WO2024248181A1 - Silicone tape composition for sensing hydrogen gas having excellent tensile strength and elongation, hydrogen gas sensing silicone tape, and method for manufacturing same - Google Patents

Abstract

The present invention relates to a silicone tape composition for sensing hydrogen gas, a hydrogen gas sensing silicone tape, and a method for manufacturing same, wherein the silicone tape composition may be simply manufactured in an adhesive or sticky tape form and thus has excellent field applicability, and has excellent tensile strength and color change visibility. The silicone tape composition for sensing hydrogen gas, according to the present invention, comprises a hydrogen-gas-sensing agent, PDMS, and a platinum catalyst.

Description

A silicone tape composition for detecting hydrogen gas having excellent tensile strength and elongation, a silicone tape for detecting hydrogen gas, and a method for producing the same

The present invention relates to a silicon tape composition for detecting hydrogen gas, a silicon tape for detecting hydrogen gas, and a method for producing the same.

More specifically, the present invention relates to a silicone tape composition for detecting hydrogen gas, which can be simply manufactured in the form of an adhesive or sticky tape and thus has excellent field applicability, excellent tensile strength and color change visibility, and excellent tensile strength and elongation, the hydrogen gas detecting silicone tape, and a method for manufacturing the same.

Regarding a hydrogen sensor that detects hydrogen gas used in hydrogen fuel cell energy sources, hydrogen cars, and various industrial fields, there is patent registration No. 10-1015088 (February 9, 2011) [Reduced PDHO thin film used in ultra-high sensitivity hydrogen sensor and method for manufacturing the same].

This registered patent includes a step of artificially producing a PdO thin film using a reactive sputtering technique (reactive DC magnetron sputtering system), and a step of obtaining a Pd thin film with nanocracks formed by subjecting the PdO thin film to a reduction reaction.

The Pd thin film formed with the above nanocracks has improved hydrogen detection characteristics, suggesting a technology suitable for use in a hydrogen detection sensor.

There is also a patent registration number 10-1269510 (May 24, 2013) [Hydrogen detection sensor capable of measuring hydrogen concentration].

This registered patent relates to a hydrogen detection sensor capable of continuously measuring changes in the concentration of hydrogen gas by changing the resistance value corresponding to changes in the concentration of hydrogen gas.

Specifically, it comprises a hydrogen detection unit that is hydrogenated when in contact with hydrogen gas, wherein when the hydrogen detection unit is hydrogenated, the resistance value of the hydrogen detection unit changes, has a first resistance value change rate at a first concentration of hydrogen gas, and has a second resistance value change rate that is different from the first resistance value change rate at a second concentration of hydrogen gas that is different from the first concentration.

However, these two patents and other prior literature are unrelated to the technology that improves field applicability or color change visibility to enable immediate detection of abnormal conditions.

Accordingly, the present invention aims to provide a silicone tape composition for detecting hydrogen gas, which can be simply manufactured in the form of an adhesive or sticky tape and thus has excellent field applicability, excellent tensile strength and color change visibility, and excellent tensile strength and elongation, the hydrogen gas detecting silicone tape, and a manufacturing method therefor.

In order to achieve the above purpose, the silicon tape composition for hydrogen gas detection according to the present invention

It consists of a hydrogen gas detector, VTP (Vinyl Terminated Polydimethylsiloxane), hTPS (Hydride Terminated Polydimethylsiloxane), and silicone gum.

In addition, the silicone tape composition for detecting hydrogen gas according to the present invention

Further comprising some or all of a visibility enhancer, an adhesion enhancer, a curing retardant, an adhesion enhancer, and a tensile strength enhancer,

The above discoloration visibility improving agent is alumina,

The above curing retardant is methylvinylcyclosiloxane (MVC).

The above hydrogen gas detector uses PdO, and the carrier is some or all of zeolite, TiO ₂ , SiO ₂ , ZnO, Al ₂ O ₃ ,

It is preferable to include 300 to 500 parts by weight of VTP, 120 to 150 parts by weight of hTPS, and 7,000 to 12,000 parts by weight of silicone gum for 100 parts by weight of hydrogen gas detector.

Furthermore, a hydrogen gas sensing silicone tape according to the present invention and a method for manufacturing the same are made using the composition.

The present invention provides a silicone tape composition for detecting hydrogen gas, which is in the form of a tape with excellent field applicability, and also has excellent tensile strength and color change visibility, and excellent tensile strength and elongation, the hydrogen gas detecting silicone tape, and a method for manufacturing the same.

Figure 1 is a comparative photograph of a hydrogen gas-detecting silicone tape according to the present invention before and after exposure to hydrogen gas.

Figure 2 is a manufacturing process diagram of a hydrogen gas detector.

Hereinafter, the present invention will be described in detail.

The present invention can have various modifications and can take various forms, and thus, the implementation examples (or examples) are described in detail in the text. However, this is not intended to limit the present invention to a specific disclosed form, and it should be understood that it includes all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention.

The terminology used herein is only used to describe specific implementations (or examples) and is not intended to be limiting of the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, it should be understood that the terms "comprises" or "consists of" and the like are intended to specify the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms defined in commonly used dictionaries, such as those defined in common dictionaries, should be interpreted as having a meaning consistent with the meaning they have in the context of the relevant art, and will not be interpreted in an idealized or overly formal sense unless expressly defined in this application.

A silicon tape composition for detecting hydrogen gas according to the present invention, a silicon tape for detecting hydrogen gas, and a method for producing the same are as follows:

It consists of a hydrogen gas detector, VTP (Vinyl Terminated Polydimethylsiloxane), hTPS (Hydride Terminated Polydimethylsiloxane), and silicone gum.

Specifically, it is preferable to comprise 300 to 500 parts by weight of VTP, 120 to 150 parts by weight of hTPS, and 7,000 to 12,000 parts by weight of silicone gum for 100 parts by weight of hydrogen gas detector.

It is also desirable to add a discoloration visibility enhancer to the tape and a catalyst, especially a platinum catalyst.

It is preferred that this discoloration visibility enhancer be alumina, in which case the alumina also helps to improve the tensile strength of the tape.

In addition, the present invention preferably further includes a curing retarder, and the curing retarder may be methylvinylcyclosiloxane (MVC).

Basically, it is desirable to use PdO (Palladium Oxide) as a hydrogen gas detector.

In addition, the hydrogen gas detector is preferably contained in a carrier considering ease of operation, material stability, and preservability. Examples of the carrier include porous materials such as zeolite, TiO ₂ , SiO ₂ , ZnO, and Al ₂ O ₃ (one, some, or all of these may be used), and among these, zeolite is suitable.

That is, PdCl ₂ is mixed and supported on zeolite, which is a carrier.

[Correction under Rule 91 13.06.2023]
Furthermore, the principle of hydrogen gas detection is as follows, and the discoloration before and after hydrogen gas detection using the tape according to the present invention can be confirmed in the comparative photograph of Fig. 1.

PdO (Brown) + H2 → Pd (Gray) + H2O

[Correction under Rule 91 13.06.2023]
[delete]

[Correction under Rule 91 13.06.2023]
[delete]

[Description of the composition's ingredients]

According to the present invention, it is preferable to adopt a silicone tape so that the hydrogen gas detection silicone tape can be stably applied to various fields, and the silicone tape is intended to improve functionality by using silicone to which a vinyl group and a hydrogen (H) group are provided (Silicone to which a hydroxyl (OH) group is provided (Hydroxyl Terminated Polydimethylsiloxane (HTPS)) is added only in the comparative example)). In addition, it is preferable that the curing reaction of the silicone is an addition reaction type and a platinum (Pt) catalyst is used.

○ Vinyl terminated polydimethylsiloxane (hereinafter referred to as ‘PDMS’)

It serves as the backbone of silicon.

○ PDMS with terminal hydrogen groups (Hydride terminated PDMS)

It acts as a cross-linker.

○ PDMS with terminal hydroxyl group (Hydroxyl terminated PDMS) (used only in comparative examples as follows)

It provides adhesive properties unique to hydroxyl groups (by providing -OH, which does not participate in additional curing, adhesive strength to the adherend can be secured).

○ Pt catalyst

Induces curing reaction of silicone.

<Silicone reaction example>

Hydride terminated PDMS + Vinyl terminated PDMS (using Pt catalyst)

{Source: Gelest catalog}

In addition, the fillers for hydrogen gas detection are as follows.

○ PdO/Carrier

PdO exhibits discoloration properties when reacted with hydrogen gas, and zeolite, TiO ₂ , SiO ₂ , ZnO, and Al ₂ O ₃ act as carriers for PdO, with zeolite being suitable.

○ Alumina (Al ₂ 2O ₃ )

It maximizes the visibility of color change (color contrast effect) of PdO (i.e., functions as a color change visibility enhancer) and also helps increase the tensile strength of the tape.

○ Curing inhibitor

Inhibitor MVC (methylvinylcyclosiloxane), a curing retardant, is used.

The present invention can be better understood through specific manufacturing examples, examples, and comparative examples (see [Table 1] and [Table 2]).

[Manufacturing Example: Manufacturing of Overall Composition and Tape for Manufacturing Hydrogen Gas Sensing Silicone Tape]

● Manufacturing of hydrogen gas detector

As can be seen in the process diagram of Fig. 2,

1. Mix and support the PdO precursor and water (H ₂ O) with the substrate (Zeolite, TiO ₂ or ZnO). The PdO precursor (PdCl ₂ ) is added at 2 to 4 phr relative to the carrier.

2. Stir for 10 minutes, the reaction temperature is room temperature (RT) ~ 60 ℃, 3. pH Control; Adjust the pH of the solution to 7 using diluted hydrochloric acid.

3. Stir for 60 minutes and the reaction temperature is room temperature to 60 ℃.

4. Pressure filter using a filter (0.2 ㎛ Membrane filter with washing).

5. Dry for 12 hours (drying temperature: 120 ℃) to obtain PdO/carrier powder.

● Manufacturing of hydrogen gas detection silicone tape

○Raw material mixing ratio

The components of each example and comparative example are mixed based on 100 parts by weight of PdO/Zeolite, a hydrogen gas detector.

Meanwhile, in this embodiment, PDMS (VTP) having a terminal vinyl group can be used by mixing those having different viscosities to help secure dispersion characteristics for PdO/carrier, which is a hydrogen gas detector. For example, it is suitable to mix and use 90 to 120 parts by weight of VTP having a viscosity of 20,000 cps and 40 to 60 parts by weight of VTP having a viscosity of 65,000 cps for 100 parts by weight of VTP having a viscosity of 1,000 cps.

○ Three Roll Milling

This is a process for crushing/dispersing particles (fillers) present in the above mixed composition.

In particular, hydrogen gas detector particles are ground and dispersed in silicon (RV100) to produce a dispersion liquid, and milling is performed with a gap of 20 ㎛ for the roll into which the raw material is fed and a gap of 5 ㎛ for the roll from which the raw material is discharged.

○ Planetary Mixing

The above dispersion and the remaining composition are mixed using a planetary mixer.

○ Observation of film formation and hydrogen gas discoloration

The PET substrate is coated with a moisture film thickness of 300 ㎛, dried at 70 to 150 °C for 7 to 30 minutes, and then cured at 100 to 150 °C for 10 to 13 minutes to form a film.

Meanwhile, as in Examples 8 and 11, the adhesive layer is prepared by additionally coating a pressure-sensitive adhesive (PSA) on the surface of the cured silicone tape. This PSA is coated with a dry film thickness of 30 to 60 ㎛, dried at 70 to 150 ° C. for 5 minutes, and then cured at 100 to 150 ° C. for 10 minutes.

The cured film is exposed to hydrogen gas to observe discoloration. The hydrogen gas exposure condition is 4% H ₂ gas to observe discoloration.

[Examples and Comparative Examples]

division
(Unit: parts by weight) Example ① Example ② Example ③ Example ④ Example ⑤ Example ⑥ Example ⑦ Example ⑧ VTP 18.04 18.04 20.48 21.95 29.25 29.25 27.72 20.49 Silicone GUM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 hTPS- Crosslinker 6.80 6.80 7.73 6.49 9.72 9.72 10.46 7.72 HTPS- 50 cps 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Catalyst
- Pt catalyst 0.60 0.60 0.93 0.77 0.58 0.29 0.94 0.47 Filler - Al ₂ O ₃ 15.00 9.90 17.04 17.04 17.04 17.05 23.07 17.05 Inhibitor 0.20 0.15 0.17 0.14 0.22 0.27 0.23 0.17 Hydrogen gas detector 15.50 25.77 5.85 4.88 7.32 7.30 7.91 5.85 MS- adhesion
promoter 5.02 5.16 5.85 9.76 7.32 7.30 7.91 5.85 hydrogen gas
Detector carrier Zeolite Zeolite Zeolite Zeolite Zeolite Zeolite Zeolite Zeolite Adhesive layer-Pressure
Sensitive
Adhesive grant grant × × × × grant ×

division
(Unit: parts by weight) Example ⑨ Example ⑩ Example ⑪ Comparative Example ① Comparative Example ② Comparative Example ③ Comparative Example ④ Comparative Example ⑤ VTP 20.50 27.72 27.72 40.56 40.54 40.50 40.51 45.62 Silicone GUM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 hTPS- Crosslinker 7.73 10.46 10.46 12.17 6.08 4.04 3.87 3.87 HTPS- 50 cps 0.00 0.00 0.00 14.00 13.94 13.97 13.98 14.51 Catalyst
- Pt catalyst 0.24 0.94 0.94 0.60 0.21 1.21 0.15 0.15 Filler - Al ₂ O ₃ 17.04 23.07 23.07 17.12 16.51 16.28 16.26 16.85 Inhibitor 0.17 0.23 0.23 0.16 0.15 0.15 0.17 0.17 Hydrogen gas detector 5.85 7.91 7.91 5.06 5.06 5.07 5.22 5.41 MS- adhesion
promoter 5.85 7.91 7.91 5.06 5.06 5.07 5.06 5.08 hydrogen gas
Detector carrier Zeolite TiO ₂ ZnO Zeolite Zeolite Zeolite Zeolite Zeolite Adhesive layer-Pressure
Sensitive
Adhesive × grant × × × × × ×

*VTP = Vinyl Terminated Polydimethylsiloxane

*hTPS = Hydride Terminated Polydimethylsiloxane

*HTPS = Hydroxyl Terminated Polydimethylsiloxane

*MS = Methacylate Silane

[Experimental example - Measurement of tensile strength and elongation]

division Tensile strength (N/㎟) Elongation (%) adhesiveness Example 1 3.51 310 200 Example 2 3.80 301 200 Example 3 4.87 297 10 Example 4 3.82 406 20 Example 5 4.67 310 20 Example 6 3.97 320 15 Example 7 4.56 353 150 Example 8 4.31 345 20 Example 9 3.59 439 30 Example 10 4.35 350 125 Example 11 4.26 347 15 Comparative Example 1 2.80 265 20 Comparative Example 2 1.46 334 20 Comparative Example 3 0.98 690 25 Comparative Example 4 1.31 796 15 Comparative Example 5 1.28 728 20

As can be confirmed in the experimental example [Table 3] above, the present invention provides a silicone tape composition for hydrogen gas detection, which has excellent tensile strength and elongation compared to the comparative example, the hydrogen gas detection silicone tape, and a manufacturing method thereof. As in the comparative example, when silicone (Hydroxyl Terminated Polydimethylsiloxane (HTPS)) having a hydroxyl (OH) group is added, it was confirmed that the tensile strength and elongation are adversely affected compared to the intention of imparting adhesive properties unique to hydroxyl groups.

Specifically, in the hydrogen gas detection silicone tape composition having excellent tensile strength and elongation according to the present invention, the hydrogen gas detection silicone tape, and the manufacturing method thereof, it is preferable to include 5.00 to 30.0 parts by weight of a hydrogen gas detection agent, 15.00 to 30.00 parts by weight of VTP, and 6.00 to 12.00 parts by weight of hTPS per 100.00 parts by weight of silicone gum.

In addition, it is preferable to include 0.20 to 1.00 parts by weight of a catalyst (e.g., Pt catalyst), 15.00 to 25.00 parts by weight of a filler (e.g., alumina (Al ₂ O ₃ )), 0.10 to 0.30 parts by weight of a curing inhibitor (e.g., MVC (methylvinylcyclosiloxane)), and 4.00 to 10.00 parts by weight of an adhesion promoter (e.g., MS = Methacylate Silane).

The adhesive layer can be optionally provided as needed.

More specifically and comprehensively, as can be confirmed from the experimental example table above, with respect to tensile strength and elongation performance, it is more preferable that VTP is 20.00 to 30.00 parts by weight (see Examples ③ to ⑧, ⑩, ⑪) per 100.00 parts by weight of silicone gum, and it is most preferable that VTP is 25.00 to 30.00 parts by weight (see Examples ⑩, ⑪).

In addition, it is more preferable that the hydrogen gas detector is 4.80 to 8.00 parts by weight, hTPS is 7.70 to 11.00 parts by weight, the catalyst is 0.45 to 1.00 parts by weight, the filler is 17.00 to 25.00 parts by weight, and the curing retardant is 0.10 to 0.23 parts by weight. (See Examples ③ to ⑧, ⑩, and ⑪ above)

In the above description, conventionally known techniques related to the silicon tape composition for detecting hydrogen gas, the silicon tape for detecting hydrogen gas, and the manufacturing method thereof have been omitted, but those skilled in the art can easily guess, infer, and reproduce them.

Claims (11)

A silicone tape composition for detecting hydrogen gas, comprising a hydrogen gas detector, VTP (Vinyl Terminated Polydimethylsiloxane), hTPS (Hydride Terminated Polydimethylsiloxane), and silicone gum. In paragraph 1, A silicone tape composition for hydrogen gas detection, characterized in that it further comprises a visibility enhancing agent. In the second paragraph, A silicone tape composition for detecting hydrogen gas, characterized in that the discoloration visibility improving agent is alumina. In paragraph 1, A silicone tape composition for hydrogen gas detection, characterized in that it further contains an adhesive improver. In paragraph 1, A silicone tape composition for detecting hydrogen gas, characterized in that a curing retarder is further added. In paragraph 5, A silicone tape composition for detecting hydrogen gas, characterized in that the curing retarder is methylvinylcyclosiloxane (MVC). In any one of claims 1 to 6, A silicone tape composition for hydrogen gas detection characterized in that an adhesion promoter is further added. In any one of claims 1 to 6, A silicone tape composition for detecting hydrogen gas, characterized in that a tensile strength improving agent is further added. In any one of claims 1 to 6, A silicone tape composition for detecting hydrogen gas, characterized in that the hydrogen gas detector uses PdO and the carrier is some or all of zeolite, TiO ₂ , SiO ₂ , ZnO, and Al ₂ O ₃ . In any one of claims 1 to 6, A silicone tape composition for detecting hydrogen gas, comprising 5.00 to 30.0 parts by weight of a hydrogen gas detector, 15.00 to 30.00 parts by weight of VTP, and 6.00 to 12.00 parts by weight of hTPS per 100.00 parts by weight of silicone rubber. Silicon for detecting hydrogen gas, manufactured using a composition according to any one of claims 1 to 10.

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