JPS59102966A - Flame-retardant coating composition - Google Patents

Abstract

PURPOSE:To prepare the titled composition having excellent flame-retardance, storage stability and adhesivity, without lowering the water resistance and mechanical strength, etc., by adding a specific amount of melamine cyanurate as an additive-type flame-retardant to a synthetic resin emulsion or a rubber latex. CONSTITUTION:The objective composition is prepared by compounding (A) (i) an emulsion of a synthetic resin preferably vinyl acetate resin, acrylic resin, vinyl versatate resin and/or ethylenic resin and/or (ii) a rubber latex preferably natural rubber latex and/or diene-type synthetic rubber latex with (B) 5- 100pts.wt., based on the solid content of the component (A), of melamine cyanurate (preferably having particle diameter of <=50mu).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flammable paint composition (7, more particularly 2) containing a specific compound of melamine cyanurate as an additive flame retardant. This invention relates to a flame-retardant coating composition containing a specific melamine cyanurate to the resin solid content of rubber latex.

Traditionally, polyolefin resins, vinyl acetate resins,
The biggest drawback of thermoplastic resins such as acrylic resins and polyester resins is their flammability, according to fire safety standards experts. Inorganic compounds such as zinc oxalate; phosphoric acid esters and phosphorus compounds such as tris(chloroethyl) phosphate, halogen-containing phosphoric acid ester compounds - ammonium polyphosphate, nitrogen-containing inorganic polymeric phosphoric acid compounds; chlorinated paraffins,
Additive flame retardants such as chlorinated polyolefins, tetra-bromo-butane, halogenated organic compounds, etc., or thermal additives such as chlorendic anhydride, tetrabromo-phthalic anhydride, phenyl-phosphonic acid, etc. An anti-plastic IC flame retardant that reacts with plastic resins and imparts solubility has been proposed.

However, the additive type flammability added above to the V resin emulsion and/or rubber latex, which is in high demand for paints, especially residual phase paints, is 611 go (7, ψ1
``Various defects occur when used as a flammable paint.

For example, in the case of inorganic compounds qlrr, which can be listed in 5. For example, the paint film after painting lacks deicing properties and smoothness, and in addition to the formation of scratches, the viscosity of the paint tends to increase over time, and in extremely severe cases. In phosphoric acid esters, phosphorus compounds, and halogenated flame retardants that gel during storage and become unusable, the compatibility with resins that are constituent components of resin emulsions and/or rubber latexes is 8! 7. Decrease in the target degree of the coating film due to increased flexibility, and decrease in adhesion to the painted object. Such disadvantages arise.

The inventors of the present invention discovered that the special properties (surface 1 aqueous property, mechanical strength, adhesion, etc.) of the composite + Jy resin emulsion and the 7-year-old rubber latex were inhibited, and the excellent flame retardancy and storage stability As a result of intensive research into additive flame retardants that exhibit excellent properties, adhesion, and smoothness of paint films, we have found that flame retardants for use in synthetic resin emulsions and/or rubber latex paints have been found to be effective. It was unexpectedly discovered that the problem could be solved all at once by adding a specific component of melamine cyanurate (7), which led to the completion of the present invention.

That is, the present invention provides an external combustible paint material containing 79,875 to 100 military parts of cyanuric acid per 100 parts by weight of the resin solid content of the synthetic resin emulsion and rubber latex. is to provide.

"Melamine cyanurate" as used in the present invention has a molecular formula of C,
Melamine (2,4,6-)riamino- with N, H,
1,3,5-) riazine) and cyanuric acid (2,4,6-trioxy-1,
3゜5-triazine) and/or a salt produced by the reaction with incyanuric acid, which is one of the tautomers of cyanuric acid. For example, a cyanuric acid suspension in an aqueous solution, Preferably, it is obtained by adding 1.0 to 105 mol of melamine to 1 mol of cyanuric acid and/or isocyanuric acid (7) and heating it to about 90°C. It is poorly soluble in water and substantially incompatible with synthetic resin emulsion and/or rubber latex resins, and the following structure can be considered.

The formulation of the above cyanuric acid melamine is based on the weight of the resin solid content of the synthetic resin emulsion and/or rubber latex.
'Hj For 100 parts by weight, 5 to 300 parts by weight, preferably 20 to 90 parts by weight, preferably 20 to 90 parts by weight &:t
A portion of 40 to 80 pieces is good. If the amount of cyanuric acid melamine is less than 5 parts, the expected flammability will not be obtained, while if it exceeds 100 parts, the adhesion of the coating film will deteriorate, which is not desirable.

The "synthetic resin emulsion", which is a component of the flame-retardant paint composition according to the present invention, refers to compounds such as vinyl acetate, acrylic esters, methacrylic esters, styrene, butadiene, etc., in water, alone or in the form of copolymerization. It refers to an emulsion in which the polymer is polymerized in the presence of a protective colloid, etc., and the secondary solvent is water, and a non-aqueous emulsion, in which the solvent is methanol, mineral turpentine, acetate, acetone, benzene, toluene, xylene, etc.

These include: vinyl acetate homopolymer emulsion, vinyl acetate 70-polymer, (acrylic acid alkyl ester having an alkyl group of 1 to 8 carbon atoms, which can be copolymerized with the vinyl acetate in 4,4 or more) , methacrylic acid alkyl ester, fumaric acid alkyl ester, maleic acid alkyl ester; vinyl ether having an alkyl group having 1 to 20 carbon atoms, etc., such as an alkyl group having 1 to 8 carbon atoms; and vinyl acetate-based resin emulsions copolymerized with vinyl esters such as vinyl propionate and vinyl persate; One type selected from the group consisting of acrylic acid ester and methacrylic ester having an alkyl group having 1 to 20 carbon atoms, preferably having an alkyl group having 2 to 8 carbon atoms. Emulsions in which two or more types of monomers are polymerized, and acrylic acid, acrylonitrile, sodium acrylate, and acrylic acid that can be copolymerized with these monomers (in excess of 30 monomers) Copolymerized with amide, glycidyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, vinyl acetate, etc. with ID2 or more (131 acrylic acid ester resin emulsion; birtic acid vinyl ester 30 Exceeded the heavy cup%,
Copolymerize with less than 7° if % vinyl acetate, etc. (A)
and (I3) emulsions other than the emulsions of 0-persistent acid-based resins; copolymerized with more than 30% by weight of ethylene and less than 70% by weight of vinyl acetate, etc., (B)
, and (C) ethylene resin emulsion other than the emulsion of ) Vinyl acetate resin emulsion, 03) Acrylic acid ester 4tl fat emulsion, (C) Hertha vinyl acetate emulsion,
(o) An emulsion of one type or two or more types selected from the group consisting of: It is preferable because it can particularly exhibit performance.

The "rubber latex" which is a component of the flame retardant coating composition according to the present invention refers to an aqueous emulsion of natural and/or synthetic rubber other than the "synthetic resin emulsion" resin.

These include natural rubber latex obtained from plants, and synthetic rubber latex such as polybutadiene, known as Buna S, styrene, and styrene.
butadiene-styrene copolymer and tonne resin, known as Buna N, copolymerized with a weight ratio of yi to about 25%,
Butadiene rubber latex such as acrylonitrile copolymer, chloroprene rubber latex such as neoprene, polychloroprene, polyisoprene, isoprene-isobutylene copolymer known as butyl rubber, and bromine modified Isoprene rubber latex such as butyl rubber, ([
! ') Diene-based synthetic rubber latex; Olefin-based synthetic rubber latex such as polyisobutylene, ethylene-propylene, and ethylene-propylene terpolymer known as Obanol, Vistanex, etc.; [F]) Acrylic acid ester-based Excluding emulsions (e.g., acrylic synthetic rubber latex such as fluorinated butyl acrylic rubber; urethane IM rubber latex such as polyol-diincyanate combination; polysulfide DW rubber latex known as thiocol rubber, etc.): Examples include silicone-based synthetic rubber latex known as silicone rubber.

The above-mentioned "rubber latex" may be one or more selected from the group consisting of (i) natural rubber latex and () diene-based synthetic rubber latex. I like L7 because it can demonstrate its performance.

The particle size of melamine cyanurate as the additive flame retardant is preferably 1-1 and preferably 50 μm or less. In the present invention, "fresh" means particles with a particle size of 50 μ or less, preferably 80 weight Ji4 or more, 1. -〈 means a grade of 90 or higher, from the viewpoint of maintaining a stable dispersion state as a flame retardant coating composition and providing a smooth coating film, etc.
The particle size of melamine cyanurate is preferably 20 μm or less, particularly preferably 10 μm or less.

Such fine melamine cyanurate can be obtained by the above-mentioned production method by a known pulverization method. Even with the same amount added, it also exhibits flame retardancy that has never been improved.

As synthetic resin emulsion and rubber latex,
Normally, the solid content concentration is 3 (] ~ 80 Juto, Tarube 100 ~ 4
0000 CI)S (BH type rotational viscometer, 20r.

Pom -25℃) can be used, but Kosai i-2
d. From the viewpoint of coating workability, a solid content concentration of 40 to 70 parts by weight and a viscosity of 100 to 30,000 C1)S-% is preferable.

As described above, the Pl-flammable coating composition of the present invention contains a specific amount of melamine cyanurate per 100 parts of the resin solid content of the synthetic resin emulsion and /f or rubber latex. - Adhesives other than these substances, such as water-soluble products such as polyvinyl alcohol, hydroxymethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and casein; crosslinking agents;
Softener; salicylic acid ester, benzophenone, penztriazole, acrylic ultraviolet absorber; fungicide;
etc. 1. It can also be used as appropriate depending on the purpose of use.

On the other hand, the silk coating material of the present invention is used for this purpose; since it uses a specific amount of cyanuric acid melamine, the storage stability of the synthetic resin emulsion and/or rubber latex is improved. , does not impair various properties such as water resistance, mechanical strength and adhesion of the coating film, and provides the coating film with excellent smoothness and flame retardancy.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example A flame-retardant coating composition was prepared using the synthetic resin emulsion listed in column J-(1) shown in Table 1 and the 7-inch rubber latex. The pulverized melamine cyanurate (reaction product of 1 mol of cyanuric acid and 1.02 mol of melamine) described in the section 1) was blended.

The product names listed in column j.(I) are related to the production of the following products, all of which use water as the solvent. Carbide Kogyo ■ Nikazole CL-] ooc・・・・・・Nicasol CL-204・・・・・・・・・Nicasol C, X-1
14H...Crossren 5A-22, manufactured by Nakamoto Kano (IDO U'fJ3)...Manufactured by Takeda Pharmaceutical Co., Ltd. In Example 14, nicazole C, T, -302 were so*=
”Z and Crosslen 5A-22 are used together with 20 layers (-7
Please use something.

Table 211 shows [,ta! 1 (combustible paint composition,
It was coated on an iron plate to a thickness of 50 μm and dried at room temperature for 1 hour to obtain a flame-retardant coating film.

The results of various V-performance tests of the coating film are shown in the right column of Table 2.1.

The test method was performed as follows.

(i) Flammability J-Impact 4] The coating film of tnm was peeled off from the iron plate, and the width was 127r.
The burning time of the strip was measured according to the vertical test method of UL Subject 94, and the burning time was 2.

The fire sag occurred at the location of the above combustion time measurement. !
- Fire sagging properties were observed and evaluated with the naked eye.

In the above combustion time measurement, "x" marks other than seconds are indicated.

It is intended to burn completely, and the fire sag is 1'.
42 was graded as follows.

Fire sag: None...0 Little...(-) Much...-- × (11) A coating film with a thickness of 50 μm was completely formed on an adhesive iron plate. Squares with a spacing of 1 mrrL were inscribed on the film, and cellophane tape was tightly pressed onto the membrane. When the cellophane tape was peeled off, the residual rate of the squares was measured. I evaluated it.

Adhesion: Residual rate 98% or more... ◎ 90 cycles or more...0 Less than 90 cycles...×riii) Smoothness Before testing the above adhesion, check the unevenness of the coating surface by touch. The properties were evaluated and graded as follows: 7 out of 1. Smoothness: No unevenness...0 Slightly uneven f: Sensible...
0 Clear unevenness... × Comparative Examples 1 to 3 The paint films shown in Table 111 were prepared in the same manner as Examples 1 to 14 and Do 1, and their performance was tested.

As Comparative Example 3, instead of using melamine cyanurate, 17 parts by weight of the resin solids of NICAZOL CI, -302 and 17 parts by weight of calcium carbonate (White Glossy Cctt
Made by Shiraishi Kogyo 61; Particle size: μ or less) A coating film was obtained from a paint silk Dy material using 40 heavy-duty particles, and the performance of the coating film was tested (-2, but completely combusted in the flammability test) At the same time, there is a lot of fire glare (completely unsuitable as a LAt flammable paint composition).
It was something that didn't exist.

As can be seen from Table 1.1, the flame retardant coating composition according to the present invention has a content of melamine cyanurate ranging from 40% to 100% by weight of the resin solid content of the synthetic resin emulsion and 7-inch rubber latex. When the melamine cyanurate had a particle size of 10 μm or less, it exhibited particularly excellent performance and had excellent storage stability (1).

Claims (4)

[Claims] (1) Using a synthetic resin emulsion and/or rubber latex resin solid content "fFr amount 100",
A flame-retardant coating composition containing 5 to 100 parts of melamine cyanurate. (2) The composite fjV resin emulsion is one or more types selected from the group consisting of vinyl acetate resin emulsion, acrylic acid ester resin emulsion, persate vinyl resin emulsion, and ethylene resin emulsion. That's 11'! rClaims 3.1
FEW products for flame-retardant paints as described in section. (3) Rubber latex is a combination of natural rubber and diene.
The f+a twisted 11P paint paste IiV product according to claim 1, which is selected from the group consisting of Y rubber latex. (4) The particle size of melamine cyanurate is mainly (-2 to 5
The flame-retardant coating composition according to claim 1, which has a particle diameter of less than oμ.