JPH0776277B2 - Prepreg coating method and prepreg coating material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a prepreg coating method for applying a heavy anticorrosion coating to a wet and dry alternating part of a marine steel structure and the like, and a prepreg coating material used therefor.

[Conventional technology and problems] Conventionally, tar epoxy resin paints, thick film polyurethane paints, thick film epoxy resin paints, etc. have been used as anticorrosion coatings for submerged parts, wet and dry alternating parts, and splash parts of marine steel structures. ing.

However, although the tar epoxy resin coating has a relatively good anticorrosion property, it is extremely inferior in impact resistance, and as a result, the coating film is easily damaged and the anticorrosion property is likely to be deteriorated. Further, the strength and hardness of the coating film are low, and the steel structure is liable to be broken during transportation or installation of the steel structure, and tar has odor, carcinogenicity, and other sanitary problems from the viewpoint of composition, which is not preferable.

Further, the thick-film polyurethane coating is inferior in terms of anticorrosion property and coating workability, and also has a problem that it lacks reliability in adhesion.

Further, the thick film epoxy resin coating composition has the problems of poor workability and impact resistance, and it is difficult to obtain a uniform thick film.

[Means for Solving Problems] The inventors of the present invention have conducted extensive studies in order to solve the problems found in the conventional anticorrosion coatings of marine steel structures, and as a result, have developed a novel method using a specific prepreg material. It was found that these problems can be solved by using various coating methods, and the present invention has been completed.

Thus, according to the present invention, (i) the surface of the steel material is coated with the epoxy resin primer composition that is reactively curable at room temperature, and the initial adhesive force with the following prepreg coating layer as the upper layer is 0.5 g / cm or more. To form an adhesive primer layer, and (ii) by impregnating the fiber processing reinforcement material with a liquid resin composition that is reaction-curable at room temperature on the adhesive primer layer, a plastic resin that is permanently deformable is obtained. A prepreg coating layer which is cured until it becomes a solid state that develops, and then (iii) the adhesive primer layer and both layers of the prepreg coating layer are completely adhered and cured. A heavy-duty protective coating prepared by impregnating a fiber-reinforced reinforcing material that has a dimensional spread with a liquid resin composition that is curable at room temperature to a certain thickness, and then curing it until it becomes a solid that exhibits permanent deformable plasticity. Use prepreg coating material is provided.

Hereinafter, the present invention will be specifically described.

A conventionally known two-pack type epoxy resin composition is used as a reaction-curable epoxy resin-based primer composition for forming an adhesive primer layer in the method of the present invention. Examples of the epoxy resin include bisphenol A
Type, bisphenol F type, bisphenol AD type, novolac type and the like, and as the curing agent, for example, modified amine type curing agent such as modified aliphatic amine, modified aromatic amine or thiol type curing agent is used.

The above-mentioned adhesive primer composition is generally applied directly to the surface of a steel material in a dry film thickness range of 10 to 100 μm and has an initial adhesive force of 0.5 g / c with a prepreg coating layer to be pasted as an upper layer.
The adhesive primer layer is obtained by reacting and curing at room temperature until it becomes m or more. Here, if the cured state of the primer layer deviates from the above conditions, that is, if the drying / curing of the primer layer does not proceed much, or if it has advanced too much,
The initial adhesion with the prepreg coating layer is insufficient, and there are problems such as displacement during sticking work, slipping off of the prepreg coating layer on a vertical surface, and peeling off of the prepreg coating layer on a curved surface. The adhesive primer composition is applied → dried →
Long-lasting tackiness in the curing process, reacting and curing at room temperature,
It is characterized by excellent adhesion and corrosion resistance to the steel base and the upper prepreg coating layer.

When it is necessary to further improve the strength and anticorrosion properties of the primer layer, it can be achieved by dispersing various known fillers such as flake pigments and rust preventive pigments in the primer composition.

Next, the heavy-duty anti-corrosion prepreg coating material that is bonded to the above-mentioned adhesive primer layer to form a prepreg coating layer is a fiber processing reinforcing material having a two-dimensional spread (hereinafter,
A "surface reinforcement" is impregnated with a liquid reaction curable liquid resin composition at room temperature to a certain thickness within a range of 0.5 to 5 mm to form a solid form that exhibits a permanently deformable plasticizer. It is a cured product.

The above-mentioned sheet-like reinforcing material has a role of helping the uniform film thickness moldability of the reaction curable liquid resin composition, preventing the coating film from being damaged by the impact of drifting matter in the ocean, and reinforcing the coating film and improving the bending resistance. Complete

As the material of the sheet-like reinforcing material, conventionally known organic fibers and inorganic fibers are used. Examples of the organic fibers include natural fibers such as cotton, hemp, wool, and silk, and synthetic fibers such as acetate, acrylic, polyether, polyurethane, polyolefin, polyamide, and polyimide, and examples of the inorganic fibers include glass, carbon·
Examples thereof include fibers such as boron, alumina, silicon carbide, silicon nitride, and stainless steel. These are used in the form of mesh-shaped molded products such as woven fabrics, non-woven fabrics, papers, mats and the like processed from long fibers or short fibers, and porous films and sheets.

The reaction curable liquid resin composition impregnated into the planar reinforcing material,
The main component is a two-component epoxy, polyurethane, an unsaturated polyester resin, etc. that is reactively cured at room temperature.

As the two-pack type epoxy resin composition, bisphenol A type, bisphenol F type, bisphenol AD type, novolac type such as phenol and cresol, modified epoxy resin such as acrylate modified, urethane modified, and polybutadiene rubber modified can be used. Has a low viscosity, excellent adhesion to the substrate, anticorrosion, impact resistance, burnability, and other characteristics.

These epoxy resins are cured by reaction with an amine-based curing agent having characteristics such as impact resistance, burnability, and water resistance.
For example, various known amine-based curing agents such as modified aliphatic amines, modified aromatic amines, heterocyclic diamines, polyamine Mannich derivatives, and aliphatic polyamine Michael adducts are used.

The polyurethane resin composition is solvent-free as a polyol component and is excellent in impact resistance, stress relaxation property, abrasion resistance, weather resistance, water resistance and the like, for example, alkoxylated bisphenol A.
Castor oil fatty acid ester, epoxy modified polyol, etc. are used, and as the isocyanate-based curing agent component, monomers such as tolylene diisocyanate, diphenylmethane diisocyanate, and meta-xylene diisocyanate,
Alternatively, it is a mixture of multimers such as biuret, allophanate, isocyanurate, and urethane adduct.

The unsaturated polyester-based resin composition includes an unsaturated dibasic acid such as (anhydrous) maleic acid, fumaric acid, and itaconic acid,
Polyester or acrylic acid or methacrylic acid mainly composed of polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerin and propylene glycol, and partially mixed with saturated polybasic acids such as phthalic anhydride, isophthalic acid and adipic acid. Unsaturated acids such as acids,
Vinyl ester resin made by reacting epoxy resin,
It is dissolved in vinyl monomers such as styrene, vinyltoluene, and acrylic ester.

In order to further improve the impact resistance, abrasion resistance, anticorrosion property, stress relaxation property and the like of the above-mentioned reaction curable liquid resin composition, various known fillers are blended as necessary.

For example, as the fine powder filler, modified polyethylene fine powder, crosslinked phenol resin fine powder, polyphenylene sulfide fine powder, phenoxy resin fine powder, and the like, and as balloon filler, glass balloon, shirasu balloon, plastic balloon, etc. Examples of the filler include titanium flakes, aluminum flakes, stainless flakes, chrome flakes, and mica flakes. Examples of extender pigments include talc, mica, tankar, barita, and silica.

The above-mentioned reaction curable liquid resin composition is impregnated into the sheet-like reinforcing material, but a low viscosity is desirable for impregnating workability, and it is desirable that the amount of solvent is small from the viewpoint of securing the film thickness and safety and hygiene. . Furthermore, it is also possible to use a low-viscosity reactive or non-reactive diluent, if necessary, such as during low temperature operation.

Examples of the impregnation method include the following methods.

(1) The impregnated resin composition is cast to a certain thickness, and the sheet-like reinforcing material is sunk from above.

(2) The sheet-like reinforcing material is immersed in a container filled with the impregnated resin composition, and an excess resin composition is scraped off and pulled up.

(3) The sheet-like reinforcing material is sandwiched between two pieces of release paper, the impregnating resin composition is filled therebetween, and two rolls having a certain clearance are passed through while squeezing.

As described above, the sheet-like reinforcing material is impregnated with the impregnated resin composition, and the mixture is reacted and cured at room temperature, and then cured until it becomes a solid that exhibits permanent deformable plasticity to prepare a prepreg coating material. The prepreg coating material is attached to the adhesive primer layer, but the prepreg coating material needs to be in the above-described cured state. If this is not the case, for example, when the liquid is not cured so much, the attaching work is very difficult, and further, the occurrence of distortion due to the volatilization of the solvent or the curing of the resin after attaching becomes large, and the coating system The durability cannot be expected, and conversely, if the hardening proceeds too much, the plasticity of the prepreg is lost and it becomes difficult to cover the steel structure other than the plan shape.

[Operation and effect] In the present invention, a completely cured film obtained by laminating a prepreg coating material on an adhesive primer layer and completely adhering and curing it can be used as a heavy anticorrosion coating layer, and its function is: (I) Impact resistance and toughness (ii) Barrier of steel corrosion factors (O ₂ , H ₂ O, Cl, etc.) (iii) Excellent adhesion to the lower layer (primer), and lower corrosion protection layer (primer) The layer () has the effect of protecting it from the environment, and (iv) the effects of (i) to (iii) above are also excellent in long-term durability.

[Examples] Hereinafter, the present invention will be specifically described based on Examples. "Parts" in the examples means "parts by weight".

Examples 1 to 4 The coating primer composition shown in Table 1 was applied to a steel material surface at 50 μm.
(Dry film thickness), dry at room temperature until the initial adhesive strength with the prepreg layer is 1g / cm, and then apply the 1.5mm thick prepreg coating material shown in Table-1 They were combined and completely cured. The completely cured film thus obtained was subjected to the performance tests shown in Table-1.

Comparative Examples 1 to 3 Instead of the prepreg coating, the paints manufactured by Kansai Paint Co., Ltd. shown in Table 1 were used.

Note) A: Araldite XPY-307 (Novolak type epoxy resin: Nippon Ciba Geigy) B: Araldite PY-302-2 (Bisphenol A / F epoxy resin: Nippon Ciba Geigy) C: Epicron 803 (Bisphenol F type epoxy resin) :
Dainippon Ink and Chemicals) D: Epiclon 5300-70 (Bisphenol A type epoxy resin: Dainippon Ink and Chemicals) E: URIC AC-003 (Alkoxylated bisphenol A and castor oil fatty ester: Ito Oil) I: DSK NS-170 ( Modified amine MXDA-AN; Henkel white water) II: Fujicure 5405 (polyamine Mannich derivative:
Fuji Kasei) III: Permapol P-780 (polyether urethane thiol: Nippon Catalysis) IV: Tight Clar SK-900 FCB (modified aliphatic polyamine: Daito Sangyo) V: Hardener XB-3149 (modified polyamide: Ciba Geigy) VI: ADEKA HARDNER EH-235 (modified aliphatic amine: Asahi Denka) VII: MDI-CR 200 (Crude MDI: Mitsui Toatsu Chemicals) a: Expance1DE # 551 (Plastic balloon: Nippon Philite) b: Glass Bubbles C15 / 250 (Glass balloon: Sumitomo 3M) c: Alpaste RRA 050 (Chromium flake paste: Toyo Aluminum) d: Chop Strand Mat MC-300N (Short glass fiber mat: Nitto Boseki) e: Glass cloth WF (Glass long fiber cloth: Nitto Boseki) f: KVP-A-2 (aramid fiber paper: Daifuku paper)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C23F 11/00 G 8414-4K B29K 105: 06 B29L 9:00 (72) Inventor Kamiji Takaaki, 1-5-26 Moto-Akasaka, Minato-ku, Tokyo Incorporated company Japan Paint Industry Association (72) Inventor Tahi Nishimura 1-5-2, Moto-Akasaka, Minato-ku, Tokyo Incorporated company Japan Paint Industry Association ( 72) Inventor Shunichi Sano 1-526 Moto-Akasaka, Minato-ku, Tokyo Incorporated company Japan Paint Industry Association (72) Toru Saiga 603-2 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa 221

Claims (2)

[Claims] 1. (i) An epoxy resin primer composition which is reactively curable at room temperature is applied to the surface of a steel material and cured until the initial adhesive strength with the prepreg coating layer below, which is an upper layer, is 0.5 g / cm or more. To form an adhesive primer layer by (ii) impregnating a fiber processing reinforcement material with a liquid resin composition that is reactively curable at room temperature on the adhesive primer layer, and is a solid that exhibits permanent deformable plasticity. A prepreg coating method, which comprises bonding prepreg coating layers that have been cured until they become uniform, and then (iii) completely adhesively curing both the adhesive primer layer and the prepreg coating layer. 2. A fiber processing reinforcing material having a two-dimensional expansion is impregnated with a liquid resin composition which is reaction-curable at room temperature to a certain thickness, until a solid state which exhibits permanent deformable plasticity is obtained. Hardened heavy-duty anti-corrosion prepreg coating material.