JP6198509B2 - Siloxane antistatic agent composition and method for producing the same - Google Patents

Description

  The present invention relates to a siloxane-based antistatic agent composition, that is, an antistatic agent composition having a siloxane skeleton and a method for producing the same. More specifically, the siloxane-based antistatic agent composition of the present invention is in a liquid state, and when an application film is formed from this composition, it exhibits an excellent antistatic effect without change over time, and is excellent. Water resistance, solvent resistance, etc. can be shown. This siloxane-based antistatic agent composition is produced by hydrolyzing tetraalkoxysilane or its oligomer and phenylalkoxysilane or its oligomer to form a siloxane skeleton in the hydrolysis product, and then adding polystyrene sulfonic acid thereto. can do.

  As is well known, antistatic agents are widely used in various fields in order to solve the problem of static electricity disturbance in the industrial world. When applied to an object to be antistatic, the antistatic agent forms a functional coating film (coating film) having a surface resistance that can quickly reduce or eliminate static electricity generated in the object, It is a coating agent that can solve obstacles. One such antistatic agent is a siloxane antistatic agent. A siloxane antistatic agent obtained by using tetraalkoxysilane or an oligomer thereof as a raw material can exhibit an antistatic effect by silanol in the siloxane skeleton. The siloxane antistatic agent is characterized in that the antistatic effect can be stably maintained over a long period of time as compared with the antistatic agent obtained by using a surfactant. However, the siloxane antistatic agent does not have sufficient water resistance depending on the application, and it is desired to further improve this point.

As an improved water resistance, a hydrolyzate obtained by adding an organoalkoxysilane represented by RSi (OR) ₃ to tetraalkoxysilane has long been known as a coating composition (Patent Document 1). However, although this composition has improved water resistance and relatively good adhesion to glass substrates, the adhesion to organic substrates different from inorganic substrates such as glass substrates. Not only is inferior, but also has poor alkali resistance and exhibits insufficient curing. There is also a proposal for an antistatic agent comprising a mixture of two types of organoalkoxysilane hydrolysates. Although this antistatic agent has been shown to improve water resistance, it has good adhesion to various substrates. There is a drawback that the performance is significantly reduced and the antistatic effect is not exhibited as expected.

  On the other hand, conductive polymers such as aniline, pyrrole, and thiophene polymers were added to the siloxane-based coating solution, such as polystyrene sulfonic acid, polyacrylic acid, methane sulfonic acid, and alkylbenzene sulfonic acid. Liquid antistatic or conductive coating compositions are known (Patent Documents 2 and 3). However, since the effect of these liquid coating compositions depends on the added conductive polymer, it is necessary to increase the amount of the conductive polymer used in order to exhibit a certain level of conductivity, that is, an antistatic effect. There is a disadvantage that transparency is impaired thereby. Moreover, the coating film formed of these organic conductive polymers does not have sufficient heat resistance.

  In addition, an antistatic agent in which polystyrene sulfonic acid (PSS) is combined with polyethylenedioxythiophene (PEDOT), which is a conductive substance, is known. However, in the case of this antistatic agent, since the conductive material itself does not have water resistance, the water resistance is maintained by adding a water-insoluble substance such as an organic polymer binder. However, the organic polymer antistatic agent has a drawback that the hardness of the coating film is lower than that of the siloxane antistatic agent and the field of use is limited.

  In order to improve the hardness of the resulting coating film, it is also conceivable to use an ultraviolet (UV) curable organic polymer binder. In this case, a coating film having high hardness and improved water resistance and other performances can be obtained, but it cannot be processed without an expensive UV curing apparatus, and it is necessary to search for uniform curing conditions. But it's not an easy method to apply.

  By the way, since the above-mentioned polystyrene sulfonic acid (PSS) has excellent heat resistance, good dispersibility, and has an antistatic function, when producing a composite material of a phenol resin, an organic sulfonic acid curing agent is used. There is an example used as an additive for the purpose of eliminating non-uniform dispersion (Patent Document 4). However, since PSS is a water-soluble anionic polymer, when it is used as an antistatic agent, there is an important drawback that the water resistance that would originally be lost is lost on the surface of the resulting coating film. .

JP 49-14535 A Japanese Patent Laid-Open No. 10-69865 JP 2010-33881 A JP 2001-98142 A

  Accordingly, an object of the present invention is to exhibit an excellent antistatic effect without change over time when a coating film is formed, and is excellent in water resistance and solvent resistance, and also has heat resistance, transparency, coating film hardness, substrate An object of the present invention is to provide a liquid siloxane-based antistatic agent composition that is excellent in adhesion and the like, and a method for producing the same. Other objects of the present invention will be understood from the following detailed description.

  As a result of diligent research to achieve the above object, the inventors of the present invention have excellent heat resistance, good dispersibility, and an antistatic function, but are soluble in water. Even an anionic polymer that could not be used in the past, namely polystyrene sulfonic acid (PSS), achieved its intended purpose when used in combination with a specific alkoxysilane polycondensate. It was discovered that a liquid siloxane-based antistatic agent composition can be provided, and the present invention has been completed.

In one aspect of the present invention,
It is obtained by hydrolyzing a mixture of tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer and then subjecting it to a polycondensation reaction, and having a siloxane bond (Si-O-Si) as a skeleton. An alkoxysilane hydrolyzed polycondensate having:
Polystyrene sulfonic acid,
The alkoxysilane hydrolyzed polycondensate and a solvent obtained by dissolving the polystyrene sulfonic acid, wherein the phenyl group of the alkoxysilane hydrolyzed polycondensate and the phenyl group of the polystyrene sulfonic acid are π · π mutual. The liquid antistatic agent composition is characterized in that a laminated structure is formed by action.

  In the liquid antistatic agent composition of the present invention, the proportion of tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer in the alkoxysilane hydrolysis polycondensate is preferably in a weight ratio. It is in the range of about 1: 0.1-1.

  The polystyrene sulfonic acid is preferably about 1.0 to 30 with respect to the total amount of tetraalkoxysilane and / or oligomer thereof and phenylalkoxysilane and / or oligomer thereof in the alkoxysilane hydrolysis polycondensate. It is mixed in an amount of 0.0% by weight.

  Furthermore, the degree of polycondensation of the alkoxysilane hydrolyzed polycondensate is usually in the range of about 2 to 10,000. This degree of polycondensation is preferably in the range of about 2-100, more preferably in the range of about 2-30.

In another aspect of the present invention, the liquid antistatic composition comprises an alkoxysilane hydrolyzed polycondensate, polystyrene sulfonic acid, and a solvent obtained by dissolving the alkoxysilane hydrolyzed polycondensate and polystyrene sulfonic acid. A method for producing an agent composition comprising:
(A) Hydrolysis polycondensation of tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer, respectively, in the presence of water and a catalyst, thereby hydrolyzing each alkoxysilane Prepare a condensate and prepare a binder liquid containing the respective alkoxysilane hydrolyzed polycondensate mixed, or else
(B) After mixing tetraalkoxysilane and / or its oligomer with phenylalkoxysilane and / or its oligomer, the resulting mixture is subjected to hydrolysis polycondensation in the presence of water and a catalyst, whereby Prepare a binder liquid containing alkoxysilane hydrolysis polycondensate,
Polystyrene sulfonic acid is added to the obtained binder liquid in an amount of 1.0 to 30.0% by weight based on the total amount of the tetraalkoxysilane and / or its oligomer and the phenylalkoxysilane and / or its oligomer. And a liquid antistatic agent composition in which the total concentration of the alkoxysilane hydrolyzed polycondensate and the polystyrenesulfonic acid in the whole solution is in the range of 1.5 to 40.0% by weight is prepared. In the method for producing a liquid antistatic agent composition.

In this production method, when the binder liquid is prepared by the step (a), the amount of each alkoxysilane in the obtained binder liquid is changed to tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer, respectively. Prepared in an amount of 1: 0.1-1 weight ratio,
Tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer are each dissolved in a solvent in such an amount that the total concentration of the respective alkoxysilane is 1.0 to 20.0% by weight,
The obtained solution is subjected to hydrolysis polycondensation in the presence of water and a catalyst added thereto to prepare respective alkoxysilane hydrolysis polycondensates, and the respective alkoxysilane hydrolysis polycondensates are mixed. It is preferable to prepare a binder liquid to be included.

  In the preparation of the solution described above, the solvent used is preferably a solvent containing isopropanol, n-butanol or ethanol alone or in combination.

Moreover, when preparing a binder liquid by a process (b), tetraalkoxysilane and / or its oligomer, and phenylalkoxysilane and / or its oligomer are mixed by the weight ratio of 1: 0.1-1.
The obtained alkoxysilane mixture is dissolved in a solvent in an amount such that the concentration of the alkoxysilane mixture is 1.0 to 20.0% by weight,
It is preferable to carry out hydrolysis polycondensation of the obtained mixed liquid in the presence of water and a catalyst added thereto to prepare a binder liquid containing the alkoxysilane hydrolyzed polycondensate of the mixture.

  Here, the solvent used for preparing the mixed solution is preferably a solvent containing isopropanol, n-butanol or ethanol alone or in combination.

In another aspect of the present invention, the liquid antistatic composition comprises an alkoxysilane hydrolyzed polycondensate, polystyrene sulfonic acid, and a solvent obtained by dissolving the alkoxysilane hydrolyzed polycondensate and polystyrene sulfonic acid. A method for producing an agent composition comprising:
Mixing tetraalkoxysilane and / or its oligomer with phenylalkoxysilane and / or its oligomer,
Polystyrene sulfonic acid is added to the resulting alkoxysilane mixture in an amount of 0.5 to 30.0% by weight based on the amount of the alkoxysilane mixture,
Dissolving the alkoxysilane mixture with the addition of polystyrene sulfonic acid in a solvent;
The obtained mixed solution is subjected to hydrolysis polycondensation in the presence of water and a catalyst added thereto, and the total concentration of the obtained alkoxysilane hydrolyzed polycondensate and the polystyrenesulfonic acid in the total solution is The present invention resides in a method for producing a liquid antistatic agent composition, which comprises preparing a liquid antistatic agent composition in a range of 1.5 to 40.0% by weight.

  In this production method, tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer are preferably mixed in a weight ratio of 1: 0.1-1.

  Furthermore, the present invention provides a method for producing an antistatic film comprising a step of applying a liquid antistatic agent composition as described above on an arbitrary substrate to form a coating film, and a liquid antistatic method as described above. In any article with an antistatic film formed from the agent composition. In the practice of the present invention, the thickness of the coating film is not particularly limited, and can be any film thickness suitable for the antistatic film.

The antistatic agent composition according to the present invention exhibits good antistatic performance of about 10 ⁶ to 10 ⁸ Ω as a surface resistance value, and can exhibit good water resistance and solvent resistance. In addition, the obtained antistatic coating film, that is, the antistatic film, can eliminate the limitation on the substrate on which it is applied. That is, even if the substrate is an inorganic substrate such as glass, or an organic substrate such as an acrylic resin or PET, it can have good adhesion, and further, polycarbonate resin and polyolefin resin which are difficult-to-adhere substrates. Also, a coating film can be satisfactorily formed on a polycycloolefin resin and a nylon resin. Furthermore, the coating film is colorless and transparent, and exhibits an antistatic effect excellent in transparency. In particular, the coating film has little change over time, and a good antistatic effect can be continued for a long period of time.

  The excellent effect as described above is that there is a siloxane skeleton (Si-O-Si) holding a phenyl group in the alkoxysilane hydrolysis polycondensate as a binder component, and polystyrene sulfonic acid (PSS) is added to this. Therefore, it is considered that this is achieved by forming a laminated structure by the π / π interaction of both phenyl groups and improving the water resistance of the siloxane-based binder and the water resistance and solvent resistance of the PSS.

  The invention will now be described with reference to its preferred embodiments. In addition, this invention is not limited to the following embodiment, A change and improvement can be arbitrarily given within the scope of the present invention.

  The present invention relates to a binder component comprising a hydrolyzed polycondensate having a siloxane bond as a skeleton obtained by hydrolyzing and polycondensating a tetraalkoxysilane and / or oligomer thereof and phenylalkoxysilane and / or oligomer thereof. And a liquid antistatic agent composition obtained by dissolving polystyrene sulfonic acid (PSS) in a solvent.

The tetraalkoxysilane and oligomer thereof used in the present invention can be represented by the following formulas: Si (OR) ₄ and Si _n O _n-1 (OR) _{2n + 2} , respectively. In these formulas, each R may be the same or different and each independently represents an alkyl group having 1 to 6 carbon atoms. Moreover, about an oligomer, the low condensate of n = 2-10 is used. Specific examples of the tetraalkoxysilane and its oligomer used in the present invention include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and in particular, tetramethoxysilane and tetraethoxysilane. Is preferred. Such a silane having a methoxy group or an ethoxy group can be obtained at a low cost, and the (co) hydrolysis reaction can proceed smoothly even in the presence of phenylalkoxysilane.

  The oligomer of tetraalkoxysilane can be obtained by hydrolyzing and condensing these alkoxysilane monomers. As described above, a dimer to a 10-mer are preferably used as such an oligomer. Commercially available products include methyl silicate 51, which is an average tetramer oligomer of tetramethoxysilane, and ethyl silicate 40, which is an average pentamer oligomer of tetraethoxy silane, and these are preferably used. Moreover, in this invention, alkoxysilane and its oligomer may each be used independently, and may mix and use both.

The phenylalkoxysilane used in combination with the tetraalkoxysilane and / or its oligomer in the practice of the present invention has the following formula: Ph _n Si (OR) _4-n (wherein Ph represents a phenyl group, R is They may be the same or different and each independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 2. Moreover, as an oligomer of phenylalkoxysilane, a 2-10 mer can be used.

  Specific examples of the phenylalkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltri-n-butoxysilane, and preferably phenyltrimethoxysilane and phenyltriethoxysilane. Used. These methoxysilanes and ethoxysilanes have an advantage that the reaction proceeds smoothly because the reaction speed is similar in the co-hydrolysis reaction with the tetraalkoxysilane described above. Further, diphenyl dialkoxysilane or the like in which two phenyl groups are bonded to silicon (Si) can also be used. In this case, the alkoxy group is preferably a methoxy group or an ethoxy group. The oligomer is preferably a dimer or trimer of the above-mentioned phenylalkoxylane condensate. Also in the phenylalkoxysilane, the phenylalkoxysilane and the oligomer thereof may be used alone or in combination.

  When preparing the hydrolyzed polycondensate, the ratio of tetraalkoxysilane and / or oligomer to phenylalkoxysilane and / or its oligomer is usually preferably in the range of about 1: 0.1 to 1 by weight. If more phenylalkoxysilane is used than tetraalkoxysilane, the adhesion to the substrate is reduced. On the other hand, if the ratio is lower than this ratio, there is no problem in terms of adhesiveness, but water resistance is lowered, which is not preferable.

  Polystyrene sulfonic acid (hereinafter also abbreviated as “PSS”) refers to a polymer obtained by sulfonating polystyrene, and is represented by the following formula.

  In the above formula, M represents hydrogen or a monovalent alkali metal, and n is a numerical value such that the weight average molecular weight (Mw) is in the range of about 10,000 to 100,000. A preferred molecular weight range is about 60,000-80,000. The polystyrene sulfonic acid may be any polystyrene sulfonic acid compound derived from the above general formula, as long as the antistatic agent composition of the present invention is not adversely affected.

  Polystyrene sulfonic acid is soluble in water, alcohols, ketones, esters and the like, and is usually marketed as a solution or dispersion containing about 10 to 30% by weight of polystyrene sulfonic acid in these solvents. Yes. The properties of such a liquid are pH of 9.0 or less, and the viscosity is about 150 mPa · s or less, although it varies depending on the PSS concentration and the type of solvent. The amount of PSS used is about 0.5 to 30.0% by weight, particularly 3.0 to 20.0%, based on the weight of the polycondensate of tetraalkoxysilane and / or oligomer and phenylalkoxysilane and / or oligomer thereof. It is preferable to add in an amount of% by weight. When the amount of PSS added is increased beyond the above range, the antistatic effect is not improved, the water resistance is significantly reduced, and the adhesiveness to the substrate is lowered. Moreover, it is not preferable to reduce the addition amount to the above range or less because the required antistatic effect cannot be exhibited.

  The liquid antistatic agent composition of the present invention can be usually produced as follows. In addition, as long as the target liquid antistatic agent composition can be manufactured, you may change arbitrarily the order of process, conditions, etc. as needed.

  First, tetraalkoxysilane or its oligomer and phenylalkoxysilane or its oligomer are hydrolyzed in a solvent, and further a polycondensation reaction is performed to prepare a binder liquid. Here, tetraalkoxysilane or oligomer thereof and two types of alkoxysilane, phenylalkoxysilane or oligomer thereof, are used. These alkoxysilanes are subjected to hydrolysis and polycondensation reaction separately, and then obtained hydrolysis The polycondensate may be mixed, or both may be mixed from the beginning and the target hydrolyzed polycondensate may be produced by cohydrolysis and polycondensation reaction.

  As the solvent used for the hydrolysis polycondensation reaction, an alcohol solvent is suitable, but isopropanol (IPA) and n-butanol (BuOH) are particularly preferable. The concentration of alkoxysilane in carrying out the reaction is usually about 1.0 to 20.0% by weight, and also in the case of an oligomer of alkoxysilane, about 1.0 to 20.0% by weight. In the case of using a mixture of oligomers, the total amount is about 1.0 to 20.0% by weight, preferably about 1.0 to 10.0% by weight.

  In the hydrolysis of phenyltrialkoxysilane and / or its oligomer, the concentration of alkoxysilane in the reaction system is usually about 1.0 to 20.0% by weight, preferably about 1.0 to 10.0% by weight. %.

  In preparing the binder liquid, for example, tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer are placed in a flask and isopropanol (IPA), n-butanol (BuOH) and / or ethyl alcohol as a reaction solvent. (EtOH) is added and hydrolyzed in the flask. It is preferable that IPA in the reaction solution is used in an amount of about 20 to 40% by weight and BuOH in an amount of about 30 to 60% by weight. In addition, EtOH may be used in an amount of about 1 to 30% by weight, and other solvents such as ethyl acetate and methanol may be added within a range of 0 to about 10% by weight as necessary. Other than the solvent, water, silane, catalyst and the like can be present in the reaction system. The reason why it is particularly preferable to use IPA and BuOH as the reaction solvent is that such a solvent is present in the antistatic agent composition finally obtained using a binder liquid obtained by hydrolysis in a solvent. This is because the formation of the coating film is advantageous.

  In the hydrolysis, the mixture of the alkoxysilane and the solvent is heated while uniformly stirring to heat the liquid temperature within a range of about 30 to 70 ° C. A desirable temperature is about 30-60 ° C. When water is added for hydrolysis, the water is preferably added after warming. The water used for the reaction is desirably added in the range of about 2.0 to 8.0% by weight so as to be in the range of about 1.0 to 10.0% by weight in the reaction solution. Hydrolysis catalysts include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid and acetic acid. A mixed system of sulfuric acid, hydrochloric acid, and phosphoric acid is most preferred, and these are each about 50 ppm to 0.00. While adding within the range of 5% by weight, the desired addition is in the range of about 100 ppm to 0.1% by weight. The reaction time of the reaction performed by adding the catalyst together with water is about 2 to 100 hours, and the reaction is performed with stirring. The preferred range of reaction time is about 4 to 60 hours.

  When preparing the binder liquid as described above, the reaction does not proceed smoothly when the amount of catalyst used is 50 ppm or less. When the catalyst is used in an amount of 0.5% by weight or more, it becomes difficult to control the reaction, and the possibility of causing gelation during the reaction increases. Although the reaction time is also related to the amount of catalyst used, it is not preferable if it is outside the above range because gelation or the like that is too long occurs.

  The binder liquid obtained by the above reaction contains about 2.0 to 40% by weight, preferably about 2.0 to 15% by weight, of a binder component having a siloxane bond (Si—O—Si) skeleton. ing. When PSS is added to the binder liquid in the form of a dispersion, and the ratio of the two is adjusted to about 99.0 to 70.0% by weight: about 1.0 to 30.0% by weight, An antistatic agent solution, that is, a liquid antistatic agent composition can be obtained. Here, the amount of the PSS dispersion to be added is appropriately changed according to the concentration of the binder component having a siloxane bond skeleton in the binder liquid. For example, a dispersion containing 20% by weight of PSS. Is practically about 3.0 to 30.0% by weight of the dispersion is added to the binder liquid. Further, a predetermined amount of PSS can be added during the hydrolysis / polycondensation reaction of alkoxysilane.

  The antistatic agent solution obtained as described above contains IPA and BuOH as preferred solvents, a component having a siloxane-based skeleton derived from tetraalkoxysilane and phenylalkoxysilane, and polystyrenesulfonic acid. The components are included in an amount of about 1.5-40% by weight, expressed as a total concentration.

  Subsequently, the present invention will be described in more detail by way of its examples. The present invention is not limited to these examples. In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Example 1
17.8 parts of an average pentamer of tetraethoxysilane (trade name “ethyl silicate 40”, manufactured by Colcoat Co., Ltd.) and 9.3 parts of phenyltrimethoxysilane are placed in a separable flask, and 120 parts of isopropyl alcohol ( IPA) and 150 parts n-butanol (BuOH) were added and the contents were heated to 40 ° C. with stirring. When the liquid temperature in the separable flask became constant at 40 ° C., 26.2 parts of water (H ₂ O) and 0.3 part of sulfuric acid (H ₂ SO ₄ ; 95%) were added, and then 40 ° C. And stirred for 10 hours. The intended reaction solution was obtained.

  The obtained reaction liquid was a binder liquid containing a cohydrolyzate from 17.8 parts of tetraethoxysilane oligomer and 9.3 parts of phenyltrimethoxysilane as a compound having a siloxane skeleton. Subsequently, 95.0 parts of binder liquid and 5.0 parts of PSS dispersion (concentration: 20% by weight, PSS molecular weight: 60,000-80,000, trade name “VERSA-TL 72”, Akzo Nobel Co., Ltd.) Was added with stirring and stirring was continued for 1 hour. The intended coating solution was obtained.

  Subsequently, the coating solution obtained as described above was uniformly applied to a 50 μm-thick polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd.), which had been washed in advance, with a bar coater # 5. It processed for 5 minutes at the temperature of 120 degreeC with the electric constant temperature dryer. A coating film having a predetermined film thickness was obtained.

〔Evaluation test〕
Evaluation of antistatic effect In order to evaluate the antistatic effect of the obtained coating film, the surface resistance value (Ω) of the coating film of the sample was measured. Using a resistivity meter (trade name “Loresta GP MCP-T610”, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) based on the 4-terminal 4-probe method, the surface resistance value was measured in accordance with JIS-K7194. The surface resistance value of the test coating film was 2.5 × 10 ⁸ (Ω) as shown in Table 1 below.

Evaluation of adhesion In order to evaluate the adhesion of the obtained coating film, a cello tape peeling test (cross-cut method) was performed in accordance with JIS-K5600-5. After making a total of 100 grids with a 1 mm interval grid cut on the surface of the coating film of the sample, a 24 mm wide adhesive tape (registered trademark “Sero Tape”, manufactured by Nichiban Co., Ltd.) ) Was immediately peeled off, and the presence or absence of peeling of the coating film was visually observed. The adhesion was evaluated by the number of squares adhered without peeling (number of adhesion eyes) / 100. The adhesion of the test coating film was 100/100 as shown in Table 1 below.

Evaluation of water resistance In order to evaluate the water resistance of the obtained coating film, a water resistance test (water immersion method) was carried out in accordance with JIS-K5600-6. After immersing the sample coating film in water at room temperature for 16 hours, the presence or absence of peeling of the coating film was visually observed. The water resistance of the test coating film was good, and as shown in Table 1 below, no change such as peeling was observed in the coating film.

Wipe test After the water resistance test was completed, the surface of the coating film of the same sample was wiped with a non-woven wipe sheet multiple times, and the presence or absence of peeling of the coating film was visually observed. As shown in Table 1 below, no change such as peeling was observed in the coating film.

Evaluation of solvent resistance In order to evaluate the solvent resistance of the obtained coating film, a solvent resistance test (solvent immersion method) was carried out in accordance with JIS-K5600-6. After immersing the sample coating film in five solvents at room temperature: methanol, ethanol, isopropyl alcohol (IPA), ethyl acetate and methyl ethyl ketone (MEK) for 16 hours, whether or not the surface resistance of the coating film changed The presence or absence of occurrence of peeling and the like was measured and visually observed. The solvent resistance of the test coating film was good, and as shown in Table 2 below, the surface resistance value did not change in the coating film, and changes such as peeling were not observed.

Evaluation of time-dependent change of antistatic effect In order to evaluate the time-dependent change of antistatic effect of the obtained coating film, the surface resistance value (Ω) of the coating film of the sample was measured for 6 months immediately after the drying treatment and under a predetermined environment. It was measured in two stages after being left for a while. The leaving environment was temperature: 23 ° C. ± 2 ° C. and relative humidity: 55 ± 5%. The measuring method is as described above. As shown in Table 3 below, the surface resistance value of the test coating film was 2.5 × 10 ⁸ (Ω) before change with time and 5.5 × 10 ⁸ (Ω) after change with time.

Evaluation of the effect of antistatic effect under low humidity environment In order to evaluate the effect of the antistatic effect of the obtained coating film under low humidity environment, the surface resistance value (Ω) of the sample coating film is dried The measurement was performed in two stages immediately after the measurement and after being left for 24 hours in a low humidity environment. The low-humidity environment was temperature: 23 ° C. ± 2 ° C. and relative humidity: 30% or less. The measuring method is as described above. As shown in Table 4 below, the surface resistance value of the test coating film is 2.5 × 10 ⁸ (Ω) before standing in a low humidity environment, and 1.2 × 10 after standing in a low humidity environment. ⁹ (Ω).

Example 2
The procedure described in Example 1 was repeated, but in this example, 10 parts of PSS dispersion (both prepared in Example 1) were added to 90 parts of the binder liquid while stirring to achieve the desired coating. A liquid was prepared. When the obtained coating film was subjected to an evaluation test for the same items as in Example 1, satisfactory results described in Tables 1 to 4 below were obtained.

Example 3
Although the procedure described in Example 1 was repeated, in this example, in order to prepare the binder liquid, instead of the average pentamer oligomer of tetraethoxysilane, methyl silicate oligomer (average tetramer; trade name “methyl” Silicate 51 "(manufactured by Colcoat Co., Ltd.) in an amount of 13.6 parts, 9.3 parts of phenyltrimethoxysilane, 120 parts of IPA and 150 parts of BuOH were added thereto, and the mixture was heated and stirred. Furthermore, 26.6 parts of water (H ₂ O) and 0.3 parts of H ₂ SO ₄ (95%) were added, and the mixture was stirred at 40 ° C. for 10 hours to carry out hydrolysis and copolycondensation reaction. . The intended binder liquid was obtained.

  The target coating liquid is obtained by adding 5.0 parts of PSS dispersion (trade name “VERSA-TL 72”, manufactured by Akzo Nobel Co., Ltd.) to 95.0 parts of the binder liquid while stirring. Was prepared. When the obtained coating film was subjected to an evaluation test for the same items as in Example 1, satisfactory results described in Tables 1 to 4 below were obtained.

Example 4
Although the procedure described in Example 3 was repeated, in this example, 10.0 parts of PSS dispersion (both described in Example 3) were added to 90.0 parts of binder liquid with stirring, The desired coating solution was prepared by stirring. When the obtained coating film was subjected to an evaluation test for the same items as in Example 1, satisfactory results described in Tables 1 to 4 below were obtained.

Example 5
Although the procedure described in Example 3 was repeated, in this example, instead of 13.6 parts, methyl silicate oligomer was used in an amount of 12.2 parts, to which 10.3 parts of phenyltrimethoxysilane. , 120 parts IPA and 150 parts BuOH were added and heated and stirred, then 25.5 parts water (H ₂ O) and 0.3 parts H ₂ SO ₄ (95%) were added and 10 ° C. at 40 ° C. The mixture was stirred for a time and subjected to hydrolysis / copolycondensation reaction to obtain a binder liquid.

  The target coating liquid is obtained by adding 5.0 parts of PSS dispersion (trade name “VERSA-TL 72”, manufactured by Akzo Nobel Co., Ltd.) to 95.0 parts of the binder liquid while stirring. Was prepared. When the obtained coating film was subjected to an evaluation test for the same items as in Example 1, satisfactory results described in Tables 1 to 4 below were obtained.

Example 6
Although the procedure described in Example 5 was repeated, in this example, 10.0 parts of PSS dispersion (both described in Example 5) were added to 90.0 parts of binder liquid with stirring, The desired coating solution was prepared by stirring. When the obtained coating film was subjected to an evaluation test for the same items as in Example 1, satisfactory results described in Tables 1 to 4 below were obtained.

Example 7
Although the procedure described in Example 5 was repeated, in this example, 15.0 parts of PSS dispersion (both described in Example 5) were added to 85.0 parts of binder liquid with stirring, The desired coating solution was prepared by stirring. When the obtained coating film was subjected to an evaluation test for the same items as in Example 1, satisfactory results described in Tables 1 to 4 below were obtained.

Example 8
Although the procedure described in Example 5 was repeated, in this example, 82.5 parts of binder liquid (as described in Example 5) was added to 17.1 parts of PSS dispersion (PPS content: 10.5). % By weight; trade name “PS-5H” (manufactured by Tosoh Organic Chemical Co., Ltd.) was added with stirring, and the desired coating solution was prepared by stirring. When the obtained coating film was subjected to an evaluation test for the same items as in Example 1, satisfactory results described in Tables 1 to 4 below were obtained.

Comparative Example 1
Although the method described in Example 1 was repeated, in this example, for comparison, a reaction was performed without adding phenyltrimethoxysilane to prepare a target binder solution. Next, 5.0 parts of PSS dispersion (as described in Example 1) was added to 95.0 parts of binder liquid to prepare a desired coating liquid. A coating film was formed from the obtained coating solution by the same method as in Example 1, and the obtained coating film was subjected to an evaluation test on the same items as in Example 1. The following Tables 1 to 4 were used. The stated results were obtained.

Comparative Example 2
Although the method described in Example 1 was repeated, in this example, for comparison, a reaction was performed without adding phenyltrimethoxysilane to prepare a target binder solution. Next, 10.0 parts of a PSS dispersion (as described in Example 1) was added to 90.0 parts of a binder liquid to prepare a desired coating liquid. A coating film was formed from the obtained coating solution by the same method as in Example 1, and the obtained coating film was subjected to an evaluation test on the same items as in Example 1. The following Tables 1 to 4 were used. The stated results were obtained.

Comparative Example 3
Although the method described in Example 3 was repeated, in this example, for comparison, a reaction was performed without adding phenyltrimethoxysilane to prepare a target binder solution. Next, 5.0 parts of PSS dispersion (as described in Example 3) was added to 95.0 parts of binder liquid to prepare a desired coating liquid. A coating film was formed from the obtained coating solution by the same method as in Example 1, and the obtained coating film was subjected to an evaluation test on the same items as in Example 1. The following Tables 1 to 4 were used. The stated results were obtained.

Comparative Example 4
Although the procedure described in Example 1 was repeated, in this example, for comparison, instead of an average pentamer of 17.8 parts tetraethoxysilane and 9.3 parts phenyltrimethoxysilane, 29. Using 5 parts of tetramethoxysilane and 2.5 parts of phenyltrimethoxysilane, adding 60.0 parts of H ₂ O and 0.5 parts of H ₂ SO ₄ (95%) to the reaction. A reaction solution was obtained.

  Next, 10.0 parts of PSS dispersion (as described in Example 1) was added to 90.0 parts of the reaction liquid to prepare a desired coating liquid. A coating film was formed from the obtained coating solution by the same method as in Example 1, and the obtained coating film was subjected to an evaluation test on the same items as in Example 1. The following Tables 1 to 4 were used. The stated results were obtained.

Comparative Example 5
Although the method described in Example 3 was repeated, in this example, for comparison, a reaction was performed without adding phenyltrimethoxysilane to prepare a target binder solution. Next, 5.0 parts of PEDOT / PSS dispersion was added to 95.0 parts of binder liquid to prepare a target coating liquid. The PEDOT / PSS dispersion used in this example is a solution in which a mixed polymer of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS) is dissolved in diethylene glycol / water at a concentration of 1 to 5% by weight. , A dispersion having a specific gravity of 1.003 and a pH of 2.2.

  Next, a coating film was formed from the obtained coating solution by the same method as in Example 1. The obtained coating film was subjected to an evaluation test for the same items as in Example 1. The following Tables 1 to 4 were used. The results listed in the table were obtained.

Comparative Example 6
Although the method described in Example 3 was repeated, in this example, for comparison, a reaction was performed without adding a methyl silicate oligomer to prepare a target binder solution. Next, 10.0 parts of a PSS dispersion (described in Example 3) was added to 90.0 parts of the binder liquid to prepare a target coating liquid. A coating film was formed from the obtained coating solution by the same method as in Example 1, and the obtained coating film was subjected to an evaluation test on the same items as in Example 1. The following Tables 1 to 4 were used. The stated results were obtained.

Comparative Example 7
Although the procedure described in Example 1 was repeated, in this example, instead of 17.8 parts of an average pentamer of tetraethoxysilane and 9.3 parts of phenyltrimethoxysilane for comparison, 1. 7 parts of tetramethoxysilane and 18.5 parts of phenyltrimethoxysilane were used, and 19.8 parts of H ₂ O and 0.2 parts of H ₂ SO ₄ (95%) were added to the reaction. A reaction solution was obtained.

  Next, 10.0 parts of a PSS dispersion (as described in Example 1) was added to 90.0 parts of the reaction liquid to prepare a target coating liquid. A coating film was formed from the obtained coating solution by the same method as in Example 1, and the obtained coating film was subjected to an evaluation test on the same items as in Example 1. The following Tables 1 to 4 were used. The stated results were obtained.

Comparative Example 8
Although the method described in Example 1 was repeated, in this example, for comparison, 30 parts of PSS dispersion (as described in Example 1) was added to 70 parts of the reaction liquid, and the target coating liquid was added. Was prepared. A coating film was formed from the obtained coating solution by the same method as in Example 1, and the obtained coating film was subjected to an evaluation test on the same items as in Example 1. The following Tables 1 to 4 were used. The stated results were obtained.

Comparative Example 9
Although the procedure described in Example 1 was repeated, in this example, instead of an average pentamer of 17.8 parts tetraethoxysilane and 9.3 parts phenyltrimethoxysilane for comparison, 14. Using 3 parts methyltrimethoxysilane and 9.3 parts phenyltrimethoxysilane, add 28.3 parts H ₂ O and 0.3 parts H ₂ SO ₄ (95%) to the reaction. To obtain a reaction solution. Next, 10.0 parts of a PSS dispersion (as described in Example 1) was added to 90.0 parts of the reaction liquid to prepare a target coating liquid. A coating film was formed from the obtained coating solution by the same method as in Example 1, and the obtained coating film was subjected to an evaluation test on the same items as in Example 1. The following Tables 1 to 4 were used. The stated results were obtained. In addition, as understood from the following results, when tetraethoxysilane does not exist as in this example, it is not possible to bring out sufficient effects regarding the water resistance and solvent resistance of the coating film.

  About the coating film obtained in each example and each comparative example, the results of evaluation of the performance of the coating film, water resistance, solvent resistance, changes with time of the coating film, the influence of the antistatic effect in a low humidity environment In summary, it is as shown in Tables 1 to 4 below.

  As can be seen from the evaluation results shown in Tables 1 to 4 above, the antistatic agent composition of the present invention is excellent in water resistance and solvent resistance when used for forming a coating film. The change in the surface resistance value with time is very small, and the decrease in the surface resistance value is extremely small even during drying (in a low humidity environment). This is a significant effect compared to the fact that the surface resistance value of an antistatic agent composition comprising only a siloxane skeleton is significantly reduced in a low humidity environment during drying.

  The coating film formed from the antistatic agent composition of the present invention shows not only good adhesion to glass, acrylic resin, polyethylene terephthalate (PET), etc., but also polycarbonate, polyolefin, Cycloolefin and nylon polymers also have adhesion, and their coating film (coating film) is also colorless and transparent, exhibiting excellent antistatic effect with excellent transparency, and little change in surface resistance of the coating film over time Since the good antistatic effect is continued, it can be used in a wide range of industrial fields.

Claims (6)

A tetraalkoxysilane and / or its oligomer, a mixture of phenyl alkoxysilane and / or its oligomer by hydrolyzing, be those obtained by polycondensation reaction further, the siloxane bond to (Si-O-Si) An alkoxysilane hydrolysis polycondensate having a skeleton;
Polystyrene sulfonic acid,
The alkoxysilane hydrolyzed polycondensate containing isopropanol and n-butanol in combination and a solvent obtained by dissolving the polystyrenesulfonic acid, the phenyl group of the alkoxysilane hydrolyzed polycondensate and the polystyrene sulfone A liquid antistatic agent composition used for forming a coating film, wherein a phenyl group of an acid forms a laminated structure by π · π interaction.   The said alkoxysilane hydrolysis polycondensate WHEREIN: The use ratio of tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer is 1: 0.1-1 by weight ratio. The liquid antistatic agent composition as described.   The polystyrene sulfonic acid is 1.0 to 30.0% by weight based on the total amount of the tetraalkoxysilane and / or its oligomer and the phenylalkoxysilane and / or its oligomer in the alkoxysilane hydrolysis polycondensate. The liquid antistatic agent composition according to claim 1 or 2, which is mixed in an amount.   The liquid antistatic agent composition according to any one of claims 1 to 3, wherein a degree of polycondensation of the alkoxysilane hydrolyzed polycondensate is 2 to 10,000. An alkoxysilane hydrolyzed polycondensate, a polystyrene sulfonic acid, a combination of isopropanol and n-butanol, and a solvent formed by dissolving the alkoxysilane hydrolyzed polycondensate and the polystyrene sulfonic acid . A method for producing a liquid antistatic agent composition used for forming ,
Tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer are mixed at a weight ratio of 1: 0.1-1;
The resulting alkoxysilane mixture was added to a solvent in an amount such that the concentration of the alkoxysilane mixture was 1.0 to 20.0% by weight,
The obtained mixed solution is subjected to hydrolysis polycondensation in the presence of water and a catalyst added thereto to produce a binder liquid containing the hydrolysis polycondensate,
Polystyrene sulfonic acid is added to the obtained binder liquid in an amount of 1.0 to 30.0% by weight based on the total amount of the alkoxysilane mixture, and the alkoxysilane hydrolyzed polycondensate in the whole solution. And a liquid antistatic agent composition having a total concentration of polystyrene sulfonic acid in the range of 1.5 to 40.0% by weight. An alkoxysilane hydrolyzed polycondensate, a polystyrene sulfonic acid, a combination of isopropanol and n-butanol, and a solvent formed by dissolving the alkoxysilane hydrolyzed polycondensate and the polystyrene sulfonic acid . A method for producing a liquid antistatic agent composition used for forming ,
Tetraalkoxysilane and / or its oligomer and phenylalkoxysilane and / or its oligomer are mixed at a weight ratio of 1: 0.1-1;
Polystyrene sulfonic acid is added to the resulting alkoxysilane mixture in an amount of 0.5 to 30.0% by weight based on the alkoxysilane mixture,
The alkoxysilane mixture to which polystyrene sulfonic acid has been added is dissolved in a solvent and mixed uniformly.
The obtained mixed solution is subjected to hydrolysis polycondensation in the presence of water and a catalyst added thereto, and the total concentration of the obtained alkoxysilane hydrolyzed polycondensate and the polystyrenesulfonic acid in the total solution is A method for producing a liquid antistatic agent composition comprising obtaining a liquid antistatic agent composition in a range of 1.5 to 40.0% by weight.