JP3203132B2 - Natural rock-like foamed decorative material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for providing a three-dimensional pattern with a thickness of several centimeters on the surface of a building or civil engineering structure such as concrete or iron, or a material for forming a natural rock-shaped lightweight body. In particular, a foamed urethane resin composition is used in forming the thickness, and the foamed layer itself has color beauty.

[0002]

2. Description of the Related Art Conventionally, various types of natural stones and artificial materials imitating natural stones have been used. Among these, the marble-like or granite-like composition containing a synthetic resin as a main component and a coloring aggregate and various fillers can be given a free shape by molding or coating. The amount is increasing. However, these materials are certainly lighter in weight than natural stones and natural stones.However, since various colored aggregates and fillers are mixed with synthetic resin, their weight is sufficient for lightweight materials. It is big. For example, Japanese Patent Application Laid-Open No. Sho 55-113529 discloses a method for producing a molded article having a marble pattern, which claims "1. Unsaturated polyester resin, reinforcing fiber, filler, thickener, and curing agent. In the process of manufacturing an SMC comprising an agent, a release agent, etc., a thickened flake of an unsaturated polyester resin containing a colorant having a different color tone from the SMC is partially scattered on the surface of the SMC as a pattern forming material. And producing a molded article having a marble characteristic by hot-pressing the SMC. "Japanese Patent Application Laid-Open No. 1-257153 discloses an imitation flower arrangement. Claims of the rock and its production method include: (1) 20 to 60% by weight of a base resin mainly composed of an acrylate ester (the same shall apply hereinafter to the total amount of the imitation granite). ,average Inorganic filler 30 in the radial 2~70μm
79% by weight and a mixture in which 1 to 40% by weight of white, black or colored inorganic particles having a particle size of 0.1 mm or more are dispersed, and a silica-based filler is used as the inorganic filler at least based on the total amount of the imitation granite. Imitation granite characterized by containing 30% by weight. "
JP-B-5-9587 discloses a method of applying a mixed material, which claims "1. A method in which a mixed material obtained by mixing moderately ground natural stone into a synthetic resin. By preparing a plurality of different colors in separate tanks in a single spray gun, and simultaneously spraying the mixed materials from separate spray ports of a multi-head spray gun having a plurality of spray ports. And a method of applying a mixed material characterized by being applied in a non-mixed multicolored form. "And JP-B-2-22028 discloses" 1. After performing, the size obtained by resin-dying a dye or pigment on mica pieces is 1 to 10 m.
m flaky colored mica and a resin liquid or paint in a weight ratio of 1:
A method for finishing a stone pattern, comprising coating a coating material containing colored mica mixed at 99 to 40:60 with a spray or a roller to form a stone pattern layer. Is described, but none of them is described as a lightweight material. On the other hand, as a lightweight material, an organic foaming material such as polyethylene foam, polyvinyl chloride foam, polystyrene foam, and polyurethane foam, and water-soluble silicate, phosphate, and cement were used as binders and foamed and cured with various foaming agents. BACKGROUND ART Inorganic foam materials have been conventionally known, and they are mainly used as lightweight heat insulating materials and cushioning materials. These materials exhibit the above-mentioned heat insulating effect and light weight effect by the bubble structure contained therein, and maintain their shape by the skeleton formed from the constituent components. However, these organic and inorganic foam materials have not yet been used as design materials by positively imparting colors and shapes, other than being used as lightweight heat insulating materials and cushioning materials. For example, JP
Japanese Patent Application Laid-Open No. 7-212219 discloses "a method for producing a rigid polyurethane foam having open cells", and the claims include "a method for producing a rigid polyurethane foam from an active hydrogen-containing compound, an organic polyisocyanate, or the like. A siloxane-polyoxyalkylene block copolymer having a general formula (AB) _n (where n is an integer of 4 or more, A is a siloxane block, and B is a polyoxyalkylene block) is used as the foaming agent. A method for producing a rigid polyurethane foam having open cells, characterized by using a combination of an organic silicon surfactant for a flexible polyurethane foam and an organic silicon-based surfactant for a flexible polyurethane foam. " Claims for a method of producing a flame-retardant polyurethane foam The scope, "polyether polyol, an organic isocyanate, water, as well as the raw material of urethane foam containing the required additives such as a catalyst and foam stabilizer, relative to the polyether polyol 100 parts by weight of 10 to 5
A method for producing a flame-retardant polyurethane foam, characterized in that 0 parts by weight of a triaryl phosphate and 5.0 to 30 parts by weight of a zirconium compound are added, mixed and foamed. However, there is no description at all about the point of imparting a color or a shape, in particular, a natural stone or a natural stone tone.

[0003]

The problem to be solved and used by the present invention is that, as described above, conventional natural stones, molded articles or coating materials imitating natural stones do not have a light weight, and conversely, What is called a lightweight body, especially in plastic foam, besides the purpose as heat insulating material, cushioning material,
It is an object of the present invention to solve both the problems of natural stone and materials that mimic natural stone at once, and to provide a composition that is lightweight and forms a natural rock-like solid shape.

[0004]

In order to solve such problems, the present inventors have conceived of using an in-situ foamed plastic foam, in which a specific foamed urethane resin composition is used. Invented a way to That is, the present invention has the following configuration. 1. OH value 300-800mgKOH / g, weight average content
Polyether polyol 1 having a molecular weight of 1,000 to 10,000
00 parts by weight, water is 1 to 5 parts by weight, tertiary amine catalyst 1 to 5 parts
Parts by weight, 1 to 5 parts by weight of organometallic catalyst, 1 to 1 surfactant
0 parts by weight of the main ingredient (A) and an NCO value of 10 to 25%
Curing agent (B) comprising HMDI-based polyisocyanate
And a colored aggregate having a particle diameter of 0.1 to 5 mm and / or
Color pigment (C) and inorganic powder having a particle diameter of 0.2 to 250 μm
A: B: C: D = 100: 150 to 350:
It is characterized by being blended at a ratio of 1 to 300: 10 to 300.
A natural rock-like foamed decorative finishing material. 2.1. Using the natural rock-like foamed decorative finishing material described in
Artificial stone made by The natural rock-like foamed decorative finishing material of the present invention comprises, based on polyether polyol, a main agent (A) composed of water, a catalyst and a surfactant, a curing agent (B) composed of HMDI-based polyisocyanate, and a coloring material ( C),
It is made of a filler (D), and is characterized in that a urea bond is generated and carbon dioxide gas is generated by a reaction between water and isocyanate. The colored polyurethane foam is formed by the generation of the carbon dioxide gas and the three-dimensional crosslinking of the urea bond and the excess isocyanate. The polyether polyol is obtained by reacting one or more polyols with one or more epoxy compounds. As the polyol used, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol,
1,2,6-hexanetriol, bisphenol A,
Examples thereof include α-methylglycoxide, sorbitol, and soucrose having an OH value of 300 to 800 mgKOH / g and a weight average molecular weight of about 1,000 to 10,000. In addition, ethylenediamine and the like can be used. Generally, propylene glycol is used, but sorbitol-based and sucrose-based high-density types are desirable for reasons such as strength. Examples of the epoxy compound include alkylene oxides, for example, ethylene oxide, propylene oxide, and the like. In general, propylene oxide is used. Catalysts used include those that have a strong tendency to activate the cross-linking reaction between isocyanate and polyol, and those that have a strong tendency to activate the carbon dioxide blowing reaction of isocyanate and water. Is the most. Representative examples of such a catalyst include a tertiary amine compound and an organometallic compound. Examples of the tertiary amine compound include monoamines such as triethylamine and N, N-dimethylcyclohexylamine, N, N, N ′, N ′.
-Tetramethylethylenediamine, N, N, N ', N'
Diamines such as -tetramethylpropane 1,3-diamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, triamines such as tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine; Cyclic amines such as N-methylmorpholine, alcohol amines such as dimethylaminoethanol and dimethylaminoethoxyethanol, and ether amines such as bis (2-dimethylaminoethyl) ether and ethylene glycol bis (3-dimethyl) -aminopropyl ether Is raised. Examples of the organometallic compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, and cobalt octoate. Is raised. One or more of these tertiary amine compounds and organometallic compounds can be used in combination, and the combined use may be appropriately adjusted so that the reaction behavior can produce the desired polyurethane foam. The mixing ratio of the tertiary amine compound is
1 to 5 parts by weight with respect to 100 parts by weight of the polyol.
You. The mixing ratio of the organometallic compound is polyether
1 to 5 parts by weight based on 100 parts by weight of polyol
You. In particular, for the balance between foamability and curability, the ratio of the tertiary amine compound to the organometallic catalyst is more preferably from 5: 1 to 1: 1. Surfactants are sufficient to emulsify water used as a foaming agent on the oil surface and function as a foam stabilizer to form uniform foam in the reaction with the isocyanate. A reactant with the oxide is used. In addition, a sulfonate, a polysiloxane-polyoxyalkylene copolymer, or the like is used as a stabilizer that functions as a stabilizer for the formed foam. Further, those that function as foam stabilizers include those based on methylpolysiloxane.
The mixing ratio of the surfactant is 1 to 10 parts by weight based on 100 parts by weight of the polyether polyol . Next, the mixing ratio of water is 1 to 5 parts by weight based on 100 parts by weight of the polyether polyol. Next, polyisocyanate is used for HMDI and its modified buret,
, Trimer, prepolymer, etc. , having an NCO value of 10 to 2
Although about 5% is mentioned, HMDI and its trimer (isocyanurate type) are more preferable in terms of yellowing resistance and weather resistance. Mixing ratio of the polyisocyanate, polyether polyol, water, catalyst, relative to 100 parts by weight base resin component (A) consisting of a surfactant, HMDI or its trimer (isocyanurate excellent yellowing resistance and weather resistance Type), 150 to 350 parts by weight
And Further, as a coloring material, a coloring pigment and / or
Alternatively, a colored aggregate can be used. Examples of such coloring pigments include inorganic and organic pigments. Examples of inorganic pigments include white such as titanium dioxide, zinc white, lithopone, and zircon oxide, and red such as synthetic iron oxide (Fe2O3) and red iron oxide. , Synthetic iron oxide (α-FeO.OH), yellow such as ocher, green such as chromium oxide, blue such as cobalt blue and ultramarine blue,
And black such as carbon black. On the other hand, organic pigments include azo pigments such as azo lakes such as Brilliant Carmine 6B and Watching Red, insoluble azo pigments such as Lake Red 4R, Permanent Red FB, Hansa Yellow G, Disazo Yellow G, and Permanent Yellow HR; Condensed azos such as Chromophtal Red, Chromophtal Yellow 3G and Nova Palm Orange HL are used as condensed polycyclic pigments as phthalocyanines such as copper phthalocyanine, chlorinated copper phthalocyanine, indanthrone, anthrapyrimidine, flavan Sulene, perinone, thioindigo, perylene and the like, quinacridone such as quinacridone red, dioxazine such as dioxazine violet, isoindolinone such as isoindolinone yellow, and isoindoline such as isoindoline yellow Phosphorus-based, quinophthalone such quinophthalone yellow, metal complexes such as azo nickel complex. Other examples include dyed lake pigments. As the colored aggregate, natural or artificial can be used. For example, natural aggregates include silica sand, river sand, mountain sand, cold water stone, white dragon stone, Hakuo, granite, mica, etc., and artificial aggregates include ceramic powder, colored glass powder, perlite, vermiculite, and colored silica sand. , Colored mica, titanium mica and the like. In addition, when combined with these colored aggregates, transparent aggregates such as glass particles and fused silica can also be used. The particle size of these colored aggregates is not particularly limited, but is 0.1 to 5 in consideration of the effect on the foaming reaction and the problem of sedimentation due to the difference in specific gravity.
mm is desirable. The mixing ratio of the coloring pigment and the coloring aggregate is 1 to 300 parts by weight based on 100 parts by weight of the component (A) . As the filler, kaolin, talc, mica, calcium carbonate, barium sulfate,
Zinc white, silica, aluminum hydroxide, alumina, fly ash, bentonite, and ceramic powder can be used, and the compounding ratio is 10 to 300 parts by weight with respect to 100 parts by weight of the component (A). Further, if necessary, fibrous materials, for example , rock wool, glass fiber, carbon fiber, steel fiber and the like can be appropriately compounded. The finishing material of the present invention may further contain a flame retardant as needed. Such flame retardants include antimony trioxide,
Modified barium metaborate, chlorinated polyolefin, melamine, aluminum hydroxide, magnesium hydroxide, calcium carbonate, chloroalkyl phosphate, dimethyl
Non-reactive substances such as methyl phosphate, polymeric phosphite, bromine-phosphorus compound, organic bromine compound, ammonium polyphosphate, diethyl bishydroxyethyl aminoethyl phosphate, neopentyl bromide-polyether, neopentyl bromide- Adipate, dibromopropanol, dibromoneopentyl glycol, trans, 2,3-dibromo-2-
Reactive ones such as butyne-1,4-diol and brominated polyether can be used, and can be appropriately added to such an extent that the foaming hardening reaction is not hindered. As described above, the finishing material of the present invention gradually starts the foaming and curing reaction by mixing the components on site. At this time, it is applied by applying with a trowel, a brush, and a roller. In addition, spraying the mixture, mixing the hardener and other components separately by spraying with a multi-head gun on the construction surface, mixing by spraying with a static mixer at the tip, and similarly finishing materials adjusted to different colors It can be sprayed in a non-mixed state with a multi-head gun, or sprayed with a tip mixed with a static mixer. In addition, colored aggregates and fillers are pre-mixed types mixed from the beginning on the main agent side, or
It may be added when mixing the main agent and the curing agent. Next, when using the natural rock-like foam decorative finish of the present invention on the surface of a building or civil engineering structure, it is necessary to apply a primer layer. As a primer, when the substrate is a concrete surface, it has excellent adhesion and sealing properties to a concrete substrate such as a one-component moisture-curable urethane resin primer, and a one-component and two-component reaction-curable epoxy resin primer. Permeable primers are preferred. In some cases, an epoxy resin filler that is emulsified and cured by a water-dispersed modified amidoamine adduct may be used.
Further, when the base is an iron part, an epoxy lead-tin primer or the like can be used. In addition to being used on the surface of buildings and civil engineering structures, the natural rock-like foamed decorative material of the present invention can be cast into a formwork, or foamed simply by flowing an appropriate amount down a horizontal plane, and used as a three-dimensional object such as a stone. Shape can be formed. The three-dimensional pattern formed from the natural rock-like foamed decorative material of the present invention can be further subjected to various decorative finishes via a primer on the surface. Examples of such a decorative coating material include aqueous and solvent-based various colored and transparent coating materials. In particular, a natural stone tone finish containing a colored aggregate having a synthetic resin emulsion as a binder is applied. In the case, the three-dimensional pattern shape becomes natural rock-like,
It has a great effect on improving the aesthetics even in distant views. In another embodiment of the present invention, instead of building and civil engineering structures, concrete plates, ALC plates, gypsum boards, slate plates, wool cement plates, glass plates, metal plates, plastic plates, etc. And foam-thickened decorative board materials which have been subjected to a foam-thickening finish or further coated with a natural stone-like coating material via a primer. Such plate materials are manufactured in advance in factories, etc.
By sticking or attaching, you can also show a solid feeling in a distant view.

[0005]

EXAMPLES (Example 1) According to Formulation Example 1 shown in Table 1,
After adjusting the main agent (A), curing agent (B), coloring material (C), and filler (D), apply a one-component modified epoxy resin-based primer to a 6 mm thick slate plate, and dry it to a thickness of 2 m.
m foamed polystyrene joint formwork
After forming a frame of 00 mm x 200 mm in width x 2 mm in depth and drying and curing the primer, (A), (B),
A mixture obtained by mixing (C) and (D) was poured to produce a foam. At this time, the foaming start time and the foaming end time, the foaming ratio and the foam density were simultaneously measured. Furthermore, as a test body with the formed foam adhered to the slate plate,
A physical property test was performed according to the test methods described below. (However, a test specimen was prepared separately only for the measurement of the compressive strength.) The components shown below were used as the components used in the formulation examples. Polyether polyol Sorbitol / polyethylene oxide “SBU polyol 0480” manufactured by Sumitomo Bayer Urethane Co., Ltd. Tertiary amine 2,4,6-tris (dimethylaminomethyl) phenol manufactured by Sumitomo Bayer Urethane Co., Ltd. “Desmorapid DB” Silicone foaming "SH193" stannous octoate Nitto Kasei Co., Ltd. "T-9" HMDI-based polyisocyanate HMDI-based isocyanurate manufactured by Sumitomo Bayer Urethane Co., Ltd. "Sumidur N3500" TDI-based polyisocyanate Sumitomo Bayer-Urethane TDI-based isocyanate “Sumidur T-80” MDI-based polyisocyanate MDI-based isocyanate “Sumidur 44V10” manufactured by Sumitomo Bayer Urethane Co., Ltd. <Compression The compressive strength was measured according to the compression test method in degrees> JIS K 7220-1983 rigid cellular plastics. According to Formulation Example 1 shown in Table 1, the base material (A), the curing agent (B), the coloring material (C), and the filler (D) were adjusted.
Mix in a 00 cc polyethylene cup to form a foam. After the foam hardening reaction is completely completed,
It was cut out into a cube of cm square and used. The moving speed of the crosshead was set at 10 mm / min. <Adhesion strength> A 40 mm x 40 mm steel jig is adhered with a two-component epoxy resin adhesive to the surface of the above test piece roughened with sandpaper in accordance with JIS K 5400 8.7 Adhesion strength test method. I do. Twenty-four hours later, a cut is made along the steel jig around the periphery to a size of 40 mm x 40 mm until the slate plate is reached, and a steel jig for lower tension and a steel backing plate are used to automatically apply a vertical force to the sample surface. The maximum tensile load was determined by applying a tensile force in the graph. <Water resistance test> The test specimen was immersed in water for 14 days and then dried at room temperature. The surface condition was observed, and the change in the condition before immersion was evaluated. The evaluation criteria were as follows: な い for no abnormality, △ for whitened, and × for surface eroded. <Acid resistance test> After immersion in a 3% hydrochloric acid aqueous solution for 7 days, the resultant was dried at room temperature, the surface state was observed, and the change in the state before immersion was evaluated. The evaluation criteria were as follows: な い for no abnormality, △ for whitened, and × for surface eroded. <Solvent resistance test> After immersion in toluene for 3 days, drying was performed at room temperature. The surface state was observed, and the change in the state before immersion was evaluated. The evaluation criterion was evaluated as 異常 when there was no abnormality, and as X when the surface was softened. <Weather resistance test> JIS K 5400 9.3 Using a sunshine carbon arc lamp type weather resistance tester specified in 9.3 Accelerated weather resistance test, perform an acceleration test for 1000 hours, dry at room temperature, observe the surface condition, and observe the condition before immersion. Changes in state were evaluated.
The evaluation criteria were as follows: ○: No abnormalities, △: Whitened,
The thing which surface eroded was set to x. Table 2 shows the results of these tests. From the results, it was found that the foam produced in Formulation Example 1 had sufficient performance in various physical properties.

[Table 1]

[Table 2] (Examples 2-3) In the same manner as in Example 1 except that each of Formulation Examples 2 and 3 were used, and a physical property test was further performed, Formulation Example 2 became granite-like and Formulation Example 2 was slightly yellowish. It became a shade of granite. The results are shown in Table 2. As in Example 1, it was found that each foam had sufficient properties in each property. (Comparative Examples 1 to 3) A physical property test was performed in the same manner as in Example 1 except that Formulation Examples 4, 5, and 6 were used. However, the foaming start time could not be measured because the reaction started immediately after mixing the main material (A) and the curing agent (B). The results are shown in Table 2. In all cases, the compressive strength and the adhesive strength were low, and it turned out to be yellow in the weather resistance test, so that it could not be used externally as a natural rock-like foam decorative finish.

[0006]

According to the present invention, there is provided a material and a method capable of giving a thick three-dimensional pattern to a base material layer of an architectural or civil engineering structure.
There is a merit that a solid design can be obtained even in a distant view. Other advantages of the present invention are listed below. (1) Despite being thick, it is lightweight, so there is no danger of peeling off. (2) Since the foamed urethane resin composition can be applied and applied on site, there is no need for a large-scale operation of manufacturing, transporting, and attaching a molded product. (3) Because of the coating work, it can be applied to any part such as unevenness or curved surface of the base. (4) Since an HMDI-based polyurethane foam is formed, it is excellent in weather resistance and acid resistance even when used externally. As a result, the surface is hardly deteriorated even by acid rain. (5) Since the closed-cell polyurethane foam is formed, it is difficult for rainwater to enter from the outside, and swelling, peeling, and freezing breakage in winter are also unlikely to occur. (6) Since the foaming-curing reaction of the foamable urethane resin composition is quick and generates heat, the construction period can be shortened and construction in cold regions is possible.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C04B 14:02 14:36 24:40) (C08G 18/09 101: 00) C04B 111: 40 (72) Inventor Susumu Yamamoto Ibaraki, Osaka 1-25-10 Shimizu Investigator, Institute of Research, Ska Kaken Co., Ltd. Hideo Tokunaga (56) References JP-A-1-257153 (JP, A) JP-A-5-186283 (JP, A) JP-A-59 JP-A-145221 (JP, A) JP-A-55-113529 (JP, A) JP-A-57-212219 (JP, A) JP-A-60-123521 (JP, A) JP-B-2-22028 (JP, B2) (58) Fields surveyed (Int. Cl. ⁷ , DB name) C04B 26/16 C04B 14:02 C04B 24:40

Claims (2)

(57) [Claims] 1. An OH value of 300 to 800 mg KOH / g,
Polyether poly having a weight average molecular weight of 1,000 to 10,000
100 parts by weight of all, 1 to 5 parts by weight of water, tertiary amine
1-5 parts by weight of medium, 1-5 parts by weight of organometallic catalyst, surface activity
A main agent (A) consisting of 1 to 10 parts by weight of an agent, and an NCO value of 10
Curing consisting of -25% HMDI-based polyisocyanate
Agent (B) and a colored aggregate having a particle diameter of 0.1 to 5 mm and / or
Or a color pigment (C) having a particle diameter of 0.2 to 250 μm
A: B: C: D = 100: 150 to inorganic powder (D)
Be mixed at a ratio of 350: 1 to 300: 10 to 300
A natural rock-like foam decorative finish material characterized by the following. 2. A natural rock-like foamed cosmetic according to claim 1.
Artificial stone made using top material.