KR100442113B1 - Adhesive composition to cellulose, and a cross-linked cotton pad for solution adsorption - Google Patents

Abstract

The present invention relates to a cellulose adhesive composition and a medical cotton pad having excellent absorption / absorption properties. More specifically, a poly (acrylic acid) resin containing a large amount of carboxyl groups and chitosan and ammonia water having hydroxy / amine groups are uniform. Cellulose adhesive composition contained as an essential ingredient within the content ratio range, and when the composition is applied to cellulose cotton wool, when chitosan and ammonia water are crosslinked when cellulose cotton wool and poly (acrylic acid) are crosslinked, It is utilized to promote three-dimensional network structure, maximizing crosslinking efficiency and supplementing water-insoluble and strength characteristics, so that it is not water-soluble but has a very high affinity / water-bonding role. Medical cotton pads that bring good liquid adsorption properties.

Description

Adhesive composition to cellulose, and a cross-linked cotton pad for solution adsorption}

The present invention relates to a cellulose adhesive composition and a medical cotton pad having excellent absorption / absorption properties. More specifically, a poly (acrylic acid) resin containing a large amount of carboxyl groups and chitosan and ammonia water having hydroxy / amine groups are uniform. Cellulose adhesive composition contained as an essential ingredient within the content ratio range, and when the composition is applied to cellulose cotton wool, when chitosan and ammonia water are crosslinked when cellulose cotton wool and poly (acrylic acid) are crosslinked, It is utilized to promote three-dimensional network structure, maximizing crosslinking efficiency and supplementing water-insoluble and strength characteristics, so that it is not water-soluble but has a very high affinity / water-bonding role. Medical cotton pads that bring good liquid adsorption properties.

Medical cotton pads are padded in a state where the volume of the cotton pad is compressed to be small, and it should be harmless to the human body and effectively absorb and remove moisture and blood flowing from the surgical site without dropping around. The medical cotton pad is compact but has good absorption / blood absorption efficiency and maintains dimensional stability even after absorption / blood absorption, so that the characteristics of the pad should not be greatly increased.

As reported so far, no research has been reported on the preparation of medical cellulose cotton pads using a poly (acrylic acid) -ammonia water / chitosan-based crosslinking reaction.

The prior art related to cotton pads is briefly summarized as follows: 1) A medical pad containing a polystyrene resin derivative and salicylic acid (European Patent EP 327327 A2 (1989)); 2) a medical pad using a group of polyester fibers containing a hydroxyl group in the presence of mercaptoethanol (Japanese Patent Laid-Open No. JP 2000-038557 A2 (2000)); 3) a pad using a polyester-cotton blended fabric containing a poly (acrylate) resin containing crotonic acid and acrylamide [Japanese Patent Publication JP 52-012314 B4 (1977)]; 4) pads using pulp treated with poly (acrylic acid) sodium salt (US Pat. No. 4,233,345 (1980)); 5) cotton pads using only poly (acrylic acid) or poly (acrylic acid-co-maleic acid) as binders (US Pat. No. 61,842,71 B1 (2001), PCT International Patent WO 98/26161 (1998)); 6) Cotton pads comprising a poly (acrylic acid), 1,2,3,4-butanetetracarboxylic acid and citric acid as binders [Anal. Chem., 72 (23), 5829-33 (2000), J. Soc. Dyers Color., 115 (10), 306-11 (1999), Journal of the Korean Fiber Society, 35 (11), 716-20 (1998)] or Blended Pads [Korean Journal of Textile Technology, 34 (8), 517-23 (19977); 7) Cotton yarn treated with poly (acrylic acid) [Eur. Polym. J., 36 (11), 2505-2511 (2000)] pads crosslinked with chitosan or citric acid / chitosan [Sen'i Journal, 55 (1), 42-7 (1999), Text. Res. J., 68 (10), 772-75 (1998); 8) Crosslinked product of chitosan and poly (acrylic acid) using glutaldehyde [Polim .: Cien. Technol., 10 (3), 116-21 (2000); 9) Crosslinking reaction of cellulose with chitosan in the presence of acid anhydride or citric acid [Vysokomol. Soedin., Ser. A Ser. B 42 (9), 1489-94 (2000), Text. Res. J., 68 (10), 772-75 (1998); 10) pads using acrylamide grafted cotton yarn [Japanese Chemical Society, 10, 1437-40 (1978)]; 11) Adsorbent using cellulose pulp treated with a dimethylol dihydroxyethylene urea derivative with a crosslinking agent [PCT International Patent WO93 / 16228 A1 (1993), Japanese Patent Application Laid-Open Patent JP2000-192371 A2 (2000), Text. Res. J., 52 (2), 101-8 (1982)], 12) Cotton pads using epoxy poly (acrylate) resin as a binder [J. Macromol. Sci., Chem., A17 (2), 311-25 (1982)].

As described above, in the manufacture of conventional cotton pads, tetracarboxylic acid, aldehyde, methyl while using cellulose cotton wool as an adhesive component (polyacrylic acid), poly (acrylamide), etc., to bond each other. A cross-linking agent containing a roll group, an amine group (chitosan) and an epoxy group is used, and a three-dimensional cross-linking cotton pad is produced by inducing crosslinking partially to bond to each other. By doing so, it is made to have a favorable property for absorption / absorption while having a small volume.

In the above-described prior art, specific crosslinking reactions are induced while hot air drying by inducing binding to cellulose in a specific manner. For example, in the case of the prior arts 1) to 6), a hydroxy group of cellulose and a poly (acrylic acid) resin which is an adhesive or citric acid, crotonic acid, 1,2,3,4-butanetetracarboxylic acid, and the like are used. Ester bonds are induced between poly (acrylic acid) to be contained, and in the case of the prior art 7), acrylic graft cotton wool is crosslinked with citric acid / chitosan, and in the case of the prior art 8), aldehyde and chitosan (amine group) Amide bonds are induced between the poly (acrylic acid), and in the case of the prior art 9), an acid anhydride / chitosan (amine group) is used to crosslink the cellulose cotton, and in the case of the prior art 10), acrylamide Graft cotton wool is used as an adhesive ingredient and cellulose cotton wool as it is, and in the case of the prior art 11), it induces ether linkage between dimethylol urea and cellulose, and in the case of the prior art 12), epoxy is contained. Resin is inducing crosslinking reaction with the hydroxyl group of cellulose cotton wool. The above-described prior art has in common meant to induce chemical bonds between cellulose cotton wools to more compactly and neatly maintain the physical appearance of the loose cotton wool.

Cellulose cotton wool containing a large amount of hydroxy groups is difficult to melt and bond with each other due to the strong hydrogen bonding of the cellulose structure, in particular, it is known that the reaction for removing water between hydroxy groups is almost impossible even at high temperatures. Thus, by inducing a chemical bond to the cellulose group cotton wool containing hydroxy group cross-linking reaction of the carboxyl group of the water-soluble adhesive of poly (acrylic acid) resin with a certain portion of ester, amide, etc., cotton pad in contact with the wound site The adhesive or additive used in the solution was not allowed to move inside the body in solution. In addition, in order to further activate the crosslinking reaction, other organic-based carboxyl groups, amine groups, acid anhydrides, and epoxy groups have been utilized. When heated and dried, water molecules can be removed from carboxyl group and hydroxyl group or carboxyl group and carboxyl group, but energy is consumed and ester structure is generated during condensation. Is more effective if used, citric acid, etc. was used in related studies. Acid anhydrides or acrylamides react with poly (acrylic acid) resins or hydroxy groups to induce another ester or amide bond between the molecules, and crosslinking by inducing another ester or ether bond between poly (acrylic acid) and epoxy Will have

On the other hand, urea containing chitosan and methylol groups containing hydroxy and amine groups simultaneously forms amide or ester bonds when crosslinking with poly (acrylic acid). The organic crosslinking agent utilized in these crosslinking reactions induces a complete reaction by increasing the reactivity with polyfunctionality so that the cotton pads prepared in this way are transferred from the cotton pads to the primary solution when absorbed / sucked and do not enter the secondary body. must do it.

Finally, in the related conventional invention, as a crosslinking agent between hydroxy groups of cellulose cotton wool, bifunctional or more organic substances such as methylolurea, alkoxy metal salt, aldehyde, epoxy, isocyanate, acid anhydride and carboxylic acid have been used. As crosslinking agents between the carboxylic acid groups of the poly (acrylic acid) resin to be utilized, bifunctional or more than organic substances such as amine, aldehyde, epoxy, and methylolurea have been used. However, the hydroxyl group of cellulose cotton or the carboxyl group component of the poly (acrylic acid) resin, which is an adhesive component, can be easily chemically bonded by the above method, but the crosslinking agent methylolurea, alkoxy metal salt, aldehyde, epoxy, isocyanate The back is toxic and cannot be used for absorption or vampire function to clean wounds. Therefore, as a crosslinking agent that can be applied to prepare a cotton pad for medical use, it is considered to use a natural or relatively toxic and water-soluble monomolecular organic matter. In addition, in the conventional invention, instead of using methylolurea, alkoxy metal salt, aldehyde, epoxy, isocyanate, etc. which are excellent in crosslinking reactivity with the hydroxy group of cellulose cotton wool, the acidity is higher than that of poly (acrylic acid) resin. In some cases, ester crosslinking reaction is promoted by utilizing citric acid, tetracarboxylic acid, or the like.

On the other hand, in the case of chitosan having a hydroxy group and an amine group at the same time, when the adhesive component is diluted, solubility in water decreases a lot, and some may precipitate. In particular, when aldehyde, citric acid, and acid anhydride are used together with chitosan, the chitosan reaction may reduce the crosslinking effect of chitosan.

The inventors of the present invention, even if applied to the surgical site and wound area, there is no fear of introducing toxic substances into the body, as well as excellent adsorption properties for water or blood, as well as maintaining the dimensional stability after absorption / blood absorption, the volume of the pad Research efforts have been made to prepare a medical cotton pad having the characteristics of effectively absorbing and removing moisture and blood from the surgical site by not causing a significant increase. As a result, when poly (acrylic acid) resin is used as an adhesive component between cotton cellulose, and ammonia water and chitosan are used in a certain content ratio range as a crosslinking agent, the cellulose cotton wool components are poly (acrylic acid) -ammonia water / chitosan crosslinking agent. It is known that it can provide chemical bonds between cellulose, which is the main component of cotton pad, while maintaining its compact shape by having a mechanical property as a support, and can produce a cotton pad having excellent absorption / sorption properties while being harmless to the human body. Thus, the present invention has been completed.

The present invention provides a cellulose adhesive composition comprising a poly (acrylic acid) resin, chitosan having a hydroxy / amine group, and ammonia water as an essential component within a predetermined content ratio, and a medical cotton pad prepared using the same. It is done.

Referring to the present invention in more detail as follows.

The present invention contains a small amount of chitosan having a hydroxy / amine group that has been utilized for wound healing while containing poly (acrylic acid) resin containing more carboxyl groups as an adhesive to utilize cellulose cotton swabs for medical absorption / blood absorption pads. By supplementing the degree of crosslinking and using ammonia water at the same time, the crosslinking degree is further strengthened to the poly (acrylic acid) resin used as an adhesive for cellulose cotton wool. It relates to a cellulose adhesive composition obtained at the same time and a medical cotton pad excellent in the absorption / blood absorption applied thereto. The cellulose adhesive composition according to the present invention, when applied to cellulose cotton wool, newly formed ester bonds, amide bonds, etc. in addition to the carboxyl group, the amine group, and the hydroxy group, and thus are not water soluble in water but have high affinity with water. It acts as an adhesive / crosslinking component, thereby producing a compact cotton pad as well as providing good liquid adsorption characteristics upon absorption / blood absorption. That is, an ester or an amide bond is formed between the carboxyl group of the poly (acrylic acid) resin and the amine group of ammonia water / chitosan, and the cellulose cotton pad is a main component of the cotton pad while maintaining a certain shape due to the crosslinked polymer. It has a chemical bond between cellulose.

In general, cellulose is a mixture of microfibers, such as flow cells, and short fibers, such as wood fibers and conduits, and the liquid easily penetrates into the pores of the fiber yarn and has high hydrophilicity. In particular, when the cellulose cotton yarn containing short fibers or microfibers is formed into an absorbent structure, the voids between the fibers are filled with short fibers or microfibers, so that the density becomes high and the absorbency worsens. However, there is also an advantage that the surroundings of the absorbent material are kept clean since it is difficult to release them once they are absorbed. In other words, when the cellulose cotton wool itself is used for the absorption and release of the liquid, an adhesive and a crosslinking agent are added at the same time, and the internal crosslinking reaction between the cellulose cotton wool becomes more efficient, thereby obtaining a higher liquid absorbency and releasing property.

Cellulose adhesive composition according to the present invention contains 0.5 to 1.5% by weight of poly (acrylic acid) resin, 0.4 to 0.9% by weight of ammonia water (28%), 0.01 to 0.06% by weight of chitosan and 0.6 to 1.7% by weight of acetic acid It is an aqueous solution.

In the adhesive composition, the poly (acrylic acid) resin is used in the range of 0.5 to 1.5% by weight. When the amount of the poly (acrylic acid) resin is less than 0.5% by weight, the morphological stability is lowered. There is a problem. In particular, a poly (acrylic acid-co-maleic anhydride) copolymer, which is a copolymer of poly (acrylic acid) and maleic anhydride, may be used as the poly (acrylic acid) -based resin. It is preferable to copolymerize within the range of%, and when the copolymer component ratio of maleic anhydride is less than 10% by weight, the addition effect of the carboxyl group is lowered. When using a (acrylic acid) resin, it is difficult to complete the copolymer as a raw material.

As the crosslinking agent of the adhesive component, in the present invention, ammonia water and chitosan are used together to compensate for their respective disadvantages. The amount of the crosslinking agent depends on the nature of the crosslinking agent, adhesion to cellulose cotton wool, and reactivity. In the case of ammonia water (28% basis), it is used in the range of 0.4 to 0.9% by weight in the adhesive composition. If the amount is less than 0.4% by weight, the crosslinking effect is insufficient. .

In the case of chitosan, it is used in the adhesive composition in the range of 0.01 to 0.06% by weight. If the amount is less than 0.01% by weight, the crosslinking effect is low. Becomes

Acetic acid is used in the adhesive composition in the range of 0.6 to 1.7% by weight, and it is a solvent that dissolves chitosan. If its amount is insufficient, it does not completely dissolve chitosan and precipitates some, and if it is used excessively, the solvent smell remains for a long time even after crosslinking reaction. This is undesirable.

Applying a cellulose adhesive composition consisting of the composition as described above to the cotton wool to prepare a medical cotton pad, the adhesive composition may be contained in the range of 3 to 8 parts by weight based on 1 part by weight of cotton, other than this range Non-uniform dispersion or loss out of cotton wool increases.

Referring to the manufacturing process of the cotton pad using the cellulose adhesive composition described above in detail.

First, a poly (acrylic acid) resin is diluted in distilled water, and then ammonia water and chitosan are mixed to prepare a cellulose adhesive composition. Then, the mixed solution is sufficiently deposited on a swelled cellulose cotton pad layer. Then, it is placed on a polished stainless steel plate, and pressed and dewatered with a rubber roller 3 to 10 times in the front-rear direction for 3 to 40 seconds using a force of 0.5 to 2 kgf / cm ² . At this time, the concentration of the solid content in the cotton wool after the compression process is adjusted to 0.1 to 2.0% by weight to maintain the degree of crosslinking. And hot air drying at 40-80 degreeC, and crosslinking is carried out. When the ammonia water is added at room temperature, salts are formed and the viscosity is greatly increased even though the solid content is small, so that hot air drying is performed at 40 to 80 ° C. for 0.5 to 6 hours for chemical reaction between the amine groups and the carboxyl groups.

Cellulose cotton pads prepared through the above process will show a difference in the thickness, strength and flexibility of the layer of the corresponding cellulose cotton pad according to the resin content and the amount of the crosslinking agent constituting the adhesive composition used.

As described above, in the present invention, an appropriate amount of ammonia water necessary for crosslinking between the cellulose cotton wool and the poly (acrylic acid) resin used as an adhesive is added and amidated, and a small amount of chitosan is put together to utilize the wound. By using a smaller amount of chitosan, a cellulose cotton pad using a poly (acrylic acid) resin crosslinking technique which is uniform and has a relatively high crosslinking speed can be obtained.

The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example

Next, a cellulose adhesive solution having a composition as shown in Table 1 was prepared, and 1 part by weight of cotton wool was sufficiently moistened with 4 parts by weight of the mixed solution, followed by a wet cotton swab (2.5 cm in length, 10 cm in height, 0.5 cm in height). Was placed on a polished stainless steel plate, pressed with a rubber roller four times in the front-rear direction for 10 seconds using a force of 0.8 kgf / cm ² , and then dried in a 60 ° C. oven for 4 hours to form a cellulose cotton pad. Was prepared.

In addition, the cotton pads prepared were observed for absorption, form stability, color change, etc. in the following manner.

1) Absorption Rate:

After sufficiently moistening with the amount of distilled water absorbed per unit weight of cellulose cotton pad, the increased weight was measured.

2) Form stability:

After drying, the mixture was left at room temperature for 24 hours, warping of forms and the presence of destruction.

3) Color:

After drying and left at room temperature for 24 hours, color change was observed (○: no color change detected, △: color change detected, ×: color change recognized immediately).

division Adhesive composition (% by weight) Pad properties Polyacrylic acid Crosslinking agent solvent Absorption rate (g / g-pad) Shape stability color Acrylic acid Maleic anhydride Ammonia water ^a Chitosan ^b Acetic acid water Example 1 0.60 0.15 0.35 0.02 0.67 98.21 1.54 ○ ○ Example 2 0.75 - 0.35 0.02 0.67 98.21 1.53 ○ ○ Example 3 0.90 0.12 0.50 0.03 1.00 97.45 1.82 ○ ○ Example 4 1.02 - 0.50 0.03 1.00 97.45 1.77 ○ ○ Example 5 1.20 0.10 0.65 0.04 1.33 96.68 2.09 ○ ○ Example 6 1.30 - 0.65 0.04 1.33 96.68 2.07 ○ ○ Example 7 1.35 0.08 0.85 0.05 1.67 96.00 2.23 ○ ○ Example 8 1.43 - 0.85 0.05 1.67 96.00 2.25 ○ ○ Comparative Example 1 1.50 0.05 1.05 0.07 2.00 95.33 2.11 ○ △ Comparative Example 2 1.55 - 1.05 0.07 2.00 95.33 2.14 ○ △ Comparative Example 3 1.70 0.03 1.20 0.08 2.33 94.66 2.07 △ △ Comparative Example 4 1.73 - 1.20 0.08 2.33 94.66 2.08 △ △ Comparative Example 5 1.00 0.20 1.08 0.09 2.45 95.18 1.10 △ △ Comparative Example 6 0.55 0.40 0.55 0.06 1.23 97.21 0.98 ○ △ Comparative Example 7 1.00 0.11 0.30 0.01 0.93 97.65 1.65 △ ○ Comparative Example 8 0.92 - 0.97 0.03 1.00 97.08 0.74 △ △ Comparative Example 9 0.92 - 0.30 0.03 1.00 97.75 1.02 △ ○ Comparative Example 10 0.70 0.05 0.55 0.12 0.95 97.63 1.37 ○ × Comparative Example 11 0.93 - 0.60 - 1.00 97.47 1.22 △ ○ Comparative Example 12 1.02 - 0.40 0.03 1.80 96.75 1.75 ○ ○ Comparative Example 13 1.13 - 0.60 0.12 0.40 97.75 1.12 △ △ Comparative Example 14 ^c 1.44 ○ ○ ^a 28% ammonia water is used. ^b Chitosan (Aldrich) from 5 to 40 cp is used. ^c Similar foreign products (Surgical patties, trade name Codman, J & J)

As described above, when the proper amount of each component of the adhesive was used, all of the physical properties showed good properties in terms of absorption rate, shape stability, and color. However, when the poly (acrylic acid) component and the crosslinking agent component are large as in Comparative Examples 1 to 4, or when the crosslinking agent component is relatively large as in Comparative Example 5, the crosslinking effects are too large, which is a problem in color and form stability. Maleic anhydride in the (acrylic acid) -based component is more than an appropriate amount, causing problems in color, Comparative Example 7 is too small a crosslinking effect, each has a problem in morphological stability, Comparative Examples 8 and 9 have a greater than the appropriate amount of ammonia in the cross-linking component There is a problem in shape stability and color, and Comparative Examples 10 and 11 have more or less chitosan in the crosslinking agent component than the appropriate amount, so there is a problem in the color and crosslinking effect, and Comparative Examples 12 and 13 have more or less acetic acid as the chitosan solvent. Odor remained on cotton pads or some chitosan caused precipitation and crosslinking effects, and water absorption was reduced.

In the present invention, in bonding a poly (acrylic acid) adhesive to a cellulose cotton pad, the cellulose group is cross-linked with a hydroxyl group, and a natural resin such as ammonia water or chitosan is used as an amine group-containing crosslinking agent, so that By increasing the crosslinking efficiency and by controlling the thickness, strength and flexibility of the cotton pad in this process and maintaining the cotton pad shape, cellulose is maintained even during absorption / blood absorption. The present invention relates to a cellulose cotton pad for absorption / sorption using poly (acrylic acid) -ammonia water / chitosan crosslinking using cotton wool.

Claims (5)

Cellulose, characterized in that the aqueous solution containing 0.5 to 1.5% by weight of poly (acrylic acid) resin, 0.4 to 0.9% by weight of ammonia water (based on 28%), 0.01 to 0.06% by weight of chitosan and 0.6 to 1.7% by weight of acetic acid Adhesive composition. The cellulose adhesive composition according to claim 1, wherein the poly (acrylic acid) resin is a poly (acrylic acid-co-maleic anhydride) copolymer which is a copolymer of poly (acrylic acid) and maleic anhydride. According to claim 2, wherein the component ratio of the maleic anhydride in the poly (acrylic acid-co-maleic anhydride) copolymer is copolymerized in the range of 10 to 40% by weight compared to the poly (acrylic acid). Composition. 1 part by weight of cotton wool is immersed and mixed by 3 to 8 parts by weight of the composition for cellulose adhesion of claim 1, and the deposited cellulose cotton wool is placed on a polished stainless steel plate, 0.5 to 2 kgf / cm Medical cotton pads comprising the step of pressing the rubber roller 3-10 times in the front and rear direction for 3 to 40 seconds using a force of ² , followed by hot air drying at 40 to 80 ° C. for 0.5 to 6 hours. Manufacturing method. Medical cotton pad characterized in that it is prepared by the method of claim 4.