JPH0730147B2 - Curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition curable by light, heat, a combination of light and heat, or an electron beam, which comprises a novel acrylamide oligomer.

[0002]

2. Description of the Related Art In recent years, in the fields of paints, UV-curable resist inks used in the production of printed wiring boards, and insulating varnishes, interest in resins curable by light, heat, light and heat, or electron beams has increased. Is coming. Conventionally, this type of resin has been proposed using a hydroxyalkyl acrylate half ester of polybasic acid, a hydroxyalkyl acrylate of styrene-maleic anhydride, a polyester resin having a carboxyl group, an acrylic resin, a rosin, a maleinized rosin, etc. Has been done.

[0003]

However, all of the above-mentioned resins are not satisfactory in terms of heat resistance, electrical characteristics and rapid curing.

[0004]

[Means for Solving the Problems] The inventors of the present invention maintain excellent heat resistance and electrical characteristics of epoxy resin,
The present invention has been achieved as a result of intensive research on a resin composition that itself undergoes radical polymerization curing or photocuring. That is, the present invention provides (a) the general formula (I)

[0005]

[Chemical 3]

(In the formula (I), Ar is represented by the general formula (II)

[0007]

[Chemical 4]

[0008] shows, n is 2-10. General formula (I
In I), Ar ′ represents a C _{6 to} C ₂₀ aromatic hydrocarbon, R is a hydrogen atom or a methyl group, and n ′ is 1 to 4
Which is an integer of 1), and (b) a photopolymerization initiator, a photosensitizer, or a radical polymerization initiator. A resin composition that can be cured with light, heat, or electron beams is included.

The acrylamide oligomer represented by the general formula (I) of the present invention is, for example, the general formula (III)

[0010]

[Chemical 5]

(In the formula, Ar ″ has one glycidyl group.
That C ₆ represents an aromatic hydrocarbon ~C _20, R, n 'is obtained by ring-opening polymerization without a solvent or in a solvent a glycidyl group of glycidyl compound represented by the same) to the Lewis acid as a catalyst To be At this time, it is preferable to add a radical polymerization inhibitor such as hydroquinone in order to prevent thermal polymerization of the acrylamide group. The compound represented by the general formula (III) has the general formula (V
I)

[0012]

[Chemical 6]

(In the formula, A is C ₆ -C having one hydroxyl group.
₂₀ represents an aromatic hydrocarbon, R is a hydrogen atom or a methyl group, and n is an integer of 1 to 4) and epihalohydrin are added, and then dehydrohalogenation reaction is carried out with alkali. It is manufactured by Such a compound and its production method are disclosed in Japanese Patent Application No. 58-2374.
This is disclosed in detail in Japanese Patent Publication No. 93.

The compound represented by the general formula (VI) is, for example, an aromatic hydrocarbon having a phenolic hydroxyl group and N-methylolacrylamide or N-methylolmethacrylamide, or an alkyl ether of N-methylolacrylamide or N-methylolmethacrylamide. It can be easily obtained by condensing a derivative (hereinafter, referred to as N-methylolacrylamides) with an acid catalyst. For example, when 2,6-xylenol and N-methylol acrylamides are used as starting materials, a glycidyl compound represented by the following structural formula (IV) can be obtained.

[0015]

[Chemical 7]

(In the formula, R represents a hydrogen atom or a methyl group, and n is 1 or 2.) When orthocresol and N-methylolacrylamide are used as starting materials, they are represented by the following structural formula (V). A glycidyl compound can be obtained.

[0017]

[Chemical 8]

(In the formula, R represents a hydrogen atom or a methyl group, and n is 1 or 2.)

The Lewis acid used in the present invention is Sn
_{Cl 4, TiCl 4, BF 3} · O (C 2 H 5) 2, BF 3 · O (C 4 H 9) 2 or amine complex such as boron trifluoride monoethylamine complex of boron trifluoride, trifluoride Boron piperidine complex,
Other examples include complexes of boron trifluoride with benzylamine, triethylamine and the like. Lewis acids have the general formula (III)
It is usually used in the range of 1 to 6 parts by weight with respect to 100 parts by weight of the glycidyl compound.

The photopolymerization initiator or photosensitizer used in the present invention is a compound which easily generates radicals or ions upon irradiation with light (usually ultraviolet rays), and includes azidobenzene and 4-azidobenzoic acid. , 4,4'-diazidobiphenyl, 1,2-bis (4-azidophenyl) ethylene, 4-aminophenyl-4'-azidophenylmethane, 4,4'-diazidobenzophenone, 2,6-bis ( 4-azidobenzene) Cytarohexane and other azide compounds: benzophenone, benzophenone oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, α-haloketone, ω-bromoacetophenone carbonyl compounds such as cyclohexanone: diphenyl monosulfide, S- Sulfur compounds such as acyl-dithiocarbamate: Azo compounds such as azoisobutyl nitrile: Organic peroxides such as benzoyl peroxide, di-t-butyl peroxide: Dialkyldithiocarbamate stearate, t-butylanthraquinone, 2-
Examples thereof include mercaptobenzothiazole. The amount used is usually in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the acrylamide oligomer.

The radical polymerization initiator used in the present invention is used for the purpose of accelerating heat curing, and an organic peroxide which is widely used for initiation of radical polymerization is suitable. However, it is necessary to select one that decomposes within a desired time at the temperature at which the curing reaction is performed. Specifically, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxypiperate, t-butyl peroxy. Benzoate or the like can be used. The amount used is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylamide oligomer. These radical polymerization initiators are
You may use together with the said photoinitiator, a photosensitizer, or those combinations.

The resin composition of the present invention comprises the above-mentioned photopolymerization initiator or photosensitizer, or radical polymerization initiator (b).
It can be easily cured by light (ultraviolet rays), heat, light and heat, electron beam, etc. The photo-curing is performed by irradiating a mercury lamp or other ultraviolet rays. The temperature for thermosetting may be usually in the range of 100 to 200 ° C.

The resin composition of the present invention is used in various applications such as paints, cast products, molded products, laminates, insulating varnishes, resist inks, resin modifiers and compatibilizers. Various additives can be added to the resin composition of the present invention as desired, as long as the characteristics inherent to the composition are not impaired. These additives include monofunctional or polyfunctional hydroxy compounds (meth) acrylic acid ester, (meth) acrylic acid epoxy ester, and (meth) acrylic acid alkenyl for the purpose of adjusting adhesiveness or flexibility. Esters of (meth) acrylic acid such as esters and prepolymers thereof; polyallyl compounds such as diallyl phthalate, divinylbenzene, diallylbenzene and prepolymers thereof; dicyclopentadiene and prepolymers thereof; polyvinyl acetal resin; butadiene-acrylonitrile copolymerization Coalescence or the like is appropriately used.

As the reinforcing material and the filler, glass fiber such as chopped mat and cloth, carbon fiber, quartz glass or silica, alumina, aluminum hydroxide, calcium carbonate, calcium silicate and the like can be used. In addition to these, in order to improve coating suitability and printability, as necessary, a thickener, a leveling agent, a fluidity improver, a matting agent, a coupling agent, a plasticizer, a pigment, a dye, a defoaming agent, A thixotropic agent or the like can be appropriately added and used.

[Examples] Next, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. In the following examples, “parts” means “parts by weight”. Reference Example 1 100 parts of N- (4-glycidyloxy-3,5-dimethylphenylmethyl) acrylamide (the above structural formula (IV) wherein R is a hydrogen atom , n = 1 ), boron trifluoride monoethylamine 6 Parts and hydroquinone 0.01
Part of the mixture was reacted in a flask equipped with a reflux condenser at 140 ° C. for 4 hours with stirring to carry out ring-opening polymerization of glycidyl groups. The end point of the reaction was determined to be 10.95μ by IR spectroscopy.

[0026]

[Chemical 9]

The point at which the absorption of [1] disappeared was set. The obtained oligomer was a viscous liquid at the reaction temperature and a solid at room temperature.
The polystyrene-equivalent molecular weight was 1,100.

Example 1 100 parts of the oligomer obtained in Reference Example 1, 10 parts of acetone
0 parts, 3 parts of benzoin ethyl ether and 4 parts of leveling agent (BYKETOL SPECIAL) are mixed,
Apply on a glass plate to create a coating film with a thickness of about 10μ, and air dry 2
After 0 minutes, ultraviolet rays were irradiated for 10 minutes from a distance of 15 cm using a 400 W high pressure mercury lamp. The resulting coating film was transparent and had a pencil hardness of 4H.

Example 2 100 parts of the oligomer obtained in Reference Example 1, 10 parts of acetone
0 part, 3 parts of benzoin ethyl ether, 3 parts of t-butyl peroxybenzoate and 4 parts of the leveling agent (used in Example 1) were mixed and about 100 μm on a Teflon plate.
Apply so that it becomes a thick film, and air dry 30 minutes later 40
Ultraviolet rays were irradiated from a distance of 15 cm for 10 minutes using a 0 W high pressure mercury lamp. After that, after-curing was performed at 160 ° C. for 30 minutes. The cured film obtained was transparent and brown, and had a tensile strength of 5.8 kg / mm ² and a tensile elastic modulus of 330 kg / mm.
^{Was 2} .

Reference Example 2 Structural formula

[0031]

[Chemical 10]

100 parts of a glycidyl compound represented by the above structural formula (V) wherein R is a hydrogen atom , n = 1
A mixture of 6 parts of boron trifluoride monoethylamine and 0.01 part of hydroquinone was subjected to ring-opening polymerization of a glycidyl group in the same manner as in Reference Example 1. The obtained oligomer was a viscous liquid at the reaction temperature and a solid at room temperature. The polystyrene-equivalent molecular weight was 910.

Example 3 100 parts of the oligomer obtained in Reference Example 2 and 10 parts of acetone
0 part, 3 parts of benzoin ethyl ether and 4 parts of the leveling agent (used in Example 1) were mixed, and a coating film was formed on a glass plate in the same manner as in Example 1. The obtained coating film was transparent and had a pencil hardness of 3H.

Example 4 100 parts of the oligomer obtained in Reference Example 2 and 10 parts of acetone
0 part, 3 parts of benzoin ethyl ether, 3 parts of t-butyl peroxybenzoate and 4 parts of the leveling agent (used in Example 1) were mixed and a cured film was prepared in the same manner as in Example 1. The obtained film was transparent in brown and had a tensile strength of 5.6 kg / mm ² and a tensile elastic modulus of 320 kg / mm ² .

[0035]

EFFECT OF THE INVENTION The resin composition of the present invention provides a cured product which is fast-curing and has excellent mechanical properties while maintaining heat resistance and electrical properties.

Claims (1)

[Claims] 1. (a) General formula (I): [Chemical 2] The indicated, n represents an 2-10. In general formula (II), A
r ′ represents a C _{6 to} C ₂₀ aromatic hydrocarbon, R is a hydrogen atom or a methyl group, and n ′ is an integer of 1 to 4), and (b) photopolymerization. A resin composition curable by light, heat, a combination of light and heat, or electron beam, which comprises one or more of an initiator, a photosensitizer or a radical polymerization initiator.