Antibacterial fabric

Abstract

The invention discloses an antibacterial fabric. A compound A and a compound B are attached to single fibers forming the fabric, the compound A is a silver-containing inorganic compound, the compound B is a polyurethane compound and / or a polyacrylate compound, the structural formula of the polyurethane compound comprises an alicyclic group, and the structural formula of the polyacrylate compound comprises an alicyclic group. The structural formula of the polyacrylate compound contains an epoxy group. The fabric provided by the invention not only has excellent antibacterial property, but also has excellent washing durability, and can be used for making underwear, short sleeves and other clothing textiles.

Description

Technical Field

[0001] The present invention relates to an antibacterial fabric. Background Art

[0002] In daily life, people inevitably come into contact with various microorganisms such as bacteria and fungi. Excessive pathogenic microorganisms invading the human body will pose serious potential hazards to people's health. As an indispensable part of people's daily life, textiles have important practical significance in developing fabrics with antibacterial effects.

[0003] For example, Chinese Patent Document CN101165242A discloses a nano-film antibacterial textile. Specifically, more than 85% of the fibers in the textile are film fibers. The film fibers have single fibers, and a nano-film resin layer is compounded on the surface of the single fiber. There are nano-scale antibacterial particles in the nano-film resin layer, resulting in a textile with antibacterial effects. However, since the surface of the textile fibers is covered with a film, there is a problem that the films rub against each other and are damaged or even fall off after multiple washes, resulting in poor antibacterial durability. Summary of the Invention

[0004] The purpose of the present invention is to provide an antibacterial fabric with excellent antibacterial properties and good washing durability.

[0005] In order to achieve the above purpose, the technical solution of the present invention is as follows:

[0006] In the antibacterial fabric of the present invention, compound A and compound B are attached to the single fibers forming the fabric. Compound A is a silver-containing inorganic compound, and compound B is a polyurethane compound and / or a polyacrylate compound. Among them, the structural formula of the polyurethane compound contains an alicyclic group, and the structural formula of the polyacrylate compound contains an epoxy group.

[0007] The antibacterial fabric of the present invention has obtained excellent antibacterial properties and greatly improved washing durability by attaching compounds with specific components to the single fibers of the fabric, and can be used for producing products such as underwear and short sleeves. Detailed Embodiments

[0008] In the antibacterial fabric of the present invention, compound A and compound B are attached to the single fibers forming the fabric. Compound A is a silver-containing inorganic compound. This is because the silver-containing inorganic compound will slowly release silver ions on the fabric. When the released silver ions come into contact with bacteria, since the cell membrane of the bacteria itself has a negative charge, the silver ions are adsorbed to the cell membrane through Coulomb attraction and further penetrate the cell wall into the cell, reacting with sulfhydryl groups, amino groups, etc. in the cell, destroying the proteins and DNA of the cell, and inactivating the bacteria on the fabric, thereby achieving the antibacterial effect.

[0009] The compound B is a polyurethane compound and / or a polyacrylate compound. This is because the molecular chain segments of the polyurethane compound are composed of hard segments and soft segments. The hard segment part is composed of urethane linkages, and the soft segment part is composed of polyester chains. Through the hydrogen bonds, van der Waals forces and other interactions between the hard segments and the soft segments, a structurally stable network resin film can be cross-linked on the fiber surface. The isocyanate group (-NCO) in the molecular chain has a highly unsaturated structure, resulting in high reactivity, and can react with the active groups (such as carboxyl groups, hydroxyl groups, etc.) in the fiber. At the same time, when using fabrics containing carboxyl groups and hydroxyl groups, since the urethane bonds, ester bonds, ether bonds, etc. in the molecular chain can also form hydrogen bonds with polar groups, the resin film and the fiber can be more firmly combined, greatly improving the antibacterial durability of the fabric. Among them, the structural formula of the polyurethane compound contains an alicyclic group. This is because the alicyclic group is a cyclic carbon framework formed by carbon atoms connected in a ring, and its alicyclic ring tension is small, which can form a stable rigid structure, ensuring the stability of the urethane group (-NHCOO) in the polymer main chain, improving the stability of the cross-linked network resin film. Under the action of external forces, the network film formed on the fiber surface is not easily damaged, further improving the antibacterial durability of the fabric.

[0010] When the polyacrylate compound adheres to the single fibers of the fabric, functional groups such as amide groups and amino groups in the molecular structure can undergo self-crosslinking to form cross-linked macromolecules with a network structure, forming a network resin film on the surface of the fiber. At the same time, when using fabrics containing carboxyl groups and hydroxyl groups, functional groups such as amino groups in the molecular structure can also generate interaction forces with the carboxyl groups and hydroxyl groups on the fiber to form hydrogen bonds, making the resin film on the fiber surface more firm and not easily damaged or fallen off during the washing process, thereby improving the antibacterial durability of the fabric. Among them, the structural formula of the polyacrylate compound contains an epoxy group. This is because the epoxy group is a cyclic structure formed by two adjacent carbon atoms connected by an oxygen atom, with high stability and reactivity. When using fabrics containing carboxyl groups and hydroxyl groups, the epoxy group can undergo cross-linking reactions with the hydroxyl groups, carboxyl groups in the molecular chain and the hydroxyl groups in the fiber, improving the film-forming property of the polymer on the fiber and the binding force between the network resin film and the fiber, making the resin film on the fiber surface more firmly combined with the fiber and not easily damaged or fallen off during the washing process, thereby further enhancing the antibacterial durability of the fabric.

[0011] Preferably, the mass ratio of silver to Compound B on the antibacterial fabric of the present invention is 1:10 to 40, where the silver refers to silver ions and / or silver metal. Considering that silver has antibacterial properties, but if it is directly attached to the fiber surface, only adhesion exists between the two, and the intermolecular force is small. After washing, the silver on the fiber surface is likely to fall off, resulting in poor antibacterial durability. Compound B can be used as a crosslinking agent to firmly bond the dispersed silver-containing inorganic compound to the fiber surface. If the mass ratio of silver to Compound B on the fabric is less than 1:10, the mass of Compound B is too low, and the crosslinking reaction of the polyurethane compound and / or polyacrylate compound is incomplete, resulting in the inability to form a continuous network resin film on the fiber surface. When under washing or other external forces, friction is likely to occur between fibers, causing the resin film to break and fall off, and the amount of silver-containing inorganic compound dispersed in the resin film decreases, and the antibacterial and durability of the fabric tend to decline. Therefore, it is not preferred. If the mass ratio of silver to Compound B on the fabric is greater than 1:40, the mass of Compound B is too high, and molecular aggregation of Compound B will occur on the fiber surface, resulting in poor fluidity of Compound B on the fiber surface. During the crosslinking reaction on the fiber surface, it will accumulate, and the silver-containing inorganic compound dispersed in the resin film may be coated by the resin film, easily causing the dissolved silver ions to be unable to contact bacteria, and the antibacterial and durability of the fabric tend to decline. Therefore, it is not preferred.

[0012] Preferably, for the antibacterial fabric of the present invention, the antibacterial activity value against Staphylococcus aureus measured by the bacterial liquid absorption method according to ISO 20743:2021 at the initial stage of the fabric and after washing 30 times according to the JIS L 1930:2014 C4G method is above 2.2. The higher the antibacterial activity value, the better the antibacterial performance.

[0013] For the antibacterial fabric of the present invention, Compound A is a silver-containing inorganic compound. Considering that there are no hydrophilic or hydrophobic groups in its structure and it is not easy to react when contacting with water molecules, it will not affect the water absorption of the fabric. Therefore, when performing resin processing, it is preferred to use the silver-containing inorganic compound in combination with a water absorbent to obtain a fabric with excellent water absorption and antibacterial properties. When the particle size of the silver-containing inorganic compound is 1000 nm or less, when it adheres to the single fiber of the fabric, it is not easy to block the gaps between the fibers, which is beneficial to the diffusion of water molecules on the fiber. Therefore, the particle size of the silver-containing inorganic compound is preferably 1000 nm or less.

[0014] For the antibacterial fabric of the present invention, its texture is not particularly limited and can be a woven fabric or a knitted fabric. The texture of the woven fabric can be the three basic weaves of plain weave, twill weave, and satin weave and their modified weaves; the texture of the knitted fabric can be plain stitch, rib, purl, tricot, chain stitch, etc.

[0015] For the antibacterial fabric of the present invention, the fiber raw materials are not particularly limited and can be composed of cellulose fibers and / or synthetic fibers. Here, the cellulose fibers include natural cellulose fibers and regenerated cellulose fibers. Among them, examples of natural cellulose fibers are cotton fibers (C), hemp fibers, etc., examples of regenerated cellulose fibers are viscose fibers (R), modal fibers, etc., and examples of synthetic fibers are ordinary polyester fibers (PET), cationic dyeable polyester fibers (CDP), spandex (PU), polyamide fibers (also known as nylon, Ny6), polyacrylonitrile fibers (also known as acrylic fibers, Ac), etc. Considering excellent antibacterial durability, the fiber raw materials preferably contain cellulose fibers such as cotton fibers and viscose fibers.

[0016] The antibacterial fabric of the present invention can be prepared by the following method: pre-treating the grey fabric, intermediate setting, dyeing (optional), resin processing, and finishing setting. Among them, the resin liquid composition used in resin processing includes silver-containing inorganic compounds, polyurethane compounds, and / or polyacrylate compounds to obtain the product of the present invention.

[0017] Resin processing preferably adopts padding processing, and the conditions used in padding processing can be adjusted as needed. One-dip-one-roll treatment is preferably adopted. The finishing setting is not particularly limited, and the preferred temperature is 120 - 180 °C and the time is 2 - 4 min.

[0018] The silver-containing inorganic compounds, polyurethane compounds, and polyacrylate compounds used in the present invention can be commercially available products or can be synthesized according to the well-known techniques in the art, and their dosages can be adjusted as needed. For example, the preferred dosage of the silver-containing inorganic compound is between 5 - 30 g / L, the preferred dosage of the polyurethane compound is between 10 - 40 g / L, and the preferred dosage of the polyacrylate compound is between 10 - 40 g / L.

[0019] The present invention will be further described below in conjunction with examples and comparative examples. Among them, the physical property parameters involved in the present invention are tested by the following methods.

[0020] (1) Qualitative analysis

[0021] Take 1 g of the fabric as the test sample, crush the test sample into powder with a pulverizer, mix it with 100 mg of dried potassium bromide, grind it in an agate mortar for 2 - 3 min, transfer all the uniformly ground mixture to a potassium bromide press mold, and under a pressure of about 14 MPa, evacuate and press for 2 - 3 min to obtain a transparent sheet for standby. Place the prepared film sheet on the sample holder of the infrared spectrometer and start the scanning program of the infrared spectrometer.

[0022] If the following characteristic peaks appear, it is confirmed that there are polyurethane compounds in the single fibers of the fabric and the structural formula of this type of compound contains alicyclic groups: 1700 - 1750 cm -1The stretching vibration peak of C=O appears at 3200 - 3500 cm -1 The stretching vibration peak of N-H appears at 2960 - 2850 cm -1 C-H stretching vibration appears in the range of 1485 - 1355 cm -1 The stretching vibration peak of C-C appears in the range of 1465 - 1375 cm -1 The bending vibration peak of C-H appears in the range of 770 - 720 cm -1 The ring stretching vibration peak appears in the range.

[0023] If the following characteristic peaks appear, it is confirmed that there are polyacrylate compounds in the single fiber of the fabric and the structural formula of this type of compound contains epoxy groups: 3310 cm -1 The stretching vibration peaks of -OH and -NH appear near 2960 cm -1 The stretching vibration peak of -C-H- appears near 1730 cm -1 The stretching vibration absorption peak of -COO- appears near 1450 cm -1 The asymmetric deformation vibration peak of -CH3 appears near 1380 cm -1 The symmetric deformation vibration peak of -CH3 appears near 1170 cm -1 The stretching vibration peak of -C-O-C- appears near 827 cm-1 and the characteristic absorption peak of epoxy group appears at 915.16 cm-1.

[0024] Take a 2 cm * 2 cm fabric as the sample to be tested, fix the sample on the sample stage, put it into a scanning electron microscope & energy dispersive spectrometer (SEM&EDS) analyzer, select silver element in the instrument for energy spectrum analysis. If the test result shows the existence of silver element, it indicates that there are silver-containing inorganic compounds on the fabric.

[0025] (2) Quantitative analysis

[0026] After confirming the presence of polyurethane compounds and polyacrylate compounds on the single fibers of the fabric using the above qualitative analysis, weigh 10 g ± 0.5 g of the fabric, cut it into pieces, and use it as a sample. Place it in a 500 mL beaker, add 50 mL of a mixed solution of trifluoroacetic acid and chloroform. After the fabric is fully dissolved, that is, when no solids are observed in the beaker. Pipette the dissolved solution into a methanol solution to precipitate the solids. Repeat the dissolution and precipitation of the sample 3 - 5 times to obtain a purified solid sample. Place the purified solid sample in a vacuum drying oven and dry it at 80 °C for 24 hours. Then weigh 20 mg and place it in a nuclear magnetic resonance tube, and add deuterated reagent D2O; Test the sample dissolved in D2O using a nuclear magnetic resonance spectrometer to obtain nuclear magnetic resonance hydrogen spectrum data. If the following characteristics appear in the nuclear magnetic resonance hydrogen spectrum, it is confirmed as a polyurethane compound: δ = 7.5 is the hydrogen proton on the carbamate, δ = 4.0 is the methylene peak where the carbamate is connected to the diol, δ = 0.7 - 1.4 is the proton peak on the aliphatic ring and the hydrogen proton of the methylene in the repeating unit of the diol; If the following characteristics appear, it is confirmed as a polyacrylate compound: at about δ = 6.3 and δ = 6.3 is the absorption peak of CH2=CH-, and at about δ = 1.62 is the absorption peak of the active hydrogen of the hydroxyl group.

[0027] Use a gas chromatography - mass spectrometry (GC - MS) instrument to perform quantitative analysis on polyurethane compounds and polyacrylate compounds. The specific operations are as follows: Dilute the standard solutions of polyurethane compounds and polyacrylate compounds into seven different concentrations (100.0000 wt%, 10.0000 wt%, 1.0000 wt%, 0.1000 wt%, 0.0100 wt%, 0.0010 wt%, 0.0001 wt%) of standard solutions respectively; Put these seven concentrations of standard solutions into the gas chromatography - mass spectrometry instrument for analysis and testing respectively; Draw a relationship curve graph of the mass of the compound and the peak area based on the mass spectrometry graphs of the seven standard solutions; Weigh 10 g of the fabric as the sample to be tested, and use 40 mL of ethyl acetate solution to extract the fabric (polyurethane compounds and polyacrylate compounds are soluble in ethyl acetate). Pass the extract through the gas chromatography - mass spectrometry instrument to obtain the mass spectrometry graphs of polyurethane compounds and polyacrylate compounds respectively; According to the peak area of the mass spectrometry graph and the relationship curve of the mass of the corresponding compound and the peak area, calculate the mass x of the polyurethane compound and the mass y of the polyacrylate compound. Among them, x and y take the average value of three tests.

[0028] Quantitatively analyze the silver on the fabric using an inductively coupled plasma optical emission spectrometer (ICP-OES). Weigh 0.5 g ± 0.05 g of the fabric, cut it into pieces and use it as a sample. Put it into a test tube for dissolution. After the fabric is fully dissolved, take the supernatant and test it with an inductively coupled plasma optical emission spectrometer to obtain the silver content z on the fabric. Among them, the result z of the silver content is the average value of three tests.

[0029] The mass ratio of the silver on the fabric to the compound B is z * 10 -5 :(x + y).

[0030] (3) Water absorption

[0031] Determined according to the dropping method of JIS L 1907:2010.

[0032] (4) Antibacterial property

[0033] Determined according to the bacterial liquid absorption method of ISO 20743:2021, and the tested bacterial strain is Staphylococcus aureus.

[0034] (5) Washing

[0035] Water absorption: Wash 10 times according to the C4G method of JIS L 1930:2014. Among them, the washing powder used is Kao Jebao Bright White Washing Powder.

[0036] Antibacterial property: Wash 30 times according to the C4G method of JIS L 1930:2014. Among them, the washing agent is JAFET standard compound washing agent.

[0037] The agents used in the following examples and comparative examples are as follows:

[0038] Agent A: Silver-containing inorganic compound (manufactured by Haiyi Co., Ltd.)

[0039] Agent B: Polyurethane compound (manufactured by Rudolph Chemical Industry (Dongguan) Co., Ltd., containing alicyclic groups) Agent C: Polyacrylate compound (manufactured by Haiyi Co., Ltd., containing epoxy groups) Agent D: Polyether organosilicon compound (manufactured by Nantong Dongrou Co., Ltd.)

[0040] Agent E: Polyurethane compound (manufactured by Shanghai Hete Chemical Co., Ltd., without alicyclic groups) Agent F: Polyacrylate compound (manufactured by Shinakamura Chemical Industry Co., Ltd., without epoxy groups)

[0041] Example 1

[0042] Select a fabric with a gram weight of 175 g / m 2, A plain-knit knitted grey fabric made of 71% cotton fiber / 25% cationic-dyeable polyester fiber / 4% spandex fiber (C 71% / CDP 25% / PU 4%) is subjected to the following processes: conventional pretreatment → intermediate setting (180°C * 1 min) → dyeing of cationic-dyeable polyester fiber (115°C * 40 min, cationic dye 3% owf, acetic acid 2 g / L, leveling agent 1 g / L) → soaping (70°C * 20 min, soaping agent 2 g / L) → dyeing of cotton (60°C * 60 min, reactive black 3% owf, sodium sulfate 30 g / L, soda ash 5 g / L) → soaping (80°C * 20 min, soaping agent 2 g / L) → drying → resin processing (padding once and squeezing, the expression rate is 75 ± 5%) → finishing setting (130°C * 2 min), to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 1.

[0043] The composition of the resin solution is as follows:

[0044] Agent A 10 g / L

[0045] Agent C 20 g / L

[0046] The rest is water.

[0047] Example 2

[0048] Replace Agent C with Agent B, and adjust the dosage to 25 g / L. The rest is the same as in Example 1, to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 1.

[0049] Example 3

[0050] The resin solution is composed of the following components, and the rest is the same as in Example 1, to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 1.

[0051] Agent A 10 g / L

[0052] Agent B 15 g / L

[0053] Agent C 10 g / L

[0054] The rest is water.

[0055] Example 4

[0056] Adjust the dosage of Agent C to 10 g / L. The rest is the same as in Example 1, to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 1.

[0057] Example 5

[0058] Adjust the dosage of Agent C to 35 g / L. The rest is the same as in Example 1, to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 1.

[0059] Example 6

[0060] Adjust the dosage of agent C to 60 g / L, and the rest is the same as in Example 1, to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 1.

[0061] Example 7

[0062] Adjust the dosage of agent C to 5 g / L, and the rest is the same as in Example 1, to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 2.

[0063] Example 8

[0064] Select a plain knit fabric with a gram weight of 110 g / m 2 and formed by 88% cationic dyeable polyester fiber / 12% spandex fiber (CDP88% / PU12%). After conventional pretreatment → intermediate setting (180 °C * 1 min) → cationic dyeable polyester fiber dyeing (115 °C * 40 min, cationic dye black 3% owf, acetic acid 2 g / L, leveling agent 1 g / L) → soaping (70 °C * 20 min, soaping agent 2 g / L) → drying → resin processing (padding once, the padding rate is 75 ± 5%) → finishing setting (130 °C * 2 min), and the rest is the same as in Example 1, to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 2.

[0065] Example 9

[0066] The resin solution consists of the following components, and the rest is the same as in Example 8, to obtain the antibacterial fabric of the present invention. The test results of various properties are shown in Table 2.

[0067] Agent A 10 g / L

[0068] Agent C 20 g / L

[0069] Agent D 20 g / L

[0070] The rest is water.

[0071] Comparative Example 1

[0072] The resin solution consists of the following components, and the rest is the same as in Example 1, to obtain an antibacterial fabric. The test results of various properties are shown in Table 2.

[0073] Agent A 20 g / L

[0074] The rest is water.

[0075] Comparative Example 2

[0076] The resin solution consists of the following components, and the rest is the same as in Example 1, to obtain an antibacterial fabric. The test results of various properties are shown in Table 2.

[0077] Agent A 10 g / L

[0078] Agent E 25 g / L

[0079] The balance is water.

[0080] Comparative Example 3

[0081] The resin solution consists of the following components, and the rest is the same as in Example 1, obtaining an antibacterial fabric. The test results of various properties are shown in Table 2.

[0082] Agent A 10 g / L

[0083] Agent F 30 g / L

[0084] The balance is water.

[0085] Table 1

[0086]

[0087] Table 2

[0088]

[0089] According to the above table,

[0090] (1) As can be seen from Example 6 and Example 5, under the same conditions, when comparing the fabric with the mass ratio of silver to Compound B on the fabric being 1:55 and the fabric with the mass ratio of silver to Compound B on the fabric being 1:40, the antibacterial property of the former is inferior to that of the latter.

[0091] (2) As can be seen from Example 7 and Example 4, under the same conditions, when comparing the fabric with the mass ratio of silver to Compound B on the fabric being 1:8 and the fabric with the mass ratio of silver to Compound B on the fabric being 1:10, the antibacterial properties (before washing) of the two are comparable, but the antibacterial property of the former (after washing 30 times) is inferior to that of the latter.

[0092] (3) As can be seen from Comparative Example 1 and Example 1, under the same conditions, when comparing the fabric with only silver-containing inorganic compounds attached to the single fiber and the fabric with silver-containing inorganic compounds and polyacrylate compounds attached to the single fiber, the antibacterial properties before washing of the two are comparable, but the antibacterial property of the former after washing 30 times is far inferior to that of the latter.

[0093] (4) As can be seen from Comparative Example 2 and Example 2, under the same conditions, when comparing the fabric with polyurethane compounds (without alicyclic groups) attached to the single fiber and the fabric with polyurethane compounds (containing alicyclic groups) attached to the single fiber, the antibacterial properties of the two before washing are comparable, but the antibacterial property of the former after washing 30 times is far inferior to that of the latter.

[0094] (5) It can be seen from Comparative Example 3 and Example 1 that under the same conditions, compared with the fabric of polyacrylate compounds (without epoxy groups) on single fibers and the fabric of polyacrylic compounds (with epoxy groups) on single fibers, the antibacterial properties before washing are comparable for both, but the antibacterial property of the former is far inferior to that of the latter after 30 washes.

Claims

1. An antibacterial fabric, characterized in that: Compound A and compound B are attached to the single fibers forming the fabric. Compound A is a silver-containing inorganic compound, and compound B is a polyurethane compound and / or a polyacrylate compound. Among them, the structural formula of the polyurethane compound contains an alicyclic group, and the structural formula of the polyacrylate compound contains an epoxy group.

2. The antibacterial fabric according to claim 1, characterized in that: The mass ratio of silver to compound B on the fabric is 1:10 to 40.

3. The antibacterial fabric according to claim 1 or 2, characterized in that: According to the test by the bacterial liquid absorption method of ISO 20743:2021, the antibacterial activity values of the fabric against Staphylococcus aureus in the initial stage and after 30 washes are both above 2.2.

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