JPS58117207A - Ultraviolet ray-curable resin composition - Google Patents

Abstract

PURPOSE:The titled composition capable of forming a thin film layer when irradiated with ultraviolet rays and suitable for small film condensers, containing a specified (meth)acrylate resin. CONSTITUTION:An ultraviolet ray-curable resin composition containing above 50wt% at least one of a dihydrodicyclopentadiene containing (meth)acrylate ester of the formula (wherein R is H or CH3, n is 0 or 1 and R' is a 2-6C alkylene group or a 4-6C alkylenehetero (Oor S)-alkylene group) and an unsaturated resin MW 500-5,000, having butadiene bonds or isoprene bonds in the molecule and further having at least one (meth)acrylate group on the molecular terminal. This composition can form thin film layers excellent in dielectric property and is suited best for, especially, small film condensers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ultraviolet curable resin composition, particularly an ultraviolet #M curable resin composition suitable for use in small film capacitors.

A plastic film capacitor is made of two thin film electrodes insulated from each other by an insulating plastic film.

The volume per unit capacitance wrinkle is calculated by the following formula (1)%
(Formula %) (1) As the thin film electrode, foil or air-vaporized* film of AI or Sn is used, and these are well known as wound-type foil-electrode capacitors and wound-type vapor-deposited electrode capacitors, respectively. . The thickness of the 11E electrode is approximately 5 to 10 μm in the case of a foil electrode, while it is extremely thin at 0.1 μm in the case of a vapor-deposited electrode, and as is clear from the above equation (1), the thickness of the electrode is approximately 5 to 10 μm in the case of a foil electrode. Electrode capacitors are smaller for the same capacity. As electronic devices have become smaller and more dense in recent years, there has been a growing demand for smaller film capacitors. In order to meet these demands, there has been a strong push to make plastic films thinner, and now films with a thickness of 2 to 3 μm, the ultimate value that can be handled as a single film, are being produced. ing. However, in any case, in the method using a film, there is a limit to the thickness of the film that can be handled alone, and therefore there is also a limit to miniaturization.

Therefore, we have developed a new small film capacitor (thin film capacitor jTF capacitor) that breaks through these limitations.
A manufacturing method was developed. This method first vapor-deposits gold maple on both sides of a plastic film (base film), then coats polymer Mm on one side of this double-sided metal vapor layer film, evaporates it by heating and drying the bath, and forms a thin polymer film. It forms a layer. Film capacitor (T) capacitor obtained in this way? ) The structure of the 418 capacitor itself is the same as that of the previous ones, or in the case of TF capacitors, a thin polymer film layer is formed by coating, so the film thickness can be made thinner than 2 to 3 μm. This makes it possible to create smaller film capacitors. By the way, plastics for film capacitors include polyester (polyethylene terephthalate), polypropylene, and polystyrene.

Polycarbonate, etc. Table 1 shows the various properties of these films.

(Margins below) Table 1 Polystyrene, polyethylene, and polypropylene have better dielectric properties (lower dielectric loss tangent) than polyethylene terephthalate, but are inferior to polyethylene terephthalate in heat distortion temperature and tensile strength. . Polycarbonate exhibits intermediate properties between polypropylene and polyethylene 7-talate. In the manufacturing process of TF capacitors, it is necessary to heat and dry the cutting process. Therefore, as the base film, it is necessary to use a plastic material having a low heat deformation temperature and high tensile strength when heated, and among the above-mentioned films, polyethylene terephthalate is particularly used. - Polycarbonate is used as the coating polymer (face) from the viewpoints of solubility, heat resistance, and mechanical properties.

From the perspective of improving the performance of TF capacitors, it is better to use polypropylene or polyethylene as the base film, which has better performance than polyethylene terephthalate. It could not be used in the manufacturing method of TF capacitors.

Therefore, the inventors conducted extensive research to see if polypropylene, which has excellent sieving properties, could be used as a base film. Ultraviolet 1111 with a thin film layer (film) cedar formation ability! We believe that the objective can be achieved by using a dielectric resin composition and curing it by ultraviolet irradiation instead of heat treatment to form a thin film layer, and we developed an ultraviolet curable resin composition that can form a thin film layer with excellent dielectric properties. We arrived at this invention after a lot of research and development.

That is, the gist of the present invention is an ultraviolet curable resin composition characterized by containing at least 10,000 of the following components (c) and (c) in an amount of soT7Lts or more.

(Meth)acrylic acid ester having the general formula. ~5000 unsaturated resins.

Next, this invention will be clearly explained.

Generally, an ultraviolet curable resin composition (UV curable resin face) consists of the following components (1) to (4), and the composition is determined depending on the purpose.

■ Unsaturated resin (reactive oligomer) Prepolymers with acrylate or methacrylate groups at the molecular ends such as epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate, unsaturated polyester resins, and the above (
Liquid polybutadiene etc. having meth)acrylate groups.

@゛ High boiling point, =2. Compounds (photonicity% 71-) methyl methacrylate, 2-hydroxyethyl methacrylate, n-butyl (meth)acrylate, glycidyl methacrylate, tetraethylene glycol diacrylate)
, Low molecular weight (meth)acrylates such as 1.6-hexanethiol di(meth)acrine-trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, dicyclopentenyl acrylate, styrene, diallyl phthalate 0 ・■ Hikari 1 Representative initiators include benzophenone, benzoin ether, and benzyl group. Usually, it is blended in a range of 1 to 1 O* (weight, hereinafter referred to as -) relative to the total amount number of the above-mentioned ■■.

■ Other additives fillers, pigments, non-reactive polymers, thermal polymerization inhibitors, leveling agents, antifoaming agents.

The ultraviolet curable resin composition of the present invention has a film-forming ability with particularly good fermentation properties compared to the general ultraviolet curable resin compositions mentioned above.

Component (iii) of the ultraviolet curable resin composition of the present invention is a (meth)acrylic ester having dihydrodicyclopentadiene represented by the above general formula.

This material has a viscosity of a few tens of centimeters at room temperature, and has excellent photoreceptivity. Moreover, the adhesion of the resulting film to gold after curing is desirable, and its dielectric properties are also excellent. For example, in the general formula R=H, n=Q
The dielectric loss tangent at I KHz of a film prepared by photopolymerizing acrylic acid ester alone is 2X10, which is superior to polyethylene terephthalate. This single polymer film can also be used in a TF capacitor, but since it is somewhat lacking in flexibility, it may be further copolymerized with a photopolymerizable monomer to impart flexibility. As such a photo-merizable monomer for imparting flexibility, for example, (meth)acrylate compounds having a long-chain alkyl or aralkyl group in the side chain as shown in the following It is effective to use

2-Etherhexyl (meth)acrylate isodecyl (
meth)acrylates and such photoconvertible heptamers impart flexibility through copolymerization, but do not deteriorate dielectric properties. is an unsaturated resin having a butadiene bond or an isoprene bond in the molecule, one or more (meth)acrylate groups at the end of the molecule, and a molecular cap of 500 to 5,000. Materials having such a butadiene or isoprene skeleton are highly flexible, non-polar, and have excellent dielectric properties. And at the end like above (meta)
An unsaturated resin having an acrylate group can be synthesized, for example, as in Harigi. In other words, OH at the end
By reacting TDI (tolylene diisocyanate) with the hostile polybutadiene having the terminal group 1 (g-type polybutadiene having the N GO group), and then reacting it with hydroxyethyl acrylate (HEA), the terminal Unsaturated resins having acrylate groups can be synthesized. Such resins are also commercially available.
A UV curable liquid silicone resin containing 50% of the component and (c) component alone or in combination may be used. Such a photocurable silicone resin is obtained by copolymerizing methylvinyldichlorosilane and dimethyldichlorosilane, and is expressed by the general formula, and has a vinyl group in its side chain. . Further, a UV-curable liquid silicone resin having an acrylic group can also be synthesized by the following reaction.

This UV-curable liquid silicone resin can form a film with excellent flexibility and dielectric properties.

On the other hand, the dielectric loss tangent of the ultraviolet curable silicone resin film manufactured by Shin-Etsu Silicone Co., Ltd. is as small as 4×1O.

Since the ultraviolet curable resin composition of the present invention has the following structure, it can form a thin film layer with excellent dielectric properties. It will now be possible to manufacture film capacitors using polypropylene film, which has low but excellent dielectric properties, and by applying ultraviolet treatment that does not apply heat instead of heat treatment, making it possible to realize extremely high-performance TF capacitors.

Next, a practical explanation will be given along with a comparative example.

[Example 1] Dicyclopentenyl acrylate (Hitachi Chemical Co., Ltd.)
e FA-511A), dicyclopentenyloxy-
Ethyl acrylate (Hitachi Chemical (closed).

FA-512A) and acrylic benzoate ester of neopentyl glycol (Dainippon Ink Co., Ltd., TD-153OA) represented by the above formula They were blended and mixed in the proportions shown in the table to form a mixed varnish. Next, apply 1 part of light to 100 parts of this mixed varnish (1 or less is the same).
A UV curing varnish was obtained by processing 3 parts of benzophenone as a polymerization initiator and 1 part of hydroquinone as a stabilizer. This varnish was applied onto an aluminum plate and a high pressure mercury lamp (oak) was applied.
It was irradiated until completely cured using an IMW-3511I ink water-cooled lamp (IMW-3511I ink water-cooled lamp, output 80 jaws, 3 lamps) manufactured by UV Conveyor Co., Ltd.).

The exposure lid varies depending on the varnish, but is 1000 to 300
0mJ/cd outside prefecture line light wrinkle meter (Oak Co., Ltd. i UV3
Exposure k was measured using 30). 100-20 after curing
After peeling off the 0 μ thick film from the M plate and cutting it to an appropriate size, deposit N on both sides and take out the 3 electrodes.
*Characteristics were measured. The results are shown in Table 2, and it can be seen that all the films had excellent dielectric properties.

[Example 2] Terminal acrylic modified liquid polybutadiene resin (Nippon Soda (
Co., Ltd., TE2000) and 2-ethylhexyl methacrylate in the proportions shown in Table 3 to make a mixed varnish, and for 100 parts of this mixed fest, benzyl dimethyl ketal (Ciba Geigy Co., Ltd., A UV-curing varnish was prepared by adding 3 parts of Irgacure 651) and 0.1 part of hydroquinone as a stabilizer. Then, a UV cured film was obtained in the same manner as in Example 9Ill. In this case, the cliff light required for curing is 3000 ~
It was 4000 mJ/d. The dielectric properties of the obtained films are as shown in Table 3, and both films have vj
It can be seen that the dielectric properties are excellent.

[Example 3] Terminal acrylic-modified polybutadiene resin (Nihonshokai (redacted) + "' 2000) + "-butyl acrylate and dicyclopentenyl acrylate (Hitachi Kasei Ikuri Co., Ltd., FA-511A) were 3 parts of benzoin isopropyl ether as a photopolymerization initiator and 0.1 part of hydroquinone as a stabilizer were added to 100 parts of the mixed varnish in the same proportion as above to prepare a UV-containing varnish, and the same procedure as in Example 1 was made. A UV cured film was obtained.

The exposed lid that has undergone curing is 3000-4000 WLJ/d.
Met. The dielectric properties of the obtained films are shown in Table 4, and it can be seen that all the films have excellent dielectric properties.

[Reference example]

Varnish T, 5.8 used in the above example was coated with a thickness of 2 μm by roll coating on one side of both IkJA1 vapor-deposited polypropylene film (film thickness 9 μm IL) and meat vapor beak polyethylene terephthalate film (film thickness 9 μm). A TF capacitor was obtained by curing the product by irradiating it with ultraviolet rays. l due to differences in the base film of the obtained TF capacitor
Table 5 shows the difference in #h electric loss tangent at W-Hz.

Claims (2)

[Claims] (1) An ultraviolet curable resin composition containing at least one of the above-mentioned components (1) and (2) in an amount of 50jILi1'- or more. It has dihydrodicyclopentadiene represented by (
meth)acrylic acid ester. (An unsaturated resin having a butadiene bond or an imprene bond in the molecule, and one or more (meth)acrylate groups at the end of the molecule, and a molecular weight of 500 to 5,000. (2) The ultraviolet curable resin composition according to Claim 1JJ1, which contains a photopolymerizable hexamer together with the component (c).