JP5463558B2 - Manufacturing method of solar energy utilization device - Google Patents

Description

  The present invention relates to a method for manufacturing a solar energy utilization device. More specifically, the present invention relates to a method for manufacturing a solar energy utilization device that forms a water- and oil-repellent antifouling film chemically bonded to the outermost surface of the light-receiving surface using an aqueous solvent.

  In general, a chemical adsorption solution consisting of a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent can be used for chemical adsorption in the liquid phase to form a monomolecular film-like water / oil repellent / antifouling chemical adsorption film. Is already well known (see, for example, Patent Document 1).

The principle of production of a chemisorbed monolayer in such a solution is to form a monolayer using a dehydrochlorination reaction between active hydrogen such as hydroxyl groups on the substrate surface and chlorosilyl groups of chlorosilane-based adsorbents. It is in.
Japanese Patent Laid-Open No. 05-193056

  However, the conventional water-repellent treatment method using a chlorosilane-based water- and oil-repellent antifouling chemical adsorbent can only use a non-aqueous organic solvent, so the treatment liquid is expensive and the environmental load is highly recommended. It wasn't possible.

  Further, since a dehydrochlorination reaction between the active hydrogen group and the chlorosilyl group on the substrate surface is used for film formation, hydrochloric acid is generated and there is a great drawback that it cannot be used in the atmosphere.

  The present invention provides a method for producing a solar energy utilization device capable of forming a water- and oil-repellent and antifouling film excellent in wear resistance and water resistance without using a conventional non-aqueous organic solvent. Objective.

      It is another object of the present invention to provide a method for manufacturing a solar energy utilization apparatus that does not generate hydrochloric acid gas when forming a film and can form a film in a normal air atmosphere.

  In order to achieve the above object, the first invention specifically provided includes at least a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, water, an alcohol, and / or a surfactant. A method for manufacturing a solar energy utilization device, wherein a water / oil repellent / antifouling film is formed on the outermost surface of a light receiving surface using a water / oil repellent / antifouling treatment agent.

  According to a second invention, in the first invention, the substance mainly comprising a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, water, alcohol and / or a surfactant, and further comprising an alkoxysilyl group as a main ingredient. A method for manufacturing a solar energy utilization device, characterized in that a substance to be added is added.

According to a third invention, in the first and second inventions, ethanol, propyl alcohol, butanol, ethylene glycol, and a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 1) are used as a surfactant. It is the manufacturing method of the solar energy utilization apparatus characterized.

According to a fourth invention, in the first to third inventions, CF ₃ — (CF ₂ ) _n — (CH ₂ ) _{2 is} used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. -Si (OA) ₃ or _{[CF 3 - (CF 2)} n - (CH 2) 2] 2 -Si (OA) 2, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA , CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —SiA (OA) ₂ (n is an integer of 0 or 16 or less, A is an alkyl group), and a method for producing a solar energy utilization device It is.

According to a fifth invention, in the second to third inventions, Si (OA) ₄ or (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA ) ₃ (n is an integer of 0, 1 or 2 and A is an alkyl group).

  A sixth invention is a method for manufacturing a solar energy utilization device according to any one of the first to fifth inventions, wherein the pH of the treatment liquid is 5 to 11.

  More specifically, the present invention relates to a water / oil repellent / antifouling agent comprising at least a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, water, alcohol and / or a surfactant. The present invention provides a method for manufacturing a solar energy utilization device that uses a treating agent to form a water- and oil-repellent antifouling film chemically bonded to the outermost surface of the light-receiving surface.

Here, as alcohols, so-called alcohols are all possible, but in particular, ethanol, propyl alcohol, butanol, ethylene glycol is a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, or alkoxysilyl. A substance containing a group as a main component is preferable because it can be efficiently dispersed in water.
On the other hand, when a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 1) is used as the surfactant, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group or an alkoxysilyl group is mainly used. Conveniently, the component substances can be dispersed efficiently in water.

Further, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [CF ₃ — (CF ₂ ) can be used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. _{n - (CH 2) 2]} 2 -Si (OA) 2, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA, CF 3 - (CF 2) n - (CH 2) 2 Use of —SiA (OA) ₂ (n is an integer of 0 or 16 and A is an alkyl group) is advantageous in improving the water / oil repellent / antifouling effect.

On the other hand, Si (OA) ₄ or (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (n is an integer of 0 or 1, ₂ ) When an alkyl group is used, it is convenient because durability such as abrasion resistance of the water / oil repellent / antifouling film can be improved.

  Further, controlling the pH of the treatment liquid to 5 to 11 is convenient for forming a coating film with high density.

  As described above, according to the present invention, without using an organic solvent, the sun formed with a water- and oil-repellent and antifouling film excellent in wear resistance and water resistance chemically bonded to the outermost surface on the light receiving surface side. There exists an effect which can manufacture and provide an energy utilization apparatus.

  In the present invention, a water / oil / oil repellent / antifouling agent containing at least a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and water, an alcohol and / or a surfactant is used. Provided is a method for producing a solar energy utilization device in which a water- and oil-repellent and antifouling film excellent in wear resistance and water resistance chemically bonded to the outermost surface on the light receiving surface side by reaction is formed.

  Therefore, there is no generation of hydrochloric acid gas at the time of film formation, and there is an effect that a solar energy utilization device can be manufactured in a normal air atmosphere. Moreover, since an organic solvent is not used, there exists an effect | action which can reduce the global environmental load at the time of manufacture.

  Hereinafter, specific examples of the present invention will be described. In the following examples, the molecular composition ratio means a molar ratio unless otherwise specified. Further, “%” not specifically mentioned means “% by weight”. In addition, this invention is not limited at all by these Examples.

First, a glass plate 1 as a light incident side transparent base material of a solar cell which is a typical example of a solar energy utilization apparatus as shown in FIG. 1 is prepared in advance, and the ITO transparent electrode 2 and silver are printed on the back surface using a printing method. A paste comb electrode 3, an n-type amorphous Si layer 4 and a p-type amorphous Si layer 5 were formed in this order, and an aluminum back electrode 6 serving also as a reflective film was formed thereon by vapor deposition to form a solar cell 7.
On the other hand, as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, for example, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (Si (OCH ₃ ) ₃ ) and an alkoxysilyl group are used. Si (OCH ₃ ) ₄ as a main component is weighed so as to have a molecular composition ratio of 2: 1, and mixed in an aqueous solvent containing 10% ethanol by volume so as to be 0.01 mol / L. When treated with a homogenizer (so-called ultrasonic disperser may be used) for about 10 minutes, a part of each —Si (OCH ₃ ) ₃ group is hydrolyzed to —Si (OH) ₃ group, ═Si (OH ) A completely transparent composite film forming solution containing a substance converted into _two groups or ≡SiOH groups was prepared.

      It should be noted that the simple stirring with a stirrer only yielded a slightly turbid liquid, and if left to stand, the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group would be immediately separated and stable. The treated liquid was not obtained.

  Next, solar cells 7 that were thoroughly washed and dried were prepared, and this composite film forming solution was applied to the outermost surface on the light-receiving surface side in the air (relative humidity 57%, 70% in another experiment). .) It was applied to the surface of the solar cell and allowed to stand for about 1 hour. At this time, most of the water-alcohol solvent evaporates, but since the surface of the solar battery cell contains a large number of hydroxyl groups, the substance containing the fluorocarbon group, hydrocarbon group, and alkoxysilyl group as the main component or alkoxysilyl group. The portion converted to ≡SiOH group of the group-based material and the hydroxyl group on the surface of the solar battery cell undergo a dehydration reaction, and the fluorocarbon group and the hydrocarbon group chemically bonded to the surface over the entire surface of the solar battery cell A composite film 10 including a substance 8 containing a silyl group as a main component and a substance 9 containing a siloxane group as a main component can be formed on the outermost surface of the solar cell 7 on the light receiving surface side. (Fig. 1 (a))

  Therefore, before the aqueous ethanol solvent of the composite film forming solution remaining on the surface completely evaporates, that is, before the film is completely cured, excess fluorocarbon groups and hydrocarbons that have not reacted with ethanol. When a substance mainly composed of a group and an alkoxysilyl group or a substance mainly composed of an alkoxysilyl group is washed and removed, the substance 2 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group having a thickness of about 5 nm. And a composite film containing a substance 9 containing siloxane groups as main components could be formed on the surface of the solar cell. In addition, when it wiped off with the waste containing ethanol, it became thickness of about 10-20 nm.

At this time, a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group or a substance mainly composed of an alkoxysilyl group in the composite film forming solution is an alkoxysilyl group in a mixed solvent of water and alcohol. Is partly hydrolyzed and converted to -Si (OH) ₃ groups, and the surface of the solar battery cell 7 contains a large number of hydroxyl groups, that is, active hydrogens. Therefore, the -Si (OH) ₃ group and the solar battery cell 7 The hydroxyl group on the surface of the substrate undergoes a dehydration reaction, and a substance 8 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group is mixed with a substance 9 mainly composed of a siloxane group via a —SiO— bond. To the surface of the solar battery cell 7.

  However, in this state, a portion 11 of the —SiOH group remains in the film without causing a dehydration reaction. (FIG. 1 (a)) Therefore, when the solar cell 7 on which the composite film is further formed is heated in air at 120 to 300 ° C. for about 30 minutes, the unreacted —SiOH group is completely dehydrated. Thus, a polysiloxane bond is formed to change to a network-like silica film 12, and the main component is a fluorocarbon group, a hydrocarbon group, and a silyl group that are excellent in wear resistance and water separation (also referred to as water slidability). The solar cell panel 14 covered with the water / oil repellent / antifouling composite film 13 having a water droplet contact angle of 116 degrees and comprising the material 8 to be formed and the material 9 having a siloxane group as a main component could be produced. (Fig. 1 (b))

  Here, when a heat treatment at 300 to 400 ° C. for about 30 minutes is performed in a nitrogen gas atmosphere that is an inert gas, the coating is not oxidized, and the water and oil and oil repellents are excellent in wear resistance. A solar panel covered with a dirty composite film could be manufactured.

  In Example 1, a step of washing away or wiping off an unreacted extra fluorocarbon group, hydrocarbon group, and alkoxysilyl group as a main component or a substance having an alkoxysilyl group as a main component As a result, a film having a surface water droplet contact angle of approximately 113 degrees and a film thickness of several tens of nanometers was obtained. Even under these conditions, the transparency was not significantly impaired, and even if the base was a solar energy utilization device such as a solar battery cell, there was no practical problem.

  In Examples 1 and 2, the molecular composition ratio of a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and a substance mainly composed of an alkoxysilyl group is preferably 1: When the ratio was 10: 1: 0 (more preferably 1: 3-3: 1), the surface energy of the coating could be controlled between 20-5 mN / m.

In addition, since the water droplet contact angle of the antifouling solar cell at this time depends on the composition of the substance 2 and the substance 3, for example, if the composition is changed in the range of 1:10 to 1: 0, the critical surface energy is changed. The water droplet contact angle could be controlled in the range of 105 ± 13 degrees. Moreover, in the case of 1: 3-3: 1, the falling angle with respect to the 0.02 mol / L water droplet was controllable to 25-12 degree | times, and the draining at the time of washing | cleaning became good.
Furthermore, the same film was obtained even when the total concentration of the substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group and the substance mainly composed of alkoxysilyl group was 0.05 mol / L. When prepared so as to be 0.01 to 0.0001 mol / L, the gelation of the treatment liquid can be prevented, and the lifetime can be secured up to about one month.

In Example 1, a water- and oil-repellent and antifouling solar battery cell was prototyped under the same conditions except for the substance Si (OCH ₃ ) ₄ having an alkoxysilyl group as a main component. The contact angle with water, which is the basic performance of the coating film obtained in this case, was 118 degrees. Further, the drainage characteristic ability and high durability are slightly inferior to those of Example 1, but other physical property values are almost the same as those of Example 1, and an antifouling solar cell panel that can be put to practical use can be produced. It was.

  On the other hand, in Example 1, a water-alcohol solvent was prepared so that the tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 2), which is a cationic surfactant, was 0.0005 mol / L. A similar experiment was conducted in place of the surfactant solvent, but an antifouling solar cell panel that could be practically used could be produced.

  Furthermore, in Example 1, a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 2), which is a cationic surfactant, was further added to a water-alcohol solvent so that the amount was 0.005 mol / L. As a result of the experiment, an antifouling solar cell panel that can be practically used in the same manner was produced.

  In Examples 1, 2, 3, and 5, all so-called alcohols could be used as the alcohol, but good results were obtained with ethanol, propyl alcohol, butanol, and ethylene glycol.

As the surfactant, any neutral or weakly alkaline surfactant can be used. However, a high-performance film could not be formed unless the pH of the preparation treatment liquid was 5 to 11. When the pH was less than 5, a high-density film could not be formed. On the other hand, when the pH exceeded 12, a part of the coating was destroyed.
In addition, among the tetraalkylammonium salts represented by the following chemical formula (Chemical Formula 1), a particularly preferable one has R ¹ having 12 to 16 carbon atoms.

Furthermore, as a substance mainly composed of only a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, the following substances are generally exemplified.
_{CF 3 - (CF 2) n} - (R) m SiX p (OA) 3-p
(Where n is an integer of 0 or 16 or less, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing silicon or an oxygen atom, m is 0 or 1, X is H, an alkyl group or an alkoxy group. , A fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, p is 0, 1 or 2, A is an alkyl group such as CH ₃ , C ₂ H ₅ , C ₃ H ₇ )

Specifically, the general formula _{CF 3 - (CF 2) n} - (CH 2) 2 -Si (OA) 3 or _{[CF 3 - (CF 2)} n - (CH 2) 2] 2 -Si (OA) ₂ , [CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ ] ₃ —SiOA (n is an integer of 0 or 16 or less, A is an alkyl group).

More specifically, the following substances (1) to (20) can be mentioned.
(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OCH ₃ ) ₃
(8) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) _{3
(9) CF 3 (CH 2} ) 2 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
(10) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
(13) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(14) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OC ₂ H ₅ ) ₃
(15) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OCH ₃ ) ₂
(16) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOCH ₃
(17) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OC ₂ H ₅ ) ₂
(18) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOC ₂ H ₅
(19) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂
(20) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiC ₂ H ₅ (OCH ₃ ) ₂
Further, as a substance mainly composed of an alkoxysilyl group, generally, Si (OA) ₄ or (AO) ₃ Si (OSi (OA) ₂ ) _n OSi (OA) ₃ (n is 0 or 1, An integer of 2 and A is an alkyl group).

More specifically, the following substances (1) to (8) can be mentioned.
(1) Si (OCH ₃ ) ₄
(2) SiH (OCH ₃ ) ₃
(3) SiH ₂ (OCH ₃ ) ₂
(4) (CH ₃ O) ₃ SiOSi (OCH ₃ ) ₂ OCH ₃
(5) Si (OC ₂ H ₅ ) ₄
(6) SiH (OC ₂ H ₅ ) ₃
(7) SiH ₂ (OC ₂ H ₅ ) _{2
(8) (H 5 C 2} O) 3 SiOSi (OC 2 H 5) 2 OC 2 H 5

      The present invention can be applied to any solar energy utilization device. Specifically, there are a solar water heater, a greenhouse, etc. in addition to a solar battery panel.

The manufacturing process of the water-repellent / oil-repellent antifouling solar battery cell of the present invention is shown, (a) is the solar battery cell after the formation of the composite film in Example 1, and (b) is after the firing in Example 1. The cross-sectional conceptual diagram which expanded each antifouling photovoltaic cell in which the composite film of this was formed to the molecular level.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 The glass plate used as the light-incidence side transparent base material of a solar cell 2 ITO transparent electrode 3 Silver paste comb electrode 4 n-type amorphous Si layer 5 p-type amorphous Si layer 6 Aluminum back electrode 7 Solar cell 8 Fluorocarbon group Substances having hydrocarbon groups and silyl groups as main components 9 Substances having siloxane groups as main components 10 Composite films containing many hydroxyl groups 11 Hydroxyl groups 12 Reticulated silica films 13 Water- and oil-repellent and antifouling composite films 14 Water-repellent Oil-repellent antifouling solar panel

Claims (3)

At least a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and water and an alcohol and a surfactant, or a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group and water. In the step of forming a water-repellent / oil-repellent / anti-fouling composite film on the outermost surface of the light-receiving surface using a water / oil-repellent / anti-fouling agent containing a surfactant, A substance having a silyl group as a main component is added, and CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si is used as the substance having a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group as main components. (OA) ₃ or _{[CF 3 - (CF 2)} n - (CH 2) 2] 2 -Si (OA) 2, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA, CF _{3 - (CF 2) n -} (CH 2) 2 -SiA ( _A) 2 (n is 0 or 16 an integer, A is using an alkyl group), wherein the alkoxy Si silyl group as a material mainly containing _{(OA) 4 or, (AO) 3 Si (OSi} (OA) 2 ) _N OSi (OA) ₃ (n is an integer of 0, 1 or 2 and A is an alkyl group), and a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, and an alkoxysilyl group A method for producing a solar energy utilization device, characterized in that the composition of a substance having a main component is 1: 3 to 3: 1 and the total concentration is adjusted to 0.01 to 0.0001 mol / L. 2. The solar energy utilization device according to claim 1, wherein ethanol, propyl alcohol, butanol, ethylene glycol, and a tetraalkylammonium salt represented by the following chemical formula (Chemical Formula 1) are used as the surfactant. Production method.

The method for producing a solar energy utilization device according to claim 1 or 2, wherein the pH of the water / oil repellent / antifouling agent is 5 to 11.

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