KR20190080324A - Composition for forming a film at room temperature and method for forming a film at room temperature using the same - Google Patents

Abstract

The present invention relates to a composition for forming a film, like an artificial skin, on an object such as skin and the like by being cured in a short time at room temperature, and a method for forming the film using the same. The composition for forming a cured film at room temperature comprises: a first composition comprising a silicone-based first polymer having two or more vinyl end groups; a second composition comprising a silicone-based second polymer having two or more hydrogen end groups; a catalyst included in any one or more of the first composition and the second composition and promoting a hydrosilylation reaction of the first composition and the second composition; and an additive included in any one or more of the first composition and the second composition, and comprising an organic silane compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for forming a room-temperature curing film, and a film forming method using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a film forming technique, and more particularly, to a composition for forming a film such as artificial skin on a subject such as skin by curing at room temperature within a short time, and a film forming method using the same.

Currently, the technology related to artificial skin is a technology that has become a big issue in various industrial fields such as biopharmaceuticals, electric / electronic fields, and robotics fields. In particular, it is difficult to estimate the utilization of artificial skin related technologies in medical and cosmetic fields such as therapeutic agents for skin damaged by burns and ulcers, medicines and cosmetics carriers, and functional products that impart elasticity to aged skin.

Korean Patent Registration No. 10-0428491

In order to solve the above problems, it is an object of the present invention to provide a composition for forming a film such as artificial skin on a subject such as skin by curing at room temperature within a short time, and a film forming method using the same.

In order to achieve the above object, the present invention provides a room temperature curing film-forming composition comprising a first composition comprising a first silicone-based polymer having at least two vinyl end groups, a second composition comprising a second silicone-based polymer having at least two hydrogen end groups 2 composition, at least one of the first composition and the second composition, and is contained in at least one of the first composition and the second composition as a catalyst for promoting the hydrogen saccharification reaction of the first composition and the second composition And an additive comprising an organic silane compound.

The room-temperature-cured film composition of the present invention and the method of forming a room-temperature cured film using the same provide curing within a short time at room temperature, thereby forming a film such as artificial skin on a subject such as skin. Accordingly, when the object is skin, it is possible to harden only the temperature of the skin, thereby eliminating the need for a separate heat source for curing.

Further, by including the organosilane compound, when applied to a subject such as skin, the spreadability and adhesive force are further improved, and the effect of improving the wrinkles is remarkably excellent. Further, by including the nano-level fibrous polymer, a film excellent in physical properties such as tensile strength can be formed.

1 is a photograph showing a procedure of a film forming method using the room temperature curing film forming composition of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings in order to fully understand the present invention. The embodiments of the present invention may be modified into various forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail below. Throughout this specification, when an element is referred to as " including " an element, it is understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The room-temperature curing film-forming composition of the present invention and the film-forming method using the same are for forming a film such as artificial skin on a subject such as skin through hydrosilylation. Herein, the term "artificial skin" Refers to a film that is artificially made close to the physical appearance, feel, and texture of actual skin, and which satisfies the same or similar physical skin properties and physical properties. It means a film made by using a substance such as a polymer, not a film produced by culturing a living tissue, a cell, or the like.

The room temperature curing film-forming composition of the present invention comprises a first composition, a second composition, a catalyst, and an additive.

The first composition comprises a first silicone-based polymer having at least two vinyl end groups.

The second composition includes a second silicone-based polymer having at least two hydrogen end groups.

More specifically, the first polymer and the second polymer are preferably silicone-based polymer compounds having a skeleton composed of repeating units represented by the following general formula (1). Where n is the molar ratio and can be from 1 to 10,000.

More specifically, it is preferable that the first polymer is a compound represented by the following formula (2). Here, n is a molar ratio, and may be a number of 0 to 10,000, preferably 0 to 8,000, more preferably 0 to 6,000.

For example, the first polymer may be selected from the group consisting of vinyl terminated polydimethylsiloxane, vinyl terminated polydiethylsiloxane, vinyl terminated polydiphenylsiloxane, vinyl terminated diethylsiloxane-dimethylsiloxane copolymer, vinyl terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl Dimethylsiloxane-terminated vinyltrimethylsiloxane-dimethylsiloxane copolymer, vinyltrimethylsiloxane-dimethylsiloxane copolymer, vinyltrimethylsiloxane-dimethylsiloxane copolymer, vinyltrimethylsiloxane-dimethylsiloxane copolymer, vinyltrimethylsiloxane-dimethylsiloxane copolymer, Methylsiloxane homopolymers, vinylmethylsiloxane-octylmethylsiloxane-dimethylsiloxane copolymers, vinylmethylsiloxane-phenylmethylsiloxane-dimethylsiloxane copolymers, vinylmethoxysiloxane homopolymers, vinylethoxysiloxane homopolymers and vinylethoxysiloxane- Lt; RTI ID = 0.0 > ethoxysiloxane < / RTI > copolymer May include, and in particular, it is preferred that the vinyl dimethicone (vinyl dimethicone).

And the second polymer is a compound represented by the following formula (3). Here, n is a molar ratio, and may be a number of 0 to 10,000, preferably 0 to 8,000, more preferably 0 to 6,000.

As an example, the second polymer may be selected from the group consisting of polysiloxane having at least one of hydride-terminated polydimethylsiloxane, hydride-terminated polydiethylsiloxane, hydride-terminated polydiphenylsiloxane, hydride-terminated polyphenylmethylsiloxane, trimethylsiloxy-terminated methylhydrosiloxane- Copolymers, hydride-terminated methylhydroxysiloxane-dimethylsiloxane copolymers, trimethylsiloxy-terminated polymethylhydroxylsiloxane, triethylsiloxy-terminated polyethylhydroxylsiloxane, hydride-terminated polyphenyl- (dimethylhydroxyloxy) silane, hydride End methylhydroxysiloxane-terminated methylhydroxysiloxane-terminated methylhydroxysiloxane-terminated methylhydroxysiloxane-phenylmethylsiloxane copolymer, and methylhydroxysiloxane-octylmethylsiloxane copolymer, and is preferably hydrogen dimethicon.

The first polymer and the second polymer may have a viscosity of 0.1 to 5,000,000 cP, respectively.

Preferably, the first polymer and the second polymer are contained in an amount of 15 to 30% by weight based on the total weight of the first composition or the second composition, respectively, and are preferably contained in the same or similar amounts.

If the first polymer and the second polymer are less than 15 wt%, the amount of the first polymer and the second polymer that cause cross-linking, that is, the hydrogen saccharification reaction, may be small and the film may not be formed. Similar problems arise when the difference in the content of two polymers is large.

The catalyst may be included in at least one of the first composition and the second composition for accelerating crosslinking between the first polymer and the second polymer, that is, hydrocyanation reaction, at room temperature, The composition is included in any one of the selected compositions.

More specifically, it is preferable that the catalyst contains at least one of platinum (Pt) and rubidium (Rb), and it is particularly preferable that a platinum catalyst is contained in a large amount because it has an excellent effect on the reaction rate.

On the other hand, the catalyst is preferably contained in an amount of 0.01 to 1% by weight based on the total weight of the first composition or the second composition. If the amount of the catalyst is less than 0.01 wt%, the hydrogenation reaction of the first polymer and the second polymer may not occur at room temperature. If the amount of the catalyst is more than 1 wt%, the effect of increasing the reaction rate may be insignificant.

The additive is contained in at least one of the first composition and the second composition in order to maximize the performance of the film formed by the room-temperature cured film-forming composition of the present invention. Examples include an organic silane compound .

Here, the organosilane compound is preferably an organosilane compound composed of at least one of alkoxysilane and alkylalkoxysilane, more specifically, tetraethoxysilane, tetramethoxysilane, tetranomal isopropoxysilane, tetraisopropoxysilane , Tetranomal butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, normal propyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyl But are not limited to, trimethoxysilane, trimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, normalpropyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, phenyltri Ethoxysilane, vinyltriethoxysilane, trifluoropropyltrimethoxysilane, diethyldimethoxysilane, dimethyldimethoxysilane, diethyldiethoxy Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trimethalethoxysilane, and triethylethoxysilane. [0035]

Among them, tetraethoxysilane or tetraethylorthosilicate (TEOS) is preferable, and the room-temperature cured film-forming composition of the present invention containing tetraethoxysilane is more excellent in wetting and adhesion, , The effect of wrinkle improvement is very excellent.

On the other hand, the organosilane compound is preferably contained in an amount of 0.1 to 20% by weight based on the total weight of the first composition or the second composition.

In addition to the organosilane compounds, the additives may also include chelating agents, emulsifiers, pH adjusters, preserved agents, skin conditioning agents, wetting agents and perfumes, , And it is preferable that each of such additives is included in an amount of 0.01 to 10% by weight based on the total weight of the first composition or the second composition.

More specifically, the sequestering agent is preferably included in the first composition and the second composition, respectively, and serves to block the activity of metal ions that can be incorporated into the first composition and the second composition. For example, ethylenediaminetetraacetate (EDTA) may be used and may be included in an amount of 0.02 to 0.1% by weight based on the total weight of the first composition or the second composition.

The emulsifier is preferably contained in the first composition and the second composition, respectively, and serves to uniformly mix the first composition and the second composition. For example, TR-1 (acrylate / c10-30 alkyl acrylate crosspolymer) may be used and may be contained in an amount of 0.2 to 0.5% by weight based on the total weight of the first composition or the second composition.

The pH adjusting agent is preferably contained in the first composition and the second composition, respectively, and serves to adjust the pH so that the hydrogenation reaction of the first composition and the second composition occurs. For example, tromethamine may be used and may be included in an amount of 0.15 to 0.5% by weight based on the total weight of the first composition or the second composition.

The preservative is preferably contained in the first composition and the second composition, respectively, and serves to keep the first composition and the second composition for a long period of time. For example, phenoxyethanol may be used and may be contained in an amount of 0.4 to 1% by weight based on the total weight of the first composition or the second composition.

The skin conditioning agent is preferably contained in the first composition and the second composition, respectively, and serves to restore the flexibility of an object such as skin. For example, ethylhexyl glycerin may be used and may be contained in an amount of 0.1 to 0.5% by weight based on the total weight of the first composition or the second composition.

The wetting agent is preferably included in the first composition and the second composition, respectively, and serves to increase the moisture retention of the object such as the skin. As an example, glycerin may be used and may be included in an amount of 5 to 8% by weight based on the total weight of the first composition or the second composition.

The fragrance is preferably contained in the first composition and the second composition, respectively, and various kinds may be used depending on the purpose. The fragrance may be included in an amount of 0.2 to 1% by weight based on the total weight of the first composition or the second composition.

Meanwhile, the room-temperature curing film-forming composition of the present invention preferably comprises a fibrous polymer.

The fibrous polymer is contained in at least one of the first composition and the second composition to improve the performance of the film formed by the room temperature cured film forming composition of the present invention. In particular, the fibrous polymer improves the tensile strength , And has an effect of shortening the film formation time.

More specifically, the fibrous polymer is preferably composed of a natural polymer, and examples thereof include cellulose, carboxymethyl cellulose, pectin, dextrose, fibrin, ethylcellulose And at least one fibrous polymer selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylcellulose, chitin, and chitosan.

Among them, cellulose is most preferable to be used as a fibrous polymer because it is non-toxic, has excellent biocompatibility, has an effect of reducing wound pain and bacterial infection, and has an excellent effect on skin regeneration.

The fibrous polymer is preferably a nano-level fibrous polymer having a diameter of 0.1 nm to 1,000 nm and a length of 100 nm to 1,000 nm. This is because the diameter and the length of the fibrous polymer should fall within the above-mentioned range to form a film having improved durability. More specifically, if the diameter and the length are too small, the improvement of the physical properties of the film may be insignificant, If it is too large, the hydrogen silylation reaction of the first polymer and the second polymer may not be performed properly, which may interfere with film formation.

On the other hand, the fibrous polymer is preferably contained in an amount of 1 to 10% by weight based on the total weight of the first composition or the second composition. If the content of the fibrous polymer is less than 1% by weight, improvement in physical properties such as tensile strength may be insignificant. If the content is more than 10% by weight, the flexibility of the film may decrease and the tensile strength may be lowered.

Meanwhile, it is preferable that the first polymer, the second polymer, the catalyst, the additive, and the fibrous polymer described above are mixed and diluted with a solvent to be contained in the first composition and / or the second composition in a completely dissolved state. Here, the solvent may be any solvent that contains at least one of water, distilled water, alcohol, and glycerol, but is not limited thereto. Any solvent that can dissolve the first polymer, the second polymer, the catalyst, Applicable.

FIG. 1 is a photograph showing a procedure of a film forming method using the room temperature cured film forming composition of the present invention. As shown in FIG. 1, the room temperature curing film forming method of the present invention comprises: (a) (B) forming a second layer made of another composition not selected in the step (a); and (c) forming a first layer made of a composition selected from the first composition and the second composition. (c) forming a film by hydrosilylation of the first composition and the second composition, wherein steps (a), (b), and (c) .

In the step (a), the first layer may be formed by directly applying a composition selected from the first composition and the second composition onto the surface of the object, A method of impregnating a substrate such as a sheet, and then adhering or adhering it on the surface of the object.

In the step (b), the second layer may be formed by directly applying another composition not selected in step (a) directly onto the surface of the object, Or a method of impregnating a substrate such as a sheet and then adhering or adhering it on the surface of the object or the like.

In step (b), the second layer may be formed on the surface of the first layer, as shown in FIG. 1, so that the hydrogenation reaction of the first polymer and the second polymer may occur, It is preferable that the second layer is first formed on the peripheral portion where the first layer is formed and then the first layer and the second layer are mixed with each other using a hand or a tool It is possible.

It is preferable that the weight of the first polymer or the second polymer used in step (a) be the same as the weight of the first polymer or the second polymer used in step (b).

When the first layer and the second layer are brought into contact with or mixed with each other through steps (a) and (b), the first polymer and the second polymer contained in the first and second layers are cured by hydrocyanation reaction , And step (c) in which a film is formed.

It is preferable that all of steps (a), (b), and (C) are performed at room temperature of about 20 to 40 ° C. If the object is skin, Curing can be smoothly and quickly carried out even at a temperature alone to form a film.

Hereinafter, the present invention will be described in more detail with reference to Comparative Examples and Examples. The following Comparative Examples and Examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

division Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 1st or 2nd
Composition One 2 One 2 One 2 One 2 One 2 One 2 Solvent ¹⁾ 74.93 78.91 74.93 78.41 74.93 77.91 74.93 76.41 74.93 73.91 74.93 68.91 Metal ion
Blockade ²⁾ 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 The first polymer ³⁾ 15 - 15 - 15 - 15 - 15 - 15 - Second polymer ⁴⁾ - 15 - 15 - 15 - 15 - 15 - 15 Catalyst ⁵⁾ - 0.02 - 0.02 - 0.02 - 0.02 - 0.02 - 0.02 Emulsifier ⁶⁾ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 pH
⁷⁾ 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Preservatives ⁸⁾ 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 skin
Conditioning ⁹⁾ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Wetting agent ¹⁰⁾ 5 5 5 5 5 5 5 5 5 5 5 5 Spices 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Fibrous
Polymers ¹¹⁾ 4 - 4 - 4 - 4 - 4 - 4 - Organosilane
Compound ¹²⁾ - - - 0.5 - One - 2.5 - 5 - 10 Sum 100 100 100 100 100 100 100 100 100 100 100 100

As shown in Table 1, room temperature cured film compositions according to Comparative Examples, Examples 1, 2, 3, 4, and 5 were respectively prepared. Thereafter, a temperature of 25 to 30 占 폚 was maintained, and the first composition was directly applied on the surface of the wrinkled object to form a first layer. Thereafter, the second composition was applied directly onto the surface of the first layer to form a second layer. Thereafter, the first layer and the second layer were rubbed at a constant speed for 100 to 200 seconds so as to be uniformly mixed with each other, followed by holding and curing, thereby completing the film formation.

Tin 1) of Table 1 is DI Water, Tin 2) is Ethylenediaminetetraacetate (EDTA 2Na, manufactured by Daebong LS), and Tin 3) is vinyl dimethicone (manufactured by KCC) having a viscosity of 10,000 cP. , Tin 4) is hydrogen dimethicone (manufactured by KCC) having a viscosity of 10,000 cP, tin 5) is a platinum catalyst, tin 6) is TR-1 (manufactured by Lubrizol) Tin 8) is phenoxyethanol (manufactured by Galaxy), tin 9) is ethylhexylglycerin (manufactured by Schuelke & Mayr), and tin 10) is glycerin glycerin, manufactured by ACID CHEM), tin 11) is a cellulose nanofiber having a length of 100 nm to 500 nm (synthesis), tin 12) is tetraethoxysilane (TEOS) Weight%.

Initial (0 min) 10 minutes Comparative Example 0.82mm 0.56mm Example 1 0.82mm 0.41mm Example 2 0.82mm 0.40mm Example 3 0.82mm 0.42mm Example 4 0.82mm 0.41mm Example 5 0.82mm 0.41mm

Table 2 shows the relationship between the depth of the wrinkles and the depth of the wrinkles using a mechanism in which the contrast of the transmitted light is changed according to the thickness of the replica according to the shape of the object when the produced replicas are taken in order to objectively confirm the wrinkle- (0 min) of the object using a visiometer (MPA 580, CK Electronic) and a wrinkle depth after 10 minutes of film formation, respectively.

As shown in Table 2, in the case of Examples 1 to 5, the wrinkle depth was reduced by about 50%, which was more than 20% higher than that of the wrinkle depth reduced by about 30% ≪ 0.05).

Evaluation items Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Brittle 2 5 5 5 4 4 Adhesion 3 5 5 4 3 3 Spreadability 3 5 5 3 3 2 1: very bad 2: poor 3: normal 4: good 5: very good

The results are shown in Table 3. Table 3 shows that the room temperature cured film composition according to Comparative Example 1, Example 1, Example 2, Example 3, Example 4 and Example 5 was selected from 30 panelists, After the ball was used around the ball, the ball was evaluated on the basis of a score of 5, and the average of the ball was measured, and the spreadability, adhesion, and spreadability were evaluated.

As shown in Table 3, in Examples 1 to 5, the rubbing resistance was remarkably superior to that of the Comparative Examples, and the adhesion and spreadability were also excellent. Particularly, it was confirmed that Examples 1 and 2 containing 0.5% by weight and 1% by weight of the organosilane compound, based on the total weight of the second composition, were excellent in spreadability, adhesion and spreadability .

The composition for forming a room-temperature-cured film of the present invention and the method for forming a film using the same are only preferred embodiments of the present invention to enable a person skilled in the art to easily carry out the present invention. The present invention is not limited thereto. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims. It will be apparent to those skilled in the art that various substitutions, modifications and variations are possible within the scope of the present invention, and it is obvious that the parts easily changeable by those skilled in the art are included in the scope of the present invention .

Claims (12)

A first composition comprising a silicone-based first polymer having at least two vinyl end groups;
A second composition comprising a second silicone-based polymer having at least two hydrogen end groups;
A catalyst contained in at least one of the first composition and the second composition, the catalyst promoting hydrosilylation of the first composition and the second composition; And
Wherein the composition comprises at least one of an organic silane compound and an additive. The method according to claim 1,
Wherein the first polymer is contained in an amount of 15 to 30% by weight based on the total weight of the first composition. The method according to claim 1,
Wherein the second polymer is contained in an amount of 15 to 30% by weight based on the total weight of the second composition. The method according to claim 1,
Wherein the catalyst comprises at least one of platinum and rubidium,
Is 0.01 to 1% by weight based on the total weight of the first composition or the second composition. The method according to claim 1,
Wherein the organosilane compound is an organosilane compound containing at least one of an alkoxysilane and an alkylalkoxysilane. 6. The method of claim 5,
The organosilane compound may be selected from the group consisting of tetraethoxysilane, tetramethoxysilane, tetranomal isopropoxysilane, tetraisopropoxysilane, tetranomal butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane , Normal propyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, But are not limited to, normal propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, trifluoropropyltrimethoxysilane, diethyldimethoxysilane , Dimethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trimethalethoxysilane, trie The silane either room temperature curable film-forming composition comprising one or more of the. The method according to claim 1,
Wherein the organosilane compound is contained in an amount of 0.1 to 20% by weight based on the total weight of the first composition or the second composition. The method according to claim 1,
Wherein the additive comprises at least one of a sequestering agent, an emulsifier, a pH adjusting agent, a preservative, a skin conditioning agent, a wetting agent, and a flavoring agent,
Wherein each of the additives is contained in an amount of 0.01 to 10% by weight based on the total weight of the first composition or the second composition. The method according to claim 1,
Wherein at least one of the first composition and the second composition is a composition comprising
Wherein the composition comprises 1 to 10% by weight of a fibrous polymer based on the total weight of the first composition or the second composition. 10. The method of claim 9,
Wherein the fibrous polymer comprises at least one fibrous polymer selected from the group consisting of cellulose, carboxymethylcellulose, pectin, dextrose, fibrin, ethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, chitin and chitosan. Forming composition. 11. A method of forming a film using the composition of any one of claims 1 to 10,
(a) forming a first layer of a composition selected from the first composition and the second composition on a surface of an object;
(b) forming a second layer of another composition not selected in step (a); And
(c) forming a film by hydrosilylation of the first composition and the second composition,
Wherein the step (a), the step (b), and the step (c) proceed at room temperature. 12. The method of claim 11,
Wherein in the step (b), the second layer is formed on the surface of the first layer.

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