JPS6032822A - Resin composition curable with actinic energy radiation - Google Patents

Abstract

PURPOSE:To obtain a curable resin composition giving excellent adhesivity to substrate, by compounding a compound having epoxy group with a compound having >=2 aziridinyl groups and a compound giving a Lewis acid with actinic energy radiation. CONSTITUTION:The objective composition can be obtained by mixing (A) 1- 99.5pts.wt. of a compound having >=1 epoxy groups in the molecule (e.g. epoxide ester), (B) 0.5-99pts.wt. of a compound having >=2 aziridinyl groups in the molecule (e.g. omega-aziridinyl-propionic acid 2,2-dihydroxymethylbutanol triester) and (C) 0.1-10pts.wt., based on 100pts.wt. of A+B, of a compound capable of producing a Lewis acid with actinic energy radiation (e.g. aromatic halonium salt, aromatic diazonium salt and aromatic sulfonium salt of complex halide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a cured product having excellent adhesion to a base material.
The present invention relates to active energy ray-curable resin compositions useful as coatings and electric/phi/electronic materials.

Epoxy resins have traditionally been used as coatings and electrical/electronic materials from the viewpoint of corrosion resistance and electrical properties, but their curing methods include adding curing agents such as acid anhydrides and amines, and curing them with heat or at room temperature. The main method is curing. On the other hand, in recent years, from the viewpoint of saving resources and energy, curing methods that involve irradiation with active energy rays such as ultraviolet rays and electron beams have been developed for the purpose of short-time curing at room temperature.
That is, active energy ray curable compositions have been proposed. The active energy ray curable composition is cured by a method using radical reaction, joint name 1z. therefore,
In order to increase the radical curing ability of the epoxy resin to 14, it is necessary to modify the epoxy resin with acrylate or methacrylate.

However, cured products obtained by acrylate-modified or methacrylate-modified epoxy resins, so-called epoxy polyacrylates cured with active energy rays, have excellent corrosion resistance and electrical properties, but have poor adhesion to substrates, such as metal plates. Recently, proposals have been made for active energy ray-curable resin compositions that can be cured in a short time at room temperature without modifying the epoxy resin. A composition with sufficient adhesion has not yet been found, and there is a strong desire for an energy ray-curable resin composition that provides a cured product with excellent adhesion.

As a result of intensive research, the inventors of the present invention, Mizo et al., found that compounds having one or more epoxy groups in the molecule, compounds having two or more aziridinyl groups in the molecule, and compounds that generate Lewis acids when irradiated with active energy rays. It has been discovered that a composition containing a compound in a certain arrangement and proportion gives a hard crack that exhibits extremely good adhesion to a substrate, and has completed the present invention. It's arrived.

That is, the active energy ray-curable resin composition of the present invention contains (a) 1 to 99.5 parts by weight of a compound having one or more epoxy groups in the molecule, (b) two or more aziridinyl groups in the molecule. and (C) a compound that generates a Lewis acid under active energy ray irradiation; the total of the components (a) and (b) is 31100 parts by weight.
It is characterized in that it consists of 0.1 to 10 parts by weight.

The epoxy compound used as component (a) in the present invention is:
Any compound may be used as long as it has one or more epoxy groups in the molecule, but preferably: (i) Epoxide ester having two epoxycycloalkyl groups; (i) Bisphenol A, Bisphenol F , diglycidyl ether of bisphenol S; (m) polyepoxidized phenol novolak resin or cresol novolak resin; (iv) polyglycidyl ether of polyhydric alcohol; (V) cycloalkyl hydrocarbon, alkylcycloalkyl hydrocarbon or ether and (Vi) any mixture of the foregoing.

Among these, the commercially available epoxide esters include 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylene-1.
(Union Carbide Co., Ltd. ER1, -4221; Chi/Hekaigy Co., Ltd. CY-179), Bis(3,4-epoxy-
6-methylcyclohexylmethyl)adipate (Union Carbide Co., Ltd. URL-4289) and bis(3,4-
Examples of the diglycidyl ether of hisphenol A include Araldite 6010 from Ciba Geigy, DER331 from Dow Chemical Company, and Epon 828 from Shell Chemical Company. can be mentioned.

Polyepoxidized phenol novolak resins are available as DEN-431 and 438 from Dow Chemical Co., Ltd., and polyepoxidized cresol novolak resins are available as Adaldai 1-538 from Ciba-Kygyi Co., Ltd., etc.

As polyglycidyl ethers of polyhydric alcohols, those derived from butane-1,4-diol such as Ciba Geigy's Araltite RD-2 are available, and those derived from glycerin such as Shell Chemical's Epon 812 are available. It is.

Furthermore, the diepoxide of alkylcycloalkyl hydrocarbon is vinylcyclohexene dioxide (Union Carbide ERL-4208), and the dieboxide of cycloalkyl ether is bis(2,3-epoxycyclopentyl) ether (Union Carbide ERL).
Compounds having two or more aziridinyl groups in the molecule which are component (b) of the present invention include tetramethylenebis-N, N-ethyleneurea, hexamethylenebis- N, N
~Ethylene urea, tris(1-aziridinyl)phosphine oxyto, ω-aziridinylpropio 7%-2,2-
Examples include dihydroxymethylbutanol-triester, but especially ω-aziridinylpropionic acid-2,2
-dihydroxymethylbutamer-triester is preferred.

The compound (C) of the present invention, which generates a Lewis acid under active energy ray irradiation, has the following formula (1): %Formula%)(1) (wherein R is a monovalent aromatic organic group) , R1 is a divalent aromatic organic group; X and XI are respectively 1, Br, C1
, F; h is sb, Fe, Sn, 'B
i, A1, Ga, In, Ti, Zr, Sc, V,
Transition metal elements such as Cr, Mn, Cs, La, Ce,
Lanthanide elements such as Pr, Nd, Th, Pa,
II, actinide elements such as Np, B, P, A
Elements such as s; a is an integer of 0 or 2; b is an integer of 0 or l; e is an integer of 2 to 7; valence; d is an integer greater than e up to 8; ) is the valence of 2 or X, and has the relationship c=de; rM
Examples of complex anions represented by XI d)-(d-e) include BF, -, PF6-5 AsF, -, SbF6.
FeCl, pp-lSnCl62-1S:16-,
Aromatic halonium history represented by the following formula (II): (In the formula, M, X', c, d, e are the same as above; Y
represents a nitro group, a halogen element, an N-morpholino group, an alkyl group, an alkoxy group, an aryl group, an amino group, an arylamino group, an alkylamino group, an arylmercapto group, etc.) and complex halogens. Examples include aromatic sulfonium salts of compounds,
Aromatic sulfonium salts of complex halides are preferred since they do not have drawbacks such as foaming.

Aromatic sulfonium salts of complex halides include triphenylsulfonium tetrafluoroporate troantimonate, 5-phenyldibenzothiophenium fluoroporate, phenacyltetramethylenesulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate. etc. can be mentioned.

In the resin composition of the present invention, the blending ratio of the epoxy compound used as component (a) and the aziridicol compound used as component (b) is 1 to 99.5 by weight:
It needs to be 0.5-89. If the blending ratio of the epoxy compound exceeds the above upper limit, the storage stability of the blend will deteriorate, and if it is below the above lower limit, the resulting coating film will have insufficient adhesion.

In addition, the blending ratio of the compound that generates a Lewis acid under active energy ray irradiation used as component (C) is as described in (a) above.
0.1 per 100 parts by weight of component and component (b)
~10 parts by weight is required. If this blending ratio exceeds the above upper limit, the storage stability of the blend will deteriorate,
If it is less than the lower limit, the curing of the compound will be insufficient.

The composition of the present invention contains, in addition to the bivalent compounds, commonly used additives, initiators, colorants, and plasticizers.

Optional components such as inorganic fillers and polymerization inhibitors can be included.

In addition, as active energy rays for curing the composition of the present invention, gamma rays, ultraviolet rays, and electrons can also be used [X-rays, etc. can be used, but
Preferred are ultraviolet rays and electron beams.

The cured product obtained from the active energy ray-curable resin composition of the present invention has extremely excellent adhesion compared to conventional products.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

[Example I 80 parts by weight of cobisphenol A diglycidyl ether resin (manufactured by Shell Chemical Co., Ltd., Ebicor 828) and 20 parts by weight of ω-aziridinylpropion@-2,2-dihydroxymethylbutanol-triester were mixed. To this, 5 parts by weight of triphenylsulfonium hexafluoroantimonate was added, and after thorough stirring and mixing, the mixture was coated on a mild steel plate using a bar coater No. 22.

This coated plate was heated for 1 time using an 80 W/cm ultraviolet lamp.
When irradiated for 5 seconds, a coating film with excellent adhesion and a pencil hardness of 2H was obtained.

[Comparative Example 1] 5 parts by weight of triphenylsulfonium hexafluoroantimone I was added to 100 parts by weight of the bisphenol A diglycidyl ether resin used in Example 1, and then the same procedure as in Example 1 was carried out. hardened coating II on mild steel plate
I got I. However, only a coating film with insufficient adhesion and a low pencil hardness of HB was obtained.

[Example 2] 40 parts by weight of 3.4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Union Carbide Co., ERL-4221) and 60 parts by weight of lith(1-aziridinylphosphine oxide) To this was added 5 parts by weight of triphenylsulfonium hexafluoroarsenate, and after thorough stirring and mixing, it was applied to a mild steel plate using a bar coater No. 22. This coated plate was coated with an 80W When irradiated for 15 seconds using an ultraviolet light lamp of /cm, a coating film with a pencil hardness of 3H and excellent adhesion was obtained.

[Comparative Example 21 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylene-6 used in Example 2
1.5 parts by weight of triphenylsulfonium hexafluoroarsene was simply added to 100 parts by weight, and then a cured coating film was obtained on a soft steel board in the same manner as in Example 2.

However, only coating 11 with insufficient adhesion was obtained.

[Example 3] The formulation used in Example 1 was similarly applied on a soft rope board,
When the electron beam was irradiated in air at 5 Mrad, there was some tackiness immediately after irradiation, but it became tack-free after 24 hours, and the pencil hardness was HB with 1p of adhesion.
A coating film was obtained.

r Example 4] 80 parts by weight of Epon 152 (manufactured by Shell Chemical Co., Ltd.), which is a novolanc type epoxy resin, and 10 parts by weight of ω-aziridinylpropionic acid-2,2-dihydroxymethylbutanol-triester were mixed, To this was added 1.5 parts by weight of trinoenylsulfonium tetrafluoropole, and after thorough stirring and mixing, the mixture was coated on a mild steel plate using a bar coater No. 22. This coated plate is 80W/
When irradiated for 10 seconds using a cm ultraviolet lamp, a coating film with a pencil hardness of H and excellent adhesion was obtained.

Claims (1)

[Scope of Claims] 1 (a) 1 to 99.5 parts by weight of a compound having one or more epoxy groups in the molecule, (b) 0.5 to 88 parts by weight of a compound having two or more aziridinyl groups in the molecule parts by weight, and (c) a compound that generates a Lewis acid upon irradiation with active energy rays; total of the above components (a) and (b) 1
An active energy ray-curable resin composition comprising 0.1 to IO parts by weight per 00 parts by weight. 2. The resin composition according to claim 1, wherein the compound having two or more aziridinyl groups in the molecule is ω-aziridinylpropionic acid-2,2-dihydroxymethylbutanol-triester. 3. The resin composition according to claim 1, wherein the active energy ray is an ultraviolet ray or an electron beam. 4. The resin composition according to claim 1, wherein the compound that generates a Lewis acid upon irradiation with active energy rays is an aromatic sulfonium salt of a complex halide.