JPS6063263A - Temporary rust preventing composition for metallic surface - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating a curable unsaturated radically reactive resin having a specific acid value with a specific alkyd resin in a specific proportion, and capable of forming films having improved rust preventing property, dealkalizing property of the films and machine oil resistance, etc. CONSTITUTION:A temporary rust preventing composition obtained by incorporating (A) 60-90wt% unsaturated radically reactive resin having 10-60 acid value, e.g. an unsaturated epoxy resin, curable with active energy radiation, e.g. a high-pressure mercury lamp, and if necessary an unsaturated radically reactive monomer, [e.g. 2-hydroxyethyl (meth)acrylate], with (B) 10-40wt% alkyd resin having >=45% oil length and 10-20 acid value, e.g. castor oil. EFFECT:Improved storage stability and coating performance, etc.

Description

[Detailed description of the invention] The present invention applies j↓ to 1 to a temporary rust preventive composition for metal surfaces.

More specifically, the present invention relates to a temporary rust preventive composition for metal surfaces that can form a coating film with excellent rust prevention properties, alkali tax avoidance properties, machine oil resistance, and the like.

Traditionally, metal products such as steel materials have been treated with mineral oil-based rust inhibitors and dry-type rust inhibitors to prevent rust, damage, and contamination during handling, storage, and processing. Anti-caking agents, crystalline viscous oils such as vaseline, and water-soluble resin-type rust inhibitors were used.

However, most of these rust preventives do not dry at all or are slow to dry, resulting in dripping or run-off of the rust preventive agent, and contamination of the working environment due to volatilization of the solvent contained. In addition, water-soluble resin-type rust inhibitors have various practical drawbacks, such as requiring a large amount of heat and a long time for drying due to water evaporation. .

By the way, on the one hand, the coating material has a non-sticky surface, there is no concern about environmental pollution, and can be cured in a short period of time.
Compositions curable with active energy rays have been proposed.

However, conventional active energy ray-curable compositions generally have low adhesion to metals, are difficult to remove with alkaline coatings, and are susceptible to machine oil and other deposits adhering to the object. It has the disadvantage that it has a tendency to be easily contaminated and, therefore, cannot fully exhibit its coating film performance.

However, conventional active energy ray-curable compositions have a problem in that the working width of the actual coating line is very narrow, and in addition, they are very expensive. In view of the various problems mentioned above, Kinoe Akiyoshi et al. arrived at the present invention after much effort.

Therefore, the present invention provides a material that has good adhesion to metals, excellent rust prevention and alkaline film removability, and also has excellent applicability to surfaces to which machine oil and the like are attached (prevention of repelling).
The purpose is to provide a temporary rust-preventing compacted product.

That is, the present invention provides (a) an acid value of 10 that can be cured by active energy rays;
~60 unsaturated radical anti-Lf-resin and optionally unsaturated radical-reactive monomer...
・・・・・・・・・・・・ To 6 0・ 9 0 η[
Alkyd resin with an oil length of 45% or more and an acid value of 10 to 20...
・・・・・・・・・ 10〜ao! ! The present invention relates to a temporary rust preventive composition for metal surfaces, which can be removed by an alkaline aqueous solution consisting of t%.

The above-mentioned "unsaturated radical-reactive resin" used in the present invention is a conjugative polymer set or oligomer having an acid value of 10 to 60 that loses unsaturated bond groups in the resin.

Examples of such resins include commercially available ultraviolet curing or radiation curing epoxy resins, unsaturated urethane resins, unsaturated polyester resins, etc., which may be used as they are in the present invention. 〇Specifically, it is not
As the 1-wa polyester resin, for example, Nippon Gosei Kagaku 1
Part name manufactured by Kuwa Co., Ltd. such as Goselac UV-100; unsaturated acrylic resin manufactured by Shin Nakamura Chemical Co., Ltd. IJ product name Panaresin DR-004 etc.; unsaturated epoxy resin manufactured by Nippon Ubica 0 Vermilion) wound surface product name Yupica Coat EX900
4. AC3301, thin layer chemical (Tama) part name UV-2
25, etc.: Examples of the unsaturated urethane resin include Dainippon Ink & Chemicals Co., Ltd.'s wound surface product name Unidic 17-.

By the way, if the unsaturated radical-reactive resin of the invention has an acid value of less than 10, it will be difficult to remove the film using an alkaline aqueous solution. Conversely, when the acid value exceeds 60, the rust prevention properties of the coating film decrease.

Therefore, neither case is favorable.

In the present invention, "active energy rays" refer to ultraviolet rays from high-pressure mercury lamps, metal halide lamps, xenon lamps, X-rays, alpha rays, electronic radiation, and the like.

In the 11 compositions of the present invention, the above-mentioned unsaturated radical-reactive H# fat can be used as is. Unsaturated tll radical-reactive monomers such as monomers may be mixed if necessary. Examples of such monomers include monomers having at least one or more unsaturated groups in the molecule, such as (i) (meth) Examples include acryloyl group-containing monomers, ←) aromatic vinyl group-containing monomers, and (c) aliphatic vinyl group-containing monomers.

To be more specific, examples of 0) include hydroxyl group-containing particles such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; methoxyethyl (meth)acrylate and ethoxyethyl Ether compounds of the above hydroxyl group-containing photomer such as (meth)acrylate, tetrahydrofurfuryl acrylate and alkyl alcohol or steel-like alkyl alcohol = methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, Ester compounds of (meth)acrylic acid and alkyl alcohol such as ne-quaternary glycol di(meth)acryle-1-1i-6 hexanediol di(meth)acrylate and trimethylolpropane tri(meth)acrylate; mono( 2-hydroxyethyl acrylate) acid phosphate, mono(2
Examples include phosphoric acid esters of acrylic acid or methacrylic acid containing a hydroxyl group, such as -hydroxyethyl methacrylate) acid phosphate and di(2-hydroxyethyl acrylate) acid phosphate.

Examples of (b) include styrene, vinyltoluene, and the like.

Furthermore, examples of the above-mentioned compounds include vinyl acetate, vinylidene chloride, and the like.

These may be used alone or as a mixture of two or more.

Next, the "alkyd resin" used in the composition of the present invention includes oils such as castor oil, cottonseed oil, dehydrated castor oil, linseed oil, safflower oil, soybean oil, and tung oil; fatty acids such as ethylene glycol; Polyhydric alcohols such as , propylene glycol, pentaerythritol, glycerin, trimethylol deronon, quaternary glycol, etc.; maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, etc. The saturated resin is a resin obtained by esterifying an unsaturated polycarboxylic acid or its acid solution at a molecular weight of about 150 to 2,800 in accordance with a conventional method.

The alkyd resin has an oil length of about 45% seri,
And the acid curve is for 1 nail of about 10-5u.

In the case where the oil length is as high as 45%, the viscosity of the composition is high, the adhesion is poor, and the applicability to mechanical curved surfaces is reduced. ``Also, if the acid value is less than 10, the deodorizing property is poor. vice versa,
If the acid value exceeds 60, the rust prevention properties of the coating film will deteriorate. Therefore, it is good in both cases.

In the composition of the present invention, (a) is an ingredient; ii
The radical reacting resin and the radical reacting monomer and the alkyd resin as component (b) have a content of 60 to 90% by weight, preferably 70 to 80% by weight, of the former. The latter is 10~4o! [5e, preferably 20~
The rate shall be 30% blasphemy.

If the proportion of the alkyd resin is less than 10 mP% in the above ratio, the applicability to mechanically curved surfaces will decrease and the price of the composition will also increase. On the other hand, if it exceeds 40M%, the drying properties immediately after irradiation with active energy rays will be poor and the blocking resistance will be significantly reduced. Therefore, either case is not good.

Composition t of the present invention has the above-mentioned (al component) and (b) ff component as basic components, and can sufficiently achieve various objects of the present invention as it is. However, the composition is irradiated with active energy rays. After that, in order to further harden and dry the alkyd resin, a metal dryer (for example, organic acids such as naphthenic acid and octenoic acid, metals such as lead, cobalt, manganese, and zinc), which is normally used for alkyd resins that dry at room temperature, is used. One type or a mixture of two or more types of salts may be added and mixed in a proportion of 0.1 to 5 mol of salt to the component (b).

Particularly when the composition of the present invention is used as an ultraviolet curable composition, known photosensitizers such as C, henzin, pentwin methyl ether, pentwin isozoropyl ether, pentwin, benzophenone, etc. , anthraquinone, naphthoquinone, chloranthraquinone, tetramethylthiuram disulfide, diphenyl disulfide, 2.
One type or a mixture of three or more of 2-jetoxyacetophenone, penzoylno-9-oxide, azobisisobutyronitrile, 2.2-azobispropane, etc.
wood r3. +1 fJiJ composition, about 0.0
Add and mix 1 degree of W11 to 5 to 5 layers 9.

Furthermore, in addition to the above-mentioned ingredients, the monthly composition of the present invention may also contain, if necessary, extender pigments such as talc, calcium carbonate, and barium sulfate, nystrontium, and anticorrosion pigments such as nitrite, mineral spirits, kijirol, and triol. It is also possible to add and mix various organic acids such as dyes, machining agents, etc.

In addition, the composition of the present invention can be prepared by simply mixing the components.

The thus obtained composition d1 of the present invention, brush coating, ironing, spray coating, dipping coating, shower coating,
It is applied to the copper phase by a method such as roll coating, and then cured by irradiation with active energy rays.

The obtained coated material is treated with an alkaline aqueous solution when necessary.
It can simply be demembraned. In this case, the core material is preserved by coating with excellent rust prevention and moisture resistance.

The effects of the present invention can be summarized as follows: According to the composition of the present invention, conventional painting lines can be used up to that point. Moreover, there is no shadow @ 5 (cissing, etc.) caused by machine oil, etc., so work 1] is large. Furthermore, the cost of the composition can be reduced considerably. Furthermore, the rust prevention properties, film removability, and other properties of the coating film obtained from the composition of the present invention are comparable to those of conventional active energy curing type temporary protection 'fN compositions. Therefore, it can be said that the present invention is very useful industrially.The details of the present invention will be explained below with reference to Examples. Example 1
Part "1%" is expressed as "1 part Ii'r part" or "% by weight."

Example 1 f, v i41 urethane resin [manufactured by Dainippon Ink Chemical Co., Ltd. Part name Unidic 17 872 o f'r
? Tsukuda 127] 4oQB, 820 parts of 2-human mixidemipyl acrylate, alkyd resin (soybean oil fatty acid modified 11",
Mix 40 parts of oil length 659 with % acid value 15), mineral spirit 101i, 2 parts of Muranzoin isozorobyl apur, 0.2 part of lead dryer and 0.05 part of cobalt dryer to obtain the temporary preventive agent of the present invention. I got the Writ 41i dare.

Polishing the composition with solvent degreasing? Steel plate (o, 8X 70
X t , 5017 m), threat thickness 15-2 U
After coating to obtain a coating film, a coating film was obtained by irradiating 1α for 3 seconds at a distance of 15° with an 80 Wlm air pressure water lamp.

The results of a comparative trial run are summarized for the first rock.

Example 2 Unsaturated epoxy resin [Product name UV-
225; acid value 30] 40 parts, 10 parts of tetrahydrofurfuryl acrylate, 10 parts of trimethylolzoronof2/triacrylate, alkyd #1 (soybean oil fatty acid modified, oil length 55%, monovalent 20) 40 10 parts of mineral spirit, 2 parts of benzoin isopropyl ether, 0.2 parts of lead dryer, and 5 parts of cobalt P dryer o, o to obtain the temporary fN-resistant phosphor composition of the present invention.

After applying the same method as in Example 1 to eliminate numbness, the sample was subjected to a comparative test. The results are shown in P1.

Example 3 60 parts of unsaturated urethane resin (same as Example 1), 30 parts of 2-hydroxyethyl acrylate, 10 parts of alkyd resin (modified with soybean oil, oil length 65%, acid value 20), mineral spirit 2 parts of benzoin isobutyl ether, 3 parts of benzoin isobutyl ether, 0.5 parts of a ship dryer, and 0.05 parts of a ship dryer were mixed together in a dryer of 0.01 and 0.01 BB1 to obtain a product of Kikaimei Bo[1]. The coating film was then subjected to an injected vinegar test in the same manner as in Example 1.The results are shown in Figures 2 and 1.

Example 4 Unsaturated VPN resin [converted to Dainichi ink? engineering tac)
#Product name Unidic 16-824; Acid value 17] 60 parts, Tetravitrofurfuryl acrylate 30 parts, Alkyd resin (Afni oil fatty acid modified, Oil length 45, lθfi
ln 2 Q) I Part 0, Mineral Subiritu 1-1
0 parts of benzoin isobutyl ether, 0.05 parts of lead dryer, and 0.01 parts of manganese dryer to prepare the composition of the present invention.

Then, a coating film was obtained in the same manner as in Example gi+1, and then subjected to a scolding test.

The results are shown in Table 1.

Example 5 Unsaturated epoxy tail ) tl￥ L Japan Ubika (i
'i:) Product Name Yupika Coat E X 9 [104:
r ('r value 37) 55 parts, 2-hydroxyzolopyl acrylate L2ON1 (Furuchito 9 resin c Daiko oil fatty acid rich, oil length 65%, 11 value 15) 25 parts, mineral spirit 5 parts, benzoin iso Zoropylether 2, 5
A mixture of 0.1 part Ml, 0.1 part Ml and 0.02 part U Raman dryer was used to dry the Aa composition of the present invention.

Next, the same method as in Example 1 (after obtaining the offspring H'a, it was subjected to a comparative test 1, the results of which are summarized in the first column).

Comparative Example 1 70 parts of unsaturated urethane resin (same as Example 1), 30 parts of 2-hydroxyethyl acrylate, and 3 parts of hypenzoin isopropyl ether were mixed, and then a coating film was formed in the same manner as in Example 1. After obtaining it, it was subjected to a comparative test.

The results are shown in Table 1.

Comparative Example 2 40 parts of unsaturated urethane resin (same as Example 1), 20 parts of 2-hydroxypropyl acrylate, polyester resin face [Dainippon Ink & Chemicals Co., Ltd. Product name: Parnock DI Knee 140-70: f 1i11i5 ] 40 parts and 2 parts of benzoin isopropyl ether were mixed, and then a coating film was obtained in the same manner as in Example 1, and then subjected to a comparative test.

The results are summarized in Table 1.

Comparative Example 3 Unsaturated epoxy resin [Dainippon Ink & Chemicals Co., Ltd., product name Unidic V-5502: acid value 3] 6Q HIJ
% 2-Hydrogiene acrylate-1.20 parts,
20 parts of alkyd resin (same as Example 5), 2.5 m% mineral spirit, 0.1 part of lead dryer, 0 manganese dryer
．． After mixing 0.02 parts and obtaining an imperial pancreas in the same manner as in Example 1, it was subjected to a comparative test.

The results are summarized in Table 1.

Comparative example 4 Unsaturated epoxy resin (same as real 1j14 1i 2) 4
0 parts, 2-hydroxyethyl acrylate 10 parts, alkyd resin (same as Example 8) 15) 50 parts, mineral spirit 10 parts, benzoin isopropyl ether 1.5
part, lead r dryer 0.25 group, manganese dryer 0.
After mixing 0.05 parts of cobalt dryer and 0.05 parts of cobalt dryer, a coating film was obtained in the same manner as in Example 1, and then subjected to a comparison test.

The P and LP are summarized in Table 1.

Ratio Example 5: 60 parts of unsaturated urethane resin (same as Example 2), 15 parts of 2-hydroxyethyl acrylate, 25 parts of alkyd resin (modified with soybean oil fatty acid, oil length 65%, acid value 20),
5 parts of mineral spirit, 2.5 parts of benzoin isopropyl ether, 0.15 parts of lead dryer and 0.02 part of manganese dryer were mixed uniformly, and then Example 1
He obtained a coating film in the same manner and submitted it for comparative examination.

The results are shown in Table 1.

Comparison f++ 6 70 parts of unsaturated epoxy resin [Nihon Ubika (good) wound surface product name Upika Coat AC3301; acid value 90), 20 parts of 2-hydroxyethyl acrylate, alkyd resin (Example 3)
10 parts of mineral spirit, 2 parts of benzoin isopropyl ether, 0.05 part of a ship's dryer, and 0.01 part of a man's dryer, and then coated in the same manner as in Example 1. It was then subjected to a comparative test.The results are shown in the first rock.

Comparative Example 7 55 parts of unsaturated epoxy resin (same as Example 5), 20 parts of 2-hydroxypropyl acrylate, alkyd resin (
25 parts of soybean oil fat tw modified, oil length 65%, acid value 40),
5 parts of mineral spirit, 2.5ttB of benzoin isopropyl ether, 0.15 parts of MP Lye-Y and 0.02 parts of manganese dryer were mixed, and then a coating film was prepared in the same manner as in Example 1 (comparative test after soaking). Served.

The results are shown in the first column.

Example 8: 60 parts of unsaturated urethane fat (same as Example 1), 20 parts of tetrahydrofurfuryl acrylate, alkyd (equipment (soybean oil J finger rib acid denatured, oil length 55, acid value 5) 20 parts 1 part, mineral spirit 5 parts, benzoinpropyl ether 2.5 parts, lead dryer 0.1 part and manganese dryer Tested.

The results are summarized in the first article.

From the above comparative test results, it is clear that the composition of the present invention has excellent storage stability, as well as excellent applicability to squid oil-adhered surfaces.
(It can be seen that the rust prevention, water resistance, and film removability of M11 or above are also very excellent.

On the other hand, compositions outside the scope of the present invention have poor storage stability, poor applicability to mechanical oil surfaces, poor rust prevention properties of coating films, etc.
Either water resistance or film removability was extremely poor, and therefore it could not be put to practical use.

11r Permit Applicant Dainippon Nuri Old Co., Ltd. Procedure Supplement tE f! 1. Indication of the case 1982 Patent Application No. 17 ++ 9
! l f1 Bow 2, Title of the invention: Temporary anti-rust composition for metal surfaces 3, Relationship with the case of the person making the amendment Applicant name (332) Dainippon Toyo Co., Ltd. 4, Agent 5, Date of amendment order Imma 1 Departure

Claims (1)

[Claims] +11 (a) Can be cured by active energy rays, but
Unsaturated radically reactive resin with an acid value of 10 to 60 and optionally an unsaturated radically reactive monomer...
・・・・・・・・・60~90% (b) Oil length 4
Alkyd resin with a content of 5% or more and an acid value of 10 to 2 degrees...
... Old... Temporary antirust composition for the surface of gold Ij4 that can be removed by using an alkaline aqueous solution containing 10 to 40% heavy carbon.