WO2022182089A1 - Self-healing porous substrate and method for manufacturing same - Google Patents

Abstract

The present invention relates to a self-healing and temperature change detecting porous substrate, and a method for manufacturing same. Specifically, the present invention relates to a temperature change detecting porous substrate and a method for manufacturing same, wherein the temperature change detecting porous substrate is formed of a polymer containing a urea group, a thiourethane group, or a mixture thereof, and in which a porous pore structure is dispersed.

Description

Self-healing porous substrate and manufacturing method thereof

The present invention provides a self-healing porous substrate capable of self-healing at room temperature without additional heat treatment or light irradiation when damaged, and having high toughness, and a method for manufacturing the same.

Specifically, the present invention provides a self-healing porous substrate including a porous substrate obtained from a polymer including a disulfide group while including at least one polymer unit of a urea group or a thiourethane group, and a method for manufacturing the same.

The coating composition and coating film material for paint protection having anti-scratch, anti-chip, or anti-stone functions have many applications for vehicles, military, and IT.

For vehicles, damage to the surface of the vehicle body or headlights can be prevented by debris or sand while the vehicle is running, and it is also necessary for aesthetic purposes. In military use, even a small scratch on the surface of a helicopter wing can be fatal, so an anti-chip coating film is essential. For IT, it is also necessary for the purpose of protecting displays such as smartphones and TVs from external damage and for preventing damage to the wings caused by ice on the surface of the drone.

The major properties required for this anti-chip coating technology are transparency, abrasion resistance, solvent resistance, and the like. In the 2000s, anti-chip coating films with added functionality related to self-healing began to be developed. The self-healing function refers to the property of returning to a clean original state without scratches by self-healing when scratches occur on the coating surface.

The present inventors have been conducting a lot of research on polymers such as polyurea and thiourea having a self-healing function as described above.

However, most of the above studies have only been conducted with respect to coating agents that self-heal damage to surfaces, and studies on functions such as temperature sensors using the same are still insufficient.

When storing and distributing meat and fish that are sensitive to temperature in recent years, there is a risk of loss of freshness and deterioration due to temperature rise. However, as described above, it is not possible to check the history of whether or not it is exposed to more than a set temperature in the distribution process or storage process and decays. In particular, in the case of products that are necessarily stored at low temperature or room temperature as in the case of vaccines to respond to COVID-19 recently, or products that are exposed to unexpected high temperatures and are likely to lose their functions, in the case of products that are Whether it is stored and distributed is very important.

Also, for example, it must be stored at 25°C or lower, and in the case of vaccine products that lose their effectiveness at 35°C or higher, it is very important whether or not they have been exposed to more than 35°C at least once during the distribution process. As such, when a self-healing web-film having an onset point of 10°C is used as a temperature sensor according to the difference between the storage temperature and the exposure temperature (referred to as the “onset temperature”), if it is a web-film that maintains opacity, storage and distribution It can be trusted that the freshness was kept constant during the process. On the other hand, if it is a film having transparency, it means that it has been maintained at a temperature of 10°C or higher for a certain period of time during storage and distribution. can provide Accordingly, the temperature sensor including the self-healing web-film according to the present invention may be an irreversible temperature sensor. Although there is a Korean Patent Application Laid-Open No. 10-2020-0081820 (applied on Jul. 03, 2020) previously filed by the present inventors, there is a problem in that the sensitivity for self-healing is low.

Accordingly, an object of the present invention is to provide a self-healing porous substrate, and to provide a function of a temperature sensor by causing a change in light transmittance when exposed at an on-set temperature or higher.

Specifically, in the present invention, when the light-transmitting porous self-healing substrate is exposed to an on-set temperature or higher, a self-healing effect appears and the porous pores are closed to change into a uniform film, resulting in a change in light transmittance. The purpose of this is to provide a function that can function as a temperature sensor.

As a result of research to achieve the above object, the present invention by providing a temperature change sensing type porous substrate made of a polymer having a disulfide group while including a urea group, a thiourethane group, or a mixture thereof, and formed by dispersing a porous pore structure The invention was completed.

The polymer may be a temperature-sensitive porous substrate, which is a self-healing polymer having a disulfide group.

The polymer may be a temperature change-sensing porous substrate prepared by reacting a monomer including a monomer including an amine or thiol group having two or more active hydrogen groups and a monomer including polyisocyanate.

The monomer may be a temperature change-sensing porous substrate further comprising a polyol.

The monomer having an active hydrogen group is a monomer having two or more active groups in which diol, diamine, dithiol, or functional groups thereof are mixed, and may be a temperature change-sensing porous substrate that is a monomer or a mixture thereof necessarily containing an amine or thiol group. .

The monomer having a disulfide group may be a monomer of Formula 1 below.

[Formula 1]

R ₁ -A ₁ -SSA ₂ -R ₂

(The above A ₁ and A ₂ are each independently (C ₁ -C ₁₀ )alkylene, (C ₄ -C ₃₀ )cycloalkylene, C ₆ -C ₃₀ arylene, wherein R ₁ and R ₂ are independent of each other is selected from hydroxy (OH), amino (NH ₂ ), and thiol (-SH), but R 1 and R 2 are not only monomers in which R ₁ and R ₂ are simultaneously hydroxyl groups, and among the functional groups of alkylene, cycloalkylene or arylene one or more hydrogen atoms are C ₁ -C ₁₂ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₃ -C ₃₀ cycloalkyl, halogen, carboxylic acid, aldehyde, amino, nitro, cyano, hydroxy and C ₁ -C ₁₀ It may be further substituted with any one or more selected from alkoxy.)

The substrate may be a temperature change-sensing porous substrate that is any one selected from a film, a web, and a non-woven fabric.

In addition, it may be to provide a temperature sensor including the temperature change sensing type porous substrate of the various types of the present invention.

In addition, the present invention comprises the steps of preparing a self-healing polymer by polymerizing a composition comprising the above monomer having two or more active hydrogen groups containing a disulfide group, a polyisocyanate, and a polyol;

Spinning the polymer to prepare a self-healing porous substrate;

It may be to provide a method of manufacturing a self-healing temperature change sensing type porous substrate comprising a.

In the above spinning method, electrospinning, melt spinning and solution spinning may be used, and electrospinning is more preferred in order to provide a fine pore structure, but is not limited thereto.

The monomer having two or more active hydrogen groups containing a disulfide group may be a method for preparing a temperature change-sensing porous substrate, which is a monomer of Formula 1 below.

[Formula 1]

R ₁ -A ₁ -SSA ₂ -R ₂

(The above A ₁ and A ₂ are each independently (C ₁ -C ₁₀ )alkylene, (C ₄ -C ₃₀ )cycloalkylene, C ₆ -C ₃₀ arylene, wherein R ₁ and R ₂ are independent of each other is selected from hydroxy (OH), amino (NH ₂ ) and thiol (-SH), but R 1 and R 2 are not only monomers in which R ₁ and R ₂ are simultaneously hydroxyl groups, and among the functional groups of alkylene, cycloalkylene or arylene one or more hydrogen atoms are C ₁ -C ₁₂ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₃ -C ₃₀ cycloalkyl, halogen, carboxylic acid, aldehyde, amino, nitro, cyano, hydroxy and C ₁ -C ₁₀ It may be further substituted with any one or more selected from alkoxy.)

The substrate may be any one selected from a film, a web, and a nonwoven fabric to provide a method for manufacturing a temperature change sensing type porous substrate.

The fiber constituting the substrate may be a method for manufacturing a temperature change sensing type porous substrate that is 0.01 μm to 200 μm.

The present invention is a self-healing porous substrate that is produced as a self-healing sheet or film capable of transmitting light, and then, when the substrate is exposed to an onset temperature or higher, a self-healing effect appears and the porous pores are closed to form a uniform film or sheet. By changing and causing a change in light transmittance, a function as a temperature sensor can be given.

By manufacturing and utilizing the self-healing porous substrate of the present invention, it is intended to check the history of whether or not it is exposed to more than a set temperature in the distribution process or storage process and decays. In particular, as in the case of a vaccine to respond to COVID-19 recently, if it needs to be stored at a low temperature or at room temperature, in the case of a product that is exposed to an unexpected high temperature and may lose its function, store it in a safe temperature range during the distribution process. It is known whether or not it has been distributed.

The present invention will be described in more detail through the following specific examples or examples. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

In order to achieve the above object, the present invention provides a film, nonwoven fabric, web and The present invention was completed by preparing a porous substrate such as a sheet.

[Structural Formula 1]

The porous substrate produces a nonwoven fabric, a web, or a film by spinning or electrospinning, so that the matrix polymer migrates by self-healing at a certain temperature or higher to close the pores, thereby causing a change in light transmittance so that the substrate is stored at a temperature above the storage temperature. It can function as a temperature sensor to check whether it is exposed.

That is, the porous substrate made of the self-healing polymer contains a light-scattering pore structure, and the pores included in the substrate by a change in temperature collapse into a uniform film by diffusion of the self-healing polymer included in the substrate. It is to provide a temperature change sensing type porous substrate by light transmittance, characterized in that it causes a change in light transmittance.

That is, the present invention intends to check the history of whether or not the self-healing porous substrate having the above characteristics is manufactured and utilized, and whether it is exposed to a temperature higher than a set temperature during a distribution process or a storage process and decays. In particular, the present invention provides a safe temperature range in the distribution process for products that are likely to lose function due to exposure to unexpected high temperatures when stored at low temperature or at room temperature as in the case of vaccines to respond to recent COVID-19. It is to be able to know whether it has been stored and distributed in

In addition, the present invention provides a substrate such as a self-healing porous polymer film having a polyurea or polythiourea unit and a disulfide unit having an "onset point", a method for manufacturing the same, and a temperature sensor manufactured by the manufacturing method, Self-healing does not occur below the onset point, and self-healing may be triggered above the onset point. Accordingly, the terms “onset point” and “critical temperature” are used herein as interchangeable terms.

The self-healing polymer may be obtained by, for example, polymerizing a monomer having the following formula (1) and polyisocyanate.

[Formula 1]

R ₁ -A ₁ -SSA ₂ -R ₂

(The above A ₁ and A ₂ are each independently (C ₁ -C ₁₀ )alkylene, (C ₄ -C ₃₀ )cycloalkylene, C ₆ -C ₃₀ arylene, wherein R ₁ and R ₂ are independent of each other is selected from hydroxy (OH), amino (NH ₂ ) and thiol (-SH), but R 1 and R 2 are not only monomers in which R ₁ and R ₂ are simultaneously hydroxyl groups, and among the functional groups of alkylene, cycloalkylene or arylene one or more hydrogen atoms are C ₁ -C ₁₂ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₃ -C ₃₀ cycloalkyl, halogen, carboxylic acid, aldehyde, amino, nitro, cyano, hydroxy and C ₁ -C ₁₀ It may be further substituted with any one or more selected from alkoxy.)

The present invention can provide a polymer having excellent self-recovery rate according to temperature change and high toughness recovery rate by preparing polythiourethane, polythiourea, and a copolymer including the disulfide group introduced therein.

In the present invention, the polyisocyanate is not particularly limited, but when using a branched acyclic aliphatic polyisocyanate, not only when using an ether-based polyol as an additional polyol component, but also when using an ester and carbonate-based polyol Although recovery performance and toughness recovery rate can be improved, it is not limited thereto.

As described above, the self-healing elastomer according to the present invention can obtain a self-healing polymer by introducing a disulfide structure into its chemical structure. In particular, when an aromatic disulfide structure is introduced, it is more preferred because the self-healing force can be introduced more excellently.

In detail, the self-healing polymer according to an embodiment of the present invention may be polymerized from a composition comprising an aromatic disulfide diamine represented by the following Chemical Formula 2, a branched acyclic aliphatic polyisocyanate, and a polyol.

[Formula 2]

NH ₂ -Ar ₁ -SS-Ar ₂ -NH ₂

(In Formula 2, Ar ₁ and Ar ₂ may be each independently a substituted or unsubstituted C ₆ -C ₁₈ arylene group, wherein the arylene is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₀ halogenated selected from alkyl, C ₃ -C ₃₀ cycloalkyl, halogen (-F, -Cl, -Br or -I), carboxylic acid, aldehyde, amino, nitro, cyano, hydroxy and C ₁ -C ₁₀ alkoxy Any one or more may be further substituted.)

In Formula 2, the arylene is, more specifically, a substituted or unsubstituted, phenylene group, a biphenylene group, a naphthylene group, a terphenylene group, an anthrylene group, a phenanthrylene group, a phenalenylene group, a tetraphenylene group, and It may be any one selected from a pyrenylene group and the like. However, 6 to 30 carbon atoms of the cycloalkylene described in Formula 1 do not include the carbon number of the substituent.

Another aspect of the present invention is a self-healing porous substrate prepared using a self-healing polymer comprising polymerizing a composition comprising an aromatic disulfide diamine, polyisocyanate and polyol represented by Formula 2 above, and a method for preparing the same. may be provided.

In one aspect of the present invention, the polyisocyanate is any one or two selected from propylene-1,2-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. It may be a mixture of the above.

In one aspect of the present invention, the polyol may be any one or a mixture of two or more selected from ether-based polyols, ester-based polyols and carbonate-based polyols.

In addition, the aliphatic polyol for preparing the polymer polymer in the present invention may preferably have a number average molecular weight of 5000 g/mol or less, and in the case of the disulfide-based monomer represented by the above formula, the molecular weight is not particularly limited, but the molecular weight is 1000 g/mol mol or less, preferably 500 g/mol or less, is preferred because it has better self-healing properties, but is not limited thereto.

As a reactive functional group of the monomer for preparing the self-healing polymer in the present invention, the molar ratio of isocyanate and active hydrogen to the functional group is not particularly limited, but for example, [NCO]: ([OH] + [NH ₂ ] +[SH]) = 1: may be polymerized in a ratio of 0.9 to 1.1.

In addition, the self-healing polymer satisfies high mechanical properties, excellent self-healing at room temperature, and high light transmittance at the same time, and thus a temperature change detection sensor for preventing spoilage of refrigerated or frozen food and medical supplies that may be altered according to temperature has excellent applicability.

For application of the temperature change sensor, the self-healing polymer is opaque at a low temperature, but increases in transparency at a high temperature above a critical temperature, so it may be desirable to have a characteristic having a certain level of transparency or more.

As a specific example, when the self-healing polymer is formed into a film to form a dense film, the change in light transmittance according to temperature change may be insignificant due to the high transparency of the polymer material. In order to maximize the change in light transmittance, light scattering of incident light is generated in the film, so that it is opaque at a low temperature, but at a high temperature above the critical temperature, light scattering is reduced, and it may be desirable to have a characteristic having a certain level of transparency or more.

In order to implement the transparency change characteristics as described above, the self-healing elastomer article is not densified and is made of a porous substrate such as a non-uniform self-healing film, non-woven fabric, web or sheet including pores on the inside or surface of the article By doing so, it can be utilized as a temperature change detection sensor.

The shape and size of the pores are sufficient as long as they can generate light scattering of light incident on the article in a visible light region having a wavelength band of 380 to 780 nm, and are not limited to a specific shape or size within a specific range. Illustratively, the average diameter of the pores or irregularities may be 10 nm to 500 μm, preferably 100 nm to 100 μm, and more preferably 150 nm to 10 μm.

In the case of the porous self-healing porous substrate including pores in the interior of the article, the porosity of the article may be 10 to 95%, specifically 20 to 85%, more specifically 40 to 80%.

The shape of the article is not limited to a specific shape, and specific examples thereof include a porous substrate such as a porous film, a porous sheet, a nonwoven fabric, or a web.

One aspect of the present invention may be a porous film, wherein the porous film may be formed of microfibers of the self-healing polymer, and self-value in which microfibers made of a plurality of self-healing polymers form a network structure. It can also be prepared in the form of an oily web.

More specifically, the self-healing web-type film is prepared by fine fibers and agglomeration of the self-healing polymer, and has opaque properties in a web state. However, above the critical temperature, the microfiber is diffused into the surrounding pores and the empty space of the web is filled, and the light transmittance is changed by having a behavior that is changed into a homogeneous and dense film. It is possible to know if it has been exposed to a specific temperature.

The microfibrillation of the self-healing polymer may be prepared by solution spinning or melt spinning.

In the case of the solution spinning, there are various spinning methods such as dry spinning, wet spinning and electrospinning, but in the case of the electrospinning, the diameter of the fiber ranges from nanometer level (~102 nm) to micrometer level (~102 μm). It is preferable because it can be easily adjusted.

Accordingly, the present invention provides a method for producing a web-type film by spinning, in particular a self-healing web-type film by an electrospinning method (hereinafter referred to as a web-film).

Specifically, the self-healing web-film manufacturing method comprises the steps of: S1) dissolving the self-healing polymer in an organic solvent to prepare a self-healing spinning solution; S2) forming microfibers by electrospinning the self-healing spinning solution; and S3) obtaining a web-film made of the microfibers.

Electrospinning may be performed using spinning equipment including a nozzle unit for discharging a polymer solution or melt for electrospinning, a high voltage generator, and a current collector. Also, it may be a method in which a microfiber aggregate having a random structure is implemented by the strength of an electric field applied to the discharge.

The concentration of the electrospun polymer solution is not particularly limited as long as the electrospinning is possible. In addition, in constituting the polymer solution, the solvent may be used without limitation as long as it is a solvent capable of dissolving the polymer and capable of electrospinning.

According to an aspect of the present invention, the electrospinning may be electrospinning on a coagulation bath.

The coagulation bath may include water, and a current collector may be included in the coagulation bath to be electrospinning on the water surface. As the coagulation bath contains water, the solvent included in the polymer solution is preferably a solvent miscible with water, and water may be a poor solvent for the polymer.

In addition, by including a current collector plate in the coagulation bath during electrospinning, the self-healing polymer microfibers are spun on the water surface of the coagulation bath, and thus the self-healing web-film in the form of a pure non-woven fabric free from impurities and solvents This can be easily obtained.

The self-healing web-film produced by the electrospinning may have a very dense nonwoven structure by combining microfibers having a diameter of a nanometer level (10 nm) to a micrometer level (500 μm). Specifically, the average diameter of the microfibers may be 0.01 μm to 200 μm, preferably 0.05 μm to 100 μm, and more preferably 0.1 μm to 50 μm.

In addition, the thickness of the self-healing web-film produced by the electrospinning may be 0.1 μm to 200 μm, preferably 0.5 μm to 150 μm, and more preferably 1 μm to 100 μm.

As the self-healing web-film includes microfibers of the average diameter and forms a network structure, a difference in light transmittance according to temperature change in the visible region can be clearly observed with the naked eye, and the self-healing web - The durability of the film can be increased.

By having such a structure, incident light is light-scattered through the network structure formed by the microfibers in the web state, and thus has opaque properties. However, at a high temperature above the critical temperature, the microfiber loses its fibrous shape, and the self-healing polymer diffuses into the surrounding pores to fill the empty space of the web, resulting in a homogeneous and densified form. (dense) It has a behavior that is changed into a film. According to this behavior, the self-healing web-film may have high light transmittance above the critical temperature or higher.

The self-healing web-film may have a light transmittance of 25% or less at a wavelength of 380 to 780 nm at a temperature below the onset point, preferably 15% or less, and more preferably 10% or less can be

The self-healing web-film may have an onset point at a temperature of 10° C. or higher. At a temperature above the onset point, the microfibers are irreversibly self-fused to each other, thereby increasing transparency. This means that the self-healing web-film maintains the non-woven form at a temperature below the onset point, and is converted from the non-woven form to the film form at a temperature of 10° C. or more while increasing the transparency.

Specifically, the onset point may be 15°C or higher, specifically 20°C or higher, and may be 30°C or lower without limitation, but it is not limited to a specific numerical range because it corresponds to a design variable that may vary according to application examples.

For example, when storing and distributing temperature-sensitive meat and fish, there is a risk of loss of freshness and deterioration due to temperature rise. Accordingly, when a self-healing web-film having an onset point of 10°C is used as a temperature sensor, it can be trusted that the freshness is constantly maintained during storage and distribution if the web-film maintains opacity. On the other hand, if it is a film having transparency, it means that it has been maintained at a temperature of 10°C or higher for a certain period of time during storage and distribution. can provide Accordingly, the temperature sensor including the self-healing web-film according to the present invention may be an irreversible temperature sensor.

In one aspect of the present invention, the self-healing polymer may satisfy the following Relational Equation 1.

[Relational Expression 1]

(In Relation 1, M [disulfide group] is the total number of moles of monomers providing disulfide groups in the polymer, and M [active hydrogen group] is the total number of monomers having functional groups having active hydrogens such as hydroxyl, amine and thiol groups in the composition. It is forfeited.)

In addition, as a non-limiting example, the aromatic disulfide diamine represented by Formula 2 may be a compound of Formula 3 below, but is not limited thereto.

[Formula 3]

NH ₂ -Ph-SS-Ph-NH ₂

In one aspect of the present invention, the branched acyclic aliphatic polyisocyanate may be used without particular limitation as long as it is a branched acyclic aliphatic compound having two or more isocyanate groups. Specifically, for example, any one or a mixture of two or more selected from propylene-1,2-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. and is not limited thereto.

In addition, in order for the self-healing polymer to self-restore at room temperature, it is preferable to appropriately control the ratio between the compound containing an active hydrogen group and the polyisocyanate compound, preferably the ratio between the branched acyclic aliphatic polyisocyanate compound. In this case, the hydroxyl group-containing compound may refer to both an aromatic disulfide diol and a polyol containing two or more hydroxyl groups.

Specifically, for example, the molar ratio of the active hydrogen group of the active hydrogen group-containing compound to the isocyanate group of the isocyanate group-containing compound may be 1:0.8 to 1.2, and more preferably 1:0.9 to 1.1. In the above range, the self-healing polymer can be effectively polymerized, and when the polymer is damaged, it can self-restore at room temperature, while ensuring excellent solvent resistance, abrasion resistance, and high transparency that the polymer must have.

In addition, in one aspect of the present invention, in order for the self-healing polymer to have an excellent self-healing rate and high toughness, it is preferable to appropriately control the content of the monomer having a disulfide group in the composition. When the content of the disulfide group is too low, the self-recovery rate and the toughness recovery rate at room temperature may be greatly reduced.

Specifically, the composition for preparing the self-healing polymer may contain a monomer having an active hydrogen group having a disulfide group to satisfy the following Relational Equation 1, wherein the upper limit of M [disulfide group] / M [active hydrogen group] is Although not particularly limited, it may be, for example, 0.8.

[Relational Expression 1]

(In Relation 1, M [disulfide group] is the total number of moles of monomers providing disulfide groups in the polymer, and M [active hydrogen group] is the total number of monomers having functional groups having active hydrogens such as hydroxyl, amine and thiol groups in the composition. It is forfeited.)

More specifically, in the above relation 1, M [disulfide group] / M [active hydrogen group] may be 0.1 or more, more specifically 0.2 or more, in this case, the self-healing polymer has a self-healing rate of 70% or more under a temperature condition of 30 ° C. and may have a toughness recovery rate of 60% or more. More preferably, M [disulfide group] / M [active hydrogen group] may be 0.3 or more, in this case, the self-healing polymer may have a self-healing rate of 80% or more under a temperature condition of 30 ° C., and a toughness recovery rate of 70% or more. can have More preferably, it may be 0.5 or more, and in this case, the self-healing polymer may have a self-healing rate of 100% under a temperature condition of 30°C, and may have a toughness recovery rate of 80% or more.

The present invention also provides a method for preparing a self-healing polymer.

Specifically, the method for preparing a self-healing polymer according to an embodiment of the present invention may include polymerizing a composition comprising an aromatic disulfide diamine represented by the following Chemical Formula 2, a branched acyclic aliphatic polyisocyanate, and a polyol.

[Formula 2]

NH ₂ -Ar ₁ -SS-Ar ₂ -NH ₂

(In Formula 2, Ar ₁ and Ar ₂ may be each independently a substituted or unsubstituted C ₆ -C ₁₈ arylene group, wherein the arylene is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₀ halogenated selected from alkyl, C ₃ -C ₃₀ cycloalkyl, halogen (-F, -Cl, -Br or -I), carboxylic acid, aldehyde, amino, nitro, cyano, hydroxy and C ₁ -C ₁₀ alkoxy Any one or more may be further substituted.)

In Formula 2, the arylene is, more specifically, a substituted or unsubstituted, phenylene group, a biphenylene group, a naphthylene group, a terphenylene group, an anthrylene group, a phenanthrylene group, a phenalenylene group, a tetraphenylene group, and It may be any one selected from a pyrenylene group and the like. However, 6 to 30 carbon atoms of the cycloalkylene described in Formula 1 do not include the carbon number of the substituent.

At this time, the type and content of each compound is the same as described above, and a duplicate description is omitted.

In one embodiment of the present invention, the polymer may be polymerized using an organic solvent. The organic solvent may be used without particular limitation as long as it is commonly used in the art, and specifically, for example, an alcohol-based solvent such as methanol, ethanol, methoxyethanol, propanol, isopropanol, butanol, isobutanol; acid solvents such as acetic acid and formic acid; nitro solvents such as nitromethane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, and 3-methoxy-3-methyl butyl acetate; amine solvents such as dimethylformamide, methyl pyrrolidone, and dimethylacetamide; ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl ether and dibutyl ether; and the like, but is not limited thereto.

The amount of the solvent to be added is not particularly limited, but the compound to be added is sufficiently dissolved so that it can be mixed uniformly, and it can be added in an amount that can be easily applied to form a coating film. Specifically, for example, 1 to 2,000 ml of the organic solvent may be added with respect to 1 mol of the aromatic disulfide diol, and more preferably 100 to 1,500 ml of the organic solvent may be added.

When each compound is uniformly mixed, the composition can be polymerized to prepare a self-healing polymer. Polymerization conditions may be used without particular limitation as long as the self-healing polymer is polymerized. Specifically, for example, the polymerization reaction may be performed at a temperature of 20 to 200° C. for 30 minutes to 24 hours, but is not necessarily limited thereto. .

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Measurement of transmittance]

In the present invention, transmittance was measured using a UV-VIS spectrophotometer (UV-2600, Shimadzu Co.) from frozen (-20 ℃) to refrigerated (5 ℃) and room temperature (20 ℃) for 24 hours, respectively. The light transmittance (T%) of the microfiber-based web-film having an area of 3 × 3 cm2 was measured under the same green light (λ=560 nm) light source (slit size=2 mm).

[Example 1]

Polytetramethylene Ether Glycol (Polytetramethylene Ether Glycol, PTMEG, 20.0 mmol, number average molecular weight 1,000 g/mol) was added to a two-necked separable flask equipped with a mechanical stirrer, and then the moisture was removed by vacuum drying. Then, at 70 °C, 8 ml of dimethylacetamide (DMAc) in which isophorone diisocyanate (42.0 mmol) and dibutyltin dilaurate (70 mg) were dissolved was slowly added dropwise and nitrogen atmosphere for 2 hours. under stirring.

Next, after cooling the temperature to about 30 ℃, Bis(4-aminophenyl) Disulfide (NH ₂ C ₆ H ₅ SSC ₆ H ₅ NH ₂ ) (20.0 mmol, 4.97 g) was dissolved in 15ml of DMAc was added dropwise to 40 ℃ After stirring for 1.5 hours, 29 ml of DMAc was further added dropwise to complete polymerization into a solution having a solid content of 40 wt%, and then the solid content was recovered by vacuum drying in an oven at 80°C.

The obtained polymer resin was dissolved in a complex solvent composed of DMAc and tetrahydrofuran (THF) in a mass ratio of 3:7 at a concentration of 20 wt%.

After the prepared solution was filled in the cylinder, a voltage of 6.5 kV was applied to the polymer solution using a high voltage generator, and the mixture was spun for 2 minutes and 30 seconds. At this time, the spinning nozzle was 24 gauge with a diameter of 0.31 mm, the solution discharge rate was 1 mL/hr, and the distance from the nozzle to the metal collector was 15 cm. A coagulation bath filled with distilled or tap water was placed under the spinning nozzle to collect the film in the form of a microfiber-based web from which impurities such as residual solvent and dust were removed. At this time, the average fiber diameter of the spun fibers was 0.5 μm.

The microfiber-based web-film collected on the upper part of the coagulation bath was taken as a square frame with outer and inner side lengths of 5 and 3 cm, respectively, and dried at room temperature (20 ° C) for about 30 minutes to obtain a web-film with a thickness of 5 μm. It was manufactured, and the microfiber-based web-film protection PET film (SKC) was attached to the top and bottom to measure the light transmittance (%) with a UV-VIS spectrophotometer (UV-2600, Shimadzu Co.), and the results are shown in the table. 1 is included.

[Example 2]

In Example 1, in place of Bis(4-aminophenyl) Disulfide, 2-Hydroxyethyl disulfide (10.0 mmol, 1.54 g) and 1,6-hexanediamine (10.0 mmol, 1.16 g) were used in the same manner except that a mixture was used. The results are listed in Table 1.

[Example 3]

In Example 1, in place of Bis (4-aminophenyl) Disulfide, 2-Hydroxyethyl disulfide (10.0 mmol, 1.54 g) and 1,6-hexanedithiol (10.0 mmol, 1.51 g) was carried out in the same manner except that a mixture was used and the results are listed in Table 1.

[Example 4]

After filling the hopper with the polymer resin of Example 1, the polymer melt is spun through a melt-blown spinning nozzle. At this time, the hot air temperature is 250 °C, the hot air pressure is 24 psi, the nozzle temperature is 170 °C, and the distance from the nozzle to the conveyor belt to which the mesh current collector is attached is 25 cm. The microfiber-based web-film is collected while maintaining the conveyor belt speed at 60 cm/min. (Average fiber diameter: 10 μm to 200 μm)

The microfiber-based web-film collected on the mesh current collector is taken as a square frame with outer and inner side lengths of 5 and 3 cm, respectively, and the microfiber-based web-film protection PET film (SKC) is attached to the upper and lower parts to UV -VIS spectrophotometer (UV-2600, Shimadzu Co.) to measure the light transmittance (%), and the results are listed in Table 1.

[Comparative Example 1]

The same procedure was performed except that 1,6-hexanediol (20.0 mmol, 2.36 g) was used instead of Bis(4-aminophenyl)disulfide in Example 1, and the results are listed in Table 1.

[Comparative Example 2]

In Example 1, the same procedure was performed except that 1,6-hexanediamine (20.0 mmol, 2.32 g) was used instead of Bis(4-aminophenyl)disulfide, and the results are listed in Table 1.

[Comparative Example 3]

In Example 1, the same procedure was performed except that 1,6-hexanedithiol (20.0 mmol, 3.01 g) was used instead of Bis(4-hydroxyphenyl)disulfide, and the results are listed in Table 1.

temperature change detection sensor	Permeability (%)
	-20℃	5 °C (24 hours exposure)	20 °C (24 hours exposure)
Example 1	0.2	12.5	24.5
Example 2	0.1	8.9	16.8
Example 3	0.2	8.6	16.4
Example 4	0.2	10.5	22.0
Comparative Example 1	0.1	6.8	13.1
Comparative Example 2	0.1	6.4	12.8
Comparative Example 3	0.2	7.1	13.3

As shown in Table 1, in the web-film prepared from microfibers according to the present invention, the permeability is remarkably changed and increased as the microfibers are fused by the self-healing principle under certain temperature range conditions to become a uniform film. that can be checked

Therefore, the microfiber-based web-film produced according to an embodiment of the present invention confirmed that the change in transmittance visible to the naked eye became effective, and applied as a temperature change sensor to prevent spoilage of refrigerated or frozen food and medical supplies. suggests that this is possible.

The present invention described above is merely exemplary, and those of ordinary skill in the art to which the present invention pertains will appreciate that various modifications and equivalent other embodiments are possible therefrom. Therefore, it will be well understood that the present invention is not limited to the forms recited in the above detailed description. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims described below, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (12)

1. A temperature change-sensing porous substrate made of a polymer containing a urea group, a thiourethane group, or a mixture thereof, and having a porous pore structure dispersed therein.
2. The method of claim 1,

   The polymer is a temperature-sensitive porous substrate, which is a self-healing polymer having a disulfide group.
3. The method of claim 1,

   The polymer is a temperature change-sensing porous substrate prepared by reacting a monomer containing a monomer having two or more active hydrogen groups and a monomer containing a polyisocyanate.
4. 4. The method of claim 3,

   The temperature change sensing type porous substrate, wherein the monomer further comprises a polyol.
5. 4. The method of claim 3,

   The monomer having an active hydrogen group is a temperature change-sensing porous substrate comprising a monomer having two or more active groups including an amine and a thiol group.
6. 3. The method of claim 2,

   The temperature change sensing type porous substrate, wherein the monomer having a disulfide group comprises the following formula (1).

   [Formula 1]

   R ₁ -A ₁ -SSA ₂ -R ₂

   (The above A ₁ and A ₂ are each independently (C ₁ -C ₁₀ )alkylene, (C ₄ -C ₃₀ )cycloalkylene, C ₆ -C ₃₀ arylene, wherein R ₁ and R ₂ are independent of each other as hydroxy (OH), amino (NH ₂ ) and thiol (-SH), and R ₁ and R ₂ do not include only monomers in which at the same time a hydroxy group, the alkylene, cycloalkylene or arylene At least one hydrogen atom in the functional group is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₃ -C ₃₀ cycloalkyl, halogen, carboxylic acid, aldehyde, amino, nitro, cyano, hydroxy and C ₁ - It may be further substituted with any one or more selected from C ₁₀ alkoxy.)
7. The method of claim 1,

   The substrate is a temperature change-sensing porous substrate that is any one selected from a film, a web, and a non-woven fabric.
8. A temperature sensor comprising the temperature change sensing type porous substrate according to any one of claims 1 to 7.
9. Preparing a self-healing polymer by polymerizing a composition containing a monomer, a polyisocyanate and a polyol containing a monomer having two or more active hydrogen groups containing a thiol group or an amine group containing a disulfide group, and spinning the polymer to self-heal A method of manufacturing a self-healing temperature change sensing type porous substrate, comprising the steps of preparing a porous substrate.
10. 10. The method of claim 9,

    The method for producing a self-healing temperature change sensing type porous substrate, wherein the monomer having a disulfide group includes the following Chemical Formula 1.

    [Formula 1]

    R ₁ -A ₁ -SSA ₂ -R ₂

    (The above A ₁ and A ₂ are each independently (C ₁ -C ₁₀ )alkylene, (C ₄ -C ₃₀ )cycloalkylene, C ₆ -C ₃₀ arylene, wherein R ₁ and R ₂ are independent of each other as hydroxy (OH), amino (NH ₂ ), and thiol (-SH), and R ₁ and R ₂ do not include only monomers in which at the same time a hydroxy group, the alkylene, cycloalkylene or arylene At least one hydrogen atom in the functional group is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₃ -C ₃₀ cycloalkyl, halogen, carboxylic acid, aldehyde, amino, nitro, cyano, hydroxy and C ₁ - It may be further substituted with any one or more selected from C ₁₀ alkoxy.)
11. 10. The method of claim 9,

    The method of manufacturing a temperature change sensing type porous substrate, wherein the substrate is any one selected from a film, a web, and a nonwoven fabric.
12. 12. The method of claim 11,

    The fiber constituting the substrate is 0.01 μm to 200 μm, a method for producing a temperature change sensing type porous substrate.