JPWO2011114966A1 - Plate-shaped cured body - Google Patents

Abstract

A novel plate-shaped cured body having excellent design properties and excellent fireproof performance, breathability and the like is obtained. A plate-shaped cured body containing a synthetic resin and a granular material at a specific weight ratio, and the plate-shaped cured body has a dispersion peak of loss tangent tan δ measured using a dynamic viscoelasticity measuring device at least −20 ° C. It shall have in each temperature range of -80 degreeC (T1) and -150 degreeC --100 degreeC (T2).

Description

  The present invention relates to a novel plate-shaped cured body that can be used for building materials and the like.

  As building materials for interiors of buildings, natural stones, which are relatively thick in the image of natural stones, and those having various design patterns, such as those having various uneven patterns and those having a profound feeling are being adopted.

  In recent years, interest in safe and comfortable living spaces has increased, and building materials for interior use have various design features such as fire resistance, anti-contamination performance, indoor dew condensation prevention, mold generation prevention, and antibacterial properties. It is required to have functionality and to be excellent in workability due to flexibility and weight reduction. Along with this, many products have been developed.

  For example, in Patent Document 1, a reinforcing material is laminated with a binder such as an acrylic resin emulsion and a spray material in which natural aggregate or artificial aggregate is blended, and a transparent sheet is formed on the surface via an adhesive. The decorative material is described. Patent Document 2 describes a building material having fireproof performance containing a hygroscopic material and a hydraulic substance.

JP-A-4-347251 JP 2003-96930 A

  However, the decorative material such as Patent Document 1 contains a large amount of organic resin components such as a synthetic resin, a synthetic fiber fabric, an adhesive, and a transparent sheet. Moreover, since a transparent sheet is provided on the surface, the air permeability may be inferior. On the other hand, when a hydraulic substance is employed as a binder as in Patent Document 2, excellent fireproof performance can be exhibited, but design properties may be inferior.

  This invention is made | formed in view of such a point, and it aims at obtaining the plate-shaped hardening body which has the performance excellent in fireproof performance, breathability, etc. while being excellent in the designability.

  As a result of intensive studies to achieve the above object, the present inventor has identified a dispersion peak of loss tangent tan δ measured using a dynamic viscoelasticity measuring device with synthetic resin and powder as constituent components. The present inventors completed the present invention by conceiving a plate-like cured body having a range.

That is, the plate-shaped cured body of the present invention has the following characteristics.
1. A plate-like cured body including a synthetic resin and a granular material, wherein the plate-shaped cured body includes 200 to 4000 parts by weight of the granular material with respect to 100 parts by weight of the synthetic resin in a solid content weight ratio, The plate-like cured body has at least −20 ° C. to 80 ° C. (T ₁ ) and −150 ° C. to −100 ° C. (T ₂ ) dispersion peaks of loss tangent tan δ measured using a dynamic viscoelasticity measuring device. A plate-like cured body having a temperature range.
2. The above synthetic resin has a dispersion peak of loss tangent tan δ measured using a dynamic viscoelasticity measuring device at least at −20 ° C. to 80 ° C. (T ₁ ) and −150 ° C. to −100 ° C. (T ₂ ). 1. It has what is in the range. 2. The plate-like cured product according to 1.
3. The synthetic resin contains an acrylic resin and a silicone resin in a solid content weight ratio of 95: 5 to 30:70. ~ 2. The plate-shaped hardening body in any one of.
4). The synthetic resin is a graft polymer of acrylic resin and silicone resin. ~ 3. The plate-shaped hardening body in any one of.

5. The granular material includes colored aggregates and hygroscopic powder. ~ 4. The plate-shaped hardening body in any one of.
6). The powdery particle further contains a photocatalytic metal oxide. ~ 5. The plate-shaped hardening body in any one of.
7). 1. The above-mentioned granular material further contains a chemical substance adsorbent. ~ 6. The plate-shaped hardening body in any one of.
8.1. ~ 7. A plate-like cured body, wherein a moisture-permeable overcoat layer is laminated on the cured body according to any one of the above.
9. A synthetic resin and a method for producing a plate-like cured body including a granular material, wherein the synthetic resin has a dispersion peak of loss tangent tan δ measured using a dynamic viscoelasticity measuring device at least from −20 ° C. to 80 ° C. (T ₁ ) and −150 ° C. to −100 ° C. (T ₂ ), each having a temperature ratio of 200 to 4000 parts by weight of the granular material with respect to 100 parts by weight of the synthetic resin. mixing a first step of forming a second step, the manufacturing method of the plate-like cured product which comprises a curing at a temperature greater than the dispersion peak temperature (T ₁₎ of the synthetic resin.

  The present invention relates to a plate-like cured body comprising a synthetic resin and a granular material, and containing 200 to 4000 parts by weight of the granular material with respect to 100 parts by weight of the synthetic resin in a solid content weight ratio, The plate-like cured product is excellent in that the dispersion peak of loss tangent tan δ measured using a dynamic viscoelasticity measuring device is at least in the respective temperature ranges of −20 ° C. to 80 ° C. and −150 ° C. to −100 ° C. Designability, fireproofing, air permeability, etc. can be exhibited.

  Hereinafter, the best mode for carrying out the present invention will be described.

The plate-like cured product of the present invention comprises (A) a synthetic resin and (B) a granular material in a specific ratio, and is also referred to as a dynamic mechanical spectrometer (hereinafter referred to as “DMS”). ) Of the loss tangent tan δ (tan δ curve) measured using) at least from −20 ° C. to 80 ° C. (T ₁ ) and from −150 ° C. to −100 ° C. (T ₂ ). It has in each temperature range. This mechanism of action is not clear, added dispersion peak above T _1, by having a temperature range of above T _2, exhibits excellent breathability under normal circumstances the plate-like cured product is used that Can do. In addition, by adding a dispersion peak to T ₁ and having a temperature range of T ₂ , even when a large amount of powder is included, it has good moldability, and as a result, design and fire resistance. It is possible to obtain a plate-like cured body excellent in the above.

  The DMS measurement uses a plate-like cured body having a length of 40 mm, a width of 10 mm, and a thickness of 2 mm as a sample, and using a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.), measurement temperature range: -150 ° C. ˜80 ° C., temperature rising rate: 4 ° C./min, measurement frequency: 1 Hz.

(A) Synthetic Resin The synthetic resin of the present invention (hereinafter also referred to as “component (A)”) is not particularly limited. For example, acrylic resin, silicone resin, acrylic silicone resin, fluororesin, vinyl acetate resin, acrylic Vinyl acetate resin, vinyl chloride resin, urethane resin, acrylic / urethane resin, epoxy resin, alkyd resin, polyvinyl alcohol resin, polyester resin, ethylene resin, polyvinyl alcohol, cellulose and its water-dispersed type, water-soluble type, NAD type, solvent-soluble type, solventless type and the like can be mentioned, and one-component type, two-component type and the like are not particularly limited and can be used.

In the present invention, the dispersion peak of loss tangent tan δ measured using DMS as component (A) is at least −20 ° C. to 80 ° C. (T ₁ ) and −150 ° C. to −100 ° C. (T ₂ ). It is preferable to use what has. By including such component (A), excellent air permeability can be exhibited. Also, unless impair the effects of the present invention may have other dispersion peak in the temperature range other than the T ₁ and the T _2.

Such a component (A) is not particularly limited.
A synthetic resin having a tan δ curve dispersion peak at T ₁ and a synthetic resin having a tan δ curve dispersion peak at T ₂ ; a synthetic resin having a tan δ curve dispersion peak at T ₁ ; Examples thereof include a polymer in which a synthetic resin having a tan δ curve dispersion peak at T ₂ is chemically bonded.

  In addition, DMS measurement of the above synthetic resin is a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments Inc.) using a sample of (A) component formed into a dry film thickness of 0.1 mm (length 40 mm × width 10 mm). DMS6100) is used under the conditions of measurement temperature range: −150 ° C. to 80 ° C., heating rate: 4 ° C./min, measurement frequency: 1 Hz.

Specifically, in the present invention as the component (A), an acrylic resin having a dispersion peak in the above temperature range T ₁ (a1) (hereinafter, also referred to as "component (a1)".), And the above-mentioned temperature range T ₂ It is preferable to use those containing a silicone resin (a2) having a dispersion peak in (hereinafter also referred to as “component (a2)”). The solid content weight ratio of the acrylic resin and the silicone resin in the component (A) is usually 95: 5 to 30:70, preferably 90:10 to 40:60, and more preferably 85:15 to 60:40. By including both components in such a ratio, breathability and fireproofing can be improved.

  The acrylic resin (a1) is a polymer mainly composed of (meth) acrylic acid ester, and is obtained by copolymerizing other monomers as necessary. Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , N-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (Meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like. The amount of the (meth) acrylic acid alkyl ester used is usually 30% by weight or more, preferably 40 to 99.9% by weight, more preferably 50 to 99.9%, based on all monomers constituting the component (A). 5% by weight.

  In the present invention, the (meth) acrylic acid ester preferably contains a (meth) acrylic acid ester having 6 or more carbon atoms in the alkyl group as an essential component. Among these, 2-ethylhexyl acrylate is particularly preferable. In the present invention, the (meth) acrylic acid ester having 6 or more carbon atoms in the alkyl group is 10% by weight or more, preferably 15% by weight or more and 50% by weight, based on all monomers constituting the component (A). It is preferable to include the following. In this case, fire resistance of the obtained plate-like cured body can be enhanced.

  Examples of other monomers include carboxyl group-containing monomers, amino group-containing monomers, pyridine monomers, hydroxyl group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, and alkoxysilyl group-containing monomers. And aromatic monomers. The usage-amount of these monomers is 0.1 to 60 weight% normally with respect to all the monomers which comprise (A) component, Preferably it is 0.5 to 50 weight%.

  Among these, when a carboxyl group-containing monomer is copolymerized to obtain a carboxyl group-containing acrylic resin, various physical properties of the plate-like cured body can be improved by separately adding a compound capable of reacting with the carboxyl group. it can. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid or a monoalkyl ester thereof, itaconic acid or a monoalkyl ester thereof, fumaric acid or a monoalkyl ester thereof. Among these, at least one selected from acrylic acid and methacrylic acid is particularly preferable. The usage-amount of a carboxyl group-containing monomer is 0.1 to 40 weight% normally with respect to all the monomers which comprise (A) component, Preferably it is 0.5 to 20 weight%.

  Moreover, as a compound which can react with a carboxyl group, the compound which has 1 or more types of functional groups chosen from a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group etc. is mentioned, for example.

  The silicone resin (a2) is obtained by polymerizing a siloxane compound. Examples of the siloxane compound include cyclic siloxane compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. When polymerizing such a cyclic siloxane compound, a linear siloxane compound, a branched siloxane compound, an alkoxysilane compound, or the like can also be used. Of these, as the alkoxysilane compound, a silane compound having one or more alkoxyl groups in the molecule can be used. For example, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ- Silane coupling agents such as (meth) acryloyloxytrimethoxysilane and 3-mercaptopropyltrimethoxysilane can be used. The average molecular weight of the silicone resin is usually 10,000 or more, preferably 50,000 or more.

  As the component (A), a graft polymer of the acrylic resin (a1) and the silicone resin (a2) is preferable. By being a graft polymer, it is possible to improve the fire resistance and flexibility by making use of the texture of the granular material described later. In addition, advantageous effects can be obtained in each physical property such as water resistance, weather resistance, and contamination resistance. Furthermore, when the hygroscopic powder is included as the granular material, the performance can be sufficiently exhibited. Although the mechanism of this action is not clear, the component (a2) is moderately easy to move in a normal environment where a plate-like cured body is used, so that other physical properties can be improved while exhibiting excellent air permeability. it is conceivable that. Such a graft polymer can be obtained, for example, by copolymerizing the siloxane compound, the (meth) acrylic acid ester, and a graft crossing agent. Examples of the graft crossing agent include polyfunctional alkoxysilanes containing a vinyl polymerizable functional group and / or a mercapto group.

As the component (A) of the present invention, a synthetic resin emulsion (water-dispersed resin) can be used. Breathability can be enhanced by using such a synthetic resin emulsion. Furthermore, it is possible to obtain a plate-like cured body excellent in fire resistance and flexibility while taking advantage of the texture of the granular material described later. Examples of the component (A), for example, an acrylic resin emulsion having a dispersion peak in the above temperature range T _1, and a mixture of silicone resin emulsion having a dispersion peak in the above temperature range T ₂ can be used.

  Moreover, it is also possible to use an acrylic-silicone synthetic resin emulsion (A-1) (hereinafter also referred to as “(A-1) component”) in which the component (a1) and the component (a2) are mixed in the emulsion particles. it can. The form of the (a1) component and the (a2) component in the component (A-1) is not particularly limited, and may be a uniformly mixed form, but a form separated from each other by a sea-island structure or the like is preferable.

  Furthermore, as the component (A) in the present invention, a synthetic resin emulsion (A-2) in which the graft polymer of the acrylic resin (a1) and the silicone resin (a2) is present in the emulsion particles is preferable. The component (A-2) can be obtained, for example, by emulsion polymerization of the siloxane compound, the (meth) acrylic acid ester, and the graft crossing agent in the presence of an emulsifier.

  Furthermore, it is preferable that the component (A) of the present invention forms a film having a reflective region having a reflectance of 10% or more, preferably 15% or more at a wavelength of 300 to 500 nm. By using such (A) component, when a photocatalyst metal oxide is included as a granular material, the photocatalytic activity can be improved. The action mechanism is not clear, but the light irradiated to the plate-shaped cured body of the present invention is diffused / reflected in the plate-shaped cured body and absorbed by the photocatalytic metal oxide described later dispersed in the plate-shaped cured body. This is thought to be easier.

  The reflectance is obtained by forming a component (A) into a film having a dry film thickness of 0.1 mm, a black plate is placed behind the sample, and a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) is used. ). In addition, let the black board piled up behind the sample be a blank, and let it be the converted value. Specifically, it is obtained by subtracting the reflectance of the black plate from the reflectance of the sample at each wavelength.

(B) Granules In the present invention, (B) 200 to 4000 parts by weight, preferably 300 to 3500 parts by weight, and more preferably 500 to 3000 parts by weight with respect to 100 parts by weight of component (A) described above. It is a waste. It is preferable that at least (b1) colored aggregates and (b2) moisture-absorbing / releasing powders are included as the above-mentioned granular material.

  (B1) The colored aggregate (hereinafter, also referred to as “component (b1)”) can give a fine unevenness to the surface of the plate-like cured body and can express a three-dimensional design having a shadow feeling. Further, unlike the case of using a coloring pigment having a small particle diameter, etc., it is possible to change the color tone, texture, etc. by mixing colored particles, and the small point of the component (b1) present on the plate-like cured body surface is It is visually recognized as a colorful pattern and has excellent decorativeness. The component (b1) suitable for the present invention is not particularly limited, and any of natural products and artificial products can be used. Specifically, for example, heavy calcium carbonate, cryolite, kaolin, clay, porcelain clay, china clay, talc, aluminum hydroxide, magnesium hydroxide, barite powder, marble, granite, serpentine, granite, fluorite, cold water Examples thereof include pulverized materials such as stone, feldspar, silica stone, and silica sand, ceramic pulverized materials, ceramic pulverized materials, glass beads, glass pulverized materials, resin beads, resin pulverized materials, and metal particles. Colored ones can also be used.

  The average particle size of the component (b1) is desirably 0.01 to 5 mm. When it is such a range, while being able to express the outstanding design, a plate-shaped hardening body can be manufactured stably. In addition, the average particle diameter of (b1) component is a value obtained by sieving using the metal net sieve prescribed | regulated to JISZ8801-1: 2000, and calculating the average value of the weight distribution.

  The amount of component (b1) is preferably 200 to 3400 parts by weight, more preferably 300 to 2000 parts by weight, and even more preferably 500 to 1500 parts by weight with respect to 100 parts by weight of the solid content of component (A). By including many (b1) components with respect to (A) component like the said range, the outstanding designability which utilized the texture of the aggregate can be obtained, and breathability can be improved further.

  (B2) Hygroscopic powder (hereinafter referred to as “component (b2)”) includes, for example, boehmite, silica gel, zeolite, sodium sulfate, alumina, allophane, diatomaceous earth, siliceous shale, sepiolite, attapulgite, montmorillonite, zonorite, Imogolite, Otani stone powder, activated clay, charcoal, bamboo charcoal, activated carbon, wood powder, shell powder, porous synthetic resin particles, etc. can be used. The average particle diameter of the hygroscopic powder is usually 0.001-1 mm, preferably 0.01-0.5 mm, more preferably 0.01-0.1 mm, and still more preferably 0.01-0.09 mm. It is. In addition, the average particle diameter of (b2) component is a value of the 50% particle diameter measured by the centrifugal sedimentation type particle size distribution measuring apparatus.

  Such a component (b2) has a moisture absorption rate of 10% or higher, preferably 20% or higher, at a temperature of 20 ° C. and a relative humidity of 90%. By having such a moisture absorption rate, functions such as discomfort suppression by adjusting humidity can be further improved, and a more comfortable living space can be obtained. Moreover, the dew condensation on the base material or the back surface of the base material, generation of mold, and the like can be prevented.

  The component ratio of the component (b2) is preferably 1 to 600 parts by weight, more preferably 5 to 500 parts by weight, and still more preferably 10 to 300 parts by weight with respect to 100 parts by weight (solid content) of the component (A). It is preferable. In the case of such a range, sufficient humidity control can be exhibited, and excellent strength and flexibility can be provided.

  Furthermore, in this invention, it is preferable that (b3) photocatalyst metal oxide (henceforth "(b3) component") is included as (B) granular material. A photocatalytic substance is an effective component for preventing decomposition and re-release of harmful gases. Furthermore, it also has the capability of decomposing contaminants (such as tobacco dust) adhering to the plate-like cured body. Furthermore, in the present invention, as the component (b3), in the reflective region where the reflectance of the coating formed by the component (A) out of the wavelength of 300 to 500 nm is 10% or more (hereinafter also simply referred to as “reflective region”) What shows a photocatalytic action is preferable. By including such a component (b3), the photocatalytic activity can be efficiently exhibited. The photocatalytic action of the present invention means that when the catalyst is exposed to light (ultraviolet rays and / or visible light), the catalyst absorbs and excites light, and the resulting excited electrons and holes are oxidized and reduced. Acid radicals and active oxygen are generated, and the hydroxyl radicals and active oxygen have an action of decomposing organic substances.

  Examples of the component (b3) include metal oxides such as titanium oxide, tin oxide, zinc oxide, ferric oxide, dibismuth trioxide, and tungsten trioxide, or composite oxides thereof. 1 type (s) or 2 or more types can be used. The average particle size of the component (b3) is 0.3 μm or less, preferably 0.1 μm or more and 0.25 μm or less. When the photocatalytic metal oxide in the above range is used, it has an excellent photocatalytic action and can further utilize the texture of the aggregate of the plate-like cured body. The average particle size referred to here is obtained from measurement by centrifugal sedimentation or the like.

  In particular, it is preferable to use titanium oxide as the component (b3) of the present invention. Titanium oxide may be either anatase-type titanium oxide or rutile-type titanium oxide. In the present invention, it is particularly preferable to use anatase-type titanium oxide. When titanium oxide is used as the component (b3), the photocatalytic action is excellent, the total calorific value at the time of fire can be suppressed, and fire resistance can be improved. The action mechanism is presumed to be because titanium oxide can block radiant heat and suppress the temperature rise of the plate-like cured body. Furthermore, fireproofness improves more by using anatase type titanium oxide. The mechanism of action is not clear, but it is considered that the catalytic action of anatase-type titanium oxide by heating is involved. Further, the amount of exhaust gas can be reduced by the decomposition action of anatase type titanium oxide. Furthermore, the anatase-type titanium oxide has a lower effect of concealing the coating film than the rutile-type titanium oxide, so that the texture of the aggregate can be further utilized.

  The amount of component (b3) is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 25 parts by weight, and even more preferably 0.5 to 100 parts by weight of the solid content of component (A). 20 parts by weight. In such a range, excellent photocatalytic action and fire resistance can be exhibited.

  In this invention, it is preferable that (b4) chemical substance adsorbent is included as (B) granular material. By including the component (b4), it is effective for the adsorption and re-release prevention of harmful gases (for example, formaldehyde, ammonia, hydrogen sulfide, methyl mercaptan, trimethylamine, etc.). Examples of the component (b4) include amine compounds, urea compounds, amide compounds, imide compounds, hydrazide compounds, azole compounds, azine compounds, layered phosphate compounds, and aluminosilicates. Among these, at least one selected from a layered phosphate compound and an aluminosilicate is preferable, and an aluminosilicate is particularly preferable. The average particle size of such a chemical substance adsorbent is usually about 0.5 to 100 μm (preferably 1 to 50 μm).

  Examples of the layered phosphate compound include layered zirconium phosphate, layered zinc phosphate, layered titanium phosphate, layered aluminum phosphate, layered magnesium phosphate, layered cerium phosphate, and the like. An amine compound is included in these layered phosphate compounds. Intercalated ones are preferred. Examples of the amine compound include methylamine, ethylamine, aniline, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, and tripropylenetetramine.

  Examples of the aluminosilicate include a composite oxide of at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, and zirconium, and aluminum and silicon.

  The amount of component (b4) is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, and even more preferably 1 to 25 parts by weight per 100 parts by weight of the solid content of component (A). Part. In such a range, it is effective for adsorption of toxic gas.

  In the present invention, it is particularly preferable to use the component (b3) and the component (b4) in combination. By using these together, practical performance can be obtained in the adsorption / decomposition / re-release prevention of harmful gas, and a harmful gas filter effect can be imparted to the plate-like cured body. In the present invention, it is possible to obtain the adsorption / decomposition / re-release prevention performance of the invading harmful gas, particularly on both the indoor side and the base material side.

  In the present plate-like cured product, for the purpose of improving the decorativeness and the like, aggregate (C) (hereinafter referred to as “component (C)”) having an average particle diameter of more than 5 mm can be mixed or dispersed. . The component (C) suitable for the present invention includes, for example, pulverized products such as natural stone, silica, and silica sand, ceramic pulverized products, ceramic pulverized products, mica, shells, glass pulverized products, glass beads, resin pulverized products, and resin beads , Rubbers, plastics, plant fibers, plants such as plant pieces, metals such as alumina flakes, and those whose surfaces are colored and coated.

  Moreover, unless the effect of this invention is impaired remarkably, a well-known additive can be included as needed. Examples of such additives include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, algaeproofing agents, antibacterial agents, Examples include deodorants, dispersants, antifoaming agents, adsorbents, flame retardants, color pigments, extender pigments, fibers, water repellents, crosslinking agents, ultraviolet absorbers, antioxidants, and catalysts.

The plate-shaped cured product of the present invention can be laminated on a substrate. Examples of the base material include gypsum board, plywood, concrete, mortar, tile, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, resin board or sheet (film), woven fabric, nonwoven fabric, paper, etc. There is no particular limitation. Particularly in the present invention, the thickness is 0.05 to 1.5 mm (preferably 0.1 to 1 mm, more preferably 0.25 to 0.5 mm), basis weight 5 to 300 g / m ² , (preferably 10 to 10 mm). 200 g / ^{m 2,} more preferably a woven or nonwoven fabric is preferably comprises inorganic fibers 20~100g / ^{m 2).} Examples thereof include woven fabrics and nonwoven fabrics made of inorganic fibers such as mineral fibers and glass fibers. In particular, in the present invention, those having flexibility are preferred, and nonwoven fabrics having a structure in which fibers are superposed on a three-dimensional structure are preferred.

  Moreover, the base material which laminated | stacked the glass mesh, the glass cloth, etc. on the woven fabric or the nonwoven fabric can be used. When the base material in the above range is used, the contact interface with the plate-like cured body is increased, and thus the adhesiveness is excellent. Furthermore, when it constructs on a wall surface etc., since a base material contains inorganic fiber, a plate-shaped hardening body can be supported stably. For this reason, the prevention of curling and warping of the plate-like cured body at the time of fire and the prevention of falling off are improved, and the fire resistance and flame resistance are excellent. Moreover, by laminating the base material and the specific plate-like cured body, it is possible to easily cut into an arbitrary shape at the time of construction, and it is possible to appropriately perform the edge processing of the cut surface.

  Although the manufacturing method of the plate-shaped hardening body of this invention is not specifically limited, For example, it can manufacture with the manufacturing method containing the following processes. According to this method, the target plate-like cured product can be stably produced, and it is also preferable from the standpoint of effect expression.

A composition for hardened body (hereinafter also referred to as “cured body composition”) in which 200 to 4000 parts by weight of (B) granular material is mixed with 100 parts by weight of (A) synthetic resin in a solid weight ratio. A first step of forming a plate, and a second step of curing at a temperature (T ₃ ) higher than the dispersion peak temperature (T ₁ ) of the component (A).
(However, the component (A) has at least −20 ° C. to 80 ° C. (T ₁ ) and −150 ° C. to −100 ° C. (T ₂ ) dispersion peaks of loss tangent tan δ measured using a dynamic viscoelasticity measuring device. ) In each temperature range.)

In the second step, by curing with the component (A) of the dispersion peak temperature (T ₁₎ higher temperature than (T _3), the effect of the plate-like cured product of the present invention it is likely to be expressed. This mechanism of action is not clear, but when cured at the above temperature (T ₃ ), the resin component having a dispersion peak in the temperature range (T ₂ ) is easily oriented on the surface of the plate-shaped cured body. As a result, it is considered that an effect excellent in fire resistance, contamination resistance and the like can be exhibited.

In the first step, the method for molding the plate-shaped cured body is not particularly limited, and for example, it may be molded using a mold having releasability. Moreover, what is necessary is just to laminate | stack by the following method, for example, when laminating | stacking a base material on a plate-shaped hardening body.
(1) A method of laminating a composition for a plate-shaped cured body on a substrate, drying and curing (2) A method of molding a plate-shaped cured body using a mold and laminating the substrate

  In the above (1), when laminating the composition for a cured body, for example, a method using means such as spray, roller, trowel, brush coating, reciprocating, coater, pouring, etc. can be employed. Here, if the viscosity of the composition for hardening bodies is set to about 5-100 Pa.s, the target laminated body will be obtained easily. In addition, the viscosity said here is a viscosity in 20 rpm by a BH type viscometer, and measurement temperature is 23 degreeC.

In the above (2), as the mold to be used, for example, a mold made of silicon resin, urethane resin, metal, or the like, or a mold provided with release paper can be used. Moreover, as a method of laminating the base material, for example,
(I) A method of pouring a composition for a cured body into a mold, drying and demolding to form a plate-shaped cured body, and then laminating a substrate with an adhesive or the like,
(II) A method of pouring a composition for a cured body into a mold, laminating a substrate before the composition for a plate-shaped cured body is dried, drying, demolding, and the like.
Moreover, when pouring a hardening body composition in said (I) (II), the method similar to the lamination | stacking method in said (1) is employable.

  In said (1) and (2), as for the thickness of a plate-shaped hardening body, 1.0 mm or more and 5.0 mm or less are preferable. In such a case, it is possible to form a concavo-convex pattern that is excellent in fire resistance and deeply carved, so that it is possible to obtain excellent design with shadow and profound feeling. In addition, the thickness of a plate-shaped hardening body excludes a base-material part.

  In addition, as long as the effects of the present invention are not hindered, for example, a reinforcing material (ceramic paper, synthetic paper, glass cloth, mesh, etc.) is laminated, a concavo-convex pattern is formed for the purpose of improving decorativeness, etc. Can also be sprayed. Examples of the decorative material include colored aggregates, mica, shells, plants, alumina flakes, glass flakes, metals, rubbers, plastics, and the like.

  For example, when manufacturing by the method of said (1), formation of a concavo-convex pattern and dispersion | distribution of a decoration material should just be performed before the composition for hardening bodies hardens | cures, and formation of a concavo-convex pattern is performed with a trowel, embossing A method using a roller or the like can be employed, and a known or commercially available spreader or the like can be used for spraying the decoration material. Moreover, when manufacturing by the method of said (2), since the formation of an uneven | corrugated pattern becomes a plate-shaped hardening body surface, it can provide by adjusting the shape inside a formwork, and is a decoration material. In the case of spraying, the composition for the plate-shaped cured body may be poured after the decorative material is scattered on the bottom surface in the mold using a known or commercially available sprayer.

  Furthermore, if it is in the range which does not inhibit the effect of this invention remarkably, an overcoat layer can also be laminated | stacked in order to improve the surface protection property etc. of a plate-shaped hardening body. The top coat layer only needs to have moisture permeability and transparency (clear layer). In this case, the design property (hue) of the plate-like cured body can be utilized as it is, and further, air permeability, fire resistance, etc. The effect of can also be demonstrated. The overcoat layer may be a color clear layer to which various pigments are added within a range having transparency. Such an overcoat layer can be formed by applying a known water-based or solvent-type paint. In the present invention, an emulsion paint containing colloidal silica is preferred. In this case, surface strength, contamination resistance, etc. can be improved. Furthermore, the inclusion of colloidal silica is effective in improving fire resistance as compared with a known top coating.

  Examples of the emulsion containing colloidal silica include a mixture of a synthetic resin emulsion and colloidal silica, a colloidal silica composite emulsion in which a synthetic resin emulsion and colloidal silica are chemically bonded, and the like in the present invention. It is preferable to use it. It does not specifically limit as said synthetic resin emulsion, If it does not impair the effect of this invention, it can use suitably. Moreover, it is preferable that the synthetic resin component and colloidal silica in the emulsion containing colloidal silica are 95: 5-40: 60 by solid content weight ratio. The particle size of colloidal silica is preferably 10 nm to 100 nm. In such a range, it is possible to improve the surface protection and fire resistance of the plate-shaped cured body without inhibiting the effects of the present invention.

  These coatings may be performed by a known coating method, and a coating tool such as a spray, a coater, a roller, or a brush can be used.

  The plate-like cured body of the present invention can be applied mainly as an interior building material for buildings. That is, interior finishing can be performed by pasting on each part of the building interior surface. Specifically, it can be applied to walls, partitions, doors, ceilings, etc. in houses, condominiums, schools, hospitals, stores, offices, factories, warehouses, restaurants, etc. Examples of the base constituting such a part include gypsum board, plywood, concrete, mortar, tile, fiber-mixed cement board, cement calcium silicate board, and slag cement pearlite board. These bases may be those having an existing coating film on the surface thereof, or those already having wallpaper attached thereto. The plate-shaped cured body of the present invention is applied to such a base so that the plate-shaped cured body faces the indoor side.

  Moreover, what is necessary is just to stick to a base | substrate using an adhesive agent, an adhesive, an adhesive tape, a nail, a wrinkle, etc. when constructing this invention plate-shaped hardening body. In addition, it can also be fixed using pins, fasteners, rails or the like. Especially, it is preferable to stick the plate-shaped hardening body of this invention to a base | substrate using an adhesive agent.

  It does not specifically limit as an adhesive agent, What is necessary is just to use a well-known thing. For example, the synthetic resin used for the adhesive is not particularly limited, but ethylene resin, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, phenol resin, melamine resin, amino resin , Polycarbonate resin, acrylic silicon resin, acrylic vinyl acetate resin, acrylic styrene resin, acrylic urethane resin, silicone resin, water-soluble type such as fluorine resin, water dispersion type, etc. Can be used.

  In addition, powder components, hollow particles, porous particles, fibers, etc. may be added to give various performances such as workability, finish, adhesive strength, fire resistance, etc., and coloring materials and extender pigments may be added as necessary. Commonly used additives such as dispersants, viscosity modifiers, antifoaming agents, antifungal agents, preservatives, and algaeproofing agents can be added as appropriate.

  When the plate-shaped cured bodies are pasted with an adhesive, adjacent plate-shaped cured bodies can be abutted and pasted, or joints can be provided between the plate-shaped cured bodies. When affixing and affixing, it is preferable that the adhesive does not protrude. Moreover, when providing a joint, the space | interval at the time of sticking a plate-shaped hardening body is not specifically limited, What is necessary is just about 1 mm-30 mm. If it is such a range, interior finishing which makes use of a joint pattern can be performed. An adhesive agent can be exposed between plate-shaped hardening bodies, and a joint part can be formed easily. Moreover, you may smooth the adhesive of a joint part with a spatula etc. as needed. The ambient temperature at which the adhesive is cured can be set as appropriate, but is usually room temperature.

  Examples are given below to clarify the features of the present invention.

<Synthetic resin A>
(Synthetic Resin 1 to Synthetic Resin 3)
As structural components, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane Graft copolymerization was carried out to produce an acrylic-silicone graft copolymer type synthetic resin emulsion. These were designated as synthetic resins 1 to 3. Each synthetic resin has the following characteristics.
・ Synthetic resin 1
Acrylic component and silicone component weight ratio 80:20
DMS dispersion peak temperature: 55 ° C, -130 ° C
Solid content 50% by weight
・ Synthetic resin 2
Acrylic component and silicone component weight ratio 80:20
DMS dispersion peak temperature: 75 ° C, -130 ° C
Solid content 50% by weight
・ Synthetic resin 3
Weight ratio of acrylic component to silicone component 90:10
DMS dispersion peak temperature: 55 ° C, -130 ° C
Solid content 50% by weight

(Synthetic resin 4 to synthetic resin 6)
The following acrylic resin emulsion and silicone resin emulsion were mixed to obtain synthetic resins 4-6.
Acrylic resin emulsion (component: t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate), solid content 50% by weight
Silicone resin emulsion (emulsified dispersion of dimethylsiloxane compound), solid content 50% by weight
Synthetic resin 4; acrylic resin emulsion: silicone resin emulsion (solid content weight ratio) = 80: 20, DMS dispersion peak temperature: 55 ° C., −130 ° C.
Synthetic resin 5; acrylic resin emulsion: silicone resin emulsion (solid weight ratio) = 50: 50, DMS dispersion peak temperature: 55 ° C., −130 ° C.
Synthetic resin 6; acrylic resin emulsion: silicone resin emulsion (solid weight ratio) = 90: 10, DMS dispersion peak temperature: 55 ° C., −130 ° C.

・ Synthetic resin 7
Acrylic resin emulsion (component: t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate), solid content 50% by weight, DMS dispersion peak temperature: 55 ° C.

  The above-mentioned synthetic resins 1 to 7 were applied to a release paper and dried to prepare a film having a thickness of 0.1 mm, and the reflectance of the film was measured. In addition, the reflectance of the film was performed using the spectrophotometer (the Shimadzu Corporation make, UV-3100). The results are shown in Table 1.

  As a result, the synthetic resins 1, 2, 4, 5, and 6 have a region in which the ultraviolet reflectance is 10% or more in the wavelength region of 300 nm to 500 nm. In addition, the synthetic resin 3 has a region where the ultraviolet reflectance is 10% or less in a region having a wavelength of 400 nm or more, and the ultraviolet reflectance is 10% or more in a region having a wavelength of less than 400 nm. On the other hand, the synthetic resin 7 had an ultraviolet reflectance of less than 10% in the wavelength region. Table 1 shows the ultraviolet reflectance at wavelengths of 380 nm, 400 nm, and 500 nm as typical values.

(Manufacture of plate-shaped cured body)
According to the composition shown in Table 2 and Table 3, compositions 1 to 14 for cured bodies were produced by mixing and stirring each raw material by a conventional method. In addition, the following were used as a raw material.

(B) Powder (b1) component / aggregate 1: colored silica sand (light yellow, average particle size 80-120 μm)
-Aggregate 2: Heavy calcium carbonate (average particle size 50-150 μm)
(B2) Component / Hygroscopic powder: Silica gel (average particle size 20 μm, bulk specific gravity 0.30 g / ml, moisture absorption 80% (under 20 ° C., 90% RH atmosphere))
(B3) Component / photocatalytic oxide 1: UV-responsive anatase-type titanium oxide (excitation wavelength: 200 to 380 nm, average particle size 0.2 μm)
Photocatalytic oxide 2: Visible light-responsive anatase-type titanium oxide (excitation wavelength: 400 to 650 nm, average particle diameter of 15 nm)
(B4) Component / Chemical substance adsorbent: Zinc aluminosilicate (average particle size 3 μm)
(Additive)
・ Thickener (hydroxyethylcellulose, urethane associative thickener), water

(Test Examples 1-14)
The cured body compositions 1 to 14 were poured into a silicon mold so that the dry film thickness was 2 mm, dried at 100 ° C. for 30 minutes, and demolded to obtain plate-shaped cured bodies 1 to 14.

Each plate-like cured body is cut into 40 mm × 10 mm (thickness: 2 mm), used as a DMS measurement specimen, and measured using a DMS6100 manufactured by Seiko Instruments Inc., measuring temperature range: −150 ° C. to 80 ° C. Measurement was performed under conditions of a temperature rate of 4 ° C./min and a measurement frequency of 1 Hz. Table 4 shows the measured dispersion peak temperature of loss tangent tan δ.

・ Evaluation A
On a base material (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the above plate-shaped cured body compositions 1 to 14 are applied so that the thickness of the plate-shaped cured body after drying is 2 mm. And dried at 100 ° C. for 30 minutes to obtain laminates 1A to 14A of plate-like cured bodies.

  Each laminate was evaluated for design properties, fire resistance, flexibility, and air permeability. The results are shown in Table 5.

<Design evaluation>
The texture and concealment due to the aggregates of the plate-like cured bodies of the laminates 1A to 14A were visually evaluated. The evaluation standard is a four-step evaluation (excellent: A>B> C) where “A” is the material with good texture and concealment of the aggregate and “D” is the material with the insufficient texture and aggregate. > D: Inferior).

<Fireproof evaluation>
As a base material for testing, a gypsum board of 100 mm × 100 mm × 12.5 mm was used, an adhesive was applied to the base material, and each laminate 1A to 14A was attached, at 23 ° C. and 50 ± 10% RH. The specimens cured for 24 hours were used as test specimens.

The total calorific value of the test specimen after 20 minutes was measured with a cone calorimeter defined by ISO 5660. As the corn calorimeter, “CONE2A” (manufactured by Atlas) was used, and the heating intensity was 50 kW / m ² .
The evaluation criteria for the exothermic test are as follows.
A: Total calorific value after heating time of 20 minutes is 6.0 MJ / m ² or less B: Total calorific value after heating time of 20 minutes exceeds 6.0 MJ / m ² and is 8.0 MJ / m ² or less C: Heating It exceeds the total calorific value 8.0MJ / m ² at time 20 minutes, 10.0 mJ / m ² or less D: the total amount of heat generated at the heating time of 20 minutes exceeds 10.0MJ / m ^2, 12.0MJ / m ² or less E: Total calorific value after heating time of 20 minutes exceeds 12.0 MJ / m ²

<Flexibility evaluation>
As a base material for testing, an aluminum plate of 70 mm × 150 mm × 0.8 mm was used, an adhesive was applied to the base material, each laminate 1A to 14A was attached, and at 23 ° C. and 50 ± 10% RH. The specimens cured for 24 hours were used as test specimens. A copper rod having a diameter of 10 mm was applied to the center of the back surface of the test body, bent with the plate-like cured body surface facing outward, and the angle at which cracks occurred on the surface was evaluated.

<Hygroscopic evaluation 1>
As a base material for testing, a gypsum board of 100 mm × 100 mm × 12.5 mm was used, an adhesive was applied to the base material, and each laminate 1A to 14A was attached, at 23 ° C. and 50 ± 10% RH. The specimens cured for 24 hours were used as test specimens. Each specimen was left in an atmosphere of 23 ° C. and 90% RH, and the moisture absorption after 24 hours was evaluated (g / m ² ). The evaluation criteria for hygroscopicity are as follows.
A: 100 g / m ² or more B: 90 g / m ² or more and less than 100 g / m ² C: less than 90 g / m ² Note that the adhesive is made of synthetic resin 1, titanium oxide, heavy calcium carbonate, dispersant, thickening. An agent, an antifoaming agent, and water produced by uniformly stirring and mixing were used.

  Then, the following evaluation was performed.

・ Evaluation B
On the base material (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the cured body compositions 1-14 were applied so that the thickness of the plate-shaped cured body after drying was 2 mm, It dried for 30 minutes under the temperature shown in Table 6 and 7, and obtained laminated body 1B-16B of the plate-shaped hardening body.

<Contamination evaluation 1>
The surface of each of the laminates 1B to 16B was brushed with coffee, and after 5 minutes, wiped with a wet cloth and visually evaluated for contamination. The evaluation criteria were a four-step evaluation (excellent: A>B>C> D: poor), where “A” is the one from which the dirt has been removed and “D” is the one from which the dirt remains significantly.

<Hygroscopic evaluation 2>
A test specimen was prepared in the same manner as in the hygroscopic evaluation 1 except that each laminate after the evaluation of the pollution evaluation 1 was used. Each specimen was left in an atmosphere of 23 ° C. and 90% RH, and the moisture absorption after 24 hours was evaluated (g / m ² ). The evaluation criteria for hygroscopicity are the same as for hygroscopic evaluation 1.

  Then, the following evaluation was performed.

・ Evaluation C
On the base material (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the thickness of the plate-shaped cured body after drying the compositions 1 to 6 and 9 to 13 is 2 mm. And dried at 100 ° C. for 30 minutes to obtain laminates 1C to 11C of plate-like cured bodies.

<Photocatalytic test>
Each laminate was used as a test body, and a solution obtained by adding 2% sodium hydroxide to an ethanol solution of 1.0 wt% phenolphthalein was applied to the surface of the test body and then exposed to sunlight (wavelength region 305 to 4045 nm). Exposure was made for a total of 36 hours, and the color difference before and after that was measured. The decomposition of phenolphthalein by the action of the photocatalyst was evaluated based on the color difference ΔE. The color difference was measured using a color difference meter (CM-3700d, manufactured by Minolta Co., Ltd.).
The evaluation criteria for the photocatalytic test are as follows.
A: 6 ≦ ΔE
B: 5 <ΔE <6
C: ΔE ≦ 5

Claims (9)

It is a plate-like cured body containing a synthetic resin and powder,
The plate-like cured body contains 200 to 4000 parts by weight of a granular material with respect to 100 parts by weight of a synthetic resin in a solid content weight ratio,
The plate-like cured body has at least −20 ° C. to 80 ° C. (T ₁ ) and −150 ° C. to −100 ° C. (T ₂ ), respectively, of dispersion peaks of loss tangent tan δ measured using a dynamic viscoelasticity measuring device. A plate-like cured body having a temperature range of The above synthetic resin has a dispersion peak of loss tangent tan δ measured using a dynamic viscoelasticity measuring device at least at −20 ° C. to 80 ° C. (T ₁ ) and −150 ° C. to −100 ° C. (T ₂ ). The plate-like cured body according to claim 1, which has a range.   The plate-shaped cured product according to any one of claims 1 to 2, wherein the synthetic resin contains an acrylic resin and a silicone resin in a solid content weight ratio of 95: 5 to 30:70.   The plate-like cured body according to any one of claims 1 to 3, wherein the synthetic resin is a graft polymer of an acrylic resin and a silicone resin.   The said granular material contains a colored aggregate and a moisture absorption / release powder, The plate-shaped hardening body in any one of Claims 1-4 characterized by the above-mentioned.   The plate-like cured product according to any one of claims 1 to 5, further comprising a photocatalytic metal oxide as the powder.   The plate-like cured product according to any one of claims 1 to 6, further comprising a chemical substance adsorbent as the powder and granular material.   A plate-shaped cured body, wherein a moisture-permeable overcoat layer is laminated on the cured body according to any one of claims 1 to 7. A method for producing a synthetic resin and a plate-like cured body containing a powder,
The above synthetic resin has a dispersion peak of loss tangent tan δ measured using a dynamic viscoelasticity measuring device at least at −20 ° C. to 80 ° C. (T ₁ ) and −150 ° C. to −100 ° C. (T ₂ ) Have in the range,
A first step of mixing and molding 200 to 4000 parts by weight of a granular material with respect to 100 parts by weight of a synthetic resin at a solid content weight ratio,
A second step of curing at a temperature higher than the dispersion peak temperature (T ₁ ) of the synthetic resin.