CN112537107A - High-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and production method thereof - Google Patents
High-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and production method thereof Download PDFInfo
- Publication number
- CN112537107A CN112537107A CN202011419283.5A CN202011419283A CN112537107A CN 112537107 A CN112537107 A CN 112537107A CN 202011419283 A CN202011419283 A CN 202011419283A CN 112537107 A CN112537107 A CN 112537107A
- Authority
- CN
- China
- Prior art keywords
- styrene
- block copolymer
- synthetic leather
- butadiene block
- fiber synthetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002649 leather substitute Substances 0.000 title claims abstract description 101
- 239000000835 fiber Substances 0.000 title claims abstract description 97
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 85
- 238000003490 calendering Methods 0.000 claims abstract description 49
- 239000004744 fabric Substances 0.000 claims abstract description 48
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 26
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 26
- 238000013329 compounding Methods 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 239000004088 foaming agent Substances 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 150000008301 phosphite esters Chemical class 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229920001410 Microfiber Polymers 0.000 claims 6
- 239000002174 Styrene-butadiene Substances 0.000 claims 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims 1
- 239000003658 microfiber Substances 0.000 claims 1
- 239000011115 styrene butadiene Substances 0.000 claims 1
- 238000000889 atomisation Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 95
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 95
- 238000002360 preparation method Methods 0.000 description 13
- 229920001971 elastomer Polymers 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000005060 rubber Substances 0.000 description 12
- 239000010985 leather Substances 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and a production method thereof, and relates to the technical field of superfine fiber synthetic leather. The invention adopts four-roller calendering, thermoplastic compounding and vacuum grain-absorbing technology to directly compound a styrene-butadiene block copolymer film on the superfine fiber synthetic leather base cloth, and then forms patterns on the surface of the styrene-butadiene block copolymer through the vacuum grain-absorbing technology to obtain the high-performance styrene-butadiene block copolymer based superfine fiber synthetic leather. The production process of the high-performance SBS superfine fiber synthetic leather is clean and environment-friendly, soft and full in hand feeling, fine and vivid in surface texture, small in atomization value of 4mg, small in smell of 3 grades, high in surface wear resistance of 4 grades, capable of being used as a vamp material, good in bonding strength with an SBS injection molding sole, capable of producing high-performance anti-skidding sports shoes and capable of being used as an environment-friendly skin material of an automobile seat.
Description
Technical Field
The invention belongs to the technical field of superfine fiber synthetic leather, and relates to high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and a production method thereof.
Background
Because the raw leather resources for producing the natural leather are limited, and the production of the natural leather is a process with high energy consumption and high pollution, the production method can bring great pollution load to the environment. In recent years, new standards have been proposed for the safety of natural leather itself, and toxic chemicals such as Cr (vi), azo dyes, pentachlorophenol (PCP), and free formaldehyde, which are present in natural leather, are strictly limited. The production and use of natural leather face significant challenges from the standpoint of hide resources, environmental protection, product safety, and the market.
For the above reasons, development of new materials to replace natural leather is accelerated in all countries of the world. Wherein the development of the superfine fiber synthetic leather can be regarded as a model of the mutual combination of new materials. The superfine fiber synthetic leather is prepared by using superfine fiber non-woven as a base material, soaking polyurethane slurry with an open pore structure and processing through a series of complex processes. The superfine fiber has nanometer size and great specific surface area, and is similar to the fascicular collagen fiber in natural leather, and has physical performance similar to that of natural leather.
However, the continuous decline of the leather industry has been inevitable due to the shortage of raw hides and environmental pollution problems. Therefore, the high-performance superfine fiber synthetic leather is applied.
At present, superfine fiber synthetic leather is gradually applied to various fields, a sports shoe material is one of the largest application fields of the superfine fiber synthetic leather, particularly, in recent years, antiskid high-grade sports shoes adopt styrene-butadiene block copolymer (SBS) to inject soles, and the existing superfine fiber synthetic leather with polyurethane surface is difficult to adhere to the SBS soles, so that the bottleneck technical problem is formed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and a production method thereof, and solves the problem that the existing polyurethane-surfaced superfine fiber synthetic leather is difficult to be effectively bonded with styrene-butadiene block copolymer-based materials.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather, which comprises the following components in percentage by weight: the composite fabric comprises a styrene-butadiene block copolymer film and superfine fiber synthetic leather base cloth, wherein the styrene-butadiene block copolymer film is compounded with the superfine fiber synthetic leather base cloth, and the styrene-butadiene block copolymer film has surface textures.
Preferably, the thickness of the styrene-butadiene block copolymer film is 0.08mm to 1.2 mm.
Preferably, the superfine fiber synthetic leather base cloth is island-shaped superfine fiber synthetic leather base cloth, non-island shaped superfine fiber synthetic leather base cloth or orange petal shaped superfine fiber synthetic leather base cloth.
The invention also discloses a production method of the high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather, which comprises the following steps: the styrene-butadiene block copolymer film is compounded and attached to the superfine fiber synthetic leather base cloth by adopting thermoplastic compounding treatment, and the surface of the styrene-butadiene block copolymer film forms textures by adopting vacuum grain absorption treatment, so that the high-performance styrene-butadiene block copolymer based superfine fiber synthetic leather is obtained.
Preferably, the styrene-butadiene block copolymer film is prepared by calendering and film forming, and specifically comprises the following operations:
a four-roll calendering production line is adopted, the calendered material of the styrene-butadiene block copolymer is preheated in a high-speed kneader, then is internally mixed in an internal mixer, and is plasticated in a plasticating machine to obtain sizing material, and the obtained sizing material is processed by a four-roll calender to obtain the styrene-butadiene block copolymer film.
Further preferably, the formulation of the calendered styrene-butadiene block copolymer material is: the adhesive comprises, by mass, 50-80 parts of a styrene-butadiene block copolymer, 1-5 parts of a toner, 0.2-1.8 parts of an AC foaming agent, 5-15 parts of No. 10 white oil, 1-2.5 parts of stearic acid, 1-3 parts of titanium dioxide and 0.1-0.2 part of tetrol phosphite ester.
Further preferably, the preheating temperature is 70-80 ℃, and the preheating time is 5-10 min.
Further preferably, the banburying temperature is 140-180 ℃, and the banburying time is 2-5 min; the plasticating temperature is 160-190 ℃, and the plasticating time is 5-10 min.
More preferably, the rolling temperature is 150 ℃ to 180 ℃, and the rolling thickness is 0.08mm to 1.2 mm.
Preferably, the clearance of the thermoplastic composite treatment is 50 to 70 percent of the sum of the thicknesses of the styrene-butadiene block copolymer film and the superfine fiber synthetic leather base cloth, and the pressure is 4 to 5kg/cm2。
Preferably, the temperature of the vacuum suction line treatment is 160-190 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather, which is prepared by compounding and attaching a styrene-butadiene block copolymer film with surface textures and a fine fiber synthetic leather base cloth styrene-butadiene block copolymer (SBS) film, and effectively solves the problem that the existing polyurethane-made superfine fiber synthetic leather is difficult to be effectively bonded with the styrene-butadiene block copolymer because the styrene-butadiene block copolymer film and the existing styrene-butadiene block copolymer-based product have the same main chain structure composition and high compatibility. The high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather prepared by the invention has soft and full hand feeling, fine and vivid surface texture, and the atomization value is less than 4mg, the smell is less than 3 grades, the surface wear resistance is more than 4 grades, and the synthetic leather can be used as a vamp material; meanwhile, the high-performance anti-skid sports shoe can be used for producing high-performance anti-skid sports shoes and can also be used as an environment-friendly skin material of an automobile seat because the high-performance anti-skid sports shoe has good bonding strength with the existing SBS injection molded sole.
The invention also discloses a production method of the high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather, which directly compounds a styrene-butadiene block copolymer (SBS) film on superfine fiber synthetic leather base cloth by adopting a thermoplastic compound treatment process technology to realize the compound lamination of the styrene-butadiene block copolymer film and the superfine fiber synthetic leather base cloth, and forms patterns on the surface of the styrene-butadiene block copolymer film by adopting a vacuum pattern absorption treatment process technology. Therefore, the production method of the high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather has the advantages of clean and environment-friendly production process.
Furthermore, the invention realizes the rolling preparation of the styrene-butadiene block copolymer film by adopting the process technology of a four-roller rolling production line; in addition, the four-roller calendering equipment, the thermoplastic composite laminating equipment and the vacuum grain sucking equipment are connected in series, so that continuous production can be realized.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The present invention will be described in detail with reference to the following specific examples:
example 1
1) Preparation of styrene-butadiene Block copolymer (SBS) calendered Material
Weighing 50 parts of SBS, 1 part of toner, 0.2 part of AC foaming agent, 5 parts of No. 10 white oil, 1 part of stearic acid, 1 part of titanium dioxide and 0.1 part of tetrol phosphite ester by mass parts, and mixing to obtain the SBS calendering material.
2) Preparation of high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather
Rolling to form a film: putting the SBS calendered material obtained in the step 1) into a high-speed kneader and stirring for 5min, obtaining a preheated material after the temperature of the obtained SBS calendered material reaches 70 ℃, putting the preheated material into an internal mixer, gradually raising the temperature, internally mixing for 2min at 140 ℃, then putting the material into a plasticator, gradually raising the temperature, plasticating for 5min at 160 ℃ to obtain a rubber material, putting the rubber material into a four-roll calender, controlling the calendering temperature to be 150 ℃, and calendering the thickness to be 0.08 mm; obtaining an SBS film;
thermoplastic compounding: directly attaching the pressed SBS film to the island-shaped superfine fiber synthetic leather base cloth in a thermoplastic state at a fourth roller of a four-roller calender to obtain an SBS superfine fiber synthetic leather base cloth composite material;
wherein the clearance of the thermoplastic composite treatment is 50 percent of the sum of the thicknesses of the styrene-butadiene block copolymer film and the island type superfine fiber synthetic leather base cloth, and the pressure is 4kg/cm2；
③ vacuum suction texturing: and (3) enabling the SBS superfine fiber synthetic leather base cloth composite material to pass through a vacuum grain sucking machine to form patterns on the surface of the SBS film, wherein the temperature of vacuum grain sucking treatment is 160 ℃, and thus obtaining the high-performance styrene-butadiene block copolymer (SBS) base superfine fiber synthetic leather.
The high-performance styrene-butadiene block copolymer (SBS) based superfine fiber synthetic leather prepared by the embodiment has soft and full hand feeling, fine and vivid surface texture, atomization value of less than 4mg, smell of less than 3 grades and surface wear resistance of more than 4 grades, can be used as a vamp material, has good bonding strength with an SBS injection molded sole, can be used for producing high-performance anti-skid sports shoes, and can also be used as an environment-friendly skin material of an automobile seat.
Example 2
1) Preparation of styrene-butadiene Block copolymer (SBS) calendered Material
Weighing 80 parts of SBS, 5 parts of toner, 1.8 parts of AC foaming agent, 15 parts of No. 10 white oil, 2.5 parts of stearic acid, 3 parts of titanium dioxide and 0.2 part of tetrol phosphite ester by mass parts, and mixing to obtain the SBS calendering material.
2) Preparation of high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather
Rolling to form a film: putting the SBS calendered material obtained in the step 1) into a high-speed kneader and stirring for 10min, obtaining a preheated material after the temperature of the obtained SBS calendered material reaches 80 ℃, putting the preheated material into an internal mixer, gradually increasing the temperature, internally mixing for 5min at 180 ℃, then putting the material into a plasticator, gradually increasing the temperature, plasticating for 10min at 190 ℃ to obtain a rubber material, putting the rubber material into a four-roll calender, controlling the calendering temperature to be 180 ℃ and the calendering thickness to be 1.2 mm; obtaining an SBS film;
thermoplastic compounding: directly attaching the pressed SBS film to the non-island type superfine fiber synthetic leather base cloth in a thermoplastic state at a fourth roller of a four-roller calender to obtain an SBS superfine fiber synthetic leather base cloth composite material;
wherein the clearance of the thermoplastic composite treatment is 70 percent of the sum of the thicknesses of the styrene-butadiene block copolymer film and the non-figured superfine fiber synthetic leather base cloth, and the pressure is 5kg/cm2；
③ vacuum suction texturing: and (3) enabling the SBS superfine fiber synthetic leather base cloth composite material to pass through a vacuum grain sucking machine to form patterns on the surface of the SBS film, wherein the temperature of vacuum grain sucking treatment is 190 ℃, and obtaining the high-performance styrene-butadiene block copolymer (SBS) base superfine fiber synthetic leather.
The high-performance styrene-butadiene block copolymer (SBS) based superfine fiber synthetic leather prepared by the embodiment has soft and full hand feeling, fine and vivid surface texture, atomization value of less than 4mg, smell of less than 3 grades and surface wear resistance of more than 4 grades, can be used as a vamp material, has good bonding strength with an SBS injection molded sole, can be used for producing high-performance anti-skid sports shoes, and can also be used as an environment-friendly skin material of an automobile seat.
Example 3
1) Preparation of styrene-butadiene Block copolymer (SBS) calendered Material
Weighing 70 parts of SBS, 3 parts of toner, 0.7 part of AC foaming agent, 10 parts of No. 10 white oil, 1.8 parts of stearic acid, 1.5 parts of titanium dioxide and 0.16 part of tetrol phosphite ester by mass parts, and mixing to obtain the SBS calendering material.
2) Preparation of high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather
Rolling to form a film: putting the SBS calendered material obtained in the step 1) into a high-speed kneader and stirring for 7min, obtaining a preheated material after the temperature of the obtained SBS calendered material reaches 73 ℃, putting the preheated material into an internal mixer, gradually increasing the temperature, internally mixing for 3min at 165 ℃, then putting the material into a plasticator, gradually increasing the temperature, plasticating for 8min at 180 ℃ to obtain a rubber material, putting the rubber material into a four-roll calender, controlling the calendering temperature to be 175 ℃, and the calendering thickness to be 0.09 mm; obtaining an SBS film;
thermoplastic compounding: directly attaching the pressed SBS film to orange petal type superfine fiber synthetic leather base cloth in a thermoplastic state at a fourth roller of a four-roller calender to obtain an SBS superfine fiber synthetic leather base cloth composite material;
wherein the clearance of the thermoplastic composite treatment is 60 percent of the sum of the thicknesses of the styrene-butadiene block copolymer film and the orange petal type superfine fiber synthetic leather base cloth, and the pressure is 4.6kg/cm2；
③ vacuum suction texturing: and (3) enabling the SBS superfine fiber synthetic leather base cloth composite material to pass through a vacuum grain sucking machine to form patterns on the surface of the SBS film, wherein the temperature of vacuum grain sucking treatment is 183 ℃, and obtaining the high-performance styrene-butadiene block copolymer (SBS) base superfine fiber synthetic leather.
The high-performance styrene-butadiene block copolymer (SBS) based superfine fiber synthetic leather prepared by the embodiment has soft and full hand feeling, fine and vivid surface texture, atomization value of less than 4mg, smell of less than 3 grades and surface wear resistance of more than 4 grades, can be used as a vamp material, has good bonding strength with an SBS injection molded sole, can be used for producing high-performance anti-skid sports shoes, and can also be used as an environment-friendly skin material of an automobile seat.
Example 4
1) Preparation of styrene-butadiene Block copolymer (SBS) calendered Material
Weighing 63 parts of SBS, 2 parts of toner, 1.1 parts of AC foaming agent, 12 parts of No. 10 white oil, 1.7 parts of stearic acid, 2 parts of titanium dioxide and 0.18 part of tetrol phosphite ester by mass parts, and mixing to obtain the SBS calendering material.
2) Preparation of high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather
Rolling to form a film: putting the SBS calendered material obtained in the step 1) into a high-speed kneader and stirring for 9min, obtaining a preheated material after the temperature of the obtained SBS calendered material reaches 78 ℃, putting the preheated material into an internal mixer, gradually increasing the temperature, internally mixing for 4min at 150 ℃, then putting the material into a plasticator, gradually increasing the temperature, plasticating for 7min at 170 ℃ to obtain a rubber material, putting the rubber material into a four-roll calender, controlling the calendering temperature to be 160 ℃, and calendering the thickness to be 1.1 mm; obtaining an SBS film;
thermoplastic compounding: directly attaching the pressed SBS film to the island-shaped superfine fiber synthetic leather base cloth in a thermoplastic state at a fourth roller of a four-roller calender to obtain an SBS superfine fiber synthetic leather base cloth composite material;
wherein the clearance of the thermoplastic composite treatment is 55 percent of the sum of the thicknesses of the styrene-butadiene block copolymer film and the island-shaped superfine fiber synthetic leather base cloth, and the pressure is 4.2kg/cm2；
③ vacuum suction texturing: and (3) enabling the SBS superfine fiber synthetic leather base cloth composite material to pass through a vacuum grain sucking machine to form patterns on the surface of the SBS film, wherein the temperature of vacuum grain sucking treatment is 168 ℃, and thus obtaining the high-performance styrene-butadiene block copolymer (SBS) base superfine fiber synthetic leather.
The high-performance styrene-butadiene block copolymer (SBS) based superfine fiber synthetic leather prepared by the embodiment has soft and full hand feeling, fine and vivid surface texture, atomization value of less than 4mg, smell of less than 3 grades and surface wear resistance of more than 4 grades, can be used as a vamp material, has good bonding strength with an SBS injection molded sole, can be used for producing high-performance anti-skid sports shoes, and can also be used as an environment-friendly skin material of an automobile seat.
Example 5
1) Preparation of styrene-butadiene Block copolymer (SBS) calendered Material
Weighing 75 parts of SBS, 4 parts of toner, 0.4 part of AC foaming agent, 8.5 parts of No. 10 white oil, 1.3 parts of stearic acid, 2.2 parts of titanium dioxide and 0.13 part of tetrol phosphite ester by mass parts, and mixing to obtain the SBS calendering material.
2) Preparation of high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather
Rolling to form a film: putting the SBS calendered material obtained in the step 1) into a high-speed kneader and stirring for 8min, obtaining a preheated material after the temperature of the obtained SBS calendered material reaches 76 ℃, putting the preheated material into an internal mixer, gradually raising the temperature, internally mixing for 3min at 172 ℃, then putting the material into a plasticator, gradually raising the temperature, plasticating for 8min at 162 ℃ to obtain a rubber material, putting the rubber material into a four-roll calender, controlling the calendering temperature to be 155 ℃, and calendering the thickness to be 1.13 mm; obtaining an SBS film;
thermoplastic compounding: directly attaching the pressed SBS film to the non-island type superfine fiber synthetic leather base cloth in a thermoplastic state at a fourth roller of a four-roller calender to obtain an SBS superfine fiber synthetic leather base cloth composite material;
wherein the clearance of the thermoplastic composite treatment is 65 percent of the sum of the thicknesses of the styrene-butadiene block copolymer film and the non-figured superfine fiber synthetic leather base cloth, and the pressure is 5kg/cm2；
③ vacuum suction texturing: and (3) enabling the SBS superfine fiber synthetic leather base cloth composite material to pass through a vacuum grain sucking machine to form patterns on the surface of the SBS film, wherein the temperature of vacuum grain sucking treatment is 175 ℃, and thus obtaining the high-performance styrene-butadiene block copolymer (SBS) base superfine fiber synthetic leather.
The high-performance styrene-butadiene block copolymer (SBS) based superfine fiber synthetic leather prepared by the embodiment has soft and full hand feeling, fine and vivid surface texture, atomization value of less than 4mg, smell of less than 3 grades and surface wear resistance of more than 4 grades, can be used as a vamp material, has good bonding strength with an SBS injection molded sole, can be used for producing high-performance anti-skid sports shoes, and can also be used as an environment-friendly skin material of an automobile seat.
Example 6
1) Preparation of styrene-butadiene Block copolymer (SBS) calendered Material
Weighing 55 parts of SBS, 1.5 parts of toner, 0.6 part of AC foaming agent, 6.9 parts of No. 10 white oil, 1.4 parts of stearic acid, 2.2 parts of titanium dioxide and 0.12 part of tetrol phosphite ester by mass parts, and mixing to obtain the SBS calendering material.
2) Preparation of high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather
Rolling to form a film: putting the SBS calendered material obtained in the step 1) into a high-speed kneader and stirring for 6min, obtaining a preheated material after the temperature of the obtained SBS calendered material reaches 72 ℃, putting the preheated material into an internal mixer, gradually increasing the temperature, internally mixing for 5min at 143 ℃, then putting the preheated material into a plasticator, gradually increasing the temperature, plasticating for 10min at 163 ℃ to obtain a rubber material, putting the rubber material into a four-roll calender, controlling the calendering temperature to be 152 ℃, and calendering the thickness to be 1.17 mm; obtaining an SBS film;
thermoplastic compounding: directly attaching the pressed SBS film to orange petal type superfine fiber synthetic leather base cloth in a thermoplastic state at a fourth roller of a four-roller calender to obtain an SBS superfine fiber synthetic leather base cloth composite material;
wherein the clearance of the thermoplastic composite treatment is 65 percent of the sum of the thicknesses of the styrene-butadiene block copolymer film and the orange petal type superfine fiber synthetic leather base cloth, and the pressure is 4.5kg/cm2；
③ vacuum suction texturing: and (3) enabling the SBS superfine fiber synthetic leather base cloth composite material to pass through a vacuum grain sucking machine to form patterns on the surface of the SBS film, wherein the temperature of vacuum grain sucking treatment is 172 ℃, and thus obtaining the high-performance styrene-butadiene block copolymer (SBS) base superfine fiber synthetic leather.
The high-performance styrene-butadiene block copolymer (SBS) based superfine fiber synthetic leather prepared by the embodiment has soft and full hand feeling, fine and vivid surface texture, atomization value of less than 4mg, smell of less than 3 grades and surface wear resistance of more than 4 grades, can be used as a vamp material, has good bonding strength with an SBS injection molded sole, can be used for producing high-performance anti-skid sports shoes, and can also be used as an environment-friendly skin material of an automobile seat.
In conclusion, the invention relates to the technical field of superfine fiber synthetic leather, and particularly relates to high-performance SBS (styrene butadiene styrene) based superfine fiber synthetic leather and a production method thereof. The invention relates to high-performance SBS (styrene butadiene styrene) superfine fiber synthetic leather, which is a flexible composite material with a two-layer composite structure, wherein the upper layer is a styrene-butadiene block copolymer (SBS) film for short, and the lower layer is superfine fiber synthetic leather base cloth. The production method adopts four-roller calendering, thermoplastic compounding and vacuum grain-absorbing technology, directly compounds a styrene-butadiene block copolymer (SBS) film on the superfine fiber synthetic leather base cloth, and forms patterns on the surface of SBS through the vacuum grain-absorbing technology, thus obtaining the high-performance SBS superfine fiber synthetic leather. The production process of the high-performance SBS-based superfine fiber synthetic leather is clean and environment-friendly, the hand feeling is soft and full, the surface texture is fine and vivid, the atomization value is less than 4mg, the smell is less than 3 grades, the surface wear resistance is more than 4 grades, and the high-performance SBS-based superfine fiber synthetic leather can be used as a vamp material and has good adhesive strength with an SBS injection molded sole, so that the high-performance SBS-based superfine fiber synthetic leather can be used for producing high-performance anti-skidding sports shoes and can also be used as an environment-friendly skin material of.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather is characterized by comprising: the composite fabric comprises a styrene-butadiene block copolymer film and superfine fiber synthetic leather base cloth, wherein the styrene-butadiene block copolymer film is compounded with the superfine fiber synthetic leather base cloth, and the styrene-butadiene block copolymer film has surface textures.
2. The high-performance styrene-butadiene block copolymer-based microfiber synthetic leather according to claim 1, wherein the thickness of the styrene-butadiene block copolymer film is 0.08mm to 1.2 mm.
3. The high-performance styrene-butadiene block copolymer-based ultrafine fiber synthetic leather according to claim 1, wherein the ultrafine fiber synthetic leather base cloth is island-fixed ultrafine fiber synthetic leather base cloth, non-island-fixed ultrafine fiber synthetic leather base cloth or orange-petal type ultrafine fiber synthetic leather base cloth.
4. A production method of high-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather is characterized by comprising the following steps: the styrene-butadiene block copolymer film is compounded and attached to the superfine fiber synthetic leather base cloth by adopting thermoplastic compounding treatment, and the surface of the styrene-butadiene block copolymer film forms textures by adopting vacuum grain absorption treatment, so that the high-performance styrene-butadiene block copolymer based superfine fiber synthetic leather is obtained.
5. The production method according to claim 4, wherein the styrene-butadiene block copolymer film is obtained by calendering to form a film, and specifically comprises the following operations:
preheating a styrene-butadiene block copolymer calendered material in a high-speed kneader by adopting a four-roll calendering production line, banburying in an internal mixer, plasticating in a plasticating machine to obtain sizing material, and preparing the obtained sizing material into a styrene-butadiene block copolymer film by a four-roll calender;
the formula of the styrene-butadiene block copolymer calendered material is as follows: the adhesive comprises, by mass, 50-80 parts of a styrene-butadiene block copolymer, 1-5 parts of a toner, 0.2-1.8 parts of an AC foaming agent, 5-15 parts of No. 10 white oil, 1-2.5 parts of stearic acid, 1-3 parts of titanium dioxide and 0.1-0.2 part of tetrol phosphite ester.
6. The production method according to claim 5, wherein the preheating temperature is 70 ℃ to 80 ℃ and the preheating time is 5min to 10 min.
7. The production method according to claim 5, characterized in that the banburying temperature is 140-180 ℃ and the banburying time is 2-5 min; the plasticating temperature is 160-190 ℃, and the plasticating time is 5-10 min.
8. The production method according to claim 5, wherein the calendering temperature is 150 ℃ to 180 ℃ and the calendering thickness is 0.08mm to 1.2 mm.
9. The production method according to claim 4, wherein the thermoplastic composite processed gap is styrene-butadiene block copolymerization50-70% of the sum of the thicknesses of the object film and the superfine fiber synthetic leather base cloth, and the pressure is 4-5 kg/cm2。
10. The production method according to claim 4, wherein the temperature of the vacuum texturing is 160 ℃ to 190 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011419283.5A CN112537107A (en) | 2020-12-07 | 2020-12-07 | High-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011419283.5A CN112537107A (en) | 2020-12-07 | 2020-12-07 | High-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and production method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112537107A true CN112537107A (en) | 2021-03-23 |
Family
ID=75016309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011419283.5A Pending CN112537107A (en) | 2020-12-07 | 2020-12-07 | High-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112537107A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114277581A (en) * | 2021-12-27 | 2022-04-05 | 陈永裕 | Synthetic leather and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200905033A (en) * | 2007-07-16 | 2009-02-01 | China General Plastics Corp | Polystyrene elastomer artificial leather and their preparation thereof |
| CN101701425A (en) * | 2003-07-18 | 2010-05-05 | 东丽株式会社 | Leather-like article in sheet form, and method for their production |
| CN111719317A (en) * | 2020-06-11 | 2020-09-29 | 浙江众成包装材料股份有限公司 | Environment-friendly styrene thermoplastic elastomer artificial leather and preparation method thereof |
-
2020
- 2020-12-07 CN CN202011419283.5A patent/CN112537107A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701425A (en) * | 2003-07-18 | 2010-05-05 | 东丽株式会社 | Leather-like article in sheet form, and method for their production |
| TW200905033A (en) * | 2007-07-16 | 2009-02-01 | China General Plastics Corp | Polystyrene elastomer artificial leather and their preparation thereof |
| CN111719317A (en) * | 2020-06-11 | 2020-09-29 | 浙江众成包装材料股份有限公司 | Environment-friendly styrene thermoplastic elastomer artificial leather and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 马兴元，冯见艳，张韬琳编著: "《合成革化学与工艺学》", 30 November 2015 * |
| 高士刚，孙家珏主编: "《鞋靴材料》", 31 January 2012 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114277581A (en) * | 2021-12-27 | 2022-04-05 | 陈永裕 | Synthetic leather and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101748613A (en) | Method for producing real leather intimating polyurethane synthetic leather | |
| KR101248276B1 (en) | A method for preparation sinthetic leather | |
| CN101509313B (en) | Thermoplastic polyurethane floor tile and technique for producing the same | |
| CN1228500C (en) | Post finishing process for superfine fiber artificial leather | |
| CN103031744A (en) | Manufacture method of half microfiber sports shoe leather | |
| US11542365B2 (en) | Curative | |
| CN109624422B (en) | TPU high-low temperature film composite mesh cloth and preparation method thereof | |
| CN102234937A (en) | Production process of top layer leather-simulated super-fibre synthetic leather | |
| CN109112846B (en) | High-strength wear-resistant coated PVC artificial leather | |
| KR20170030244A (en) | Artificial leather fabric for ventilating seat and manufacturing method thereof | |
| CN101956329B (en) | Process for preparing bright printing coating polyester fabric | |
| CN103451959B (en) | Imitation sheepskin ultrafine fiber polyurethane synthetic leather and manufacturing method thereof | |
| CN112537107A (en) | High-performance styrene-butadiene block copolymer-based superfine fiber synthetic leather and production method thereof | |
| CN110219434B (en) | High-wear-resistance TPU stone plastic floor and preparation method thereof | |
| CN104404785A (en) | Process for producing color-changed leather | |
| CN110561865A (en) | inflatable surfboard composite material and preparation method thereof | |
| CN104358131A (en) | High-temperature fine Yangbuck resin for synthetic leather and preparation method thereof | |
| CN114479428B (en) | Shoe outsole containing reclaimed rubber, preparation method thereof and shoe sole | |
| CN110216953A (en) | A kind of TPU alloy floor and preparation method thereof | |
| CN105086013A (en) | No-blooming wear-resistant rubber and preparing method thereof | |
| CN113622199B (en) | Solid silica gel leather and preparation method thereof | |
| CN105568701A (en) | Preparation method of pearlescent anti-crease waterproof moisture-permeable polyurethane synthetic leather | |
| CN113306249A (en) | Water-based coating PVC artificial leather and preparation method thereof | |
| CN105585756A (en) | Process method for manufacturing resilient floor | |
| CN111016232A (en) | Preparation method of artificial leather with color change and product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210323 |