JPS60199026A - Photosetting epoxy resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved curing properties at the deep of a cured film, preventing phenomena of surface waviness, obtained by blending a resin composition comprising an epoxy resin and a catalyst for photo-setting with a specific ratio of an inorganic filler. CONSTITUTION:(A) 100pts.wt. epoxy resin (e.g., bisphenol A, etc.) is blended with (B) a catalyst for photo-setting (e.g., Lewis acid aryl diazonium salt, etc.), and (C) >=30pts.wt., preferably >=50pts.wt. inorganic filler (e.g., silica powder, titanium dioxide powder, etc.), to give the desired composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photocurable epoxy resin composition that starts curing when exposed to light energy, and more particularly relates to a photocurable epoxy resin composition that starts curing when exposed to light energy. The present invention relates to a photocurable epoxy resin composition that exhibits excellent deep-curing properties without any single undulations on the surface of the cured layer by incorporating an inorganic filler into the product.

[Technical background of the invention and its problems]

Epoxy resin has excellent adhesive properties, electrical properties9 mechanical properties,
Because it has chemical and water resistance, it is widely used in various applications that require high performance. Curing of such epoxy resins generally involves adding and mixing an active amine-containing compound or a carboxylic acid anhydride to the epoxy resin.
A liquid type and a one-component type in which a latent curing agent such as an amine complex of a Lewis acid is added have been practically applied.
: In the two-component type, not only is the formulation complicated, but the curing time often takes several hours.

In addition, in the L-liquid type, since the latent curing agent works usefully as a curing agent (-, it often requires high temperatures of 100°C or more, Special C: coating devices that are sensitive to heat such as sophisticated electronic components). It cannot be used to

On the other hand, demands for resource saving, energy saving, and low pollution are increasing, and in response to these trends, we have developed an ultraviolet-curing epoxy resin that does not require heating and has an extremely short curing time. compositions are showing promise. Such an ultraviolet curable epoxy resin composition may contain a photocuring catalyst that liberates a Lewis acid when the epoxy resin is irradiated with ultraviolet St, such as an onium salt or an aryl diazonium salt of Group F/a Lewis acid. Examples of solid materials include those in which epoxy resin I: an organoaluminum compound and a silicon compound that produces silanol groups upon irradiation with ultraviolet rays are blended.

These epoxy resin compositions containing photocurable catalysts have the characteristic that they easily exhibit catalytic activity when exposed to ultraviolet irradiation energy and are cured in a short time.

However, if the cured layer of epoxy resin has a thickness of 1 cm or more, for example, when using an epoxy resin such as a bisphenol A epoxy resin, the resin itself absorbs ultraviolet rays useful for curing. It is impossible to harden to a deeper level, and after-curing by heating is often essential.

Further C: Light irradiation 1: The surface hardens in a short time, but the amount of UV rays effective for curing is insufficient or does not reach the inside at all, making curing extremely slow and causing a difference in the curing speed with the surface layer. Due to the curing shrinkage stress of the resin, so-called 1 is formed on the surface of the cured resin.
There was a drawback that it could not be put to practical use because it caused a waving phenomenon.

[Purpose of the invention]

The present invention has been made to overcome the above-mentioned drawbacks, and has the following features: No undulations 1 can be seen on the surface due to photocuring, and
The object of the present invention is to provide a photocurable epoxy resin composition that can be cured to a deep portion.

[Summary of the invention]

The present invention provides an epoxy resin composition containing an effective amount of a photo-curing catalyst capable of causing curing of the epoxy resin by light irradiation, with the addition of 30% by weight or more based on 100 parts by weight of the epoxy resin as a third component. It has been discovered that by incorporating an inorganic room photoresist, no undulating phenomenon on the resin surface is observed during photocuring, and it exhibits excellent deep curing properties.

In other words, all the epoxy resins that are normally used for photocuring can be used as the two-phase epoxy resins of the present invention.

Examples: Eva, bisphenol A type epoxy resin; bisphenol F type epoxy resin; phenol novolak type epoxy resin; alicyclic epoxy resin; gold wave monocyclic epoxy resin such as triglycidyl isocyanate and hydantoin epoxy; hydrogenated bisphenol A type epoxy resin'; , aliphatic epoxy resins such as propylene glycol digucidyl ether and pentaerythritol polyglycidyl ether; epoxy resins obtained by the reaction of aromatic, aliphatic or alicyclic carboxylic acids with epichlorohydrin; spiro ring-containing epoxy resins 〇-Glycidyl ether tbWl, which is a reaction product of an allylphenol novolak compound and epichlorohydrin! Epoxy resin;
Examples include glycidyl ether type epoxy resins, which are reaction products of epichlorohydrin and diallylbisphenol compounds having an allyl group at the ortho position of each hydroxyl group of bisphenol.

As a photocuring catalyst, U.S. Patent No. 3,708,296
Examples include aryldiazonium salts of Lewis acids, PF, -, etc., disclosed in No. et al.

Other photocuring catalysts include Japanese Patent Publication No. 52-1427
Aromatic halonium salt of Lewis acid disclosed in 7 others,
Onium salts also contain alkoxy groups, phenoxy groups, acyloxy groups, and β-diketonato groups on the aluminum atom.

A peroxysilane group is added to an organoaluminium complex compound to which an 0-carbonylphenolad group or the like is bonded.

Examples include binary catalysts made of silicon compounds that produce silanol groups upon irradiation with light that contain either an O-nitrobenzyloxy group or an α-ketosilyl group. It's okay.

The inorganic resin material as the third component, which is an essential component according to the present invention, is generally used in epoxy resin compositions for heat curing or room temperature curing. All can be used except those with strong basicity that reduce activity. For example, silica powder, titanium dioxide powder.

Alumina powder, clay, calcium carbonate, glass peas,
Examples include glass fiber.

The photocurable epoxy resin composition of the present invention includes fC as described above.
In addition to 3C10, if necessary, photosensitizers, viscosity modifiers, pigments, surfactants, silane coupling agents, etc.
It can be added freely within a range that does not impair photocurability.

The photocurable epoxy resin composition of the present invention is usually 180-
600 nm, preferably 300-400 nm, the light irradiation time varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 1 to 180 minutes, preferably <Fi1
~60 minutes. If necessary, use a combination of photo-curing with heating and after-curing with heating after photo-curing for 4fiL.

As the light source for photocuring, any light source commonly used as a light source for photocuring can be used, such as a high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, an argon glow discharge chamber metal halide lamp, or the like.

〔Effect of the invention〕

These inorganic chamber optical fiber tubes are 30 parts by weight or more, preferably 50 parts by weight or more, based on 100 parts by weight of an epoxy resin composition containing an effective amount of a photocuring catalyst capable of causing curing of the epoxy resin by light irradiation. By doing so, in addition to the effect of reducing the relative content of the epoxy resin itself in the photocurable epoxy resin composition that absorbs ultraviolet rays, the ultraviolet rays are repeatedly reflected diffusely on the inorganic surface and reach deep into the composition. A photocurable epoxy fat collection composition that has deep curability and can be cured to a much thicker wall than when no inorganic adhesive is added. When the composition is photocured, the amount of ultraviolet rays that reach the interior is extremely small, and so-called 1-wave undulations are observed on the surface due to the difference in curing speed between the resin surface and the interior. In this case, the feature is that no single wave phenomenon is observed at all.

[Embodiments of the invention]

Next, examples according to the present invention and comparative examples not according to the present invention will be described. In these Examples and Comparative Examples, all parts indicate parts by weight. Examples 1 to 3 The epoxy resins were Celoxide 2021 (alicyclic epoxy resin manufactured by Daicel, epoxy equivalent: 145),
, Ebiko) 828 (Bisphenol A manufactured by Shell
type epoxy resin, epoxy equivalent weight 190), Epicoat 1001 (Bisphenol A type epoxy resin manufactured by Shell Co., epoxy equivalent weight 450') were used, and the photocuring catalyst used was diphenyldiazonium tetrafluoroboron, triphenylsulfonium hexafluoroantimony. , and using trisethyl acetoacetatoaluminum and triphenyl(0-nitrobenzyloxy)silane, and using 810 dew powder as a filler,
A photocurable epoxy resin composition tv4 according to the present invention having the composition ratio shown in Table 1 was prepared. Pour these compositions into a mold with a thickness of 10 cm [7], then add 80 w/w air-cooled water lamp 3
A book was introduced into a photocuring box placed at a height of 15a++ from the conveyor surface, photocured for a predetermined period of time, and the thickness of the cured resin was measured. The results are shown in Table 1.

Comparative Examples 1 to 3 Inorganic room fiberglass materials used in Examples 10. Except that no powder was used, all the resins had the same composition and were photocured in the same manner as in the examples, and the thickness of the cured resin was measured.

Claims (1)

[Claims] An epoxy resin composition containing an effective amount of a photocuring catalyst that can cause curing of the epoxy resin by light irradiation is added with an inorganic filler in an amount of - (by weight) or more per 100 parts by weight of the epoxy resin as a third component. A photocurable epoxy resin composition characterized in that: 1.