JP4573324B2 - Quaternary ammonium silicate derivatives - Google Patents

Description

  The present invention relates to a quaternary ammonium silicate derivative that can be used for castings, detergent builders, and the like.

  Alkali metal silicate compounds such as water glass are widely used in various industries such as castings, detergent builders, civil engineering architecture, paper pulp, adhesives, and ceramics. It is also frequently used as a raw material for silica and aluminosilicates.

  A silicate using a quaternary ammonium such as tetramethylammonium as a counter cation without using a metal cation such as sodium (a quaternary ammonium silicate, for example, see Non-Patent Document 1) is a mesoporous compound (see Patent Document 1) or high purity. In addition to being used as a raw material for quartz glass (see Patent Documents 2 and 3), it is also used as a cleaning composition (see Patent Documents 4 and 5) for removing plasma etching residues.

  Quaternary ammonium silicate is superior in affinity to organic compounds compared to alkali metal silicates (see Non-Patent Document 2), and therefore various compositions mainly composed of organic compounds such as castings and detergents. It can be applied to builders, civil engineering architecture, paper pulp, adhesives, ceramics, silica raw materials, aluminosilicate raw materials, paints, metal corrosion inhibitors, abrasives, resin additives, etc.

  However, in general, quaternary ammonium silicate has strong alkalinity. Therefore, when it is applied to a composition having low alkali resistance, for example, a resin having low alkali resistance, there is a problem that the resin is deteriorated.

On the other hand, a quaternary ammonium silicate treated product having a relatively low alkalinity can be obtained by acid treatment of quaternary ammonium silicate with hydrochloric acid. However, a silicate having a Q ₃ structure in a low alkali state [bonded to a certain Si atom. Silica having a Q ₄ structure is reduced (including Si atoms in an atomic arrangement in which three of the four oxygen atoms are further bonded to adjacent metal atoms (eg, Si atoms)). By increasing the number of all four oxygen atoms bonded to the Si atom, including the Si atoms in the atomic arrangement bonded to the next metal atom (for example, Si atom), the quaternary Polymerization (gelation) of silicate in the processed product of ammonium silicate has progressed (Non-patent Document 3), and structural and functional characteristics such as reduced dispersibility of quaternary ammonium silicate have been lost. There was to cause such problems. Moreover, the method of lowering the pH using hydrochloric acid is not preferable because hydrochloric acid is a strong acid and causes corrosion of equipment. At the same time, since chlorine is contained, there is also a problem of reducing the strength of iron and iron alloys.
VDHoebbel, W. Wieker, Z. Anorg. Allg. Chem., 384, 43 (1971) RF Mortlock, AT Bell, CJ Radke, J. Phys. Chem., 95, 7847 (1991) CA Fyfe, G. Fu, J. Am. Chem. Soc., 117, 9709 (1995) US Pat. No. 5,057,296 JP 63-129026 A Japanese Patent Publication No. 8-25753 JP-A-10-97082 JP 2001-312074 A

The present invention has a high affinity for organic compounds, it indicates the nature of the weakly alkaline to neutral, many silicate take Q ₃ structure, therefore, silanolate group ^- quaternary with many (Si-O group) An object is to provide an ammonium silicate derivative.

That is, the gist of the present invention is as follows.
[1] Ratio of the peak area A ₃ constituting the signal attributed to Q ₃ in the ²⁹ Si NMR spectrum to the peak area A ₄ constituting the signal attributed to Q ₄ [A ₃ / (A ₃ + A quaternary ammonium silicate derivative in which A ₄ )] is 0.2 or more and the pH of a 1% by weight aqueous dispersion at 25 ° C. is 9.5 or less,
[2] The chemical composition of the anhydride is represented by the following general formula (2):
R ₂ O · xSiO ₂ (2)
(Wherein R represents a molecule that becomes a quaternary ammonium cation, and x satisfies 0 <x ≦ 50) and an organic acid (AH that generates m H ⁺ upon dissociation) _m ) and a quaternary ammonium silicate derivative obtained by mixing [3] and an anhydride having a chemical composition represented by the following general formula (2):
R ₂ O · xSiO ₂ (2)
(Wherein R represents a molecule that becomes a quaternary ammonium cation, and x satisfies 0 <x ≦ 50) and an organic acid (AH that generates m H ⁺ upon dissociation) _m ) and a method for producing a quaternary ammonium silicate derivative,
About.

  The present invention provides a quaternary ammonium silicate derivative that is excellent in affinity with an organic compound and can be applied to various compositions mainly composed of an organic compound, in particular, a composition having low alkali resistance.

The quaternary ammonium silicate derivative of the present invention (hereinafter sometimes referred to simply as a derivative) is obtained by mixing a quaternary ammonium silicate and a specific organic acid and reacting both as described later. . Derivatives of the present invention so obtained, unlike those conventional manner quaternary ammonium silicate and an acid treatment with an inorganic acid such as hydrochloric acid, with indicates the nature of the weakly alkaline to neutral, take Q ₃ structure has many holding the silicate, thus, silanolate groups; ^- having many (silanolate group SiO group). For this reason, it is excellent in affinity with an organic compound and can be applied to various compositions mainly composed of an organic compound, in particular, a composition having weak alkali resistance. Moreover, it can exist stably as a fine silicate particle, without gelatinizing, and its dispersibility is also favorable. It was first demonstrated in the present invention that a quaternary ammonium silicate derivative having excellent performance as described above can be obtained by the reaction of such a quaternary ammonium silicate with an organic acid.

Specifically, the derivative of the present invention has a ratio of the peak area A ₃ constituting the signal attributed to Q ₃ to the peak area A ₄ constituting the signal attributed to Q ₄ in the ²⁹ Si NMR spectrum. [A ₃ / (A ₃ + A ₄ )] is a quaternary ammonium silicate derivative having a pH of 9.5 or less at 25 ° C. of a 1 wt% aqueous dispersion of 0.2 or more.

Si atoms in the silicate are bonded to adjacent atoms with four adjacent oxygen atoms intervening. When a certain Si atom is bonded to n Si atoms via adjacent oxygen, the Si atom is referred to as a “Si atom of Q _n structure (or simply Q _n )”.

That is, Q ₃ is attributed to a Si atom in an atomic arrangement in which three of the four oxygen atoms bonded to the Si atom are further bonded to an adjacent metal atom (for example, Si atom), Q ₄ is attributed to an Si atom in an atomic arrangement in which all of the four oxygen atoms bonded to the Si atom are further bonded to the adjacent metal atom (for example, Si atom).

In the Si atom of Q ₃ , one of the four oxygen atoms bonded to the Si atom is in a free state and constitutes a Si—O 2 ^— group. When many such groups are present, fine silicate particles are likely to be generated, and even if blended in a certain composition, it can be stably blended in a highly dispersed state, and is applicable to various compositions mainly composed of organic compounds. It is considered that the functions required for silicate compounds such as these are easily expressed.

In the derivative of the present invention, the abundance of the Si—O 2 ^— group is represented by A ₃ / (A ₃ + A ₄ ), and the value is 0.2 or more. From the viewpoint of improving the performance of the derivative of the present invention, it is preferably 0.25 or more, more preferably 0.3 or more.

The measurement of ²⁹ Si NMR spectrum of the derivative of the present invention and signal assignment can be performed by known methods (for example, see Non-Patent Documents 2 and 3).

For example, when no metal atom other than Si atom is present in the silicate network, a signal having a peak at −94 to −104 ppm vs. TMS in the ²⁹ Si NMR spectrum is Q ₃ , −105 to −115 ppm vs. a signal having a peak to TMS attributed with Q _4. “Vs. TMS” indicates that tetramethylsilane (TMS) was used as an external standard.

Further, other metal atoms Z in the silicate network (e.g., Z = Al, Ga, etc.) If exists by isomorphous replacement and Si atoms (molar ratio Z / Si = 0.4 or higher), in ²⁹ Si NMR spectrum A signal having a peak at −80 to −88 ppm vs. TMS is assigned as Q ₃ , and a signal having a peak at −89 to −102 ppm vs. TMS is assigned as Q ₄ . Note that the presence of metal atoms Z other than Si atoms by isomorphous substitution with Si atoms can be confirmed using the NMR spectrum of metal atoms Z (for example, ²⁷ Al when Z = Al). . For example, in the case of Z = Al, the peak constituting the signal attributed to the Al atom isomorphously substituted with the Si atom in the ²⁷ Al NMR spectrum is observed at 50 to 75 ppm vs. AlCl ₃ .

The values of A ₃ and A ₄ can be obtained by obtaining the peak areas of the peaks constituting each signal as the integrated value of the signal.

  On the other hand, the 1% by weight aqueous dispersion of the derivative of the present invention has a pH of 9.5 or less at 25 ° C. From the viewpoint of improving the performance and versatility of the derivative, it is preferably 9 or less, more preferably 8.5 or less. Usually, the lower limit of the pH is about 4. The pH can be measured by the method described in the examples.

  The derivative of the present invention having the above characteristics can be easily obtained by, for example, producing according to the method for producing the derivative of the present invention described later.

As the derivative of the present invention, for example, the chemical composition of an anhydride has the following general formula (1):
R ₂ O · xSiO ₂ · yAH _m (1)
(In the formula, R represents a molecule that becomes a quaternary ammonium cation, AH _m represents an organic acid that generates m H ⁺ upon dissociation, x represents 0 <x ≦ 50, and m × y represents 0.1 ≦ m ×. A quaternary ammonium silicate derivative represented by y ≦ 2 is preferred. From the viewpoint of improving the performance of the derivative and reducing the cost, x is more preferably 2 ≦ x ≦ 20, further preferably 4 ≦ x ≦ 15, and particularly preferably 8 ≦ x ≦ 12. Further, from the same viewpoint, m × y (product of m and y) is more preferably 0.5 ≦ m × y ≦ 2, more preferably 1.2 ≦ m × y ≦ 1.9, and particularly preferably 1.6 ≦ m × y ≦. 1.8. In the formula, A represents an organic residue constituting an organic acid.

In addition, metal elements other than the above composition may be included as long as the performance and stability of the derivative are not lowered. For example, if it contains alkali metal (M) belonging to the periodic table Group IA, the content of alkali metal (molar ratio), if the alkali metal is assumed to be present as _{M 2 O, M 2 O /} SiO 2 ≦ 1 is preferable, M ₂ O / SiO ₂ ≦ 0.5 is more preferable, M ₂ O / SiO ₂ ≦ 0.1 is more preferable, and M ₂ O / SiO ₂ ≦ 0.01 is particularly preferable.

Such a derivative of the present invention has, for example, the following chemical formula (2):
R ₂ O · xSiO ₂ (2)
(Wherein R represents a molecule that becomes a quaternary ammonium cation, and x satisfies 0 <x ≦ 50) and an organic acid (AH that generates m H ⁺ upon dissociation) _m ) and the two are reacted. Therefore, the quaternary ammonium silicate derivative thus obtained is included in the present invention. In addition, the suitable range of x in General formula (2) is the same as the suitable range of x of General formula (1).

The present invention also provides a method for producing the derivative of the present invention as described above. The production method includes a step of mixing a quaternary ammonium silicate having a chemical composition of an anhydride represented by the general formula (2) and the organic acid (AH _m ).

  The quaternary ammonium silicate used in the present invention is not particularly limited, and tetraalkylammonium silicate, or at least one of the alkyl groups of the silicate is a hydrocarbon group such as an aryl group or an alkenyl group, or an arbitrary group. Quaternary ammonium silicate which is a hydrocarbon group having a substituent is exemplified, and tetraalkylammonium silicate is preferably used.

  The tetraalkylammonium silicate is not particularly limited, but usually the length of the alkyl chain is preferably about 1 to 8 carbon atoms.

  Examples of the tetraalkylammonium silicate include tetramethylammonium silicate, tetraethylammonium silicate, tetranormalpropylammonium silicate, tetraisopropylammonium silicate, and tetranormalbutylammonium silicate from the viewpoint of performance improvement and cost reduction of the derivative of the present invention. Among them, tetramethylammonium silicate, tetraethylammonium silicate, tetranormalpropylammonium silicate, and tetranormalbutylammonium silicate are more preferable. Examples of quaternary ammonium silicates containing aryl groups include benzyltrimethylammonium silicate.

  Such quaternary ammonium silicate is not particularly limited, but can be produced by a known method (for example, see Non-Patent Document 1).

  The quaternary ammonium silicate can be produced, for example, by using quaternary ammonium hydroxide and a Si-containing compound (Si source) as raw materials and reacting them in a dispersion. The order of mixing the raw materials is not particularly limited. For example, the Si source may be added to the quaternary ammonium hydroxide solution, or the quaternary ammonium hydroxide solution may be added to the Si source.

  The quaternary ammonium hydroxide is not particularly limited. For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetranormalpropylammonium hydroxide, tetranormalbutylammonium hydroxide, tetranormalpentylammonium hydroxide, Examples thereof include tetranormal hexyl ammonium hydroxide and benzyl trimethyl ammonium hydroxide. From the viewpoint of improving the performance and productivity of the derivatives of the present invention, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetranormal propyl ammonium hydroxide Tetranormal butylammonium hydroxide is preferred.

  The Si source is not particularly limited, and various Si-containing compounds such as silica powder, silica colloid, alkali metal silicate, and tetraalkoxysilane can be used. However, the performance and productivity of the derivative of the present invention can be used. From the viewpoint of improvement and simplification of the production process, silica powder and silica colloid are preferred.

  Examples of the solvent for the dispersion of the quaternary ammonium hydroxide and the Si source include water, organic solvents (for example, hydrophilic methanol, ethanol, etc.), water-organic mixed solvents, and the like. From the viewpoint of improving the performance and productivity of these derivatives, water is preferred. As water, distilled water and ion exchange water are more preferable.

The mixing ratio of the quaternary ammonium hydroxide and the Si source in producing the quaternary ammonium silicate is not particularly limited. From the viewpoint of improving the performance of the derivative of the present invention and reducing the cost, the quaternary hydroxide is used. ammonium represented by R ₂ O (R has the same meanings as in formula) represents the Si source in SiO _2, the molar ratio of R ₂ O and SiO ₂ of _{(SiO 2 / R 2 O)} x In this case, it is preferable that 0 <x '≦ 50, more preferably 2 ≦ x ′ ≦ 20, further preferably 4 ≦ x ′ ≦ 15, and particularly preferably 8 ≦ x ′ ≦ 12. .

The concentration of the Si source used for producing the quaternary ammonium silicate is not particularly limited, but from the viewpoint of improving the performance of the derivative of the present invention, reducing costs, and improving productivity, the concentration in terms of SiO ₂ weight is 0.1 to 50% by weight is preferred, 1 to 40% by weight is more preferred, and 3 to 20% by weight is even more preferred.

  The reaction temperature for producing the quaternary ammonium silicate is not particularly limited, but is preferably 0 to 100 ° C., more preferably 10 to 80 ° C. from the viewpoint of improving the performance and productivity of the derivative of the present invention. Preferably, 20 ° C to 60 ° C is more preferable.

  The reaction time is not particularly limited and depends on the reaction temperature, but from the viewpoint of improving the performance and productivity of the derivative of the present invention, it is preferably 1 minute to 240 hours, more preferably 1 to 48 hours, 2 to 24 hours is more preferable.

  As described above, a quaternary ammonium silicate used for the production of the derivative of the present invention is obtained. The silicate may be used as a solution after preparation, or a concentrated solution may be used, and further dried. You may use what was made into the powder or the crystal | crystallization by crystallization.

On the other hand, the organic acid used for the production of the derivative of the present invention is not particularly limited, but has excellent solubility in a solvent used when mixing the quaternary ammonium silicate and the organic acid, and is uniformly mixed. Preferably it is possible. In addition, from the viewpoint of maintaining the stability of the Q ₃ structure, the logarithmic value (pKa) of the reciprocal of the acid dissociation constant in an aqueous solution at 25 ° C. is preferably 0 to 10, more preferably 1 to 8, and more preferably 1 to 7 Are more preferred. The molecular weight of the organic acid is not particularly limited, and may be an oligomer having a molecular weight exceeding 10,000 or a polymer having a molecular weight exceeding 100,000. Further, the acidic functional group of the organic acid is not particularly limited. For example, an organic acid having a functional group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group can be used.

  Examples of such organic acids include alginic acid, acrylic acid, adipic acid, ascorbic acid, aspartic acid, benzoic acid, formic acid, acetic acid, citric acid, glycolic acid, succinic acid, cysteine, tartaric acid, lactic acid, fumaric acid, maleic acid, Examples include malic acid, aniline sulfonic acid, adenosine phosphoric acid, polyacrylic acid, polymalic acid, polyaspartic acid, polyglutamic acid, and the like, and adipic acid, acetic acid, citric acid from the viewpoint of performance improvement and cost reduction of the derivatives of the present invention. Succinic acid, tartaric acid, maleic acid and malic acid are preferred.

  The mixing method of the quaternary ammonium silicate and the organic acid in the production of the derivative of the present invention is not particularly limited, and a general mixing method can be used. For example, the mixing may be performed using shaking mixing, magnetic stirring, motor stirring, a homomixer, or the like. The mixing order of the quaternary ammonium silicate and the organic acid is not particularly limited, and the organic acid may be added to the quaternary ammonium silicate, the quaternary ammonium silicate may be added to the organic acid, A quaternary ammonium silicate and an organic acid may be simultaneously added to the solvent and mixed.

  The time for adding the quaternary ammonium silicate or the organic acid to the solvent is not particularly limited, and is preferably 1 second to 24 hours, and preferably 1 minute to 1 hour from the viewpoint of improvement in uniformity of mixing and productivity. 1 to 10 minutes is more preferable.

  The mixing form of the quaternary ammonium silicate and the organic acid is not particularly limited, and any of solid phase-solid phase mixing, solid phase-liquid phase mixing, and liquid phase-liquid phase mixing may be used. From the viewpoint of improving the performance and reducing the cost, solid-liquid phase mixing and liquid-liquid phase mixing are preferable, and liquid-liquid phase mixing is more preferable.

  The solvent used for the solid-liquid phase mixing or the liquid-liquid phase mixing is not particularly limited, but a solvent having good compatibility with the quaternary ammonium silicate and the organic acid is preferable. For example, water, an aqueous organic solvent such as alcohol, or a mixed solvent thereof can be used, but water is preferable from the viewpoint of improving the performance of the derivative of the present invention and reducing costs.

The mixing ratio of the quaternary ammonium silicate and the organic acid is not particularly limited, but R in the general formula (2) of the quaternary ammonium silicate is used from the viewpoint of improving the performance of the derivative of the present invention and reducing the cost. When expressed as a molar ratio (H / R) of H to H in organic acid (AH _m ), it is preferably 0.05 to 1, more preferably 0.1 to 1, and 0.2 to 1. More preferably, it satisfies 0.6 to 0.9, more preferably 0.8 to 0.9.

Further, the preparation concentration of the quaternary ammonium silicate when the derivative of the present invention is produced by solid phase-liquid phase mixing or liquid phase-liquid phase mixing is not particularly limited, but the performance improvement of the derivative of the present invention, From the viewpoint of cost reduction and productivity improvement, the SiO ₂ weight conversion concentration is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and further preferably 2 to 20% by weight.

  The reaction temperature between the quaternary ammonium silicate and the organic acid is not particularly limited, but is preferably 0 to 100 ° C, more preferably 10 to 80 ° C, from the viewpoint of improving the performance of the derivative of the present invention and reducing costs. More preferably, -60 ° C.

  In addition, the reaction time is not particularly limited, but from the viewpoint of performance improvement, cost reduction, and productivity improvement of the derivative of the present invention, 1 minute to 120 hours is preferable, 1 to 48 hours is more preferable, and 2 to 24 is preferable. Time is more preferred.

  The derivative of the present invention obtained by solid phase-liquid phase mixing or liquid phase-liquid phase mixing of a quaternary ammonium silicate and an organic acid is obtained as a dispersion, but it may be used as it is or after removing the solvent. It may be used as a solid (wet state or dry powder state). From the viewpoint of improving the performance of the derivative of the present invention and good versatility, it is preferably used as a solid.

  As described above, the derivative of the present invention is obtained. The derivatives can be suitably used, for example, for castings, detergent builders, civil engineering architecture, paper pulp, adhesives, ceramics, silica raw materials, aluminosilicate raw materials, paints, metal corrosion inhibitors, abrasives, resin additives, and the like. However, the application is not limited to these.

  The methods for measuring physical properties of samples used in Examples and the like are summarized below.

(NMR measurement of sample)
The sample was subjected to ²⁹ Si NMR measurement using tetramethylsilane (TMS) as an external standard by an NMR spectrometer (manufactured by Varian, INOVA UNITY 300, spin speed 5 kHz). In the obtained ²⁹ Si NMR spectrum, a peak attributed to Q ₃ was observed at −100 ppm vs. TMS, and a peak attributed to Q ₄ was observed at −110 ppm vs. TMS, and peak separation was performed by Gaussian fitting. peak area was calculated the ratio a ₃ / (a ₃ + a ₄₎ of the peak area a ₄ of which are attributable to the peak area a ₃ and Q ₄ of which are assigned to Q _3.

(PH of sample)
At room temperature (25 ° C), 9.9 g of water was added to 0.1 g of the sample and mixed to obtain a 1% by weight aqueous dispersion of the sample. Then, the sample was allowed to stand at 25 ° C for 2 hours, and the pH electrode (9621-10D , Manufactured by HORIBA, Ltd.), and the pH of the aqueous dispersion at 25 ° C. was measured.

Production Example 1
A quaternary ammonium silicate as a sample raw material was produced as follows. That is, by adding 44 g of water to 30 g of silica (fumed silica, manufactured by Aldrich), adding 259 g of a 10% tetranormal butyl ammonium hydroxide aqueous solution (manufactured by Wako Pure Chemical Industries), and shaking and mixing at 45 ° C. for 1 day, A tetranormalbutylammonium silicate aqueous dispersion (SiO ₂ concentration in terms of 9% by weight) was obtained. In addition, when the chemical composition of the anhydride of the silicate was expressed as the general formula (2), x was 10.

Example 1
While stirring at room temperature (25 ° C.), 10 g of an aqueous solution in which 0.15 g of citric acid (manufactured by Wako Pure Chemical Industries) was dissolved in 10 g of the tetranormalbutylammonium silicate aqueous dispersion of Production Example 1 was added dropwise over 1 minute. After stirring for 15 hours, the sample was freeze-dried to obtain a white powder sample (tetranormal butylammonium silicate derivative).

Example 2
While stirring at room temperature (25 ° C.), 10 g of an aqueous solution in which 0.14 g of maleic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 10 g of the tetranormalbutylammonium silicate aqueous dispersion of Production Example 1 was added dropwise over 1 minute. After stirring for 15 hours, the sample was freeze-dried to obtain a white powder sample (tetranormal butylammonium silicate derivative).

Comparative Example 1
Under stirring at room temperature (25 ° C.), 10 g of an aqueous solution in which 0.42 mL of concentrated hydrochloric acid (HCl 35 wt% aqueous solution, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 10 g of the tetranormalbutylammonium silicate aqueous dispersion of Production Example 1 for 1 minute. The mixture was added dropwise, stirred at room temperature for 15 hours, and then freeze-dried to obtain a white powder sample (tetranormal butylammonium silicate hydrochloric acid treated product).

Comparative Example 2
A sample was prepared according to Comparative Example 1. When an aqueous solution in which 0.84 mL of concentrated hydrochloric acid was dissolved was added dropwise to the aqueous dispersion in the same manner, gelation occurred immediately after the addition. The obtained gel was allowed to stand at room temperature for 15 hours and then freeze-dried to obtain a white powder sample (tetran-butylammonium silicate hydrochloric acid treated product).

Comparative Example 3
Under stirring at room temperature (25 ° C.), 10 g of the aqueous tetranormalbutylammonium silicate dispersion of Production Example 1 was freeze-dried to obtain the white silicate.

The production conditions and properties of the samples of Examples 1 and 2 and Comparative Examples 1 to 3 are summarized in Table 1. The mixing molar ratio indicates the molar ratio (H / R) between R when tetranormal butyl ammonium silicate is represented by the general formula (2) and H when the organic acid used is represented by AH _m. . Moreover, the value of x and m * y about a sample shows the value at the time of expressing the chemical composition of the sample's anhydride as the said General formula (1). The pH indicates the pH of a 1% by weight aqueous dispersion of the sample.

As is clear from the comparison of the results of Examples 1 and 2 and Comparative Examples 1 and 2, by mixing organic acid such as citric acid and maleic acid with tetranormal butyl ammonium silicate, compared with mixing with hydrochloric acid. Q low pH of tetra-n-butyl ammonium silicate derivatives that are obtained can be seen in ₃ state structure was more hold. In addition, the comparative example 3 shows the property of the tetranormal butyl ammonium silicate at the time of not mixing with an organic acid in Example 1 and 2. FIG.

  Suitable for a wide range of applications such as castings, detergent builders, civil engineering architecture, paper pulp, adhesives, ceramics, silica raw materials, aluminosilicate raw materials, paints, metal corrosion inhibitors, abrasives, resin additives, etc. Quaternary ammonium silicate derivatives are provided that can be used in

Claims (5)

Ratio of the peak area A ₃ constituting the signal attributed to Q ₃ in the ²⁹ Si NMR spectrum to the area A _{4 of} the peak constituting the signal attributed to Q ₄ [A ₃ / (A ₃ + A ₄ ) Is a quaternary ammonium silicate derivative having a pH of 9.5 or less at 25 ° C. of a 1% by weight aqueous dispersion , wherein the chemical composition of the anhydride is represented by the following general formula (1):
R ₂ O · xSiO ₂ · yAH _m (1)
(In the formula, R represents a molecule that becomes a quaternary ammonium cation, AH _m represents an organic acid that generates m H ⁺ upon dissociation , x represents 0 <x ≦ 50, and m × y represents 0.1 ≦ m ×. a quaternary ammonium silicate derivative represented by y ≦ 2 . The chemical composition of the anhydride is represented by the following general formula (2):
R ₂ O · xSiO ₂ (2)
(Wherein R represents a molecule that becomes a quaternary ammonium cation, and x satisfies 0 <x ≦ 50) and an organic acid (AH that generates m H ⁺ upon dissociation) _The quaternary ammonium silicate derivative according to claim 1, which is obtained by mixing _m ). The quaternary ammonium silicate derivative according to claim 2, which is 0.05 to 1 when the mixing ratio of the quaternary ammonium silicate and the organic acid is represented by a molar ratio of R and H (H / R). The chemical composition of the anhydride is represented by the following general formula (2):
R ₂ O · xSiO ₂ (2)
(Wherein R represents a molecule that becomes a quaternary ammonium cation, and x satisfies 0 <x ≦ 50) and an organic acid (AH that generates m H ⁺ upon dissociation) The manufacturing method of the quaternary ammonium silicate derivative | guide_body of Claim 1 which has the process of mixing _m ). The production method according to claim 4, wherein the mixing ratio of the quaternary ammonium silicate and the organic acid is 0.05 to 1 when expressed in terms of a molar ratio of R and H (H / R).