JP2003146629A - Porous inorganic composite and resin composition compounded with this composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous inorganic composite which has a high specific surface area and excellent absorbability while holding the uniformity and dispersibility of porous inorganic particles. SOLUTION: This porous inorganic composite consists of a composite formed by carrying and supporting inorganic particulates on a carrier consisting of porous inorganic particles and satisfies specific grain size characteristics, such as an average particle size, dispersion coefficient and sharpness.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a porous inorganic composite and a resin composition containing the composite, and more specifically to a porous inorganic composite having improved absorption and the composite. The present invention relates to a resin composition containing the body. The porous inorganic composite of the present invention is a catalyst, a drug, a microorganism, an antibacterial agent,
Deodorant, dehumidifier, sustained release agent, bactericide, insect repellent, ultraviolet absorber, light diffuser, polymerization dispersant, filter agent, molding aid, food additive, desiccant, aromatic, ceramic raw material, dental Toothpaste, plastics, rubber, papermaking, thermal recording paper, sealing agent, antiblocking agent for synthetic resin film, extender pigment for ink, raw material for paint, lake pigment, cosmetics, acid resistance, porosity, heat stability It is effective in various fields that require affinity with resins, transparency, dispersibility, absorbability, and the like.
Further, by combining the above various uses, further new uses can be expected.

[0002]

2. Description of the Related Art Calcium phosphate, zeolite, silica, calcium silicate and the like have been known as porous inorganic particles, and they include a moisture absorbent, a sustained release agent, a carrier such as a catalyst, a thickener,
It is used as a molding aid and as an internal filler for papermaking. As an application of these porous inorganic particles, for example, when they are used for a coating layer pigment for inkjet paper, they are disclosed in JP-A-10-195.
Japanese Patent No. 796 discloses that the use of calcium phosphate-based porous particles provides a pigment having excellent ink absorptivity and resolution. However, as the printing speed of inkjet printers further increases, it is becoming indispensable to further improve the ink absorption speed. Further, in the case of inkjet recording paper, especially for photo grades, it is necessary to have an inkjet recording paper that retains glossiness, image density, ink absorbency, and fixability as characteristics of its coating layer surface. .

[0003]

The object of the present invention is to improve the absorption rate and to stabilize the optical characteristics of the porous inorganic composite particles while maintaining the uniformity and dispersibility of such conventional porous inorganic particles. It is about synthesizing the body industrially and providing it at low cost.

[0004]

[Means for Solving the Problems] The present inventors have already applied for a matting agent for paints, which is composed of porous particles of calcium phosphate or the like, for the purpose of imparting a matting effect with a constant gloss and luster to the paint. (Japanese Patent Application No. 2001-150686). However, there are optical differences, paint viscosity differences, and the like, which are merely alternatives to commonly used various silica and the like, and it is easy to be limited to specific fields. Further, in recent years, due to the VOC problem caused by sick house syndrome, paint pigments having higher absorbency have been required. As a result of intensive studies conducted by the present inventors in view of the above-mentioned problems, the inorganic inorganic particles are supported on the porous inorganic particles to form a composite, thereby maintaining the uniformity and dispersibility of the particles of the porous inorganic particles. As a result, they have found that a porous inorganic composite having an improved absorption rate and stable optical properties can be provided, and completed the present invention.

That is, the first aspect of the present invention is to support inorganic fine particles (hereinafter, referred to as inorganic receptor (V)) on a carrier composed of porous inorganic particles (hereinafter referred to as porous carrier (Z)). Which is composed of the following formula (a):
A porous inorganic composite (hereinafter, referred to as a porous composite (ZV)) characterized by satisfying (d). (A) 0.1 ≦ Dzv ≦ 30 (μm) (b) 1 ≦ αzv ≦ 5 where α = dzv50 / Dz
v (c) 0 ≦ βzv ≦ 2 where β = (dzv90-d
zv10) / dzv50 (d) 40 ≦ Szv ≦ 800 (m ² / g) where Dzv: average particle size (μm) αzv: porous of the porous composite (ZV) measured by a scanning electron microscope (SEM) photograph Coefficient βzv of porous composite (ZV): Sharpness of porous composite (ZV) dzv: 50% average particle diameter (μm) dzv90 of porous composite (ZV) measured by Microtrac FRA laser particle size distribution meter : Cumulative 90% particle diameter (μm) on the sieve passage side of the porous composite (ZV) measured by Microtrac FRA laser particle size distribution meter dzv10: Porous composite (ZV) measured by Microtrac FRA laser particle size distribution meter ) Sieve passing side cumulative 10% Particle size (μm) Szv: B of porous composite (ZV) by nitrogen adsorption method
ET specific surface area (m ² / g)

The second aspect of the present invention is to provide the above porous composite (Z
V) is blended with a resin, which is a content of the resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The porous carrier (Z) used in the present invention has an average particle diameter (Dz) measured from an SEM photograph of 0.1 to 20 μm.
And the dispersion coefficient (αz) and sharpness (βz) measured from the particle size distribution system are 1 ≦ αz ≦ 5 and 0 ≦ βz ≦, respectively.
2, and further has a BET specific surface area (Sz) of 5 to 300 m ² /
Must be g. When Dz is less than 0.1 μm, the dispersibility of the primary particles cannot be maintained and the particles agglomerate, causing a problem in complexing with the inorganic receptor (V). On the other hand, when it exceeds 20 μm, the surface of the resin composition is liable to be rough or fallen off, for example, in the application of the resin composition, so that the application is extremely limited. The same applies to the dispersion coefficient (αz) and the sharpness (βz). If the dispersion coefficient (αz) and the sharpness (βz) are not within the above ranges, a uniform porous composite (Z
V) is not suitable for making. Therefore, preferably 1 ≦
αz ≦ 2 and 0 ≦ βz ≦ 1. When the BET specific surface area is less than 5 m ² / g, a uniform composite cannot be obtained in the composite with the inorganic receptor (V). Also, 300m ²
If it exceeds / g, if the composite ratio of the inorganic receptor (V) is small, a deviation occurs and a uniform composite cannot be obtained. Preferably 30 to 250 m ² / g, more preferably 50 to 20
It is 0 m ² / g.

The porous carrier (Z) is not particularly limited as long as it satisfies the above requirements, for example, JP-A-9-25.
As disclosed in Japanese Patent Publication No. 108, it is preferable to use porous calcium phosphate-based particles having a high specific surface area and high specific surface area, calcium silicate, synthetic zeolite, porous spherical silica, etc., which may be used alone or in combination of two or more. Although used in combination, among them, porous calcium phosphate is more preferable in terms of particle size control and dispersibility.

The most stable crystal form of calcium phosphate is hydroxyapatite. The Ca / P atomic ratio of calcium phosphate is not particularly limited, but is usually 16.7 or less, preferably 5.56 or less. When the Ca / P atomic ratio exceeds 16.7, the ratio of the porosity decreases, so that it is difficult to obtain a uniform composite in the composite with the inorganic receptor (V). When it is used as a layer pigment, the ink absorptivity is biased, which tends to cause unevenness and bleeding. Also,
The lower limit is not particularly limited, but 1.
57 or more is suitable. Therefore, it is more preferably 1.60 to 4.17, and further preferably 1.80 to 3.34 from the viewpoint of the bias of the composite and the crystal stability.

The inorganic receptor (V) used in the present invention is not particularly limited as long as it is an inorganic fine particle, and examples thereof include silica (colloidal silica), alumina (colloidal alumina, alumina sol, pseudo-boehmite, aluminum oxide), silicic acid. Aluminum, magnesium silicate, calcium silicate,
Examples thereof include diatomaceous earth, magnesium carbonate, magnesium hydroxide, talc, kaolin, calcium sulfate, zinc oxide, titanium oxide, zinc sulfide, zinc carbonate, calcium phosphate, calcium carbonate, etc., which may be used alone or in combination of two or more as necessary. Further, the particle size of the inorganic receptor (V) is not particularly limited, but in order to uniformly combine with the porous carrier (Z), the average particle size (Dv) measured from the TEM photograph is usually 0.001 to The range of 1 μm is preferable. If it is less than 0.001 μm, the dispersion due to the aggregation of particles tends to be large, while if it exceeds 1 μm, it may cause peeling or falling off when it is combined with the porous carrier (Z).
For example, when used as a coating layer pigment for inkjet paper,
The paper may not be fed because it falls off from the coating layer component. Therefore, it is more preferably 0.01 to 0.5 μm.

The BET specific surface area (Sv) of the inorganic receptor (V) is not particularly limited, but is usually preferably in the range of 50 to 1000 m ² / g from the viewpoint of improving the absorbability. If it is less than 50 m ² / g, it tends to cause peeling or dropping when it is combined with the porous carrier (Z), while it is 100
When it exceeds 0 m ² / g, the absorption performance is too high and the absorption persistence tends to be extremely short, and the application is likely to be extremely limited.
Therefore, more preferably 100~700m ² / g, more preferably from 200 to 500 m ² / g. As the inorganic receptor (V) satisfying the above physical properties, colloidal silica, alumina, and calcium phosphate can be preferably used.

The porous composite (ZV) according to the present invention is preferably a composite in which the shape of the porous carrier (Z) and the absorption capacity of the inorganic receptor (V) are retained as much as possible. Therefore, the average particle diameter (Dzv) measured from the SEM photograph is
The dispersion coefficient (αzv) and the sharpness (βzv) measured from the particle size distribution system are each 1 ≦ α in the range of 0.1 to 30 μm.
zv ≦ 5, 0 ≦ βzv ≦ 2, and further BET specific surface area (S
zv) needs to be 40 to 800 m ² / g. If it is intended to be used for advanced industrial materials, the dispersion coefficient and sharpness of the particles are 1 ≦ αzv ≦
It is preferable that 2 and 0 ≦ βzv ≦ 1. Also BE
T specific surface area, since the absorption rate is improved, which is one of the purposes of the present invention, preferably 100~700m ² / g, more preferably 150~500m ² / g. 800 m ²
When it exceeds / g, it means that the specific surface area of the porous carrier (Z) or the inorganic receptor (V) exceeds 800 m ² / g, and as described above, each of them tends to cause a problem in stability.

In the present invention, the average particle diameters of the porous composite (ZV) and the porous carrier (Z) measured by SEM photograph were obtained from the projected circle equivalent diameter of each particle in the photograph taken at 10,000 times. It is calculated by the average value. Further, the average particle size of the inorganic receptor (V) measured by the TEM photograph was 25.
It is determined by the average value obtained from the projected circle equivalent diameter of each particle of the photograph taken at 10,000 times. The diameter equivalent to the projected circle is defined as the diameter of a circle with the same area.

The composite ratio of the porous carrier (Z) and the inorganic receptor (V) in the porous composite (ZV) of the present invention is not particularly limited, but from the viewpoint of improving the absorbency of the composite, the porous carrier is preferred. The inorganic receptor (V) is preferably in the range of usually 1 to 1000 parts by weight with respect to 100 parts by weight of (Z). If the amount is less than 1 part by weight, the advantages of the composite are difficult to obtain, and if the amount exceeds 1000 parts by weight, peeling or dropping is caused, and as described above, when used in the advanced industrial material field, it is likely to have an adverse effect. The term "composite" as used in the present invention means that the fine particles which are the inorganic receptors (V) physically adsorb to the porous carrier (Z), or
It includes both cases of chemisorption, that is, deposition and precipitation to form a crystalline layer.

In the case of wet mixing, when the predetermined amount of the inorganic receptor (V) is added to the predetermined amount of the porous carrier (Z) water suspension, the porous carrier (Z) and the inorganic receptor (V) are mixed. The mixing may be performed with a stirring force or a liquid concentration that allows uniform stirring, and the mixing time is usually about 1 to 2 hours. If the mixed solution is pulverized by spray drying or the like, the desired porous composite (Z
V) can be prepared. A paddle, a turbine, a dissolver, an impeller, etc. can be used as the stirring mechanism. In the case of dry mixing, since the porous carrier (Z) easily adsorbs water, a predetermined amount of the porous carrier (Z) is first added to a mixer such as a Henschel mixer, a tumbler mixer, etc. To keep the temperature as low as possible, a temperature of 80-1
After stirring and holding at about 50 ° C. for about 10 to 30 minutes, a predetermined amount of inorganic receptor (V) was added, and the temperature was maintained at 1
The desired porous composite (ZV) can be prepared by mixing for about 0 to 30 minutes.

In order to further improve the dispersibility, stability, etc. of the particles of the porous composite (ZV) of the present invention, or depending on the intended use, a fibrin compound, a siloxane compound, a fatty acid,
Resin acids, organic acids such as acrylic acid, methacrylic acid, oxalic acid and citric acid, inorganic acids such as tartaric acid, phosphoric acid, condensed phosphoric acid and fluoric acid, polymers of these organic acids and inorganic acids, salts thereof, or One or more of surface treatment agents such as esters, dispersants such as surfactants, titanate coupling agents, coupling agents such as silane coupling agents, dispersants such as surfactants, etc. It is preferably used after surface treatment according to a conventional method, and these treating agents are generally used in an amount of 5 to 30% by weight or less based on the particles. Among these treatment agents, fatty acids and fatty acid salts represented by stearic acid and the like, fibrin compounds represented by carboxymethyl cellulose and the like, or siloxane compounds represented by methyl hydrogen silicone oil and the like, Polyoxyalkylene compounds and the like are preferable.

The porous composite (ZV) of the present invention can be suitably used especially for various resins. For example, when blended in a papermaking resin as a coating layer pigment, excellent absorbency,
Demonstrates high resolution, and when compounded in paint resins,
It has excellent luster or matteness, water resistance and absorbency. The resin with which the porous composite (ZV) of the present invention is mixed is not particularly limited, and for example, it is used as a resin for papermaking, such as vinyl-based, debun-based, cellulose-based, melamine-based, urea-based, polyurethane-based, polyester. -Based, acrylic-based, alkyd-based liquid resins, phenol-based, alkyd-based, unsaturated polyester-based, amino-based, epoxy-based, vinyl-based, acrylic-based, polyurethane-based, silicone-based, fluorine-based resins used as paint resins Examples of such liquid resins are: Any of these may be used alone or in combination of two or more as required.

The amount of the porous composite (ZV) according to the present invention to be blended with the resin varies depending on the type and application of the resin. For example, when the porous composite (ZV) is used as a resin for ink jet paper, it is 50 to 100 parts by weight of the resin. 2000 parts by weight, preferably 100 to 500 parts by weight. If it is less than 50 parts by weight, it is difficult to impart sufficient thixotropy. If it exceeds 2000 parts by weight, the viscosity tends to be too high and the workability tends to deteriorate.
When it is used as a coating resin, it is 1 to 1000 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the resin. If it is less than 1 part by weight, it is difficult to obtain a matting effect, while if it exceeds 1000 parts by weight, the coating film tends to be adversely affected.

In addition to the above, the resin composition of the present invention contains, for adjusting viscosity and other physical properties, pigments such as colloidal silica, talc, kaolin, zeolite, resin balloons and glass balloons such as dioctyl phthalate, Plasticizers such as dibutyl phthalate, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and butane, petroleum solvents such as gasoline, ketones such as acetone and methyl ethyl ketone, ether esters such as cellosolve acetate, etc. Examples of the solvent, such as additives such as silicone oil and fatty acid ester-modified silicone oil, and other various adjusting agents may be used alone or in combination of two or more.

The porous composite (ZV) of the present invention has an improved absorption rate by improving the specific surface area while maintaining good uniformity and dispersibility as compared with the conventional porous carrier (Z). Since it can be dramatically increased and the manufacturing cost is low, various carriers such as pharmaceuticals, microorganisms, antibacterial agents, photocatalysts, deodorants, dehumidifiers, sustained-release bodies, bactericides, insect repellents, and UV absorption Agents, light diffusing agents, dispersants for polymerization, filtering agents, molding aids, food additives, drying agents, fragrances, ceramic raw materials,
Dental dentifrice, plastics, rubber, papermaking, thermal paper,
It can be used for a wide range of applications such as sealing materials, anti-blocking agents for synthetic resin films, extender pigments for inks, pigments for paints, lake pigments, and cosmetics.

[0021]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following description,% and parts represent% by weight and parts by weight, unless otherwise specified.

Examples 1 to 6 and Comparative Examples 1 to 11 (1) Preparation of Porous Carrier (Z) (a) Porous Carriers 1 to 3 First, an aqueous suspension dispersion A of calcium carbonate was prepared by the following method. It was prepared in. A furnace gas having a carbon dioxide concentration of 27% by weight was introduced into 700 liters of lime milk (a water suspension of calcium hydroxide) having a specific gravity of 1.055 and a temperature of 8 ° C. at a flow rate of 24 m ³ and p
The carbonation reaction was performed up to H9, and then the mixture was aged with stirring at 40 to 50 ° C. for 5 hours to elute the alkali between particles to disperse them to pH 10.8, and the solid content concentration was 25%, and the average measured from an electron micrograph. With a particle size of 0.05 μm,
An aqueous calcium carbonate suspension having an average particle diameter of 0.48 μm measured with a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) was prepared. Then, according to the raw materials and the reaction / aging conditions shown in Table 1, a stainless steel tank with a baffle plate and a stirring blade having one turbine blade having a diameter of 0.6 m were used.
Into a 4 m ³ stainless steel tank, the diluted concentration was adjusted, the temperature-controlled calcium carbonate aqueous suspension dispersion was added, and a diluted aqueous solution of phosphoric acid was added dropwise under stirring and aged according to the aging conditions shown in Table 1. , Calcium phosphate-based porous carriers (Z) 1 to 3 having a petal-like structure were prepared.

(B) Porous Carriers 4 to 6 Porous carriers (Z) 4 to 6 were prepared in the same manner as above except that the aqueous suspension dispersion B of calcium carbonate shown below was used. Maruo Calcium heavy calcium carbonate "Super SSS" (1.2m ² / g) was added and mixed with water, then TK
Measured with a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) with stirring and dispersion with a homomixer (5000 rpm, 15 minutes), a solid content concentration of 25%, and an average particle diameter of 3 μm measured from an electron micrograph. An aqueous calcium carbonate suspension having an average particle diameter of 3.4 μm was prepared.

(C) Porous carrier 7 to 10 As shown in Table 1, commercially available calcium silicate (trade name: Fluorite R, manufactured by Tokuyama) as the porous carrier 7 and commercially available light carbonic acid as the porous carrier 8. Calcium (trade name:
Light calcium carbonate, manufactured by Maruo Calcium), commercially available heavy calcium carbonate as a porous carrier 9 (trade name: Super SS, manufactured by Maruo Calcium), and a porous carrier 10.
Commercially available hydroxyapatite (trade name: tricalcium phosphate, manufactured by Yoneyama Chemical Co., Ltd.) was prepared as a porous carrier (Z).

(2) Preparation of Porous Composite (ZV) In Examples 1 to 6, the prepared slurries of the porous carriers (Z) 1 to 5 and 7 obtained in (1) above are shown in Table 2. The inorganic receptor (V) was added and mixed, and spray-dried to prepare a porous composite (ZV). The spray drying conditions were such that the particle size during spraying was about 0.1 μm and the hot air temperature at the inlet was 250 ° C. In Comparative Examples 7 to 10, the porous carrier (Z) 6-1 obtained or prepared in the above (1) was used.
Inorganic receptor (V) shown in Table 2 was compounded in a slurry having a solid content concentration of 25% with a porous composite (Z
V) was prepared. Further, in Comparative Examples 1 to 6, the above (1)
Porous carrier (Z) 1-5 and 7 obtained or prepared in
Was used as it was instead of the porous composite (ZV).

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

Examples 7 to 12 and Comparative Examples 12 to 22 Using the porous composites (ZV) and porous carriers (Z) obtained in Examples 1 to 6 and Comparative Examples 1 to 11, the following compositions were used. A composition for coating the ink absorbing layer was prepared. (Raw materials and formulations) Samples (Examples, Comparative Examples) 100 parts Polyvinyl alcohol 40 parts Ammonium chloride 5 parts Water 300 parts On the other hand, a high-quality paper having a basis weight of 80 / m ² was used as a substrate, and Dry coating amount of coating composition 20g / m
^A coating layer was coated by a blade coater method at a ratio of ² and dried by a conventional method to obtain a recording sheet. Table 4 shows the results of evaluation of recording characteristics. From Table 4, it can be seen that the paper compositions prepared in Examples 7 to 12 have excellent water absorption characteristics and image characteristics.

<Evaluation of recording characteristics> 1) Dot shape factor Commercially available ink jet printer (PM-8 manufactured by EPSON)
30C), a single color dot made of black ink is printed, and as an evaluation of ink bleeding, the dot perimeter and the dot area are measured with an image analyzer (Luzex 5000, manufactured by Nireco), and the shape factor SF2 is determined. I calculated.
The shape factor SF2 is an index that is closer to 100 as it approaches a perfect circle.

2) Evaluation of ink absorbency and image sharpness The degree of ink bleeding at the boundary between solid color solid print portions was visually determined. ◎ 、 ○ 、 △ 、 × 、
It was divided into four ranks.

3) Evaluation of Image Density The area solidly printed with black ink was measured using a reflection densitometer (Macbeth RD 918). The higher the numerical value, the higher the image density, which is good, but normally, 1.25 or more is good.

4) Glossiness Glossiness was visually evaluated from the lateral angle of 20 ° with respect to the printed portion according to the following criteria. ⊚: It has the same level of glossiness as silver halide color photographs. ◯: Inferior to a color photograph, but has a high glossy feeling. Δ: It has a glossiness comparable to that of coated paper printing. X: A glossy feeling similar to that of general PPC.

5) Evaluation of coating layer strength The surface of the ink receiving layer was rubbed with a black cloth, and the amount of the coating layer attached to the black cloth was visually evaluated according to the following criteria. ⊚: Does not adhere. ○: Adhered only slightly. Δ: Slightly adhered. X: Adhesion is noticeable.

6) Comprehensive Evaluation The suitability as a resin composition for the ink absorbing layer coating layer was evaluated according to the following criteria as a comprehensive judgment. A: Preferred as recording paper. B: Relatively preferable as recording paper. C: It is not preferable as a recording sheet. D: Not preferable as recording paper.

[0036]

[Table 4]

Examples 13 to 18 and Comparative Examples 23 to 33 A vinyl acetate resin emulsion coating composition was prepared by adding the raw materials having the following formulations and mixing them by vigorous stirring with a dissolver. Table 5 shows the paint evaluation results. From Table 5, it can be seen that the coating compositions prepared in Examples 13 to 18 have excellent viscosity characteristics, dispersion characteristics, and work characteristics.

(Raw materials and formulation) 7 parts of each sample (Example, Comparative example) Resin component / vinyl acetate resin emulsion 45 parts Coloring pigment, titanium dioxide (anaters type) 40 parts Extender pigment, heavy calcium carbonate 35 parts Thickener / Nitrocellulose 4 parts Plasticizer / DOP 60 parts 7 parts of water

<Evaluation of Paint> 1) Matte Effect The prepared paint was applied to mirror-coated paper using Barcoder # 4 and left at room temperature for 24 hours to prepare a coated plate. The obtained coated plate was measured with a digital gloss meter (GM-3D,
Murakami Color Research Laboratory) 60 ° and 75
The gloss was measured.

2) Paint viscosity The obtained paint was measured with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 60r.
pm, viscosity of 20 rpm and Ti value (20 rpm / 60 rp
m) was measured.

3) Appearance The obtained coating material was actually applied to the inner wall surface of concrete, and the spots on the surface of the coating film were visually judged according to the following criteria. A: No spots are observed. B: A few spots are observed. C: Some hard spots are recognized. D: Many spots are recognized.

4) Stability over time After the prepared coating material was allowed to stand at room temperature for half a year, the sedimentation state was visually evaluated according to the following criteria. A: No sediment is observed. B: A slight sediment is observed, but there is no problem as a paint. C: Some precipitate is observed, but it is within a usable range as a paint. D: A considerable amount of sediment is observed, and it is difficult to recover the sediment, which is problematic as a paint.

5) Workability during coating preparation and application Workability was evaluated in two stages: good (A) and bad (B).

6) Comprehensive Evaluation The suitability as a matte coating composition was evaluated according to the following criteria as a comprehensive evaluation: A: Matte coating composition is preferable. B: Relatively preferable as a matte coating. C: If anything, it is not preferable as a matte coating. D: Not desirable as a matte coating.

[0045]

[Table 5]

[0046]

As described above, the porous inorganic composite of the present invention exhibits a high specific surface area while maintaining the uniformity and dispersibility of the particles of the porous carrier. Therefore, when blended in a papermaking composition, it exhibits excellent water absorption characteristics and image characteristics, and when blended in a coating composition, it exhibits excellent viscosity characteristics, dispersion characteristics, and work characteristics. You can

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) C09D 7/12 C09D 7/12 201/00 201/00 (72) Inventor Hiroshi Shibata Uozumi-cho, Akashi-shi, Hyogo Nishioka 1455 Address F Maruo Calcium Co., Ltd. F-term (reference) 4J002 AA011 AA021 AB011 AB041 BB001 BD121 BG001 CC031 CC161 CC181 CC191 CD001 CF001 CF211 CK021 CP031 DE076 DE106 DE136 DE146 DE01 KD046A01401 010 DK01 DJ01 DJ0360 EE03 4J038 HA446 KA20

Claims (9)

[Claims] 1. A composite comprising a carrier comprising porous inorganic particles (hereinafter referred to as a porous carrier (Z)) on which inorganic particles (hereinafter referred to as an inorganic receptor (V)) are carried, A porous inorganic composite (hereinafter referred to as a porous composite (ZV)), characterized in that the composite satisfies the following formulas (a) to (d). (A) 0.1 ≦ Dzv ≦ 30 (μm) (b) 1 ≦ αzv ≦ 5 where α = dzv50 / Dz
v (c) 0 ≦ βzv ≦ 2 where β = (dzv90-d
zv10) / dzv50 (d) 40 ≦ Szv ≦ 800 (m ² / g) where Dzv: average particle size (μm) αzv: porous of the porous composite (ZV) measured by a scanning electron microscope (SEM) photograph Coefficient βzv of porous composite (ZV): Sharpness of porous composite (ZV) dzv: 50% average particle diameter (μm) dzv90 of porous composite (ZV) measured by Microtrac FRA laser particle size distribution meter : Cumulative 90% particle diameter (μm) of sieve composite of porous composite (ZV) measured by Microtrac FRA laser particle size distribution meter dzv10: Porous composite (ZV) measured by Microtrac FRA laser particle size distribution meter ) Sieve passing side cumulative 10% Particle size (μm) Szv: B of porous composite (ZV) by nitrogen adsorption method
ET specific surface area (m ² / g) 2. The inorganic receptor (V) is represented by the following formula (e):
Porous composite (Z
V). (E) 0.001 ≦ Dv ≦ 1 (μm) (f) 50 ≦ Sv ≦ 1000 (m ² / g) where Dv: average of the inorganic receptor (V) measured by a transmission electron microscope (TEM) photograph Particle size (μm) Sv: BET of inorganic acceptor (V) by nitrogen adsorption method
Specific surface area (m ² / g) 3. The porous carrier (Z) has the following formula (g):
The porous composite (ZV) according to claim 1 or 2, which satisfies (j). (G) 0.1 ≦ Dz ≦ 20 (μm) (h) 1 ≦ αz ≦ 5 where α = dz50 / Dz (i) 0 ≦ βz ≦ 2 where β = (dz90-dz1
0) / dz50 (j) 5 <Sz <300 (m ² / g) where Dz: average particle diameter (μm) αz of the porous carrier (Z) measured by a scanning electron microscope (SEM) photograph: porous Dispersion coefficient βz of carrier (Z): Sharpness of porous carrier (Z) dz: Microtrack FRA 50% average particle diameter (μm) of porous carrier (Z) measured by laser type particle size distribution meter dz90: Microtrack FRA 90% particle size (μm) dz10: cumulative total of porous carrier (Z) passing through sieve of porous carrier (Z) measured by laser type particle size distribution meter 10% particle size (μm) Sz: BET of porous carrier (Z) by nitrogen adsorption method
Specific surface area (m ² / g) 4. The composite amount of the inorganic receptor (V) is 1 to 1000 parts by weight relative to 100 parts by weight of the porous carrier (Z), according to any one of claims 1 to 3. The porous composite (ZV) described. 5. The porous carrier (Z) comprises Ca / P = 16.
The porous composite (ZV) according to any one of claims 1 to 4, which is a calcium phosphate-based compound having 7 or less. 6. The porous composite (ZV) according to any one of claims 1 to 5, wherein the inorganic receptor (V) is colloidal silica. 7. A resin composition comprising the porous composite (ZV) according to claim 1 and a resin. 8. The resin composition according to claim 7, wherein the resin is a resin for paper. 9. The resin composition according to claim 7, wherein the resin is a paint resin.