JP3391630B2 - Synthetic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a synthetic resin composition. More specifically, the present invention relates to a synthetic resin composition excellent in dew condensation prevention and humidity control effect.

[0002]

A coating composition comprising a coating binder and a hydrous magnesium silicate clay mineral is disclosed in Japanese Patent Application No. 62-616.
55, and a sheet material in which a hydrous magnesium silicate clay mineral is mixed in a vinyl chloride resin layer is disclosed in JP-A-62-28.
Although disclosed in Japanese Patent No. 2926 and Japanese Patent Application Laid-Open No. 62-228927, they have excellent odor absorbing properties, but there is room for improvement in dew condensation prevention, humidity control effect and the like. Further, a humidity control agent using a porous material in which the average pore diameter is in the range of 1 to 10 nm, and 50% or more of the pore diameters are distributed in the range of ± 5 nm around the average diameter is , JP-A-6
As disclosed in JP-A-304437, the humidity control paper mixed and made with cellulose fiber, which is one of the forms, can be expected to have dew condensation prevention and humidity control effects, but when used as an interior material, etc. However, there is room for improvement in terms of low powder strength, low water resistance, durability, etc. and easy scratching of the surface.

[0003]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks of the prior art and to provide a synthetic resin composition excellent in dew condensation prevention, humidity control effect and the like. is there.

[0004]

[Means for Solving the Problems] First to solve the above problems
The synthetic resin composition of the invention has a central pore diameter of 1 to 10 nm.
In the range of, and the porous body made of an inorganic substance that contains more than 60% of the total pore volume in the range of the range of ± 40% of the mean pore diameter, Ri Do and a synthetic resin, wherein the porous body, the synthetic resin
5 to 200 parts by weight based on 100 parts by weight of the solid component of
Those characterized that you have been blended with enclosed.

The synthetic resin composition of the second invention for solving the above-mentioned problems is an inorganic substance having one or more peaks at a diffraction angle (2θ) corresponding to a d value of 1 nm or more in X-ray diffraction. a porous body composed of, Ri Do and a synthetic resin,
The porous body has 100 parts by weight of the solid component of the synthetic resin.
Those characterized that you have been compounded in a range of 5 to 200 parts by weight against.

[0006]

[Operation and effect of the invention]

(1) The first invention A porous body having a central pore diameter in the range of 1 to 10 nm and having 60% or more of the total pore volume within ± 40% of the central pore diameter (hereinafter, referred to as the first The porous body shown in the invention and the second invention is referred to as a mesoporous body) having uniform pores and having an adsorption / desorption isotherm in which capillary condensation occurs when the relative humidity increases and the amount of moisture absorption rapidly increases. The humidity at which the amount of absorbed moisture increases can be estimated from the pore diameter of the mesoporous material by the following Kelvin equation.

In (P / Po) = − (2γVm / rRT) cos θ [P / Po × 100: relative humidity, γ: surface tension of water, V
m: molar volume of water, r : pore radius , R: gas constant, T:
Absolute temperature, θ: contact angle] Therefore, by changing the pore diameter of the mesoporous material within the range of 1 to 10 nm, the relative humidity at which the amount of moisture absorption rapidly increases is arbitrarily set within the range of 10% to 90%. be able to.

Since the mesoporous material has a large pore volume, a high water absorption can be expected. By mixing this mesoporous material with a synthetic resin, powder will not fall off and necessary physical properties such as strength and durability will not be impaired. Therefore, it absorbs moisture well when the relative temperature rises, and releases moisture when it is in a normal atmosphere to prevent condensation, or when the amount of condensation is large or the condensation rate is too high to absorb moisture. Condensed water can be absorbed to reduce surface dew condensation.

It can be expected that some odorous components will be adsorbed. (2) In the second invention X-ray diffraction, the mesoporous material having one or more peaks at the position of the diffraction angle (2θ) corresponding to the d value of 1 nm or more is a period of the d value corresponding to the peak angle. Means that the structure is in the material. That is, the mesoporous material of the present invention reflects the regularity of the structure, has high crystallinity, more uniform pores, and when relative humidity increases, capillary condensation occurs and the moisture absorption sharply increases sharply. It has adsorption and desorption isotherms.

Since the mesoporous material also has a large pore volume, a high water absorption can be expected. Therefore, by mixing the mesoporous material with the synthetic resin, powder does not fall off, and necessary physical properties such as strength and durability are not impaired. Therefore, it absorbs moisture well when the relative temperature rises, and releases moisture when it is in a normal atmosphere to prevent condensation, or when the amount of condensation is large or the condensation rate is too high to absorb moisture. Condensed water can be absorbed to reduce surface dew condensation.

It can be expected that some odorous components will be adsorbed.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION [1] Mesoporous Material As this mesoporous material, for example, a heat-resistant layered silica porous material synthesized by reacting a layered silicate surfactant can be used (T. Yanagizawa ct., Bu.
ll. Chem. Soc. Jpn. , 63.988-
992 (1990)). The heat-resistant layered silica porous body has a plurality of plate-shaped sheet layers of crystalline layered silicate laminated, and the adjacent sheet layers are reduced in width at a bonding point by a siloxane bond and widened between the bonding points. And has a honeycomb-like porous structure in which micropores are formed.

In the X-ray diffraction pattern of this heat-resistant layered silica porous material, at least one peak is observed, including a diffraction peak having maximum intensity at a position having a d value of 2 nm or more. In addition, among them, 2 to 4 diffraction peaks showing a hexagonal structure are seen, and a honeycomb-like skeleton structure is observed in the transmission electron micrograph (S. Ina).
gaki, et al. J. Chem. Soc. , C
hem. Commu. , No. 8,680-682 (1
993)).

The content of alkali metal ions contained in this crystalline layered silicate is preferably 0.2% by weight or less, and the specific surface area is preferably 700 m ² / g or more. When the content of the alkali metal ion exceeds 0.2% by weight, the movement of atoms is promoted at a relatively low temperature and crystallization into cristobalite or the like occurs. Therefore, the specific surface area of the layered silica porous material is reduced, and further the heat resistance is reduced. Further, the specific surface area of the layered silica porous material is 700 m ²
When it is less than / g, the activity cannot be sufficiently exhibited when the synthetic resin is supported on the layered silica porous material, and the ability to adsorb organic substances is low when used as an adsorbent.

A typical layered silica porous material is shown in FIG.
As shown in to FIG. 1 (c), the composition of the backbone in the SiO _2,
The plate-shaped sheets 1 have a structure in which they are vertically stacked, and each sheet 1 is curved or bent in the vertical direction. The upper and lower sheets 1 are partially connected to each other to form a honeycomb-shaped skeleton. The diameter of the fine holes 2 of the honeycomb is 1 to 60Å
Is.

The sheet layer is a silicate layer formed by two-dimensionally bonding SiO ₄ tetrahedra.
_Since the connecting points of the tetrahedra can be bent, the sheet layer as a whole can be curved or bent. The sheet layer is made of magnesium ions (Mg ²⁺ ), aluminum ions (A
It does not include octahedra that hinder the flexibility of the sheet layer, such as l ³⁺ ). Further, the above-mentioned sheet layers are laminated by sandwiching an alkali metal ion such as Na ⁺ and H ⁺ . Further, specifically, as the crystalline layered silicate, for example,
Kanemite (NaHSi ₂ O ₅ .3H ₂ O) is preferred.

Further, as other crystalline layered silicates, sodium disilicate (Na ₂ Si ₂ O ₃ ) and macatite (N
_{a 2 Si 4 O 9 · 5H} 2 O), Airaaito (Na ₂ S
i ₈ O ₁₇ · XH ₂ O), magadiite (Na ₂ Si ₁₄
O ₂₉ · XH ₂ O), Kenyaite (Na ₂ Si ₂₀ O ₄₁ · X
H ₂ O) and the like are typical but not limited to these.

Regarding the method for producing the above layered silica porous material, the alkali metal ion existing between the layers in the crystalline layered silicate having a water content of 10% by weight or more is ion-exchanged with the organic cation, and the organic cation is intercalated. Introduced into the interlayer widening step, a washing step to remove the alkali metal ions liberated by the ion exchange, by firing the washed crystalline layered silicate, by burning the organic cations of the porous There is a method for producing a heat-resistant layered silica porous body including a porosification step of obtaining a layered silica porous body.

The crystalline layered silicate can be synthesized from an amorphous silicate. Examples of amorphous silicates include commercially available powdered sodium silicate and powders obtained by drying water glass. For example, when synthesizing kanemite, which is one type of crystalline layered silicate, it is preferable to use amorphous sodium silicate having a composition as close as possible to Na ₂ O / SiO ₂ = 2.

This amorphous sodium silicate was mixed with 65% in air.
When baked at 0 to 750 ° C., it crystallizes into δ-type Na ₂ Si ₂ O ₅ . Β or γ-type Na at temperatures below 650 ° C
₂ Si ₂ O _5, the at temperatures above 750 ° C. alpha-type Na ₂
Crystallize to Si ₂ O ₅ . The α, β, γ type does not form a crystalline layered silicate due to the reaction with water. Next, this δ-type Na
₂ Si ₂ O ₅ is dispersed in 2 to 50 times water,
After stirring for an hour, filter. As a result, δ-type Na ₂ S
Part of Na ⁺ of i ₂ O ₅ is replaced with H ^{+ in} water,
Si ₂ O ₅ · 3H ₂ O is obtained, and kanemite which is a crystalline layered silicate is obtained.

The water content of the crystalline layered silicate is 1
It is 0% by weight or more. If it is less than 10% by weight, the crystalline layered silicate aggregates, the dispersibility in water decreases in the next interlayer widening step, and the exchange of organic cations and alkali metal ions becomes difficult to occur. When the amount is 10% by weight or more, the crystalline silicate is well dispersed in water during the next interlayer widening step, and the ion exchange between the interlayer alkali metal ion and the organic cation is smoothly carried out in a short time. As a result, an excellent heat-resistant layered mesoporous material having a specific surface area of 700 m ² / g or more and a residual amount of alkali metal ions of 0.2% by weight or less can be obtained.

In the interlayer widening step, the alkali metal ions in the crystalline layered silicate are ion-exchanged with the organic cations. Since organic cations are bulkier than alkali metal ions, the layers of the crystalline layered silicate are widened. As a result, the sheet layer is curved so as to surround the organic cations. At the same time, except for the portion where the organic cations are introduced, the silanol (S
i-OH) is dehydrated and condensed to form a siloxane bond (S
i-O-Si) is formed. As a result, the adjacent sheet layers are partially bonded by the siloxane bond to form a three-dimensional honeycomb-shaped layer structure.

Examples of the above organic cations include alkyltrimethylammonium, dimethyldialkylammonium, alkylammonium and benzyltrimethylammonium. At the time of the above ion exchange, the pH is adjusted to 8-9.
It is preferable to adjust Furthermore, after that, 30-9
It is preferable to heat at 0 ° C. In the washing step, alkali metal ions liberated by the ion exchange, counterions of organic cations, or unreacted organic cations are removed. In particular, the content of liberated alkali metal ions is 0.2% by weight or less.

In the step of forming a porous body, the organic cations taken in between the layers are burned to form fine micropores. It also stabilizes the three-dimensional skeleton of the siloxane bond. The firing temperature is 600 to 1200 ° C. in an oxidizing atmosphere.
It is desirable to do in. If the temperature is lower than 600 ° C. or if the atmosphere is other than the oxidizing atmosphere, the organic cations cannot be sufficiently removed. On the other hand, if the temperature exceeds 1200 ° C, the sintering proceeds excessively, the fine pores are broken, and the specific surface area decreases, which is not preferable.

Since the layered silica porous material has an alkali metal ion content of 0.2% by weight or less, it is difficult to crystallize even at a high temperature of 800 ° C. or higher, and the micropores are stable. Therefore, it has excellent heat resistance. Further, since it has a specific surface area of 700 m ² / g or more, it exhibits excellent adsorption performance.
Further, as another mesoporous material, there is a mesoporous molecular sieve (MCM-41) synthesized by using a micelle structure of a surfactant as a template (Kresge eta).
l. , Nature, 359, 710 (1992)).
This MCM-41 also has a structure in which cylindrical pores having a diameter of 1 to 10 nm are regularly arranged and has a honeycomb-shaped cross section, but the structure in the pore wall is different from that of the above material. In the X-ray diffraction pattern of this MCM-41, at least one peak is observed at a position having a d value of 2 nm or more, including a diffraction peak having the maximum intensity.

No clear diffraction peak is observed in the X-ray diffraction pattern of conventional porous silica such as silica gel. The X-ray diffraction peak means that the material has a periodic structure of d value corresponding to the peak angle. From this, silica gel has at least d =
It does not have a periodic structure of 0.15 to 12 nm (corresponding to 0.7 <2θ <60 °). That is, it indicates that it is amorphous. On the other hand, the mesoporous material of the present invention has one or more peaks including the strongest peak at a d value of 2 nm or more and has a periodic structure.

Specifically, these peaks have a diameter of 1 to
This reflects a structure in which 10 nm pores are regularly arranged at intervals of 2 nm or more. As a result, the diameter of the pores in the structure is non-uniform because the structure of conventional silica gel is irregular, whereas the mesoporous material of the present invention reflects the regularity of the structure, It will be uniform. The composition of the mesoporous material of these oxides may be pure silica, but silica (aluminum (Al), titanium (T)
i), magnesium (Mg), zirconium (Zr),
Gallium (Ga), Beryllium (Be), Yttrium (Y), Lanthanum (La), Tin (Sn), Lead (P
It may be a mixture of b), vanadium (V), boron (B) and the like. [2] Method for Measuring Pore Distribution of Mesoporous Material The pore distribution curve has a value (dV / dD) obtained by differentiating the pore volume (V) with the pore diameter (D) with respect to the pore diameter (D). The plotted curve. The pore distribution curve is created, for example, by the gas adsorption method shown below.

The most frequently used gas in this method is nitrogen. First, the liquid nitrogen temperature (-196)
Nitrogen gas is introduced at (° C) and the adsorption amount is determined by the constant volume method or the gravimetric method. That is, the adsorption isotherm is created by gradually increasing the pressure of nitrogen gas introduced into the filler, which is a mesoporous material, and plotting the adsorption amount of nitrogen gas with respect to each equilibrium pressure. From the created adsorption isotherm, for example, Cranston-Inkray method, Pollimo
The pore size distribution can be obtained by using the calculation method of the re-Heal method.

The reason that 60% or more of the total pore volume is included in the diameter range of ± 40% of the pore diameter (central pore diameter) showing the maximum peak in this pore diameter distribution curve is as follows. I can explain. For example, when the maximum peak in the pore size distribution curve is 2.7 nm, the pore diameter is 1.62.
The total volume of pores in the range of ˜3.78 nm accounts for 60% or more of the total pore volume. Specifically, the pore diameter of the pore distribution curve is 1.62 to 3.7.
The integrated value in the range of 8 nm accounts for 60% or more of the total integrated value of the curve. In the mesoporous material in which the pore diameter range of ± 40% of the pore diameter showing the maximum peak in the pore distribution curve is less than 60% of the total pore volume, the pore diameters are non-uniform, and the size of the pore diameter is Not suitable for effective use. [3] Synthetic Resin Examples of the synthetic resin include conventionally used synthetic resins such as thermoplastic resins, thermosetting resins, and reaction-curable resins, their solutions, and polymer latex.

The thermoplastic resin is a resin that can be softened by applying heat and can be molded. Specifically, for example, polyamide such as polyvinyl chloride, polyurethane, nylon, polyethylene, polypropylene, polystyrene, polymethacrylic acid and its ester. And the like, or a mixture thereof or a copolymer thereof. These may be appropriately mixed with a colorant such as a dye or a pigment, a plasticizer, and if necessary, an additive such as a filler or a flame retardant. For example, as the plasticizer, various esters such as TCP (tricresyl phosphate) -based phosphate ester and adipate-based ester can be used. In particular, examples of plasticizers for vinyl chloride resins include primary plasticizers such as DOP (dioctyl phthalate), DBP (dibutyl phthalate), DIDP (diisodecyl phthalate), and secondary plasticizers such as chlorinated paraffins and petroleum plasticizers. Examples of stabilizers for vinyl chloride resins include Ba-Zn organic composites, Ba-Zn composite soaps, chelators, and epoxidized soybean oil. Further, as the synthetic resin filler, talc, clay, silicic acid anhydride, silica, calcium carbonate, muscovite, mica, silica gel, or those surface-treated with stearic acid or its calcium salt or a surfactant, etc. Is mentioned. As flame retardant, TCP
Non-halogen-containing phosphates such as (tricresyl phosphate), halogen-containing phosphates such as CRP (tris (dichloropropyl) phosphate) and tris (2.3dipromopropyl) phosphate, chlorinated paraffins, TBE (tetrahydrate). Examples thereof include halogen-containing organic compounds such as promoethane) and inorganic compounds represented by antimony dioxide.

The polymer latex includes synthetic resin latex and rubber latex. Among them, the synthetic resin latex is composed of resin colloid particles as a dispersant, water as a dispersion medium, and the like. Fusing occurs and acts effectively as a binder. Specific examples of the synthetic resin latex include polyvinyl chloride latex, polyvinylidene chloride latex, polyurethane latex, acrylic resin latex, polyvinyl acetate latex, polyacrylonitrile latex, and their modified products and copolymers. A particularly preferred acrylic resin is a polymer emulsion containing a (meth) acrylic acid ester as a main component. Examples of the (meth) acrylic acid ester as the main component include (meth)
Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate,
Examples thereof include 2-hydroxyethyl (meth) acrylate. Copolymerizable ethylenically unsaturated monomers are used in combination with this main component, and the monomers include styrene, (meth) acrylonitrile, and (meth).
Acrylic acid amide, N-methylol acrylic acid amide,
Examples thereof include vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, (meth) acrylic acid, itaconic acid, fumaric acid, crotonic acid and maleic acid.

When used in combination with the above monomers, the content of the (meth) acrylic acid ester as the main component is 50% by weight.
The above is preferable. Further, the acrylic resin is preferably formed by an emulsion polymerization method. For example, water, an ethylenically unsaturated monomer, an emulsifier (sodium dodecylbenzene sulfonate, polyoxyethylene alkyl ether, etc.), and a radical polymerization initiator are added to a reaction vessel that has been replaced with nitrogen, and the mixture is heated and stirred at a predetermined temperature. Polymerize. The particle size of the acrylic resin can be controlled by adjusting the concentration of the emulsifier during emulsion polymerization.

Specific examples of the rubber latex include natural rubber, styrene butadiene rubber, acrylonitrile rubber, acrylonitrile butadiene rubber, isoprene isobutyl rubber, polyisobutylene, polybutadiene, polyisoprene, polychloroprene and polyethylene propylene. To be The butadiene copolymer is preferably one containing 20 to 80% by weight of butadiene and 20 to 80% by weight of an unsaturated monomer copolymerizable therewith. As the unsaturated monomer, methacrylic acid ester, acrylic acid ester, styrene, acrylonitrile, methacrylonitrile, acrylic acid amide, N-methylol acrylic acid amide, vinyl acetate, vinyl chloride,
Vinylidene chloride, acrylic acid, itaconic acid, fumaric acid,
Crotonic acid, maleic acid, etc. can be used.

The butadiene copolymer has a copolymer composition of 20 to 60% by weight of butadiene and 40 to (meth) acrylic acid ester when heat resistance and weather resistance are required as in the case of use for vehicles. It is desirable that it is 80% by weight, and 0 to 20% by weight of other unsaturated monomer. In the present invention,
At least one of the above synthetic resins is used. Also,
When the polymer latex is used for the sheet skin material, it is desirable that the glass transition temperature (hereinafter referred to as Tg) when the film is formed is in the range of -70 ° C to + 15 ° C. Since the polymer latex having a Tg of -70 ° C or less is too soft, physical properties such as a decrease in moisture absorption function due to coating the mesoporous material at the time of forming the film and stickiness of the film become a problem, Not preferable. The polymer latex having a Tg of + 15 ° C. or more is too hard, and thus the mesoporous material or the like may fall off when applied to a cloth or the like and processed or used, and the texture is bad.
Not preferable. Examples of the resin having Tg of −70 ° C. to 15 ° C. include acrylic resin, ethylene-vinyl acetate resin, polyurethane resin, butadiene resin and the like, and at least one of them is used. [4] Synthetic resin composition The amount of the mesoporous material in the synthetic resin composition is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin,
It is more preferably in the range of 10 to 150 parts by weight. Within this range, the function of the mesoporous material can be easily exerted sufficiently.

The method for producing the synthetic resin composition comprising the mesoporous material and the synthetic resin is not particularly limited, and any production method may be used. For example, the mesoporous material can be mixed with a thermoplastic resin, which can be subsequently heat kneaded and molded. Various methods such as calendering, coating and extrusion can be used for molding.

For example, a porous silica material can be mixed with a reaction curable resin, which can be subsequently cured and molded by heating, irradiation with ultraviolet rays or the like. For example, the mesoporous material is kneaded with water in which a surfactant is dissolved. Next, a polymer latex is added and further kneaded to obtain a synthetic resin composition to be applied to a cloth. Alternatively, a dry mixture of a mesoporous material and a surfactant may be dispersed in water, and a polymer latex may be added and kneaded. Alternatively, a dry mixture of the mesoporous material and the surfactant may be kneaded with the polymer latex diluted with water. Further, in the above-mentioned three kinds of production methods, the surfactant may be used in several times. For example, the first use is to use a small amount for forming a dispersant and a protective colloid, and additionally use a surfactant as a thickener for a synthetic resin composition obtained by adding a polymer latex to adjust the viscosity. Good.

The amount of the mesoporous material is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the solid content of the polymer latex. Within this range, the function of the mesoporous material is fully exerted, and the properties of the synthetic resin composition, that is, the improvement in the dimensional accuracy of the fabric, the prevention of the fraying of the yarn and the opening of the yarn, become good. Also,
Since the mesoporous material exhibits acidity when suspended in water, for example, when it is used with a polymer latex stabilized in an alkaline region (usually pH 8 to 10) such as an acrylic resin latex, the pH is adjusted with ammonia water or the like. It is preferable to carry out. Alternatively, it is preferable to use a polymer latex stabilized in an acidic region such as vinyl acetate resin latex.

Further, the non-volatile content of the synthetic resin composition is preferably adjusted to 20 to 60% by weight from the viewpoint of productivity, workability and the like in the steps of coating and drying the cloth. Here, the surfactant is added as a dispersant for assisting the peptization / dispersion of the mesoporous secondary particles, and as a thickener for adjusting the viscosity of the synthetic resin composition required depending on the coating method. It is preferable to use a necessary amount according to the coating method, and the weight average molecular weight of the surfactant is preferably 150 or more. When the weight average molecular weight is 150 or less, the surfactant may penetrate deep into the pores of the mesoporous material to deteriorate the hygroscopic function, which is not desirable.

Specifically, sodium tripolyphosphate,
Tripolyphosphates such as sodium tetraphosphate and sodium hexametaphosphate, sodium alkylnaphthalene sulfonates, alkylaryl sulfonates such as sodium alkylbenzene sulfonate, sodium polyacrylate, polyvinyl alcohol, styrene-
Examples thereof include synthetic polymers such as maleic acid copolymers, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose, and polyoxyalkylene aryl ethers such as polyoxyethylene phenol ether and polyoxybutylene phenol ether.

When the surfactant is added, the addition amount is preferably within the range of 0.1 to 20 parts by weight per 100 parts by weight of the mesoporous material. Within this range, the function of the surfactant can be more easily exerted. Further, the above synthetic resin composition, other additives, in the range that does not impair the characteristics,
For example, a flame retardant, a conductive agent, a crosslinking agent, a stabilizer, and a filler may be added.

As the flame retardant, there are inorganic flame retardants and organic flame retardants, and antimony compounds, phosphorus compounds, chlorine compounds, bromine compounds, guadinine compounds, boron compounds, ammonium compounds, bromine diaryl oxides. , Brominated allenes and the like are known, and one or more of them can be used. As a specific example, antimony trioxide, antimony pentoxide, primary ammonium phosphate,
Diammonium phosphate, phosphoric acid triester, phosphite ester, phosphonium salt, phosphoric acid triamide,
Chlorinated paraffin, dechlorane, ammonium bromide, tetrabromobisphenol A, tetrabromoethane, guanidine hydrochloride, guanidine carbonate, guanidine phosphate, guanylurea phosphate, sodium tetraborate decahydrate (borax), ammonium sulfate, sulfamine Examples thereof include ammonium acid, decabromodiphenyl oxide, hexabromophenyl oxide, bentabromophenyl oxide, and hexabromobenzene.

As the conductive agent, conductive carbon black, conductive polymers such as polyacetylene, polypyrrole, etc.,
Metal powder such as copper, aluminum and stainless steel, conductive fiber material such as carbon fiber and metal fiber, etc. alone or 2
You may mix and use 1 or more types. As the stabilizer, a semicarbazide compound or the like is used.

As the filler, for example, sepiolite,
In order to add other functions such as hygroscopicity enhancement and deodorant, porous adsorbent materials and deodorants such as hydrous magnesium silicate clay minerals such as palygorskite, activated carbon, activated carbon fibers, silica gel, synthetic zeolite, and cristobalite. You may add 1 or more types. Further, pigments such as titanium oxide, carbon black, titanium yellow, polyazolet and phthalocyanine blue, inorganic powders such as calcium carbonate, clay, kaolin, silica, talc, glass and silica sand, silver, copper, nickel, aluminum, stainless steel, iron, etc. It is also possible to use the above metal powder, resin, organic powder such as wood, and the like. [5] Embodiment of Synthetic Resin Composition The synthetic resin composition of the present invention is molded and used as necessary. Any molding means may be used, but the shape thereof can be determined according to the place of use and method. For example, the synthetic resin composition may be molded and used alone,
Alternatively, it may be laminated on a substrate.

The substrate is not particularly limited, and paper,
Continuously flexible sheet base materials such as woven cloth, non-woven cloth, knitted cloth, laminated sheet, etc., as well as gypsum board, plywood board, concrete, metal board and the like which are commonly used in the site of use can be used. For example, a synthetic resin composition composed of a mesoporous material and a polymer latex is applied to a fabric, and a seat skin in a vehicle compartment, a chair skin in a house, an office, etc., and a product such as a bed that a human body comes into contact with, a seat skin in manufacturing them. The unevenness can be reduced by molding using a molding method for attaching the.

In this case, the amount of the synthetic resin composition applied to the cloth was 5 as a silica porous material per square meter of the cloth.
It is preferably g or more. When the amount is 5 g or less, the amount of mesoporous material is small, and thus the unevenness reducing performance becomes insufficient. Further, when a soft touch such as flexibility is required as the physical properties of the sheet skin material, the amount of the synthetic resin composition applied to the fabric is preferably 200 g or less as the solid content of the synthetic resin composition per 1 m 2 of the fabric.

The method of applying the synthetic resin composition to the fabric is as follows:
The method is not particularly limited and any commonly used method may be used. For example, floating knife coater, knife over roll coater, reverse roll coater, roll doctor coater, gravure roll coater, air knife coater, curtain coater, kiss roll coater, nip roll coater, cast coater, cona direct coater ,
Examples include a reverse coater, a slit coater and a spray method, and a laminating or bonding method can also be used.

Further, the synthetic resin composition may be mechanically or chemically foamed and then applied, or the synthetic resin composition may be chemically foamed at the time of film formation after application. Following these coatings, the synthetic resin composition is usually formed into a film by heating and drying to obtain a sheet skin material. The fabric is not particularly limited as long as it has breathability and is used as a seat cover. Usually a woven fabric made of natural fibers, synthetic fibers or both of these,
Knitted fabric or non-woven fabric is used.

Specifically, fabric, moquette, towel cloth,
Tricot, double russell, circular knitting, needle punching, etc. may be mentioned. Also, as the fibers referred to here, cotton,
Natural fibers such as hemp, silk and wool, or rayon, acetate, protein fibers, chlorinated rubber, polyamide, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyester, polyethylene, polypropylene, polyurethane, polyvinylidene cyanide , Synthetic fibers such as polyfluoroethylene and modified fibers thereof. Alternatively, a fabric composed of both of these fibers may be used.

Further, a conductive cloth used for effectively dissipating static electricity may be used. The conductive cloth here means copper, aluminum, stainless steel,
A conductive material such as carbon or a conductive polymer is mixed in the organic fiber in the form of particles, the surface of the organic fiber is coated by a vacuum deposition method, or the organic fiber is clad with the conductive material, or a conductive material. A conductive fiber made of a conductive substance itself is added to the above fabric. The method for adding the conductive fibers to the fabric may be any of mixing in a fiber state, mixing in a sliver state, twisted yarn in a yarn form, mixed or twisted yarn in a filament form, and arrangement on a texture.

Further, leather having holes, a waterproof / moisture permeable sheet, etc. may be used. In addition, the following uses are also possible. 1) Synthetic resin composition for sheet material-Fab reduction fabric (see JP-A-63-276532) -Diapers and sanitary products 2) Mixing with paints (for wall coverings) that have a dew condensation prevention effect, acrylic resin emulsion, etc. Then, it is applied to gypsum board etc. to prevent dew condensation and control humidity (Japanese Patent Application No. 62-
61655).

Fields: Interiors and exteriors of houses, offices, basements, tunnels, etc. ・ Packaging materials that dislike dryness and dew condensation, furniture (cases, shoe boxes, etc.),
3) Insole 3) It is placed in a sheet material for interior, for example, vinyl chloride resin, to mainly prevent dew condensation (Japanese Patent Laid-Open Nos. 62-282926 and 62-28).
2927, JP-A-62-129335, JP-A-2-187433).

Wall covering material in which granular aggregate is adhered to the base material through an adhesive mount * Spray the mesoporous material on the base material sheet coated with the acrylic resin emulsion adhesive to remove excess granules -After the removal, it is dried to fix the particles to the base material sheet. * Spray and fix granules such as synthetic resin containing mesoporous material on the base sheet.

* A decorative material in which a mesoporous material is adhered onto a sticky sheet without any gaps and a synthetic resin is coated thereon (see Japanese Patent Application Laid-Open No. 2-49849) * Expandable granules are applied on a base material sheet A spray-tone foamed wallpaper (see Japanese Patent Application Laid-Open No. 2-113934) which has been sprayed on and heat-foamed.

[0054]

EXAMPLES The present invention will now be described in more detail by way of examples. The synthetic resin composition of this example has a central pore diameter of 1
It is composed of a synthetic resin and a mesoporous material made of an inorganic material in the range of 10 nm to 60% or more of the total pore volume within a range of ± 40% of the central pore diameter.

Hereinafter, a method for producing this synthetic resin composition will be described, and will be replaced with a detailed description of the constitution. [1] manufacture of the mesoporous silica material (FSM16) Nippon Chemical Industrial Co., Ltd. powder sodium silicate (SiO ₂ /
Na ₂ O = 2.00) was calcined in air at 700 ° C. for 6 hours to crystallize sodium disilicate (δ-Na ₂ Si ₂ O ₅ ). 50 g of this crystal was dispersed in 500 ml of water and stirred for 3 hours. Then, the solid content was collected by filtration to obtain kanemite crystals. 50 g of dry weight of kanemite was added to an aqueous solution of 0.1 M hexadecyltrimethylammonium chloride (C ₁₆ H ₃₃ N (CH ₃ ) ₃ Cl) 10
It was dispersed in 00 ml and heated at 70 ° C. for 3 hours with stirring. The pH at the beginning of heating was 12.3. Then 7
While heating and stirring at 0 ° C., 2N hydrochloric acid was added to lower the pH of the dispersion liquid to 8.5. Then, it heated at 70 degreeC for 3 hours, and was stood to cool to room temperature. The solid product was once filtered, dispersed in 1000 ml of ion-exchanged water, and stirred. Repeat this filtration and dispersion stirring 5 times, then 60 ℃
And dried for 24 hours. This sample was placed in air at 550 ° C for 6
A silica-based mesoporous material was obtained by firing for a time.

The structure of the obtained silica-based mesoporous material was analyzed. First, the powder X-ray diffraction pattern of the synthesized silica-based mesoporous material was measured. The X-ray diffraction was performed at 2 degrees (2θ) / minute using CuKα as a radiation source using a Rigaku RAD-B apparatus. The slit width is 1 degree-0.3 mm-1 degree. As a result, several peaks were observed at a diffraction angle (2θ) of 10 degrees or less, and when the diffraction angle of the peak was converted to a d value, a strong peak corresponding to d = 3.7 nm and 1.4 to
Several weak peaks at 2.5 nm were observed. These peaks were indexed into a hexagonal structure. From the result of the X-ray diffraction pattern, it can be seen that this silica-based mesoporous material has a regular periodic structure.

Next, the pore distribution curve of the mesoporous material was determined from the nitrogen adsorption isotherm. The nitrogen adsorption isotherm was measured as follows. The device is equipped with a pressure sensor (MKS, Ba
raton 127AA, range 1000 mmHg) and two control valves (MSK, 248A) are connected, and the introduction of nitrogen gas into the vacuum line and the sample tube can be automatically performed. About 40 mg of the mesoporous material sample was placed in a glass sample tube and connected to a vacuum line. 13 sample tubes
Vacuum degassed at 0 ° C. for about 1 hour. Ultimate vacuum is 10-4m
It was mHg. The sample tube is immersed in liquid nitrogen, and nitrogen gas having a predetermined pressure is introduced into the vacuum line section. After the pressure has stabilized, open the control valve of the sample tube and, after the pressure becomes constant, record the equilibrium pressure. Equilibrium pressure is 0-80
The same operation was repeated at 16 to 18 points in the range of 0 mmHg. The time until equilibration varies depending on the pressure,
It was in the range of 60 minutes. By plotting the adsorption amount obtained from the equilibrium pressure and the pressure change, a nitrogen adsorption isotherm of the silica-based mesoporous material is created, and from this nitrogen adsorption isotherm, a pore distribution curve is obtained by the Cranston-Inklay method. It was The pore diameter (central pore diameter) showing the maximum peak in the pore distribution curve is 2.7 nm, and the total pore volume of the pore volumes included in the pore range of ± 40 wt% of the central pore diameter The ratio was 80% by weight or more. [2] Preparation of synthetic resin composition The obtained silica-based mesoporous material was sieved to 100 mesh or less, and a synthetic resin composition was prepared by the following procedure.

First, 100 parts by weight of vinyl acetate-acrylic copolymer latex (nonvolatile content 50%), 40 parts by weight of a silica-based mesoporous material of 100 mesh or less, 150 parts by weight of water, 10 parts by weight of titanium oxide, antifungal agent. 2 parts by weight were sufficiently mixed and dispersed using a homodisper manufactured by Tokushu Kika Co., Ltd. to obtain a synthetic resin composition. The obtained synthetic resin composition was sprayed onto a 9 mm thick gypsum board using a spray gun (air pressure 4 kg / cm ² ) of 750 g per 1 m ² , and then an uneven pattern was formed by roller finishing. Drying was performed by natural drying.

According to Section 16 JASS23M-102 lightweight aggregate spray material in the standard specifications for spraying construction established by the Architectural Institute of Japan for the dew resistance of the obtained gypsum board laminate having the synthetic resin composition layer, It investigated by the following method. First, the obtained laminate was cut into 70 mm × 150 mm, the cut surface was sealed with paraffin, and this was used as a test piece 10. Next, the coated surface 10a of the test piece 10 was placed on the constant temperature water tank 11 adjusted to 50 ° C. ± 3 ° C. with the coated surface 10a facing the water surface. The state at this time is shown in FIG.

Next, the weight of the test piece 10 was measured, and the dew resistance of the coating composition of this example was calculated as the weight absorbed when the coating was 1 m ² × 1 mm ^t . The result is shown in FIG. At the same time, when the appearance of the paint surface 10a was observed and the presence or absence of dew condensation was checked, no dew condensation was found on the paint surface 10a. In addition, as a comparative example, in the production of the synthetic resin composition of the above example, except that the mesoporous material is not used,
Prepare a gypsum board laminate having a synthetic resin composition layer prepared by the same operation as in the example, and also for the gypsum board laminate of this comparative example, the dew resistance was examined in the same manner as in the example, and the result was obtained. It is shown in FIG. At the same time, as a result of observing the appearance of the coated surface of the synthetic resin composition, dew condensation was found on the coated surface from the time of the first observation (1 hour after the start of the test).

As is clear from FIG. 3, the amount of moisture absorption in the comparative example hardly increased over time, and there was a significant difference from the amount of moisture absorption in the example.
Therefore, it can be seen that the synthetic resin compositions of the examples are excellent in dew condensation prevention and humidity control effects.

[Brief description of drawings]

FIG. 1 is an explanatory view showing the structure of a mesoporous material according to the present invention.

FIG. 2 is a schematic cross-sectional view showing a state of a test.

FIG. 3 is a graph showing the amount of moisture absorption in Examples and Comparative Examples in a test.

[Explanation of symbols]

1 ... Sheet 2 ... Micropore 10 ... Test piece 1
0a ... Painted surface 11 ... Constant temperature water tank

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (2)

(57) [Claims] 1. The pore diameter showing the maximum peak in the pore diameter distribution curve (hereinafter referred to as central pore diameter) is 1 to 10.
in the range of nm, and the porous body made of an inorganic substance that contains more than 60% of the total pore volume in the range of the range of ± 40% of the mean pore diameter, Ri Do and a synthetic resin, wherein the porous body, the Synthesis
5 to 200 parts by weight based on 100 parts by weight of the solid component of the resin
Synthetic resin composition characterized that you have been blended in the range of. 2. A X-ray diffraction, the position of the diffraction angles d value corresponds to more than 1 nm (2 [Theta]), and the porous body made of inorganic material having one or more peaks, Ri Do and a synthetic resin,
The porous body has 100 parts by weight of the solid component of the synthetic resin.
Synthetic resin composition characterized that you have been compounded in a range of 5 to 200 parts by weight against.