JPS60208313A - Photo-setting material - Google Patents

Abstract

PURPOSE:The titled material, obtained by incorporating a photo-setting material containing tricyclodecanedimethylol diester as a photo-setting component with a specific organic phosphoric acid ester, and having improved setting characteristics, etc. and remarkably improved adhesion to coating materials, etc. CONSTITUTION:A photo-setting material obtained by incorporating (A) a photo- setting material containing a diester of tricyclodecane dimethylol, e.g. 3,8-bis (hydroxymethyl)tricyclo[5.2.1.0<2>,<6>]decane, with an alpha,beta-unsaturated carboxylic acid, preferably acrylic acid with (B) an organic phosphoric acid ester of the formula (R1 is H or methyl; R2 is alkylene; m is an integer >=1; n is 1 or 2), e.g. 1,2-acryloyloxyethyl acid phosphate. The amounts of the components (A) and (B) are preferably >=15wt% and 0.5-6wt% respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has a short curing time and is superior to coating materials.
The invention relates to a photocurable material that exhibits excellent adhesion.

Instead of the conventional heat curing method that consumes a large amount of energy or the room temperature curing method that requires a long drying time (1'+), this method cures the coating film in a short time by irradiating it with ultraviolet rays or electron beams. has been attracting attention in recent years.Since this photocurable material is usually used without a solvent, it does not contaminate the working environment and is excellent in terms of safety.

However, photocurable materials generally have a high crosslinking density and therefore have poor flexibility, and often have problems with their adhesion to coating materials. For example, the recently developed tricyclodecane-based photocurable material is known to have low viscosity and good curing properties, as well as excellent chemical resistance and abrasion resistance. -2357, 57-1
No. 64163), the adhesion with the covering material is not sufficient, so it can be used on polycarbonate, PVC resin, etc.
It was limited to S resin, aluminum foil, Zolaimer-treated metal, etc.

Therefore, the present inventors conducted intensive studies to improve this drawback of the conventional technology, and found that it was possible to blend a specific organic phosphate ester into a tricyclodecane-based photocurable material without impairing its original properties. It was discovered that the adhesion was significantly improved, and the present invention was completed.

According to the present invention, a photocurable material containing tricyclodecane dimethylols and a diester of α,β-unsaturated carginic acid as a photocurable component is added to a photocurable material containing a general formula (wherein R4 is Provided is a photocurable material comprising an organic phosphoric acid ester represented by hydrogen or a methyl group, R2 is an alkylene group, m is an integer of 1 or more, and n is ] or 2. .

The above tricyclodecane dimethylols are obtained by oxo reaction of dicyclointadiene or its lower alkyl substituted product, and are specifically 3,8-bis(
hydroxymethyl)tricyclo[512,1,02I6
] decane, 4,9-bis(hydroxymethyl)tricyclo[5,211,02.6]decane, and the like.

On the other hand, specific examples of the above α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, and crotonic acid, but acrylic acid is the most prized in terms of curing speed.

The tricyclodecane dimethylol diester used in the present invention can be synthesized according to conventional methods. For example, α, β-
Use ~3 times the molar amount of unsaturated carbon, sulfuric acid, p-
80~ in the presence of an acid catalyst such as toluenesulfonic acid etc.
At a reaction temperature of 120°C, hydroquinone, if necessary,
It can be easily obtained by reacting with the addition of a polymerization inhibitor such as hydroquinone monomethyl ether.

Such tricyclodecane dimethylol diester may be used alone, but it can also be used in combination with other commonly used photocurable resins. Specific examples of photocurable resins that can be used in combination (for example, acrylate-modified resins based on epoxy resins, urethane, polyesters, silicone resins, I-liptadiene, alkyd resins, phenolic resins, Ishibari resins, etc.) Examples include tricyclodecane dimethylol diester and methacrylate modified products.Although the proportion of the combination can be selected as appropriate, the amount of tricyclodecane dimethylol diester is usually 10% by weight or more, preferably 15% by weight based on the entire curable component.
It is appropriate to set it above υ.

Since the tricyclodecane dimethylol diester used in the present invention has an extremely low viscosity, it does not necessarily require other photocurable diluents, but when it is made to have a high viscosity by using other photocurable resins If necessary, commonly used photocurable diluents can be added, such as methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate,
Tricyclodecane monomethylol acrylate, 1.4
-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane) to IJr) acrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, these compounds Examples include methacrylates and N-vinylpyrrolidone corresponding to . However, even in this case, the amount of tricyclodecane dimethylol diester can be adjusted to 0% by weight or more, preferably 15% by weight of all curable components.
It is appropriate to set it to 100% or more.

In the present invention, an organic phosphoric acid ester represented by the above general formula is used as another essential component. In the formula, R2
is a lower alkylene group, specific examples of which include ethylene group, alkyl-substituted ethylene group, and butylene group. Moreover, m is an integer of 1 or more, preferably 1-3.

Specific examples of such compounds include acrylic acid or methacrylic acid and ethylene glycol, zolopylene glycol, ], 4-butanediol, diethyter, and diester. In the present invention (6) it is an essential requirement that n is 1' or 2,
Even if phosphoric acid triester is used, the effects of the present invention cannot be achieved.

Blend 1 of such organic phosphate esters can be appropriately selected depending on the purpose of use, but usually 01 to 1 of the total photocurable components.
0% by weight, preferably 0.5-6% by weight.

If this amount is too small, the effect of the present invention will be small, and if it is more than necessary, I# will occur in economical efficiency.

In the present invention, a commonly used photopolymerization initiator is blended to promote photocuring by ultraviolet rays or the like. Specific examples of such photopolymerization initiators and 1, [i; , diacetyl,
Examples include carbonyl compounds such as acetophenone, jetoxyacetophenone, and anthraquinone, sulfide compounds such as diphenyl disulfide, and halodane compounds such as pentachlorobutadiene, and are usually 0.1 to 100 parts by weight per 100 parts by weight of the photocurable component. It is used in a ratio of 10 parts by weight.

Further, if necessary, a photosensitizer can be added. Specific examples thereof include n-butylamine, sea-n-butylamine, etc. Examples include triethylamine, 2-zomethylanoethanol, N-methyljetanolamine, triethanolamine, etc. Other additives such as pigments, fillers, plasticizers, lubricants, etc. may be added as necessary. It's okay.

The photocurable material according to the present invention has improved adhesion without sacrificing the original features of tricyclodecane dimethylol-based materials, and can be used more widely than conventional products. For example, it is suitable as a coating material for various metals and glass, and is particularly useful as a rust-preventing coating material for steel materials. It can also be used to cover other general resin molded products.

As a light source for photocuring, a violet 1A ray generating device such as a high pressure mercury lamp or a metal halide lamp is usually used.
However, generators such as electron beams, X-rays, and r-bonds can also be used.

Next, the present invention will be explained in more detail with reference to Examples. Note that parts in the examples represent parts by weight.

Example 1 45 parts of tricyclodecane dimethylol diacrylate,
Trifunctional oligoester acrylate) 50 parts (manufactured by Toagosei Chemical Co., Ltd., Aroex M-6200°2000-3
000 cplI/25°C), 5 parts of the compounding agents listed in Table 1, 3 parts of methyl benzoyl formate (Stuffer J.F.
, ・Mix well 55) to prepare a photocurable material, and knead it to test various coating materials.
It was applied with a 2 kW high-pressure mercury wrap H20fl OL/6 (manufactured by Next Summer Denzai ■) with a strength of 8 ow/m at a conveyor speed of 6 m/min at a conveyor speed of 6 m/min for irradiation and curing. .

Table 1 shows the test results. The curing speed was expressed as the number of passes through a mercury lamp required for dryness to the touch, and the adhesion was expressed in the following four grades based on a base tape peel test. ◎
: No peeling, ○: Peeling within 15%, (9) △: Peeling 15-65%, ×: Peeling #65% - Methacroyloxyethyl acid phosphate, large chemical classification*3 disfucaru-2-afryloylmexyethyl) Ll lephate
, 7 (Chemistry 71% 1 * 4 Diphenyl-2-acryloyl material is phosphate, Ohe Kagaku Co., Ltd. prison 5
γ-methacryloxyglopyltrimethoxysilane, Shin-Etsu Silicone As a result, it can be seen that the monthly coating of the present invention has extremely excellent adhesion.

Example 2 Tricyclodecane dimethylol noacrylate and 2-acryloyloxyethyl acid phosphate (AR-
200, manufactured by Ohe Kagaku Kogyo Co., Ltd.) in a predetermined ratio of 100
Part 55 (Stow 7 Aja fn ■) 3
Different photocurable materials were prepared and tested under the same curing conditions as in Example 1.

The results are shown in Table 2.

Table 2 (1])

Claims (1)

[Scope of Claims] l. A photocurable material containing tricyclodecane dimethylols and a diester of α,β-unsaturated carginic acid as a photocurable component has a general formula (wherein R4 is hydrogen). or a methyl group, R2 is an alkylene group, m is an integer of 1 or more, and n is 1 or 2).