JPS61278521A - Photocurable resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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, photocurable resins based on urethane oligomers that have even better hardness and tensile strength than conventional ones are currently being developed.

Means for solving the D1 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 (meth)acrylate consisting of a reaction product of the component and (c) component (a') an organic diisocyanate (b) a trihydric or higher polyhydric alcohol (c) ) A compound represented by the following general formula (1) (wherein R
The present inventors have discovered that a photocurable resin characterized by containing H or CH3 (n=1 to 10) produces a cured product with excellent hardness and tensile strength, and has accomplished the present invention.

The urethane (meth)acrylate used in the present invention is
For example, it is manufactured as follows.

Trivalent or higher polyhydric alcohol (b) and organic diisocyanate (a) are charged in a ratio of hydroxyl groups per isocyanate group (OH/NC0)≦1 (1 mole),
Produce a terminal isocyanate oligomer. Then the expression (
The ratio of hydroxyl groups per isocyanate group (OH
/NC0>≧1 and react.

The reaction may be carried out without a solvent or in a solvent such as tetrahydrofuran or methyl ethyl ketone. As a reaction catalyst, metal salts such as dibutyltin dilaurate, lead naphthenate, etc.
grade amines, etc.

Further, hydroquinone, p-benzoquinone, p-cresol, etc. may be added as a polymerization inhibitor. The reaction temperature is 80
℃ or less is preferable.

The organic diisocyanate of component (a) is 2.4
-tolylene diisocyanate, 2.6-tolylene diisocyanate, 2.4 and 2.6-tolylene diisocyanate mixture, 4.4'-diphenylmethane diisocyanate, tophenylene diisocyanate, xylylene 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,
4I-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate,
1.5-naphthalene diisocyanate, 1.5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, etc. are used.

Typical examples of the polyhydric alcohol of 31 or more as component (b) include trimethylolpropane, trimethylolethane, pentaerythritol, and the like.

Function In the present invention, the reactive diluent only needs to have a polymerizable ethylenically unsaturated group, and typical examples include trimethylolpropane tri(meth)acrylate, 1,6-hexanegelylcol, etc. Di(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, styrene.

Examples include methyl (meth)acrylate and mixtures thereof.

In the present invention, the photopolymerization initiator is arbitrarily selected from known initiators that generate radicals upon irradiation with light, such as benzophenone, acetophenone, benzyl, O-benzoyl-benzoic acid, and methyl O-benzoyl-benzoate. It is possible to use it as

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 The contents of the present invention will be explained in more detail by Examples and Comparative Examples. Note that the present invention is not limited to the examples.

[Example 1] Tolylene diisocyanate (TOI) 174 was placed in a 1λ four-bottle flask equipped with a thermometer, cooling tube, and stirrer.
g (1,0 mol) and trimethylolpropane 67 g (0
, 5 mol) and tetrahydrofuran (T)-IF
') Added 500d.

Next, 0.2 g of dibutyltin dilaurate was added, heated, and reacted for 3 hours while keeping the temperature around 50°C.

To this solution were further added 230 g (1.0 mol) of Plaxel FA-1* (manufactured by Daicel Chemical Industries, Ltd.) and 0.02 SF of hydroquinone monomethyl ether (MEHQ), and the mixture was reacted at 50°C for 10 hours. When THF was distilled off from this solution by drying under reduced pressure, a viscous substance was obtained.

*Note) Plaxel FA-1 cl-&-at-1coochcH2occH2c)-
12c) -12chc warehouse OH [Example 2] Everything was carried out in the same manner as in Example 1, except that tolylene diisocyanate was changed to isophorone diisocyanate, and Plaxel FA-1 was changed to Plaxel FA-5* (manufactured by Daicel Chemical Industries, Ltd.). , a transparent viscous substance was obtained.

*Note) Plaxel FA-5 CH2=CHC00CH2CHzO(6C1+CHzC
H2C)tzcHzo) 5H [Comparative Example 1] Tolylene diisocyanate 174ff (1 mol) and polyethylene glycol #400 2009 (0
, 5 mol) was added. Then dibutyltin dilaurate
0.2 g was added and heated, and the temperature was kept around 50° C., and the reaction was carried out for 3 hours.

Furthermore, 2-hydroxyethyl acrylate 1 is added to the reaction solution.
0.029 g (1.0 mol) of droquinone monomethyl ether (MEHQ) 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 tolylene diisocyanate in Comparative Example 1 was changed to isophorone diisocyanate.

Using the (meth)acrylate compounds obtained in Example 1.2 and Comparative Example 1.2, photocurable resins were obtained with the formulations shown in Table 1.

The resin obtained with the formulation shown in Table 1 was applied onto a steel plate, and
A coating film was obtained by exposing to light directly under a high-pressure mercury lamp 10α with an output of W/cm for 10 seconds. Table 2 shows the physical property test results of the obtained coating film.

Procedure Masaru Nyama (self-proposal) August 23, 1985 Patent Application No. 121669 2, Name of the invention Photocurable resin composition 3, Name of the person making the amendment (234> Sanyo National Policy Pulp Co., Ltd.〒1
01 Ei Building 3rd floor Telephone (252) 6619 (Main) , -? ),.

Name (6348) Patent attorney Kiyoshi Meiura
,′″.

L: 1
, 2 moles)" was corrected.

2. On the second line of the same page r67g (0.5 mol)" r54g (0.4 mol)" was corrected.

3. On the 7th line of the same page It says "r230g (1.0 mol)" r276g (1.2 moles)" was corrected.

Claims (1)

[Scope of Claims] In a photocurable resin composition containing a base resin, a reactive diluent, and a photopolymerization initiator as main components, part or all of the base resin includes the following components (a), (b), as well as(
A photocurable resin composition containing urethane (meth)acrylate which is a reaction product of component c). (a) Organic diisocyanate (b) Trivalent or higher polyhydric alcohol (c) Compound represented by the following general formula (I) ▲ Formula,
There are chemical formulas, tables, etc.▼...(I) (In the formula, R_1 is H or CH_3, n = 1 to 10)