JPH0260971A - Flame retardant elastic paint with moisture permeability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) This invention relates to a flame-retardant coating with moisture permeability used for the interior and exterior of buildings. The main subject is a new moisture-permeable/flame-retardant FL elastic paint whose coating film has moisture permeability J3 and flame retardancy and is capable of following cracks in the substrate.

(Prior art) Conventionally, waterproof multi-layer finishing coating materials (hereinafter referred to as elastic materials) have been used as coating materials that can follow cracks in the base material of non-alloy materials such as concrete and rutal. is used in Yur.

This elastic material follows the cracks that occur in the inorganic material, and by expanding and contracting the paint film, it has the function of preventing the intrusion of mountain water from the outside and protecting the building.

However, in order for this elastic material to follow ground cracks and exhibit excellent performance, it contains 40 to 70 parts (hereinafter simply referred to as parts) of resin, and the resin component is flammable. Acrylic ester emulsions, acrylic ester/sulfrene copolymer emulsions, etc., which have poor moisture permeability and moisture permeability, are used, and their TP is generally not moisture permeable, and when painted on buildings, indoor The water vapor generated condenses and condenses inside the wall, reducing insulation performance and promoting the growth of mold and moss.Furthermore, moisture concentrates on the back side of the paint, causing blistering and peeling. there were. This was particularly noticeable in cold regions as a result of frost damage. In addition, the coating film is self-combustible and meets JISA1321-1975 F.
``Flame retardant testing of interior materials and construction methods for buildings'' (hereinafter referred to as
It did not pass the flame retardant grade of the JIS standard (abbreviated as “JIS standard”).
In many cases, it is not set as a material equivalent to the base material. For this reason, as an interior material, from the above points, it is best to
It is i-shaped.

On the other hand, materials that have passed the flame retardant grade of the JIS standard are:
No. 001), inorganic sand wall-like blown square material (certified material 11 base material equivalent No. 0003), FjM sand wall-like sprayed material (certified material base equivalent No. 0004), composite decorative finishing material (certified material base material No. 0004), No. 0005), foamed fireproofing materials, and fireproofing chemicals, but these coatings are too hard to follow cracks in the base.

In addition, in order to impart flame retardancy to soft resins such as flammable acrylic ester emulsions and acrylic ester/styrene copolymer emulsions, coating materials containing 100 to 400 parts of a flame retardant such as aluminum hydroxide are used. However, the coating film has poor elongation, substrate crack followability, and alkali resistance V.
The coating film's performance is 0, but it produces smoke in the combustion test and does not pass the flame retardant grade.

(Problems to be Solved by the Invention) Therefore, the present inventor developed a new flame-retardant elastic paint with moisture permeability that overcomes the above-mentioned conventional drawbacks when painting inorganic materials such as concrete. The purpose of the present invention is to ensure that the paint film has elasticity, and that when it is applied to the base of a free material such as concrete that is likely to crack, the purpose of the present invention is to prevent cracks in the base material, such as concrete. It has conformability, can compensate for cracks, and has moisture permeability.
A flame-retardant material that can prevent indoor condensation and mold and frost damage in cold regions, has a flame-retardant coating, and passes the flame-retardant grade of the above-mentioned J[S standard. Bullet f! l
? 'nThe -f- stage of the first invention to achieve the above object is a flame-retardant acrylic ester emulsion, an ethylene/vinyl acetate/vinyl chloride copolymer emulsion with a vinyl chloride modification rate of 10 to 50%, and a vinylidene chloride modified emulsion. rate 5-5
A resin emulsion selected from the group of 0% vinylidene chloride/acrylic acid ester copolymer emulsion and yurium chloride/ethylene/acid-resistant vinyl coemulsion with a vinylidene chloride modification rate of 5 to 50%. and the acrylic ester moiety or vinyl acetate moiety has been modified by 5 to 50% of the entire resin component of the resin emulsion with an acrylic ester or methacrylic acid ester having a terminal OH2, and i-dopolymer resin emulsion with a Jd content of 30 to 70%]
14 to 70 parts by weight of one or more of these are blended, no inorganic flame retardant is blended, the elongation rate of the coating film is 50% or more, and the ability of the coating film to follow cracks in the base is 1 mm.
This is the elastic paint that is used.

The means of the second invention includes flame-retardant acrylic acid ester emulsilane and ethylene with a vinyl chloride modification rate of 10 to 50%.
A resin emulsion selected from the group of vinyl acetate/vinyl chloride copolymer emulsions, in which the acrylic ester portion or the vinyl acetate portion has a terminal 0111, is used as a resin component of the resin emulsion. 5 for the whole
・-50% modified and the resin content a is 30
~70% polymer resin emulsion, 14 to 60 parts of one or more of these, and 1 part of an inorganic flame retardant.
~14 parts is blended to produce an elastic paint with a coating film elongation rate of 50% or more and a coating film's substrate crack followability of 1 mm or more Lt'.

7 & 3 The means of the invention has a vinylidene chloride modification rate of 5-50
% of ethylene/vinyl acetate/vinylidene chloride copolymer emulsion, and vinylidene chloride/acrylic acid ester copolymer emulsion of 5% to 50% of vinylidene chloride modification, the resin emulsion comprising: The varnish portion or the vinyl acetate portion is modified by 5 to 50% of the total resin component of the resin emulsion with an acrylic ester or methacrylic acid ester having a terminal group, and the resin content is 30.~70%r A coating material is used that has a polymer resin emulsion with a substrate crack followability of 1 mm or more.

The means of the 71st invention is based on the paint using the means of the first invention, the means of the second invention, and the means of the third invention with an average particle size of 0.5.
It is said to be an elastic paint containing 1 to 30 parts of resin particles of ~50 μm.

The coating film obtained from each of the elastic paints of the first, second, third, and fourth inventions is flame retardant and has an elongation that can follow cracks in the base.

The polymer resin used in the present invention is a flame-retardant polymer resin that does not contain styrene, and more specifically, it is a flame-retardant polymer resin that has moisture permeability. Examples of the flame-retardant polymer resin include flame-retardant acrylic acid ester emulsion, ethylene/vinyl acetate/vinyl chloride copolymer emulsion with vinyl chloride modification rate of 10□-50%, vinyl chloride 1
Vinylidene chloride/acrylic acid ester copolymer emulsion with a modification rate of 5 to 50%, and a vinylidene chloride modification rate of 5
- 50% vinylidene chloride/ethylene/vinyl acetate copolymer emulsion, the acrylic ester portion or vinyl acetate portion of which has an acrylic ester or methacrylic ester having a terminal 01-1 u to form the resin of the resin emulsion. Polymer emulsions modified by 5 to 50% of the total components (coating film elongation of 50% or more, glass transition temperature of 20° C. or less) are suitable. The resin content of the resin emulsion is 30 to 70%, preferably 40 to 60%.

In the fourth invention, the resin particles used in the invention are mixed in order to improve the moisture permeability.

The resin composition can be hard or soft, and the resin particles have an average particle size of 0.5 to 50% from the viewpoint of finish quality of the coating film.
μm is the most suitable, and when the particle size is less than 0.5 μm, there is almost no difference in moisture permeability between when it is added and when it is not, and no effect is observed. If it exceeds 50 μm, the moisture permeability is significantly improved, but particles appear on the surface of the coating, resulting in poor finish, elongation, and a decrease in waterproof properties.

The elastic paint of each invention can be a clear A7-paint mainly composed of a flame-retardant polymeric resin having moisture permeability, a translucent paint containing an extender pigment, or a colored paint containing a colored pigment. The paint of the present invention is an emulsion paint whose ingredients are adjusted in an aqueous medium, and both are finishing paints that dry at room temperature.

14 to 70 for blending flame retardant polymer resin that improves moisture permeability
If the division is suitable and the number is 14 or less, the Kll with 1q lowered! J
The flexibility is poor, and deterioration phenomena such as yellowing are observed in the alkali resistance and weather resistance tests in J3. When the amount is 70 parts or more, the resulting coating film becomes highly adhesive, the surface of the coating film is easily stained, and the amount of smoke generated per unit area and the area exceeding the standard temperature curve increase in the combustion test. The vinyl chloride modification rate of the ethylene/vinyl/vinyl chloride copolymer emulsion is 10 to 5.
The most suitable value is 0%, and if the modification rate is less than 10%, no self-extinguishing effect can be obtained. In addition, if the modification rate is 50% or more, the adhesiveness of the paint film becomes strong, and the paint film surface becomes rough. The dehydrochlorination occurs due to the alkaline components of the base and ultraviolet rays, causing the deterioration of the shade, in which the paint film turns yellow.

Vinylidene chloride/acrylic acid-[Stell copolymer emulsion] and vinylidene chloride/ethylene/vinyl acetate copolymer emulsion are most suitable for a vinylidene chloride modification rate of 5 to 50%. If the modification rate is 50% or more, dehydrochloric acid will occur due to the alkaline component of the base and ultraviolet rays, and the paint film will turn yellow.These vinyl chloride and vinyl chloride T A copolymer of 100% and 100% is added to provide self-extinguishing properties to the coating.

In particular, the resin emulsion used in the present invention is modified with an acrylic ester or methacrylic ester having one group at the end. Examples of esters of acrylic acid or esters of methacrylic acid containing non-E O+-1 groups include 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate,
-Hydro 4-siedyl methacrylate, polyethylene glycerol monomethacrylate, 2-hydroxypropyl methacrylate, polypropylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol J-
polytetramethylene glycol monomethacrylate,
Glycerol monomethacrylate, Glyhy[1-dimethacrylate, Glycerol methacrylate acrylate, Glycerol methacrylate alkylate, 2-
Hydroxyb1]pyruacryle-1~, ε-canrolactone-modified 2-hydroxyethyl acrylate, N-methyl L1-ylacrylamide, etc. are suitable, and the most suitable modification rate is 5 to 50% based on the entire resin. , denaturation rate 5
If it is less than %, the formed coating film will have poor moisture permeability, and the modification rate will be 50%.
% or more, the resin as a whole becomes more hydrophilic and its water resistance deteriorates. These esters of acrylic acid or Nissal of methacrylic acid containing 0 to 1 terminal group are blended in order to impart moisture permeability to the coating film.

As the inorganic gas burner, powder of aluminum hydroxide 11 or magnesium hydroxide is mainly used. Aluminum hydroxide is 200℃, magnesium hydroxide is 300℃
'C decomposes and releases large amounts of water vapor. This water vapor reduces the self-extinguishing properties of the coating film by 1r1, resulting in a more flame-retardant coating film. The flame retardant is flame retardant acrylic acid Esdel Emulsi 5! When using a self-extinguishing ethylene/vinyl acetate/vinyl chloride copolymer emulsion, 1 to 10 parts can be added.
Vinylidene chloride/acrylic acid ester copolymerization 1Marsi=
When a vinylidene chloride/ethylene/vinyl acetate copolymer emulsion is used, it is used in an amount of 1 to 50 parts. If the flame retardant is in the above-mentioned predetermined range of 4 or more, the coating film will have less flexibility and will not be able to follow cracks in the base.

If necessary, extender pigments, coloring pigments, fine aggregates, and fibers can be added to the elastic paints of each invention.

As extender pigments, calcium carbonate, precipitated barium sulfate, titanium oxide, etc. can be used. The compounding needle for the extender pigment is 5
The amount is 0 parts or less, preferably 30 to 50 parts. Coloring pigments include butane oxide, carbon black, chrome vermilion, Bengara, Shinkasha red, lakelet, yellow ocher, Hansa yellow, titanium yellow, ultramarine blue, senior blue, etc., in a range of about 0.5 to 30 parts. used within.

For example, 3 to 20 parts of fine aggregate and about 10 parts of fiber are added when it is desired to increase the coating thickness.

Each of the elastic paints of the first invention, second invention, third invention, and fourth invention has good painting workability, and like conventional elastic paints, spraying with a mortar gun or airless can cause painting and porous Quality [1-Can be easily painted by coating means such as roller coating with a roller or the like.

When the coating has a dry film thickness of about 0.5 to 5 mm, the ability to follow cracks in the base is particularly good. The object to be coated can be widely applied to materials such as concrete and mortar.

(Function) The elastic paints of each invention contain polymer resin emulsions such as ethylene/vinyl acetate/vinyl chloride copolymer emulsions modified with acrylic esters or methacrylic esters having terminal OH groups, so The film is moisture permeable and has elasticity that allows it to follow cracks in the base.3 When a non-I flame retardant is added, the self-extinguishing properties of the coating film are increased, and when resin particles are added, the film becomes moisture permeable. is enhanced.

(Experiment example) Next, the present invention will be explained in detail.

Each of the ingredients shown in Table 1 was sequentially added to a mixer for each experimental example, and thoroughly stirred to prepare each coating material of experimental examples 1 to 17.

(The following continues on the next page.) Next, using 17 types of paints from Experimental Examples 1 to 17,
Immediately paint the test board of the pawn material and perform each test on the test bracken. In addition, as controls for each test, Comparative Examples 1 to
A conventional elastic paint of /I was prepared and similarly applied to a test panel to serve as a control specimen, and this control painted surface was compared with the painted surfaces of each experimental example.

The test plate was prepared by applying 140 q of each of the paints of Experimental Examples 1 to 17 and the paints of Comparative Examples 1 to 4 to an inorganic material per 1TIt.
Finished in one coat using a porous roller at a rate of 0 g.

Each test plate of Experimental Examples 1 to 17 and each test plate of Comparative Examples 1 to 4 was held horizontally for each test. Low-temperature stability was tested for raw paint. Resistance to cracking due to initial drying was tested immediately after painting. Adhesive strength, resistance to repeated heating and cooling, water permeability, impact resistance, weather resistance, elongation rate, Deterioration over time, water resistance, alkali resistance, ground crack followability, amount of smoke per unit area, measurement of area exceeding the standard temperature curve,
Regarding the measurement of moisture permeability, tests were carried out before and after being left indoors for 14 days.

The tests for each item were conducted according to the following methods.

Test items for low temperature stability, adhesion strength, resistance to repeated heating and cooling, water permeability, impact resistance, and weather resistance are JISA.
-6910.

Crack resistance due to initial drying...JISA-691
By 0. The test plate was placed in a wind tunnel adjusted to a wind speed of 3 m/sec ±10% for 6 hours, and it was judged as passing if there were no cracks on the surface.

Elongation rate: According to JISA-6910. The dried coating film was adjusted to have an thickness of 1 mmI. Dumbbell-shaped test piece 2
Formed into a number shape and immersed in water at +20°C and -10°C for 7 times.
After heating at 80±2℃ for 7 days, each test was carried out using a tensile tester (the maximum load at the time of the test was in the range of 15-85% of its capacity), an automatic recording device for load and elongation, and a constant temperature of 110℃. It is equipped with a constant temperature bath that can be adjusted to ±2℃ and 20±2℃, the tension speed can be adjusted to 200 m+/min, and the test piece can be pulled 8 times the distance between the gauge lines).
The test piece was processed at a tensile speed of 00rIvR/1n until it broke.

Deterioration during elongation: Based on JISA-8910. The shape of the test piece is a dumbbell shape. Marked line opening ta40m
The test piece was stretched so as to have a marked line open path of 1Ilt60InIn, and left to stand at 80±2°C for 7 days.The test piece was judged to be passed if there was no peeling, warping, or twisting, and there was no breakage or cracking of the main material.

Water resistance and alkali resistance: Compliant with JIS-5400.

Substrate crack followability: Cutting grooves on a 70X150X5/M flexible board (depth 2.55III+, width 3.0
m), adjust the dry coating to 1 liter, apply it to the surface to be tested, heat cure at 40±2℃ for 120 hours, and then coat both longitudinal ends of the test piece with a thickness of 4m. After supporting the flexible plate with a spacer and applying light pressure with your fingers to prevent damage to the paint film to generate cracks in the flexible board, pull it using a tensile tester and set the end point at the point where an abnormality is observed in the paint film. This was used as the base crack follow-up point.

Amount of smoke generated per unit area: Based on JrSA-1321. 30 or less passes the flame retardant grade.

Area exceeding the standard temperature curve: According to JISA-1321.

0°C-m1n passes the flame retardant grade.

Moisture permeability: Based on JIS 7-0208. The test piece was prepared by adjusting the dry coating thickness to 1.
It was attached to a moisture-permeable cup specified in Z-0208, placed in a tank with a humidity of 25°C and 90%, and taken out after 24 hours, and the water absorbed by calcium chloride in the moisture-permeable cup was weighed. From that value, the amount of moisture permeation per unit area was calculated.

As is clear from the test results in Table 2, this experimental example 7-7
It can be seen that each coating film of No. 7 is superior to the coating films of Comparative Examples 1 to 4 in flame retardancy, elongation, ground crack followability, and moisture permeability.

Comparative Examples 1 to 4 exceeded the specifications in terms of the amount of smoke generated per unit area and the area exceeding the standard temperature curve, and failed the flame retardant grade. Furthermore, the 1τ ground crack followability and moisture permeability against cracks in the base were also low.

Each of the paints in Experimental Examples 1 to 17 was used in Comparative Example 1, which is a conventional paint.
This solves the disadvantages of 4 to 4.

(Effects of the Invention) The elastic paints of the first, second, third, and fourth inventions have a property that makes the coating film moisture permeable, 1j1 flammable, and elastic.
Since the emulsion is blended, it has good paintability and forms a coating film at room temperature, and the coating film is
Flame retardant that passes the flame retardant grade of S standard, has a coating film elongation rate of 50% or more, has a base crack followability of 1 item or more, and has sufficient elasticity to follow cracks in the base. It is.

The elastic paints of the second and third inventions are made of inorganic n
Since it contains a flame retardant, it has greater flame retardancy than the elastic paint of the first invention which does not contain an inorganic flame retardant.

Since the elastic paint of the fourth invention contains resin particles that improve moisture permeability, it has greater moisture permeability than the elastic paints of the first, second, and third inventions that do not contain resin particles. .

Therefore, the elastic paint of the present invention is flame retardant according to the JIS standard.
It has high commercial value because it can be handled as a grade-approved product and has moisture permeability. And, the elastic paint of this invention can be used on concrete, etc.! When applied to a base of quality materials, the coating film can follow cracks in the base to prevent rainwater from entering from the outside, and its high moisture permeability allows moisture inside the structure to be released to the outside, preventing condensation and cold regions. It prevents frost damage, and the coating is flame retardant, making it effective against fires.

Claims (4)

[Claims] (1) Flame-retardant acrylic ester emulsion, ethylene/vinyl acetate/vinyl chloride copolymer emulsion with vinyl chloride modification rate of 10-50%, vinylidene chloride modification rate of 5-50%
A resin emulsion selected from the group of a 50% vinylidene chloride/acrylic acid ester copolymer emulsion and a vinylidene chloride/ethylene/vinyl acetate copolymer emulsion with a vinylidene chloride modification rate of 5 to 50%, and the acrylic ester thereof. or vinyl acetate moiety has been modified with an acrylic ester or methacrylic ester having a terminal OH group in an amount of 5 to 50% based on the entire resin component of the resin emulsion, and the resin content is 30 to 70%. Consisting of a certain polymer resin emulsion, 14 to 70 parts by weight of one or more of these are blended,
No inorganic flame retardant is added, and the elongation rate of the coating film is 50.
% or more and a coating film having a base crack followability of 1 mm or more. (2) Flame-retardant acrylic ester emulsion and ethylene/vinyl acetate with a vinyl chloride modification rate of 10 to 50%.
A resin emulsion selected from the group of vinyl chloride copolymer emulsions, wherein the acrylic ester portion or vinyl acetate portion thereof has an acrylic ester or methacrylic ester having a terminal OH group, and the entire resin component of the resin emulsion is 14 to 60 parts by weight of one or more of these and 1 to 14 parts by weight of an inorganic flame retardant. 1. A flame-retardant elastic paint having moisture permeability, characterized in that the elongation rate of the paint film is 50% or more and the ability of the paint film to follow substrate cracks is 1 mm or more. (3) A resin emulsion selected from the group of ethylene/vinyl acetate/vinylidene chloride copolymer emulsion with a vinylidene chloride modification rate of 5 to 50%, and vinylidene chloride/acrylic acid ester copolymer emulsion with a vinylidene chloride modification rate of 5 to 50%. and the acrylic ester part or vinyl acetate part has been modified by 5 to 50% of the entire resin component of the resin emulsion with an acrylic ester or methacrylic ester having a terminal OH group, and It is made of a polymer resin emulsion with a resin content of 30 to 70%, containing 14 to 70 parts by weight of one or more of these and 1 to 50 parts by weight of an inorganic flame retardant, and the elongation rate of the coating film is 50% or more. A flame-retardant elastic paint with moisture permeability, characterized in that the coating film has a base crack followability of 1 mm or more. (4) 1 to 30 resin particles with an average particle size of 0.5 to 50 μm
4. The flame-retardant elastic paint having moisture permeability according to claim 1, wherein the moisture permeable flame-retardant elastic paint is blended in parts by weight.