CN107074564B - Hydrophobic silica and method for producing same - Google Patents
Hydrophobic silica and method for producing same Download PDFInfo
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- CN107074564B CN107074564B CN201580045419.1A CN201580045419A CN107074564B CN 107074564 B CN107074564 B CN 107074564B CN 201580045419 A CN201580045419 A CN 201580045419A CN 107074564 B CN107074564 B CN 107074564B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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Abstract
The present invention relates to hydrophobic silica and a method for producing the same. The amount of silicone oil released from the hydrophobic silica (i) in toluene was less than 0.2% by mass of the hydrophobic silica, and the amount of the released silicone oil was obtained by dispersing the hydrophobic silica (i) in toluene at a concentration of 2% and comparing the amount of the released silicone oil with that before the dispersion after 24 hours at 20 ℃. The method comprises the following steps: the hydrophobic silica is obtained by coating the surface of wet-process synthetic silica with silicone oil in the presence of a strong acid strong base type neutral salt compound and then subjecting the coated silicone oil to a condition in which the coated silicone oil forms a siloxane bond with a silanol group of the wet-process synthetic silica. Disclosed is a hydrophobic silica which can reduce silanol groups and unreacted silicone oil on the surface of a silica that has been released and eluted, while maintaining the degree of hydrophobization indicated by the M value and the DBA adsorption at target values after a hydrophobization treatment.
Description
Technical Field
The present invention relates to hydrophobic silica and a method for producing the same. More specifically, the present invention relates to hydrophobic silica in which release of silicone oil is suppressed, and a method for producing the same.
Cross reference to related applications
Priority of japanese patent application No. 2014-250355 filed 12/10/2014, the entire disclosure of which is incorporated by reference in this specification as a specific disclosure.
Background
A pigment in which the surface of a hydrophilic powder pigment is coated with a hydrophobic dimethylpolysiloxane compound (hereinafter referred to as "silicone oil") to make the surface hydrophobic is widely known. In particular, hydrophobic wet process synthetic silica (hereinafter referred to as "hydrophobic silica") hydrophobized with silicone oil on the surface thereof is widely used as an antifoaming agent, a matting agent for coating materials, an anti-blocking agent for films, and the like.
When hydrophobic silica is used for coating applications, in addition to the conventional matting performance, the water repellency of the surface of the coating film can be improved, and not only the antifouling function, the alkali resistance function, and the chemical resistance function are imparted, but also the flaw resistance of the surface of the coating film can be improved. Due to such characteristics, the use of hydrophobic silica has recently increased, particularly in the use of delusterants for plastic coatings for application to the surfaces of home appliances or electronic devices.
Further, the use of hydrophobic silica having an average particle diameter made fine is also used for the purpose of imparting antiglare properties in addition to the above-mentioned functions in applications to transparent films and glass surface coating agents (for example, patent document 1).
Further, when the silica is filled in a resin or a film material, it has advantages such as easy processing and improved transparency because it absorbs less moisture as compared with untreated wet-process synthetic silica, and thus has attracted attention.
Hydrophobic silica having a hydrophobic function can be produced by merely mixing a wet synthetic silica as a raw material with a silicone oil, but various methods have been studied for the purpose of improving the hydrophobic performance.
For example, in patent document 2, a silicone oil having a viscosity of 50 centistokes (unit: cSt) is sprayed onto a wet-process synthetic silicic acid, and the resultant is heated at a temperature of 250 to 350 ℃ for about 1/2 to 2 hours to obtain a hydrophobic silica.
As a method for obtaining hydrophobic silica having higher hydrophobicity, patent document 3 describes a method in which a hydroxide of an alkali metal (sodium hydroxide) is added to wet-process synthetic silica to be used as a catalyst. Further, patent document 4 proposes to use ammonia, amines, or the likeA method of heat treatment at a relatively low temperature of 60 to 150 ℃ using the catalyst. Patent document 5 proposes the use of SiO2100 parts by weight of Al2O3A method for hydrophobizing silica containing 0.5 parts by weight or more of aluminum at a low temperature of about room temperature to 100 ℃.
In the above-mentioned method for the purpose of imparting hydrophobic properties to hydrophilic wet process silica and improving the hydrophobic properties, the object is achieved by covering hydrophilic silanol groups (-SiOH) present on the surface of the wet process silica with hydrophobic silicone oil.
As a technique for imparting higher hydrophobicity, a method is also known in which a part of siloxane bonds (-Si-O-Si-) in a silicone oil is cleaved by heating or the like, and a dehydration condensation reaction is caused with silanol groups of wet silica to thereby chemically bond the siloxane bonds (-Si-O-Si-) to the silanol groups of the wet silica. Specifically, it is believed that the hydrophobization of the surface proceeds by the reaction described in the following formula 1.
[ solution 1]
Reaction of polysiloxanes with silica
As a method for determining the degree of hydrophobization of the surface of the hydrophobic silica, the DBA (di-n-butylamine) adsorption amount and M value were used.
The principle of expressing the degree of hydrophobicity by the DBA adsorption amount (unit: m. mol/kg) will be described below.
In general silica (silica before hydrophobization), a large number of silanol groups are present on the surface thereof, and DBA is adsorbed on the silanol groups on the surface of the silica particles in an ion-bonding manner. In the surface-treated hydrophobic silica, silanol groups present on the surface of the silica are coated with silicone oil or react with each other to disappear. When there is a silanol group remaining on the surface of the hydrophobic silica, the silanol group is bonded to DBA, and the amount of the remaining silanol group is known from the bonding amount. Therefore, it is utilized as a means for knowing the hydrophobization degree of silica. A low value of the DBA adsorption amount indicates a change of silanol groups to siloxane bonds, and generally means a high degree of hydrophobization.
On the other hand, the M value is a concentration expressed by% by volume of methanol at which the treated powder starts to be wet in a mixed solution of water and methanol. A higher value of the M value means a higher degree of hydrophobization (a maximum value of about 70%).
Both the DBA value and the M value represent the hydrophobized state of the hydrophobic silica, but the values do not show a unique correlation. For example, in a hydrophobic silica obtained by mixing only a hydrophilic silica with a large amount of silicone oil or a hydrophobic silica obtained by hydrophobizing only the surface of an aggregate, the amount of remaining silanol groups is large, and the DBA adsorption amount shows a high value. However, since the silicone oil covers the surface of the silica, the value of M is high. Therefore, in order to well grasp the hydrophobized state of the hydrophobic silica, it is preferable to monitor both the DBA value and the M value.
The wet-process synthetic silica used as a raw material is synthesized by a neutralization reaction between sodium silicate and an inorganic acid, and roughly classified into a precipitation-process synthetic silica synthesized in an alkaline region and a gel-process synthetic silica synthesized in an acidic region.
Patent document 1: japanese patent No. 3504338
Patent document 2: japanese examined patent publication (Kokoku) No. 42-26179
Patent document 3: japanese laid-open patent publication No. Sho 47-12770
Patent document 4: japanese examined patent publication (Kokoku) No. 57-2641
Patent document 5: japanese laid-open patent publication No. 6-316408
Patent document 6: japanese laid-open patent publication No. 8-176462
The entire disclosures of patent documents 1 to 6 are specifically incorporated by reference in the present specification as disclosures.
Disclosure of Invention
Problems to be solved by the invention
Hydrophobic silica is often difficult to cope with by the above-mentioned conventional techniques due to diversification and high functionality of user demands.
For example, when hydrophobic silica is used as a delustering agent for coating applications, an antifouling function, an alkali-resistant function, a chemical-resistant function, and a flaw-resistant property can be imparted as described above. However, in the stage of forming a coating film as a paint and curing the coating film, a part of the unreacted oil is eluted to the surface of the coating film, and a problem of so-called color unevenness occurs.
In the field of films, when the hydrophobic silica is applied to a film and then the film is wound, the silicone oil released during winding moves into the film, and a problem such as contamination occurs.
Similarly, when the resin composition is used as an anti-blocking agent for a film, the use of hydrophobic silica has an advantage of improving transparency, but the bleeding (ブリード) of silicone oil causes problems such as a partial difference in haze ( degrees) of the film, and the quality of the entire film is impaired.
In these phenomena, the bleeding of the remaining unreacted silicone oil is a cause, suggesting that the silanol group on the silica surface is not completely bonded to the silicone oil.
However, the hydrophobic silicas in which the above problems have occurred all exhibit a high M value and a sufficiently low DBA adsorption amount, and when the M value and the DBA adsorption amount are used as indices, the hydrophobic silicas are said to have a high degree of hydrophobization, and in reality, the amount of unreacted silica that affects the performance of the hydrophobic silicas cannot be understood by using only the M value and the DBA adsorption amount. In addition, if the amount of unreacted silicone oil is to be reduced, a long-term heat treatment is required, which is disadvantageous in terms of commercial production.
The present inventors have studied a method for simply reducing the amount of silicone oil to be treated in order to solve the above-mentioned problems. However, if such a method is employed, the hydrophobization is insufficient, and unreacted silicone oil is inevitably present even when the conventional method is applied (for example, even when the method is applied to heating conditions), and the problem cannot be solved. For example, partial hydrophobization described in patent document 6 has been attempted. However, even if the amount of silicone oil to be treated is reduced, the amount of unreacted silicone oil as an eluted component cannot be reduced, and the problem cannot be solved.
As another method, the following studies have been made: the amount of unreacted silicone oil is reduced by selecting silicone oil with a large molecular weight and reducing the number of molecules per unit weight. However, the viscosity of silicone oil having a large molecular weight increases, and it is difficult to uniformly mix the silicone oil with silica.
In the above-mentioned prior art, in the methods described in patent documents 3 and 4 in which an alkali metal hydroxide, ammonia, or amine is added as a catalyst to wet-process synthetic silicic acid, silica is alkaline, and weakly alkaline wet-process synthetic silica causes a change in surface properties such as a decrease in specific surface area with the passage of time, and thus has a problem that stable performance cannot be exhibited.
In addition, the method described in patent document 5 has an advantage that surface treatment can be performed at a low temperature. However, the object is to improve the M value and the DBA value, and the hydrophobic silica treated by such a method tends to increase the elution amount of the silicone oil.
In other studies, it was found that elution of silicone oil can be reduced when heat treatment is performed at a high temperature of 350 to 400 ℃ for a long period of time of 6 hours or more in order to complete chemical bonding between the silicone oil and the silanol group. However, since a part of the silicone oil itself is decomposed and deteriorated by the heat of treatment, the desired performance cannot be exhibited. Further, the treatment at a high temperature for a long time causes only significant deterioration of the production efficiency and increase of the cost, and is not practical.
In general, the silica particles of raw powder have a high BET specific surface area, have micropores, and the size of the particles is a size of several micrometers, so that it is difficult to uniformly treat silicone oil having viscosity on a molecular level, and generation of free silicone oil cannot be effectively suppressed even using any method of the related art.
Accordingly, the present inventors have conducted intensive studies to provide a hydrophobic silica capable of reducing silanol groups and unreacted silicone oil on the surface of a silica, which has been released and eluted, while maintaining the degree of hydrophobization indicated by the M value and the DBA adsorption amount at target values after the hydrophobization treatment.
Means for solving the problems
As a result, it has been found that when a strong acid strong base type neutral salt compound represented by sodium sulfate is attached to the surface of wet-process synthetic silica, the neutral salt exerts a catalytic effect in the formation of a siloxane bond between a silanol group and a silicone oil, and has an effect of remarkably reducing a free silicone oil by a treatment at a relatively low temperature, and it has been difficult in the prior art to reduce the free silicone oil. As a result, the present inventors have succeeded in effectively developing hydrophobic silica with a small amount of silicone oil eluted at a low temperature in a short time, and have completed the present invention.
The present invention is as follows.
[1]
A hydrophobic silica obtained by subjecting wet-process synthetic silica to surface treatment with silicone oil, wherein,
the characteristics of the hydrophobic silica are as follows:
(i) the amount of elution of silicone oil from hydrophobic silica in toluene was less than 0.2% by mass of hydrophobic silica, wherein the amount of elution was obtained by dispersing the hydrophobic silica in toluene at a concentration of 2% and comparing the amount of elution with that before dispersion after 24 hours at 20 ℃.
[2]
Such as [1]]The hydrophobic silica according to (1), wherein the content of the sodium component in the hydrophobic silica is Na20.20 to 1.20 wt% in terms of O, and the content of sulfur component is SO30.25 wt% to 1.30 wt% in terms of weight.
[3]
Such as [1]]Or [2]]The hydrophobic silica as described in (1), wherein the hydrophobic silica is contained in an amount of 100m per raw material silica2BET specific surface area/g, and the treatment amount of the silicone oil is 3 to 9 parts.
[4]
The hydrophobic silica as described in [1] or [2], wherein,
(ii) m is 20% or more, and/or
(iii) The DBA adsorption capacity is less than 100 m.mol/kg.
[5]
A method for producing hydrophobic silica, which is a method for producing hydrophobic silica in which wet-process synthetic silica is surface-treated with silicone oil, the method comprising:
the hydrophobic silica is obtained by coating the surface of wet-process synthetic silica with silicone oil in the presence of a strong acid strong base type neutral salt compound and then subjecting the coated silicone oil to a condition in which the coated silicone oil forms a siloxane bond with a silanol group of the wet-process synthetic silica.
[6]
The production method according to [5], wherein the strong acid and strong base type neutral salt compound is sodium sulfate, sodium chloride, potassium sulfate, potassium chloride or a mixture thereof.
[7]
The production method as described in [5] or [6], wherein the strong acid and strong base type neutral salt compound is present on the surface of the wet-process synthetic silica in an amount ranging from 0.3% to 3.0%.
[8]
The production process according to any one of [5] to [7], wherein the amount of elution of the silicone oil from the hydrophobic silica in toluene is less than 0.2% by mass of the hydrophobic silica, and the elution amount is a silicone oil elution rate obtained by dispersing the hydrophobic silica in toluene at a concentration of 2% and comparing the elution amount with that before the dispersion after 24 hours at 20 ℃.
[9]
The production method according to any one of [5] to [7],
the hydrophobic silica
(i) M is 20% or more, and/or
(ii) The DBA adsorption capacity is less than 100 m.mol/kg.
[10]
The production method according to any one of [5] to [9], wherein the silicone oil has a kinematic viscosity of 500 centistokes or less.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a hydrophobic silica surface-treated with a silicone oil, which is capable of providing a stable coating film surface without elution of the silicone oil to the surface even after the hydrophobic silica is added to a coating material and applied to form a coating film. The hydrophobic silica of the present invention can be suitably used for metal coatings, matting agents for plastic coatings, coatings on antiglare films, resin fillers, film antiblocking agents, and the like.
Detailed Description
[ hydrophobic silica of the present invention ]
The hydrophobic silica of the present invention is obtained by surface-treating wet-process synthetic silica with silicone oil, and satisfies the following (i).
(i) The amount of silicone oil eluted in toluene was less than 0.2% by mass relative to the mass of hydrophobic silica. The elution amount is a silicone oil elution rate obtained by dispersing the hydrophobic silica in toluene at a concentration of 2% and comparing the dispersion with that before the dispersion after 24 hours at 20 ℃.
< amount of dissolved Silicone oil >
The amount of silicone oil released from the hydrophobic silica of the present invention is less than 0.2% of the total amount of the hydrophobic silica as compared with the state before dispersion, and the amount of silicone oil released from the hydrophobic silica is 2% of the amount of silicone oil released from the hydrophobic silica dispersed in a toluene solution after 24 hours at room temperature. When the amount of the silicone oil released is 0.2% or more, part of the unreacted oil is released from the surface of the coating film at the stage of forming the coating film as a coating material and curing the coating film, resulting in color unevenness; or, when the film is wound after being applied to the film, the silicone oil released during winding moves into the film and causes a problem such as contamination, that is, the above-described various problems represented by deterioration of oil bleeding characteristics occur. In order to further solve the problem, the amount of the silicone oil released is preferably less than 0.15%, more preferably 0.10% or less, and still more preferably 0.08% or less.
When dispersed in a paint or the like, the amount of silicone oil eluted when the resin is compounded is difficult to measure by a direct analysis method, and the amount of unreacted silicone oil can be measured easily and accurately by selecting a method in which hydrophobic silica is dispersed in a toluene solvent and the amount of silicone oil eluted into toluene after 24 hours has elapsed.
The hydrophobic silica of the present invention is a hydrophobic silica satisfying the above (i), and more preferably satisfies the following (ii) and/or (iii).
(ii) The M value is 20% or more.
(iii) The DBA adsorption capacity is less than 100 m.mol/kg.
The state of the surface treatment of the hydrophobic silica can be expressed by the DBA adsorption amount and the M value as described above, and in the hydrophobic silica of the present invention, from the viewpoint of satisfying the physical properties of the conventional hydrophobic silica, it is preferable that the M value is 20% or more and the DBA adsorption amount is less than 100M · mol/kg.
< M value >
When the M value (the M value is represented by the volume% of methanol at which wetting of the powder to be processed in a mixed solution of water and methanol starts) is less than 20%, the hydrophobicization degree itself of silica is generally low (hydrophilic groups remain), and the M value is preferably 20% or more. The M value of the hydrophobic silica of the present invention is more preferably 40% or more, and still more preferably 55% or more.
< amount of DBA adsorption >
When the DBA adsorption amount (which represents the amount of silanol groups (hydrophilic groups) remaining on the surface of the hydrophilic silica as a raw material) is 100m · mol/kg or more, a large amount of hydrophilic groups generally remain in the hydrophobic silica. (it is likely to occur when the heat treatment described later is insufficient, and this also causes elution of silicone oil.) if the DBA adsorption amount is less than 100 m.mol/kg, adsorption of the pigment or the curing agent due to interaction between hydrophilic groups does not occur when dispersed in the solvent-based coating material, and this does not cause adverse conditions such as abnormal increase in viscosity immediately after dispersion or occurrence of coagulation when blended in a resin. The value of DBA adsorption amount of the hydrophobic silica of the present invention is more preferably less than 60m mol/kg, and still more preferably less than 20m mol/kg.
The kind and physical properties of the wet-process synthetic silica used in the present invention are not particularly limited. Both precipitated silica and gel silica can be used without problems.
The precipitated silica usually has a BET specific surface area of 20m2/g～300m2(g) BET specific surface area of gel-process silica of 250m2/g～700m2In the case of hydrophobicization, per 100m2The amount of the silicone oil treated per gram must be 3 to 9 parts. For example, if the BET specific surface area is 300m2The amount of the silicone oil to be treated is preferably 9 to 27 parts per gram of silica.
The hydrophobic silica of the present invention may not be completely hydrophobized for the purpose of preventing elution of silicone oil, as long as the amount of silicone oil to be treated is per 100m2The BET specific surface area/g is in the range of 3 to 9 parts, and the amount of the treatment may be selected as required depending on the purpose of use. In general, the smaller the treatment amount, the less completely hydrophobized the silica surface; conversely, the larger the treatment amount, the more completely hydrophobized the product. By controlling the amount of silicone oil to be treated per 100m2The BET specific surface area/g is 3 parts or more, and the degree of hydrophobization itself is reduced, so that the efficacy as a hydrophobic silica can be sufficiently obtained. On the other hand, if the treatment amount is 9 parts or less, there is no excess silicone oil on the silica surface, and silanol groups on the surface of wet-process synthetic silica for bonding with silicone oil molecules are sufficiently present, so that not only the remaining amount of unreacted silicone oil but also the elution amount can be suppressed, and the object of the present invention can be further achieved. The amount of silicone oil to be treated is preferably 100m2The BET specific surface area/g is suitably in the range of 4 parts to 8 parts, and the amount of treatment may be varied within this range depending on the use or purpose.
The object of the present invention is mainly to be used in coating applications such as paints and adhesives, resin fillers, and anti-blocking agents for films, and thus the hydrophobic silica can be suitably used in accordance with the object in the range of an average particle diameter of 1 μm to 15 μm by a laser method, similarly to untreated wet synthetic silica. When the average particle size is small, the resin composition is often used in fields requiring fine matting properties such as matting of clear paints and matting of paints for plastics, or in resin fillers or antiblocking agents for films requiring higher transparency; when the particle size is large, the composition is often used in a field where high matting is required, such as matting of a metal coating or a coating for building materials. The average particle size is usually adjusted by pulverization and classification, and the adjustment can be performed in both the raw material stage and after the hydrophobic property-imparting treatment, or can be performed by a combination of the above.
By adjusting the particle size by adjusting the degree as a raw material stage and fine-adjusting after the hydrophobic property-imparting treatment, it is possible to accurately produce silica having a desired particle size.
The silicone oil used in the present invention is not limited as long as it can be mixed with the wet-process synthetic silica. A commercially available dimethylsilicone oil having only methyl groups and phenyl groups (generally referred to as pure silicone oil (ストレートシリコーンオイル)) is generally used, and a modified silicone oil having an organic substituent on a silicon atom may be used. Examples of the substituent include polyether, epoxy, amine, and carboxyl, and many modified silicone oils are commercially available. Examples of the modified silicone oil include the following.
< modified Silicone oil manufactured by shin-Etsu chemical industries Co. >
KF-868、865、859、393、250、889、2001、2004、99、9901、8010、8012、8008、105、6000、6001、6002、6003、6123、2200、9701、2012、857、8001、858、351A、353、354L、355A、945、640、642、643、644、6020、6204、6011、6015、6017、412、413、414、4003、4917、7235B、50、53、54、54SS、X-22-343、2000、2046、4741、4039、4015、161A、161B、9490、163、163A、163B、163C、169AS、169B、164、164AS、164A、164B、164C、164E、4952、4272、167B、167C、162C、5841、2445、1602、168AS、168A、168B、173BX、173DX、170BX、170DX、176DX、176GX-A、174ASX、174BX、2426、2475、3710、2516、821、822、7322、3265、
< modified Silicone oil manufactured by Toray Dow Corning Corp. >
SF 8417、BY 16-205、BY 16-213、BY 16-871、BY 16-893、SF 8411、BY 16-880、SF8427、BY 16-201、SF 8428、BY 16-846、SF 8419、FS 1265、SH 510、SH 550、SH 710、SH8400、FZ-77、L-7604、
< modified Silicone oil manufactured by Momentive Performance Materials Inc. >
TSF4440、4441、4445、4446、4452、4460、4700、4701、XF42-B0970、
< modified Silicone oil manufactured by Wacker-Chemie Corp. >
L03、033、066、L653、655、656、662、WT1250、65000VP、AP100、150、200、500、AR20、200、
Since the silicone oil is mixed with wet-process synthetic silica having a low bulk relative density, when a silicone oil having a high molecular weight and a high viscosity is used, it is necessary to take measures such as dilution with a solvent or the like. Therefore, it is generally preferable to use a silicone oil having a relatively low viscosity of 500 centistokes (500cSt) or less. Examples of the silicone oil having a kinematic viscosity of 500 centistokes or less include the following.
< Silicone oil manufactured by shin-Etsu chemical industries Co., Ltd >
KF-96-10cs、20cs、30cs、50cs、100cs、200cs、300cs、350cs、500cs、
< Silicone oil manufactured by Toray Dow Corning Corp. >
SH200-0.65cs、1cs、1.5cs、2cs、3cs、5cs、10cs、20cs、50cs、100cs、
200cs、350cs、500cs、
< Silicone oil manufactured by Momentive Performance Materials Inc. >
TSF451-0.65、5A、10、20、30、50、100、200、300、350、500、
< Silicone oil manufactured by Wacker-Chemie Corp. >
AK0.65、1、10、35、50、100、350、500
[ method for producing hydrophobic silica of the present invention ]
The present invention includes a method for producing hydrophobic silica by surface-treating wet-process synthetic silica with silicone oil. The manufacturing method comprises the following steps: the hydrophobic silica is obtained by coating the surface of wet-process synthetic silica with silicone oil in the presence of a strong acid strong base type neutral salt compound and then subjecting the coated silicone oil to a condition in which the coated silicone oil forms a siloxane bond with a silanol group of the wet-process synthetic silica.
A strong acid strong base type neutral salt compound (which functions as a catalyst) such as sodium sulfate (Na) is added to wet-process synthetic silica as a raw powder before surface treatment with silicone oil2SO4) Pretreatment of the components and the like. Examples of the strong acid and strong base type neutral salt compound include sodium sulfate, sodium chloride, potassium sulfate, potassium chloride, and a mixture thereof. The amount of the strong acid and strong base type neutral salt compound present on the surface of the wet-process synthesized silica is preferably in the range of, for example, 0.3% to 3.0%. The method of pretreatment is not particularly limited, and the following methods may be mentioned: water washing was carried out until sodium sulfate (Na) was produced as a by-product of the reaction when the synthesis reaction of silica was terminated2SO4) After reaching a predetermined amount, the pH can be adjusted for use; after washing with sufficient water, a predetermined amount of sodium sulfate (Na) was added in a slurry state2SO4) A method of adjusting pH with an alkali such as sodium hydroxide (NaOH) as required; first, only a predetermined amount of sulfuric acid (H) is added to a silica slurry2SO4) And then pH adjustment is performed using sodium hydroxide (NaOH); and so on.
Thereafter, the resultant is subjected to drying, pulverization, and classification steps to obtain wet-process synthetic silica having a desired particle diameter. In this case, the Na content in the wet-process synthetic silica as the raw powder is adjusted to Na2The content of S is adjusted to be SO in a target range of approximately 0.3 to 1.4 wt% in terms of O3The target range is approximately 0.36 wt% to 1.44 wt% in terms of conversion. Tables of these valuesThe amount of impurities in the starting powder tends to be slightly different from the amount of impurities contained in the hydrophobic silica as a final product. If Na2When the amount of O is small, the effect as a catalyst is reduced; on the contrary, in Na2When the amount of O is increased, not only a remarkable improvement in catalytic effect cannot be expected, but also a large amount of salts is contained in the silica, which is not preferable. In addition, S and SO3The alkali metal salt is an acidic component for suppressing the alkali change due to Na, and the alkali bias can be suppressed by setting the amount to the above range.
When silica synthesized by a wet method as a raw powder is pretreated with only an alkaline component such as sodium hydroxide (NaOH), or only sulfuric acid (H)2SO4) When the wet-process synthetic silica as the raw powder is pretreated with an acidic component, the wet-process synthetic silica component becomes alkaline and acidic, respectively, which is not preferable, and it is necessary to have both components in a well-balanced state and to have a pH in the vicinity of neutral. The pH of the wet-process synthetic silica as the raw powder is preferably in the range of 5.5 to 8.0 in the vicinity of neutrality, from the viewpoint of the use and purpose. In particular, if the basicity is increased, the surface of silica is deteriorated or modified with time, and a problem different from the object of the present study is caused, which is not preferable.
Further, in the case of wet-process synthetic silica, aluminum-based impurities derived from raw material natural ores may be contained, and in the case of wet-process synthetic silica in which the amount of aluminum as impurities is large, although the reason for this is not clear, a tendency that the catalytic effect is reduced is observed. It is empirically considered that the amount of aluminum contained in the wet-process synthesized silica as the raw powder is Al2O3Preferably less than 0.5 wt% in conversion.
When the wet-process synthetic silica obtained as the raw powder in this way is subjected to hydrophobization treatment with a silicone oil, the Na component is Na as an impurity amount in the entire hydrophobic silica20.20 to 1.20 wt% in terms of O, and SO as an S component3The conversion must be 0.25 wt% to 1.30 wt%. The difference from the original powder content range is due to the fact that the hydrophobic property is formedThe weight of the silicone oil is added during treatment, so that the weight percent of impurities in the whole silicon dioxide is reduced.
The surface treatment method of hydrophobizing the wet-process synthetic silica as raw powder with the silicone oil is also not particularly limited, and is usually a treatment with dry mixing, as exemplified below. First, silica in a dry state is mixed with a predetermined amount of silicone oil and stirred uniformly by using a dry mixing and dispersing device such as an FM mixer (henschel mixer) to perform surface treatment. As described above, it is effective to perform the heat treatment after the surface treatment, but the specific heat treatment method is not particularly limited. Generally, by performing heat treatment at 250 to 400 ℃ for about 0.5 to 4.0 hours using a heat treatment apparatus such as an electric furnace, a Nesco heater, or a drying furnace, the silicon oil is chemically bonded to silanol groups on the surface of the silica, and thus the hydrophobization can be maintained for a long time.
The silicone oil has a methyl group (-CH)3) And is a typical organic group, and therefore the amount of silicone oil to be treated can also be determined by the inverse calculation by measuring the amount of carbon (C amount) in the hydrophobic silica after the hydrophobic treatment.
In the case of the hydrophobic silica of the present invention, the catalytic effect of the strong acid and strong base type neutral salt compound is utilized to efficiently produce the hydrophobic silica in which very little silicone oil is eluted even under a low temperature and short time.
The hydrophobic silica of the present invention is not limited in its use, and is mainly used as a gloss reducing agent for paints, a resin filler, an anti-blocking agent for films, and the like.
In particular, in the case of a delustering agent for a coating material (touch-comfortable coating layer) applied to a plastic surface, or in the case of film coating applications requiring both transparency and matting properties (for example, an antiglare film or an antiglare (アンチグレア) film to be stuck to a liquid crystal surface), both solvent-type and solvent-free types can be more suitably used.
Examples
The present invention will be described in more detail below based on examples. The examples are illustrative of the invention and the invention is not intended to be limited to the examples.
The measurement and test of various physical properties in examples and comparative examples were carried out by the following methods.
1) DBA adsorption amount
250mg of the dried sample was precisely weighed, 50ml of an N/500 solution of di-N-butylamine (petroleum ether (petroleum ベンジン) solvent) was added thereto, and the mixture was left to stand at 20 ℃ for about 2 hours. 5ml of chloroform and 2 to 3 drops of an indicator (crystal violet) were added to 25ml of the supernatant, and the mixture was titrated with an N/100 perchloric acid solution (acetic anhydride solvent) until the violet color turned blue, and the titration value was Aml.
The titration value for blank titration was Bml, and the DBA adsorption amount was calculated by the following equation.
DBA adsorption capacity (m.mol/kg) ═ 80(B-A) f
Wherein f is the titer of a perchloric acid solution of N/100
2) Value of M
A mixed solution of methanol and water in which the methanol concentration was changed at intervals of 5% by volume was prepared, and 5ml of the mixed solution was put into a test tube having a volume of 10 ml. Then, 0.1g to 0.2g of the test powder was added, mixed by shaking, and the mixture was allowed to stand and observed, whereby the minimum methanol concentration in the suspension of the powder was obtained and used as the M value.
3) Amount of dissolved silicone oil
The present invention relates to a method for analyzing the amount of carbon contained in a solid content, and more particularly to a method for analyzing the amount of carbon contained in a solid content, which comprises adding 1.0g of silica hydrophobized with silicone oil or the like to 50g of toluene, dispersing the silica in a homomixer at 1,000rpm × 30 minutes, transferring the resulting dispersion to a centrifuge tube, standing the dispersion at room temperature for 15 hours, observing foaming when the silicone oil is dissolved in toluene at this stage, centrifuging the tube at 3,000rpm for 5 minutes using a centrifugal separator, discarding the supernatant, adding toluene again to dissolve the supernatant, centrifuging the solution, discarding the toluene again, adding n-hexane to dissolve the toluene 2 times, centrifuging the solution, discarding the separated solution, drying the solution in a dryer at 80 ℃ for 15 hours or more, analyzing the amount of carbon contained in the remaining solid content, analyzing the amount of carbon contained in the silica in a blank, and determining the amount of silicone oil dissolved in toluene.
(formula (II))
Amount of silicone oil dissolved in toluene (%) -amount of silicone oil after toluene dissolution (%)
4) Carbon content analysis
The amount of carbon used for measuring the amount of silicone oil eluted was measured using a solid carbon analyzer (trade name: CarbonAnalyzer, model EMIA-110, manufactured by horiba, Ltd.) under conditions of 1,250 ℃ and an oxygen inflow pressure of 0.07MPa for a measurement time of 90 seconds. The amount of silicone oil treated was calculated from the amount of carbon determined using the following formula.
(formula (II))
Silicone oil treatment (%) -carbon assay measurement (%) × molecular weight of silicone oil/amount of carbon in silicone oil
5) Amount of impurities
Quantitative analysis of each element was performed using a scanning type fluorescent X-ray analyzer (model: ZSX PrimusII, manufactured by Rigaku corporation). The measurement result is converted into the amount of the oxide and output.
6) BET specific surface area
Using a fully automatic specific surface area measuring device (model: Macsorb)(R)HM model-1200, manufactured by Mountech corporation) was measured by the one-point method.
7)pH
The wet-process synthetic silica as a raw powder was measured using a pH meter (model: D-50 horiba, Ltd.). (goodhydrophobic silica is not compatible with water and therefore cannot be measured)
[ example 1]
Sodium silicate and sulfuric acid are reacted to synthesize the product with the BET specific surface area of 130m2Precipitated silica in g. And filtering and washing the synthesized precipitated silica to obtain a silica filter cake. To the silica cake, water was added and the mixture was redispersed with Na by a reciprocating rotary stirrer (manufactured by Kazaki engineering Co., Ltd.)20.50 wt% in terms of O and SO3Sodium sulfate (Na) was added in an amount of 0.60 wt% in terms of2SO4) Further, sodium hydroxide (NaOH) was added for pH adjustment to prepare a silica slurry having a pH of 7.5. Spraying the silica slurryThe resultant was dried by a mist dryer (manufactured by Dachuan chemical industries, Ltd.), and subjected to pulverization and classification to obtain precipitated silica having an average particle diameter of 6.3. mu.m. 10 parts (100 m relative to the BET specific surface area) are then added27.7 parts/g) Dimethicone KF96-50CS (manufactured by shin-Etsu chemical Co., Ltd.), and was mixed with a Henschel mixer (manufactured by Mitsui mine Co., Ltd.) for 10 minutes. After the mixing, the particle size was adjusted by heat treatment at 300 ℃ for 1 hour using a muffle furnace (manufactured by Yamato scientific corporation), and a hydrophobic wet-process silica was obtained. The physical properties of the raw powder, the physical properties after hydrophobization, and the elution amount are shown in table 1.
[ example 2]
In example 1, as Na20.32 wt% in terms of O and SO3Sodium sulfate (Na) was added in an amount of 0.38 wt% in terms of conversion2SO4) Except for this, hydrophobic silica was obtained in the same manner as in example 1.
[ example 3]
In example 1, the treatment amount of the silicone oil was changed to 100m relative to the BET specific surface area2Hydrophobic silica was obtained in the same manner as in example 1 except that the amount of the silica/g was 3.8 parts.
[ example 4]
In example 1, as Na20.90 wt% in terms of O and SO3Sodium sulfate (Na) was added in an amount of 1.08 wt% in terms of2SO4) Except for this, hydrophobic silica was obtained in the same manner as in example 1.
[ example 5]
The starting silica was changed to commercial precipitated silica Nipsil N-300A (BET specific surface area 150 m)2/g) the amount of silicone oil treated was changed to 100m relative to the BET specific surface area2Hydrophobic silica was obtained in the same manner as in example 1 except that the amount of the silica/g was changed to 6.7 parts.
[ example 6]
The treatment amount of the silicone oil of the precipitated silica of example 5 was changed to 100m in terms of BET specific surface area2The same method as in example 1 was used except that the amount of the polymer particles/g was 3.3 partsThe method obtains hydrophobic silicon dioxide.
[ example 7]
The raw material silica was changed to commercial gel silica NIPGE L AZ-200(BET specific surface area 300 m)2/g) the amount of silicone oil treated was changed to 100m relative to the BET specific surface area2Hydrophobic silica was obtained in the same manner as in example 1 except that the amount of the silica/g was 5.3 parts.
[ example 8]
The raw material silica was changed to commercially available gel silica NIPGE L BY-601(BET specific surface area 500 m)2/g) the amount of silicone oil treated was changed to 100m relative to the BET specific surface area2Hydrophobic silica was obtained in the same manner as in example 1 except that the amount of the silica/g was 3.0 parts.
Comparative example 1
In example 1, sodium sulfate (Na) was not added2SO4) Hydrophobic silica was obtained in the same manner as in example except that no pH adjustment was performed.
Comparative example 2
Hydrophobic silica was obtained in the same manner as in comparative example 1 except that in comparative example 1, sodium hydroxide (NaOH) was added for pH adjustment to prepare a silica slurry having a pH of 10.8.
Comparative example 3
In example 5, sodium sulfate (Na) was not added2SO4) Hydrophobic silica was obtained in the same manner as in example 5 except that no pH adjustment was performed.
Comparative example 4
In comparative example 3, sulfuric acid (H) was added2SO4) Hydrophobic silica was obtained in the same manner as in comparative example 3 except that a silica slurry having a pH of 3.2 was prepared by adjusting the pH.
Comparative example 5
As an example of a commercially available hydrophobic silica, Nipsil SS-50B was used.
Comparative example 6
In factIn example 7, sodium sulfate (Na) was not added2SO4) Hydrophobic silica was obtained in the same manner as in example 7 except that no pH adjustment was performed.
Comparative example 7
As an example of a commercially available hydrophobic silica, Nipsil SBY-61 was used.
Industrial applicability
The present invention is useful for a method for producing hydrophobic silica.
Claims (9)
1. A hydrophobic silica obtained by subjecting wet-process synthetic silica to surface treatment with silicone oil, wherein,
the amount of unreacted silicone oil in the hydrophobic silica is less than 0.2% based on the amount of silicone oil eluted in toluene relative to the mass of the hydrophobic silica,
the elution amount is a silicone oil elution rate obtained by dispersing the hydrophobic silica in toluene at a concentration of 2% and comparing the dispersion with that before the dispersion after 24 hours at 20 ℃.
2. The hydrophobic silica according to claim 1, wherein the content of the sodium component in the hydrophobic silica is Na20.20 to 1.20 wt% in terms of O, and the content of sulfur component is SO30.25 wt% to 1.30 wt% in terms of weight.
3. Hydrophobic silica according to claim 1 or 2, characterized in that it is present per 100m with respect to the starting silica2BET specific surface area/g, and the treatment amount of the silicone oil is 3 to 9 parts.
4. The hydrophobic silica according to claim 1 or 2,
(ii) m is 20% or more, and/or
(iii) The DBA adsorption capacity is less than 100 m.mol/kg,
the M value is a concentration of methanol represented by% by volume of a mixed solution of water and methanol in which hydrophobic silica starts to wet,
the DBA adsorption amount indicates an adsorption amount of di-n-butylamine adsorbed on silanol groups remaining on the surface of the hydrophobic silica.
5. A method for producing hydrophobic silica, which is a method for producing hydrophobic silica in which wet-process synthetic silica is surface-treated with silicone oil by dry-mixing, the method comprising:
adding a strong acid strong base type neutral salt compound to wet-process synthetic silica, and coating silicone oil on the surface of the obtained wet-process synthetic silica in which the strong acid strong base type neutral salt compound exists by dry mixing, wherein the existence amount of the strong acid strong base type neutral salt compound on the surface of the wet-process synthetic silica is in the range of 0.3-3.0%;
and then the coated silicone oil and silanol groups of the silica synthesized by a wet method form siloxane bonds under the catalysis of the strong acid strong base type neutral salt compound to obtain the hydrophobic silica.
6. The method according to claim 5, wherein the strong acid and strong base type neutral salt compound is sodium sulfate, sodium chloride, potassium sulfate, potassium chloride or a mixture thereof.
7. The production process according to claim 5 or 6, wherein the amount of the hydrophobic silica released from toluene is less than 0.2% by mass of the hydrophobic silica, and the amount of the hydrophobic silica released from toluene is a silicone oil release rate obtained by dispersing the hydrophobic silica in toluene at a concentration of 2% and comparing the dispersion with that before the dispersion after 24 hours at 20 ℃.
8. The manufacturing method according to claim 5 or 6,
the hydrophobic silica
(i) M is 20% or more, and/or
(ii) The DBA adsorption capacity is less than 100 m.mol/kg,
the M value is a concentration of methanol represented by% by volume of a mixed solution of water and methanol in which hydrophobic silica starts to wet,
the DBA adsorption amount indicates an adsorption amount of di-n-butylamine adsorbed on silanol groups remaining on the surface of the hydrophobic silica.
9. The method according to claim 5 or 6, wherein the silicone oil has a kinematic viscosity of 500 centistokes or less.
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| PCT/JP2015/084377 WO2016093221A1 (en) | 2014-12-10 | 2015-12-08 | Hydrophobic silica and method for producing same |
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| CN110204979A (en) * | 2019-05-29 | 2019-09-06 | 安徽集友新材料股份有限公司 | Dumb paint and preparation method thereof |
| CN110202893A (en) * | 2019-05-29 | 2019-09-06 | 安徽集友新材料股份有限公司 | Dumb light transfer paper and preparation method thereof and dumb light shift extrusion coating paper |
| KR102214188B1 (en) * | 2020-12-24 | 2021-02-08 | 전순분 | Opv composition for overprinting on packing film |
| KR102605531B1 (en) * | 2021-11-02 | 2023-11-22 | (재)울산테크노파크 | Epoxy adhesive composition and manufacturing method thereof |
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| JP6393177B2 (en) | 2018-09-19 |
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