JP4534587B2 - Functional particle adhering material and method for producing the same - Google Patents

Description

  The present invention relates to a material in which functional particles are attached to a substrate and a method for producing the same.

  Conventionally, there has been a demand for exerting various functions by attaching or kneading some functional particle material to a base material constituting various things from buildings to electrical appliances and clothes.

  In response to these demands, materials have been developed in which various functional particles are adhered to the substrate (hereinafter referred to as “functional particle adhering materials” as appropriate), but many of them have functional particles mixed in a binder. It was manufactured by the method of making it adhere to a base material.

  However, the conventional functional particle-attached material manufactured by such a method has a problem that the binder is deteriorated over time and the functional particles are easily peeled off. In particular, when these materials are applied to clothes, etc., the functional particles attached to the substrate easily peel off due to the physical and chemical action of washing, so that the peeling of the functional particles is suppressed. Technology was sought.

  In order to suppress exfoliation of functional particles, the easiest way is to increase the amount of binder used. However, there is a limit to the effect of suppressing peeling only by increasing the amount of the binder, and if a large amount of binder is used, various properties of the base material are impaired, and functional particles hinder the performance of the intended function. There was also a case.

  For example, when a porous material is used as the functional particle, if a large amount of binder is used, the binder will block or fill the pores of the porous material, so the adsorption / release performance of the porous material, etc. There was a problem that the function of the pores could not be fully exhibited. The adsorption / release performance mentioned here is manifested in the property of adsorbing the porous material such as the adsorption performance of the porous material to adsorb the substance in its pores and the release performance of releasing the adsorbed substance. It refers to various performances (humidity control, heat generation, antibacterial, antifungal, etc.) and a so-called sustained release function that dissipates a drug or the like previously supported in the pores.

  In view of such a situation, there has been a demand for a technique for effectively suppressing peeling of functional particles without interfering with the characteristics of the base material and the functions of the functional particles in the functional particle-attached material. As such a technique, Patent Document 1 discloses that when a composite oxide is adhered to a fiber with a binder resin, a coupling agent is added to a processing solution containing the binder resin and the composite oxide, It is stated that the adhesion to the binder resin is reinforced and the durability is improved by applying to the material.

  On the other hand, a material obtained by kneading various functional particles on a substrate (hereinafter referred to as “functional particle kneading material” as appropriate) has no problem such as peeling of functional particles as described above. Has been made. For example, Patent Document 2 describes that a polyester fiber is kneaded with a surface-treated antibacterial agent obtained by treating an antibacterial inorganic compound containing silver with a specific silane coupling mixture.

JP 2003-336168 A JP 2003-301330 A

  However, in the technique described in Patent Document 1, there is no description about specific types of coupling agents, and the types of coupling agents and types of binder resins, composite oxides, and fibers are not optimized. Therefore, the effect obtained thereby is unknown. In addition, there is no difference from the conventional functional particle adhesion material technology in that the composite oxide is adhered to the fiber mainly by the adhesive force of the binder resin, and there is a limit to the delamination suppression effect of the functional particles. it is conceivable that.

  On the other hand, in the functional particle kneading material represented by Patent Document 2, there is no possibility that the functional particle is peeled off or dropped off unlike the functional particle adhering material, but the functional particle is contained in the base material such as resin. Since the particles are kneaded, the characteristics of the base material and the functions of the functional particles may be hindered. Moreover, since a step of kneading the functional particles in the base material is required at the time of manufacturing the raw material, there is a problem that contamination is caused by putting the functional particles in the kneader in addition to being very laborious. . Furthermore, a raw material cannot be manufactured using an existing base material and functional particles, and there is a problem in terms of efficiency.

  The present invention has been made in view of the above-described problems. That is, the present invention is a material obtained by immobilizing functional particles on a base material, and can be efficiently produced using an existing base material and functional particles, and the characteristics and functional particles of the base material have It aims at proposing the raw material which can suppress effectively peeling and dropping | offset | release of a functional particle, and its manufacturing method, without disturbing a function.

  Accordingly, as a result of intensive studies to solve the above problems, the present inventors have made functional particles adhere to the base material by bringing the coupling agent into contact with the base material and further bringing the functional particles into contact therewith. In addition, it is possible to obtain a material in which functional particles are bonded to a substrate via a coupling agent (hereinafter referred to as “functional particle adhering material” as appropriate). According to the present invention, it is possible to efficiently manufacture using an existing base material and functional particles, and without effectively interfering with the characteristics of the base material and the functions of the functional particles, and effectively removing and dropping the functional particles. It became possible to suppress and found that the said subject was solved effectively, and came to complete this invention.

That is, the gist of the present invention is that the functional particles are attached to at least a part of the substrate, and at least a part of the functional particles is silica gel having a mode pore diameter of 2 nm to 50 nm, A binder in which at least some of the functional particles are bonded to the substrate via a silane coupling agent , and at least some of the functional particles have a glass transition temperature of −80 ° C. or higher and 110 ° C. or lower. The functional particle adhering material is characterized in that it is adhering to the base material.
Further, another gist of the present invention is a method for producing the functional particle-adhered material described above, wherein a first step of bringing a silane coupling agent into contact with a substrate, and after the first step, Furthermore, it exists in the manufacturing method of a functional particle attachment raw material characterized by having at least the 2nd process which makes a functional particle contact a base material.

  The functional particle-attached material of the present invention can be produced efficiently using an existing base material and functional particles, without interfering with the characteristics of the base material and the functions of the functional particles, It is possible to effectively suppress peeling and falling off.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

  The functional particle-attached material of the present invention (hereinafter abbreviated as “the material of the present invention” or the like as appropriate) has functional particles attached to at least a part of a substrate and at least a part of the functional particles. Is bonded to the substrate via a coupling agent. Moreover, it is preferable that at least a part of the functional particles is further attached to the base material by a binder.

[I. Ingredients of the material]
[I-1. Base material〕
The base material used in the material of the present invention is not particularly limited as long as the functional particles described below can be attached by a coupling agent, and any material can be used depending on the purpose and use of the material. Can be used. Examples include films, sheets, plates, fabrics and the like made of fiber, paper, plastic, wood, concrete, metal, leather and the like. Any one of these substrates may be used alone, or two or more thereof may be used in any combination.

  In particular, as described later, when the material of the present invention is produced by impregnating a base material with a coating solution, it is preferable to use an impregnating material (impregnating member) as the base material. The type of the impregnating member is not particularly limited, but a fiber is a particularly preferable example.

  The fiber may be either a natural fiber or a synthetic fiber, or a fiber using both of these. Moreover, the thing of arbitrary forms, such as a woven fabric, a knitted fabric, a nonwoven fabric, can also be used as the form.

  Specific examples of the fiber include woven fabric, moquette, towel cloth, tricot, double raschel, circular knitting, needle punch and the like. In addition, the fibers referred to herein include natural fibers such as cotton, hemp, silk, and wool, or rayon; acetate; protein fibers; chlorinated rubber; polyamides such as nylon 6, nylon 66, and nylon-12; polyvinyl alcohol; Polyvinyl chloride; Polyvinylidene chloride; Polyacrylonitrile; Polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, etc .; Polyethylene; Polypropylene; Polyurethane; Polycyanide cyanide; Polyfluoroethylene And fibers composed of blends. Among these, cotton, hemp, polyester, and polyamide are preferably used from the viewpoint of versatility. In addition, these may contain additives such as polymers, matting agents, flame retardants, antistatic agents and pigments.

  The shape of the fiber is not particularly limited, and any shape such as a thread, a fabric, or a sheet may be used. In particular, in the case of synthetic fibers, the cross-sectional shape and the shape in the longitudinal direction can be freely designed. Specifically, examples of the cross-sectional shape include a round cross-section, a hollow cross-section, a multi-leaf cross-section such as a trilobe cross-section, and other irregular cross-sections, and examples of the shape in the longitudinal direction include long fibers and short fibers. Any of these can be arbitrarily selected. As the fabric, a woven fabric or a knitted fabric can be used depending on the application. A plain woven fabric, a twill weave fabric, a satin weave fabric, a combination thereof, or a knitted fabric may be used.

  Among these, as the base material, a substance having a large number of functional groups that easily react with various coupling agents described later is preferable. Examples include fiber, paper, etc. Among them, cellulosic fiber and paper having a highly reactive OH group are preferable (hereinafter, these cellulosic fiber and paper are collectively referred to as “cellulosic fiber”). Shall be.) Cellulose fibers include (i) natural fibers derived from various plants such as cotton, hemp, bamboo, etc., and (ii) these natural fibers dissolved and chemically modified. Examples thereof include recycled fibers and semi-synthetic fibers obtained (viscose rayon, bembel rayon (copper ammonia rayon, cupra), various rayons such as acetate rayon, etc.), and the like. Any of these can be suitably used, but cotton or cotton-containing fiber material is preferred because of the large number of reactive functional groups on the substrate surface.

[I-2. Functional particles)
There are no particular restrictions on the functional particles used in the material of the present invention, and any particles can be used. However, for the purpose of the present invention, it is usually a substance that is difficult to directly bond to the above-mentioned substrate. Is mainly used. Here, a substance that is difficult to be directly bonded to the substrate is a substance that does not form a covalent bond or a coordinate bond with the above-described substrate, more specifically, a covalent bond or a coordinate with a functional group of the substrate. A substance having substantially no functional group forming a coordinate bond.

  As a specific type of functional particles, an appropriate particle may be selected and used according to the function to be imparted to the material. Therefore, although the kind does not ask | require organic substance and an inorganic substance, an inorganic substance is preferable from viewpoints, such as economical efficiency at the time of a synthesis | combination. In particular, when an organic substance is used as a base material, it is usually difficult to directly bond an inorganic substance as a functional particle thereto, so that the effect of application of the present invention is increased. Also, from the viewpoint of enhancing the functionality of the material, a porous material that can be expected to absorb and release various materials, various functions associated therewith, and the sustained release performance of the supported material is preferable. Therefore, an inorganic porous material is particularly preferable as the functional particle. Specific examples of the inorganic porous material include silica gel and alumina. Among these, silica gel is particularly preferable because precise control of physical properties is easy by the method described below. These exemplified functional particles may be used alone or in combination of two or more.

  In the case where a porous substance is used as the functional particles, various functions can be provided by controlling the pore characteristics. The detailed pore characteristics may be appropriately adjusted according to the intended use of the material, but generally speaking, it is preferable that the pore diameter distribution has a sharp and uniform structure. As a result, the functional particles have a uniform strength, and as a result, the material of the present invention can stably exhibit high durability.

The shape and size of the functional particles are not particularly limited, and an appropriate shape and size may be selected according to the use / purpose of the material, the type of the base material used in combination, and the like.
Specifically, examples of the shape of the functional particles include a spherical shape, a substantially spherical shape, a crushed shape, an ellipsoidal shape, a polyhedral shape, a flat shape, and the like. Spherical and crushed shapes are preferred.

  The particle diameter of the functional particles is preferably 0.1 μm or more, particularly 0.5 μm or more, more preferably 1 μm or more, and usually 300 μm or less, especially 250 μm or less, and more preferably 200 μm or less. By making the particle diameter within this range, it becomes easy to uniformly disperse the functional particles when producing the material of the present invention by the method described later. In particular, when fibers are used as the base material, the particle size of the functional particles is usually 0.1 μm or more, particularly 0.2 μm or more, and usually 5 μm or less, from the viewpoint of the texture of the material and washing durability. In particular, the range is preferably 2 μm or less.

[I-3. Silica gel (preferred example of functional particles)]
In the present invention, it is particularly preferable to use a specific silica gel as the functional particles. Hereinafter, the silica gel suitably used in the present invention (hereinafter, appropriately abbreviated as “silica gel of the present invention” or the like) will be described in detail.

  The silica gel of the present invention has a pore volume value measured by a nitrogen gas absorption / desorption method of usually 0.3 ml / g or more, particularly 0.4 ml / g or more, more preferably 0.6 ml / g or more, It is preferably 3 ml / g or less, particularly 2.5 ml / g or less, more preferably 2.0 ml / g or less. By using silica gel having a pore volume in this range, it is possible to impart high absorption / release performance to the material of the present invention. The pore volume of silica gel can be determined from the amount of nitrogen gas adsorbed at an adsorption isotherm relative pressure of 0.98.

The silica gel of the present invention has a BET specific surface area value of usually 100 m ² / g or more, particularly 200 m ² / g or more, more preferably 300 m ² / g or more, particularly 350 m ² / g or more, and usually 1000 m ^2. / G or less, in particular 900 m ² / g or less, more preferably 800 m ² / g or less, particularly preferably 700 m ² / g or less. By using silica gel having such a large specific surface area, it is possible to impart high absorption / release performance to the material of the present invention. Specifically, for example, the adsorption performance of various substances can be enhanced. The value of the specific surface area of silica gel can be measured by the BET method by nitrogen gas adsorption / desorption.

Further, the silica gel of the present invention is obtained from the isothermal desorption curve measured by the nitrogen gas adsorption / desorption method from the BJH method described in EP Barrett, LG Joyner, PH Haklenda, J. Amer. Chem. Soc., Vol. 73,373 (1951). Is the mode of the pore distribution curve calculated by the above equation, that is, the frequency on the graph plotting the differential nitrogen gas adsorption amount (ΔV / Δ (logd); V is the nitrogen gas adsorption volume) against the pore diameter d (nm). The value of the pore diameter (D _max ) is usually 2 nm or more, and usually 50 nm or less, preferably 30 nm or less. If the mode pore diameter (D _max) is smaller than this range, the space in the silica gel becomes small, so that the absorption / release performance may be lowered. Further, if the mode pore diameter ( _Dmax) is larger than this range, the strength of the silica gel is weakened, the pore structure is easily broken over time, and the binder component described later easily enters the pores. Therefore, there is a possibility that the absorption / release performance is lowered. However, since the preferred mode pore diameter (D _max ) varies depending on the purpose and use of the material, it is desirable to use different silica gels having various mode pore sizes (D _max ) depending on the purpose and use of the material.

Furthermore, the silica gel of the present invention has a total volume of pores having a diameter within the range of ± 20% of the value of the most frequent pore diameter (D _max ), usually 50% or more of the total pore volume, especially 60 % Or more, preferably 70% or more. This means that the pore diameters of the silica gel are uniform around the most frequent pore diameter (D _max ), that is, the pore diameter distribution is extremely narrow (sharp). The upper limit of this ratio is not particularly limited, but is usually 90% or less. In general, when a part of the silica gel is brittle, the pore structure of the part is easily broken. However, if the pore size distribution is small as described above, the structure of the silica gel becomes uniform and the silica gel strength is increased. Since it is difficult for variations to occur, it is possible to prevent partial brittle portions from occurring. Therefore, by using silica gel with a pore size distribution in the above range, the entire material exhibits high durability, and as described later, a binder component having a specific resin size enters the pores. It becomes possible to control with high accuracy. In addition, when the pore size distribution of the silica gel is sharp, functions such as humidity control, moisture absorption exothermicity, sustained release, etc. are enhanced, so that the material of the present invention containing this also has high humidity control, moisture absorption exothermic, sustained release. It will exhibit functions such as sex.

In relation to such characteristics, the silica gel of the present invention has a differential pore volume ΔV / Δ (logd) at the most frequent pore diameter (D _max ) calculated by the BJH method of usually 2 ml / g or more, particularly 3 ml. / G or more, more preferably 5 ml / g or more, and usually 40 ml / g or less, particularly 30 ml / g or less, more preferably 25 ml / g or less (where d is the pore diameter) (Nm), V represents the nitrogen gas adsorption volume). In the case where the differential pore volume ΔV / Δ (logd) is included in the above range, it can be said that the absolute amount of pores whose diameters are aligned in the vicinity of the most frequent pore diameter (D _max ) is extremely large.

  The silica gel of the present invention is preferably non-crystalline, that is, no crystalline structure is observed in view of its three-dimensional structure in addition to the above pore structure characteristics. This means that when the silica gel of the present invention is analyzed by X-ray diffraction, substantially no crystalline peak is observed. In this specification, the non-amorphous silica gel refers to a silica having a peak of at least one crystal structure at a position exceeding 6 angstroms (Å Units d-spacing) in the X-ray diffraction pattern. Amorphous silica gel is extremely excellent in productivity as compared with crystalline silica gel.

Furthermore, regarding the structure of the silica gel of the present invention, a characteristic result can be obtained even by analysis by solid-state Si-NMR measurement. That is, in the solid Si-NMR measurement, Q ⁴ / Q indicating the molar ratio of Si (Q ³ ) with ³ —OSi bonded to Si (Q ⁴ ) with ⁴ bonded —OSi in the silica gel of the present invention. The value of ³ is usually in the range of 1.2 or more, particularly 1.4 or more. The upper limit is not particularly limited, but is usually 10 or less. In general, it is known that the higher the value, the higher the thermal stability of the silica gel. That is, since the silica gel of the present invention is less likely to break the structure due to heat, the material of the present invention including this can be used stably over a long period of time. On the other hand, some crystalline micelle template silicas have a Q ⁴ / Q ³ value of less than 1.2 and have low thermal stability, particularly hydrothermal stability. The value of Q ⁴ / Q ³ performs a solid Si-NMR measurement can be calculated based on the result. Further, analysis of measurement data (determination of peak position) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function.

  In addition, the silica gel of the present invention has a total content of metal elements (metal impurities) excluding silicon constituting the skeleton, which is usually 500 ppm or less, particularly 100 ppm or less, more preferably 10 ppm or less, and is extremely low. High purity is preferred. In the present specification, “ppm” represents a ratio to weight. Thus, by suppressing the content rate of the metal impurities in the silica gel, it is possible to suppress undesirable effects due to the metal impurities, and to exhibit excellent properties such as high durability, heat resistance, and water resistance in the silica gel. In addition, by using silica gel with few metal impurities, it is possible to suppress the occurrence of light deterioration, heat deterioration, deterioration with time, etc. due to contact between the binder component and metal impurities in the material, and the material can be stably used over a long period of time. Can be used. The metal impurity content in the silica gel can be determined by various elemental analysis methods represented by the ICP emission analysis method and flame flame method used in Examples described later.

  Furthermore, the silica gel of the present invention has one of its features that even if it is subjected to a heat treatment in water (hydrothermal test), there is little change in pore characteristics. Changes in the pore characteristics of silica gel after the hydrothermal test are observed as changes in physical properties related to porosity such as specific surface area, pore volume, and pore size distribution. Specifically, when the silica gel of the present invention is subjected to a hydrothermal resistance test under certain conditions described later, the ratio of the specific surface area after the test to the specific surface area before the test (specific surface area remaining ratio) is usually 20% or more. Of these, a range of 35% or more, particularly 50% or more is preferred. Silica gel having such characteristics is preferable because the porous characteristics are not lost even under severe use conditions for a long time.

  Furthermore, the silica gel of the present invention produced by the method described later has very little deterioration in the characteristic that the pore size distribution is sharp even after this hydrothermal resistance test, and the change in pore volume is extremely small. It has a characteristic that is not found in conventional silica gels, that is, there is little or an increase in pore volume.

  The “hydrothermal resistance test” in the present invention refers to bringing silica gel into contact with water at a specific temperature (200 ° C.) for a fixed time (6 hours) in a closed system. If all of the silica gel is present in water, even if the inside of the closed system is completely filled with water, a part of the system has a gas phase part under pressure. There may be. In the latter case, the pressure in the gas phase is usually 60,000 hPa or higher, preferably 63000 hPa or higher. The error of the specific temperature is usually within ± 5 ° C., preferably within ± 3 ° C., and more preferably within ± 1 ° C.

  The particle diameter of the silica gel of the present invention is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and usually 300 μm or less, especially 250 μm or less, and more preferably 200 μm or less. By setting the particle diameter of the silica gel within this range, it becomes easy to uniformly disperse the silica gel when used for the material of the present invention.

The silica gel production method of the present invention having the characteristics described above is not particularly limited, and can be produced by any known method. Examples of methods often used for the production of silica gel include the following methods.
i. A method of gelling after neutralizing water glass with an acid such as sulfuric acid.
ii. A method in which alkoxysilane is hydrolyzed and then gelled.
iii. A method of forming pores using alkoxysilane or water glass as a raw material and using a surfactant as an organic template (so-called micelle template silica).

  The method for producing the silica gel of the present invention is not particularly limited as described above, and among them, the silica hydrogel is hydrothermally treated, and the water content in the liquid component of the obtained slurry is 5% by weight or less. Then, it is preferable to dry it. Specifically, the raw material silicon alkoxide is hydrolyzed, and the obtained silica hydrogel is preferably hydrothermally treated without substantially aging to remove water in the obtained silica slurry. In addition, you may include the process made to contact with a hydrophilic organic solvent after hydrothermal treatment. Hereinafter, this production method (hereinafter abbreviated as “silica gel production method of the present invention” or the like as appropriate).

  The manufacturing method of the silica hydrogel used as a raw material is arbitrary, For example, the silica hydrogel obtained by hydrolyzing a silicic acid alkali salt or the silica hydrogel obtained by hydrolyzing a silicon alkoxide is mentioned. Among them, silica hydrogel obtained by hydrolyzing silicon alkoxide is preferable because it can increase the purity of silicon alkoxide as a raw material and can easily prevent impurities from being mixed into silica hydrogel.

  Specific examples of silicon alkoxide that can be used as a raw material include trimethoxysilane, tetramethoxysilane, triethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and other trialkyls having a lower alkyl group having 1 to 4 carbon atoms. Or tetraalkoxysilane or those oligomers are mentioned. Among these, tetramethoxysilane, tetraethoxysilane, and oligomers thereof, particularly tetramethoxysilane and oligomers thereof are preferable because silica gel having good pore characteristics can be obtained. The main reason is that silicon alkoxide is easily purified by distillation to obtain a high-purity product, and is therefore suitable as a raw material for high-purity silica gel. The total content of metal elements (metal impurities) belonging to the alkali metal or alkaline earth metal in the silicon alkoxide is usually 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm or less. The content rate of these metal impurities can be measured by the same method as the measurement method of the metal impurity content rate in the silica gel mentioned above.

  In the silica gel production method of the present invention, first, in the hydrolysis / condensation step, silicon alkoxide is hydrolyzed in the absence of a catalyst, and the obtained silica hydrosol is condensed to form a silica hydrogel.

  Hydrolysis of silicon alkoxide is usually 2 mol times or more, preferably 3 mol times or more, particularly preferably 4 mol times or more, and usually 20 mol times or less, preferably 10 mol times or less with respect to 1 mol of silicon alkoxide. Particularly preferably, it is carried out using 8 mol times or less of water. Hydrolysis of the silicon alkoxide produces a silica hydrogel and an alcohol, and the produced silica hydrosol is successively condensed into a silica hydrogel.

  The temperature at the time of hydrolysis is usually room temperature or higher and 100 ° C. or lower, but it can also be performed at a higher temperature by maintaining the liquid phase under pressure. The reaction time required for hydrolysis depends on the composition of the reaction solution (type of silicon alkoxide and molar ratio with water) and the reaction temperature, and since the time until gelation differs, it is not generally specified. In order to obtain silica having excellent pore characteristics such as the silica gel of the present invention, it is preferable that the reaction time is set so that the fracture stress of the hydrogel does not exceed 6 MPa.

  In this hydrolysis reaction system, hydrolysis can be promoted by allowing an acid, an alkali, a salt, or the like to coexist as a catalyst. However, the use of such a catalyst causes aging of the produced hydrogel, as will be described later, and thus is not very preferable in the method for producing silica gel of the present invention.

  In the hydrolysis of the above-mentioned silicon alkoxide, it is important to sufficiently stir. For example, when a stirrer equipped with a stirring blade on the rotating shaft is used, the stirring speed (the number of rotations of the rotating shaft) depends on the shape, the number of the stirring blades, the contact area with the liquid, etc., but usually 30 rpm Above, preferably 50 rpm or more.

  In general, if the stirring speed is too high, droplets generated in the tank block various gas lines or adhere to the inner wall of the reactor to deteriorate the heat conduction, which is an important temperature control property. It may affect management. In addition, the deposits on the inner wall may peel off and enter the product, deteriorating the quality. For these reasons, the stirring speed is preferably 2000 rpm or less, and more preferably 1000 rpm or less.

  In the method for producing silica gel of the present invention, any stirring method can be used as the stirring method for the two separated liquid phases (aqueous phase and silicon alkoxide phase) as long as the method promotes the reaction. Among them, examples of an apparatus for further mixing the two liquid phases include the following (A) and (B).

(A): An apparatus having a stirring blade in which a rotating shaft is inserted perpendicularly or slightly at an angle with respect to the liquid surface, and the liquid flows vertically.
(B): A stirrer having a stirring blade provided with a rotation axis direction substantially parallel to the interface between the two liquid phases and causing stirring between the two liquid phases.

  The rotational speed of the stirring blade when using the above-described apparatuses (A) and (B) is usually 0.05 m / s or more, particularly 0.1 m / s, as the peripheral speed of the stirring blade (stirring blade tip speed). s or more, and usually 10 m / s or less, preferably 5 m / s or less, and more preferably 3 m / s or less.

  The shape and length of the stirring blade is arbitrary, and examples of the stirring blade include a propeller type, a flat blade type, an angled flat blade type, a pitched flat blade type, a flat blade disk turbine type, a curved blade type, a fiddler type, Examples include a bull margin type.

  The width, number of blades, inclination angle, etc. of the blades may be appropriately selected according to the shape and size of the reactor and the target stirring power. For example, the ratio (b / D) of the blade width (blade length in the rotation axis direction) to the tank inner diameter (the longest diameter of the liquid phase surface forming a plane perpendicular to the rotation axis direction) of the reactor is 0.05 to A suitable example is 0.2, an inclination angle (θ) of 90 ° ± 10 °, and a stirring device of 3 to 10 blades.

  Among these, the structure in which the above-described rotating shaft is provided above the liquid level in the reaction vessel and the stirring blade is provided at the tip of the shaft extending from the rotating shaft is preferably used from the viewpoint of stirring efficiency and equipment maintenance. .

  In the above silicon alkoxide hydrolysis reaction, the silicon alkoxide is hydrolyzed to form a silica hydrosol. Subsequently, a condensation reaction of the silica hydrosol occurs, the viscosity of the reaction solution increases, and finally gelation occurs. Silica hydrogel.

  Next, in the silica gel production method of the present invention, as a physical property adjustment step, hydrothermal treatment of the silica hydrogel is performed without substantial aging so that the hardness of the silica hydrogel produced by the hydrolysis does not increase. Hydrolysis of silicon alkoxide produces a soft silica hydrogel. In order to stabilize the physical properties of the hydrogel, it is usually difficult to produce the silica gel of the present invention by a method of aging or drying, followed by hydrothermal treatment.

  The hydrothermal treatment immediately performed without substantially aging the silica hydrogel produced by hydrolysis as described above means that the next hydrothermal treatment is performed while maintaining the soft state immediately after the silica hydrogel is produced. It means to be used for. Specifically, it is preferable that the silica hydrogel is hydrothermally treated usually within 10 hours, particularly within 8 hours, more preferably within 6 hours, and particularly within 4 hours from the time when the silica hydrogel is formed.

  Moreover, in an industrial plant etc., the case where the silica hydrogel produced | generated in large quantities is once stored in silos etc. and hydrothermal treatment is performed after that can be considered. In such a case, the silica hydrogel is considered to have a case where the time from when the silica hydrogel is formed to when it is subjected to hydrothermal treatment, the so-called standing time, exceeds the above range. In such a case, for example, the liquid component in the silica hydrogel may be prevented from drying during standing in the silo so that aging does not substantially occur. Specifically, for example, the inside of the silo may be sealed or the humidity may be adjusted. Alternatively, the silica hydrogel may be allowed to stand in a state where the silica hydrogel is immersed in water or another solvent.

  The temperature at the time of standing is preferably as low as possible, for example, 50 ° C. or less, particularly 35 ° C. or less, particularly preferably 30 ° C. or less. Further, as another method for preventing aging substantially from occurring, there is a method of preparing a silica hydrogel by controlling the raw material composition in advance so that the silica concentration in the silica hydrogel is lowered.

  Considering the effect obtained by hydrothermal treatment without substantially aging the silica hydrogel and the reason why this effect is obtained, it is as follows.

  First, when the silica hydrogel is aged, a macroscopic network structure due to —Si—O—Si— bonds is considered to be formed in the entire silica hydrogel. It is considered that this network structure is present in the entire silica hydrogel, so that this network structure becomes an obstacle during hydrothermal treatment, and it becomes difficult to form mesoporous materials. Moreover, the silica hydrogel obtained by previously controlling the raw material composition so that the silica concentration in the silica hydrogel is low can suppress the progress of crosslinking in the silica hydrogel that occurs during standing. Therefore, it is thought that silica hydrogel does not age. Therefore, in the silica gel production method of the present invention, it is important to perform hydrothermal treatment without aging the silica hydrogel.

  Adding an acid, alkali, salt, or the like to the silicon alkoxide hydrolysis reaction system or making the temperature of the hydrolysis reaction too strict is not preferable from the standpoint of aging the hydrogel. Also, temperature and time should not be taken more than necessary in washing, drying, leaving, etc. in post-treatment after hydrolysis.

  Further, the silica hydrogel obtained by the hydrolysis of silicon alkoxide has an average particle size of 10 mm or less, particularly 5 mm or less, more preferably 1 mm or less, particularly 0.5 mm or less before hydrothermal treatment. It is preferable to perform a pulverization process or the like.

  As described above, in the silica gel production method of the present invention, a method of immediately hydrothermally treating the silica hydrogel immediately after the production of the silica hydrogel is important. However, in the silica gel production method of the present invention, it is sufficient that the hydrothermally-treated silica hydrogel is not matured. Does not require heat treatment.

  As described above, when the hydrothermal treatment is not performed immediately after the formation of the silica hydrogel, the hydrothermal treatment may be performed after specifically confirming the aging state of the silica hydrogel. The means for specifically confirming the ripening state of the hydrogel is arbitrary, and examples thereof include a method of referring to the hardness of the hydrogel measured by a method as shown in Examples described later. That is, as described above, silica gel having a physical property range defined in the present invention can be obtained by hydrothermally treating a soft hydrogel having a fracture stress of usually 6 MPa or less. This fracture stress is preferably 3 MPa or less, more preferably 2 MPa or less.

  As conditions for this hydrothermal treatment, water may be in either a liquid state or a gas state. Among them, water in a liquid state is used, and this is added to silica hydrogel to form a slurry to perform hydrothermal treatment. Is preferred. In the hydrothermal treatment, first, the silica hydrogel to be treated is usually 0.1 times or more, preferably 0.5 times or more, particularly preferably 1 or more times, and usually 10 times the weight of the silica hydrogel. Double or less, preferably 5 times or less, particularly preferably 3 times or less of water is added to form a slurry. The slurry is usually 40 ° C. or higher, preferably 100 ° C. or higher, preferably 150 ° C. or higher, particularly preferably 170 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower. Hydrothermal treatment is performed for a period of time or more, preferably 1 hour or more, and usually 100 hours or less, preferably 10 hours or less. If the temperature of the hydrothermal treatment is too low, the pore distribution is difficult to be sharp, and it may be difficult to increase the pore volume.

  Note that the water used for the hydrothermal treatment may contain a solvent. Specific examples of the solvent include lower alcohols such as methanol, ethanol, and propanol. This solvent may be alcohols derived from alkoxysilane, which is a raw material, when hydrothermally treating a silica hydrogel obtained by hydrolyzing alkoxysilane, for example.

  The content of such a solvent in the water used for the heat treatment is arbitrary, but it is preferably smaller. For example, when hydrotreating a silica hydrogel obtained by hydrolyzing an alkoxysilane as described above, the silica hydrogel is washed with water, and the washed water is subjected to a hydrothermal reaction. Even when the hydrothermal treatment is performed with the temperature lowered, silica having excellent pore characteristics and a large pore volume can be produced. Moreover, even if hydrothermal treatment is performed using water containing another solvent, the silica gel of the present invention can be easily obtained by performing hydrothermal treatment at a temperature of about 200 ° C.

  The hydrothermal treatment method is also applied to a material in which silica gel is formed into a film or a layer on a substrate such as a particle, substrate or tube for the purpose of making a membrane reactor or the like. It is also possible to perform hydrothermal treatment by changing the temperature conditions using a hydrolysis reaction reactor, but the optimum conditions are usually different between the hydrolysis reaction and the subsequent hydrothermal treatment. In general, it is difficult to obtain the silica gel of the present invention by a method carried out without newly adding water.

  In the above hydrothermal treatment conditions, when the temperature is increased, the diameter and pore volume of the resulting silica gel tend to increase. The hydrothermal treatment temperature is preferably in the range of 100 ° C to 200 ° C. Further, with the treatment time, the specific surface area of the silica gel obtained tends to decrease gradually after reaching the maximum once. Based on the above tendency, it is necessary to appropriately select the conditions according to the desired physical property values, but since hydrothermal treatment is intended to change the physical properties of silica gel, it is usually at a higher temperature than the hydrolysis reaction conditions described above. It is preferable to do.

  In order to produce silica gel with excellent microstructural homogeneity, it is necessary to set fast heating rate conditions so that the temperature in the reaction system reaches the target temperature within 5 hours during hydrothermal treatment. preferable. Specifically, when the tank is filled and processed, the average rate of temperature increase from the start of temperature increase to the arrival of the target temperature is usually 0.1 ° C / min or more, particularly 0.2 ° C / min or more, Usually, it is preferable to adopt a value in the range of 100 ° C./min or less, particularly 30 ° C./min or less, and more preferably 10 ° C./min or less.

  A heating method using a heat exchanger or the like or a heating method in which hot water prepared in advance is used is preferable because the heating rate can be shortened. Moreover, if the temperature increase rate is in the above range, the temperature may be increased stepwise. When it takes a long time for the temperature in the reaction system to reach the target temperature, the aging of the silica hydrogel progresses during the temperature rise, and the microstructural homogeneity may be lowered.

  The temperature raising time until the above target temperature is reached is preferably within 4 hours, more preferably within 3 hours. In order to shorten the temperature raising time, the water used for the hydrothermal treatment may be preheated.

If the hydrothermal treatment temperature and time are set outside the above ranges, it may be difficult to obtain the silica gel of the present invention. For example, if the temperature of the hydrothermal treatment is too high, the pore diameter and pore volume of the silica gel become too large, and the pore distribution also widens. On the other hand, if the hydrothermal treatment temperature is too low, the resulting silica gel has a low degree of crosslinking, poor thermal stability, no peaks in the pore distribution, or Q ⁴ / Q in the aforementioned solid Si-NMR. ³ value becomes extremely small.

  When the hydrothermal treatment is performed in ammonia water, the same effect can be obtained at a lower temperature than in pure water. In addition, when hydrothermal treatment is performed in ammonia water, the finally obtained silica generally becomes hydrophobic as compared with hydrothermal treatment using water not containing ammonia. At this time, the hydrothermal treatment temperature is preferably 30 ° C. or higher, particularly 40 ° C. or higher, and usually 250 ° C. or lower, particularly 200 ° C. or lower. The ammonia concentration used here is usually 0.001% by weight or more, preferably 0.005% by weight or more, and usually 10% by weight or less, preferably 5% by weight or less.

  The obtained silica gel is dried at a temperature of usually 40 ° C. or higher, preferably 60 ° C. or higher, and usually 200 ° C. or lower, preferably 120 ° C. or lower. The drying method is not particularly limited, and it may be a batch type or a continuous type, and can be dried under normal pressure or reduced pressure. Among these, vacuum drying is preferable because not only can drying be performed quickly, but also the pore volume and specific surface area of the resulting silica gel are increased.

  If necessary, when a carbon component derived from the raw material silicon alkoxide is contained, it can be removed usually by baking at 400 ° C. or more and 600 ° C. or less. Moreover, in order to control a surface state, it may bake at the temperature of a maximum of 900 degreeC. Furthermore, the final silica gel of the present invention is obtained by pulverizing and classifying as necessary.

  After the hydrothermal treatment, it is preferable to replace the water contained in the silica gel with a hydrophilic organic solvent and dry. As a result, silica gel shrinkage in the drying process can be suppressed, the pore volume of the silica gel can be maintained large, and silica gel having excellent pore characteristics and a large pore volume can be obtained. The reason for this is not clear, but is thought to be due to the following phenomenon.

  Many of the liquid components in the silica gel slurry after the hydrothermal treatment are water. Since this water interacts strongly with the silica component, it is considered that a large amount of energy is required to completely remove the water from the silica gel.

  When a drying process (for example, heat drying) is performed under a condition where a large amount of water is present, the water subjected to thermal energy reacts with unreacted silanol groups, and the structure of the silica gel changes. Among the structural changes, the most remarkable change is the condensation of the silica gel skeleton, and it is considered that the silica gel locally increases in density due to the condensation. Since the silica gel skeleton has a three-dimensional structure, local condensation of the skeleton (densification of the silica gel skeleton) affects the pore characteristics of the entire silica particles constituted by the silica gel skeleton, and as a result, the particles It is considered that the pore volume and the pore diameter shrink due to the shrinkage.

  Therefore, for example, by replacing the liquid component (containing a large amount of water) in the silica gel slurry with a hydrophilic organic solvent, it is possible to remove the water in the silica gel slurry and suppress the shrinkage of the silica gel as described above. Become.

  Any hydrophilic organic solvent may be used as long as it dissolves a lot of water based on the above-described idea. Among them, those having large intramolecular polarization are preferable, and those having a relative dielectric constant of 15 or more are preferable.

  In the silica gel production method of the present invention described here, it is necessary to remove the hydrophilic organic solvent in a drying step after removing water with the hydrophilic organic solvent in order to obtain a highly pure silica gel. Therefore, as the hydrophilic organic solvent, those having a low boiling point that can be easily removed by drying (for example, heat drying, vacuum / vacuum drying, etc.) are preferable. Specifically, the boiling point of the hydrophilic organic solvent is usually 150 ° C. or lower, preferably 120 ° C. or lower, particularly preferably 100 ° C. or lower.

  Specifically, the hydrophilic organic solvent includes alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and diethyl ketone, nitriles such as acetonitrile, amides such as formamide and dimethylformamide, and aldehydes. And ethers. Among these, alcohols and ketones are preferable, and lower alcohols such as methanol, ethanol, and propanol, and acetone are particularly preferable. In the present invention, among these exemplified hydrophilic organic solvents, one kind may be used alone, or two or more kinds may be used in an arbitrary combination and in an arbitrary ratio.

  If water can be removed, the hydrophilic organic solvent to be used may contain water. However, it is naturally preferable that the water content in the hydrophilic organic solvent is small. Specifically, the water content is usually 20% by weight or less, particularly 15% by weight or less, more preferably 10% by weight or less, and particularly 5% by weight or less. It is preferable.

  Neither the temperature nor the pressure during the substitution treatment with the above-described hydrophilic organic solvent is particularly limited. Specifically, the treatment temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and usually 100 ° C. or lower, especially 60 ° C. or lower. The pressure during the treatment may be normal pressure, pressurization, or reduced pressure.

  The amount of the hydrophilic organic solvent brought into contact with the silica gel slurry is arbitrary. However, if the amount of the hydrophilic organic solvent used is too small, the rate of progress of the substitution with water is not sufficient, and conversely if too large, the substitution efficiency with water increases, but there is an effect commensurate with the increase in the amount of use of the hydrophilic organic solvent. This is not economically favorable. Therefore, the amount of the hydrophilic organic solvent to be used is usually in the range of 0.5 volume times or more and 10 volume times or less with respect to the bulk volume of the silica gel. This replacement operation with a hydrophilic organic solvent is preferably repeated a plurality of times because water replacement is more reliable.

  The method of contacting the hydrophilic organic solvent and the silica gel slurry is arbitrary, for example, a method of adding the hydrophilic organic solvent while stirring the silica gel slurry in a stirring tank, or packing silica filtered off from the silica slurry into a packed tower, Examples thereof include a method in which a hydrophilic organic solvent is passed through the packed tower, a method in which silica is immersed in a hydrophilic organic solvent, and a method of allowing to stand.

  The completion of the replacement operation with the hydrophilic organic solvent may be determined by measuring the water content in the liquid component of the silica gel slurry. For example, the silica gel slurry is periodically sampled to measure the water content, and the end point may be that the water content is usually 5% by weight or less, preferably 4% by weight or less, more preferably 3% by weight or less. . The method for measuring moisture is arbitrary, and for example, the Karl Fischer method can be mentioned.

  The silica gel of this invention can be manufactured by isolate | separating the obtained silica and hydrophilic organic solvent after substitution operation with a hydrophilic organic solvent, and drying. As the separation method at this time, any conventionally known solid-liquid separation method may be used. That is, solid-liquid separation may be performed by selecting a method such as decantation, centrifugation, and filtration according to the size of the silica gel particles. One of these separation methods may be used alone, or two or more may be used in any combination.

[I-4. (Coupling agent)
The coupling agent used in the material of the present invention is not particularly limited as long as it is a substance that can be bonded to both the base material and the functional particles, depending on the type of base material and functional particles used in combination. Any one can be selected and used. In particular, a functional group capable of forming a covalent bond, a coordination bond and / or a hydrogen bond with the functional group of the base material, and a covalent bond, a coordination bond and / or a hydrogen bond with the functional group of the functional particle. A coupling agent provided with the functional group to be obtained is preferred.

  Examples of coupling agents include titanium coupling agents and silane coupling agents, but silane coupling agents are preferable from the viewpoint of versatility. In particular, when silica gel is used as the functional particle as described above, it is strongly between the OH group of the silica gel and the hydrolyzable group / highly reactive non-hydrolyzable group of the silane coupling agent. This is preferable because a covalent bond / hydrogen bond is formed.

  Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxyxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, p-aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminoethylamino Methylphenethyltrimethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chloropheny Trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, styrylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, Examples include vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. It is done.

  In particular, when inorganic functional particles composed of silica and alumina are immobilized on a substrate such as a cellulose fiber having a hydroxyl group, it is most preferable to use a silane coupling agent containing an epoxy group.

  More preferably, the silane coupling agent has a highly reactive functional group in the non-hydrolyzable group. While the hydrolyzable group binds to functional particles such as silica gel as described above, these highly reactive non-hydrolyzable groups react with the substrate to form a bond. Thus, the functional particles can be more firmly attached. Examples of highly reactive non-hydrolyzable groups include epoxy groups, amino groups, vinyl groups and the like. Among them, when a material having a hydroxyl group on the surface thereof, for example, a cellulose fiber or the like is used as a base material, a silane coupling agent having an epoxy group is used because it is easy to form a bond with the hydroxyl group of these base materials. preferable.

In particular, the silane coupling agent is preferably a compound having a structure represented by the following general formula (I) and an oligomer compound obtained by condensing a plurality of these compounds using the compound as a monomer compound.
_{X m -Si-Y n (I} )
In the general formula (I), X represents a hydrolyzable group, and Y represents a non-hydrolyzable group. M and n each independently represent a natural number of 0 or more and 4 or less. However, m + n = 4. When m and n are 2 or more, the plurality of X and Y may be the same or different from each other.

  Examples of the hydrolyzable group for X include a group represented by —OR, a group represented by —COZ (a group derived from a carboxylic acid such as an ester, an acid halide, an acid anhydride, and an amide), a halogen, and the like. It is done. In addition, although R and Z can be each independently any organic group, hydrocarbon groups such as alkyl groups and aryl groups are preferable, and alkyl groups are particularly preferable. The carbon number of R and Z is not particularly limited, but is usually in the range of 1 to 6 from the viewpoint of availability of the reagent, and particularly in the case of an alkyl group, preferably in the range of 1 to 4. These hydrocarbon groups may further have some substituent as long as the hydrolyzability of X is not hindered. When X is a group represented by -OR, the type is not particularly limited, but R is a carbon group represented by an alkyl group such as a methyl group, an ethyl group or a propyl group, or an aryl group such as a phenyl group or a benzyl group. Preferred examples include a hydrogen group or a carbonyl-containing group such as an acetyl group, an acrylic group, and a methacryl group. Also, when X is a group represented by -COZ, the kind thereof is not particularly limited, but is preferably an ester group (that is, Z is a hydrocarbon group or the like). Specific examples include a methyl ester group, an ethyl ester group, a propyl ester group, and a phenyl ester group. On the other hand, when X is halogen, examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among them, a chlorine atom is preferable.

  On the other hand, the kind of non-hydrolyzable group of Y is not particularly limited, but at least one Y is required to be a highly reactive group. Examples of non-hydrolyzable highly reactive groups include epoxy groups, amino groups, vinyl groups, hydroxyl groups, thiol groups, carboxyl groups, amide groups (acetamido groups, benzenesulfonamide groups, etc.), sulfonic acid groups, alkoxy groups Alkyl group (methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-ethoxyethyl group, etc.), aryl group, aryloxyalkyl group, alkylaryl group, aryloxyaryl group, styryl group, acryloxy group, methacryloxy group , Ureido groups, halogen-substituted alkyl groups (chloromethyl groups, bromomethyl groups, chloroethyl groups, bromoethyl groups, chloropropyl groups, etc.), mercapto groups, sulfide groups, isocyanate groups, heteroatoms (N, O, S, etc.) Ring-containing groups (eg furan, thiophene, pyrrole, pyran, Opiran, pyridine, cyclic ether, lactone, cyclic imine, groups derived from a variety of heterocyclic compounds such as lactams) and the like. Among these exemplified groups, the group containing a carbon atom usually has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. Of these, an epoxy group, an amino group, a methacryloxy group, and a vinyl group are more preferable.

  Further, a group obtained by substituting a low-reactivity non-hydrolyzable group with these high-reactivity non-hydrolyzable groups can also be suitably used as the high-reactivity non-hydrolyzable group. . The type of the low-reactivity non-hydrolyzable group substituted by the non-hydrolyzable group is not particularly limited, but a hydrocarbon group such as an alkyl group or an aryl group (a hetero atom such as N or O in the hydrocarbon chain) May be included), and an alkyl group is particularly preferable. The carbon number of the hydrocarbon group is not particularly limited, but is usually in the range of 1 to 6 from the viewpoint of availability of the reagent, and particularly in the case of an alkyl group, preferably in the range of 1 to 4. Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.

  Since the silane coupling agent used in the present invention has the above-described highly reactive non-hydrolyzable group as Y, it can be bonded to the base material. Therefore, it is desirable to select an appropriate highly reactive non-hydrolyzable group according to the type of substrate to be used in combination (specifically, the type of functional group that the substrate has on the surface). For example, when a substrate such as a cellulose fiber having a hydroxyl group is used, the highly reactive non-hydrolyzable group is preferably an epoxy group or a hydrocarbon group substituted by an epoxy group.

  On the other hand, when Y is a group other than a highly reactive group, the type of the group is not particularly limited, but examples include hydrocarbon groups such as alkyl groups and aryl groups (hetero atoms such as N and O in the hydrocarbon chain). May be included), and an alkyl group is particularly preferable. The carbon number of the hydrocarbon group is not particularly limited, but is usually in the range of 1 to 6 from the viewpoint of availability of the reagent, and particularly in the case of an alkyl group, preferably in the range of 1 to 4. Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.

  In addition, when the compound of formula (I) (monomer compound) is condensed to form an oligomer, the number of condensation (the number of monomers to be condensed) is not limited, but is usually 2 or more and usually 500 or less, preferably Is in the range of 100 or less, more preferably 50 or less. Further, the monomer compounds to be condensed may be one kind or two or more kinds, and in the case of two or more kinds, the combination of the monomer compounds is not particularly limited (as long as condensation is possible). Moreover, although a condensation reaction changes with structures of a monomer compound, the condensation by a hydrolysis reaction etc. are mentioned, for example.

  On the other hand, silicates such as tetramethoxysilane and tetraethoxysilane that do not have non-hydrolyzable groups, and partially hydrolyzed / condensed silicate oligomers with siloxane skeletons should also be used as silane coupling agents. Can do. Silicate oligomers can be produced with different degrees of condensation (average molecular weight) by adjusting the conditions for hydrolysis and condensation, but those having a weight average molecular weight of about 150 to 3000 are preferred. Used. A silicate having a large amount of silanol groups obtained by further hydrolyzing and condensing the silicate oligomer in alcohol may be used.

  The size of the functional particles is submicron to several μm, whereas the size of the coupling agent is approximately equal to the molecular size of the monomer of the coupling agent in a state where hydrolysis / condensation has not progressed. Therefore, the difference in size between the two is large. When such functional particles are firmly attached to the substrate, the size of the coupling agent particles is important. As the hydrolysis / condensation between the monomer molecules of the coupling agent proceeds, the particle size of the coupling agent increases. Specifically, the size of the coupling agent is preferably in the range of the monomer molecular size to 100 nm, and most preferably the monomer molecular size. In particular, when the raw material of the present invention is produced by a method in which a functional agent is subsequently applied to a base material after pre-treatment as a pretreatment as described later, after the pretreatment with the coupling agent It is preferable that the entire surface of the substrate is uniformly covered with a coupling agent at the molecular level. In addition, as a method for measuring the particle size of the coupling agent (the degree of progress of condensation), a method of measuring the molecular weight by GPC (gel permeation chromatography) and converting the molecular weight, or a method of measuring by X-ray small angle scattering Etc.

[I-5. Binder)
In the material of the present invention, it is not essential to use a binder, but it is preferable to use a binder in order to attach the functional particles more firmly to the base material. There is no restriction | limiting in particular in the kind of binder, Arbitrary things can be used. Usually, an appropriate binder may be appropriately selected according to the use and purpose of the material, the base material to be used together, the functional particles, the coupling agent, and the like.

  However, when a porous material such as silica gel (hereinafter, abbreviated as “porous functional particles” or the like as appropriate) is used as the functional particles, a binder component is added when the porous functional particles are attached to the base material. However, it is preferable not to fill the pores of the porous functional particles. As the pore size of the porous functional particles, it is preferable to use a mode in which the mode pore size is usually in the range of 2 nm or more and 50 nm or less. Therefore, considering that fact, the purpose of not filling the pores is suitable. In order to achieve this, it is required that the binder component to be used satisfies at least one of the following conditions (α) and (β).

Condition (α): Molecular weight is usually 10,000 or more, preferably 20,000 or more, more preferably 30,000 or more, further preferably 35,000 or more, and usually 1,000,000 or less, preferably 800,000 or less, more preferably Uses a binder component of 500,000 or less. By setting the molecular weight of the binder component to 10,000 or more, the binder component can be prevented from filling the pores of the porous functional particles, and by setting the molecular weight to 1,000,000 or less, the binder component and the porous functionality are prevented. When the particles are used as a paint together with a solvent, it is possible to prevent the viscosity from becoming excessively high and handling properties from being lowered.

In order to prevent the binder component from entering the pores of the porous functional particle when the binder component is in a freely movable state, “(molecular weight of the binder component) / (porous functional particle) the ratio between the most frequent pore diameter (D _max)) represented by the "modal pore diameter (D _max) (unit in the individual molecular weight and the porous functional particles of binder component is defined as" nm ".) of The value of is usually not less than 200, particularly not less than 25,000, more preferably not less than 3,000, particularly not less than 35,000, and usually not more than 500,000, particularly not more than 100,000, more preferably not more than 50,000. desirable. This also prevents the binder component from filling the pores of the porous functional particles, and when the binder component and the porous functional particles are used as a paint together with a solvent, the viscosity becomes too high and the handling property is lowered. Can be prevented.

Condition (β): Glass transition temperature Tg is usually −80 ° C. or higher, preferably −70 ° C. or higher, more preferably −50 ° C. or higher, further preferably −30 ° C. or higher, and usually 110 ° C. or lower, preferably 40 A binder component in the range of not higher than ℃, more preferably not higher than 30 ℃, and further preferably not higher than 15 ℃ is used. This condition is also an important factor from the viewpoint of preventing the binder component from filling the pores of the porous functional particles.

  The binder component used in the present invention may satisfy only one of the above condition (α) and condition (β), or may satisfy both. As will be described later, when the binder component and the porous functional particles are mixed in a solvent and used as a paint, when an organic solvent is used as the solvent, the condition (α) is preferably satisfied, and an aqueous solvent is used. When used, it is preferable to satisfy the condition (β).

  By using a binder component that satisfies the above-mentioned condition (α) and / or condition (β), even when the binder component is in a freely movable state, it prevents entry into the pores of the porous functional particles. Can do. The reason is not clear, but it is presumed as follows.

  In order to prevent the binder component from penetrating into the pores of the porous functional particles, for example, the binder component is made to have a larger diameter than the pores of the porous functional particles. What is necessary is just to make it impossible to enter into the pores of the porous functional particles. Here, the diameter of the binder component generally refers to the molecular diameter of the binder component, but in the state where the binder component is dissolved or dispersed in a solvent such as an organic solvent or an aqueous solvent, particles in which the binder component molecules are aggregated ( For example, the diameter of the aggregated particles is regarded as the diameter of the binder component.

  The diameter (size) of the binder component is related to the molecular weight of the binder component, and it is known that the binder component having a higher molecular weight has a larger diameter. Therefore, in order to increase the diameter of the binder component so as not to enter the pores of the porous functional particles, for example, a binder component having a molecular weight larger than a predetermined value may be selected.

A binder component having a molecular weight within the above range as defined in the condition (α), or a binder component having a ratio of the molecular weight to the mode pore diameter (D _max ) of the porous functional particles within the above range, It has a diameter that does not enter the pores of the porous functional particles. Therefore, by using a binder component that satisfies the condition (α), even if the binder component can move freely in the solvent, it can enter the pores of the porous functional particles and fill the pores. Can be prevented.

The molecular weight of the binder component can be measured by, for example, GPC (gel permeation chromatograph) or viscosity measurement of a solution in which the binder component is dissolved.
The diameter D (nm) of the binder component in the solid state is usually calculated by the following formula (i) using the density a (g / ml) of the binder component in the solid state and the molecular weight M of the binder component. Can do.
(Equation 1)
D = (0.003183 × M / a) ^1/3 formula (i)

  Moreover, the diameter of the binder component in the state melt | dissolved or disperse | distributed in a solvent can be measured from the light scattering intensity | strength obtained by irradiating a solvent with a laser beam using a multi-angle light scattering detector (MALS) etc. In addition, a method of measuring the diameter by observing the binder component with a transmission electron microscope, a method of measuring the diameter from the turbidity of the solvent in which the binder component is dissolved or dispersed, a CHDF (Capillary Hydrodynamic Fractionation) method, etc. Also, the diameter of the binder component can be measured.

Even when the binder component is dissolved or dispersed in the solvent, when the concentration of the binder component is high, the polymer chain of the binder component is in a string shape, and the molecular diameter is close to the molecular diameter of the solid state. It is thought that it has. However, in a state where the binder component is not dissolved in the solvent, the polymer chain is present in a state of being shrunk into a spherical shape, but in a state where it is dissolved in the solvent, a plurality of molecules are entangled or swelled by absorbing the solvent. This may increase the molecular size. Therefore, even if the binder component diameter calculated from the molecular weight is smaller than the mode pore diameter ( _Dmax ) of silica, the binder component can be prevented from entering the pores of the porous functional particles in the solvent. is there. As a specific example, in the case of an acrylic resin having an average molecular weight of 95,000, the diameter (molecular size) is 6 nm. For example, fine particles of porous functional particles having a mode pore diameter (D _max ) of 15 nm are used. It does not block the hole.

In addition, the molecular size of the binder component in a dissolved state varies depending on the solubility of the binder component and the solvent. However, in any state, if the ratio of the molecular weight of the binder component to the mode pore diameter (D _max ) of the porous functional particles, or the molecular weight of the binder component is within the above range, the binder component is porous. Filling the pores of the functional particles can be prevented.

  In particular, when the binder component is colloidal in a solvent (particularly an aqueous solvent) to form an emulsion, the binder component (colloid) in the emulsion has a structure in which molecules are aggregated, and the surfactant (protective colloid). ) And is large enough not to enter the pores of the porous functional particles. That is, the diameter of the binder component (here, the diameter of the colloid of the binder component in the emulsion) is larger than the diameter of the pores of the porous functional particles.

  Even if the molecular weight of the binder component is not within the above range, the size of the binder component colloid is usually large enough not to enter the pores of the porous functional particles regardless of the molecular weight of the binder component. Become. Therefore, as long as the colloid of the binder component is stable, the binder component can be prevented from entering the pores of the porous functional particles.

  By the way, the stability of the binder component colloid in the emulsion is related to the glass transition temperature Tg. Therefore, by using a binder component having a glass transition temperature Tg at which the colloid is stable, it is possible to prevent the binder component from entering the pores of the porous functional particles of the present invention in an emulsion using a solvent. Specifically, if a binder component having a glass transition temperature Tg within the above range is used, it is possible to prevent the binder component from entering the pores of the porous functional particles in an emulsion together with the solvent. it can.

  Further, by setting the glass transition temperature Tg of the binder component to a value larger than the lower limit of the above range, the binder component can have an appropriate strength. In addition, there is no possibility that the physical properties and handleability such as stickiness are deteriorated, and the porous functional particles are easily dispersed. Further, by setting the glass transition temperature Tg to a value smaller than the upper limit of the above range, the binder component does not become too hard, and in the case of using the material of the present invention, there is no possibility that the functional particles are detached. In addition, the texture can be improved.

  Emulsions are classified into colloidal dispersion (particle diameter: 10 nm to 50 nm), emulsion (50 nm to 500 nm), suspension (0.5 μm to 10 μm), etc., depending on the diameter of dispersed particles.

  As described above, in the binder component used in the material of the present invention, it is desirable that either the molecular weight or the glass transition temperature Tg satisfies the above conditions, but naturally both the molecular weight and the glass transition temperature Tg satisfy the above conditions. It is more desirable to satisfy.

  Furthermore, the diameter of the binder component also increases when the degree of crosslinking of the binder component is large. Accordingly, a binder component having a high degree of crosslinking is preferable. Therefore, it is also preferable to appropriately mix a crosslinking agent that crosslinks the binder component. The degree of crosslinking of the binder component can be measured by examining the solubility in an organic solvent.

  Specific examples of binders include ester celluloses such as nitrocellulose, cellulose acetate, and butyrate, ether celluloses such as methyl cellulose and ethyl cellulose, polyamide resins, chlorinated rubber, cyclized rubber, polyvinyl chloride resins, vinyl chloride / Examples thereof include thermoplastic resins such as vinyl acetate copolymer resins, ethylene / vinyl acetate copolymer resins, chlorinated polypropylene, and acrylic resins. Alkyd resins, amino alkyd resins, urea resins, melamine resins, melamine / urea resins, phenol resins, resorcinol resins, furan resins, epoxy resins, unsaturated polyester resins, polyurethane resins Further, thermosetting resins such as polyimide, polyamideimide, polybenzimidazole, and polybenzothiazole are also used.

  In addition, processed oils and fats such as fats and oils, boiled oil, boiled sea urchin oil, tung oil stand oil, oily phenol resin, maleated oil; drying oil-modified phthalic acid resin, non-drying oil-modified phthalic acid resin, modified alkyd resin, Oils such as epoxy-fatty acid ester resins, epoxy-alkyd resins, oil-knitted polyurethane resins, or fatty acid-modified phthalic acid resins, unsaturated polyester resins, fluorine-modified polyester resins, silicone-modified polyester resins, urethane-modified polyesters A polyester resin such as a resin, a silicone resin, an acrylic silicone resin, a fluorine-containing resin, an inorganic resin, and the like are also preferably used.

  In addition to styrene maleic resins, polyvinyl chloride resins, polyvinyl acetate resins, acrylic resins, polyurethane resins, epoxy ester resins, polyamine resins, natural rubber, recycled rubber, styrene-butadiene. Rubber such as rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), ethylene propylene rubber, block copolymer rubber (SBS, SIS, SEBS, etc.), binder Can be used as an ingredient.

  Furthermore, as described later, when a binder component and functional particles are mixed with an aqueous solvent (hydrophilic solvent) to form a paint, the binder component includes a polyester elastomer, polyurethane, a heat-reactive urethane resin, It is preferable to use polymers such as NBR, SBR, acrylic, isocyanate resin, vinyl alcohol resin, polyacrylic acid emulsion, silicone resin, epoxy resin, melamine resin, and polymer latex.

  Among them, when using a fiber or cloth as a base material, acrylic resin, acrylic polyurethane resin, acrylic silicone resin, polyurethane resin, etc. are used from the viewpoint of flexibility, strength, weather resistance, abrasion resistance, etc. In consideration of the texture, polyurethane resins, acrylic silicone resins, and silicone resins are more preferable, and silicone resins are particularly preferable.

  From the viewpoint of adhesiveness, it is preferable to use a resin contained in the polymer latex as the binder component. Examples of the polymer latex include synthetic resin latex and rubber latex.

  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 modified products and copolymers thereof. Accordingly, examples of the binder component in this case include polyvinyl chloride, polyvinylidene chloride, polyurethane, acrylic resin, polyvinyl acetate, polyacrylonitrile, and modified products and copolymers thereof.

  A particularly preferred acrylic resin latex is a polymer emulsion mainly composed of (meth) acrylic acid ester. Examples of the (meth) acrylic acid ester as the main component of the binder resin in the polymer emulsion include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2 -Ethylhexyl, (meth) acrylic acid glycidyl ester, (meth) acrylic acid 2-hydroxyethyl, etc. are mentioned. There are copolymerizable ethylenically unsaturated monomers that are used in combination with this main component, and the monomers include styrene, (meth) acrylonitrile, (meth) acrylic acid amide, N-methylol acrylic. Examples include acid amide, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, (meth) acrylic acid, itaconic acid, fumaric acid, crotonic acid, maleic acid and the like.

  When used in combination with the above monomer, the content of the (meth) acrylic acid ester as the main component is preferably 50% by weight or more. The acrylic resin is preferably formed by an emulsion polymerization method. For example, water, an ethylenically unsaturated monomer, an emulsifier (sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether, etc.), and a radical polymerization initiator are added to a nitrogen-substituted reaction vessel, 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 the emulsion polymerization.

  Specific examples of the binder component contained in the rubber latex include natural rubber, styrene butadiene rubber, acrylonitrile rubber, acrylonitrile butadiene rubber, isoprene isobutyl rubber, polyisobutylene, polybutadiene, polyisoprene, polychloroprene, and polyethylene propylene. Can be mentioned.

  The butadiene copolymer contains butadiene in a proportion of 20% by weight or more and 80% by weight or less, and contains an unsaturated monomer copolymerizable with the butadiene in a proportion of 20% by weight or more and 80% by weight or less. Is preferred. As unsaturated monomers, 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 and the like can be used.

  When the copolymer composition of the butadiene copolymer requires heat resistance and weather resistance, for example, when used for a vehicle, butadiene is 20% by weight or more and 60% by weight or less, and (meth) acrylic acid ester is 40%. It is desirable that the ratio is not less than 80% by weight and other unsaturated monomers are not less than 0% by weight and not more than 20% by weight.

  Furthermore, examples of the binder component having a glass transition temperature Tg of −80 ° C. to 110 ° C. include acrylic resins, ethylene-vinyl acetate resins, polyurethane resins, butadiene resins, and the like. Moreover, the said binder component may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[I-6. Others]
In addition to these components, the raw material of the present invention may contain various other components in order to increase production efficiency and impart various properties. These components will be described later.

[II. Material production]
The method for producing the material of the present invention is not particularly limited, but it is usually produced by mixing and contacting the above-mentioned base material, functional particles and coupling agent, and a binder used as necessary.

  There are no particular restrictions on the order in which the base material, the functional particles, the coupling agent, and the binder used as necessary are mixed or contacted. Further, these components may be mixed and brought into contact all at once, or these components may be mixed in multiple stages in any combination and brought into contact. However, in the present invention, for the purpose of more firmly attaching the functional particles to the base material, the base material is further contacted with a coupling agent in advance, and then the functional particles and binder components are further added to the base material. It is preferable to employ a step-by-step manufacturing method of contacting and acting. In the following description, the manufacturing method that steps in this way, that is, the step of bringing the coupling agent into contact with the base material (pretreatment step: first step), and further functioning on the base material after the pretreatment step The method for producing the material of the present invention will be described in detail by a method (hereinafter referred to as “the production method of the present invention” as appropriate) having at least a step of bringing the conductive particles and the binder component into contact (attachment step: second step). .

  Moreover, when manufacturing the raw material of this invention, it is also possible to use various solvents together. In particular, in the case of the production method of the present invention, a coupling agent is dissolved or dispersed in a solvent to form a coating liquid (hereinafter referred to as “pretreatment coating liquid” as appropriate), and the binder component and functional particles are also used. A coating solution dissolved or dispersed in another solvent (hereinafter referred to as “attaching coating solution” as appropriate. Also, when the pretreatment coating solution and the attaching coating solution are referred to without distinction, they are simply referred to as “coating solution”.) It is preferable to carry out the above-mentioned pretreatment step and the attaching step by sequentially applying these coating liquids to the substrate or impregnating the substrate. The following description will be made on the assumption that a pretreatment coating solution and an attachment coating solution are prepared using a solvent, and a pretreatment step and an attaching step are performed using these.

  The solvent used for the preparation of the pretreatment coating solution and the application coating solution may be the same or different, and any solvent may be a solvent composed of a single type of compound, or two or more types. The solvent which mixed these compounds by arbitrary combinations and compositions may be sufficient.

  When a solvent is used, there is no particular limitation on the method for removing the solvent after coating and impregnation. As specific examples, various known methods such as natural drying by standing in the atmosphere, heat drying, vacuum drying, baking, ultraviolet irradiation, and electron beam irradiation can be arbitrarily selected. However, the decomposition start temperature of each of the binder component, the coupling agent-derived component, and the functional particles, and the volatilization behavior of the components supported on the functional particles when the functional particles are porous substances, are also fully considered. The process must be completed.

  Moreover, the timing which removes a solvent is also arbitrary. In particular, in the case of the production method of the present invention, the solvent is removed immediately after the base material is treated with the coupling agent in the pretreatment step, and the solvent is removed after the functional particles are added in the addition step. For example, the solvent may be removed in two stages, but after the base material coupling agent treatment in the pretreatment step and the functional particle treatment in the attachment step are successively carried out, the last step is collectively. Solvent removal may be performed. The timing of removing these solvents can be appropriately selected depending on the situation.

  The solvent used for the preparation of the pretreatment coating solution is not particularly limited as long as it is a compound that can dissolve or disperse the above-described coupling agent. However, it is not preferable to react with the coupling agent to impair its function or to adversely affect the base material, functional particles, and binder components. Therefore, the coupling agent, base material, functional particles, binder to be used are not preferable. It is necessary to select a suitable solvent depending on the components. Specifically, either an organic solvent or an aqueous solvent may be used as the solvent. Examples of organic solvents include methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol, diglyme, hexane, cyclohexane, pentane, benzene, toluene, xylene, tetrahydrofuran, dichloromethane, chloroform, tetrahydrofuran, sulfolane, acetic acid, acetone, methyl ethyl ketone, various Silicone oil etc. are mentioned. In addition, ionic liquids such as imidazolium salt, pyridinium salt, and ammonium salt, and various supercritical materials are also preferably used. However, in consideration of economics and influence on the human body / environment, it is preferable to use an aqueous solvent as the solvent, and it is particularly preferable to use water.

  In particular, when a hydrolyzable coupling agent typified by a silane coupling agent is used, water is usually used as a solvent. By making the hydrolyzable coupling agent into a dilute aqueous solution state, the hydrolysis reaction of the coupling agent proceeds. In the case of a coupling agent having low solubility in water, an aqueous solution whose pH is controlled by an acid such as acetic acid or oxalic acid may be used. Moreover, you may add alcohol, such as ethanol and methanol, to these water and aqueous solution controlled pH. Furthermore, after the coupling agent is first dissolved in an alcohol solution containing an amount of water necessary for hydrolysis, it may be further diluted with water. Depending on the type of coupling agent, these operations are essential for preserving the pretreatment coating solution in a stable state.

  In addition, when using a coupling agent that cannot be uniformly coated at the molecular level, the hydrolysis / condensation progresses rapidly in a solvent consisting only of water. A pre-treatment solution is prepared using a solvent in which water and a non-aqueous solvent typified by alcohol such as methanol and ethanol are mixed in an arbitrary ratio, or a solvent composed only of a non-aqueous solvent, and this is used for pre-treatment. It is good to carry out a process. By using such a mixed solvent or a non-aqueous solvent, hydrolysis / condensation between coupling agent monomers is suppressed, so that the substrate surface is uniform at the molecular level of the coupling agent monomer, not the coupling agent particles. This is because coating can be performed and the retention of functional particles can be improved. In addition, when using a base material having an OH group such as cotton, if a mixed solvent containing such a non-aqueous solvent is used, a hydrolysis reaction occurs on the base material surface, and coupling agent monomer molecules are bonded to each other on the base material surface. It can be efficiently hydrolyzed / condensed and uniform coating is possible.

  In the case of using a hydrolyzable coupling agent, it is preferable to shorten the time required for applying or impregnating the pretreatment coating solution to the substrate after adjustment of the pretreatment coating solution. The specific time interval cannot be generally specified because the rate of hydrolysis reaction varies depending on the type of coupling agent, but generally within one month, especially within two weeks after the preparation of the pretreatment coating solution. Further, it is preferable to use within 1 day, particularly within 3 hours. In particular, when an epoxy group-containing silane coupling agent is used, it may be applied to a substrate or impregnated immediately after it is dissolved in water and hydrolysis occurs. After dilution in water, the condensation of the coupling agent progresses over time, and fine particles are formed between the coupling agents, making it difficult to uniformly treat the substrate surface with molecular size without gaps. This is because the retention force of the functional particles becomes weak. The state in which the coupling agent uniformly covers the surface of the substrate with the molecular size of the monomer by the pretreatment step, that is, the monomer molecule of the coupling agent and the functional group such as OH group present on the substrate surface are 1 It is preferable that a state of being paired 1 is obtained.

  In addition, after applying or impregnating the pretreatment coating liquid, when it is dried to remove water, condensation between the monomer molecules of the coupling agent proceeds if time is completely dried. Since it is not preferable, it is preferable not to completely remove the solvent, but to proceed to the next attaching step and completely apply or impregnate the attaching application liquid before completely drying. Therefore, the drying method is preferably room temperature drying rather than heat drying. Also, since the condensation of the coupling agent proceeds with time, it is not preferable, and air drying is preferable from the viewpoint of shortening the processing time. Or it is also preferable not to dry after application | coating or impregnation of the coating liquid for pre-processing, and to apply | coat or impregnate the next application | coating liquid for attachment continuously.

  The concentration of the coupling agent in the pretreatment coating solution is usually 0.005% by weight or more, especially 0.01% by weight or more, more preferably 0.02% by weight or more, and usually 95% by weight or less, especially 40% by weight. % Or less, more preferably 1% by weight or less. If the concentration of the coupling agent exceeds this range, a large amount of expensive coupling agent is used, which is economically disadvantageous, and the texture when applied to fibers, cloth materials, leather products, sponge products, etc. It is bad and not preferable. On the other hand, when the concentration of the coupling agent is less than this range, there is a possibility that the ability to retain the functional particles will be insufficient.

  On the other hand, the solvent used for the preparation of the coating solution for attachment is not particularly limited as long as it is a compound that can dissolve or disperse the porous functional particles and the binder component described above, and an organic solvent or an aqueous solvent. Either of these can be used. However, those that impair the function exhibited by the functional particles, those that react with the binder components to decompose them or break the emulsion-based binder system are not preferable. Moreover, the thing which impairs the property of the base material used as application | coating or an impregnation is also unpreferable. Therefore, it is necessary to select a suitable solvent according to the functional particles, binder component, base material and the like to be used. Furthermore, what can be easily removed by drying or heating is preferred. In consideration of economics and influence on human body / environment, it is preferable to use water, but it is not limited to this.

  In particular, when a porous material is used as the functional particle and a binder component satisfying the above condition (α) and / or the condition (β) is used, the solvent for the attachment coating solution is selected according to the following criteria: It is desirable to do.

  First, when the binder component satisfies the above condition (α), it is preferable to use an organic solvent as the solvent. In this case, the attachment coating solution is one in which at least a binder component and porous functional particles are contained in an organic solvent.

  On the other hand, when the binder component satisfies the above condition (β), it is preferable to use an aqueous solvent as the solvent. In this case, the attachment coating solution contains a binder component and porous functional particles in an aqueous solvent. In addition, when using what is already an aqueous emulsion in an aqueous solvent as a binder component, an attachment coating liquid is produced without further mixing an aqueous solvent when mixing with porous functional particles. be able to.

  In addition, in any of the organic solvent and the aqueous solvent, the state taken by the attachment coating solution is not particularly limited, and may be in any state such as a solution, a dispersion, an emulsion, etc. Since the conductive particles are not dissolved in the solvent, they often exhibit a dispersed liquid or emulsion state.

  Hereinafter, the organic solvent and the aqueous solvent that can be used for the coating solution for attachment will be described in detail. In the following description, when the organic solvent and the aqueous solvent are described without distinction, they are simply referred to as “solvent”.

  When using an organic solvent, there is no restriction | limiting in particular in the kind, A well-known organic solvent can be used arbitrarily. Specific examples thereof include chain hydrocarbons such as neopentane, n-hexane, n-heptane, and solvesso; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; methanol, ethanol, Alcohols such as isopropanol and n-butanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and n-butyl acetate; ethers such as cellosolve, butylsolve and cellosolveacetate; mineral spirits (hydrocarbons) Oil). Any one of these organic solvents may be used alone, or two or more thereof may be used in any combination and ratio.

  When an organic solvent is used, if a material that does not easily penetrate into the pores of the porous functional particles (for example, a material having a large contact angle with respect to the porous functional particles) is selected, The binder component can be prevented from entering the pores of the porous functional particles, which is preferable.

  It is also preferable to select an organic solvent that is a poor solvent for the binder component, or to add a partial poor solvent to the solvent. As a result, the polymer chain of the binder component can be dissolved in the organic solvent without being completely extended (that is, kept intertwined), and the binder component is prevented from entering the pores of the porous functional particles. be able to.

  Furthermore, it is also preferable to use an organic solvent having a high viscosity from the viewpoint of not extending the polymer chain of the binder component. However, in consideration of the usage, the operation may be difficult when coating, for example.

  On the other hand, the type of the aqueous solvent is not particularly limited, and a known aqueous solvent can be arbitrarily used. As described above, when the glass transition temperature Tg of the binder component is in the predetermined range, the binder component forms a colloid, so there is no possibility of entering the pores of the porous functional particles. That is, when an aqueous emulsion is used, since the diameter of the binder component (resin size) in the dispersed state can be expected to be considerably larger than the pore diameter of the porous functional particles, as described above, the fineness of the porous functional particles is reduced. It is possible to prevent the binder component from entering the hole.

  Use of an aqueous solvent eliminates the need for explosion-proof equipment. In addition, there is an advantage that the use and generation of environmentally undesirable substances can be suppressed. This is because it is preferable not to generate an organic solvent as much as possible when complete sealing is difficult. Furthermore, it has been found that the use of an aqueous solvent can generally improve the adhesion of functional particles to a substrate when the material of the present invention is molded.

  In addition, when the binder component is made into an aqueous emulsion using an aqueous solvent, the state of the emulsion can be adjusted so that the coagulation characteristics are exhibited at an appropriate temperature according to the type of substrate, application, use environment, etc. desirable. Thereby, even when using a thing with low heat resistance as a base material, an attachment coating liquid is applicable. The temperature at which the coagulation characteristics of the aqueous emulsion are manifested is the temperature at which the emulsion loses its fluidity and solidifies when the emulsion containing various additives is heated with stirring, such as an additive that lowers the dew point. It is possible to adjust the coagulation temperature by adding.

  In addition, when an aqueous coating solution is used as the solvent and the coating solution to be attached is an aqueous emulsion, the porous functional particles are dispersed in the aqueous solvent in water before the binder component. The inside of the pores is stabilized by being filled with water, and the binder component to be mixed later is also stabilized outside the pores. Therefore, when the components to be stabilized are mixed with each other, the binder component is separated into individual polymer chains. It is considered that it is unlikely to melt and penetrate into the pores of the porous functional particles.

  Specific examples of the aqueous solvent that can be used include water. Moreover, you may use the mixed solvent which mixed water and the above-mentioned organic solvent 1 type, or 2 or more types.

  As other solvents, ionic liquids such as imidazolium salts, pyridinium salts, and ammonium salts, and various supercritical substances are also preferably used.

  The ratio of the solvent in the coating solution for attachment is usually 20% by weight or more, especially 30% by weight or more, more preferably 40% by weight or more, and usually 90% by weight or less, especially 80% by weight or less, and further 70% by weight or less. It is preferable to set it as the range. If the content of the solvent is smaller than this range, the coating property of the coating liquid may be lowered, and if it is larger than this range, the amount of the binder component and porous functional particles contained in the coating solution is small. This is because it becomes too much, and it takes time to dry and workability may be deteriorated.

  The proportion of functional particles in the coating solution for attachment varies depending on the purpose and application, but is usually 0.05% by weight or more, particularly 0.1% by weight or more, more preferably 0.2% by weight or more, and usually 90% by weight. % Or less, preferably 80% by weight or less, and more preferably 60% by weight or less. If the content of the functional particles is smaller than this range, the desired function may not be sufficiently exhibited. If the content is larger than this range, the binder component may not be able to hold the functional particles. is there.

  In particular, when fibers are used as the base material, the proportion of the functional particles in the application liquid for attachment is usually 0.05% by weight or more, particularly 0.1% by weight or more, more preferably 0.2% by weight or more, Usually, it is preferably 50% by weight or less, more preferably 20% by weight or less, and further preferably 10% by weight or less. When impregnating the fibers, the concentration of the functional particles in the coating solution and the squeeze rate are optimized to determine the amount of functional particles applied to the substrate.

  In addition, the ratio of the binder component in the attachment coating solution is usually 0.01% by weight or more, especially 0.02% by weight or more, more preferably 0.05% by weight or more, and usually 30% by weight or less, especially 20% by weight. % Or less, more preferably 10% by weight or less. If the ratio of the binder component is smaller than this range, the functional particles may not be retained completely, and if it is larger than this range, the desired function may not be sufficiently exhibited. In particular, since the base material and functional particles are connected by a coupling agent in the material of the present invention, even when using a binder component, the amount can be smaller than before, and various functions can be expressed by the functional particles. There is no risk of interference.

  Furthermore, the ratio of the functional particles to the binder component (weight of functional particles / weight of binder component) is usually 0.1 or more, particularly 0.5 or more, more preferably 0.8 or more, and usually 50 or less, It is preferably 20 or less, more preferably 10 or less. If the above ratio is less than this range, the resulting material may not be able to fully perform its intended function, and if it is greater than this range, the binder component cannot fully retain the functional particles. There is a risk of disappearing. In particular, since the base material and functional particles are connected to each other by a coupling agent in the material of the present invention, the ratio of functional particles to the binder component can be increased more than before, and various functions can be exhibited more efficiently. Can be made.

  It is also preferable to color the application liquid for attachment according to the application. Examples of the coloring method include a method in which a coloring material is directly dissolved or dispersed in an attachment coating solution, a method in which a coloring material is mixed in advance with functional particles, and colored functional particles are used.

  The type of the color material is not particularly limited, and various known color materials can be arbitrarily selected and used. Examples of the color material include inorganic pigments, organic pigments, dyes, and the like.

  Specific examples of inorganic pigments include natural inorganic pigments such as clay, barium sulfate, calcium carbonate, mica, mica-like iron oxide, and ocher; lead white, red lead, yellow lead, silver vermilion, ultramarine, bituminous, cobalt oxide, titanium dioxide , Titanium dioxide coated mica, Strontium chromate, Titanium yellow, Titanium black, Carbon black, Graphite, Zinc chromate, Iron black, Molybdenum red, Molybdenum white, Resurge, Litopon, etc. Synthetic inorganic pigments: Aluminum, gold, silver, copper, zinc And metals such as iron.

  Specific examples of organic pigments include dye rakes in which dyes are dyed on extender pigments and raked with a precipitating agent; azo pigments such as soluble azo, insoluble azo and condensed azo; phthalocyanine pigments; nitroso pigments; nitro pigments; Examples include basic dye pigments; acid dye pigments; vat dye pigments; mordant dye pigments.

  Specific examples of organic dyes include direct dyes, vat dyes, sulfur dyes, naphthol dyes, reactive dyes, inglein dyes, acid dyes, acid mordant dyes, metal complex hydrochloric acid dyes, disperse dyes, cationic dyes, fluorescent brighteners Etc.

  Examples of other colorants that can be used include granular, sandy or powdery glass, ionomer, AS, ABS, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, polyamide, polyethylene, polyethylene terephthalate, polychlorinated Thermoplastic resins (plastic) such as vinylidene, polyvinyl chloride, polycarbonate, polyvinyl acetate, polystyrene, polybutadiene, polypropylene, epoxy resin, xylene resin, phenol resin, unsaturated polyester resin, polyimide, polyurethane, maleic acid resin, melamine resin And thermosetting resins such as urea resins. These may be colored or non-colored.

  Any one of the color materials exemplified above may be used alone, or two or more may be used in any combination and ratio.

  In addition to the above-described components, various additives may be added to the pretreatment coating solution and the application coating solution. The type of additive is not particularly limited, but examples include those described below.

  First, a surfactant is mentioned as an example of an additive. By adding a surfactant, the coating solution can be brought into a stable emulsion state. The type of the surfactant is not particularly limited, and various known surfactants can be arbitrarily selected and used. Examples include tripolyphosphates such as sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, alkylaryl sulfonates such as sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium polyacrylate, polyvinyl alcohol, styrene-maleic acid. Synthetic polymers such as acid copolymers, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, polyoxyalkylene aryl ethers such as polyoxyethylene phenol ether and polyoxybutylene phenol ether, and the like can be used. These surfactants may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Moreover, a pH adjuster is mentioned as an example of another additive. In particular, when a pH adjusting agent is used for the application liquid for attachment, for example, a polymer latex that is stabilized in an alkaline region (usually pH 8 to 10) such as an acrylic resin latex, and silica gel that exhibits acidity in an aqueous solvent. When used in combination, the binder component can be stabilized in the coating solution. The kind of pH adjuster is not particularly limited, and various known pH adjusters can be arbitrarily selected and used, for example, ammonia water or the like. These pH adjusters may be used alone or in combination of two or more in any combination and ratio.

  Furthermore, a flame retardant is mentioned as an example of another additive. The kind in particular of a flame retardant is not restrict | limited, A well-known various flame retardant can be selected arbitrarily and can be used, and both an inorganic type flame retardant and an organic type flame retardant can be used. In general, antimony compounds, phosphorus compounds, chlorine compounds, odorous compounds, guanidine compounds, boron compounds, ammonium compounds, brominated diaryl oxides, brominated allenes, and the like are known as flame retardants. Specific examples include antimony trioxide, antimony pentoxide, primary ammonium phosphate, secondary ammonium phosphate, phosphate triester, phosphite, phosphonium salt, phosphate triamide, chlorinated paraffin, dechlorane, Ammonium bromide, tetrabromobisphenol A, tetrabromoethane, guanidine hydrochloride, guanidine carbonate, guanidine phosphate, guanyl urea phosphate, sodium tetraborate decahydrate (borax), ammonium sulfate, ammonium sulfamate, decabromodi Examples include phenyl oxide, hexabromophenyl oxide, bentabromophenyl oxide, hexabromobenzene and the like. These flame retardants may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  Moreover, a conductive agent is mentioned as an example of another additive. The type of the conductive agent is not particularly limited, and various known conductive agents can be arbitrarily selected and used. Examples include conductive polymers such as conductive carbon black, polyacetylene, and polypyrrole; metal powders such as copper, aluminum, and stainless steel; conductive fiber materials such as carbon fibers and metal fibers. These electrically conductive agents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  Furthermore, a filler is mentioned as an example of another additive. The type of the filler is not particularly limited, and various known fillers can be arbitrarily selected and used. Examples include hydrous magnesium silicate clay minerals such as sepiolite and palygorskite; and porous adsorbent materials such as activated carbon, activated carbon fiber, silica gel, synthetic zeolite, and cristobalite. These fillers may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Moreover, a stabilizer is mentioned as an example of another additive. By using a stabilizer, it is possible to improve various durability such as light resistance, heat resistance, water resistance and solvent resistance of the coating solution. The type of the stabilizer is not particularly limited, and various known stabilizers can be arbitrarily selected and used. Examples include antioxidants, ultraviolet absorbers, hydrolysis inhibitors and the like. These stabilizers may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Furthermore, a crosslinking agent is mentioned as an example of another additive. By using the cross-linking agent, it is possible to increase the degree of cross-linking of the binder component and improve various durability such as light resistance, heat resistance, water resistance, and solvent resistance. The kind of the crosslinking agent is not particularly limited, and various known crosslinking agents can be arbitrarily selected and used. Examples include epoxy resins, melamine resins, isocyanate compounds, aziridine compounds, polycarbodiimide compounds, and the like. These crosslinking agents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Other additives include water-repellent agents such as silicone and fluorine, hydrophilic agents such as polyethylene glycol, dispersants such as pigment dispersants, reinforcing fillers, plasticizers, deterioration inhibitors, antistatic agents, Curing agents, emulsifiers, drying agents, antifoaming agents, preservatives, antifreezing agents, thickeners, and the like can also be used. Also about these, 1 type may be used independently and 2 or more types may be used together by arbitrary combinations and a ratio.

  In this way, by adding various additives to the coating solution, chemical resistance, deodorant properties, abrasion resistance, weather resistance, antibacterial properties, combustion resistance, flame resistance, heat retention, heat insulation, UV protection It is possible to impart desired properties to the material of the present invention, such as properties, aromaticity, light diffusibility, conductivity, stability, and sustained release.

  For both the pretreatment step and the attaching step, two methods of coating or impregnation can be used.

  In the case of coating, the coating method is not particularly limited, and a commonly used method can be arbitrarily selected and used. Specific examples include brushing, spraying, electrostatic coating, roll coating, dip coating, bar coating, floating knife coater, knife over roll coater, reverse roll coater, roll doctor coater, gravure roll coater, air Examples include knife coaters, curtain coaters, kiss roll coaters, nip roll coaters, cast coaters, contour direct coaters, contour reverse coaters, slit coaters, laminates, bonding methods, pad methods, blade coating methods, and ink jet methods. These methods are preferably used in various ways depending on the viscosity and amount of the paint, the characteristics of the paint, the characteristics of the substrate to be applied, and the like. Further, these coating methods may be appropriately combined.

  Also, the method for drying and removing the solvent after coating is not particularly limited as described above, and any method can be used. For example, a method such as natural drying, heat drying, vacuum drying, baking, ultraviolet irradiation, electron beam irradiation, or the like may be used as appropriate depending on the properties of the application liquid for attachment. These drying methods may be combined appropriately.

  Further, when molding is performed by impregnation, an impregnating material (hereinafter referred to as “impregnating member”) is used as a base material, impregnated with a coating solution for attachment, and then the solvent is removed to perform coupling. The material of the present invention is obtained by solidifying the agent-derived component, the functional particles, and the binder component.

  The type of impregnating member is arbitrary, and its material and shape can be arbitrarily selected according to the application. Specific examples include felt, nonwoven fabric, cloth material, paper, ceramic sheet, leather, waterproof / breathable sheet made of natural fiber, synthetic fiber, rock wool, glass fiber, carbon fiber and the like.

  Depending on the purpose and application of the material, as the impregnating member, a material having a structure in which only a part of the impregnating member is impregnated but not impregnated may be used. For example, in the thickness direction of the impregnating member, it is possible to impregnate the coating liquid only on one side and not impregnating the coating liquid on the other side, so that the properties on one side and the other side of the impregnating member It is also possible to use a technique such as making a difference (easiness of bonding) and utilizing this difference (such as making the other side an adhesive surface).

  Examples of particularly suitable impregnating members include fibers. The fiber may be either a natural fiber or a synthetic fiber, or a fiber using both of these. Moreover, the form is not particularly limited, and any form such as woven fabric, knitted fabric, and non-woven fabric can be used.

  Specific examples of the fiber include woven fabric, moquette, towel cloth, tricot, double raschel, circular knitting, needle punch and the like. In addition, the fibers referred to herein include natural fibers such as cotton, hemp, silk, and wool, or rayon; acetate; protein fibers; chlorinated rubber; polyamides such as nylon 6, nylon 66, and nylon-12; polyvinyl alcohol; Polyvinyl chloride; Polyvinylidene chloride; Polyacrylonitrile; Polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, etc .; Polyethylene; Polypropylene; Polyurethane; Polycyanide cyanide; Polyfluoroethylene And fibers composed of blends. Among these, cotton, hemp, polyester, and polyamide are preferably used from the viewpoint of versatility. In addition, these may contain additives such as polymers, matting agents, flame retardants, antistatic agents and pigments.

  The shape of the fiber is not particularly limited, and any shape such as a thread, a fabric, or a sheet may be used. In particular, in the case of synthetic fibers, the cross-sectional shape and the shape in the longitudinal direction can be freely designed. Specifically, examples of the cross-sectional shape include a round cross-section, a hollow cross-section, a multi-leaf cross-section such as a trilobe cross-section, and other irregular cross-sections, and examples of the shape in the longitudinal direction include long fibers and short fibers. Any of these can be arbitrarily selected. As the fabric, a woven fabric or a knitted fabric can be used depending on the application. A plain woven fabric, a twill weave fabric, a satin weave fabric, a combination thereof, or a knitted fabric may be used.

  Furthermore, you may use the electroconductive cloth currently utilized in order to dissipate static electricity effectively. The conductive fabric here is a mixture of conductive substances such as copper, aluminum, stainless steel, carbon, and conductive polymer in the form of particles in the organic fiber, or vacuum deposition method on the surface of the organic fiber. Coated with the organic fiber, clad with the organic fiber, or a conductive fiber made of a conductive substance itself is mixed with the fabric. As a method of mixing the conductive fibers into the fabric, any of fiber-like mixing, sliver-like mixing, yarn-like twisted yarn, filament-like mix or twisted yarn, and arrangement on the structure may be used.

  In addition, the single yarn fineness of the fiber is preferably 0.01 dtex or more, particularly 0.1 dtex or more, more preferably 1 dtex or more, and usually 100 dtex or less, especially 10 dtex or less. If it is below the upper limit of this range, since there exists a sufficient surface area as a fiber, since moisture absorption performance can fully be exhibited, it is preferable. Moreover, if it is more than the lower limit of this range, even when impregnated with silica, practical mechanical strength as a fiber can be secured, which is preferable.

  In addition, when using the raw material of this invention as a light-diffusion sheet, it is preferable to use a transparent member as an impregnating member, and it is more preferable to use a colorless and transparent member. Examples of the transparent impregnating member include synthetic resins such as polyethylene terephthalate, polyethylene naphthalate, acrylic resin, polycarbonate, polystyrene, polyolefin, cellulose acetate, and vinyl chloride. When a transparent impregnating member is used, the thickness thereof is not particularly limited, but it is usually preferably in the range of 50 μm or more and 250 μm or less.

  There is no restriction | limiting in particular about the method of impregnating a base material with a coating liquid, Arbitrary methods can be selected and used. For example, a method of immersing the impregnating member in a tank (so-called dipping) and a method of applying from one side or both sides of the impregnating member by a known application means can be mentioned. After the dressing coating solution has sufficiently penetrated, the excess is scraped or removed by a suitable scraping device or removal device such as a suction doctor, doctor roll, or a wire bar in which a wire is wound around a round bar. Is impregnated into the impregnating member. These impregnation methods may be combined as appropriate.

  After impregnation, the material of the present invention can be obtained by drying the impregnating member to remove the solvent. The method for drying the impregnating member is not particularly limited, and any method can be used as in the case of coating.

  In addition, when performing the above-mentioned pre-processing process and an attaching process separately, these processes may be performed by the same method (application | coating or impregnation), one is an application | coating technique and the other is an impregnation technique. You can do it.

  By the above procedure, a composite composed of functional particles, a coupling agent, and a binder component (hereinafter referred to as “attachment composite” as appropriate) is formed in a state of being immobilized on the substrate. Here, the shape and properties of the material of the present invention can be controlled by forming the composite into an arbitrary shape, for example, a shape such as a coating film.

  When a layered material is formed using a composite of functional particles, a binder, and a coupling agent, it is configured as a single layer structure consisting of only a layer containing the composite of functional particles, a binder, and a coupling agent. Alternatively, it may be configured as a laminated structure including a plurality of layers including a layer containing a composite of functional particles, a binder, and a coupling agent.

  In order to produce a laminated structure, for example, a layer made of another material may be laminated on one side or both sides of a layer containing the composite of the functional particles, binder and coupling agent of the present invention. As a laminating method, for example, a method of melt-extruding another resin or the like to a film or sheet of a composite of the functional particles, binder and coupling agent of the present invention, and conversely, the present invention is applied to a substrate made of another resin. A method of melt-extruding the composite of functional particles, binder and coupling agent of the invention, a method of co-extruding the composite of functional particles, binder and coupling agent of the present invention and another resin, and the present invention A film of a composite of functional particles, a binder, a coupling agent, a sheet and a film of another base material, and a sheet are laminated using a known adhesive such as an organic titanium compound, an isocyanate compound, or a polyester compound Etc. In addition, the film said to this invention means the film in a broad sense including forms, such as a sheet | seat, a tape, a pipe | tube, a container.

  In addition, when porous materials are used as functional particles to obtain the absorption / release performance of the materials, the associated heat generation / humidity control performance, or to provide sustained release performance of the supported drug, it is particularly porous When silica gel is used as the particle, 30% or more of the pore volume of the porous functional particle (silica gel) in the state of the material (silica gel) is usually 40% or more, and more than 50% is open to the outside of the material. It is preferable that the inside of the pores and the outside of the material are in communication with each other. In addition, the ratio of the volume of the pores opened to the outside of the material includes the pore volume of the material, the pore volume of the porous functional particles used, and the binder component that has undergone the same process as the production of the material. It can be calculated by measuring the pore volume of each.

  The shape of the material of the present invention is arbitrary, and for example, it can be formed into a flat shape, a sheet shape, a block shape, a pipe shape or the like. Among these, a sheet shape is preferable from the viewpoint of versatility. Furthermore, the material of the present invention may be subjected to various treatments as necessary, for example, heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing. , Tube processing, split processing, etc. can also be performed.

  Moreover, when forming the above-mentioned composite_body | complex in the shape of a coating film, this can also be implemented in combination with another coating film or layer. As a specific example, it can be combined with a primer layer or a makeup coat.

  The primer layer is a layer formed between a base material and a coating film containing functional particles, and is a layer made of an appropriate material according to the type of base material and the nature of the application liquid to be attached. By forming the primer layer, for example, the adhesion of the coating film to the base material is improved to improve the durability of the product, the smoothness of the base material surface is improved, and the coating film of the attachment coating liquid is improved. It is effective to form uniformly. Moreover, when a base material consists of metals, the effect of rust prevention can also be acquired by forming a suitable primer layer.

  The decorative coat is a layer that is usually formed on the outside of the coating film and is a layer that is formed in order to improve the designability (designability) of the substrate. As a method of applying makeup, there are methods such as coloring, printing, embossing, and wiping coating. These makeup methods can be applied in combination of two or more as appropriate. Moreover, you may form a transparent resin protective layer in the outermost surface which gave the makeup | decoration by application | coating of a transparent resin paint, or the lamination of a transparent resin sheet. However, when the application liquid for attachment includes a coloring material, it is possible to improve the design by using the application liquid itself for drawing or the like instead of using a cosmetic coat.

  In addition, these primer layers, cosmetic coats, transparent resin protective layers, etc. are directly formed on the base material or the material of the present invention such as a coating film, and are applied to other members such as appropriate paper and plastic sheets, You may make it install what was produced as a separate sheet | seat from the raw material of this invention, such as a base material or a coating film. Furthermore, an adhesive layer or a pressure-sensitive adhesive layer may be provided between the substrate, the primer layer, the coating layer, the decorative coat, the transparent resin protective layer, and the like.

  Although the manufacturing method of the present invention has been described above, the method of manufacturing the material of the present invention is not limited to this, and may be manufactured by other methods. For example, you may shape | mold by techniques, such as press molding, extrusion molding (T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.), injection molding. Moreover, a material with good dimensional accuracy can also be obtained by using a technique such as two-color molding or injection blow molding.

[III-3. Material Features]
The ratio of the functional particles in the raw material of the present invention is usually 0.1% by weight or more, particularly 0.15% by weight or more, more preferably 0.2% by weight or more, and usually 99% by weight as the ratio in the attached composite. % Or less, preferably 90% by weight or less, and more preferably 80% by weight or less. If the ratio of the functional particles is smaller than this range, there is a possibility that the functional particles cannot sufficiently exhibit functions such as absorption / release performance. If the ratio is larger than this range, the coupling agent and binder There is a possibility that the component cannot hold the functional particles.

  The ratio of the binder component in the material of the present invention is usually 0.01% by weight or more, particularly 0.05% by weight or more, more preferably 0.1% by weight or more, and usually 90% as a ratio in the impregnated composite. It is preferable to set it in the range of not more than wt%, particularly not more than 80 wt%, and further not more than 60 wt%. If the content of the binder component is smaller than this range, the functional particles may not be retained, and if the content is larger than this range, the functional particles sufficiently exhibit functions such as absorption / release performance. There is a possibility that it cannot be done.

  Further, the ratio of the component derived from the coupling agent in the material of the present invention is usually 0.005% by weight or more, particularly 0.01% by weight or more, more preferably 0.02% by weight or more, as a ratio in the attached composite. Usually, it is preferably 50% by weight or less, particularly 40% by weight or less, and more preferably 30% by weight or less. If the content of the coupling agent-derived component is smaller than this range, the functional particles may not be retained, and if the content is larger than this range, the functional particles have sufficient functions such as absorption / release performance. There is a possibility that it cannot be demonstrated. In addition, the coupling agent-derived component here refers to the structure after the coupling agent is chemically bonded to the base material or functional particles during the treatment, and the hydrolyzable functional group is hydrolyzed, When calculating the weight ratio, only the part that was originally included in the coupling agent was taken into account for the part chemically bonded to the base material or functional particles, taking into account the type of reaction of the chemical bond. In consideration of the hydrolyzed portion, the portion added with the hydrolysis is also taken into consideration.

  Further, in the material of the present invention, the weight ratio of the functional particles to the binder component (the weight of the functional particles / the weight of the binder component) is usually 0.1 or more, particularly 0.5 or more, more preferably 0.8 or more. Also, it is usually 50 or less, preferably 20 or less, and more preferably 10 or less. If the above ratio is smaller than this range, the functional particles may not sufficiently exhibit functions such as absorption / release performance. If the ratio is larger than this range, the binder component may cause functional particles to be removed. There is a risk that it cannot be held.

Furthermore, in the material of the present invention, the weight ratio of the functional particles to the coupling agent-derived component (the weight of the functional particles / the weight of the coupling agent-derived component) is usually 0.1 or more, particularly 0.5 or more. Is preferably 0.8 or more, and usually 1000 or less, particularly 500 or less, and more preferably 200 or less. If the above ratio is smaller than this range, the functional particles may not sufficiently exhibit functions such as absorption / release performance. If the ratio is larger than this range, the coupling agent may be functional particles. May not be able to be held. In addition, since it is calculated | required by the following formula | equation, if the processing amount of a coupling agent assumes that it processed with the monomolecular film from the minimum coating area of a coupling agent, you may refer to this value.
Coupling agent throughput =
(Weight of material to be treated (g)) × (specific surface area of material to be treated (m ² / g))
/ Minimum coating area of coupling agent

  As described above in detail, since the material of the present invention is obtained by bringing the coupling agent into contact with the base material and further bringing the functional particles into contact with each other, the existing base material and functional particles are used. It is possible to manufacture efficiently. In addition, since the functional particles are bonded to the base material via the coupling agent, the functional particles can be effectively prevented from peeling off or falling off. Further, even when a binder is used, the amount thereof is small, and there is no possibility that the characteristics of the base material and the functions of the functional particles are hindered.

  In addition, as a functional particle, a specific silica gel having excellent durability and water resistance (silica gel of the present invention) is used, and a binder component, a coupling agent, and other types of components used in combination so as not to impair this property. If is appropriately selected, high durability, water resistance, and weather resistance can be provided.

  Furthermore, while using a porous substance typified by the above-mentioned silica gel as the functional particles, and making most of the pore volume of the porous functional particles open to the outside of the material, excellent absorption / release performance, etc. The function can be fully exhibited. In addition, since a large amount of substance can be carried in the pores of the porous functional particles, it is possible to exhibit excellent sustained release properties. Furthermore, since the coating object is covered with a porous material having a large pore volume, it exhibits excellent physical properties such as waterproofness and soundproofing.

  Further, when any substance such as moisture (water) is adsorbed on the pores of the porous substance, heat of adsorption is generated. Since the material of the present invention adsorbs a large amount of substance (for example, water) as described above, the heat of adsorption generated thereby increases. In other words, this means that the material of the present invention also has excellent hygroscopic heat generation. In addition, when the pore size distribution of the porous functional particles is sharp, the adsorption rate is increased, so that the heat generation rate is also increased.

  Furthermore, the material of the present invention can efficiently impart various functions to the material depending on the type of functional particles and the combination with the base material. For example, by using a porous substance as the functional particles, it is possible to provide functions such as high absorption / release performance, hygroscopic heat generation, and sustained release. Therefore, for example, it can be used widely and suitably in the following fields.

  In the field of production and treatment of products in industrial facilities, for example, various catalysts and catalyst carriers (acid-base catalysts, photocatalysts, noble metal catalysts, etc.), wastewater / waste oil treatment agents, odor treatment agents, gas separation agents, industrial desiccants , Bioreactors, bioseparators, membrane reactors and the like.

  In the building material field, for example, applications such as a humidity control agent, a soundproofing / sound absorbing material, a refractory material, and a heat insulating material can be cited.

  In the air conditioning field, for example, there are applications such as desiccant air conditioners, heat pump heat storage agents, and the like.

  In the paint / ink field, for example, there are uses such as a matting agent, a viscosity adjusting agent, a chromaticity adjusting agent, an anti-settling agent, an antifoaming agent, an ink back-through preventing agent, a stamping foil, and a wallpaper.

  In the field of resin additives, for example, anti-blocking agents for films (polyolefin films, etc.), plate-out inhibitors, silicone resin reinforcing agents, rubber reinforcing agents (for tires, general rubbers, etc.), fluidity improvers, powders Anti-caking agent for glassy resin, printability improver, matte agent for synthetic leather and coating film, filler for adhesive / adhesive tape, translucency adjuster, antiglare adjuster, for perforated polymer sheet Examples include fillers.

  In the papermaking field, for example, thermal paper fillers (such as residue adhesion inhibitors), ink jet paper image enhancement fillers (ink absorbers, etc.), diazo photosensitive paper fillers (photosensitive density adjusters, etc.), and improved traceability for tracing paper. Examples thereof include agents, fillers for coated paper (writing properties, ink absorbability, antiblocking property improving agents, etc.), fillers for electrostatic recording, and the like.

  In the food field, for example, beer filter aids, soy sauce, sake, wine and other fermented product lowering agents, various fermented beverage stabilizers (such as turbidity factor protein and yeast removal), food additives, and powdered food solids. Uses such as anti-caking agents are mentioned.

  In the pharmaceutical and agrochemical field, for example, tableting aids for pharmaceuticals, grinding aids, dispersion / pharmaceutical carriers (dispersion / sustained release / delivery improvement, etc.), agrochemical carriers (oily agrochemical carrier / hydration dispersibility alteration, (Slow release / delivery improvement, etc.), agricultural chemical additives (anti-caking agent / powder property improving agent, etc.), agricultural chemical additives (anti-caking agent, anti-settling agent, etc.), etc.

  In the field of separation materials, for example, uses such as a chromatographic filler, a separating agent, a fullerene separating agent, an adsorbent (protein, dye, odor, etc.), a dehumidifying agent and the like can be mentioned.

  In the agricultural field, for example, there are applications such as feed additives, fertilizer additives and the like.

  In life-related fields, for example, humidity control agents, desiccants, cosmetic additives, antibacterial agents, deodorants / deodorants / fragrances, detergent additives (surfactant powdering, etc.), abrasives (for toothpastes, etc.), powders Applications include fire extinguishing agents (powder improvers, anti-caking agents, etc.), antifoaming agents, battery separators and the like.

  In the clothing field, for example, humidity control fibers, hygroscopic heat generation fibers, sustained release fibers, etc., general clothing such as shirts, blouses, pants, jackets, sweaters, blousons, inners and stockings, sports clothing such as athletic wear and windbreakers, and uniforms In addition, there are applications such as work clothes and hats other than dust-proof clothing.

  Furthermore, the material of the present invention can be a material having sustained release performance of various drugs by using a sustained release agent as the functional particles.

  Specifically, the above-described porous particles such as silica gel are used as a sustained-release carrier, and anti-aging agents, curing agents, agricultural chemicals, fertilizers, bactericides, disinfectants, antibacterial agents, and insecticides for polymer materials are used. Supporting chemical substances (medicine, etc.) having various functions and actions, such as insecticides, herbicides, fragrances, insect repellents, various drugs and physiologically active substances, as supported components A sustained-release agent that retains the components and gradually releases them over time is obtained.

The drug or the like to be supported on the sustained release carrier can be freely selected according to the use.
For example, pesticides for agricultural chemicals include salicione, marathon, dimethoate, diazinon, diethylamide, 2-ethylthiomethylphenyl = methyl carbamate, thiophosphoric acid, 2-methyl-3-cyclohexene-1-carboxylic acid and the like.

  Examples of the bactericides include copper nonylphenol sulfonate, dineb, anzep, thiuram, polyoxin, and cycloheximide.

  Examples of the herbicide include chloromethoxynyl, nitralin, 3- (3,3-dimethylureido) phenyl = tertiary-butyl carbamate and the like.

  Examples of the antibacterial agent include hinokitiol.

  Examples of the pest repellent include phenolic compounds.

  Examples of the antioxidant for plastic include bisphenol such as 2,2-bis (4-hydroxydiphenyl) propane, a condensate of cyclohexane, disalicylic resorcin, and phosphite.

  Examples of the anti-aging agent include amine compounds such as phenyl-β-naphthylamine, phenol compounds such as styrenated phenol, thiourea derivatives, and benzimidazoles.

  Examples of the fertilizer include ammonia compounds such as urea, ammonium sulfate and ammonium nitrate, phosphorus compounds such as lime superphosphate and lime heavy perphosphate, and compounds containing potassium.

  Furthermore, examples of drugs and physiologically active substances include antihypertensive diuretics, vasodilators, arrhythmia therapeutic agents, cardiotonic agents, hormonal agents, immune regulators, antibiotics, antitumor agents, antiulcer agents, antipyretic agents, analgesics, anti-inflammatory agents. And drugs classified into antitussives, sedatives, muscle relaxants, antiepileptics and the like. Specific examples of these pharmaceutical / physiologically active substances include drugs described in the Medical Products Handbook 5th Edition (published by Yakuho Hokpo Co., Ltd.) or similar drugs.

  However, the drugs listed above are merely examples, and drugs that can be supported on a sustained-release carrier are not limited to these.

  Although the present invention has been described above, the present invention is not limited to the above description and can be implemented with appropriate modifications.

  Further, the application and usage of the material of the present invention are not limited to those described above, and it is of course possible to use it in other applications and configurations.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention can be arbitrarily changed and implemented in the range which does not deviate from the summary, without being restrict | limited to a following example.

(1) Analysis method:
(1-1) Pore volume, specific surface area:
About the sample, BET nitrogen adsorption isotherm was measured by AS-1 manufactured by Cantachrome, and the pore volume and specific surface area were determined. Specifically, the pore volume is a value when the relative pressure P / P ₀ = 0.98, and the specific surface area is 3 points of P / P ₀ = 0.1, 0.2, 0.3. It calculated using the BET multipoint method from the nitrogen adsorption amount.

For those having a mode pore diameter (D _max ) of 5 nm or less, the HK method or SF method known to those skilled in the art, and those having a mode pore diameter of 5 nm or more by the BJT method, respectively, the pore distribution curve and the mode pore diameter. The differential pore volume at (D _max ) was determined. The interval between the points of the relative pressure to be measured was 0.025.

(1-2) Powder X-ray diffraction:
Using a RAD-RB apparatus manufactured by Rigaku Corporation, the powder X-ray diffraction pattern of the sample was measured using CuKa as the radiation source. The measurement conditions were a diverging slit 1/2 deg, a scattering slit 1/2 deg, and a light receiving slit 0.15 mm.

(1-3) Content of metal impurities:
After adding 15 ml of hydrofluoric acid to 2.5 g of the sample and heating to dryness, water was added to make 50 ml. ICP emission analysis was performed using this aqueous solution. Sodium and potassium were analyzed by flame flame light method.

(1-4) Solid Si-NMR measurement:
Using a Bruker solid-state NMR apparatus (MSL300), a resonance frequency of 59.2 MHz (7.05 Tesla), and a 7 mm sample tube, measured under the conditions of a CP / MAS (Cross Polarization / Magic Angle Spinning) probe did.
Specific measurement conditions are shown in Table 1 below.

Analysis of measured data (Q ⁴ Determination of the peak position) was performed in a method of extracting each peak by the peak division. Specifically, waveform separation analysis using a Gaussian function was performed. For this analysis, waveform processing software “GRAMS386” manufactured by Thermogalatic was used.

(2) Method for measuring pore volume of silica gel opened to the outside of the material:
In the same manner as the analysis method described in (1-1), the pore volume V _p (ml / g) of only the silica gel used for the material, the pore volume V _q (ml / g) of the material containing silica gel, The pore volume V _r (ml / g) of a material produced in the same manner except that it does not contain silica gel was determined.

Next, assuming that the weight ratio of the silica gel in the material is a%, the weight ratio of the components other than the silica gel is b%, and a + b = 100%, the following formula (1) is used to calculate the fine silica gel open to the outside of the material. The pore volume S was determined.
S = (V _q −V _r × b / 100) × 100 / a (1)

Moreover, the ratio T (%) of the pore volume of the silica gel opened to the outside of the raw material with respect to the pore volume of the silica gel was obtained by the following calculation formula (2).
T = S / V _p × 100 (2)

(3) Production of silica gel (reference example):
(Manufacturing method of silica gel)
1000 g of pure water was charged into a 5 L separable flask (with a jacket) which was a glass mold and was fitted with a water-cooled condenser open to the atmosphere at the top. While stirring at 80 rpm, 1400 g of tetramethoxysilane was charged into this over 3 minutes. The water / tetramethoxysilane molar ratio is about 6/1.

  Stirring was continued while passing 50 ° C. warm water through the jacket of the separable flask, and the stirring was stopped when the contents reached the boiling point. Subsequently, hot water at 50 ° C. was passed through the jacket for about 0.5 hour to gel the produced sol.

  Thereafter, the gel was quickly taken out and pulverized through a nylon net having an opening of 600 microns to obtain a powdery wet gel (silica hydrogel). 450 g of this hydrogel and 450 g of pure water were charged into a 1 L glass autoclave and hydrothermally treated at 170 ° C. After hydrothermal treatment for 3 hours, the liquid was drained through a nylon net having an opening of 100 microns, and the filter cake was dried under reduced pressure at 150 ° C. until it became a constant weight without washing with water to obtain silica gel.

This silica gel was pulverized using a pulverizer (wet circulation type pulverizer SC-50 manufactured by Mitsui Mining Co., Ltd.). Specifically, first, 200 g of silica gel and 1800 g of water were slurried in a separate container using a high-speed stirrer. The obtained slurry was wet pulverized for 20 minutes while circulating at a circulating liquid amount of 1 L / hr to obtain a silica gel slurry having an average particle diameter of 1 μm. As pulverization conditions, 0.11 kg of ZrO ₂ balls having a diameter of 0.2 mm was used as a pulverization medium, and stirring was performed at a rotational speed of 2400 rpm using a rotor.

About the silica gel thus obtained (silica gel of Reference Example), the pore volume having a diameter in the range of mode pore diameter (D _max ), pore volume, specific surface area, mode pore diameter (D _max ) ± 20% Table 2 shows the ratio of the total pore volume and the measurement results of Q ⁴ / Q ³ . These physical properties were measured after drying the silica gel slurry.

  According to the powder X-ray diffraction pattern, no crystalline peak appeared, and no low-angle peak (2θ ≦ 5 deg) due to the periodic structure was observed.

  The impurity concentration of the obtained silica gel was 1 ppm or less for all of sodium, potassium, calcium, magnesium, titanium, and chromium, except that 2 ppm each of iron and aluminum were detected.

(4) Production of material:
Example 1
An ethanol solution (pretreatment coating solution) containing a silane coupling agent (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. KBM403) at a concentration of 0.15% by weight was prepared. The pretreatment coating solution was impregnated with cotton fabric, squeezed at a squeezing rate of 100%, and dried at room temperature. The aperture ratio (%) is defined by the following formula.
Drawing ratio = (weight of coating solution impregnated on substrate / weight of substrate) × 100

  Further, a silica slurry (solid content 10%) 20% by weight obtained using the silica gel of Reference Example, a silicone emulsion (Kitahiro Chemical Co., Ltd. TF-3500, solid content approximately 45%) 1.5% by weight, water 78 A solution consisting of 5% by weight (attaching coating solution) was prepared. After this impregnating coating liquid was impregnated with the above-mentioned coupling agent-treated (pre-treated) cotton fabric, it was squeezed at a squeezing rate of 150% and then dried at 110 ° C.

(Example 2)
Silane coupling agent (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. KBM403) 0.15 wt%, silica slurry obtained using silica gel of reference example (solid content 10%) 20 wt% %, Silicone emulsion (Kitahiro Chemical Co., Ltd. TF-3500) 1.5% by weight was diluted with water to prepare a solution (pretreatment and attachment coating solution). After this solution was impregnated with cotton fabric, it was drawn with a drawing rate of 150% and then dried at 110 ° C.

(Comparative example)
In Example 1, silica gel and a binder were applied to cotton by the same operation except that no treatment with a silane coupling agent was performed.

(Washing durability test)
The obtained sample cloth was washed five times with a general washing machine using a general laundry detergent (Attack, Kao Corporation). The amount of silica gel adhered to the sample cloth before and after washing was measured using TG-DTA6300 (manufactured by Seiko). The analysis conditions were as shown in the following table.

The residual silica gel ratio of the sample cloth after washing was determined by the following formula.
Silica gel remaining rate (%)
= {(Silica gel adhesion after washing) / (silica gel adhesion before washing)} × 100

  From the results of Table 4, the materials of Example 1 and Example 2 that were treated with the coupling agent were significantly improved in durability to washing compared to the material of the comparative example that did not use the coupling agent. I understand that

  Since the functional particle-adhered material of the present invention has the above-described advantages, it is used for building materials, for catalysts, for air conditioning, for paints and inks, for resin additives, for papermaking, for food, for pharmaceuticals and agricultural chemicals. It can be used in various fields such as fields, separation material fields, agricultural application fields, life-related fields, and clothing fields.

Claims (11)

While functional particles are attached to at least a part of the substrate,
At least a portion of the functional particles,
Silica gel having a most frequent pore diameter of 2 nm to 50 nm,
Bonded to the substrate via a silane coupling agent ,
A functional particle adhering material, wherein the functional particle adhering material is attached to the base material by a binder having a glass transition temperature of -80C to 110C . The functional particles and the substrate do not directly form a covalent bond or a coordinate bond,
The functional particle attachment according to claim 1, wherein the silane coupling agent forms a covalent bond, a coordination bond and / or a hydrogen bond with both the base material and the functional particle. Material . The functional particle-attached material according to claim 1 or 2, wherein pores of 30% or more of the pore volume of the silica gel are open to the outside of the material . About the silica gel
(A) The pore volume is 0.3 ml / g or more and 3.0 ml / g or less,
(B) a specific surface area, 100 m ² / g or more, and a 1000 m ² / g der Ru <br/> be hereinafter functional particle impregnated material according to any one of claims 1 to 3. The functional particle-attached material according to any one of claims 1 to 4 , wherein at least a part of the substrate is a fiber. 6. The functional particle-attached material according to claim 5 , wherein at least a part of the base material is cotton . The functional particle-attached material according to any one of claims 1 to 6 , wherein the silane coupling agent has an epoxy group . The functional particle-adhered material according to any one of claims 1 to 7, wherein the binder has a molecular weight of 10,000 or more and 1,000,000 or less . The functional particle-attached material according to any one of claims 1 to 8 , wherein the binder is a silicone-based resin. It is obtained by a method comprising at least a first step of bringing a silane coupling agent into contact with a base material and a second step of bringing functional particles into contact with the base material after the first step. The functional particle-attached material according to any one of claims 1 to 9 . A method for producing the functional particle-attached material according to any one of claims 1 to 9 ,
A function comprising at least a first step of bringing a silane coupling agent into contact with a substrate and a second step of bringing the functional particles into contact with the substrate after the first step. Manufacturing method of conductive particle attachment material.