that urethane oligomers with various different structures depending on their properties can be developed.

C1 Problems to be Solved by the Invention As mentioned above, when producing urethane oligomers,
Since isocyanate is highly reactive, it is possible to design various molecules, and although it has many possibilities, there are only a few types of urethane oligomers that are actually commercially available.

Among these, there is currently a demand for a photocurable resin whose main component is a urethane oligomer that has even better hardness, flexibility, and adhesion than conventional ones.

Means for solving the D0 problem In a photocurable resin composition containing a base resin, a reactive diluent, and a photopolymerization initiator as main components, the following components (a) and (b) are used as part or all of the base resin. A photocurable resin composition characterized by containing a urethane oligomer consisting of a reaction product of component ) and component (c) (a) polyvalent isocyanate-1, (b) spiroglycol (c) the following general A compound represented by the formula (I> in which R
1 is H or CH3. = 1 to 10) produces a cured product with excellent hardness, adhesion to iron surfaces, and flexibility, leading to the present invention.

The urethane oligomer of the present invention is produced, for example, as follows.

A polyvalent isocyanate and a spiroglycol are charged in a ratio of hydroxyl groups per isocyanate group (OH/NGO>≦1 (1 mole) to produce a terminal isocyanate oligomer. Then, a polyvalent isocyanate oligomer represented by general formula (1) is prepared. Caprolactone (meth)acrylate is added and reacted at a ratio of hydroxyl groups per isocyanate group (OH/NGO>≧1).The reaction is preferably carried out in a solvent such as tetrahydrofuran or methyl ethyl ketone.As a reaction catalyst, dibutyltin dilaurate, Metal salts such as lead naphthenate, tertiary amines, etc. are used. Hydroquinone, p-benzoquinone, p-cresol, etc. may also be added as a polymerization inhibitor. The reaction temperature is preferably 80'C or lower.

Examples of the polyvalent isocyanate include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. 2
, 4 and 2.6-Drylene diisocyanate mixture, 4
, 4'-diphenylmethane diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester,
1.4-cyclohexylene diisocyanate, 4,4'
-dicyclohexylmethane diisocyanate, 3.3
'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,
4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, etc. are used.

E1 action In the present invention, the reactive diluent only needs to have a polymerizable ethylenically unsaturated group, and representative examples thereof include trimethylolpropane tri(meth)acrylate, 1,6-hexane gelicoldi (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, styrene.

Examples include methyl (meth)acrylate and mixtures thereof.

In the present invention, the photopolymerization initiator may be arbitrarily selected from known initiators that generate radicals upon irradiation with light, such as hensifhenone, acetophenone, pencil, o-hensiphenone, o-benzoylbenzoate, and methyl o-benzoylbenzoate. It is possible to use the

Although the blending ratio of the composition of the present invention can vary widely depending on the application, a blending ratio of urethane oligomer compound:reactive diluent=10:1 to 10:10 is usually suitable. In addition, the photopolymerization initiator is a resin 1 consisting of an oligomer and a diluent.
0.01 to 10 parts, preferably 0.5 to 10 parts
It is appropriate to mix 4 parts.

The thus obtained photocurable resin of the present invention can be irradiated with light using a xenon lamp, a germicidal lamp, a low pressure to ultra-high pressure mercury lamp, etc. to obtain a cured product.

F. Examples and effects of the invention Examples are shown below.

(Example 1) 2,4-Tolylene diisocyanate (TDI) was added to the fourth flask of 1 and e equipped with a thermometer, cooling tube, and stirrer.
(manufactured by Tokyo Kasei ■) 174g (1.0 mol) and spiroglycol [Mitsubishi Gas Chemical ■IQ) 1529 (0,
5 mol) and tetrahydrofuran (THF>500m) were added. Next, 0.29 mol of dibutyltin dilaurate was added and heated.

Heat is generated at the same time as the reaction starts, but the maximum temperature during the reaction is 72
It was ℃. After the temperature rise due to heat generation is over, the temperature reaches 60℃.
Stirring was continued for about 2 hours. To the obtained reaction product were added 0.029 g of hydroquinone monomethyl ether (MEHQ) and 230 g (1.0 mol) of a compound of the following formula (trade name: Plaxel FA-1) (manufactured by Daicel Chemical Industries, Ltd.).

In this case as well, the maximum temperature during the reaction was 70°C.

After the exotherm had ended, stirring was continued at 60'C for about 1 hour. The obtained reaction product was dried under reduced pressure (5 mH9) at 40° C. for 3 hours after THF was distilled off using an evaporator to obtain a solid pale yellow substance.

[Example 2] The above tolylene diisocyanate was replaced with isophorone diisocyanate, and Plaxel FA-1 was replaced with a compound of the following formula (trade name: Plaxel FA-5> (Daicel Chemical Industry 1).
A transparent viscous substance was obtained in the same manner except that the material was changed to (manufactured by No. 1).

[Comparative Example 1] Tolylene diisocyanate 174y (1 mol) was placed in a four-bottle flask equipped with a thermometer, a cooling tube, and a stirring device.
and polyethylene glycol #400 2009 (0,
5 mol) was added. Next, dibutyltin dilaurate 0.
2 g was added and heated, the temperature was kept around 50'C and the reaction was carried out for 3 hours.

Furthermore, 2-hydroxyethyl acrylate 11 was added to the reaction solution.
69 (1,0 mol) hydroquinone monomethyl ether (
MEHQ) 0.029 was added and reacted at 50°C for 10 hours.

[Comparative Example 2] A urethane oligomer was obtained in the same manner as in Comparative Example 1 except that the tolylene diisocyanate was replaced with isophorone diincyanate.

Using the urethane oligomers obtained in Example 1.2 and Comparative Examples 1 and 2, photocurable resins were obtained with the formulations shown in Table 1.

Table-1 The resin prepared according to the formulation shown in Table-1 was applied onto a steel plate, and 12
A high-pressure mercury lamp with an output of 0 W/cm was placed directly under the lamp 10 cm and exposed for 10 seconds to form a coating film of 1 q. Table 2 shows the physical property test results of the coated film.

Table-2 (*1) Evaluation (■ is based on the residual rate of the coating film.

(*2)○...No cracks.

Claims (1)

[Claims] (1) In a photocurable resin composition containing a base resin, a reactive diluent, and a photopolymerization initiator as main components, the following components (a), (b), and ( A photocurable resin composition comprising a urethane oligomer made of a reaction product of component c). (a) Polyvalent isocyanate (b) Spiroglycol ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) Compounds represented by the following general formula (I) ▲ Mathematical formula,
There are chemical formulas, tables, etc. ▼ (In the formula, R_1 is H or CH_3, n = 1 to 10)