JP2003119340A - N-vinyl-based polymer composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily suppress the clouding of an aqueous solution of an N-vinyl- based polymer at a low cost. SOLUTION: The N-vinyl-based polymer composition is prepared by using a dried product of a water-soluble N-vinyl-based polymer and an antimicrobial agent. The ratio of the antimicrobial agent is about 0.1-1,000 ppm (mass basis) based on the N-vinyl-based polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an N-vinyl polymer-containing resin composition (such as a polyvinylpyrrolidone-containing resin composition) useful for cosmetics, pharmaceuticals and the like.

[0002]

2. Description of the Related Art N-vinyl polymers, such as polyvinylpyrrolidone, have excellent human compatibility and are used in cosmetics (hair care products, foundations, sunscreens,
It is used as a base material for lipsticks), a binder for pharmaceuticals, a surface treatment agent for catheters, a moisturizing agent for stockings, etc.

The N-vinyl polymer is distributed as a powder, and when it is used for the base material or the like, it is often dissolved in water before use. As this water, ion-exchanged water is used to prevent chlorine from being mixed into the product.

However, if the N-vinyl polymer dissolved in ion-exchanged water is left for a long time (for example, 2 weeks or more) without immediate use, it becomes turbid with time. Therefore, it may be an obstacle depending on the application (especially, the application that comes into contact with the human body).

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its purpose is N-
It is to suppress turbidity of an aqueous vinyl polymer solution easily at low cost.

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have pursued the cause of turbidity. Since ion-exchanged water does not contain chlorine, microorganisms such as bacteria and fungi are latent. After the N-vinyl-based polymer was dissolved, it was found that the microorganisms were active in the solution, so that they became cloudy by the microorganisms themselves or by their carcasses and excrements.

(1) In order to suppress the above-mentioned bacterial growth, it is effective to add an antimicrobial agent, and (2) the antimicrobial agent is added at the stage of an aqueous solution in which bacteria easily grow. However, since the N-vinyl polymer is distributed as a powder, it is necessary to add an antimicrobial agent when the powder user prepares the aqueous solution, which imposes a heavy work burden on the user. (3) Even if an aqueous solution containing an antimicrobial agent is circulated instead of the N-vinyl-based polymer powder, the transport weight at the time of distribution is increased and the cost is increased. On the other hand, in the stage of the N-vinyl polymer powder, there is no possibility that bacteria will grow in the stage of the N-vinyl polymer powder, but it is considered that it is not necessary to add an antimicrobial agent to the N-vinyl polymer powder stage. With antimicrobial The present invention has been completed by discovering that if powders are blended, it is sufficient to circulate the powder as in the conventional method at low cost, and that the user does not need to blend an antimicrobial agent and can easily suppress turbidity. . If the powder is mixed with an antimicrobial agent, it is possible to prevent mold from growing on the powder itself.

That is, the resin composition according to the present invention contains a water-soluble N-vinyl polymer dry product (preferably N-vinyl lactam dry product) and an antimicrobial agent, and the ratio of the antimicrobial agent is: With respect to the N-vinyl polymer, 0.
The gist is that it is 1 to 1000 mass ppm [preferably 0.1 to 900 mass ppm].

By dissolving the N-vinyl polymer composition in water, it can be used for various purposes (preferably, for use in contact with the human body such as cosmetics and pharmaceuticals).

The N-vinyl polymer composition is N-
It can be produced by drying a solution or slurry containing a vinyl polymer and an antimicrobial agent. It can also be produced by mixing N-vinyl polymer powder (or a dried product thereof) with an antimicrobial agent. In the present specification, the concentration unit “ppm” indicates a concentration on a mass basis, unless otherwise specified.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The N-vinyl polymer used in the present invention is a nonionic water-soluble polymer. Such a polymer has a property of easily becoming turbid when dissolved in water (ion-exchanged water, etc.), but in the present invention, since an antimicrobial agent is incorporated, the occurrence of turbidity can be prevented.

The N-vinyl polymer can be obtained by homopolymerization or copolymerization (preferably homopolymerization) of an N-vinyl monomer in an aqueous solvent. The N-vinyl-based monomer is not particularly limited as long as it has a nonionic hydrophilic site (polar site) for imparting water solubility to the polymer. For example, a monomer having an amide bond (or a lactam bond), A monomer having a carbamic acid bond, a monomer having a plurality of hetero atoms (nitrogen atom, oxygen atom, sulfur atom, etc.) can be used. Also N-
The vinyl-based monomer may be a cyclic N-vinyl-based monomer (a compound in which a vinyl group is bonded to a nitrogen atom of a nitrogen-containing heterocycle) or an acyclic N-vinyl-based monomer.

Among N-vinyl monomers having an amide bond (or lactam bond), examples of the cyclic N-vinyl monomer include N-vinyl-β-propiolactam and N-
Vinylpyrrolidone (N-vinyl-γ-butyrolactam), N-vinylsuccinimide, N-vinyl-δ-valerolactam, N-vinyl-ε-caprolactam, N-
Examples thereof include a 4- to 7-membered ring (preferably a 5- to 6-membered ring) cyclic N-vinyl-based monomer (N-vinyllactam) such as vinyl-glycocyamidine. The acyclic N- vinyl monomer, N- vinyl formamide (N- vinylformamide, N- vinyl -N- like N- vinyl -N-C _0-3 alkyl formamides such as dimethylformamide), N- vinylacetamide Class (N-vinylacetamide, N-vinyl-N-methylacetamide, and other N-
Vinyl-N-C _0-3 alkylacetamide, etc.), N-
Examples thereof include N-vinyl C _1-4 carboxylic acid amides (N-vinyl amides) such as vinyl propionamides.

Among the N-vinyl monomers having a carbamic acid bond, the cyclic N-vinyl monomer is N
-A cyclic N-vinyl-based monomer having a 4- to 7-membered ring (preferably a 5- to 6-membered ring) such as vinyloxazolidone. As the acyclic N-vinyl-based monomer, N-vinyl-methyl carbamate (such as methyl N-vinyl carbamate and methyl N-vinyl-N-C _1-4 alkyl carbamate), N-vinyl-ethyl carbamate Type, N-
Examples thereof include N-vinyl-carbamic acid C _1-4 alkyl esters such as vinyl-carbamic acid propyls.

The monomer having a plurality of heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) includes a plurality of heteroatoms such as N-vinylimidazolidine, N-vinylpiperazine and N-vinylmorpholine as ring-constituting atoms. As a heterocyclic compound (preferably a 4- to 7-membered ring compound, especially 5
~ 6-membered ring compound).

The N-vinyl monomer is preferably used for the polymer obtained (cosmetics, pharmaceuticals, etc.).
Considering the above, it is desirable that it is excellent in safety for the human body, and N-vinyl lactams such as N-vinyl pyrrolidone and N-vinyl-ε-caprolactam have high safety,
Particularly preferred.

Examples of the monomer copolymerizable with the N-vinyl monomer include (meth) acrylic monomers [(meth) acrylic acid C _1-6 alkyl ester, (meth) acrylic acid hydroxy C _1-6 alkyl ester, etc. (Meth) acrylic acid esters of: (meth) acrylamide,
N-mono C _1-3 alkyl (meth) acrylamide, N,
(Meth) acrylamides such as N-diC _1-3 alkyl (meth) acrylamides], basic unsaturated monomers [dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine, vinyl Imidazole, etc.], unsaturated carboxylic acid or acid anhydride thereof [(meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid anhydride, etc.], vinyl esters (vinyl acetate, vinyl propionate, etc.) ), Vinyl ethylene carbonates, styrenes, (meth) acrylic acid-2-sulfonic acid esters (ethyl ester, etc.), vinyl sulfonic acids, vinyl ethers (methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, etc.), olefins (ethylene ,propylene, Octene, butadiene, etc.) and the like.

The polymerization initiator is not particularly limited as long as it is a known water-soluble polymerization initiator, and for example, hydrogen peroxide,
Azo compounds such as 2,2′-azobis (2-amidinopropane), persulfates such as potassium persulfate, redox type initiators (such as a combination system of ascorbic acid and hydrogen peroxide)
Etc. can be used.

The aqueous solvent is not particularly limited as long as it contains at least water, and may be water alone or a mixture of a solvent miscible with water and water. As the miscible solvent, for example, alcohols (methanol, ethanol, isopropanol, n-butyl alcohol, diethylene glycol, etc.), ketones (acetone, etc.), ethers (tetrahydrofuran, dimethoxyethane, etc.) and the like can be used.

The polymerization reaction is not particularly limited as long as it is carried out in an aqueous solvent, and known polymerization methods (for example, solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization, etc.) can be employed.

The N-vinyl polymer solution obtained as described above may or may not be dried.
When drying, the drying method can be appropriately selected depending on the viscosity of the N-vinyl polymer solution. That is, when the viscosity of the N-vinyl polymer solution is low (for example, when the N-vinyl polymer has a low molecular weight), the solution may be sprayed and spray-dried. Further, when the viscosity of the N-vinyl polymer solution is high (for example, when the N-vinyl polymer has a high molecular weight), it may be dried using a dryer such as a drum dryer or a belt dryer, and the obtained dried The product may be crushed if necessary.

Then, the N-vinyl polymer obtained as described above (N-vinyl polymer solution or a dried product thereof; hereinafter referred to as raw material N-vinyl polymer) is mixed with an antimicrobial agent, An N-vinyl polymer composition containing an antimicrobial agent can be produced by drying if necessary. Hereinafter, the method for producing the N-vinyl polymer composition will be described separately for the case of drying and the case of not drying.

(1) When Drying A raw material N-vinyl polymer and an antimicrobial agent are used to prepare a solution or slurry (hereinafter, the solution and the slurry are referred to as raw material solution without distinction), and this raw material is used. The N-vinyl polymer composition can be produced by drying the solution. As the raw material N-vinyl polymer, either an N-vinyl polymer solution or a dried product thereof may be used. However, when using a dried product, it is necessary to use a solvent in addition to the N-vinyl polymer and the antimicrobial agent. As this solvent, various solvents (organic solvents having no affinity for water, aqueous solvents, etc.) can be used, but it is preferable to use aqueous solvents.

As the above-mentioned antimicrobial agent, as long as it is possible to kill microorganisms such as bacteria (bacteria), fungi (including molds), protozoa, rickettsia or viruses, or to prevent their growth. It is not particularly limited as far as possible, and may be either an antibacterial agent (antibacterial agent) or an antifungal agent. The antimicrobial agent includes an inorganic antimicrobial agent, an organic antimicrobial agent, and the like.

Examples of the inorganic antimicrobial agents include antimicrobial agents containing silver and / or copper (copper naphthenate, silver zinc,
Examples thereof include silver copper salt, silver zirconium phosphate), zeolite, and titanium oxide.

Examples of organic antimicrobial agents include natural product antimicrobial agents (chitin, chitosan, hinokitiol, tea extract, etc.), alcohol antimicrobial agents (methanol, ethanol, 2-propanol, etc.), phenolic antimicrobial agents. Agents (methylphenol, parachlorophenol, etc.),
Carboxylic acid-based antimicrobial agents (benzoic acid, sodium benzoate, propionic acid, octanoic acid, etc.), ester-based antimicrobial agents (glycerin fatty acid ester, para-hydroxybenzoic acid ester, etc.), quinoline-based antimicrobial agents (8-oxyquinoline) Etc.), pyridine antimicrobial agents [(2-pyridylthio-1-oxide) sodium etc.], thiazolone antimicrobial agents (1,2-benzothiazolone, Nn
-Butyl-1,2-benzisothiazolin-3-one,
2-methyl-4-isothiazolin-3-one etc.), imidazole antimicrobial agent [2- (4-thiozolyl) -benzimidazole etc.], biguanide antimicrobial agent (polyhexamethylene biguanide hydrochloride, chlorhexidine hydrochloride etc.) ), Thiocarbamate antimicrobial agents (ammonium-N-methyldithiocarbamate, etc.)
And so on. These antimicrobial agents may be used alone or in 2
It can be used in combination of two or more species.

Preferred antimicrobial agents are organic antimicrobial agents (particularly biguanide antimicrobial agents). If an organic antimicrobial agent is used, the resin composition (and its aqueous solution)
Can be reduced in color, and the transparency of the water-soluble solution is good. In addition, the biguanide antimicrobial agent is not only excellent in antimicrobial properties, but also particularly excellent in safety for the human body.

As the antimicrobial agent, one having a boiling point higher than that of the solvent to be removed by drying is selected. If the boiling point is lower than that of the solvent, the antimicrobial agent will disappear during drying. The boiling point of the antimicrobial agent used is, for example, 20 times higher than that of the solvent.
℃ or higher (120 ℃ or more when the solvent is water), preferably 40 ℃ or more than the boiling point of the solvent (140 when the solvent is water)
It is desirable that the temperature is 50 ° C. or higher), more preferably 50 ° C. or higher than the boiling point of the solvent (150 ° C. or higher when the solvent is water).

The amount of the antimicrobial agent in the raw material solution (the amount based on the N-vinyl polymer) is often similar to the amount in the composition described later. When a biguanide antimicrobial agent is used as the antimicrobial agent, the antimicrobial effect of the antimicrobial agent may decrease due to heating. In the case of heating such that the antimicrobial efficacy is reduced, the amount (N-
The amount based on the vinyl polymer) is about 2-10 in the composition.
It is desirable to double it.

An N-vinyl polymer composition can be obtained by drying the obtained raw material solution in the same manner as the N-vinyl polymer solution obtained by polymerization. The shape of this composition is not particularly limited, and is powdery,
It may have any shape such as a granular shape or a sheet shape.

(2) When not dried As the raw material N-vinyl polymer, a dried product (powdered dried product) is used. Then, by mixing (particularly pulverizing and mixing) the powdery N-vinyl polymer and the antimicrobial agent, an N-vinyl polymer composition can be obtained. During mixing, water may be added to the extent that there is no need for drying. As the antimicrobial agent, the same antimicrobial agent as in the case of drying can be used.

When the antimicrobial agent is not dried, there is no risk of decomposition of the antimicrobial agent due to drying.
-Amount based on vinyl polymer) is often similar to the amount in the composition described below.

N containing antimicrobial agent obtained as described above
-The amount of the antimicrobial agent of the vinyl polymer composition is 0.1 ppm or more (preferably 1 ppm or more, more preferably 5 ppm or more) with respect to the N-vinyl polymer, 1
It is 000 ppm or less (preferably 900 ppm or less, more preferably 800 ppm or less). Since the composition of the present invention contains a predetermined amount of antibacterial agent, even if it is dissolved in water and stored for a long period of time (for example, 1 month or more), the aqueous solution does not become cloudy.

When a biguanide antimicrobial agent is used, the amount in the composition may be less than the above amount. Since this antimicrobial agent has excellent antimicrobial properties, turbidity can be suppressed even when the amount is less than the above amount. The amount of biguanide antimicrobial agent in the composition is based on the N-vinyl polymer.
For example, it may be 500 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less.

The composition is a base material for cosmetics (hair care products, foundations, sunscreens, lipsticks, etc.),
It is often used for applications such as pharmaceutical binders, surface treatment agents for catheters, moisturizing agents for stockings, etc. that come into contact with the human body. It may also be used in applications such as adhesives, paints, dispersants, inks, and electronic parts.

In any of the applications, it is easy to use the composition once dissolved in water (ion-exchanged water, etc.). If dissolved in water, it is easy to mix with various raw materials corresponding to the above-mentioned use. And according to the present invention, even if the composition is dissolved in water, there is no risk of the aqueous solution becoming turbid.

[0037]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately applied within the scope of the above and the following points. It is of course possible to make changes and implement them, and all of them are included in the technical scope of the present invention.

The turbidity of the aqueous solutions obtained in Examples and Comparative Examples was measured by a turbidimeter [ND-1001 from Nippon Denshoku Industries Co., Ltd.].
DP], the sample (aqueous solution) was put into a quartz cell having a cell thickness of 10 mm for measurement.

Comparative Example 1 Polyvinylpyrrolidone powder (K value = 91) was dissolved in ion-exchanged water (cell count = 10,000 cfu / ml) (polyvinylpyrrolidone concentration = 5% by mass). The turbidity (turbidity before storage) of the obtained polyvinylpyrrolidone aqueous solution is
It was 0.2.

40 g of this polyvinylpyrrolidone aqueous solution was placed in a 50 ml glass container with a lid and sealed, and the temperature was adjusted to 30
Stored at 0 ° C for 2 weeks. The turbidity of the aqueous solution after storage is 3.5
It was 3.3, which was higher than that before storage.

Example 1 500 g of polyvinylpyrrolidone powder (K value = 91) was charged into a ball mill, and 1.0 g of an aqueous solution of polyhexamethylene biguanide hydrochloride (concentration = 20% by mass) was charged every 5 minutes while the mill was operated. It was added in 5 batches. After adding the total amount of polyhexamethylene biguanide aqueous solution,
The polyvinylpyrrolidone composition was obtained by continuing mixing for 30 minutes. The amount of polyhexamethylene biguanide hydrochloride in the composition is 400 ppm, based on polyvinylpyrrolidone.

The resulting composition was deionized water (the number of cells =
10,000 cfu / ml) (polyvinylpyrrolidone concentration = 5% by mass). When the turbidity before storage and the turbidity after storage of this polyvinylpyrrolidone aqueous solution were measured in the same manner as in Comparative Example 1, the turbidity before storage = 0.2 and the turbidity after storage = 0.2, which were the same. It was

Example 2 As an antimicrobial agent, an aqueous solution of polyhexamethylene biguanide hydrochloride (concentration = 0.05% by mass; ie 500
A polyvinylpyrrolidone composition was obtained in the same manner as in Example 1 except that (ppm) was used. The amount of polyhexamethylene biguanide hydrochloride in the composition is 1 ppm, based on polyvinylpyrrolidone.

The obtained composition was deionized water (the number of cells =
10,000 cfu / ml) (polyvinylpyrrolidone concentration = 5% by mass). When the turbidity before storage and the turbidity after storage of this polyvinylpyrrolidone aqueous solution were measured in the same manner as in Comparative Example 1, the turbidity before storage = 0.2 and the turbidity after storage = 0.4, which were almost the same. there were.

Comparative Example 2 A polyvinylpyrrolidone composition was obtained in the same manner as in Example 1 except that an aqueous solution of polyhexamethylene biguanide hydrochloride (concentration = 5 ppm) was used as the antimicrobial agent.
The amount of polyhexamethylene biguanide hydrochloride in the composition is 0.01 ppm, based on polyvinylpyrrolidone.

The composition obtained was treated with ion-exchanged water (the number of cells =
10,000 cfu / ml) (polyvinylpyrrolidone concentration = 5% by mass). When the turbidity before storage and the turbidity after storage of this polyvinylpyrrolidone aqueous solution were measured in the same manner as in Comparative Example 1, the turbidity before storage = 0.2 and the turbidity after storage = 2.8, and after storage It was increased by 2.6 as compared with that before storage.

Example 3 To 5.0 kg of a 20 mass% aqueous solution of polyvinylpyrrolidone (K value = 94) obtained by the polymerization reaction, 0.25 g of a polyhexamethylene biguanide hydrochloride aqueous solution (concentration = 20 mass%) was added. , And mixed at a temperature of 30 ° C. for 2 hours.

Using a drum dryer, the temperature is 140 ° C.,
The mixed solution was dried under the condition of rotation speed = 1 rotation / minute to form a film (drying time = 40 seconds). The obtained film was crushed to obtain a powdery polyvinylpyrrolidone composition.
The amount of polyhexamethylene biguanide hydrochloride in this composition was 50 ppm based on polyvinylpyrrolidone.

The resulting composition was deionized water (cell count =
10,000 cfu / ml) (polyvinylpyrrolidone concentration = 5% by mass). When the turbidity before storage and the turbidity after storage of this polyvinylpyrrolidone aqueous solution were measured in the same manner as in Comparative Example 1, the turbidity before storage = 0.3 and the turbidity after storage = 0.2, which were almost the same. there were.

Example 4 Polyhexamethylene biguanide hydrochloride aqueous solution (concentration =
20% by mass) was replaced with 0.25 g, and the same procedure as in Example 3 was performed except that 0.3 g of 1,2-benzothiazolone was used. The amount of 1,2-benzothiazolone (based on polyvinylpyrrolidone) in the composition was 300 ppm.

The composition obtained was treated with ion-exchanged water (the number of cells =
10,000 cfu / ml) (polyvinylpyrrolidone concentration = 5% by mass). When the turbidity before storage and the turbidity after storage of this polyvinylpyrrolidone aqueous solution were measured in the same manner as in Comparative Example 1, the turbidity before storage = 0.2 and the turbidity after storage = 0.3, which were almost the same. there were.

[0052]

According to the present invention, since the N-vinyl polymer and the antimicrobial agent are blended, even if an aqueous solution of the N-vinyl polymer is prepared, it is possible to suppress the growth of bacteria and the like, and the aqueous solution. The turbidity of can be prevented. Moreover, since the antimicrobial agent is added at the stage of the N-vinyl polymer composition, the distribution cost can be reduced and turbidity can be easily prevented.

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Claims (8)

[Claims] 1. A water-soluble N-vinyl polymer dry product and an antimicrobial agent are contained, and the proportion of the antimicrobial agent is N-.
0.1 to 1000 mass pp based on vinyl polymer
m is an N-vinyl-based polymer composition. 2. The N-vinyl polymer composition according to claim 1, wherein the proportion of the antimicrobial agent is 900 mass ppm or less based on the N-vinyl polymer. 3. The N-vinyl polymer composition according to claim 1, wherein the antimicrobial agent is a biguanide antimicrobial agent. 4. The N-vinyl polymer composition according to claim 3, wherein the proportion of the biguanide antimicrobial agent is 200 mass ppm or less. 5. The N-vinyl-based polymer according to claim 1, wherein the N-vinyl-based polymer is N-vinyllactam.
Vinyl-based polymer composition. 6. A resin solution prepared by dissolving the N-vinyl polymer composition according to claim 1 in water. 7. The method according to claim 1, wherein the solution or the slurry containing the N-vinyl polymer and the antimicrobial agent is dried.
6. A method for producing the N-vinyl polymer composition according to any one of 5 above. 8. The method for producing the N-vinyl polymer composition according to claim 1, wherein the N-vinyl polymer powder is mixed with an antimicrobial agent.