JPS63319081A - Composite coated film for concrete protection - Google Patents

Abstract

PURPOSE:To provide the high-degree crack following property and high shielding property for concrete to the title coated film by forming the film from a matrix with a dry coated film having >=50% elongation and a surface-treated cloth consisting of the fiber having >=20% elongation and having >=15kg/10mm tensile strength. CONSTITUTION:The concrete protecting composite coated film is formed from (a) a matrix (e.g., urethane rubber, acrylic rubber, etc.) with the dry coated film having >=50% elongation and (b) a cloth consisting of the fiber having >=20% elongation and surface-treated (e.g., plasma treatment, treatment with an adhesive, etc.) to improve the adhesive property to the matrix. For example, a concrete layer 1 is surface-treated with a primer, a putty, etc., coated with the matrix (a), laminated with the cloth (b), and further coated with the matrix (a) to form a coated film. In addition, the matrix (a) and the cloth (b) can be further coated.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a high-barrier composite coating, and more specifically, it has excellent flexibility, tensile strength, and adhesion, and particularly when applied to external walls such as concrete, has a high degree of The present invention relates to a composite coating film that has crack followability and exhibits high barrier properties.

[Prior art] Various types of coatings have been tried on concrete exterior walls to prevent their deterioration. In particular, coatings using polymeric epoxy resin as a vehicle have excellent barrier properties against water, chlorine ions, carbon dioxide gas, etc. Used a lot. However, this method is not fully satisfied because it is not compatible with obtaining a tough, high-barrier coating film and the ability of the coating film to conform to cracks in concrete walls, etc. On the other hand, various composite coating films or laminates that combine a matrix and a fabric have been proposed in order to impart flexibility and strength to the coating film (for example, Japanese Patent Publication No. 51-720
No. 0, JP-A-49-1161122, JP-A No. 53-136
No. 321, No. 54-160021, No. 55-4467
number, etc.). However, all of these are intended for waterproofing concrete walls, etc., and have poor adhesion between the matrix and fabric, and are not designed to prevent peeling, so they have poor long-term barrier properties, and are not suitable for wall construction of concrete structures. It's inappropriate. There have also been proposals using glass fiber as a reinforcing material, but glass fiber does not have the ability to follow cracks.
The insulation effect is significantly reduced due to cracks in the concrete, and because the nodule strength is low, durability is low at corners and protrusions, and neither is a high insulation composite coating for walls such as concrete. I didn't get it.

Problems to be Solved by the Invention The purpose of the present invention is to prevent deterioration factors such as water and chlorine ions from entering into the interior of concrete structures due to cracks caused by expansion and contraction, and to prevent the spalling of defective concrete. It is an object of the present invention to obtain a coating film with high barrier properties suitable for the purpose of preventing deterioration of exterior walls, which is effective for the purpose of preventing deterioration of exterior walls and has excellent flexibility, tensile strength, and adhesion.

Means for Solving the Problems According to the present invention, the above object is to increase the elongation rate of the dry coating film to 50%.
The above-mentioned high-barrier matrix, and a fabric made of fibers with an elongation rate of 20% or more, with a tensile strength of 15 kg/10+ nm or more, and which has been subjected to a physical or chemical surface treatment to improve adhesion with the matrix. This is achieved with a concrete protective composite coating consisting of:

In the present invention, the matrix is composed of a high-barrier resin composition, and the elongation rate of the dry coating film mainly composed of modified epoxy resin, urethane rubber, acrylic rubber, silicone rubber, styrene-butadiene rubber, chloroprene rubber, neoprene rubber, etc. 50% or more resin compositions, and all of these have so-called barrier properties, in which the effect as a barrier film lasts for a long time without causing cracks or pinholes in the composite coating film due to cracks in the coated object. It has excellent barrier properties against moisture, chlorine ions, carbon dioxide gas, etc., and is suitably used for the purposes of the present invention. In particular, a patent application filed separately by the applicant in 1983
1-218383 with a molecular weight of 2,0
01) to about 10.000, a dimer acid-modified epoxy resin and/or a nitrile rubber-modified epoxy resin having an epoxy group at the end of the molecule, and an amine group per molecule.
．． A resin for a two-component epoxy paint made by combining a liquid acrylonitrile-butadiene copolymer having 7 to 3 in a ratio of 0.5 to 2.0 equivalents of active hydrogen in amino groups per equivalent of epoxy group. When using a composition, 10
It has an extremely high elongation rate of 0% or more, high barrier properties, and tensile strength, and is extremely useful for preventing concrete deterioration. A matrix material whose dry coating film has an elongation rate of less than 50% is undesirable because it lacks followability to cracks in concrete and the like. If the matrix is to be cured or dried on-site, it is preferable to use a room-temperature curing type or a room-temperature drying type; however, if a composite coating film is to be produced on line, a heat-curing type may be used. Available for use.

In the present invention, the above-mentioned matrix is used in combination with a fabric, and as a fabric, the elongation rate of the fibers is 20% or more, the tensile strength of the fabric is 15 kg/10 mm or more, and the adhesion with the matrix is good. To tighten
Must be surface treated. If the elongation rate of the fiber is less than 20%, the fabric cannot be expected to have sufficient crack followability, and the tensile strength of the fabric is 15kg/IO+lIm.
Fabrics that are less than 100% have insufficient impact resistance and tensile strength to prevent concrete walls from deteriorating or falling off. Furthermore, the fabric must be surface-treated to improve adhesion to the matrix. Surface treatments of the fabric include physical treatments such as plasma treatment, ultraviolet irradiation, and radiation irradiation, or chemical treatments, and such surface treatments are used to further improve matrix adhesion. Chemical treatments for fabrics include treatment with adhesive liquid to improve adhesion with the matrix, etching treatment with chemicals, etc., and these chemical treatments can also be applied to the fabric used in the composite coating film of the present invention. It is. In particular, adhesive liquids include liquids containing synthetic resin adhesives such as epoxy, phenol, isocyanate, or urethane, or these synthetic resin adhesives and natural rubber latex, styrene-butadiene copolymer rubber latex, acrylonitrile-butadiene copolymer. A mixed solution with synthetic rubber latex such as latex is preferred. Further, it is preferable that the fabric be dried and heat treated after being treated with the above-mentioned adhesive liquid. Using these adhesive liquids increases the bending stiffness of the fabric, improving workability on site, and also prevents fraying at the cut end of the fabric, increasing work efficiency on site. be.

By using such a surface-treated fabric, we can solve the problem of adhesion with the matrix, and by using a stretchy fabric, we can obtain a suitable balance of flexibility, tensile strength, and adhesion, which greatly improves warpage followability. Not only does the matrix and the reinforcing fabric work together to provide excellent impact resistance and thermal expansion and contraction resistance, it also achieves the effect of preventing concrete pieces from falling off, which was previously unobtainable, and the effect lasts for a long time. It is maintained for a long time. The type of fabric is not limited and any fabric can be used as long as the elongation rate and tensile strength of the fabric are within the above-mentioned ranges, and the tensile strength of the composite coating film is usually 500 kg/
cm2 or more and elongation rate of 20% or more can be obtained,
Although the purpose can be fully achieved, typical fabrics include nylon, acrylic, vinylon, polyester,
These include synthetic fibers such as polypropylene, polyethylene, and aramid, as well as woven, knitted, and nonwoven fabrics made of a mixture of these fibers.Among these synthetic fibers, nylon 6,
Nylon fabrics such as nylon 66 are preferred.

The composite coating film according to the present invention can be obtained by applying a matrix directly to a concrete wall surface or after performing a base treatment such as a primer or putty as desired, and then laminating a fabric.
Furthermore, it is formed by applying a matrix, but if desired, the fabric and matrix are applied in layers and finally the composite horizontal relic is hardened, or the fabric impregnated with the matrix is applied to the concrete wall and hardened. or, if desired, apply an appropriate intermediate coating between these composite coatings, or apply a topcoat on the composite coating, by any method known to those skilled in the art (see Figures 1 to 5). ). Concrete exterior wall structures with a composite coating film formed on the wall surface in this way exhibit a high degree of barrier performance, crack followability, and debris peeling prevention effects, making them extremely useful for preventing deterioration of concrete structures, etc. In particular, it is suitable for concrete structures such as road bridges that are continuously subjected to repeated stress.

The present invention will be explained below with reference to Examples.

Reference example 1: Using 840 denier nylon 6 multifilament yarn with a fabric weaving elongation rate of 23%, the tensile strength is 43 kg/10 m in length.
A plain weave fabric with a width of 41 kg/10 a and 11 kg was woven.

Reference Example 2: Preparation of surface-treated fabric The fabric woven in Reference Example 1 was mixed with 100 parts by weight of pentaglycidyl ether epoxy resin, 80 parts by weight of styrene-butadiene rubber latex with a solid content of 40%, and 10% N.
The fabric was immersed in an adhesive solution consisting of 20 parts by weight of aOH aqueous solution and 300 parts by weight of water, squeezed with a mangle so that the adhesive solution uniformly impregnated and adhered to the fabric, then dried at a temperature of 110"C, and then dried at a temperature of 180"C. A heat treatment was performed for 30 seconds to produce a nylon 6 fabric surface-treated with an adhesive with an adhesive solid content adhesion rate of 4.5% based on the weight of the fabric.

Reference Example 3: Preparation of Surface-treated Fabric The same process as in Reference Example 2 was carried out to produce a surface-treated nylon 6 fabric with an adhesive having an adhesive solid content adhesion rate of 6.4% based on the weight of the fabric.

Reference Example 4: Preparation of surface-treated fabric The fabric woven in Reference Example 1 was prepared by mixing 50 parts by weight of an aqueous dispersion of polyester urethane resin with a solid content of 20 parts by weight, and 0.15 parts by weight of a urethane resin curing catalyst. The fabric was dipped in adhesive solution, squeezed with a mangle so that the adhesive solution was evenly impregnated and adhered to the fabric, then dried at +10°C, and then heat-treated at a temperature of 150°C for 60 seconds, so that the adhesive solid content adhesion rate was reduced to the fabric. A nylon 6 fabric surface-treated with 0.4% adhesive based on the weight of was prepared.

Reference Example 5: Preparation of Surface-treated Fabric The same process as in Reference Example 4 was carried out to produce a surface-treated nylon 6 fabric with an adhesive having an adhesive solid content adhesion rate of 0.6% based on the weight of the fabric.

Reference Example 6: Production of surface-treated fabric The fabric produced in Reference Example 1 was subjected to low-temperature plasma treatment under the following conditions to produce a plasma-surface-treated nylon 6 fabric.

Gas used: Argon treatment pressure: 0.7 Torr Frequency: 110 KHz Applied voltage: 2.5 KV Treatment time: 15 seconds each on front and back Example 1 23 parts by weight of epoxy resin modified with dimer acid, liquid acrylonitrile-butadiene copolymer having amino groups A matrix with an elongation rate of 250%, consisting of 18 parts by weight of the combined material, 40 parts by weight of filler, 0.4 parts by weight of additives, and 19 parts by weight of solvent, was applied to a polypropylene plate, and the material was prepared in Reference Example 2 before curing and drying. A surface-treated fabric was attached, pressed well to impregnate it, and then a matrix was applied so that the fabric was completely covered, and the matrix was cured and dried to produce a free film of the composite coating.

Zero Span Tension-Strategy (1 bow to the shadow) Instead of the above polypropylene board, a slate board for zero span tension testing is used to form a composite coating film in the same manner, and a composite coating coated slate board (see reference diagram) is created. It was then used for a zero span tension test.

Examples 2 to 5 Using the same method as in Example 1, but replacing only the surface-treated fabric of Reference Example 2 with the fabric shown in Table 1, a free film of a composite coating film and a test plate for zero span tension test were prepared. did.

(Margins below) Table 1 Example 6 A polypropylene plate was prepared by using a matrix with an elongation rate of 200% consisting of 14 parts by weight of polyether urethane resin, 4 parts by weight of amine compound, 50 parts by weight of incyanate prepolymer, and 32 parts by weight of filler. Before it hardens and dries, apply the surface-treated fabric prepared in Reference Example 5, press it well to impregnate it, then apply the matrix so that the fabric is completely covered, and let it harden and dry to form a composite coating. A free film of the membrane was prepared.

A slate plate for the zero span tension test was used in place of the polypropylene plate for zero span thinning, and a composite coating film was formed in the same manner to produce a composite coating coated slate plate, which was used for the zero span tension test.

Comparative Example 1 The same method as in Example 2 was used, except that only the matrix used in Example 2 was used as an intermediate coating for Toughguard E cloth (a product of Nippon Paint Co., Ltd., an adhesive for glass cloth made of bisphenol A type epoxy resin and modified polyamine, A free film of the composite coating film and a test plate for zero span tension test, that is, a slate plate coated with the composite coating film, were prepared instead of the dried coating film (elongation rate of 3%).

Comparative Example 2 Using the same method as in Example 2, but replacing only the surface-treated fabric of Reference Example 3 with glass cloth (fiber elongation rate: 3%, cloth tensile strength: 33 kg/I Omm), a composite coating film was prepared. Test plates for free film and zero span tension tests, namely composite coated slate plates, were prepared.

Comparative Example 3 The same method as in Example 2 was used, except that only the surface-treated fabric of Reference Example 3 was treated with vinylidene chloride cloth (fiber elongation rate was 37%,
(The tensile strength of the cloth was 15 kg/10 mm.

Comparative Example 4 Using the same method as Example 2, but using only the surface-treated fabric of Reference Example 3 with an elongation rate of 23%, using 840 denier nylon 6 multifilament yarn, and having a tensile strength of 43 kg in the longitudinal direction.
/ 15I! Instead of the plain weave of 1 m, width 41 kg/10 cities), a free film of the composite coating and a test plate for zero span tension test, that is, a slate plate coated with the composite coating were prepared.

The free films of Examples 1 to 6 and Comparative Examples 1 to 4 were tested for tensile strength, elongation, and adhesion, and the composite coated slate plates were tested for zero span tension. The results are shown in Table 2.

(Left below) (Note) Tensile strength (kg/Ω2): According to JIS-
631) Method based on 1 (however, using No. 1 dumbbells). The larger this value is, the greater the effect of preventing the composite coating from peeling.

$2...Elongation rate (%): Method based on JIS-6301.

(・However, use No. 1 dumbbells.) The larger this value is, the
It also has great crack followability.

I3...Adhesiveness: When both sides of the free film of the composite coating film are pulled, the tensile strength is 25 kg/cm" or more and there is no peeling at the fabric interface. ◎ If there is slight peeling, ○, 25%. Those with peeling above were marked as x (those with a tensile strength of less than 25 kg/Cl112 were all marked as x).

$4...Zero span tension (in): of the object to be coated,
A test method to quantify crack tracking performance. As shown in the reference drawing, a composite film was formed on a slate plate with a length of 151 cm, a width of 7 cm, and a thickness of 0.5 mm (with a groove on one side of the center part), and after it had sufficiently cured, the test specimen was A crack is made along the groove, and a tensile test is performed using a testing machine according to JIS-9-7721. The point at which a pinhole occurs in the film, the point at which the film is cut, and the magnitude of each elongation are indicated. The greater the elongation without pinholes, the greater the zero span tension. This allows us to know the crack followability, barrier properties, etc. of the composite coating film.

[Brief explanation of drawings]

Figures 1 to 5 illustrate cross-sectional views of concrete surfaces protected by the composite coating film of the present invention. In the case of two-time application, Figure 3 shows that an intermediate coating is formed between the first and second composite coating, and a top coat is applied after the second composite coating is applied. Figure 4 shows the case where a composite coating film is applied once and then a coating film is formed using a top coat.
FIG. 5 shows a cross-sectional view when a coating film is formed using an intermediate coating between the first construction and the second construction of the composite coating film. In the figure, 1 indicates a concrete layer, a indicates a matrix, b indicates a surface-treated synthetic fiber cloth, C indicates a coating film formed by an intermediate coating, and d indicates a coating film formed by a top coating. Further, reference figure (A) is a slope view of a specimen coated with a composite coating film for zero span tension tests 1 to 1 carried out for each of the examples and comparative examples, and reference figure (17) is a cross-sectional view. In the reference diagram, A is the specimen, B
C indicates a composite coating, and C indicates a crack in the specimen. patent application agent

Claims (3)

[Claims] (1) A high-barrier matrix with a dry coating elongation of 50% or more and fibers with an elongation of 20% or more, with a tensile strength of 15kg/10mm or more, and physical properties to improve adhesion with the matrix. A composite coating film for concrete protection consisting of a fabric that has been subjected to surface treatment or chemical treatment. (2) The composite coating film according to claim 1, wherein the matrix is a resin composition containing a modified epoxy resin, urethane rubber, acrylic rubber, silicone rubber, styrene-butadiene rubber, chloroprene rubber, or neoprene rubber as a main component. (3) The composite coating film according to claim 2, wherein the modified epoxy resin is a dimer acid-modified epoxy resin and/or a nitrile rubber-modified epoxy resin.