JP2000351915A - Composite material for aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composite material capable of providing an aqueous dispersion capable of forming a coating excellent in flexibility, powder falling off resistance, etc., by loading a specific amount of a surfactant on particles of a trioctahedral type aluminum-containing zinc phillosilicate, etc. SOLUTION: This composite material is obtained by loading (B) 0.05-50 pt.wt. surfactant based on 100 pts.wt. component A on (A) a trioctahedral type aluminum-containing zinc phillosilicate having preferably 30-100 m2/g BET specific surface area, preferably 0.5-10 μm volume-based media diameter (by a laser diffraction). Preferably, the component A has a composition of 5-65 mol% ZnO, 5-80 mol% SiO2 and 1-60 mol% Al2O3 based on 3 components. As the component B, an anionic surfactant, a nonionic surfactant and a cationic surfactant are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite for an aqueous dispersion, and more particularly to a trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite particle thereof. The present invention relates to a composite which imparts excellent water dispersibility to a coating formed from the aqueous dispersion, and which can impart excellent flexibility, powder fall resistance, excellent gloss and texture, and the like.

[0002]

2. Description of the Related Art Particles of a trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite thereof are provided by:
Production by synthesis is already known. Tokuhei 5
Japanese Patent Application Laid-Open No. 44406/1999 discloses that the following plane distance (2θ) relative intensity (I / I0) 11 to 14 100 24 to 26 60 33 to 35 40 37 to 39 30 44 to 46 10 59 to is measured by Cu-Kα. The X-ray diffraction image represented by 61 20 has substantially the same diffraction image as the X-ray diffraction image, and the half-value width of each of the three strong lines in the X-ray diffraction image is not more than 0.5 degrees in 2θ. A synthetic frypontite mineral consisting of crystals and aluminum-containing zinc phyllosilicate having a Hunter brightness of 80% or more and a specific surface area of 10 m ² / g or more is described.

Further, Japanese Patent Publication No. Hei 5-79602 discloses that
A porous silica or silica-alumina and aluminum-containing phyllo silicates formed on the surface of the primary particles and an amorphous, as a whole, SiO 2 ₅ to 65 mol% in the ternary ratio, MO (wherein M represents an atom selected from the group consisting of zinc and magnesium) 5 to 65 mol%,
And Al ₂ O ₃ having a chemical composition of 1 to 60 mol%;
In the line diffraction, there is substantially no peak at the plane interval (dx) of 8.40 to 6.40 angstroms, and there is a weak diffraction peak at the plane interval (dx) of 2.71 to 2.56 angstroms and the plane interval (dx) of 1.56 to 1.52 angstroms. Is 200m ² /
A composite phyllosilicate having a pore volume of 0.25 cc / g or more at a pore diameter of 10 to 300 angstroms of 0.2 g or more is described.

It is already known that the above-mentioned trioctahedral-type aluminum-containing zinc phyllosilicate or amorphous silica composite particles have excellent adsorption performance, and they are already widely used for deodorants. Have been.

[0005] JP-A-9-57094 discloses (A)
Deodorizing processing characterized by containing fine particles containing a metal silicate or metal aluminosilicate having an average particle diameter of 10 μm or less as an active ingredient, (B) a softening agent, and (C) a binder which is a polymer compound. A composition is described.

[0006]

The zinc-containing aluminum phyllosilicate is a trioctahedral-type synthetic clay mineral, has a fine primary particle size, and has a softness and a good texture peculiar to the clay mineral. It has the characteristic of having.
However, when an attempt is made to disperse an aluminum-containing zinc phyllosilicate or an amorphous silica composite thereof in an aqueous medium for the purpose of coating or the like, the tendency of coagulation and sedimentation is large, and particles having such cohesion tend to be dispersed. Coatings formed from aqueous dispersions containing the same have the disadvantages that they lack flexibility, tend to fall off powder, and have poor gloss or texture.

[0007] In order to improve the dispersibility of the inorganic fine particles in the aqueous medium, it is a general means to add a surfactant to the system. However, zinc-containing aluminum phyllosilicate or amorphous silica thereof is used. Even if a surfactant is added to the aqueous dispersion containing the particles of the composite, it is difficult to prevent aggregation and sedimentation of the particles.

Accordingly, it is an object of the present invention to provide a trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite particle thereof with an excellent anti-aggregation effect and water dispersibility. It is an object of the present invention to provide a composite which can provide a coating formed from a body with excellent flexibility, resistance to powder fall, excellent gloss and texture, and the like. It is another object of the present invention to provide a composite which exhibits excellent deodorizing and smoke eliminating properties in the form of a coating.

[0009]

According to the present invention, particles of trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite thereof are added in an amount of 0.05 to 50 parts by weight per 100 parts by weight of the particles. The present invention provides a composite for an aqueous dispersion, wherein the composite has a part of a surfactant supported thereon. In the present invention: The particles of the trioctahedral type aluminum-containing zinc phyllosilicate or its amorphous silica composite are composed of 5 to 65 mol% of ZnO, 5 to 80 mol% of SiO _2, and 1 to 60 mol of Al ₂ O _{3 based on} three components. % Of the composition; When the particles of the trioctahedral type aluminum-containing zinc phyllosilicate or its amorphous silica composite are in the range of 30 to 10
2. have a BET specific surface area of 00 m ² / g; 3. The particles of the trioctahedral type aluminum-containing zinc phyllosilicate or its amorphous silica composite have a volume-based median diameter of 0.5 to 10 μm as measured by a laser scattering method; 4. the surfactant is an anionic surfactant, a nonionic surfactant, a cationic surfactant, or a combination thereof; The composite is obtained by adding a surfactant or a concentrated solution thereof to a powder of a trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite thereof, and subjecting the mixture to high-speed shearing. It is preferably obtained. According to the present invention, there is also provided a deodorant composition containing the composite. According to the present invention, there is further provided a smoke control composition containing the composite.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Action] In the present invention, particles of trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite thereof (hereinafter sometimes simply referred to as zinc silicate-based particles) are used. It is based on the finding that the above-mentioned particles having the ability to carry an activator and carrying a surfactant significantly suppress the tendency of coagulation and sedimentation in an aqueous medium.

See the examples below. After adding 5 parts by weight of a surfactant to water, 100 parts of zinc silicate-based particles are added.
After stirring the aqueous dispersion added by weight for 3 minutes, the aqueous dispersion was allowed to stand for 60 minutes.
L (Comparative Example 5 described later). On the other hand, when the surfactant in the above-mentioned ratio is added to the powder of zinc silicate-based particles, and the one subjected to high-speed shearing is dispersed in water so as to have the above-described concentration, thereby obtaining an aqueous dispersion. In
In the same settling test, the thickness of the coagulated settled layer is suppressed to 3 mL or less (Examples 1 and 5 described later).

In the present invention, the suppression of the tendency of the zinc silicate-based particles to coagulate and settle in water has been found as a phenomenon. The reason can be considered as follows. The present invention is not bound by this for any reason.

The trioctahedral type aluminum-containing zinc phyllosilicate has a basic skeleton of a two-layer structure in which a tetrahedral layer of SiO ₄ and an octahedral layer of ZnO ₆ are combined in a layered manner. Part of Si in the tetrahedral layer of No. ₄ is replaced by Al, and part of Zn in the octahedral layer of ZnO ₆ is also replaced by Al so as to balance this, and the basic skeleton of this substituted structure is further laminated. It has a layered structure.

In this laminated structure, the tetrahedral layer is negatively charged due to lack of electric charge, while the octahedral layer is positively charged due to excess electric charge. The influence of the negative charge appears strongly, and this is considered to be the cause of aggregation between particles when dispersed in water.

On the other hand, when the trioctahedral type aluminum-containing zinc phyllosilicate or amorphous silica composite particles thereof and a surfactant are mixed under high-speed shearing, the freshness of the zinc silicate-based particles can be improved. It is believed that the surface or edge is exposed and that the surfactant binds to this surface or edge. In other words, an anionic surfactant binds to and hides the positively charged portion, and a cationic surfactant binds to and hides the negatively charged portion. It is recognized that the action is suppressed and the dispersibility is improved.

In the present invention, the suppression of aggregation and the improvement of dispersibility are achieved not only with anionic and cationic surfactants, but also with nonionic surfactants. Also in the activator, at least a part of the molecular chain of the nonionic surfactant enters at least a part between the layers of the laminated structure, the fixing is performed, and a thick hydration layer is formed on the surface of the particle. It is presumed that the above action is achieved by the above.

In the composite of the present invention, 0.05 to 50 parts by weight of surfactant, especially 0 to 50 parts by weight, per 100 parts by weight of particles of the trioctahedral type zinc-containing aluminum phyllosilicate or the amorphous silica composite thereof is used. Loading in an amount of 0.05 to 20 parts by weight is preferable in terms of preventing aggregation and improving dispersibility.

That is, if the amount of the surfactant is less than the above range, the effect of preventing aggregation and the effect of improving dispersibility are insufficient. In addition, there is no particular advantage in this respect, but rather it is worsened, adverse effects are also caused in terms of deodorizing action and smoke control, and there is also a disadvantage that the coating becomes excessively hydrophilic.

In the present invention, in order to carry a surfactant on the zinc silicate-based particles, a surfactant or a concentrated solution thereof is added to the powder of the zinc silicate-based particles, and the mixture is subjected to high-speed shearing. It is important to attach. That is, if the zinc silicate-based particles and the surfactant are mixed in an aqueous medium, the effect of preventing aggregation and the effect of improving dispersibility as in the present invention cannot be obtained.

The composite of the present invention is advantageously used for preparing an aqueous dispersion for forming a coating of zinc silicate-based particles. That is, in the aqueous dispersion prepared using this composite, the zinc silicate-based particles are maintained in a finely dispersed state without agglomeration. Are maintained in a fine state, and as a result, excellent flexibility, powder fall resistance, excellent gloss and texture, and the like are exhibited.

Furthermore, since the zinc silicate-based particles are maintained in a fine state, that is, a state in which the specific surface area is large, an advantage of being excellent in deodorant performance and smoke control performance is also achieved.

The deodorizing performance of the trioctahedral type aluminum-containing zinc phyllosilicate is derived from both the characteristics as a solid acid and a solid base specific to the above-mentioned two-layer structure. Prior to the chemisorption of the components,
It is first important to physically adsorb these components on the particle surface. In the coating of the zinc silicate-based particles formed from the composite of the present invention, since the specific surface area and the pore volume of the particles are kept large, an excellent deodorizing effect is achieved.

The particles of trioctahedral-type zinc-containing aluminum phyllosilicate and its amorphous silica composite, when applied as a coating on the surface of fibers or other polymer moldings, have an excellent smoke suppressing effect. Show. This smoke suppression effect is recognized to be due to the presence of the zinc component. However, when the zinc component is present in the form of a composition with aluminophyllosilicate or amorphous silica, the smoke suppression effect is significantly improved. This is also due to the increase in specific surface area and pore volume. However, in the coating of the zinc silicate-based particles formed from the composite of the present invention, the particles have a large specific surface area and large pore volume. Because of the dripping, it has an excellent smoke control effect.

The aluminum-containing Philo zinc silicate used in the aluminum-containing Philo zinc silicate present invention ideally following general formula _{(1) (Zn 3-x} Al x) (Si 2-x Al x) O ₅ (OH) ₄ ‥ (1) wherein x is a number from 0.1 to 1.75, and is a double-layered phylloaluminosilicate having a chemical structure represented by the following general formula: This is called tight. That is, in this chemical structure, the tetrahedral layer Si of silica is replaced with Al, and in order to balance this, part of Zn in the octahedral layer of ZnO ₆ is also replaced with Al, and these are laminated in two layers. Is used as a basic skeleton, and this basic skeleton has a structure (fly pontite type structure) in which the basic skeleton is sometimes laminated in the C-axis direction.

The aluminum-containing zinc phyllosilicate is
It can also be used in the form of a complex with amorphous silica. This complex is amorphous in consists of a porous silica and aluminum-containing phyllo zinc silicate layer formed on the surface of the primary particles of the whole as a three-component basis, SiO 2 ₅ to 80
It has a composition of 5 mol% to 65 mol% of ZnO and 1 to 60 mol% of Al ₂ O ₃ . In this composite, a layer of aluminum-containing zinc phyllosilicate is formed in the pores of the amorphous silica or on the surface of the primary particles. And is characterized by being amorphous or low crystalline. The aluminum-containing zinc phyllosilicate of this composite type is characterized by a large covering power and a large activity such as deodorant performance and smoke control. That is, although the basic skeleton of this composite zinc phyllosilicate is the same as that of frypontite, lamination in the C-axis direction of the basic skeleton is substantially prevented, and the basic skeleton is substantially in a single layer state. Present on the surface of primary particles of porous silica. For this reason,
In this composite, there is substantially no peak at a plane spacing (dx) of 8.40 to 6.40 angstroms by X-ray diffraction, and the
It has weak diffraction peaks at (dx) 2.71 to 2.56 angstroms and at a spacing (dx) of 1.56 to 1.52 angstroms.

FIG. 1 shows an X-ray diffraction image of a typical frypontite-type aluminum-containing zinc phyllosilicate. FIG.
FIG. 2 shows an X-ray diffraction image of an amorphous silica composite of aluminum-containing zinc phyllosilicate which is close to amorphous.

The production of frying-pontite type aluminum-containing zinc phyllosilicate is described in JP-A-61-10021, 61
As described in JP-A-275128 and JP-A-275-127127, (A) silica or a silicon compound capable of forming silica under reaction conditions, (B) zinc white, zinc hydroxide or hydroxylation under reaction conditions A zinc compound capable of forming zinc, and (C) alumina hydrate, aluminum hydroxide, or an aluminum compound capable of forming these under the reaction conditions, are expressed as oxides in a three-component composition ratio of Si.
O ₂ 5 to 45 mol%, ZnO 35 to 65 mol% and Al
In an amount ratio corresponding to ₂ O ₃ 0 to 60 mol%, it is carried out by reacting under presence presence of moisture. The reaction is obtained by forming a precipitate from the reactant mixture and heating the precipitate, or by hydrothermally treating the reactant mixture in an autoclave. Of course, the present invention is not limited to this production method.

This composite can be easily obtained by producing aluminum-containing zinc phyllosilicate in a silica sol or gel dispersion as described in Japanese Patent Publication No. 5-79602.

The aluminum-containing zinc phyllosilicate or its amorphous silica composite used in the present invention preferably has a certain specific surface area and a certain pore volume, and has a BET specific surface area of 30 to 1000 m ² / g. , Especially 50 to 500
m ² / g is preferred. Further, the volume-based median diameter (D ₅₀ ) measured by the laser scattering method is desirably in the range of 0.5 to 10 μm, particularly 0.5 to 5 μm. Further, the pore volume at a pore diameter of 10 to 300 Å is 0.10 mL / g or more, especially 0.2
It is desirable that it is 5 mL / g or more, and that the Hunter whiteness is 90% or more.

[Surfactant] Examples of the surfactant adhering to the aluminum-containing zinc phyllosilicate and the like include anionic surfactants, nonionic surfactants, cationic surfactants, and combinations thereof.

Examples of the anionic surfactant include primary higher alcohol sulfates, secondary higher alcohol sulfates, primary higher alkyl sulfonates, secondary higher alkyl sulfonates, and higher alkyl disulfones. Acid salt, sulfonated higher fatty acid salt, higher fatty acid sulfate ester salt, higher fatty acid ester sulfonate, higher alcohol ether sulfate, higher alcohol ether sulfonate, higher fatty acid amide alkylolated sulfate, alkylbenzene Any anionic surfactant such as a sulfonate, an alkyl phenol sulfonate, an alkyl naphthalene sulfonate, and an alkyl benzimidazole sulfonate may be used. More specific compound names for these surfactants are:
For example, it is disclosed in "Synthetic Surfactant" written by Hiroshi Horiguchi (Showa 41, Sankyo Publishing).

As the cationic surfactant, any compound known per se can be used. Suitable examples of the cationic surfactant include, but are not limited to, the following. Long-chain alkyl quaternary ammonium salts; In the formula, each of R ₁ , R ₂ , R ₃ and R ₄ is a monovalent hydrocarbon group under the condition that at least one of them is an alkyl group having 10 to 24 carbon atoms, and X is an acid anion. A quaternary ammonium salt of For example, alkyl trimethyl ammonium halide, dialkyl dimethyl ammonium halide, alkyl dimethyl benzyl ammonium halide and the like. More specifically, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, octadecyltrimethylammonium chloride,
Hexadecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium chloride and the like. The following formula (3) In the formula, R ₅ is an alkyl group having 8 to 24 carbon atoms;
(N) is a quaternary ammonium salt of a pyridine group. For example, alkylpyridinium chloride such as dodecylpyridinium chloride.

As the nonionic surfactant, a nonionic surfactant having a low HLB, particularly one having an HLB of 12 or less, most preferably 8 or less, is used. Generally, polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether are used. , Polyoxyethylene fatty acid esters, polyoxyethylene fatty acid amide ethers, polyhydric alcohol fatty acid esters. Among the polyoxyethylene polyhydric alcohol fatty acid esters, fatty acid sucrose esters, alkylolamides, polyoxyalkylene block copolymers and the like, those having an HLB within the above range are used. For example, for these nonionic surfactants,
Since HLB decreases when the content of polyoxyethylene units decreases, a desired HLB nonionic surfactant can be obtained by adjusting the number of moles of ethylene oxide added.

These surfactants can be appropriately selected depending on the required liquid properties of the coating material. For example, the surfactants may be selected so that the maximum surface activity is exhibited depending on the pH of the solution. Type is selected. Of course,
There is no such limitation when the surfactant used is a nonionic surfactant. Nonionic surfactants are
It can be used alone or in combination with an anionic or cationic surfactant.

[Composite for Aqueous Dispersion, Production and Use] In the composite of the present invention, trioctahedral-type zinc-containing aluminum phyllosilicate or amorphous silica composite thereof is added to particles of 100 wt. 0.05 to 50 per copy
Part by weight, preferably 0.05 to 20 parts by weight of surfactant is impregnated.

The means for producing the composite is not particularly limited as long as the treatment is carried out in a powder state and the addition of a surfactant is carried out, but it is generally preferred to carry out the treatment by the following means.

That is, the impregnating treatment is performed by using a high-speed shear mixer or a stirrer such as a supermixer, and mixing the powdery aluminum-containing zinc phyllosilicate or its amorphous silica composite with the liquid-solid interface. Mix with activator. As a preferred example of the impregnation treatment, powdery aluminum-containing zinc phyllosilicate or its amorphous silica composite is charged into a supermixer, and the powder particles are stirred at a low speed of 500 to 600 rpm for about 1 to 2 minutes. Stir to loosen. Next, a liquid or solid surfactant is added and mixed at a high speed of 1000 to 2000 rpm for about 3 to 5 minutes. The composite after the impregnation process is dispensed in a powder state to obtain a product. It is sufficient to perform the impregnation at room temperature, but if desired, it may be heated to a temperature of about 60C to 200C. Heating can be performed by passing hot water and steam through the jacket of the supermixer.

Complex of aluminum-containing zinc phyllosilicate or amorphous silica complex thereof according to the present invention and a surfactant (hereinafter referred to as zinc silicate-surfactant complex)
Can be used for the purpose of adding a softening agent, if necessary, together with a binder, dispersing it in an aqueous medium, and imparting deodorant properties and smoke control properties to the fibrous material.

As the binder, all binders used for coating a fibrous material and the like can be used. For example, acrylic resins, urethane resins, epoxy resins, amino resins, phenol resins, silicone resins, alkyd resins, Polyester resin, vinyl acetate resin,
An ionomer resin or the like is used alone or in combination of two or more. In general, it is desirable that the resin used has water dispersibility like an emulsion resin, and for this purpose, the resin has a carboxyl group and the carboxyl group has ammonia or amine, such as an acrylic resin or an acrylic modified resin. Those which have become self-emulsifying by being neutralized with a compound are preferred. Such an emulsion type resin has water dispersibility at the time of coating,
At the time of drying or curing, ammonia or amines are volatilized and humidity sensitivity is eliminated, which is preferable. For curing this type of resin, an amino resin, particularly a methylolated melamine resin, is preferably used as a curing agent resin. Needless to say, the resin used for this purpose is not limited to a self-emulsifying resin, and may be a resin emulsified with a surfactant or another dispersant.

As the water-dispersible resin, resins called latex can also be used.
Butadiene rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), polybutadiene (BR), polyisoprene (IIB), butyl rubber,
Natural rubber, ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), polyurethane, silicone rubber, acrylic rubber, etc .; thermoplastic elastomers, for example, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block Copolymers, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers and the like can be used.

The water-soluble polymer can be used alone or in combination with the resin. As such a water-soluble organic polymer, an anionic or nonionic water-soluble organic polymer is used. Examples of the anionic polymer include sodium polyacrylate, or a copolymer of sodium polyacrylate and polyacrylamide, sodium polymethacrylate, sodium alginate, ammonium alginate, carboxymethyl starch,
Carboxymethyl cellulose, acrylamide-acrylic acid copolymer, maleic anhydride-vinyl ether copolymer, chitosan, sodium styrenesulfonate copolymer and the like are used. Examples of nonionic polymers include polyacrylamide, polyvinyl alcohol (PVA), starch,
Cyanated starch, methylcellulose, ethylcellulose,
Examples include hydroxyethyl cellulose, veegum, gelatin, polyethylene glycol and the like.

The concentration of each component in the coating solution is generally such that the concentration of the aluminum-containing zinc phyllosilicate or its amorphous silica composite is 0.3 to 20% by weight, especially 0.5 to 10% by weight. Binder concentration of 0.5 to 2
It is preferably 0% by weight, especially 0.5 to 10% by weight.
If necessary, the above-mentioned surfactant can be additionally added to this coating liquid.

As the fibrous material, a woven fabric, a nonwoven fabric, a paper or a synthetic paper made of one or more of natural fibers, regenerated fibers, synthetic fibers, and inorganic fibers is used.
Examples of the natural fiber include cellulose fibers such as pulp fiber, cotton and ramie, and animal fibers such as wool, and examples of the regenerated fiber include regenerated cellulose fiber and acetate fiber by viscose method and copper copper method. Examples of synthetic fibers include olefin fibers made of polyethylene, polypropylene, etc., polyvinyl alcohol fibers, polyvinyl chloride fibers, vinylidene chloride resin fibers, acrylic fibers, vinyl chloride / vinylidene chloride copolymer fibers, nylon 6, nylon 6-6, and the like. Examples thereof include thermoplastic polyester fibers such as polyamide fibers and polyethylene terephthalate, fluororesin fibers such as polytetrafluoroethylene, aramid fibers, and liquid crystal polyester fibers. Examples of the inorganic fibers include glass fibers, ceramic fibers, carbon fibers, and natural or synthetic mineral fibers. A suitable example of mineral fiber is
Although not limited thereto, calcium silicate fiber, magnesium silicate fiber, basic magnesium silicate fiber such as sepiolite and asbestos, and the like can be used. The fibers constituting the fibrous material may be used alone or in combination of two or more, and even if the fiber form is a staple fiber,
It may be a filament fiber. The thickness of the single fiber is not particularly limited, but is generally 100 denier or less, particularly preferably 50 denier or less.

The coating of the fibrous material with the zinc silicate-surfactant composite can be carried out by immersing the fibrous material in the above-mentioned coating solution or spraying the coating solution on the material. Generally, the coating amount is such that the coating amount of the aluminum-containing zinc phyllosilicate or its amorphous silica composite is 0.3 to 15% by weight, particularly 0.5 to 10% by weight on the basis of the fiber. Is good. Excess water after coating is removed with a squeezing device such as a mangle, a stretching dehydrator, or the like, and dried to obtain a fibrous material having deodorizing performance.

[0045]

EXAMPLES The present invention will be described with reference to examples. In addition, the measurement in an Example was performed by the following method.

(1) Chemical composition JIS. M. Performed according to 8855.

(2) BET specific surface area, pore volume Sorptometic Series manufactured by Carlo Elba
s 1900 was used and measured by the BET method.

(3) Median diameter The average particle diameter (median diameter; μm) was measured using a laser diffraction particle size analyzer (Coulter R LS130) manufactured by Coulter Counter.

(4) Dispersibility test The aqueous slurry was adjusted so that the concentration of the zinc silicate in the zinc silicate-surfactant complex or the zinc silicate compound was 1% and 5%, respectively. After the dispersion, the mixture was allowed to stand still, and the sedimentation amount (mL) one hour later was measured.

(5) Deodorizing property test [Method for preparing processing agent] A zinc silicate-surfactant complex or a 25% dispersion of zinc silicate in a zinc silicate compound was added to an acrylic binder ( Adjust the amount of active ingredient (5%) to 20% and the amount of nonionic softener (active ingredient 20%) to 1.5%, so that the amount of impregnation to fiber samples (acrylic curtain, polyester curtain) is 1% and 5%. It was soaked so that it might become. [Processing method] The dipped sample is 100% drawn with mangle 90 ~ 1
After drying at 00 ° C for 4 minutes, 140 ° C x 1 for acrylic curtain
Cured for a minute. For polyester curtain cloth
Curing was performed at 160 ° C for 1 minute. [Deodorization test] 4 g of each cloth obtained above (about 1
2.5 × 14.5cm), put it in a 1.8L honey bottle and seal it. There is a certain concentration of bad smell (ammonia or hydrogen sulfide)
Gas (150 ppm each) was injected, and the change with time was measured by the detector tube.

(6) Smoke control test [Preparation of sheet] To 100 parts by weight of an acrylic sheet, 2 and 5 parts by weight of the sample S-1-1 prepared in Example 1 described later were respectively attached, and a 5 × 5 cm square was prepared. Created a sheet. For comparison, an acrylic sheet with no sample attached (5 ×
5cm square) was also prepared. [Specific visual density (NBS test)] Using an NBS smoke test device manufactured by Toyo Seiki Seisaku-sho, Ltd., heat radiation amount 2.5 W / cm
^The sample sheet was heated in step ² to emit smoke, and the specific visual density (D _s ) for calculating the smoke intensity from the white light transmittance of the smoke was determined. [Limited oxygen index (LOI)] JIS K. 7201
According to the method B, the limiting oxygen index (LOI value%) was measured using a candle method combustion tester manufactured by Toyo Seiki Seisaku-sho, Ltd.

(Synthesis of Zinc Silicate Compound 1) Aqueous solution of sodium silicate (SiO ₂ = 22.0 wt%, Na ₂ O
= 7.2 wt%), aqueous sodium aluminate solution (Al
₂ O ₃ = 23.6 wt%, Na ₂ O = 19.0 wt
%, Zinc sulfate aqueous solution (ZnO = 7.96 wt%, SO
₃ = 8.1 wt%) and diluted sulfuric acid at 40 ° C. so that the molar ratio was Al ₂ O ₃ / SiO ₂ / ZnO = 1/6/3, and the reaction was carried out. After the reaction, the mixture was filtered and washed, dried at 110 ° C., and pulverized by a jet mill to obtain a zinc silicate compound 1 (Z-1). Physical properties were measured, and the results are shown in Table 1.

(Synthesis of Zinc Silicate Compound 2) Aqueous solution of sodium silicate (SiO ₂ = 22.0 wt%, Na ₂ O
= 7.2 wt%), aqueous sodium aluminate solution (Al
₂ O ₃ = 23.6 wt%, Na ₂ O = 19.0 wt
%, Zinc sulfate aqueous solution (ZnO = 7.96 wt%, SO
₃ = 8.15 wt%) and diluted sulfuric acid at 40 ° C. so that the molar ratio was Al ₂ O ₃ / SiO ₂ / ZnO = 1/3/6, and the reaction was carried out. After the reaction, the mixture was filtered and washed, dried at 110 ° C., and then pulverized by a jet mill to obtain a zinc silicate compound 2 (Z-2). Physical properties were measured, and the results are shown in Table 1.

[0054]

Table 1 Physical properties Z-1 Z-2 SiO ₂ (mol%) 61.2 43.1 Al ₂ O ₃ (mol%) 7.0 7.0 ZnO (mol%) 31.8 49.9 BET specific surface area (m ² / g) 270 110 Median diameter ( μm) 4.6 3.3 Oil absorption (mL / 100g) 95 74

(Surfactant) The following surfactants were used in the examples. Anionic surfactant: Demol EP (manufactured by Kao) Anionic surfactant: POLITY A-550 (manufactured by Lion) Anionic surfactant: Rheodol Super SP-S1
0 (manufactured by Kao) Nonionic surfactant: Emulgen L-40 (manufactured by Kao) Cationic surfactant: Cotamine 24P (manufactured by Kao)

(Example 1) Zinc silicate compound 1 (Z-1) was added to a supermixer (Model SMV-20 manufactured by Kawada Seisakusho).
000 g was added, and the mixture was stirred at room temperature at 500 rpm for 1 minute. Next, an anionic surfactant (Demol EP) 10
g was slowly added and mixed well at 1500 rpm for 1 minute at room temperature to carry a surfactant, thereby obtaining a zinc silicate-surfactant complex (referred to as S-1-1). Similarly, the amount of the anionic surfactant (Demol EP) carried was changed to 50 g and mixed in the same manner to obtain a zinc silicate-surfactant complex (referred to as S-1-2).

Example 2 A zinc silicate-surfactant complex was prepared in the same manner as in Example 1 except that the surfactant was changed to an anionic surfactant (Poly A-550). I got The composite having a surfactant loading of 10 g is referred to as S-2-1, and the composite having a loading of 50 g is referred to as S-2-2.

Example 3 A zinc silicate-surfactant complex was prepared in the same manner as in Example 1 except that the surfactant was changed to a nonionic surfactant (Emulgen L-40). I got The composite having a surfactant loading of 10 g is referred to as S-3-1 and the composite having a loading of 50 g is referred to as S-3-2.

Example 4 A zinc silicate-surfactant complex was obtained in the same manner as in Example 1, except that the surfactant was changed to a cationic surfactant (Cotamine 24P). Was. The composite having a surfactant loading of 10 g is referred to as S-4-1, and the composite having a loading of 50 g is referred to as S-4-2.

(Example 5)
A zinc silicate-surfactant composite was obtained in the same manner as in Example 1 except that the heating was carried out at ℃. A composite having a surfactant loading of 10 g is referred to as S-5-1, and a composite having a loading of 50 g is referred to as S-5-2.

(Example 6)
A zinc silicate-surfactant composite was obtained in the same manner as in Example 3 except that the heating was carried out at ℃. The composite having a surfactant loading of 10 g is referred to as S-6-1, and the composite having a loading of 50 g is referred to as S-6-2.

Example 7 Example 1 was the same as Example 1 except that the anionic surfactant (Demol EP) and the nonionic surfactant (Emulgen L-40) were mixed at a ratio of 1: 1. In the same manner as described above, a zinc silicate-surfactant composite was obtained. A composite having a surfactant loading of 5 g of an anionic surfactant and 5 g of a nonionic surfactant (10 g in terms of the amount of surfactant to be loaded) was prepared using S-7-1.
And the amount of the surfactant carried is an anionic surfactant 25
The composite of g and 25 g of the nonionic surfactant (50 g as the amount of the surfactant to be carried) is referred to as S-7-2.

Example 8 A zinc silicate-surfactant composite was obtained in the same manner as in Example 1 except that the zinc silicate compound was changed to Z-2. The composite having a surfactant loading of 10 g is referred to as S-8-1, and the composite having a loading of 50 g is referred to as S-8-2.

(Example 9) In Example 1, the surfactant was changed to a cationic powdery surfactant (Reodol Super SP).
A zinc silicate-surfactant composite was obtained in the same manner as in Example 1, except that the composition was changed to -S10). A composite having a surfactant loading of 10 g was designated as S-9-1, and a loading of 5
The composite weighing 0 g is designated as S-9-2.

Comparative Example 1 Zinc silicate compound 1 (Z-
1) was used as it was (H-1-1).

Comparative Example 2 Zinc silicate compound 2 (Z-
2) was used as it was (H-2-1).

Comparative Example 3 Zinc silicate compound 1 (Z-
1) Put 1000 g and 50 g of cationic powder surfactant (Rheodor Super SP-S10) in a plastic bag,
The mixture was mixed well to obtain a complex (H-3-1).

Comparative Example 4 A composite was obtained in the same manner as in Example 1 except that the amount of the anionic liquid surfactant (Demol EP) was changed to 60 g.
4-1).

Comparative Example 5 After dissolving an anionic liquid surfactant (Demol EP) in water, a zinc silicate compound 1 (Z-1) was added to the zinc silicate compound: surfactant = 1.
The aqueous solution slurry was adjusted so as to be 00: 5 (referred to as H-5-1). In a similar procedure, the slurry was adjusted so that the ratio of the zinc silicate compound: surfactant was 100: 20 (referred to as H-5-2). A dispersibility test was performed on each of the obtained slurries.

Table 2 shows the results of the dispersibility test of the substances used in Examples and Comparative Examples, Table 3 shows the results of the deodorant test, and Table 4 shows the results of the smoke control test.

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

According to the present invention, the particles of the trioctahedral type aluminum-containing zinc phyllosilicate or the amorphous silica composite thereof have a surface activity of 0.05 to 50 parts by weight per 100 parts by weight of the particles. By pre-loading the agent, the trioctahedral type aluminum-containing zinc phyllosilicate or the particles of the amorphous silica composite thereof are given an excellent anti-agglomeration effect and water dispersibility, and formed from this aqueous dispersion. It is possible to impart excellent flexibility, powder falling resistance, excellent gloss or texture, etc. to the resulting coating. The composite exhibits excellent deodorant and smoke eliminating properties in the form of a coating.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction image of a frypontite-type aluminum-containing zinc phyllosilicate.

FIG. 2 is an X-ray diffraction image of an amorphous silica composite of aluminum-containing zinc phyllosilicate (Frypontite).

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C080 AA05 BB02 BB10 CC04 CC08 HH05 JJ05 JJ06 JJ09 KK08 LL03 LL13 MM02 NN26 QQ03 4G073 BA52 BA57 BA63 BC02 BD16 CA06 CM08 CM29 FD03 GA01 GA12 GA13 UB23 A27AA A02AA AA37A24A CC06 CC15 CC16 CC17 CC22 CC23 CC24 CC26 CC28 DD02 DD05 DD07 DD24 EE02 EE08 EE28 EE43 FF15 FF30

Claims (10)

[Claims] Claims 1. A trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite particle thereof,
A composite for an aqueous dispersion, comprising 0.05 to 50 parts by weight of a surfactant per 100 parts by weight of the particles. 2. The particles of a trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite thereof,
In three-component basis, ZnO5 to 65 mol%, the composite body according to claim 1 and has a composition of SiO ₂ 5 to 80 mol% and _Al 2 _{O 3} 1 to 60 mol%. 3. The particles of a trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica composite thereof having a particle size of 3
The composite according to claim 1, having a BET specific surface area of 0 to 1000 m ² / g. 4. The particles of the trioctahedral type aluminum-containing zinc phyllosilicate or its amorphous silica composite having a volume-based median diameter of 0.5 to 10 μm as measured by a laser scattering method. Item 4. The composite according to any one of Items 1 to 3. 5. The composite according to claim 1, wherein the surfactant is an anionic surfactant. 6. The composite according to claim 1, wherein the surfactant is a nonionic surfactant. 7. The composite according to claim 1, wherein the surfactant is a cationic surfactant. 8. The method according to claim 1, wherein the complex is obtained by adding a surfactant or a concentrated solution thereof to powder of a trioctahedral type aluminum-containing zinc phyllosilicate or an amorphous silica complex thereof;
The composite according to any one of claims 1 to 7, which is obtained by subjecting the mixture to high-speed shearing. 9. A deodorant composition comprising the composite according to claim 1. 10. A smoke-controlling composition comprising the composite according to claim 1.