KR102646275B1 - Composition for hydrogen sensing tape having excellent tensile-strength and elongation rate, tape and manufacturing method thereof - Google Patents

Abstract

The present invention is a silicone tape composition for detecting hydrogen gas that can be simply manufactured in the form of an adhesive or adhesive tape, has excellent field applicability, has excellent tensile strength and color change visibility, and has excellent tensile strength and elongation, and its hydrogen gas sensing It relates to silicone tape and its manufacturing method.
The silicone tape composition for hydrogen gas sensing according to the present invention includes a hydrogen gas sensing agent, PDMS, and a platinum catalyst.

Description

Silicone tape composition for hydrogen gas sensing with excellent tensile strength and elongation, the hydrogen gas sensing silicone tape, and the manufacturing method thereof

The present invention relates to a silicone tape composition for sensing hydrogen gas, a silicone tape for sensing hydrogen gas, and a method for manufacturing the same.

More specifically, a silicone tape composition for detecting hydrogen gas that can be simply manufactured in the form of an adhesive or adhesive tape, has excellent field applicability, has excellent tensile strength and color change visibility, and has excellent tensile strength and elongation, and the hydrogen gas Pertains to sensing silicone tape and its manufacturing method.

Patent registration No. 10-1015088 (February 9, 2011) in relation to a hydrogen sensor that detects hydrogen gas used in hydrogen fuel cell energy sources, hydrogen vehicles, and various industrial fields [Reduced hydrogen used in ultra-sensitive hydrogen sensors] PdO thin film and method for manufacturing it],

This registered patent includes the steps of artificially producing a PdO thin film using a reactive sputtering technique (reactive DC magnetron sputtering system), and performing a reduction reaction on the PdO thin film to obtain a Pd thin film with nanocracks formed,

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

There is also Patent Registration No. 10-1269510 (May 24, 2013) [Hydrogen detection sensor capable of measuring hydrogen concentration].

This registered patent relates to a hydrogen detection sensor that can continuously measure changes in the concentration of hydrogen gas by changing the resistance value corresponding to the change in concentration of hydrogen gas.

Specifically, it includes 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 the first resistance value changes. It is characterized in that it 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 concentration.

However, these two patents and other prior literature are unrelated to field applicability or technology that improves color change visibility to immediately detect abnormal conditions.

Accordingly, the present invention is a silicone tape composition for detecting hydrogen gas that can be simply manufactured in the form of an adhesive or adhesive tape, has excellent field applicability, has excellent tensile strength and color change visibility, and has excellent tensile strength and elongation, and the hydrogen gas The purpose is to provide a sensing silicone tape and a manufacturing method thereof.

In order to achieve the above object, the silicone tape composition for detecting hydrogen gas according to the present invention is

It consists of a hydrogen gas detection agent, 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

It further includes some or all of a visibility improver, an adhesion improver, a curing retardant, an adhesion improver, and a tensile strength improver,

The discoloration visibility enhancer is alumina,

The curing retardant is methylvinylcyclosiloxane (MVC),

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

For 100 parts by weight of the hydrogen gas detection agent, 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.

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

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

Figure 1 is a comparative photograph of a hydrogen gas-sensing 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 detection agent.

Hereinafter, the present invention will be described in detail.

Since the present invention can be subject to various changes and can have various forms, implementation examples (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

The terms used in this specification are merely used to describe specific implementations (or examples) and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as ~include~ or ~consist of~ are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, 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 a person of ordinary skill in the technical field to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted in an ideal or excessively formal sense unless explicitly defined in the present application. No.

The silicone tape composition for detecting hydrogen gas according to the present invention, the silicone tape for detecting hydrogen gas, and the manufacturing method are as a basic composition.

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

Specifically, with respect to 100 parts by weight of the hydrogen gas detection agent, 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.

In addition, it is preferable to add a discoloration visibility enhancer to the tape and a catalyst, especially a platinum catalyst.

This discoloration visibility enhancer is preferably alumina, and in this case, alumina also contributes to improving the tensile strength of the tape.

In addition, the present invention prefers the addition of a curing retardant, and this curing retarding agent may be methylvinylcyclosiloxane (MVC).

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

In addition, the hydrogen gas detection agent is preferably contained in a carrier considering ease of operation, material stability, and preservation, and examples of such carriers include porous materials such as zeolite, TiO ₂ , SiO ₂ , ZnO, and Al ₂ O ₃ (can be one, some or all of these) can be utilized, of which zeolites are suitable.

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

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 photos of Figure 1 and Figure 1 below.

PdO (Brown) + H2 → Pd (Gray) + H2O

[Figure 1: Comparison photo - (left) before hydrogen gas exposure, (right) after hydrogen gas exposure]

[Description of the ingredients of the composition]

The hydrogen gas sensing silicone tape according to the present invention is particularly preferably used so that it can be applied stably to various fields. The silicone tape uses silicone endowed with a vinyl group and a hydrogen (H) group to improve functionality. (Silicone with a hydroxyl (OH) group (Hydroxyl Terminated Polydimethylsiloxane (HTPS)) was added only in the comparative example). In addition, the curing reaction of silicon is an addition reaction, and it is desirable to use a platinum (Pt) catalyst.

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

It serves as the backbone of silicon.

○ PDMS (Hydride terminated PDMS) with terminal hydrogen groups

It acts as a cross-linker.

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

It provides adhesive properties unique to hydroxyl groups (adhesion to adherends can be secured by providing -OH, which does not participate in addition hardening).

○ Pt catalyst

Induces a hardening 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 characteristics when reacting with hydrogen gas, and zeolite, TiO ₂ , SiO ₂ , ZnO, and Al ₂ O ₃ serve as a carrier for PdO, and zeolite is suitable.

○ Alumina (Al ₂ 2O ₃ )

It maximizes the visibility (color contrast effect) of PdO's color change (i.e., functions as a color change visibility enhancer) and also contributes to increasing the tensile strength of the tape.

○ Curing retardant (inhibitor)

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

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

[Manufacturing example: Preparation of overall composition and tape preparation for manufacturing hydrogen gas sensing silicone tape]

● Manufacturing of hydrogen gas detection agent

As can be seen in the process diagram of Figure 2,

1. It is prepared by mixing and supporting a PdO precursor and water (H ₂ O) with a substrate (zeolite, TiO ₂ or ZnO). PdO precursor (PdCl ₂ ) is added at 2 to 4 phr compared to the carrier.

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

3. Afterwards, stir for 60 minutes, and the reaction temperature is room temperature ~ 60 ℃.

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

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

● Manufacturing of hydrogen gas sensing silicone tape

○ Raw material mixing ratio

The components of each of the following examples and comparative examples were mixed based on 100 parts by weight of PdO/Zeolite, a hydrogen gas detection agent.

Meanwhile, in this example, PDMS (VTP) having a terminal vinyl group can be used in a mixture of those having different viscosities, which can help ensure dispersion characteristics for PdO/carrier, which is a hydrogen gas detector. For example, VTP with a viscosity of 1000 cps, VTP with a viscosity of 20,000 cps, and VTP with a viscosity of 65,000 cps are mixed and used. Specifically, 90 to 120 parts by weight of VTP with a viscosity of 20,000 cps are used for 100 parts by weight of VTP with a viscosity of 1,000 cps. , it is appropriate to mix 40 to 60 parts by weight of VTP with a viscosity of 65,000 cps.

○ Three Roll Milling

This is a process of pulverizing/dispersing particles (fillers) present in the mixed composition,

In particular, the dispersion liquid is produced by grinding/dispersing the hydrogen gas sensing agent particles in silicon (RV100), and the gap of the roll into which the raw material is input is set to 20 ㎛ and the gap of the roll being discharged is set to 5 ㎛.

○ Planetary Mixing

The dispersion and the remaining composition are mixed using Planetary Mixer equipment.

○ Observation of film formation and discoloration of hydrogen gas

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

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

The cured film is exposed to hydrogen gas to observe discoloration, and the hydrogen gas exposure condition is exposed to 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 detection agent 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 detection agent 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 seen in the experimental example [Table 3], the present invention provides a silicone tape composition for hydrogen gas sensing that is superior in both tensile strength and elongation compared to the comparative example, a hydrogen gas sensing silicone tape, and a manufacturing method thereof. . As in the comparative example, when adding silicone (Hydroxyl Terminated Polydimethylsiloxane (HTPS)) to which a hydroxyl (OH) group was added, it was confirmed that it had a negative effect on tensile strength and elongation compared to the intention of providing adhesive properties unique to the hydroxyl group. .

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

In addition, 0.20 to 1.00 parts by weight of catalyst (e.g. Pt catalyst), 15.00 to 25.00 parts by weight of filler (e.g. alumina (Al ₂ O ₃ )), and 15.00 to 25.00 parts by weight of curing retarder (e.g. MVC (methyl vinyl) Cyclosiloxane) is preferably contained in an amount of 0.10 to 0.30 parts by weight, and an adhesion improver (e.g. MS = Methacylate Silane) is preferably included in an amount of 4.00 to 10.00 parts by weight.

The adhesive layer can be applied or not depending on need.

More specifically and comprehensively, as can be seen in the above experimental example table, in relation to tensile strength and elongation performance, VTP is 20.00 to 30.00 parts by weight per 100.00 parts by weight of silicone gum (see Examples ③ to ⑧, ⑩, ⑪) It is more preferable that the VTP is 25.00 to 30.00 parts by weight (see Examples ⑩ and ⑪), and most preferably,

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, ⑪ above)

In the above description, conventionally known techniques related to the hydrogen gas sensing silicone tape composition, the hydrogen gas sensing silicone tape, and the manufacturing method are omitted, but those skilled in the art can easily guess, infer, and reproduce them.

Claims (11)

Contains a hydrogen gas detection agent, VTP (Vinyl Terminated Polydimethylsiloxane), hTPS (Hydride Terminated Polydimethylsiloxane), and silicon gum,
The VTP is a mixture of those having different viscosities, and a VTP with a viscosity of 1000 cps, a VTP with a viscosity of 20,000 cps, and a VTP with a viscosity of 65,000 cps are used. A silicone tape composition for sensing hydrogen gas. According to claim 1,
When mixing VTPs of different viscosities,
A silicone tape composition for sensing hydrogen gas, characterized in that 90 to 120 parts by weight of VTP with a viscosity of 20,000 cps and 40 to 60 parts by weight of VTP with a viscosity of 65,000 cps are mixed with 100 parts by weight of VTP with a viscosity of 1,000 cps. According to claim 2,
A silicone tape composition for detecting hydrogen gas, further comprising a visibility enhancer. According to claim 3,
A silicone tape composition for sensing hydrogen gas, wherein the visibility enhancer is alumina. According to claim 1,
A silicone tape composition for sensing hydrogen gas, characterized in that a curing retardant is further added. According to claim 5,
A silicone tape composition for sensing hydrogen gas, wherein the curing retardant is methylvinylcyclosiloxane (MVC). The method according to any one of claims 1 to 6,
A silicone tape composition for sensing hydrogen gas, characterized in that an adhesion promoter is further added. The method according to any one of claims 1 to 6,
A silicone tape composition for sensing hydrogen gas, characterized in that a tensile strength improver is further added. The method according to any one of claims 1 to 6,
A silicone tape composition for sensing hydrogen gas, wherein the hydrogen gas sensing agent uses PdO, and the carrier is some or all of zeolite, TiO2, SiO2, ZnO, and Al2O3. The method according to any one of claims 1 to 6,
A silicone tape composition for detecting hydrogen gas containing 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, based on 100.00 parts by weight of silicone gum. Silicone for hydrogen gas detection manufactured using the composition according to claim 1