KR20150111137A - Hydrophilic film and composition for manufacturing the same - Google Patents

Abstract

The present invention relates to a film which has excellent moisture storage stability and excellent solubility at a low temperature and a composition for preparing the film. The composition includes: a water-soluble and water-dispersible polymer; water-dispersible or fumed silica; and a coupling agent. According to the present invention, the film is formed by the coupling of inorganic porous silica and a polymer which is an organic material. A network structure having fine pores is formed in the film to selectively include wanted active ingredients in the porous film of the network structure. The active ingredients are deposited in the fine pores and the porous tissue after the film is formed to prevent the active ingredients from being eluted to the outside, thereby adjusting the solubility of the film itself and shows the excellent solubility at the low temperature accordingly.

Description

[0001] The present invention relates to a water-soluble film and a composition for producing the same,

To a water-soluble film of the present invention and a water-soluble film composition for producing such a water-soluble film.

Currently, water soluble polymer films are widely used not only in industrial fields such as fine chemicals and electronic materials, but also in personal care products such as medicines, cosmetics, and household articles such as daily necessities. BACKGROUND ART [0002] As a universal application field of daily necessities, their use as a packaging material for packaging a specific substance and an effective ingredient to facilitate the use thereof is widely used.

Among the fields of use of the water-soluble polymer film to be applied to household goods, in particular, when it is used in a detergent composition, it is used in a field where a water-soluble polymer is used to produce a film, and a cleaning component is contained in such a film. US Patent Application No. 2005/0244444 discloses a technique of using powdered detergent and liquid detergent as a material for fraction packing. Korean Patent Application Publication No. 1999-0030414 discloses a technique of using polyvinyl alcohol , Gelatin, starch, and cellulose in a film using a water-soluble polymer to prepare a standard used amount of a teabag-type bag, thereby preventing the scattering of the powder detergent and inducing an appropriate amount of water to protect the water quality . Further, techniques for packaging a liquid detergent and a fabric softener into a water-soluble film are disclosed in U.S. Patent No. 4,605,509, Japanese Patent Application No. 58-135794, and Korean Patent Application Publication No. 2004-00676668.

The water-soluble polymer films used in some of the above prior arts have a disadvantage that the storage stability of the product is very poor, such as leakage of the contents due to the sealing of the product during transportation, and effective ingredients penetrating into the surface of the film.

In other prior arts, although the water-soluble film used as the packaging material is designed to have stability against moisture in the air and durability against the contents, it takes a considerable time to dissolve the film during washing at a low temperature, So that the residue of the film remained after washing.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a water-soluble film which is excellent in storage stability against moisture and contents, and is also excellent in low-temperature dissolution, a composition for producing such a water-soluble film, and a process for producing the water-soluble film.

In order to accomplish the above object, the present invention provides a water-soluble or water-dispersible polymer formed using a coupling agent; And a water-dispersible or fumed silica complex.

The present invention also relates to water-soluble or water-dispersible polymers; Water dispersible or fumed silica; And a coupling agent.

In the present invention, an organic-inorganic hybrid material is formed by combining a water-soluble or water-dispersible polymer and a water-dispersible silica or a fumed silica with a coupling agent to form a network structure in the film, and is designed to control the network structure of the silica and the polymer And the solubility can be adjusted according to the purpose of use. In the case of a film made of a composite having such an organic-inorganic network structure, the film has a certain void in the film, and the desired voids in the generated void and the porous silica can be selectively incorporated into the network structure, It is possible to suppress the phenomenon that the active ingredient is eluted to the surface after formation, so that it has excellent storage stability and excellent solubility even at a low temperature.

Hereinafter, the water-soluble film of the present invention and the composition for producing such a film will be described in more detail.

The film of the present invention comprises a complex comprising a water-soluble or water-dispersible polymer, and thus the composition for producing the film of the present invention includes a water-soluble or water-dispersible polymer.

The water-soluble or water-dispersible polymer used in the present invention is used for uniform film formation, and has at least one hydrophilic group such as an amino group, a carbonyl group, a carboxyl group, a sulfonic acid group, a hydroxyl group, an amide group and a polyalkylene oxide group, It is preferable that the polymer is a polymer capable of containing a metal salt.

Examples of the water-soluble or water-dispersible polymer include polyvinyl alcohol, denatured polyvinyl alcohol, polyacrylic acid, polyethylene glycol, carboxyl group-containing acrylic resin, carboxyl group-containing polyester resin, water-soluble polyamide, water-soluble polyurethane resin and maltodextrin, polydextrose, Cellulose derivatives such as carboxymethylcellulose (CMC), hydroxymethylcellulose (HMC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC) and ethylcellulose (EC), carboxymethylcellulose Napkin, pectin, gum, polyvinylpyrrolidone, pullulan, etc. may be used singly or in combination, but the present invention is not limited thereto.

The film of the present invention comprises a composite comprising water-dispersible or fumed silica, and thus the composition for making the film of the present invention comprises water-dispersible or fumed silica.

The silica used in the present invention is a component which imparts hydrophilicity and absorbs and / or adsorbs moisture in the film, and any of water-dispersible colloidal or fumed silica may be used, It can also be used.

The particle size of such silica is preferably from 5 nm to 5 mu m. When silica having a particle size of less than 5 nm is used, there is a problem that the film has insufficient hydrophilicity and the solubility of the film is decreased. When silica having a particle size exceeding 5 μm is used, The composite is formed and the water-soluble film is broken from the portion composed of the silica particles, so that the firmness of the film may be deteriorated and the stability may be deteriorated.

The weight ratio (silica weight% / polymer weight%) of the water-soluble or water-dispersible polymer and silica contained in the water-soluble film or composition of the present invention is preferably 0.05 to 5, more preferably 0.1 to 4. When the weight ratio is less than 0.05, the penetration effect by water is lowered when the film is put into water because of insufficient networking structure between silica and water-soluble polymer, and a considerable time is required until complete dissolution. When the weight ratio exceeds 5 The strength of the water-soluble film is deteriorated.

The total content of the water-soluble or water-dispersible polymer and silica is preferably 5 to 95% by weight, more preferably 10 to 80% by weight, based on the total weight of the water-soluble film and the film containing the active ingredients. When the total content of the water-soluble polymer and the water-dispersible silica is less than 5% by weight, the film-forming ability deteriorates, and when it exceeds 95% by weight, it is not economical.

The films and compositions of the present invention also include coupling agents. Such a coupling agent is a component that forms a network structure in a water-soluble film through the organic-inorganic chemical coupling of a water-soluble or water-dispersible polymer and silica. The coupling agent is used in an amount of 0.001 to 50 parts by weight per 100 parts by weight of the polymer and silica And more preferably 0.01 to 40 parts by weight. When it is used in an amount of less than 0.001 part by weight, sufficient coupling reaction can not be performed between the silica and the polymer, so that it is difficult to form a networking structure of the film itself and the solubility is reduced. When the amount exceeds 50 parts by weight, They may react with each other to increase the total silica content in the film, resulting in deterioration of the firmness of the film.

Examples of the coupling agent used in the present invention include organic titanic acid including triethanolamine titanate, titanium acetylacetonate, tetrabutyl titanate, tetraisopropyl titanate and the like; And aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldiethoxysilane, aminopropyltriethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, chloropropyltriethoxysilane, glycidyl Methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, and the like can be used. [0034] And a silane coupling agent containing a silane coupling agent.

The water-soluble or water-dispersible polymer of the present invention; Water dispersible or fumed silica; And a coupling agent preferably have a particle size of 5 nm to 100 μm, and the film thickness of the present invention is preferably 5 μm to 100 mm.

The water-soluble film of the present invention may contain various active ingredients, and such active ingredients may be selected depending on the intended use. For example, the water-soluble film of the present invention may contain a detergent, which is a surfactant, for use in the detergent field, and anionic, non-ionic, or cationic surfactant may be used as such a surfactant. The water-soluble film of the present invention may also contain, as an active ingredient, additives such as alkali builders, enzymes, peroxides, bleaching activators, fluorescent whitening agents, and the like for use in the detergent field.

As the anionic surfactant that can be used as an active ingredient, any of commonly used anionic surfactants can be used. Particularly, it is preferable to use a carboxylate compound such as a soap, a higher alcohol, a higher alkyl ester, a sulfuric ester salt compound in which an olefin is sulfate, a sulfate compound containing an alkylbenzene sulfonate, or a phosphate compound phosphorylated with a higher alcohol to be.

The nonionic surfactant may be a polyoxyalkylene alkyl phenyl ether, a polyoxyalkylene alkyl ether, a polyoxyethylene polyoxypropylene block polymer, a polyethylene glycol fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, 1 or a polyoxyalkylene alkylphenyl ether represented by the following formula (2) is preferably used.

In the general formulas (1) and (2), m is an integer of 5 to 21, and n is an integer of 1 to 20.

As the cationic surfactant, a cationic quaternary ammonium salt can be used. For example, dialkyl dimethyl ammonium chloride represented by the following formula (3), dialkyl imidazolinium salt represented by the following formula (4), dialkyl amido quartz represented by the following formula (5) Dialkylamido quaternary ammonium salt, and ester quat type. One or more of them can be selected and used.

As the solvent to be contained in the composition for preparing the water-soluble film according to the present invention, water-soluble alcohols, glycols or glycol ethers can be used. In the case of a solvent, the composition for preparing a water-soluble film contains ethanol in an amount of 5 to 90 parts by weight By weight, more preferably 10 to 70 parts by weight. When the amount of the solvent is less than 5 parts by weight, the flowability is lowered and the surface can not be made uniform in the production of the film. When the amount is 90 parts by weight or more, the flowability is drastically improved and it is difficult to control the thickness of the film.

The present invention also provides a process for producing a water-soluble film comprising the step of producing a oil-mineral composite through the reaction of a water-soluble polymer or a water-dispersible polymer, silica and a coupling agent.

The reaction of the water-soluble or water-dispersible polymer, silica and coupling agent is preferably carried out usually at 0-100 ° C, more preferably at 20-90 ° C. The reaction time is usually from 0.5 to 24 hours, and the size of the polymer and silica composite particles formed by the coupling reaction is measured to check whether or not the reaction is carried out. The pH condition varies depending on the type of coupling agent, but usually the reaction is carried out within the range of pH 2-14, preferably pH 3-12 is effective. The reaction temperature and pH conditions may vary depending on the type of coupling agent used.

The water-soluble film of the present invention is formed by bonding inorganic porous silica with an organic material to form a network structure having micropores in the film, and can selectively contain desired active ingredients in the film due to the porous and network structure. The elution of the active ingredients is suppressed even after the formation, and the solubility of the film itself is enhanced and can be completely dissolved even at a low temperature, thus leaving no residue of the film.

Hereinafter, embodiments of the present invention will be described in detail to facilitate understanding of the present invention. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

<Example of composite preparation>

350 parts by weight of a water-soluble polymer or a water-dispersible polymer was added to a reactor having a size of 1000 ml, pH was adjusted to meet the hydrolysis conditions of the coupling agent, and the temperature of the reactor was maintained at 85 캜. 150 parts by weight of water-dispersible silica or fumed silica and 30 parts by weight of a coupling agent were mixed in a separate vessel to prepare a water-soluble polymer complex having a uniform concentration for 4 hours and then added dropwise to the polymer-containing liquid .

<Preparation of Example 1-2>

The water-soluble film composition of Example 1-2, which contained the active ingredient (anionic surfactant), a solvent and a residual amount of water, was prepared according to the ingredients and composition ratios shown in Table 1 below using the oil-in-water-soluble polymer composite thus prepared .

&Lt; Preparation of Comparative Example 1-2 >

Unreacted comparative examples in which the water-soluble polymer and silica were simply mixed in place of the organic-inorganic water-soluble polymer complex of the examples include the active ingredient (anionic surfactant), solvent, and residual water in accordance with the components and composition ratios shown in Table 1 below The water-soluble film composition of Comparative Example 1-2 was prepared.

(Unit:%) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Complex ^{1 )} 50 50 - - Polyvinyl alcohol ^{2 )} - - 35 35 Water-dispersible silica ^{3 )} - - 18 18 Active ingredient (anionic surfactant ^{4 )} ) - 20 - 20 Alcohol solvent 20 20 20 20 water Balance Balance Balance Balance Sum 100 100 100 100

In Table 1, the composite ¹⁾ include polyvinyl alcohol, water-dispersible silica and a coupling agent 3-Methacryloxypropyl the oil prepared by the coupling reaction of trimethoxysilane - in was used as an inorganic composite material, and 85% even polyvinyl alcohol ²⁾ include the saponification was used as the polyvinyl alcohol, was used as the water-dispersible ^{silica. 3)} roneun a particle size of 22nm silica, was used as Linear Alkyl Benzene Sulfate) LAS (roneun anionic surface active agent ^4), the solvent alcohol was ethanol.

Each of the water-soluble film compositions prepared in Example 1-2 and Comparative Example 1-2 was applied to a release film using a applicator to a predetermined thickness, and then heated and dried at 100 ° C for 10 minutes to prepare a film sample. The applicator used the product of a three-way meter company.

&Lt; Experimental Example >

The water-soluble films prepared from the water-soluble film compositions of Examples 1-2 and 1-2 were evaluated for their performance by the following methods. The performance evaluation items for water-soluble films were divided into solubility, film elongation (hardness) and elution amount phenomenon measurement. Using the prepared film specimens, physical properties were measured according to the criteria shown in Table 2 below, and the results are shown in Table 3 below.

(Solubility)

Each of the films made from the water-soluble film composition prepared in Example 1-2 and Comparative Example 1-2 was cut into 5 × 5 cm ^2, and about 300 ml of purified water at 15 ° C. was added to a 500 ml beaker, . The time for which each film was completely dissolved after dissolution and the film was removed was measured, and the solubility was numerically determined as shown in Table 2. The results are shown in Table 3.

(Film elongation)

The elongation of each of the films prepared from the water-soluble film composition prepared in Example 1-2 and Comparative Example 1-2 was measured, and the evaluation ability of the film was numerically determined as shown in Table 2, Respectively.

(Storage stability, elution amount)

The film made of the water-soluble film composition prepared in Example 1-2 and Comparative Example 1-2 was cut into 10 × 10 cm ² , and the film was adhered to the glass specimen. After 72 hours, the glass substrate was coated with the active ingredient Was determined numerically in accordance with Table 2, and the results are shown in Table 3. &lt; tb &gt;&lt; TABLE &gt;

Evaluation results Very good Great usually Bad Solubility ◎
(Within 10 seconds) ○
(Within 30 seconds) △
(Within 5 minutes) ×
(More than 10 minutes) Film elongation ◎
300% or less ○
200% or less △
100% or less ×
Less than 100% Amount of elution ◎
(Within 1%) ○
(Within 3%) △
(Within 5%) ×
(More than 5%)

Evaluation results  Example 1 Example 2 Comparative Example 1 Comparative Example 2 Solubility ◎ ◎ × × Film elongation ◎ ◎ ◎ ◎ Amount of elution ◎ ◎ ◎ ×

As shown in Table 3 above, the water-soluble film prepared in Example 1-2 of the present invention uses a composite designed to have an organic-inorganic bond, and despite the inclusion of inorganic silica, the elongation of the film is high, It has a solid performance capable of being formulated and has excellent solubility as compared with the water-soluble film prepared in Comparative Example 1-2. In addition, in the case of Example 2, even when a liquid anionic surfactant is added as an active ingredient, it is not eluted to the surface of the film, indicating excellent storage stability.

On the other hand, the film prepared in Comparative Example 1-2 is a film prepared by simply mixing a water-soluble polymer and a water-dispersible silica. Since the solubility in water is low, a considerable time is required until complete dissolution, Residues of the film were generated in the film, and a precipitate was formed. In the case of Comparative Example 1-2, even in the case of containing the water-dispersible silica, there was no effect on the solubility because of simple mixing, and in the case of Comparative Example 2 containing the surfactant, which is an active ingredient, A phenomenon of surfactant elution occurred on the surface of the film after a lapse of time.

From the above results, it can be seen that the water-soluble film prepared from the water-soluble film composition of Example 1-2 is superior in all aspects such as solubility, film-forming ability, storage stability, etc. compared with the water-soluble film prepared from the composition of Comparative Example 1-2 have.

Claims (16)

A water-soluble or water-dispersible polymer formed through a coupling agent; And a composite of water dispersible or fumed silica. The film of claim 1, wherein the film comprises an active ingredient. The film of claim 1, wherein the particle size of the composite is between 5 nm and 100 μm. The film according to claim 1, wherein the water-dispersible or fumed silica has a particle size of 5 nm to 5 μm. The film according to claim 1, wherein the weight ratio of the silica to the polymer (silica / polymer) is 0.05 to 5. The water-soluble or water-dispersible polymer according to claim 1, wherein the water-soluble or water-dispersible polymer has at least one hydrophilic group selected from the group consisting of amino group, carbonyl group, carboxyl group, sulfonic acid group, hydroxyl group, amide group and polyalkylene oxide group, &Lt; / RTI &gt; [7] The water-soluble or water-dispersible polymer according to claim 6, wherein the water-soluble or water-dispersible polymer is at least one selected from the group consisting of polyvinyl alcohol, denatured polyvinyl alcohol, polyacrylic acid, polyethylene glycol, carboxyl group-containing acrylic resin, , A cellulose derivative, carob, a pectin, a gum, polyvinylpyrrolidone, and pullulan. The film according to claim 1, wherein the coupling agent is an organic titanic acid, a silane coupling agent or a mixture thereof. The film according to claim 1, wherein the thickness of the film is from 5 to 100 mm. Water-soluble or water-dispersible polymers; Water dispersible or fumed silica; And a coupling agent. 11. The composition of claim 10, wherein the composition comprises an active ingredient. 11. The composition of claim 10, wherein the water-dispersible or fumed silica has a particle size of from 5 nm to 5 [mu] m. The film-forming composition according to claim 10, wherein the weight ratio of the silica to the polymer (silica / polymer) is 0.05 to 5. The method of claim 10, wherein the water-soluble or water-dispersible polymer has at least one hydrophilic group selected from the group consisting of an amino group, a carbonyl group, a carboxyl group, a sulfonic acid group, a hydroxyl group, an amide group and a polyalkylene oxide group, &Lt; / RTI &gt; 15. The method of claim 14, wherein the water-soluble or water-dispersible polymer is selected from the group consisting of polyvinyl alcohol, denatured polyvinyl alcohol, polyacrylic acid, polyethylene glycol, carboxyl group-containing acrylic resin, carboxyl group- , A cellulose derivative, carbol, pectin, gum, polyvinyl pyrrolidone, and pullulan. 11. The composition according to claim 10, wherein the coupling agent is an organic titanic acid, a silane coupling agent or a mixture thereof.