JP2005179514A - Thermal insulation resin composition and coating and molding using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having an excellent thermal insulation ability. <P>SOLUTION: The thermal insulation resin composition comprises a binder resin and silica. The silica has the characteristics of (a) to (f). (a) The pore volume is larger than 1.6 ml/g and not more than 3 ml/g. (b) The specific surface area is 100-1,000 m<SP>2</SP>/g. (c) The modal pore diameter (D<SB>max</SB>) is larger than 5 nm. (d) Q<SP>4</SP>/Q<SP>3</SP>as measured by solid state Si-NMR is not less than 1.2. (e) It is amorphous. (f) The content of metal impurities is less than 100 ppm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a heat insulating resin composition containing a binder resin and silica, and a heat insulating paint and a molded body using the same.

  Conventionally, a resin composition (heat insulating resin composition) having heat insulating properties has been used for the purpose of imparting heat insulating properties to various objects from buildings to electrical appliances. By using such a resin composition at a location where heat insulation should be imparted, the heat insulation at that location can be improved.

  The heat insulating resin composition usually contains a binder resin and a heat insulating material as basic components. As the heat insulating material, silica or the like is mainly used for reasons such as low cost and excellent stability (for example, Patent Document 1).

JP 2003-42386 A

  However, the technique described in the above literature cannot be said to have sufficient heat insulation. Therefore, a resin composition having more excellent heat insulating properties has been demanded.

  The present invention has been made in view of the above-described problems. That is, the subject of this invention exists in providing the heat insulation resin composition which has the outstanding heat insulation, and the heat insulation coating material and heat insulation molding using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition having excellent heat insulating properties can be obtained by incorporating silica having specific characteristics into the resin composition as a heat insulating material. The present invention has been completed.

That is, the gist of the present invention is a heat insulating composition containing a binder resin and silica, wherein the silica has the following characteristics (a) to (f): Exists in things.
(A) The pore volume is larger than 1.6 ml / g and 3 ml / g or less (b) The specific surface area is 100 to 1000 m ² / g
(C) Moderate pore diameter (D _max ) is 5 nm or more (d) Q ⁴ / Q ³ value in solid Si-NMR is 1.2 or more (e) Noncrystalline (f) Metal impurities Content is 100ppm or less

Moreover, another gist of the present invention resides in a heat insulating paint characterized by containing the above heat insulating resin composition and a solvent.
Still another subject matter of the present invention resides in a heat insulating molded body characterized by containing the above heat insulating resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which has the outstanding heat insulation, a coating material, and a molded object can be provided.

[1] Heat insulating resin composition:
The heat insulating resin composition according to the present invention (hereinafter abbreviated as “the composition of the present invention” as appropriate) contains silica having specific characteristics and a binder resin.
Hereinafter, each component will be described.

[1-1] Silica:
The silica contained in the composition of the present invention (hereinafter referred to as “the silica of the present invention” as appropriate) will be described.

(1) Characteristics of silica of the present invention In the present invention, "silica" refers to hydrous silicic acid. The hydrous silicic acid is represented by the SiO ₂ .nH ₂ O characteristic formula. In the present invention, the effect is remarkable in so-called “silica gel” or micelle template type silica among silica.

  The silica of the present invention is characterized in that the pore volume is in a range larger than a normal value. Specifically, the value of the pore volume measured by the nitrogen gas absorption / desorption method is usually larger than 1.6 ml / g, preferably 1.8 ml / g or more, particularly preferably 1.85 ml / g or more. In addition, it is usually 3 ml / g or less, preferably 2.5 ml / g or less, particularly preferably 2.4 ml / g or less. As described above, since the pore volume of the silica of the present invention is in a large range, the composition of the present invention can have large voids therein, and thus exhibits high heat insulation. be able to. The pore volume can be determined from the amount of nitrogen gas adsorbed at an adsorption isotherm relative pressure of 0.98.

The value of the specific surface area is usually 100 m ² / g or more, preferably 200 m ² / g or more, more preferably 300 m ² / g or more, particularly preferably 350 m ² / g or more, usually 1000 m ² / g or less, Preferably it is 900 m < ² > / g or less, More preferably, it is 800 m < ² > / g or less, Most preferably, it is 700 m < ² > / g or less. The value of the specific surface area is measured by the BET method by nitrogen gas adsorption / desorption.

Furthermore, the silica 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 pore diameter (D _max ) is 5 nm or more. The upper limit is not particularly limited, but is usually 50 nm or less, preferably 30 nm or less. If the most frequent pore diameter (D _max ) is smaller than this range, the proportion of voids in the composition of the present invention is reduced, so that the heat insulating property is lowered. Further, if the mode pore diameter (D _max ) is larger than this range, the strength of silica is reduced, the pore structure of silica is broken with time, and there is a possibility that high heat insulation performance cannot be exhibited. .

In addition, the silica of the present invention has a total volume of pores in the range of ± 20% of the above-mentioned mode diameter (D _max ) value of usually 50% or more, preferably 60% of the total volume of all pores. % Or more, more preferably 70% or more. This means that the diameters of the pores of the silica of the present invention are uniform in the pores in the vicinity of the mode diameter (D _max ), that is, the pore diameter distribution is extremely narrow (sharp). . The upper limit of this ratio value is not particularly limited, but is usually 90% or less. When a partially brittle portion is generated in silica, the pore structure of the portion is broken and the heat insulating property is lowered. However, if the pore size distribution is small as described above, the structure of the silica of the present invention will be uniform, and therefore it will be difficult for the silica strength to vary and prevent the formation of partially fragile parts. Can do. For this reason, the whole composition of this invention can exhibit high heat insulation stably.

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

  Further, in addition to the characteristics of the pore structure described above, it is preferable that the silica of the present invention is amorphous, that is, no crystalline structure is observed in view of its three-dimensional structure. This means that when the silica of the present invention is analyzed by X-ray diffraction, a crystalline peak is not substantially observed. In the present specification, non-amorphous silica refers to a silica having at least one crystal structure peak at a position exceeding 6 angstroms (Å Units d-spacing) in the X-ray diffraction pattern. Amorphous silica is extremely superior in productivity in addition to high heat insulation compared to crystalline silica.

Furthermore, regarding the structure of the silica 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 —OSi bonded to the silica of the present invention. The value of ³ is usually 1.2 or more, preferably 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 this value, the higher the thermal stability of the silica. From this, it can be seen that the silica of the present invention is extremely excellent in thermal stability. That is, since the silica of the present invention is less likely to break the structure due to heat, the composition of the present invention can maintain high heat insulating properties 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 the silica of the present invention, the total content of metal elements (metal impurities) excluding silicon constituting the silica skeleton is usually 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, particularly preferably 5 ppm. In the following, it is most preferably 1 ppm or less, which is very low and extremely high purity. Such a small influence of impurities is one of the major factors that enable the silica of the present invention to exhibit excellent properties such as high heat resistance and water resistance. Moreover, since the silica of the present invention has high heat resistance and durability, the composition of the present invention can be used stably over a long period of time. In the present specification, “ppm” represents a ratio to weight.

  In addition, the silica of the present invention has one of its features that even when subjected to a heat treatment (hydrothermal resistance test) in water, the change in pore characteristics is small. Changes in the pore characteristics of silica after the hydrothermal resistance test are observed as changes in physical properties related to porosity such as specific surface area, pore volume, and pore size distribution. For example, in the silica of the present invention, when subjected to a hydrothermal resistance test at 200 ° C. for 6 hours, the specific surface area after the test is 20% or more with respect to the specific surface area before the test (the specific surface area residual ratio is 20% or more). ) Is preferable. The silica of the present invention having such characteristics is preferable because the porous characteristics are not lost even under severe use conditions for a long time. The residual ratio of the specific surface area is preferably 35% or more, particularly 50% or more.

  The silica of the present invention has very little deterioration of the characteristic that the pore diameter distribution is sharp and the change in the pore volume is very small or the pore volume is increased even after the hydrothermal treatment test. It has a characteristic that is not found in conventional silica.

  In addition, the hydrothermal resistance test in the present invention is to bring water at a specific temperature (200 ° C.) into contact with silica for a certain time (6 hours) in a closed system. Is present in water, even if the closed system is entirely filled with water, or a part of the system has a gas phase part under pressure, and there is water vapor in this gas phase part. Good. In this case, the pressure in the gas phase part may be, for example, 60000 hPa or more, preferably 63000 hPa or more. The error of the specific temperature is usually within ± 5 ° C., preferably within ± 3 ° C., particularly preferably within ± 1 ° C.

(2) Manufacturing method of the silica of this invention Then, the manufacturing method of the silica of this invention is demonstrated.
The method for producing silica according to the present invention is characterized in that silica hydrogel is hydrothermally treated, and the water content in the liquid component of the obtained slurry is reduced to 5% by weight or less, followed by drying.

  Specifically, the silicon alkoxide is hydrolyzed, and the resulting silica hydrogel is preferably hydrothermally treated without substantial aging, and then contacted with a hydrophilic organic solvent and then dried to obtain silica in the silica. It is characterized by removing water.

  The manufacturing method of silica hydrogel 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.

  The silicon alkoxide used as a raw material for the silica of the present invention includes a lower alkyl group having 1 to 4 carbon atoms such as trimethoxysilane, tetramethoxysilane, triethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Examples thereof include tri- or tetraalkoxysilanes or oligomers thereof. Among these, tetramethoxysilane, tetraethoxysilane and oligomers thereof, particularly tetramethoxysilane and oligomers thereof are preferable because silica 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. 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 of these metal impurities can be measured by the same method as the method for measuring the impurity content in general silica.

  In the present invention, first, in the hydrolysis / condensation step, the silicon alkoxide is hydrolyzed in the absence of a catalyst and the silica hydrosol obtained 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. This reaction time is preferably a time at which the fracture stress of the hydrogel does not exceed 6 MPa in order to obtain a silica having excellent pore characteristics such as the silica of the present invention.

  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 is not preferable in the production of the silica gel of the present invention because it causes aging of the produced hydrogel, as will be described later.

  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. 30 rpm or more, 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. Furthermore, the deposits on the inner wall may be peeled off and mixed into the product to deteriorate the quality. For these reasons, the stirring speed is preferably 2000 rpm or less, and more preferably 1000 rpm or less.

  In the present invention, any stirring method can be used as the stirring method for the two liquid phases (aqueous phase and silicon alkoxide phase) which are separated, 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 devices as described above (a) and (b) is the peripheral speed of the stirring blade (stirring blade tip speed), 0.05 to 10 m / s, especially 0.1. -5 m / s, more preferably 0.1-3 m / s.

  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 present invention, as a physical property adjusting step, hydrothermal treatment of the silica hydrogel is performed without substantially aging so that the hardness of the silica hydrogel generated by the above 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 difficult to produce the silica of the present invention by 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 hydrothermal treatment is generally performed within 10 hours from the time when the silica hydrogel is formed, and the hydrothermal treatment is preferably performed within 8 hours, more preferably within 6 hours, particularly within 4 hours. It is preferable.

  Moreover, in an industrial plant etc., the case where the silica hydrogel produced | generated in large quantities is once stored in a silo 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, the following can be considered.

  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 considered that the silica hydrogel does not age.

  Therefore, in 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 hydrolysis of silicon alkoxide is pulverized before hydrothermal treatment so that the average particle size is 10 mm or less, especially 5 mm or less, more preferably 1 mm or less, particularly 0.5 mm or less. Etc. are preferably applied.

  As described above, as a method for producing the silica 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 production method of the present invention, it is sufficient that the hydrothermally-treated silica hydrogel is not aged, so that it is not necessarily immediately after the formation of the hydrogel, for example, by hydrothermal treatment after standing at a low temperature for a while. Does not require hydrothermal 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 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. The fracture stress is preferably 3 MPa or less, and particularly preferably 2 MPa or less.

  As conditions for this hydrothermal treatment, the state of water may be either liquid or gas, but it is preferable to perform hydrothermal treatment using liquid water as a slurry in addition to silica hydrogel. 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 longer, preferably 1 hour or longer, and usually 100 hours or shorter, preferably 10 hours or shorter. 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 hydrothermal treatment is performed with the temperature lowered to 1, silica having excellent pore characteristics and a large pore volume can be produced. Even if hydrothermal treatment is performed with water containing a solvent, the silica 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 is formed on a substrate such as a particle, a substrate, or a tube in the form of a film or a layer 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 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 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 obtained silica tends to gradually decrease after reaching a 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 the purpose of changing the physical properties of silica, it is usually at a higher temperature than the hydrolysis reaction conditions described above. It is preferable to do.

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

  A temperature raising method using a heat exchanger or the like or a temperature raising method in which hot water prepared in advance is used is preferable because the temperature raising 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, which may reduce the microstructural homogeneity.

  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 can be preheated.

When the hydrothermal treatment temperature and time are set outside the above ranges, it is difficult to obtain the silica of the present invention. For example, if the hydrothermal treatment temperature is too high, the pore diameter and pore volume of silica become too large, and the pore distribution is also widened. On the other hand, if the hydrothermal treatment temperature is too low, the resulting silica has a low degree of crosslinking, poor thermal stability, no peaks in the pore distribution, or Q ⁴ / Q ³ value may become 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, when the temperature of the hydrothermal treatment is usually 30 ° C. or higher, preferably 40 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, the hydrophobicity is particularly high. The ammonia concentration here is preferably 0.001% by weight or more, particularly preferably 0.005% by weight or more, preferably 10% by weight or less, and particularly preferably 5% by weight.

  A large amount of water is contained in the silica obtained through the hydrothermal treatment described above. For example, the silica after hydrothermal treatment is obtained as silica containing a large amount of water (for example, silica slurry). In the method for producing silica of the present invention, it is important to remove this water. Specifically, an operation of bringing the silica slurry into contact with a hydrophilic organic solvent, replacing water with the hydrophilic solvent, and then drying the silica is most important.

  In the present invention, by replacing the water contained in the silica with a hydrophilic organic solvent and drying, the silica shrinkage in the drying process can be suppressed, and the pore volume of the silica can be maintained large. Silica having excellent properties 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 slurry after the hydrothermal treatment are water. Since this water interacts strongly with silica, it is considered that a large amount of energy is required to completely remove the water from the silica.

  When a drying process (for example, heat drying) is performed under a condition where a large amount of moisture is present, the water subjected to thermal energy reacts with unreacted silanol groups, and the structure of silica changes. Among the structural changes, the most prominent change is the condensation of the silica skeleton, and it is considered that the silica is locally densified by the condensation. Since the silica skeleton has a three-dimensional structure, local condensation of the skeleton (densification of the silica skeleton) affects the pore characteristics of the entire silica particles composed of the silica 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 slurry with a hydrophilic organic solvent, it is possible to remove the water in the silica slurry and suppress the silica shrinkage as described above. Become.

  The hydrophilic organic solvent used in the present invention may be any solvent that dissolves a lot of water based on the above-described idea. Among them, those having large intramolecular polarization are preferable. More preferably, the relative dielectric constant is 15 or more.

  In the method for producing silica according to the present invention, in order to obtain high-purity silica, it is necessary to remove the hydrophilic organic solvent in a drying step after removing water with the hydrophilic organic solvent. 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. The boiling point of the hydrophilic organic solvent is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and particularly preferably 100 ° C. or lower.

  Specific examples of hydrophilic organic solvents include 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. Of course, the water content in the hydrophilic organic solvent is preferably as low as possible, and is usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

  In the present invention, the temperature and pressure during the substitution treatment with the above-described hydrophilic organic solvent are arbitrary. The treatment temperature is usually 0 ° C. or higher, preferably 10 ° C. or higher, usually 100 ° C. or lower, and preferably 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 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 0.5 to 10 times the volume of the bulk volume of silica. This replacement operation with a hydrophilic organic solvent is preferably repeated a plurality of times because water replacement is more reliable.

  The contact method of the hydrophilic organic solvent and the silica slurry is arbitrary, for example, a method of adding the hydrophilic organic solvent while stirring the silica slurry in a stirring tank, or packing the silica separated 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 moisture in the liquid component of the silica slurry. For example, the silica 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.

  After the substitution operation with the hydrophilic organic solvent, the silica of the present invention can be produced by separating the silica and the 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 particles. One of these separation methods may be used alone, or two or more may be used in any combination.

  The obtained silica is usually dried at 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 drying can be performed quickly, but also the pore volume and specific surface area of the resulting silica are increased.

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

[1-2] Binder resin:
Subsequently, the binder resin will be described.
There is no restriction | limiting in particular about the binder resin of this invention, A well-known binder resin can be used arbitrarily.
Specific examples of the binder resin include nitrocellulose, cellulose acetate, cellulose butyrate, ethyl cellulose, polyamide resin, chlorinated rubber, cyclized rubber, polyvinyl chloride resin, vinyl chloride / vinyl acetate copolymer resin, and ethylene / vinyl acetate copolymer. Resin, thermoplastic resin such as chlorinated polypropylene or acrylic resin, alkyd resin, amino alkyd resin, urea resin, melamine resin, phenol resin, resorcinol resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide, Examples thereof include thermosetting resins such as polyamideimide, polybenzimidazole, polybenzothiazole, and polyurethane resin.

In addition to resins such as styrene maleic resin, polyvinyl chloride, polyvinyl acetate resin, acrylic resin, polyurethane resin, natural rubber, recycled rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide Rubbers such as rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), ethylene propylene rubber, block copolymer rubber (SBS, SIS, SEBS, etc.) can also be used as the binder resin.
Moreover, the said binder resin may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[1-3] Composition:
The composition of the present invention varies depending on the use, but the silica of the present invention is usually 10% by weight or more, preferably 20% by weight or more, more preferably 40% by weight or more, and usually 90% by weight or less, preferably 80% by weight. % Or less, more preferably 60% by weight or less. If the content of the silica of the present invention is smaller than this range, there is a possibility that sufficient heat insulation cannot be exhibited, and if it is larger than this range, the binder resin may not be able to hold the silica of the present invention. is there.

  In the composition of the present invention, the binder resin is usually 10% by weight or more, preferably 20% by weight or more, more preferably 40% by weight or more, and usually 90% by weight or less, preferably 80% by weight or less. Preferably it is contained in 60% by weight or less. If the content of the binder resin is smaller than this range, the silica of the present invention may not be retained, and if it is larger than this range, sufficient heat insulating properties may not be exhibited.

  Further, in the composition of the present invention, the ratio of the silica of the present invention to the binder resin (silica / binder resin) is usually 0.1 or more, preferably 0.5 or more, and more preferably 0.00 by weight ratio. It is 8 or more, usually 10 or less, preferably 8 or less, more preferably 5 or less. If the ratio is smaller than this range, sufficient heat insulation may not be exhibited, and if the ratio is larger than this range, the binder resin may not be able to hold the silica of the present invention.

  As described above, since the composition of the present invention contains the silica and binder resin of the present invention, the composition contains a large number of large pores formed in the silica of the present invention. In addition, since the silica of the present invention is amorphous, the composition of the present invention can exhibit high heat insulation because it has high heat insulation.

  Furthermore, since the pore diameter distribution of the silica of the present invention has a sharp and uniform structure, the silica of the present invention has a uniform strength, and therefore the composition of the present invention has high durability. , Stable and high heat insulation can be achieved.

  In addition to the silica and binder resin of the present invention, the composition of the present invention can be made into a composite functional composition by adding a known function by adding a known substance. Specifically, there are cases where chemical resistance, deodorant properties, abrasion resistance, weather resistance, antibacterial properties and the like are imparted.

[1-4] Use of composition:
The use of the composition of the present invention is optional, but for example, it can be used by molding into a molded body, or it can be used as a paint together with a solvent.
Hereinafter, a molded object and a coating material are demonstrated as an example of the use of the composition of this invention.

[2] Molded body:
The composition of the present invention can be used as a molded body having heat insulating properties (hereinafter, appropriately referred to as “the molded body of the present invention”) by molding into a desired shape.
The molding method is arbitrary, but for example, it can be molded by performing press molding, extrusion molding (T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.), injection molding, or the like. Further, for example, two-color molding, injection blow molding, or the like may be performed, and by these, a molded product with good dimensional accuracy can be obtained.

  In addition, the composition of the present invention may be molded as it is, but depending on the usage of the molded body, the composition of the present invention may be added with a plasticizer, a stabilizer, a surfactant, a crosslinkable substance, a filler, a colorant, After blending an appropriate amount of other components such as fibers (glass fiber, carbon fiber, etc.) as a reinforcing material, this can be used as a molded body.

The shape of the molded body of the present invention is arbitrary, and for example, it can be molded into a shape such as a flat plate shape, a sheet shape, a block shape, or a pipe shape.
Further, the molded body 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 be performed.

  In addition, when using the composition of this invention as a layered molded object, you may comprise as a single | mono layer structure which consists only of the layer containing the composition of this invention, and the layer containing the composition of this invention You may comprise as a laminated structure which consists of a several layer containing.

  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 composition of the present invention. As a laminating method, for example, a film of the composition of the present invention, a method of melt-extruding other resin or the like on a sheet, a method of melt-extruding the composition of the present invention on a substrate made of other resin, A method of co-extrusion of the composition and another resin, and further, a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, and the like. And a method of laminating using an agent. 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, and a container.

[2-2] Composition of molded body:
The ratio of the silica of the present invention in the molded body of the present invention is usually 10% by weight or more, preferably 20% by weight or more, more preferably 40% by weight or more, and usually 90% by weight or less, preferably 80% by weight or less. More preferably, it is desired to be 60% by weight or less. If the content of the silica of the present invention is smaller than this range, there is a possibility that sufficient heat insulation cannot be exhibited, and if it is larger than this range, the binder resin may not be able to hold the silica of the present invention. is there.

  The ratio of the binder resin in the molded body of the present invention is usually 10% by weight or more, preferably 20% by weight or more, more preferably 40% by weight or more, and usually 90% by weight or less, preferably 80% by weight or less. More preferably, it is desired to be 60% by weight or less. If the content of the binder resin is smaller than this range, the silica of the present invention may not be retained, and if it is larger than this range, sufficient heat insulating properties may not be exhibited.

  Further, in the molded article of the present invention, the ratio of the silica of the present invention to the binder resin (silica / binder resin) is usually 0.1 or more, preferably 0.5 or more, and more preferably 0.00 by weight ratio. It is 8 or more, usually 10 or less, preferably 5 or less, more preferably 2 or less. If the ratio is smaller than this range, sufficient heat insulation may not be exhibited, and if the ratio is larger than this range, the binder resin may not be able to hold the silica of the present invention.

  The molded body of the present invention described above has high heat insulating properties. In addition, since silica with excellent durability and water resistance is used, high durability and water resistance can be achieved by appropriately selecting the binder resin and other components to be used in combination so as not to impair this property. Can be made. Therefore, the molded body of the present invention can be used as an excellent heat insulating material. Specifically, it can be used in various places such as electronic devices such as personal computers, household electrical appliances such as refrigerators, transportation equipment such as vehicles and ships, and buildings such as houses and factories.

[3] Paint:
The composition of the present invention can also be used as a paint having heat insulating properties (hereinafter appropriately referred to as “the paint of the present invention”) by dissolving or dispersing in a solvent.
Hereinafter, the paint of the present invention will be described.

  The paint of the present invention contains the composition of the present invention and a solvent. Specifically, the above-described silica (silica of the present invention) and binder resin, which are components of the composition of the present invention, are dissolved or dispersed in a solvent. The order of blending is not particularly limited, and the silica and binder resin may be mixed first to form a composition (composition of the present invention) and then dissolved or dispersed in a solvent. You may melt | dissolve or disperse | distribute to a solvent separately. Regardless of the order of blending, it is sufficient that the finally obtained coating material contains silica and binder resin, which are components of the composition of the present invention, in a state dissolved or dispersed in a solvent.

[3-1] Solvent:
As the solvent, as long as it can dissolve or disperse the above-described binder resin and the silica of the present invention, there is no other limitation on the type thereof, without damaging the target when performing coating or impregnation, And what can be easily removed by drying or heating is preferred. In addition, as a solvent here, the water as a dispersing agent in aqueous emulsion is also included.

Specific examples of the solvent that can be used include, for example, chain hydrocarbons such as neopentane, n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as trichloroethylene and perchloroethylene, and methanol. Alcohols such as ethanol, 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 and butyl sorb, water, etc. .
The said solvent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[3-2] Composition of paint:
The ratio of the silica of the present invention in the paint of the present invention is usually 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 40% by weight or less, preferably 30% by weight or less, More preferably, it is 25% by weight or less. If the silica content of the present invention is less than this range, the paint may not exhibit sufficient heat insulation after application, and if it exceeds this range, the applicability of the composition may be reduced. It is.

  The ratio of the binder resin in the paint of the present invention is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and usually 50% by weight or less, preferably 40% by weight or less. More preferably, the content is 30% by weight or less. This is because if the binder resin content is less than this range, the adhesion of the paint may be reduced, and if it is greater than this range, the heat insulation after application of the paint may be reduced.

  Furthermore, the ratio of the solvent in the paint of the present invention is usually 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and usually 90% by weight or less, preferably 80% by weight or less, More preferably, it is 70 wt% or less. If the solvent content is lower than this range, the coating property of the paint may be lowered. If the solvent content is higher than this range, the amount of silica or binder resin contained in the paint will be too small, and drying may be caused. This is because it takes a long time and the workability may be deteriorated.

  Further, the ratio of the silica of the present invention to the binder resin (silica / binder resin) in the paint of the present invention is usually 0.1 or more, preferably 0.5 or more, more preferably 0.8 by weight ratio. In addition, it is usually 10 or less, preferably 8 or less, more preferably 5 or less. If the above ratio is smaller than this range, there is a possibility that sufficient heat insulating properties cannot be exhibited. If it is larger than this range, the binder resin retains the silica of the present invention when the paint is dried. There is a risk of being unable to understand.

[3-3] Other components in the paint:
In addition to the composition and solvent of the present invention, the paint of the present invention may contain other substances.
For example, you may mix a coloring material in order to color the coating material of this invention. As the color material, various known color materials can be arbitrarily selected and used. For example, inorganic pigments, organic pigments, dyes, and the like can be used.

  Specific examples of inorganic pigments include natural inorganic pigments such as clay, barium sulfate, calcium carbonate, mica, mica-like iron oxide, ocher, lead white, red lead, yellow lead, silver vermilion, ultramarine, bitumen, cobalt oxide, Synthetic inorganic pigments such as titanium, titanium dioxide coated mica, strontium chromate, titanium yellow, titanium black, carbon black, graphite, zinc chromate, iron black, molybdenum red, molybdenum white, risurge, lithopone, aluminum, gold, silver, copper , Metals such as zinc and iron.

  Specific examples of organic pigments include dye lakes dyed on extender pigments and raked with a precipitant, azo pigments such as soluble azo, insoluble azo, condensed azo, phthalocyanine pigments, nitroso pigments, nitro pigments Examples thereof include pigments, basic dye pigments, acid dye pigments, vat dye pigments, and mordant dye pigments.

Examples of other color materials that can be used include granular, sandy, and powdery materials such as glass, ionomer, AS, ABS, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, polyamide, polyethylene, and polyethylene terephthalate. , Polyvinylidene chloride, polyvinyl chloride, polycarbonate, polyvinyl acetate, polystyrene, polybutadiene, polypropylene and other thermoplastic resins (plastics), epoxy resins, xylene resins, phenolic resins, unsaturated polyester resins, polyimides, polyurethanes, maleic acid resins And thermosetting resins such as melamine resin and urea resin, which may be colored or non-colored.
Moreover, said color material may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Furthermore, you may mix an additive with the coating material of this invention suitably. The additive to be used is not particularly limited, and examples thereof include various plasticizers, curing agents, pigment dispersants, emulsifiers, drying agents, antifoaming agents, antiseptics, antifreezing agents, and thickeners. .

[3-4] Properties of paint:
Since the above-described coating material of the present invention contains silica and binder resin, which are the components of the composition of the present invention, the coating film obtained by applying the same comprises the composition of the present invention (or the present invention). Forming a layer containing the composition of the invention. Therefore, the coating film to which the coating material of the present invention is applied exhibits high heat insulating properties and suppresses the temperature rise, so that peeling of the coating film and deterioration of the coloring material can be prevented, and durability and weather resistance are also improved. Excellent. In addition, since the coating target is covered with silica having a large pore volume, it exhibits excellent physical properties such as waterproofness and soundproofing.

  By the way, in the coating material of the present invention, when the binder resin enters the pores of the silica of the present invention and fills the pores, there is a possibility that the heat insulating property of the coating material is lowered. Therefore, it is preferable that the binder resin does not fill the pores of the silica of the present invention. For this purpose, for example, the following method can be cited.

  For example, a binder resin and a solvent having properties that do not easily enter the pores of the silica of the present invention are selected. Examples of the binder resin and solvent having such properties include those having a large contact angle with respect to the silica of the present invention.

  For example, it is preferable to disperse the binder resin in the solvent in a state having a diameter larger than the pore diameter. That is, a binder resin that is insoluble in a solvent is selected, and the binder resin becomes an aggregate having a diameter larger than the pore diameter of the silica of the present invention. Specifically, the coating material of the present invention may be dispersed so that the binder resin becomes a colloid or particle having a diameter larger than the pores of the silica of the present invention in a solvent.

[3-5] How to use paint:
The paint of the present invention can be used for various objects, and the method of use is also arbitrary. Specific examples include applying to a base material to be applied, or separately preparing a layer of the paint of the present invention and placing the layer on the surface of the application target.

  There is no restriction | limiting in particular about the base material used as the application object of the coating material of this invention, The coating material of this invention can be apply | coated using arbitrary things as a base material. Specific examples of the substrate include films, sheets, and plate materials made of paper, plastic, wood, concrete, metal, and the like.

  Examples of the method of use include a method in which the coating material of the present invention is applied to a substrate to be coated and dried to form a coating film on the substrate surface. The formed coating film is a layer of the composition of the present invention containing the silica of the present invention and a binder resin, and has high heat insulating properties, so that the substrate on which the coating film is formed acquires high heat insulating performance. be able to.

  Here, there is no restriction | limiting in particular about the application | coating method, The method used normally can be used arbitrarily. Specific examples include brush coating, spraying, electrostatic coating, roll coating, dip coating, and bar coating. In addition, you may perform these application | coating methods combining suitably.

  Moreover, there is no restriction | limiting in particular about the method of drying the coating material of this invention after application | coating, Arbitrary methods can be used. For example, methods such as natural drying, baking, ultraviolet irradiation, and electron beam irradiation may be used as appropriate according to the properties of the paint of the present invention. These drying methods may be combined appropriately.

  As another example of the usage method, the impregnating member (hereinafter referred to as “impregnating member” as appropriate) is impregnated and solidified with the paint of the present invention, and the impregnating member is placed on the surface of the substrate to be coated. You may make it do. The above impregnating member impregnated and solidified with the paint of the present invention is obtained by molding the composition of the present invention and corresponds to the molded article of the present invention.

  The impregnating member impregnated with the coating material of the present invention is arbitrary, and the material and shape thereof can be arbitrarily selected according to the application. Specific examples thereof include felts, non-woven fabrics, cloth materials, papers, and ceramic sheets made of natural fibers, synthetic fibers, rock wool, glass fibers, carbon fibers and the like. In addition, the impregnating member here includes not only impregnating all but impregnating part of the composition of the present invention. For example, when impregnation is performed from one side of the thickness of the impregnating member, the other side is not impregnated, thereby causing a difference in properties (e.g., adhesion) between the one side of the impregnating member and the other side. This difference may be used (such as bonding the other side).

  There is no particular limitation on the impregnation method, and the impregnation may be performed by any method. For example, there are a method of immersing the impregnating member in a tank filled with the paint of the present invention (so-called dipping) and a method of applying from one or both sides of the impregnating member by a known application means. After the coating material of the present invention has sufficiently penetrated, whether the surplus is scraped or removed by a suitable scraping device or removal device such as a suction doctor, a doctor roll, or a wire bar in which a wire is wound around a round bar. Then, the impregnating member is impregnated with a predetermined amount of the composition of the present invention. These impregnation methods may be combined as appropriate.

  After impregnation, the impregnating member is dried to remove the solvent, and the impregnating member is placed on the substrate. Thereby, the heat insulation layer containing the silica of this invention and binder resin can be formed in the base-material surface, and a base material can acquire high heat insulation performance.

  Moreover, when forming a coating film in a base material using the coating material of this invention, or installing a heat insulation layer, it can also implement 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 the base material and the coating film of the coating material of the present invention, and is a layer made of an appropriate material according to the kind of the base material and the properties of the composition of the present invention. By forming the primer layer, for example, the adhesion of the paint film of the present invention to the base material is improved to improve the durability of the product, or the smoothness of the base material surface is improved. It is effective in forming a uniform coating film of the composition. 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 of the paint of the present invention, 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 by combining two or more appropriately. Further, a transparent resin protective layer may be formed on the outermost surface subjected to makeup by applying a transparent resin paint or laminating a transparent resin sheet. However, when the paint of the present invention contains a color material, it is possible to improve the design by using the paint of the present invention for drawing or the like instead of using a cosmetic coat.

  In addition, these primer layers, decorative coats, transparent resin protective layers, etc. are formed directly on the base material, coating film, heat insulating layer, etc., and are applied to another member such as appropriate paper or plastic sheet to form the base material. You may make it install what was created as a sheet | seat separate from a coating film, a heat insulation layer, etc. Further, an adhesive layer or a pressure-sensitive adhesive layer may be provided between the substrate, the primer layer, the heat insulating layer, the coating film, the decorative coat, the transparent resin protective layer, and the like.

[4] Other:
Although the present invention has been described in detail above, the present invention is not limited to the above description and can be implemented with appropriate modifications.
For example, the usage form of the heat-insulating resin composition of the present invention is not limited to the above-described molded body and paint, and can of course be used in other forms.

  The heat insulating resin composition, the heat insulating paint, and the heat insulating molded body of the present invention are, for example, buildings such as houses and factories, or roofs of structures such as refrigerators, storage tanks, trains, airplanes, cars, and ships, It is suitable for use to enhance the heat insulation properties of the ceiling, outer wall, inner wall and the like.

Claims (7)

A heat insulating resin composition containing a binder resin and silica,
The heat-insulating resin composition, wherein the silica has the following properties (a) to (f).
(A) The pore volume is larger than 1.6 ml / g and 3 ml / g or less (b) The specific surface area is 100 to 1000 m ² / g
(C) Moderate pore diameter (D _max ) is 5 nm or more (d) Q ⁴ / Q ³ value in solid Si-NMR is 1.2 or more (e) Noncrystalline (f) Metal impurities Content is 100ppm or less The heat insulating resin composition according to claim 1, wherein the silica has a pore volume of 1.8 to 3 ml / g. The heat insulating resin composition according to claim 1, wherein the mode pore diameter (D _max ) of the silica is 50 nm or less. 2. The volume of pores in which the pore diameter of the silica is in the range of ± 20% of the mode pore diameter ( _Dmax ) is 50% or more of the total pore volume. The heat insulating resin composition according to any one of -3. The heat insulating property according to any one of claims 1 to 4, wherein a differential pore volume at a mode pore diameter ( _Dmax ) of the silica is 2 ml / g or more and 40 ml / g or less. Resin composition. A heat insulating paint comprising the heat insulating resin composition according to any one of claims 1 to 5 and a solvent. A heat-insulating molded product comprising the heat-insulating composition according to any one of claims 1 to 5.