JP3175119B2 - Antimicrobial polyurethane resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antibacterial polyurethane resin and a method for producing the same.

[0002]

2. Description of the Related Art As antibacterial polyurethane homes, soft polyurethane homes in which inorganic antibacterial agents such as metal ions are dispersed and held (Japanese Patent Laid-Open No. 1-161053),
(Fluorodichloromethylthio) -phthalimide and 2-
Polyurethane home containing benzimidazole carbamic acid lower alkyl ester and / or 2- (4-thiazolyl) -benzimidazole (Japanese Patent Laid-Open No. 1-31)
No. 1168), a polyurethane home containing chitosan dispersed therein (JP-A-3-231964), and a polyurethane home containing a micronized antibacterial and antifungal agent and a micronized deodorant (JP-A-6-122746). Etc. are known.

[0003]

Several kinds of antibacterial polyurethane homes have been developed. An object of the present invention is to provide an antibacterial polyurethane resin using a newly discovered antibacterial component.

[0004]

Means for Solving the Problems The present inventor has repeatedly studied the medicinal effects of tea used for daily drinking and found that tea has an antibacterial action . Then Verify Kochi antimicrobial properties to the polyurethane resin can be imparted by incorporating tea component polyurethane resin of travel of polymerization at room temperature near rather, and completed the present invention.

That is, the antibacterial polyurethane resin of the present invention comprises tea catechin, tea saponin or tea tannin.
Antimicrobial agents such as polyols and
Blended with a resin raw material containing
Promote the polymerization reaction of the raw materials to form the porous polyurethane resin
Synthesized obtained, characterized and said antimicrobial agent that has been dispersedly contained in the matrix and the matrix consisting of the polyurethane resin, in that it consists of. Further, the method for producing the antibacterial polyurethane resin of the present invention comprises the steps of:
An antibacterial agent consisting of nin or tea tannin is blended with a resin material containing a polyol and an organic isocyanate, which are raw materials of a polyurethane resin, and the polymerization reaction of the resin material is advanced to synthesize the porous polyurethane resin, and the polyurethane resin is used. The antibacterial agent is dispersed and held in a matrix to be formed.

[0006] The tea or tea component is preferably tea catechin, tea saponin or tea tannin. The matrix is preferably foamed and porous. The antimicrobial polyurethane resin of the present invention uses tea or a tea component widely used for drinking as a kind of luxury goods as an antibacterial agent component. For this reason, it is extremely safe.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial polyurethane resin of the present invention comprises a matrix composed of a polyurethane resin and a dispersed phase composed of an antibacterial agent composed of tea or a powder containing a tea component dispersed in the matrix. Consists of
The polyurethane resin constituting the matrix has been conventionally known as a urethane resin. The form of the polyurethane resin as a matrix is a foam-like porous body .

[0008] Ru can polyurethane resin constituting the matrix is obtained by reacting a polyol and isocyanate by mixing the resin material containing the same manner polyol and isocyanate with the prior art. Besides polyol and isocyanate in the tree fat raw material, catalyst, foaming agent, and other additives can be used as well as a raw material for producing conventional polyurethane resin.

The antibacterial agent is in a powder form containing a tea component . Tea catechins are components of tea, those tea saponin or tea tannins was powdered can be used as an antimicrobial agent. Further, a powder obtained by adhering, adsorbing, and fixing a tea component to a carrier may be used as an antibacterial agent. Further, a pulverized material obtained by adsorbing an active ingredient of tea to an organic substance, for example, a fiber by dyeing or the like is also effective. In addition, as the carrier, an inorganic substance such as a clay mineral having a high adsorptivity, a zeolite as a porous body, and an organic substance imparting granulation can be used.

[0010] The tea component is, for example, what is known as tea catechin, tea saponin or tea tannin. What is known as catechin, saponin, tannin is a general term for all organic substances with a specific organic structure,
Even if it is called catechin, if the raw material plant is different, the medicinal effect will be different. The catechin, saponin and tannin of the present invention are contained as components of tea, and do not contain catechin, saponin and tannin other than the components of tea. Also,
I do not know whether catechins, saponins, and tannins other than tea components have antibacterial properties.

The amount of the antibacterial agent is not particularly limited.
Depending on the purpose, the compounding amount of the antibacterial agent can be appropriately selected. The method for producing the antibacterial polyurethane resin of the present invention comprises:
Add at least one kind of tea catechin, saponin, tannin and tea powder to a mixture of polyol and water modified with polyol, organic isocyanate, amine of catalyst, organotin compound and silicone, add isocyanate compound to this mixed to cause heavy engagement can be prepared in a conventional manner.

[0012] The tea is an antibacterial ingredient catechin, saponin, antibacterial properties can be obtained if etc. tannin emissions are added. Practically, 0.01 parts by weight or more of the antibacterial agent is good for 100 parts by weight of the polyurethane resin. More preferably, it is about 0.6 to 3.6 parts by weight. In addition, the tea may be green tea or fermented black tea. Powdered tea may be added as it is or an extract may be added.

The polyol used in the present invention can be used regardless of known hard, semi-soft or soft. As the isocyanate, a bifunctional or trifunctional isocyanate that forms a polyurethane by a polymerization reaction at a relatively low temperature can be used, but is not particularly limited. Further, as a method for producing these resins, conventionally known resins can be appropriately used. For example, a continuous method or a discontinuous method may be used, and a one-shot method, a prepolymer method, or the like may be used in a reaction step of a main raw material.

As the polyurethane resin, a foamable resin can be used.

[0015]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto. (Production method of polyurethane resin) First, a trifunctional polyol (polypropylene glycol having a molecular weight of about 3000) 1
00 parts by weight, water 6.5 parts by weight, tertiary amine (triethylamine) 0.1 part by weight, organometallic tin compound 0.1
One kind of the tea component shown in Table 1 was sufficiently mixed with 5 parts by weight and 10 parts by weight of the softener. To this mixed liquid, 75 parts by weight of diisocyanate (tolylene diisocyanate) is added at room temperature, and the mixture is mixed quickly.
The container was placed in a container having a height of 30 mm and a height of 170 m, and the reaction was allowed to proceed to obtain a foamed antibacterial polyurethane resin. Thereafter, the foamed antibacterial polyurethane resin is further added to 90
It was manufactured by leaving it in a thermostat set at a temperature of 15 ° C. for 15 to 30 minutes.

A polyurethane resin was produced in the same manner as above except that the tea component was changed. No. 1 to No. Six types of six antimicrobial polyurethane resins were prepared. In addition, as a comparative material, A foamed polyurethane resin was produced in the same manner without adding the tea component to the 50 polyol components. Table 1 shows the expansion ratios of the produced polyurethane resins.

[0017]

[Table 1] Here, green tea is a tea plant (Camallia ginens)
is) leaves are heat-treated so as not to ferment. The powdered green tea used in this experiment is catechins.
Contains 4%. The tea catechins include natural polyphenol compounds known as active ingredients of tea leaves, such as epicatechin, epicatechin gallate, epigallocatechin, epigallocatechin gallate, and the like.

The term "catechin 30% content" refers to a substance containing 38% of total polyphenols, of which 31% is contained as catechin. The content of 90% catechin is 93.1% as a total polyphenol, of which 7% is a catechin.
It is said to contain 0.5%. The crude saponin is a powder obtained by defatting tea seeds, leaching with methanol, and adding ether to a methanol solution to dry a precipitate. The saponin content is about 55%.

The "30% catechin-containing substance + crude saponin" is a mixture of the above-mentioned catechin-containing 30% substance and crude saponin in the same amount. The 90% catechin content + crude saponin is a mixture of the above 90% catechin content and the same amount of crude saponin. The tea-dyed fiber powder by Ti mordant and the tea-dyed fiber powder by Cu mordant are cotton yarn and tea extract (weight ratio 200
%), Heat-suspended, and reacted with a Ti or Cu metal compound as a desiccant to produce a dyed cotton yarn.
5 μm or less).

Further, tannic acid base saponin-dyed fiber powder Cu mordant refers to a cotton yarn treated with tannic acid, reacted with a Cu metal compound as a mordant, and then powdered with a crude saponin-dyed cotton yarn. Catechin-containing material base saponin-dyed fiber powder Cu mordant refers to a cotton yarn treated with 90% catechin-containing material, reacted with a Cu metal compound as a mordant, and then dyed with crude saponin to powder.

Green tea (200%) dyed fiber powder Cu mordant is a cotton yarn obtained by suspending and heating a cotton yarn with a 200% weight ratio of a green tea extract and subjecting a Cu metal compound as a mordant to a reactive dyeing treatment. Say things. When each of the obtained foamed polyurethane resins was observed with a microscope, the finely powdered tea component was completely embedded in a thin-walled polyurethane matrix as shown in FIG. 1, and as shown in FIG. It was observed that the polyurethane was interposed in the gaps between the thin-walled polyurethanes. Note that no tea component adhering to the surface of the wall-shaped polyurethane was observed. (Partially Improved Bacterial Growth Inhibition Test) First, antibacterial properties were examined by a partially improved bacterial growth inhibition test.

The staphylococcus aureus (Staphylo) stored at 37 ° C.
Inoculate a loopful of P. coccus aureus IFO 12732) into a normal broth medium and shake at 37 ° C for 8 hours (100 rpm).
Cultured. After diluting the obtained culture solution 10-fold,
An additional 10 in normal broth medium diluted 10-fold in BS
It was diluted by a factor of 1 to obtain a test bacterial solution. The number of bacteria at the time of dilution of this test bacterial solution is about 1 × 10 ⁶ .

Here, the ordinary broth medium refers to 50 g of beef extract, 10.0 g of peptone, and 5.0 g of sodium chloride.
Is dissolved in 1,000 ml of distilled water. Also,
PBS is a mixture of 34 g of potassium dihydrogen phosphate and 5 g of distilled water.
00ml, 4% sodium hydroxide aqueous solution about 175m
After adjusting the pH to 7.2 with 1 l, 11,000 with distilled water.
ml, and this was autoclaved at 121 ° C and 15 ° C.
It is one that has been sterilized by high-pressure steam for one minute.

Next, 0.075 ± 0.002 g was placed in a 50 ml screw-cap Erlenmeyer flask previously sterilized by high pressure steam (the amount of the sample was determined by grasping in advance the amount of the sample sufficiently immersed in 200 μl of the bacterial solution). Each of the foamed polyurethane resin samples cut so as to obtain a test microbial solution was further taken in, and 0.2 ml of the test bacterial solution was taken. The test flask thus obtained was cultured at 37 ° C. for 18 hours.

Thereafter, 20 ml of PBS was added, and the cells were shaken for 5 seconds × 5 times with a test tube mixer to disperse the cells. The number of bacteria at the start of the test was determined by dispersing the bacteria in PBS immediately after inoculating the foamed polyurethane resin sample and measuring the number of bacteria in the same manner.

The method for evaluating the antibacterial activity is as follows. From the number of colonies measured in each sample, the number of viable bacteria was determined as the number of viable bacteria = the number of colonies x 20 x dilution factor. The increase / decrease value of the bacteria and the difference between the increase / decrease values were calculated by the following formulas. Increase / decrease value = logC-logA Increase / decrease value difference = (logB−logA) − (logC−log
gA) [Bacterial growth inhibition test 1] 1, No.
3, No. 5 and No. 5 The antimicrobial activity test described below was performed on 50 foamed polyurethane resins. The number of inoculated bacteria [A] is 1.06 × 10 ⁵ ,
ogA is 5.02. Sample No. The viable cell count [B] of 50 is 4.40 × 10 ⁵ , and its logB is 5.63. The viable cell count of each sample was designated as [C].
1, No. 3, No. 4, no. 5 and No. 5 Number of samples and number of bacteria for 50 foamed polyurethane resins
The number, increase / decrease value and difference between the increase / decrease values are also shown in Table 2.

[0027]

[Table 2] Table 2 shows the results. No. 1 powdered green tea, No. 1
No. 3 catechin and No. 3 catechin. In the foamed polyurethane resin to which the tea components of catechin and crude saponin of No. 5 were added, the number of bacteria was greatly reduced, indicating excellent antibacterial properties. [Bacterial growth inhibition test 2] 1, No.
2, No. 4, no. 5 and No. 5 The antimicrobial activity test described below was performed on 50 foamed polyurethane resins. The number of inoculated bacteria [A] is 2.87 × 10 ⁵ , and the logarithmic value logA is 5.38. Sample No. The viable cell count [B] of 50 is 2.60 × 10 ⁵ , and its log
B is 5.41. The number of viable bacteria in each sample is [C], and the number of samples, the number of logs of the number of bacteria, the increase / decrease value, and the difference between the increase / decrease values for each sample are shown in Table 3.

[0028]

[Table 3] As shown in Table 3, the results were as shown in FIG. No. 1 powdered green tea, No. 1
2, No. No. 3 catechin and No. 3 catechin. In the foamed polyurethane resin to which the tea components of catechin and crude saponin of No. 5 were added, the number of bacteria was greatly reduced, indicating excellent antibacterial properties. [Bacterial growth inhibition test 3] 1, No.
2, No. 6 and no. The antimicrobial activity test described below was performed on 50 foamed polyurethane resins. The number of inoculated bacteria [A] is 2.80 × 10 ⁵ ,
ogA is 5.45. Sample No. The viable cell count [B] of 50 is 3.70 × 10 ⁵ , and its log B is 5.57. The number of viable bacteria in each sample is [C], and the number of samples, the log count of the number of bacteria, the increase / decrease value, and the difference between the increase / decrease values are shown in Table 4 for each sample.

[0029]

[Table 4] As shown in Table 4, the foamed polyurethane resin to which the tea component was added showed a decrease in the number of bacteria, indicating antibacterial properties.

In three different tests shown in Tables 2 to 4, the foamed polyurethane resin to which the tea component was added significantly reduced the number of bacteria and exhibited excellent antibacterial properties. In particular, no. 2
And No. As shown in FIG. 4, the foamed polyurethane resin containing 30% of catechin exhibited an extremely high antibacterial property with almost no bacteria. (Shake flask method) Next, the antibacterial property was examined by the shake flask method.

Staphylococcus aureus (Staphyloco) stored at 4 ° C.
ccus aureus IFO 3060) in advance on a normal agar slant
The cells were cultured at 7 ° C. for 1616 hours. The platinum loop is requisitioned in a normal broth medium and shaken at 37 ° C. for 16 hours (100 rpm).
m) Cultured. The obtained culture solution was diluted with phosphate buffer for 10 hours.
It was diluted 100-fold and then diluted 100-fold to obtain a test bacterial solution (the number of bacteria at the time of dilution was about 1 × 10 ⁵ ).

Next, 70 ml of a phosphate buffer was placed in a 200 ml screw-cap Erlenmeyer flask and sterilized with high pressure steam. Then, 5 ml of the test bacterial solution was added to the flask, and after stirring well, 1 ml was collected from any two or three points, subjected to colony counting, and the number of inoculated bacteria was measured. Subsequently, the samples of the urethane foam resin shown in Table 1 were used for 0. 75 ± 0.005 g is weighed and shredded to about 1 × 1 cm at 90 ° C.
For 5 minutes. Put this sample in a flask for about 250
Shake for 1 hour at rpm. 1m from buffer after shaking
1 was collected, diluted with a 10-fold serial dilution series, and the number of bacteria was measured by the colony counting method. A blank test was performed by shaking without adding a sample.

The bacteria reduction rate was calculated by the following equation. Sterilization rate = {(AB) / A} × 100 (%) where A indicates the number of inoculated bacteria and B indicates the number of bacteria after the test. [Shake flask test 1] 1 and
No. Shake Hula for foamed polyurethane resin No. 7
An antibacterial activity test by the scoring method was performed. Inoculum count
[A] is 1.25 × 10 ^FourIndividual. The number of samples for each sample,
Table 5 shows the viable cell count and the bacteria reduction rate.

[0034]

[Table 5] As shown in Table 5, the foamed polyurethane resin to which the tea component was added showed a decrease in the number of bacteria, indicating antibacterial properties. [Shake flask test 2] 8, N
o. 9 and No. 9 An antibacterial activity test was performed on 10 foamed polyurethane resins by a shake flask method. The number of inoculated bacteria [A] is 1.07 × 10 ⁴ . Table 6 shows the number of samples, the number of viable bacteria, and the sterilization rate of each sample.

[0035]

[Table 6] It can be seen that the foamed polyurethane resin to which the tea component is added as the dyed fiber powder greatly reduces the number of bacteria and has excellent antibacterial properties. [Shake Flask Test 3] 6, N
o. 8 and No. An antibacterial activity test was performed on the foamed polyurethane resin No. 9 by a shake flask method.
The number of inoculated bacteria [A] is 2.01 × 10 ⁴ . Table 7 also shows the number of samples, the number of viable bacteria, and the sterilization rate of each sample.

[0036]

[Table 7] Also in this test, the foamed polyurethane resin to which the tea component was added as the dyed fiber powder showed a large decrease in the number of bacteria and exhibited excellent antibacterial properties.

The results obtained by the shake flask method also indicate that the polyurethane resin has high antibacterial properties as shown in Tables 5 to 7. The antibacterial polyurethane resin of the present invention,
It is presumed that the active ingredient of tea is uniformly dispersed in the organic matter and exists with a high specific surface area.

[0038]

The antimicrobial polyurethane resin of the present invention exhibits high sterility. The antibacterial component of the present invention is a medicinal component contained in tea . Needless to say, the tea itself is used for drinking and is highly safe. Antibacterial polyurethane resin fibers touched by a person products of the present invention using the components of this tea, a large effect of hygiene be used such as tableware touching directly the food.

[Brief description of the drawings]

FIG. 1 is an enlarged schematic cross-sectional view of an antibacterial polyurethane resin of an example.

FIG. 2 is an enlarged schematic cross-sectional view of another portion of the antibacterial polyurethane resin of the example.

Continuation of the front page (72) Inventor Takami Yoshida 536 Ryuzenji-cho, Hamamatsu City, Shizuoka Prefecture (56) References JP-A-8-2570 (JP, A) JP-A-2-24351 (JP, A) JP JP-A-7-126408 (JP, A) JP-A-3-246227 (JP, A) JP-A-2-306915 (JP, A) JP-A-4-182480 (JP, A) JP-A-6-122746 (JP , A) JP-A-2-117608 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 75/04 C08G 18/28 A61L 2/16

Claims (4)

(57) [Claims] 1. Tea catechin, tea saponin or tea tannin
Poison, a raw material of polyurethane resin
Blended with resin raw materials containing
Promote the polymerization reaction of the resin raw material to form the porous polyurethane
Obtained by combining the resin, that is dispersedly contained in the matrix and the matrix consisting of the polyurethane resin
Antibacterial polyurethane resin characterized in that it consists with the antimicrobial agent. 2. The method according to claim 1, wherein the antimicrobial agent is a polyurethane resin.
The amount is from 0.01 to 3.6 parts by weight based on parts by weight.
The antibacterial polyurethane resin as described. 3. Tea catechin, tea saponin or tea tannin
An antimicrobial agent comprising a polyol and an organic isocyanate, which are raw materials of a polyurethane resin, is blended with a resin raw material, and a polymerization reaction of the resin raw material is advanced to synthesize the porous polyurethane resin, thereby forming a matrix formed of the polyurethane resin. A method for producing an antibacterial polyurethane resin, wherein the antibacterial agent is dispersed and held therein. 4. The antimicrobial agent is a polyurethane resin 100
The amount is 0.01 to 3.6 parts by weight based on parts by weight.
A method for producing the antibacterial polyurethane resin according to the above.