CN113755656A - Antibacterial and coronavirus-resistant automobile leather and preparation method thereof - Google Patents
Antibacterial and coronavirus-resistant automobile leather and preparation method thereof Download PDFInfo
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- CN113755656A CN113755656A CN202111175989.6A CN202111175989A CN113755656A CN 113755656 A CN113755656 A CN 113755656A CN 202111175989 A CN202111175989 A CN 202111175989A CN 113755656 A CN113755656 A CN 113755656A
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/44—Mechanical treatment of leather surfaces
- C14B1/56—Ornamenting, producing designs, embossing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to the field of D06N3/00, in particular to an antibacterial and coronavirus-resistant automobile leather and a production method thereof, wherein the automobile leather comprises a leather blank and a coating layer; the preparation raw materials of the coating layer comprise: resin, antiviral agent, cross-linking agent and first auxiliary agent. The prepared automobile leather has good wear resistance through the limitation of raw materials for preparing the coating layer, and tests prove that the automobile leather has good wear resistance, is wear resistant for 3000 times without damage, and is prepared by an isothiazolinone antibacterial antiviral agent, a cosolvent and a plasticizer in a weight ratio of (10-30): (10-30): (1-10) solves the problem that the leather is incompatible with antiviral agents in the prior art.
Description
Technical Field
The invention relates to the field of D06N3/00, in particular to an antibacterial and coronavirus-resistant automobile leather and a preparation method thereof.
Background
The automobile leather is a leather product with high-grade durability requirement and extremely strict safety performance requirement, the general leather finishing material is not suitable for the automobile leather, such as a shoe upper leather finishing agent, a bag leather finishing agent, a sofa leather finishing agent and the like, can not meet the requirement, and the general finishing method is also not suitable for the automobile leather, such as a cation finishing method. Automobile genuine leather finishing requires a high-performance abrasion-resistant resin coating, requires a low-VOC finishing product, requires a long-time environmental aging test, and has flame retardant performance and heavy metal restriction tests required by national laws and regulations. Under the large background of global public health safety incidents, the common automobile leather cannot meet the expectations of people on the safety of outgoing, and the development of the anti-virus automobile leather is imperative.
The use of the antiviral material in the leather industry is not the first time, for example, the cationic antiviral agent is used in the integrated process preparation of the leather and the fur, compared with the method that the antibacterial agent is added into tanning and retanning liquid like the xi group company Limited, the prepared belt releases antibacterial ions in the long-term use process, so that the belt achieves the effects of antibiosis, mildew prevention and virus resistance. Compared with the antibacterial and antiviral agent developed by the xi group company, the antibacterial and antiviral agent utilizes the synergistic cooperation of metal ions, photocatalyst and natural plant extract to achieve the high-efficiency antibacterial and antiviral effect.
Three Chinese patent inventions CN111500796A, CN111518964A and CN112410479A all disclose related production processes of automobile leather, and have no special antiviral effect, however, the production of an automobile leather with antiviral, especially coronavirus resistance, can achieve the expected effect without adding an antibacterial agent into the raw materials for preparation, so the invention designs the fresh antiviral leather in the prior art aiming at the problem.
Disclosure of Invention
The invention provides a first aspect of antibacterial and anti-coronavirus automobile leather, which comprises a leather blank and a coating layer; the preparation raw materials of the coating layer comprise: resin, antiviral agent, cross-linking agent and first auxiliary agent.
As a preferred embodiment, the preparation method of the coating layer comprises the following operations on the leather blank:
(1) priming, standing and embossing;
(2) color layer, standing;
(3) top coating and standing;
(4) and (6) vibrating to soften, and putting the measuring tape into a warehouse.
As a preferred embodiment, the resin includes at least one of an acrylic resin, a urethane resin, an aromatic binder resin, and a polishing resin.
Preferably, the resin includes acrylic resin, urethane resin, aromatic binding resin, polishing resin.
More preferably, the resin comprises aliphatic polyurethane fixed resin, aromatic bonding resin, self-crosslinking acrylic resin and hydrolysis-resistant polyurethane.
In a preferred embodiment, the crosslinking agent includes at least one of an isocyanate-based crosslinking agent, a polyisocyanate-based crosslinking agent, a polyol-based crosslinking agent, a glycidyl ether-based crosslinking agent, a benzenesulfonic acid-based crosslinking agent, and a polycarbodiimide-based crosslinking agent.
Preferably, the crosslinking agent includes an isocyanate-based crosslinking agent and a polycarbodiimide-based crosslinking agent.
As a preferred embodiment, the first auxiliary agent includes at least one of a first filler, a feel agent, a pigment, a first solvent, a matting agent, and a gloss enhancer.
Preferably, the first auxiliary agent comprises a first filler, a hand feeling agent, a pigment, a first solvent, a delustering agent and a gloss enhancer.
The first filler is not particularly limited in this invention and includes, but is not limited to, fillers manufactured by Statel Fine coatings (Suzhou) Inc. under the model number MelioMattpate C.
The present invention is not limited to particular hand feel agents, including but not limited to HM183 hand feel agents, low coefficient of friction silicone hand feel agents, and abrasion resistant macromolecular silicone hand feel agents, manufactured by Stahl Fine coatings (Suzhou).
The present invention is not limited to pigments, including but not limited to pigment pastes commonly used in automotive leather.
The first solvent is not particularly limited in this invention, and includes, but is not limited to, water.
The invention is not particularly limited to matting agents including, but not limited to, aliphatic polyurethane matting agents, polycarbonate polyurethane matting agents.
The present invention is not particularly limited to gloss enhancers, including but not limited to polyether polyester polyurethane gloss enhancers.
Preferably, the preparation method of the coating layer comprises the following operations of:
(1) priming coating: according to parts by weight, 30-60 parts of aliphatic polyurethane forming resin, 10-20 parts of aromatic bonding resin, 1-3 parts of hand feeling agent, 15-30 parts of first filler, 10-20 parts of pigment, 1-5 parts of polycarbodiimide crosslinking agent and 1-5 parts of water are adjusted to have the consistency of No. 6 Ford cup for 20-25 seconds; and finishing the base coat within 24 hours after the polycarbodiimide crosslinking agent is added, wherein the wet weight of the base coat is 10-12 g/sf. Drying in a drying tunnel at the temperature of 100 ℃ and 130 ℃, keeping the drying tunnel at the length of 10-20 m and the drying speed of 5-10m/min for 4-24h, and embossing;
(2) color layer: according to the weight portion, 10-20 portions of water, 5-15 portions of aliphatic polyurethane shaping resin, 5-15 portions of self-crosslinking acrylic resin, 5-15 portions of hydrolysis-resistant polyurethane, 10-30 portions of polycarbonate polyurethane flatting agent, 5-20 portions of aliphatic polyurethane flatting agent, 10-20 portions of pigment and 5-10 portions of isocyanate crosslinking agent. Adjusting the consistency to 28-32 seconds with a number 4 Ford cup; finishing the color layer within 2 hours after adding the aliphatic polyurethane crosslinking agent, wherein the wet weight of the coloring amount is 3-4 g/sf. Drying in a drying tunnel at the temperature of 100 ℃ and 130 ℃, wherein the length of the drying tunnel is 10-20 m, the drying speed is 5-10m/min, and standing for 1-8 h;
(3) top coating: according to parts by weight, 10-30 parts of water, 20-40 parts of polycarbonate polyurethane flatting agent, 20-40 parts of aliphatic polyurethane flatting agent, 1-10 parts of polyether polyester polyurethane brightening agent, 1-10 parts of antiviral agent, 1-6 parts of low-friction coefficient silicon hand feeling agent, 5-10 parts of abrasion-resistant macromolecular silicon hand feeling agent, 2-8 parts of pigment and 5-15 parts of isocyanate crosslinking agent. And finishing top coating within 2 hours after the isocyanate crosslinking agent is added, wherein the wet weight of the top coating is 2.5-3.5 g/sf. Drying the drying tunnel at the temperature of 100 ℃ and 130 ℃, wherein the length of the drying tunnel is 10-20 m, the drying speed is 5-10m/min, standing is 24-48h, the top coating step is repeated again, and standing is 24-48 h;
(4) and (6) vibrating to soften, and putting the measuring tape into a warehouse.
As a preferred embodiment, the raw materials for preparing the antiviral agent comprise the isothiazolinone antibacterial antiviral agent, a cosolvent and a plasticizer.
The applicant finds that the addition of conventional agents such as antibacterial agents, virus inhibitors and the like which are commonly used in the prior art in the system of the invention can not be applied to the system, and the addition of the conventional agents can cause various problems such as reaction of the antiviral agent with components in the system, change of the surface color of leather, change of the texture of the leather and the like.
Preferably, the weight ratio of the isothiazolinone antibacterial and antiviral agent to the cosolvent to the plasticizer is (10-30): (10-30): (1-10).
More preferably, the weight ratio of the isothiazolinone antibacterial and antiviral agent to the cosolvent to the plasticizer is (15-25): (10-30): (1-5).
More preferably, the weight ratio of the isothiazolinone antibacterial and antiviral agent to the cosolvent to the plasticizer is 20: 25: 3.
the isothiazolinone antibacterial antiviral agent is a common insecticide in steel smelting, oil field flooding, oil refinery and thermal power plant industrial manufacturing, and the prior art has an example that isothiazolinone is applied to leather, and is mainly used for inhibiting microorganisms in the inner and the inner of the leather, but the isothiazolinone has obvious skin irritation and is not suitable for being used as a leather outer surface coating layer directly contacting with the skin, and the isothiazolinone has poor water solubility and is not high in temperature resistance.
After extensive trials, the applicant found that the skin irritation problem of isothiazolinones can be significantly improved when co-solvents and plasticizers are added, and that the compatibility in the present system can also be improved. The reason that the applicant speculates may be that the addition of the cosolvent can accelerate the permeation of the isothiazolinone antibacterial and antiviral agent on the surface of the cooked leather, and meanwhile, the plasticizer and the fatting agent and the resin in the raw material for preparing the coating layer can perform synergistic action to form a tough film structure on the surface of the leather in a crosslinking manner, so that the direct contact of the isothiazolinone antibacterial and antiviral agent and the skin is reduced, and the skin irritation is reduced.
Preferably, the isothiazolinone antibacterial and antiviral agent comprises one of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, and 1, 2-benzisothiazolin-3-one.
Preferably, the isothiazolinone antibacterial and antiviral agent is 2-n-octyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one.
In order to improve the antibacterial and antiviral effects, the weight ratio of the 2-n-octyl-4-isothiazolin-3-ketone to the 5-chloro-2-methyl-4-isothiazolin-3-ketone is further preferably (1-3): (1-3).
Preferably, the cosolvent comprises at least one of propylene glycol, benzyl alcohol, ethanol, isobutanol, propylene glycol phenyl ether, dipropylene glycol methyl ether and ethylene glycol dimethyl ether.
In order to improve the compatibility of the antiviral agent with the finish, the cosolvent is preferably benzyl alcohol.
Preferably, the plasticizer comprises one of vaseline, rosin, chlorinated paraffin, dibutyl phthalate and dioctyl phthalate.
In order to reduce the irritation of the antiviral agent to the skin, the plasticizer is chlorinated paraffin, dibutyl phthalate.
Dibutyl phthalate can significantly reduce the irritation of antiviral agents, but it precipitates easily in the finish, resulting in a shorter duration of irritation-reducing time.
In order to improve the action effect of the plasticizer, the weight ratio of the chlorinated paraffin to the dibutyl phthalate is (2-5): 1.
as a preferred embodiment, the raw materials for preparing the skin embryo comprise: cooked leather, a tanning agent, a fatting agent and a second auxiliary agent.
The present invention is not particularly limited to hides, including but not limited to wet blue or wet white hides.
In a preferred embodiment, the tanning agent comprises at least one of a vegetable tanning agent, an aromatic sulfonic acid condensate, a phenolsulfonic acid condensate, a styrene maleic anhydride copolymer, and an acrylic resin.
Preferably, the tanning agent comprises a vegetable tanning agent, an aromatic sulfonic acid condensate and a phenol sulfonic acid condensate.
In a preferred embodiment, the fat-liquoring agent includes at least one of a vegetable fat-liquoring agent, an animal fat-liquoring agent, a mineral fat-liquoring agent, a synthetic fat-liquoring agent, a fat-liquoring complex agent and a phospholipid fat-liquoring agent.
Preferably, the fatliquor comprises synthetic fatliquor and phospholipid fatliquor.
As a preferred embodiment, the second auxiliary agent includes at least one of a second filler, a second solvent, a dye, and a pH adjuster.
Preferably, the second auxiliary agent comprises a second filler, a second solvent, a fixing agent, a dye and a pH regulator.
Preferably, the second filler comprises a protein filler.
The second solvent is not particularly limited in this invention, and includes, but is not limited to, water.
The present invention is not limited to any particular fixative, including but not limited to formic acid, modified glutaraldehyde.
The present invention is not particularly limited to dyes, including but not limited to acid dyes.
The present invention is not particularly limited to pH adjusting agents, including but not limited to baking soda.
As a preferred embodiment, the preparation method of the skin embryo comprises the following operations:
(1) according to the weight portion, the cooked leather is evenly shaved, weighed and transferred into a rotary drum, a second solvent with the weight 2-3 times of that of the cooked leather is added, the water temperature is 35-45 ℃, 0.05-0.2 portion of fixing agent is added, the speed is rotated for 50-80 minutes at 3.5rpm, the pH value is adjusted to 3.4-3.6, the water is washed for 5-20 minutes at normal temperature, after the water is drained, the second solvent with the weight 1-2 times of that of the cooked leather is continuously added, the system temperature is 25-35 ℃, 1-5 portions of fixing agent are added, the mixture is rotated for 150 minutes at 110 times, the pH value is neutralized to the pH value of 4.8-5.0, the water is washed for 5-20 minutes at normal temperature, after the water is drained, 40-60 portions of second solvent are continuously added, the second solvent is 25-35 ℃, 1-3 portions of fatting agent are added, and the rotation is carried out for 20-50 minutes.
(2) Adding 5-10 parts by weight of vegetable tanning agent, 1-3 parts by weight of amino resin, 1-3 parts by weight of aromatic sulfonic acid condensate, 2-8 parts by weight of phenol sulfonic acid condensate and 2-8 parts by weight of second filler, and rotating at 3.5rpm for 20-50 minutes;
(3) adding 1-5 parts of synthetic fatting agent and 3-8 parts of phospholipid fatting agent by weight, melting the synthetic fatting agent and the phospholipid fatting agent by hot water at 45-55 ℃ (1 part of the synthetic fatting agent and the phospholipid fatting agent and 4 parts of hot water), and rotating at 3.5rpm for 20-40 minutes;
(4) adding 5-8 parts by weight of vegetable tanning agent, 1-3 parts by weight of amino resin, 1-3 parts by weight of aromatic sulfonic acid condensate, 3-6 parts by weight of phenol sulfonic acid condensate and 3-6 parts by weight of second filler, and rotating at 3.5rpm for 80-100 minutes;
(5) adding acid dye, rotating for 200 and 260 minutes;
(6) adding 40-60 parts of water by weight, heating the water to 50-60 ℃, synthesizing fatting agent 1-3 parts, phospholipid fatting agent 4-8 parts, adding the fatting agent after melting with 45-55 ℃ hot water (adding four fatting agents in one part of water), and rotating for 80-100 minutes at 3.5 rpm;
(7) adding the fixing agent for fixing in three to four times, adjusting the pH value to 3.4-3.6 by the pH regulator after rotating at 3.5rpm for 150 minutes, and washing for 2 times with water at normal temperature, wherein each time lasts for 5-15 minutes;
(8) taking out, standing overnight, squeezing water, stretching, and vacuum drying;
(9) drying in the air, and controlling the humidity to be 12-14%.
(10) Dampening, vibrating and softening, milling, measuring and warehousing.
The second aspect of the present invention provides a method for preparing an antibacterial and coronavirus resistant automobile leather, comprising the following steps: (1) preparing a skin embryo; (2) preparing a coating layer on the surface of the leather blank in a way of primary coating, embossing, color layer and top coating, standing, and vibrating for softening to obtain the automobile leather.
Compared with the prior art, the invention has the following beneficial effects:
1. the prepared automobile leather has good wear resistance through the limitation of the raw materials for preparing the coating layer, and is wear-resistant for 3000 times without damage through test tests.
2. The automobile leather prepared by the invention has good thermal aging resistance through the limitation of a specific preparation process and preparation raw materials, and the gray scale card is 4-level after the thermal aging test of 500 hours at 90 ℃.
3. The automobile leather prepared by the method has high color fastness, is wet-wiped for 1000 times, and has a felt staining grade of 4.
4. The isothiazolinone antibacterial antiviral agent, cosolvent and plasticizer are mixed according to the weight ratio of (10-30): (10-30): (1-10) solves the problem that the leather is incompatible with antiviral agents in the prior art.
5. The preparation method comprises the following steps of (2-5) mixing chlorinated paraffin and dibutyl phthalate in a weight ratio: 1, the persistence and stability of the antiviral agent in a system are improved, and the precipitation of dibutyl phthalate on a coating layer is also inhibited.
Drawings
FIG. 1 is a report of the detection of antiviral properties of example 1.
Fig. 2 reports the bacteriostatic detection of example 1.
Detailed Description
The material information in the present invention is as follows:
the vegetable tanning agent is a tara extract available from Stewart Fine coatings (Suzhou) Inc. under the model of Granofin TA
Amino resins purchased from Smit & Zoon, model Safetan DD 001
Aromatic sulfonic acid condensates were purchased from Stahl Fine coatings (Suzhou) Ltd, and Tamol M phenolsulfonic acid condensates were purchased from TFL, and Sellan MBS
The natural animal protein mixture was purchased from Stewart Fine coatings (Suzhou) Inc. under the model termotan EF Liq
Synthetic fatting agents were purchased from Schill + Seilacher, model Lipsol FT 10
Phospholipid fatliquoring agents were purchased from Schill + Seilacher as Lipsol LQ
Special dye for acid dye purchased from Starter automobile leather
Aliphatic polyurethane styling resins were purchased from Stahl Fine coatings (Suzhou) Ltd, model RU22537
The aromatic binding resin was purchased from Stahl Fine coatings (Suzhou) Inc. under the model number of Stahl Fine coatings (Suzhou) Inc. and RU43961
Hand feel agent was purchased from Stahl Fine coatings (Suzhou) Inc. under model number HM183
The first filler was purchased from Steyr Fine coatings (Suzhou) Inc. under the model MelioMattpate C
Polycarbodiimide crosslinker was purchased from Starter Fine coatings (Suzhou) Inc. under model number XR13906
Self-crosslinking acrylic resins available from Stahl Fine coatings (Suzhou) Inc. under model number RA2312
Hydrolysis resistant polyurethanes were purchased from Steyr Fine coatings (Suzhou) Inc. under the model MelioPromul 95
The polycarbonate polyurethane matting agent was purchased from Sttalr Fine coatings (Suzhou) Inc. under the model WT13985
Aliphatic polyurethane matting agent was purchased from Starter Fine coatings (Suzhou) Inc. model WT13892
The isocyanate crosslinking agent was purchased from Sttalr Fine coatings (Suzhou) Inc. under model number XR5585
The polyether polyester polyurethane gloss enhancer was purchased from Sttalr Fine coatings (Suzhou) Inc. under model No. WT13486
Low coefficient of friction silicone-based hand feel agents are available from Sttalr Fine coatings (Suzhou) Inc. under the model number HM13377
Abrasion resistant macromolecular silicone-based hand feel agent purchased from Stahl Fine coatings (Suzhou) Inc. under the model number HM21720
5-chloro-2-methyl-4-isothiazolin-3-one CAS number: 26172-55-4
2-n-octyl-4-isothiazolin-3-one CAS number: 26530-20-1,
the chlorinated paraffin is purchased from Jiangsu Sendai chemical engineering Co., Ltd, and has a model of chlorinated paraffin-52
Example 1
The first aspect of the embodiment provides an antibacterial and coronavirus-resistant automobile leather, which comprises a leather blank and a coating layer.
The raw materials for preparing the skin embryo comprise: cooked leather, a tanning agent, a fatting agent and a second auxiliary agent.
The second auxiliary agent comprises a second filler, a second solvent, a fixing agent, a dye and a pH regulator.
The preparation raw materials of the coating layer comprise: resin, antiviral agent, cross-linking agent and first auxiliary agent.
The first auxiliary agent comprises a first filler, a hand feeling agent, a pigment, a first solvent, a delustering agent and a brightener.
The preparation method of the skin embryo comprises the following operations:
(1) according to the weight portion, the cooked skin is evenly shaved, weighed and transferred into a rotary drum, a second solvent with the weight 2.5 times of that of the cooked skin is added, the water temperature is 40 ℃, 0.1 portion of fixing agent is added, the speed is 3.5rpm and is transferred for 60 minutes, a pH regulator is added to adjust the pH value to 3.5, the water is washed for 10 minutes at normal temperature, after water drainage, the second solvent with the weight 1.5 times of that of the cooked skin is continuously added, the water temperature is 30 ℃, 2 portions of fixing agent are added, the speed is 3.5rpm and is rotated for 120 minutes, the pH regulator is added to neutralize the pH value to 4.9, the water is washed for 10 minutes at normal temperature, after water drainage, the second solvent with the weight 0.5 time of the cooked skin is continuously added, the water temperature is 30 ℃, 2 portions of fatting agent are added, and the water is rotated for 30 minutes.
The second solvent is water.
The fatting agent is a mixture of a synthetic fatting agent and a phospholipid fatting agent in a weight ratio of 2: 5.
(2) Adding 6 parts by weight of vegetable tanning agent, 2 parts by weight of amino resin, 2 parts by weight of aromatic sulfonic acid condensate, 4 parts by weight of phenol sulfonic acid condensate and 4 parts by weight of second filler, and rotating at 3.5rpm for 30 minutes;
the second filler is a natural animal protein mixture.
(3) Adding 2 parts of synthetic fatting agent and 5 parts of phospholipid fatting agent by weight, melting and adding the synthetic fatting agent and the phospholipid fatting agent by using hot water at 50 ℃ (the total amount of the synthetic fatting agent and the phospholipid fatting agent is 1 part, and the hot water is 4 parts), and rotating at 3.5rpm for 30 minutes;
the synthetic fat liquor and the phospholipid fat liquor are both conventional names in the field, and the detailed information is shown in a purchasing manufacturer.
(4) Adding 6 parts by weight of vegetable tanning agent, 2 parts by weight of amino resin, 2 parts by weight of aromatic sulfonic acid condensate, 4 parts by weight of phenol sulfonic acid condensate and 4 parts by weight of second filler, and rotating at 3.5rpm for 90 minutes;
the second filler is a natural animal protein mixture.
(5) Adding 3 parts of acid dye, and rotating at 3.5rpm for 240 minutes;
(6) adding 50 parts of water by weight, keeping the water temperature at 55 ℃, synthesizing 2 parts of fat liquor, and 5 parts of phospholipid fat liquor, dissolving the fat liquor by 50 ℃ hot water, dissolving the fat liquor by four parts of fat liquor, and rotating the mixture for 90 minutes at 3.5 rpm;
(7) adding 1 part of fixing agent for fixing in three to four times, adjusting the pH to 3.5 by using a pH regulator after rotating at 3.5rpm for 120 minutes, and washing for 2 times with water at normal temperature for 10 minutes each time;
the pH regulator is baking soda.
The fixing agent is formic acid.
(8) Taking out, standing overnight, squeezing water, stretching, and vacuum drying;
(9) and (5) hanging, airing and drying, and controlling the humidity to be 13%.
(10) Dampening, vibrating and softening, milling, measuring and warehousing.
The preparation method of the coating layer comprises the following operations of:
(1) priming coating: according to the parts by weight, 40 parts of aliphatic polyurethane setting resin, 15 parts of aromatic bonding resin, 2 parts of hand feeling agent, 25 parts of first filler, 13 parts of pigment, 3 parts of polycarbodiimide crosslinking agent and 2 parts of water are adjusted to 23 seconds by using a No. 6 Ford cup consistency; and finishing the base coat 15 hours after adding the polycarbodiimide crosslinking agent, wherein the wet weight of the base coat is 11 g/sf. Drying in a drying tunnel at 120 deg.C for 15 m, standing at a drying speed of 9m/min for 15h, and embossing;
(2) color layer: according to parts by weight, 15 parts of water, 10 parts of aliphatic polyurethane forming resin, 10 parts of self-crosslinking acrylic resin, 10 parts of hydrolysis-resistant polyurethane, 20 parts of polycarbonate polyurethane flatting agent, 15 parts of aliphatic polyurethane flatting agent, 13 parts of pigment and 7 parts of isocyanate crosslinking agent. Adjust consistency to 30 seconds with a number 4 ford cup; and finishing the color layer 1.5 hours after the aliphatic polyurethane crosslinking agent is added, wherein the wet weight of the coloring amount is 3.5 g/sf. Drying in a drying tunnel at 120 deg.C for 15 m at 9m/min, and standing for 5 hr;
(3) top coating: according to parts by weight, 17 parts of water, 30 parts of polycarbonate polyurethane flatting agent, 20 parts of aliphatic polyurethane flatting agent, 5 parts of polyether polyester polyurethane brightening agent, 5 parts of antiviral agent, 4 parts of low-friction coefficient silicon hand feeling agent, 6 parts of abrasion-resistant macromolecular silicon hand feeling agent, 4 parts of pigment and 9 parts of isocyanate crosslinking agent. And finishing top coating 1.5 hours after the isocyanate crosslinking agent is added, wherein the wet weight of the top coating is 3 g/sf. Drying in a drying tunnel at 120 deg.C for 15 m, drying at 9m/min for 40h, repeating the top coating step again, and standing for 40 h;
(4) and (6) vibrating to soften, and putting the measuring tape into a warehouse.
The solid content of the aliphatic polyurethane shaping resin is 30-35%.
The preparation raw materials of the antiviral agent comprise isothiazolinone antibacterial antiviral agents, cosolvent and plasticizer, wherein the weight ratio of the isothiazolinone antibacterial antiviral agents to the plasticizer is 20: 25: 3, compounding.
The isothiazolinone antibacterial and antiviral agent is 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and the weight ratio of the isothiazolinone antibacterial and antiviral agent to the isothiazolinone antibacterial and antiviral agent is 1: 2, compounding.
The cosolvent is benzyl alcohol.
The plasticizer is chlorinated paraffin and dibutyl phthalate, and the weight ratio of the chlorinated paraffin to the dibutyl phthalate is 4: 1, compounding.
In a second aspect, this embodiment provides a method for preparing an antibacterial and coronavirus-resistant automobile leather, comprising the following steps: (1) preparing a skin embryo; (2) preparing a coating layer on the surface of the leather blank in a way of primary coating, embossing and top coating, standing, and vibrating for softening to obtain the automobile leather.
Comparative example 1
The first aspect of the present comparative example provides an antibacterial and coronavirus-resistant automobile leather, which is prepared in the same manner as in example 1, except that the antiviral agent is prepared from isothiazolinone antibacterial and antiviral agents, and the cosolvent is 20: 15 are compounded.
In a second aspect of this comparative example, a process for the preparation of an antibacterial, anti-coronavirus auto leather is provided, the specific embodiment being the same as in example 1.
Comparative example 2
The first aspect of this comparative example provides an antibacterial, coronavirus resistant automotive leather, and the specific embodiment is the same as example 1, except that the plasticizer is dibutyl phthalate.
In a second aspect of this comparative example, a process for the preparation of an antibacterial, anti-coronavirus auto leather is provided, the specific embodiment being the same as in example 1.
Comparative example 3
The first aspect of the present comparative example provides an antibacterial and coronavirus-resistant automobile leather, which is prepared in the same manner as in example 1, except that the antiviral agent is prepared from an isothiazolinone antibacterial and antiviral agent, a nonionic surfactant, and a film-forming agent in a weight ratio of 15: 45: 73 are compounded.
The nonionic surfactant is long-chain fatty alcohol-polyoxyethylene ether which is purchased from Jinjunteng chemical Co., Ltd, and the type of the nonionic surfactant is AEO-9.
The film former was purchased from EASTMAN, model GVE.
In a second aspect of this comparative example, a process for the preparation of an antibacterial, anti-coronavirus auto leather is provided, the specific embodiment being the same as in example 1.
Performance testing
Anti-coronavirus testing: as shown in fig. 1, the automotive leathers prepared in example 1 were tested as test specimens with a size of 10cm by 10cm with reference to ISO 21702-2019. The adopted coronavirus strain is GX-P2V MDCK cell, is separated from pangolin, has homology of more than 90% with the amino acid sequence of the new coronavirus and has homology of 92.2% with S protein. The control was prepared without the antiviral agent from the starting material of example 1.
lgTCID50/cm2The log of viral titers after inoculation and incubation of the samples.
And (3) testing the bacteriostatic activity: as shown in fig. 2, the automobile leather prepared in example 1 was tested as a test sample with a size of 10cm x 10cm, and tested species were e.coli and s.aureus, with reference to ISO 22196.
Antibacterial ratio (E.coli)% | Antibacterial ratio (Staphylococcus aureus)% | |
Example 1 | 99.9 | >99.9 |
The automobile leathers prepared in examples and comparative examples were subjected to the following tests, and the test specimens were each 10cm by 10 cm.
Wear resistance: adopting a Taber abrasion tester, wherein the model of the grinding wheel is CS10, the weight is 1000g, the friction is 3000 times, the leather surface is not damaged after 3000 times of friction is 5 grades, and the damaged area of the leather surface is less than 1mm2Is 4 grade, and the surface damage area of the leather is more than or equal to 1mm2Less than 4mm2Is 3 grade, and the surface damage area of the leather is more than or equal to 4mm2Less than 9mm2Is 2 grade, and the surface damage area of the leather is more than or equal to 9mm2Is grade 1.
Thermal aging resistance: the samples were placed in an oven at 90 ℃ for 500 hours and tested for gray card rating, according to DIN EN 20105-A02.
Color fastness: and (5) wet wiping the surface of the sample for 1000 times by using a wet felt, and testing the staining grade of the felt. The reference standards are DIN EN ISO 11640, DIN EN 20105-A03.
Claims (10)
1. The antibacterial and coronavirus-resistant automobile leather is characterized by comprising a leather blank and a coating layer; the preparation raw materials of the coating layer comprise: resin, antiviral agent, cross-linking agent and first auxiliary agent.
2. The antibacterial and coronavirus resistant automobile leather of claim 1, wherein the resin comprises at least one of acrylic resin, polyurethane resin, aromatic binding resin and polishing resin.
3. The antibacterial and coronavirus resistant automobile leather according to any one of claims 1-2, wherein the cross-linking agent comprises at least one of an isocyanate cross-linking agent, a polyisocyanate cross-linking agent, a polyol cross-linking agent, a glycidyl ether cross-linking agent, a benzenesulfonic acid cross-linking agent and a polycarbodiimide cross-linking agent.
4. The antibacterial and coronavirus resistant automobile leather of any one of claims 1-3, wherein the first auxiliary agent comprises at least one of a first filler, a hand feeling agent, a pigment, a first solvent, a delustering agent and a brightener.
5. The antibacterial and coronavirus automobile leather as claimed in any one of claims 1-4, wherein the leather embryo is prepared from the following raw materials: cooked leather, a tanning agent, a fatting agent and a second auxiliary agent.
6. The antibacterial and coronavirus resistant automobile leather according to claim 5, wherein the tanning agent comprises at least one of a plant tanning agent, an aromatic sulfonic acid condensate, a phenol sulfonic acid condensate, a styrene maleic anhydride copolymer and an acrylic resin.
7. The antibacterial and coronavirus resistant automotive leather of any one of claims 5-6, wherein the fatliquoring agent comprises at least one of a vegetable fat fatliquoring agent, an animal fat fatliquoring agent, a mineral fat fatliquoring agent, a synthetic fatliquoring agent, a compound fatliquoring agent and a phospholipid fatliquoring agent.
8. The antibacterial and coronavirus resistant automobile leather as claimed in any one of claims 5-7, wherein the second auxiliary agent comprises at least one of a second filler, a second solvent, a dye and a pH regulator.
9. An antibacterial and anti-coronavirus automotive leather as claimed in any one of claims 5-8, wherein the second filler comprises a protein filler.
10. A method for preparing the antibacterial and anti-coronavirus automobile leather according to claims 5-9, wherein the method comprises the following steps: (1) preparing a skin embryo; (2) preparing a coating layer on the surface of the leather blank in a way of primary coating, embossing, color layer and top coating, standing, and vibrating for softening to obtain the automobile leather.
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JP2019112510A (en) * | 2017-12-22 | 2019-07-11 | 明成化学工業株式会社 | Crosslinking agent for fiber or leather, treatment agent and structure |
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