JPS5932483B2 - Curable composition with excellent corrosion resistance - Google Patents

Description

[Detailed description of the invention] The present invention relates to a curable composition with excellent corrosion resistance.

More specifically, the present invention relates to a curable composition having excellent corrosion resistance and containing a crosslinkable polymer, a polymerizable monomer, and a polymerization initiator. Mild steel plates, copper foil laminate plates, etc. coated with a cured film obtained from a curable composition that can be cured by light or heat, including radiation, can be coated with colored galvanized iron, printed circuit boards,
It can be applied to flexible printed circuit boards, etc., but various characteristics are required for such applications.

One such requirement is corrosion resistance that satisfies water and humidity tests. In order to solve these problems, for example, the addition of a condensate such as methylolmelamine and 2-hydroxyethyl methacrylate to the curable composition (see Japanese Patent Publication No. 49-24132), and other methods previously proposed by the present applicant. Adding a non-polymerizable imidazole compound as one component of a cured product composition has been carried out. According to the latter proposal, the cured film obtained from this curable composition has excellent adhesion to the substrate (Japanese Patent Publication No. 57-26285),
At the same time, it was found that the corrosion resistance was also satisfactory. The present invention is a further development of such a proposal made by the present applicant, in which N-vinyltriazole or N-vinylimidazole is added to a curable composition as a polymerizable monomer. By adding it in an amount of about 0.5% or more of the weight of the composition, the corrosion resistance of a cured product such as a cured film obtained from this composition is improved.

Therefore, the present invention relates to a curable composition with excellent corrosion resistance, which is an addition reaction product of an epoxy resin having no urethane bond in its molecule and an α,β monounsaturated monobasic carboxylic acid or It contains a polymerizable monomer mixture containing the acid anhydride adduct, N-vinyltriazole, N-vinylimidazole, or these N-vinyl nitrogen-containing cyclic compounds, and a polymerization initiator.

The curable composition of the present invention to which such N-vinyltriazole or N-vinylimidazole is added not only provides corrosion resistance to the cured product, but also the N-vinyl nitrogen-containing cyclic compound itself as a polymerizable monomer. Since it is cured by light irradiation or heating, it is extremely preferable because it does not evaporate or evaporate during handling of the composition or ooze out onto the surface of the cured product after curing. Furthermore, since the cured film has good adhesion to various substrates, it is not particularly necessary to pre-treat the surface of the substrate to which the curable composition is to be applied. The main components of the curable component are addition reaction products of epoxy resins that do not have urethane bonds in their molecules and α,β-unsaturated monobasic carboxylic acids, or their acid anhydride adducts (hereinafter referred to as addition reaction products). (sometimes abbreviated as ``things'') is used.

In the reaction between epoxy resin and α,β monounsaturated monobasic carboxylic acid, acrylic acid, methacrylic acid, crotonic acid, etc. are generally used. Substitution can be made with carboxylic acids such as maleic acid, adipic acid, phthalic acid, phenylmaleic acid, tetrahydrophthalic acid, head acid, nadic acid, methylnadic acid, and the like.

The reaction product of an α,β monounsaturated basic carboxylic acid partially substituted or unsubstituted with a dibasic carboxylic acid and an epoxy resin may further include maleic anhydride, phthalic anhydride, and pyromellitic anhydride. It can be reacted with polybasic carboxylic acid anhydrides such as polybasic carboxylic acid anhydrides to form the anhydride addition compounds, which can be used as crosslinkable polymers. The reaction of these epoxy resins with an α,β monounsaturated monobasic carboxylic acid or the reaction of the addition reaction product with an acid anhydride is preferably carried out using a quaternary compound such as triethylbenzylammonium chloride or tetraethylammonium iodide.
This is carried out in the presence of a catalyst such as an ammonium salt compound or a tertiary amine such as triethylamine or dimethylalinine, and in the presence of a thermal polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether. As mentioned above, the N-vinyl nitrogen-containing cyclic compound can be used alone as the polymerizable monomer that is another component of the curable component.
It is generally used in combination with other polymerizable monomers. Such polymerizable monomers include styrene, divinylbenzene, vinyl acetate, N-vinylpyrrolidone, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methoxytetraethylene glycol monomethacrylate, methoxy nonaethylene glycol monomethacrylate, Furthermore, when high-speed curing properties are required for the photocurable composition, trimethylolpropane triacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, nonaethylene glycol diacrylate, pentaerythritol tetraacrylate, and methacrylates corresponding to these can be used. , triallyl trimellitate, triallyl cyanurate, triallyl isocyanurate, diallinolephthalate, and other polyfunctional monomers are used. These polymerizable monomers can be added as a solvent for the synthesis reaction of addition reaction products from the beginning of the reaction or during the reaction. In this case, the polymerizable monomers can be added as a solvent for the reaction. It is not directly involved in the synthesis reaction. The polymerizable monomer can also be added at the time of preparing the curable composition, and it is particularly preferable that the N-vinyl nitrogen-containing cyclic compound is added at this stage. A curable composition is prepared by adding a polymerization initiator to these addition reaction products and the N-vinyl nitrogen-containing cyclic compound or a polymerizable monomer mixture containing the same. When an initiator is added, there is a photocurable composition that is photocured by ultraviolet rays, electron beams, etc., and when a thermal polymerization initiator is added, there is a thermosetting composition that is thermocured by heating or polymerization heat. Compositions are each prepared.

As photopolymerization initiators, commonly used ones such as benzoin, benzoin ethers, benzothioethers, 2-alkylanthraquinones, decyl chloride, furoin, and furoin ethers are used as the curable component of the photocurable composition. It is used in an amount of approximately 0.1 to 10% by weight, and the amount may be increased as appropriate if a coloring agent or the like is added. In addition, as a thermal polymerization initiator, peroxides such as benzoyl peroxide, lauroyl peroxide, and kyumene hydroperoxide, or these peroxides can be combined with cobalt naphthenate, diacetylacetone zinc salt, and N,N-dimethylallidate. In combination with accelerators such as nin, benzoin alkyl ethers, which are also photopolymerization initiators, are used.
The amount used is about 0.05 to 5% based on the weight of the curable component of the thermosetting composition. The cured product obtained by irradiating or heating the curable composition of the present invention to which the N-vinyl nitrogen-containing cyclic compound is added has excellent corrosion resistance and excellent adhesion to the substrate. So,
Utilizing such properties, it can be effectively used for various purposes as described at the beginning.

Next, the present invention will be explained with reference to examples.

Example 1 Epoxy resin DER-331J (epoxy equivalent weight 190)
959 and acrylic acid 369 (0.

5 mol), triethylamine 19 as a catalyst and hydroquinone 0.19 as a thermal polymerization inhibitor were added, and 8
After reacting for 3 hours at 0-130°C, the reaction mixture was diluted by adding 30% (by weight) of styrene.

2 parts of benzoin ethyl ether and 2 parts of N-vinyltriazole were added to 100 parts (by weight, the same below) of the obtained varnish with a viscosity of 27 poise (25°C) and an acid value of 0.1 or less to prepare a photocurable composition. Prepared. Example 2 Acrylic acid 36 in epoxy resin DER-331J959
9 (0.5 mol), triethylamine 29, hydroquinone monomethyl ether 0.19 and tetraethylene glycol diacrylate 569,
The reaction was carried out at ℃ for 2 hours.

2 parts of benzoin ethyl ether and N
- A photocurable composition was prepared by adding 5 parts of vinyltriazole. Example 3 Acrylic acid 369 (0.5 mol) to 1209 epoxy resin Adekal resin EP-4080 (epoxy equivalent weight 240)
, triethylbenzylammonium chloride 39 as a catalyst and phenothiazine 0 as a thermal polymerization inhibitor.
．． After adding 39 and reacting at 90 to 120°C for 3 hours,
Furthermore, 7.49 (0.025 mol) of phthalic anhydride was added thereto and reacted for 30 minutes, and 2-hydroxypropyl acrylate 679 was added to the reaction mixture to dilute it.

2 parts of 2-ethylanthraquinone and N
- A photocurable composition was prepared by adding 10 parts of vinyltriazole.

Example 4 Acrylic acid 14 in epoxy resin DER-331J959
．． 49 (0.2 mol), acetic acid 39 (0.05 mol), adipic acid 18,39 (0.125 mono(ha)), methyltriethylammonium iodide 29 and hydroquinone 0.29, and heated at 90 to 130°C. After reacting for 2 hours, phthalic anhydride 7.49 (0.025
mol) was added and reacted for 30 minutes, and the reaction mixture was diluted by adding nonaethylene glycol diacrylate 469.

A photocurable composition was prepared by adding 2 parts of benzophenone to 100 parts of a varnish prepared by adding N-vinyltriazole 469 to half of the diluted mixture. Comparative example
1 to 3 In the photocurable compositions of Examples 1 to 3, photocurable compositions in which no N-vinyltriazole was added were prepared.

Comparative Example 4 A sample with a viscosity of 190 poise (25°C
), 2 parts of benzophenone in 100 parts of varnish with an acid value of 15.8
A photocurable composition was prepared.

Comparative Example 5 In Example 3, a photocurable composition was prepared using the same amount of N-vinylpyrrolidone instead of N-vinyltriazole.

Corrosion resistance test of cured film The photocurable composition prepared in each example and each reference example was applied to a thickness of 30μ on a mild steel plate and a polyester-lined steel plate (flexible substrate) using an applicator and a bar coater, respectively. Then, the coating film was cured by irradiating it for 3 minutes from a distance of 30 cm using a 3KW ultra-high pressure mercury lamp.

After the cured film was left at room temperature for 24 hours, it was placed in a constant temperature and humidity bath at a temperature of 60°C and a humidity of 90%.The photocurable compositions of each comparative example were cured on a steel plate in 1 to 2 days. In contrast to the appearance of spot rust and discoloration on the copper plate, such phenomena were not observed even after 3 weeks with the photocurable compositions of each example. . Similar effects were observed when N-vinylimidazole was used instead of N-vinyltriazole.

Example 5 2 parts of Permek (manufactured by NOF Corporation, a mixture of 55% methyl ethyl ketone peroxide and 45% dimethyl phthalate) was added to 100 parts of the varnish prepared in Example 4 to prepare a thermosetting composition.

Claims (1)

[Claims] 1 Epoxy resin that does not have urethane bonds in the molecule and α
, addition reaction product with β-unsaturated monobasic carboxylic acid or its acid anhydride adduct, N-vinyltriazole, N
- A curable composition with excellent corrosion resistance, comprising a polymerizable monomer mixture containing vinylimidazole or an N-vinyl nitrogen-containing cyclic compound thereof, and a polymerization initiator.