JPH0480751B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a coating layer of a urethane material used in the field of building materials such as flooring materials, wall materials, waterproofing materials, and paving materials.

(Prior art) Urethane materials have excellent properties such as rubber elasticity, abrasion resistance, and mechanical strength, and are used for flooring materials, wall materials, waterproofing materials, and paving materials. Paving materials have good surface smoothness because they have self-leveling properties, but for floors and waterproofing, fine powders such as silica sand, urethane chips, rubber chips, etc. are used as non-slip materials on the surfaces to make them non-slip and matte. For paving materials, chips of urethane, EPT, rubber, etc. about 1 to 5 mm are sprinkled. In the case of wall materials, a material with non-sag properties is separately spray-painted using a reshin gun.

(Problems to be Solved by the Invention) In either case, the underlying layer and the material that creates the unevenness on the surface are different in quality and/or formulation, require two or more steps, and require a wide variety of materials. Furthermore, since the finished surfaces are made of different materials, they often feel uncomfortable and have problems with adhesion and durability.

(Means for Solving the Problems) The present inventors have arrived at the present invention as a result of various studies on non-slip or matte uneven finish coated layers that can be formed by a simple process by reducing the number of types of materials as much as possible. .

That is, the present invention involves spraying a fast-curing urethane elastomer composition consisting of a main ingredient containing a prepolymer having an isocyanate group at the end and a curing agent containing a polyol, a chain extender, a catalyst, and other auxiliary agents using a high-pressure blow foaming machine. (1) A first step in which a spray ejected under high pressure is directly sprayed onto the construction surface to harden it, thereby forming one or more smooth coating surfaces. and (2) a second step in which the center line of the spray is held at an angle of -60 to +80 degrees with respect to the horizontal direction, and the spray spray is scattered obliquely upward or downward, and then naturally falls onto a smooth coating surface. This is a textured finish coated layer of a sprayed urethane material that has a textured surface.

The coating layer applied to the horizontal surface of the present invention is formed as follows. That is, in the first step, a fast-curing urethane elastomer composition is sprayed onto the construction surface using a high-pressure spray foaming machine to form a smooth coating surface. Next, in the second step, if the composition is sprayed almost horizontally, the spray is dispersed in the air and then
It naturally falls onto the coated surface due to gravity. As a result, after adhering to the coated surface, it hardens without leveling, resulting in a good uneven finish.

Next, in the case of an uneven coating layer applied on a vertical surface,
In the first step, a smooth coating surface is formed in the same manner as before. In the second step, to form an uneven layer on the vertical coating surface, the composition is sprayed obliquely upward or downward. The spray once ascends or descends, then falls obliquely, forming a parapet line, and adheres to the vertical coating surface, forming an uneven coating layer. According to the present invention, since the urethane elastomer composition is applied in the form of a spray, a uniform uneven surface can be obtained, which is very aesthetically pleasing. In addition, the raw materials and machinery are exactly the same for the first and second steps, and the only difference is the operating method, so they can be carried out extremely simply and easily.
It is also extremely advantageous economically.

The polyisocyanates used in the production of the prepolymer in the present invention include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and an 80/20 weight ratio of both isocyanates (80/20
- TDI) or a mixture in a 65/35 weight ratio (65/35 - TDI), crude tolylene diisocyanate (crude
TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-
Diphenylmethane diisocyanate (2,2'-
MDI), isomer mixture of diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (crude MDI), toluidine diisocyanate, xylylene diisocyanate,
These include hexamethylene diisocyanate, isophorodiisocyanate, dicyclohexylmethane diisocyanate, and carbodiimide-modified products, biuret-modified products, dimers, trimers, prepolymers, etc. of these isocyanates.

Although polyisocyanates may be used alone or in mixtures, polyisocyanates particularly suitable for the present invention are mixtures of isomers of diphenylmethane diisocyanate and its carbodiimide modified product.

In the present invention, the polyols used in the production of the prepolymer and the curing agent are water, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, 1 , 5-pentanediol, 1,2-hexylene glycol, 1,10-
Decanediol, 1,2-cyclohexanediol, glycerin, 1,2,6-hexanetriol, 1,1,1-trimethylolethane, 1,
It is a polyether polyol obtained by adding one or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc. to 1,1-trimethylolpropane, pentaerythritol, etc. The preferred range of the hydroxyl value of these polyols is 20 to
150 mgKOH/g, and these polyols are used alone or in combination.

Chain extenders used in the present invention include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3-
and monomeric polyols such as 1,4-butanediol, alkanolamines such as triethanolamine and diethanolamine, aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine, methylene orthochloroaniline, and 4,4'-diphenyl. Methanediamine, aniline, 2,4-tolylenediamine, 2,
6-tolylene diamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene and mixture of both (DETDA), 1, 3,5
-triethyl-2,6-diaminobenzene, 3,
Hydroxyl value 200mgKOH/g obtained by adding ethylene oxide, propylene oxide, etc. to aromatic polyamines such as 5,3',5'-tetraethyl-4,4'-diaminodiphenylmethane and compounds with active hydrogen. These are the above compounds. Hydroxy value 200mg obtained by adding ethylene oxide and/or propylene oxide to other hydroquinone, resorcinol, aniline, etc.
Compounds with KOH/g or more can also be used.

Catalysts that can be used in the present invention are conventionally known catalysts and are not particularly limited; N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine,
N,N-dimethylethanolamine, diethylenetriamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetra Methylbutanediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,
N′,N′-tetramethylhexamethylenediamine,
Bis[2-N,N-dimethylamine)ethyl]ether, N,N-dimethylbenzylamine, N,
N-dimethylcyclohexylamine, N,N,
N',N'',N''-pentamethyldiethylenetriamine, triethylenediamine, formate and other salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines, N,N-dialkylpiperazines, etc. azacyclic compounds, various N,N′,N″-trialkylaminoalkylhexahydrotriazines, β of Japanese Patent Publication No. 52-43517
- Aminocarbonyl catalyst, β of Japanese Patent Publication No. 53-14279
-aminonitrile catalyst, etc.), organometallic urethanation catalysts (tin acetate, tin octylate, tin oleate,
tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt octoate, etc.). These catalysts may be used alone or in combination, and the amount used is 0.0001 to 10.0 parts per 100 parts of the compound having active hydrogen.

In the present invention, other auxiliary agents such as plasticizers, flame retardants, stabilizers, solvents, and colorants are used.

Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate (DOA), tricresyl phosphate (TCP), and chlorinated paraffin.

Flame retardants include tris(β-chloropropyl)phosphate (Fairol PCF), trischloroethylphosphate (CLP), tris(2,3
-dibromopropyl) phosphate (CR-10), dibromoneopentyl glycol (DBNPG), tribromoneopentyl glycol (TBNPG),
Use red phosphorus, etc.

Colorants include inorganic pigments such as chromium oxide and red iron, and organic pigments such as phthalocyanine pigments and azo pigments.

As a weathering stabilizer, the product name is Nokratsuku #300,
NS-6 (manufactured by Ouchi Shinko Kagaku), trade names Irganox 1010 and 1076 (manufactured by Ciba Geigy), Yoshinox-BHT, BB and GSY-930 (Yoshitomi Pharmaceutical)
Positionally hindered phenols such as tinuvin P-
Benzotriazoles such as 327 and -328 (manufactured by Ciba Geigy); benzophenones such as Tomisorp 800 (Yoshitomi Pharmaceutical); Sanol LS-770 and -
744, and positionally hindered amines such as tinuvin-144.

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as Isovar H and M; esters such as ethyl acetate; and ketones such as methyl ethyl ketone.

To produce the base material containing the prepolymer used in the present invention, polyisocyanate, polyol, and if necessary, a polyol-type chain extender and flame retardant are mixed, and the mixture is heated at 70 to 90°C in a nitrogen stream for 1 to 5 minutes. Allow time to react. The obtained base agent has an NCO group content of 8~
25%, viscosity 300-1500CPS/25℃. When producing the main agent, the NCO group content is appropriately adjusted by the mixing ratio of the raw materials, and the mixing ratio with the curing agent at the time of construction is made to be a 1:1 volume ratio.

The curing agent is produced by mixing a polyol, a chain extender, a catalyst, a stabilizer, a pigment, etc. using a conventional method.

When mixing the main agent and hardening agent and spraying,
The flow rate ratio between the NCO group content in the base resin and the active hydrogen content in the curing agent is adjusted so that the equivalent ratio (NCO/H) of the two is 0.95 to 1.10. Although the adjustable range of the flow rate ratio between the main agent and the curing agent varies depending on the metering and feeding function of the spraying machine, it is generally convenient to set the volume ratio to 1:1.

When forming the coating layer of the present invention on walls and floors,
First, as shown in Fig. 1, a spray gun is aimed at the construction surface and a mixture of the main agent and hardening agent is sprayed at a pressure of 70 to 140 kg/cm ² to form a smooth base surface of 1 to 4 layers.

Next, in the second step, as shown in Figure 2, keep the spray gun close to parallel to the construction surface and mix the main agent and hardener so that the center line of the spray is between -60 and +80 degrees from the horizontal direction. Emit a spray. Once the spray is dispersed in the air, it naturally falls and adheres to the construction surface.

As shown in FIG. 3, the deposited spray hardens as it is, forming a non-slip or matte uneven finish coating layer having small unevenness.

(Function) According to the present invention, since the spray of the fast-curing urethane elastomer composition is once dispersed in the air, it naturally falls and adheres to the construction surface. It cures without leveling after being applied.

(Example) Next, an example of the present invention will be described. In the examples, parts indicate parts by weight.

Example 1 852.5 parts of MDI modified with carbodiimide
365.3 parts of MDI, 571.7 parts of polyoxyalkylene diol with a hydroxyl value of 56, which is obtained by adding propylene oxide to propylene glycol and capping ethylene oxide, dipropylene glycol
10.5 parts and 200.0 parts of flame retardant Fireol PCF were mixed, and the mixture was heated and reacted at 80°C for 3 hours in a nitrogen stream.

The obtained base material 1 had an NCO group content of 17.5% and a viscosity of
It was 500cps/25℃.

Separately, 74.5 parts of polyoxyalkylene diol used in base ingredient 1, 19.0 parts of ethylene glycol, 2.0 parts of lead naphthenate catalyst (lead content 25%), 0.5 part of stabilizer Irganox 1010, red iron oxide and DOP were obtained by roll kneading. 4.0 parts of brown toner was mixed as a curing agent.

The wall surface was sprayed at a pressure of 100 kg/cm ² using a MINI-type high-pressure spraying machine manufactured by Glass Craft. After applying a primer (Mitsui Toatsu Chemical: Sun PC) as a base to the concrete wall,
The spray gun was held almost horizontally to form one smooth layer on the wall. Base agent 1 and curing agent 1 were heated to 55° C., and the flow rate ratio of both components was 1:1 (volume).
Next, the spray gun was pointed upward and sprayed while keeping the center line of the spray pointing 80 degrees above the horizontal direction. The spray hardened as it was after adhering to the wall surface, resulting in a wall surface having a matte uneven coating layer with fine unevenness.

Example 2 608.8 parts of MDI, modified with carbodiimide
260.9 parts of MDI, 913.6 parts of a polyoxyalkylene diol with a hydroxyl value of 56 which is capped with ethylene oxide after addition of propylene oxide using propylene glycol as an initiator, 16.7 parts of dipropylene glycol, fire retardant fire roll
200.0 parts of PCF was mixed and reacted by heating at 80°C for 3 hours in a nitrogen stream.

The obtained base material 2 had an NCO group content of 11.0% and a viscosity of
It was 900cps/25℃.

Separately, 76.62 parts of polyoxyalkylene diol used in main ingredient 2, 16.88 parts of DETDA, 1.0 part of lead naphthenate catalyst (lead content 25%), and Sanol LS stabilizer.
-770 0.5 parts and 5.0 parts of a brown toner obtained by roll kneading chromium oxide and DOP were mixed to prepare a hardening agent 2.

The spraying work was carried out at a pressure of 100 kg/cm ² using a high-pressure spray foaming machine H-2000 manufactured by Gasmer. After applying the primer to the concrete floor, point the spray gun downward and apply 3 coats of primer onto the floor.
layered. Base agent 2 and curing agent 2 were heated to 55° C., and the flow rate ratio of both components was 1:1 (volume). Next, the spray gun was held almost horizontally and sprayed. The spray naturally fell onto the floor surface and then hardened as it was, yielding a floor surface with an extremely beautiful non-slip coating layer with fine irregularities.

(Effects) According to the present invention, it is possible to apply an uneven coating layer having a small uneven pattern on the smooth painted surface of polyurethane elastomer, and as a result, it is possible to make the wall surface matte and the floor surface non-slip easily, in a short time, and It has become possible to do it cheaply.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing a step (first step) of forming smooth surfaces by spraying a fast-curing urethane elastomer composition onto walls and floors. FIG. 2 is a cross-sectional view showing the step (second step) of forming uneven surfaces on the wall and floor surfaces. FIG. 3 is a cross-sectional view showing the wall and floor surfaces that have been finished with the uneven coating layer. In FIGS. 1 to 3, 1 is the wall and floor to be constructed;
2 is a spray gun, 3 is a smooth coating layer, 4 is a spray, and 5 is a finished uneven coating layer.

Claims (1)

[Claims] 1. A fast-curing urethane elastomer composition consisting of a main component containing a prepolymer having an isocyanate group at the end and a curing agent containing a polyol, a chain extender, a catalyst, and other auxiliary agents is prepared using a high-pressure blowing foaming machine. In the coating layer formed by spraying and applying in the first and second steps, (1) a first layer in which the spray ejected under high pressure is directly sprayed onto the coating surface to harden it to form one or more smooth coating surfaces; Step 1 and (2) The center line of the spray is held at an angle of -60 to +80 degrees with respect to the horizontal direction, and the spray is scattered diagonally upward or downward, and then falls naturally onto a smooth coating surface. A textured finish coated layer of atomized urethane material that has a textured surface in two steps.