CN117002117B - Organosilicon automobile leather capable of being bitten by baby mouth and preparation method thereof - Google Patents

Organosilicon automobile leather capable of being bitten by baby mouth and preparation method thereof Download PDF

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Publication number
CN117002117B
CN117002117B CN202310682475.2A CN202310682475A CN117002117B CN 117002117 B CN117002117 B CN 117002117B CN 202310682475 A CN202310682475 A CN 202310682475A CN 117002117 B CN117002117 B CN 117002117B
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vinyl
parts
organic silicon
resin
silicone resin
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CN117002117A (en
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范德文
胡珊
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Jiangxi Saioteco New Material Co ltd
Zhejiang Zero Run Technology Co Ltd
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Jiangxi Saioteco New Material Co ltd
Zhejiang Zero Run Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
    • B60N2/00—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles
    • B60N2/24—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles for particular purposes or particular vehicles
    • B60N2/26—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles for particular purposes or particular vehicles for children
    • B60N2/28—Seats readily mountable on, and dismountable from, existing seats or other parts of the vehicle
    • B60N2/2881—Upholstery, padded or cushioned members therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/005—Layered products coated
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B32B2038/168—Removing solvent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Transportation (AREA)
  • Aviation & Aerospace Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Child & Adolescent Psychology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

The invention discloses organosilicon automobile leather capable of being bitten by an infant and a preparation method thereof, and relates to the technical field of synthetic leather. The organic silicon automobile leather capable of being bitten by the baby comprises an organic silicon surface layer, an organic silicon reinforcing layer and a base layer, wherein the organic silicon surface layer, the organic silicon reinforcing layer and the base layer are sequentially arranged; the organic silicon surface layer comprises the following preparation raw materials in parts by weight: 10-40 parts of vinyl polydimethylsiloxane, 30-60 parts of vinyl MT silicon resin, 1-10 parts of methyl silicon resin, 1-15 parts of hydrogen-containing polysiloxane, 5-20 parts of silicone master batch, 0.1-10 parts of platinum catalyst and 0.1-5 parts of inhibitor. According to the invention, through the selection of the preparation raw materials of the organic silicon surface layer, the performances of occlusion, wear resistance, folding resistance, joint fatigue and the like of the organic silicon automobile leather are effectively improved.

Description

Organosilicon automobile leather capable of being bitten by baby mouth and preparation method thereof
Technical Field
The invention relates to the technical field of synthetic leather, in particular to organosilicon automobile leather capable of being bitten by an infant and a preparation method thereof.
Background
Among the conventional automotive upholstery and seat covering materials, leather, polyurethane (PU) synthetic leather and polyvinyl chloride (PVC) synthetic leather have been in part of the market, however, solvents and plasticizers, which are discharged in large amounts during the production process, cause serious damage to the environment. Although the water-based PU, the solvent-free PU and the high polymer plasticizer appear in recent years, a part of environmental protection problems are solved, but the problems of choking gas hydrogen chloride released by the combustion of the PVC material, and the problems of pollution resistance, yellowing resistance, salt fog resistance, adhesion resistance, heavy metal exceeding standard and the like of the PU material cannot be thoroughly solved, and moreover, the biocompatibility of the materials is insufficient, so that the materials are easy to cause allergic reaction of susceptible people.
Although the problems are solved, the organic silicon synthetic leather is rarely reported as automobile leather, and is mainly difficult to balance various indexes such as wear resistance, folding resistance, stain resistance, joint fatigue and the like of automobile leather standards. Although there are some silicone automotive leather products in the domestic market, it is still difficult to balance the above properties. In addition, the leather material or the organic silicon synthetic leather can be used by infants, and besides the safety of the leather material, the leather material is required to meet the occlusion requirement, so that the leather material is not easy to generate powder or scraps after being occluded, and serious consequences caused by choking after infants swallow the scraps carelessly are avoided.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the organosilicon automobile leather which can be bitten by infants and the preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the organic silicon automobile leather comprises an organic silicon surface layer, an organic silicon reinforcing layer and a base layer, wherein the organic silicon surface layer, the organic silicon reinforcing layer and the base layer are sequentially arranged;
the organic silicon surface layer comprises the following preparation raw materials in parts by weight: 10-40 parts of vinyl polydimethylsiloxane, 30-60 parts of vinyl MT silicon resin, 1-10 parts of methyl silicon resin, 1-15 parts of hydrogen-containing polysiloxane, 5-20 parts of silicone master batch, 0.1-10 parts of platinum catalyst and 0.1-5 parts of inhibitor.
The methyl silicone resin is added, so that the main material of the surface layer can be reinforced, the flexibility of the surface layer can be increased, and the performances of folding resistance, wear resistance and the like of the surface layer are improved; the vinyl MT silicon resin is added to reinforce the polysiloxane main body material and improve the wear resistance of the polysiloxane main body material; the addition of silicone masterbatch further improves the bite performance of the facing. By selecting the preparation raw materials of the organic silicon surface layer, the organic silicon automobile leather can have good performances of wear resistance, folding resistance, stain resistance, joint fatigue, occlusion and the like.
Preferably, the weight average molecular weight of the methyl silicone resin in the silicone surface layer is 2500-10000, and too small or too large molecular weight affects the plasticizing or reinforcing effect thereof. Preferably, the methyl silicone resin has a volatile content of less than 0.5%, and the control of the volatile content within the above range can reduce the atomization degree of the silicone surface layer.
Preferably, one part of the silicone master batch molecular chain can form a winding structure with vinyl MT silicon resin, vinyl polydimethylsiloxane and methyl silicone resin, so that the strength and flexibility of the surface layer are improved, the folding strength and the biting strength of the surface layer are improved, the other part of the silicone master batch molecular chain can migrate to the surface of leather, the friction resistance of the surface layer is reduced, and the wear resistance and the biting performance of the surface layer are further improved.
Preferably, the vinyl MT silicone comprises vinyl MT silicone-1, vinyl MT silicone-2, and vinyl MT silicone-3; the molecular weights of the three vinyl MT silicon resins are different, the weight average molecular weight of the vinyl MT silicon resin-1 is 2000-5000, the weight average molecular weight of the vinyl MT silicon resin-2 is 10000-15000, and the weight average molecular weight of the vinyl MT silicon resin-3 is 20000-25000. Further preferably, the mass ratio of the vinyl MT silicone resin-1, the vinyl MT silicone resin-2 and the vinyl MT silicone resin-3 is vinyl MT silicone resin-1: vinyl MT silicone-2: vinyl MT silicone-3=3: (1.5-2.5): (4-6). Through the selection, the resin pellets can effectively fill gaps among the resin pellets, so that the surface layer structure is tighter, the strength and the wear resistance of the surface layer are further improved, stains are not easy to permeate, and the antifouling effect is improved.
Preferably, the preparation raw material of the organic silicon surface layer meets at least one of the following conditions:
(a) The mass fraction of vinyl in the vinyl MT silicon resin is 2% -5%, and the volatile of the vinyl MT silicon resin is less than 0.5%; the vinyl content is too little, the crosslinking degree is insufficient, the wear resistance and the antifouling property of the surface layer are affected, the vinyl content is too high, the folding resistance of the surface layer is affected, and the atomization degree of the organic silicon surface layer can be reduced by controlling volatile matters;
(b) The vinyl polydimethylsiloxane is terminal vinyl polydimethylsiloxane, and the viscosity of the vinyl polydimethylsiloxane is not limited, and is preferably 1000-20000 mPas (25 ℃); too low a viscosity, which reduces the mechanical strength and too high a viscosity, affects the control of the coating thickness, and the volatile content of the vinyl polydimethylsiloxane is less than 0.5%;
(c) The mass fraction of active hydrogen in the hydrogen-containing polysiloxane is 0.18-1.2%, and the viscosity of the hydrogen-containing polysiloxane is not limited, and is preferably 20-1000 mPa.s (25 ℃); the hydrogen-containing polysiloxane is mainly used as a cross-linking agent, the mechanical strength is influenced by too low hydrogen content, the hydrogen content is too high, the active hydrogen is excessively concentrated, incomplete reaction is easily caused by excessive steric hindrance in the curing process of the surface layer material, the wear resistance and the occlusion strength of the surface layer are influenced, in addition, the volatile component is less than 0.5%, and the atomization index is influenced by too high volatile component;
(d) The silicone master batch is a mixture of fumed silica and a siloxane polymer, and has good compatibility with a system;
(e) The organic silicon automobile leather also comprises 0-10 parts of color paste, wherein the color paste is a mixture of toner and vinyl polydimethylsiloxane;
(f) The platinum catalyst is at least one of chloroplatinic acid, platinum black, a complex of chloroplatinic acid and octanol, a complex of platinum and tetramethyl divinyl disiloxane and platinum and tetramethyl tetravinyl cyclotetrasiloxane, and the effective platinum content of the platinum catalyst is 100-20000ppm;
(g) The inhibitor is at least one of alkynol compounds, amide compounds and vinyl-containing siloxane compounds; the inhibitor is mainly used for adjusting the operation time of the surface layer and improving the processability of the surface layer, the alkynol compound comprises at least one of but not limited to 2-methyl-3-butyn-2-ol and ethynyl cyclohexanol, the amide compound comprises but not limited to N, N-diallyl formamide, and the vinyl-containing siloxane compound comprises but not limited to at least one of vinyl double seal and vinyl ring.
Preferably, the organic silicon reinforcing layer comprises the following preparation raw materials in parts by weight: 15-50 parts of vinyl polydimethylsiloxane, 15-30 parts of vinyl MT silicone resin, 1-15 parts of hydrogen-containing polysiloxane, 2-8 parts of chain extender, 3-10 parts of high-hydroxyl silicone resin, 30-50 parts of filler, 2-8 parts of silicone master batch, 2-15 parts of color paste, 0.1-10 parts of platinum catalyst and 0.1-5 parts of inhibitor, wherein the mass fraction of hydroxyl in the Gao Qiangji silicone resin is 1-3%.
The addition of the high hydroxyl silicone resin can improve the adhesion performance between the silicone surface layer and the silicone reinforcing layer and between the silicone reinforcing layer and the base cloth layer, but too high hydroxyl content can affect the coating processability. Through the optimization of the components, the surface layer is not easy to fall off from the enhancement layer in the occlusion test process, and the occlusion effect is further improved. And one part of the chain extender in the reinforcing layer reacts with vinyl polydimethylsiloxane, so that the molecular weight of the chain extender is increased, the winding function of molecules is increased, the other part of the chain extender reacts with vinyl MT silicon resin, a part of string-shaped resin structure is formed in an internal system, stress can be dispersed after the chain extender is stressed, the tensile strength and the elongation of the organosilicon automobile leather are improved, and the biting performance, the seam fatigue performance and the folding resistance are further improved.
Preferably, the preparation raw material of the organosilicon reinforcing layer satisfies at least one of the following conditions:
(I) The viscosity of the vinyl polydimethylsiloxane is not limited, but is preferably 2000 to 100000 mPas (25 ℃ C.); the viscosity has a certain influence on the mechanical property and the processing property of the surface layer, and the mechanical property and the processing property of the organic silicon surface layer can be balanced by meeting the conditions;
the vinyl content in the vinyl MT silicon resin is not limited, preferably 0.5-5 wt%, the vinyl content is too low, the crosslinking degree is insufficient, the mechanical property of the reinforcing layer is affected, the vinyl content is too high, and the folding endurance of the reinforcing layer is reduced; the weight average molecular weight of the vinyl MT silicon resin is not limited, preferably 2000-20000, the molecular weight is too small, the reinforcing effect is relatively poor, the molecular weight is too large, and the coating performance is affected;
(III) the mass fraction of active hydrogen in the hydrogen-containing polysiloxane is 0.18% -1.2%, and the viscosity of the hydrogen-containing polysiloxane is not limited, and is preferably 20-1000 mPas (25 ℃); the content of active hydrogen in the hydrogen-containing polysiloxane has the same influence on the enhancement layer as the influence on the organic silicon surface layer;
(IV) the chain extender is polydimethylsiloxane with two ends capped by active hydrogen, and the viscosity of the chain extender is 10-1000 mPa.s; too low viscosity, too small molecular weight of the chain extender itself, affecting the mechanical properties of the reinforcing layer, too high viscosity, too large molecular weight of the chain extender, affecting the end group activity and the chain extension efficiency;
(V) the weight average molecular weight of the Gao Qiangji silicone is not limited, and is preferably 3000 to 10000;
(VI) the silicone master batch is a mixture of fumed silica and a siloxane polymer, and has good compatibility with a system;
the filler (VII) is at least one of fumed silica, precipitated silica, quartz powder, calcium carbonate, mica powder, kaolin and alumina, preferably fumed silica, and the specific surface area of the fumed silica is not limited, preferably 50-400m 2 /g。
Preferably, the volatile component of the vinyl polydimethylsiloxane, the vinyl MT silicone resin, the hydrogen-containing polysiloxane and the high-hydroxyl silicone resin is less than 0.5%, and the atomization effect of the organosilicon reinforcing layer can be reduced by controlling the volatile component within the range.
Preferably, in the enhancement layer, the color paste is a mixture of toner and vinyl polydimethylsiloxane; the platinum catalyst is at least one of chloroplatinic acid, platinum black, an octanol solution of chloroplatinic acid and a complex of platinum and tetramethyl divinyl disiloxane, the effective platinum content in the platinum catalyst is preferably 100-20000ppm, the inhibitor is at least one of alkynol compounds, amide compounds and vinyl-containing siloxane compounds, the inhibitor is mainly used for adjusting the operation time of the reinforcing layer and improving the processability of the reinforcing layer, the alkynol compounds comprise at least one of but not limited to 2-methyl-3-butyn-2-ol and ethynyl cyclohexanol, the amide compounds comprise but not limited to N, N-diallyl formamide, and the vinyl-containing siloxane compounds comprise but not limited to at least one of vinyl double seal heads and vinyl ring bodies.
Preferably, the base layer is at least one of knitted fabric, woven fabric, non-woven fabric, microfiber and dermis, and the base layer is at least one of terylene, spandex, chinlon, aramid, viscose and natural cotton fiber.
Meanwhile, the invention also discloses a preparation method of the organosilicon automobile leather capable of being bitten by the baby mouth, which comprises at least one of the following steps:
(1) Mixing the preparation raw materials of the organic silicon surface layer according to a proportion, and uniformly stirring to obtain mixed slurry-1; mixing the raw materials of the organic silicon enhancement layer according to a proportion, and uniformly stirring to obtain mixed slurry-2;
(2) Coating the mixed slurry-1 on release paper, coating the paper with 3-10 filaments, and curing to obtain the organic silicon surface layer;
(3) And (3) coating the mixed slurry-2 on the organic silicon surface layer, coating the organic silicon surface layer with 10-50 filaments, attaching the base cloth, solidifying, and stripping the release paper to obtain the organic silicon automobile leather capable of being bitten by the baby mouth.
Preferably, in the step (2), in order to ensure sufficient foam removal and curing of the surface layer, the oven is composed of at least two sections of ovens, the temperature difference between the first section and the last section of ovens is at least 10 ℃, and the temperature of the ovens is 100-150 ℃; in the step (3), the curing condition is 100-150 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the preparation raw materials of the organic silicon surface layer are screened, and compared with common MQ silicon resin, the added vinyl MT silicon resin has better compatibility with a polysiloxane main body, and a hard T unit forms an abrasion-resistant effective support while reinforcing the main body material; the added methyl silicone resin can simultaneously improve the folding resistance and the wear resistance of the surface layer; the added silicone master batch further improves the wear resistance and the biting performance of the surface layer, and the organic silicon automobile leather has good folding resistance, wear resistance, antifouling performance, joint fatigue and biting performance, and can be suitable for infant groups.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The materials used in the examples and comparative examples of the present invention are available commercially unless otherwise specified.
Vinyl polydimethylsiloxane: vinyl-terminated polydimethylsiloxane having a viscosity of 5000.+ -. 500 mPa.s at 25℃and a volatile fraction of < 0.5%;
vinyl MT silicone-1: the weight average molecular weight is 3500-4000, the mass fraction of vinyl is 4.9-5.0%, and the volatile is less than 0.5%;
vinyl MT silicone-2: the weight average molecular weight is 11000-12000, the mass fraction of vinyl is 2.9-3.0%, and the volatile is less than 0.5%;
vinyl MT silicone-3: the weight average molecular weight is 21000-22000, the mass fraction of vinyl is 2.4-2.5%, and the volatile is less than 0.5%;
methyl silicone resin-1: the weight average molecular weight is 2500-3000, and the volatile component is less than 0.5%;
methyl silicone resin-2: the weight average molecular weight is 5000-5500, and the volatile component is less than 0.5%;
methyl silicone resin-3: the weight average molecular weight is 9000-10000, and the volatile component is less than 0.5%;
methyl silicone resin-4: the weight average molecular weight is 12000-13000, and the volatile component is less than 0.5%;
hydrogen-containing polysiloxane: the mass fraction of active hydrogen is 0.75%, the viscosity at 25 ℃ is 120 mPas, and the volatile is less than 0.5%;
platinum catalyst: octanol solution of chloroplatinic acid with an effective platinum content of 2000ppm;
inhibitors: 2-methyl-3-butyn-2-ol;
color paste: a mixture of toner and vinyl polydimethylsiloxane in a mass ratio of 3:7;
chain extender: polydimethyl siloxane with two ends blocked by active hydrogen and the viscosity at 25 ℃ is 550+/-50 mPa.s;
high hydroxyl silicone resin-1: the mass fraction of hydroxyl is 2.0-2.1%, the weight average molecular weight is 4500-5000, and the volatile is less than 0.5%;
high hydroxyl silicone resin-2: the mass fraction of hydroxyl is 1.4-1.5%, the weight average molecular weight is 4500-5000, and the volatile is less than 0.5%;
high hydroxyl silicone resin-3: the mass fraction of hydroxyl is 2.9-3.0%, the weight average molecular weight is 4500-5000, and the volatile is less than 0.5%;
hydroxy silicone resin-1: hydroxyl group mass fraction is 0.4-0.5%, weight average molecular weight is 4000-4500, volatile matter is less than 0.5%;
hydroxy silicone resin-2: 3.9 to 4.0 percent of hydroxyl group mass fraction, 5000 to 5500 percent of weight average molecular weight and less than 0.5 percent of volatile component;
silicone master batch: a mixture of fumed silica and silicone polymer in a mass ratio of 3:7;
and (3) filling: fumed silica having a specific surface area of 200m 2 /g；
Base cloth: weft knitting knitted fabric and polyester material.
Vinyl polydimethylsiloxane is selected from GY-208-5000 of new materials limited by Jiang-West Hua, and silicone master batch is selected from Wake chemistryPELLET S, methyl silicone resin-1, methyl silicone resin-2, methyl silicone resin-3 and methyl silicone resin-4 are respectively selected from XJY-8205-01, XJY-8205-03, XJY-8205-07 and XJY-8205-10 model products of Jia-Jiuyi New Material Co., ltd; the high-hydroxyl silicone resin-1, the high-hydroxyl silicone resin-2, the high-hydroxyl silicone resin-3, the hydroxyl silicone resin-1 and the hydroxyl silicone resin-2 are selected from XJY-8209-02, XJY-8209-01, XJY-8209-03, XJY-8205-05 and XJY-8209-04 model products of Jia Yi New material Co., jia Xin Ling; the hydrogen-containing polysiloxane and the chain extender are respectively selected from 702B-75 and 707-020 model products of Jiangxi Xinjia, new materials limited company; fumed silica is selected from the group consisting of Desoxas white carbon AEROSIL 200.
The vinyl MT silicone resins of the examples and comparative examples were prepared using the conventional synthetic route as follows: mixing deionized water and toluene, and stirring under an ice water bath to obtain a mixed solution; and simultaneously, uniformly mixing the vinyl single seal head, the methyltrichlorosilane and the toluene, dropwise adding the mixture into the mixed solution through a funnel, controlling the temperature of materials in the flask at 0-5 ℃, stirring at 80-90r/min, and continuing to react for 0.5-1.5h after the dropwise adding is finished. And (3) after the reaction is finished, washing the resin solution by using deionized water, controlling the washing temperature to be 55-65 ℃ until the resin solution is washed to be neutral, distilling the resin solution at normal pressure, concentrating the solid content to about 50-60%, adding hexamethyldisilazane into the concentrated solution, and performing resin post-treatment, wherein the treatment temperature is controlled to be 65-75 ℃ and the treatment time is 0.5-1.5h. Adding active carbon into the solution after the treatment is finished for decoloring and filtering, then removing the solvent in vacuum, and drying to obtain the vinyl MT silicon resin;
the specific preparation method of the vinyl MT silicone resin-1 of the examples and the comparative examples is as follows:
300 parts of deionized water and 60 parts of toluene are put into a four-neck flask, stirring is started, an ice water bath is adopted, the temperature of the water bath is controlled to be 0 ℃, 13 parts of vinyl single seal head, 100 parts of methyltrichlorosilane and 240 parts of toluene are uniformly mixed, and then the mixture is added into the four-neck flask through a constant pressure funnel in a dropwise manner, the dropping speed is 2 drops/s, the temperature of materials in the flask is controlled to be 0-5 ℃, the stirring speed is 80-90r/min, and the reaction is continued for 1 hour after the dropwise addition is finished. After the reaction is finished, the resin solution is washed by deionized water, the washing temperature is controlled at about 60 ℃ until the resin solution is washed to be neutral, then the resin solution is distilled under normal pressure, the solid content is concentrated to about 50-60%, and then 5 parts of hexamethyldisilazane is added into the concentrated solution for resin post-treatment, the treatment temperature is controlled at 65-75 ℃, and the treatment time is 1h. Adding active carbon into the solution after the treatment is finished to decolor and filter, then removing the solvent in vacuum, and drying to obtain vinyl MT silicon resin-1;
the specific preparation method of the vinyl MT silicone resin-2 of the examples and the comparative examples is as follows:
adding 600 parts of deionized water and 120 parts of toluene into a four-neck flask, starting stirring, adopting an ice-water bath, controlling the temperature of the water bath to be 0 ℃, simultaneously uniformly mixing 13 parts of vinyl single seal head, 180 parts of methyltrichlorosilane and 480 parts of toluene, dropwise adding the mixture into the four-neck flask through a constant pressure funnel, controlling the dropping speed to be 4 drops/s, controlling the temperature of materials in the flask to be 0-5 ℃, controlling the stirring rotating speed to be 80-90r/min, and continuing to react for 1 hour after the dropwise adding is finished. After the reaction is finished, the resin solution is washed by deionized water, the washing temperature is controlled at about 60 ℃ until the resin solution is washed to be neutral, then the resin solution is distilled under normal pressure, the solid content is concentrated to about 50-60%, and then 8 parts of hexamethyldisilazane is added into the concentrated solution for resin post-treatment, the treatment temperature is controlled at 65-75 ℃, and the treatment time is 1h. Adding active carbon into the solution after the treatment is finished to decolor and filter, then removing the solvent in vacuum, and drying to obtain vinyl MT silicon resin-2;
the specific preparation method of the vinyl MT silicone resin-3 of the examples and the comparative examples is as follows:
adding 900 parts of deionized water and 180 parts of toluene into a four-neck flask, starting stirring, adopting an ice-water bath, controlling the temperature of the water bath to be 0 ℃, simultaneously uniformly mixing 13 parts of vinyl single seal head, 280 parts of methyltrichlorosilane and 720 parts of toluene, dropwise adding the mixture into the four-neck flask through a constant pressure funnel, controlling the dropping speed to be 5 drops/s, controlling the temperature of materials in the flask to be 0-5 ℃, controlling the stirring rotating speed to be 80-90r/min, and continuing to react for 1 hour after the dropwise adding is finished. After the reaction is finished, the resin solution is washed by deionized water, the washing temperature is controlled at about 60 ℃ until the resin solution is washed to be neutral, then the resin solution is distilled under normal pressure, the solid content is concentrated to about 50-60%, 10 parts of hexamethyldisilazane is added into the concentrated solution, the resin is subjected to post-treatment, and the treatment temperature is controlled at 65-75 ℃ and the treatment time is 1h. And after the treatment is finished, adding active carbon into the solution for decoloring and filtering, then removing the solvent in vacuum, and drying to obtain the vinyl MT silicon resin-3.
Examples 1 to 9
In the embodiment of the organic silicon automobile leather capable of being bitten by infants, the preparation raw materials of the organic silicon surface layers in the embodiments 1-9 are shown in the table 1, the preparation raw materials of the organic silicon reinforcing layer are shown in the table 2, and the preparation method is as follows:
(1) Mixing the preparation raw materials of the organic silicon surface layer according to the proportion to obtain mixed slurry-1, and mixing the preparation raw materials of the organic silicon reinforcing layer according to the proportion to obtain mixed slurry-2; mixing by a planetary mixer at a stirring speed of 1000rpm for 40min;
(2) Coating the mixed slurry-1 on release paper, wherein the coating thickness is 5 filaments, respectively curing in two sections of ovens, wherein the temperature of a first section of oven is 100 ℃, the temperature of a second section of oven is 120 ℃, and fully discharging bubbles and curing to obtain the organic silicon surface layer;
(3) And (3) coating the mixed slurry-2 on the organic silicon surface layer, coating the organic silicon surface layer with 30 filaments, attaching the base cloth, fully curing at 130 ℃, and stripping the release paper to obtain the organic silicon automobile leather with the organic silicon surface layer, the organic silicon reinforcing layer and the base layer arranged in sequence.
Comparative example 1
A silicone automotive leather differing from example 2 only in that it does not contain methyl silicone resin.
Comparative example 2
A silicone car leather differing from example 2 only in the content of methyl silicone resin.
Comparative example 3
An organosilicon automotive leather differing from example 2 only in the content of silicone masterbatch in the top layer.
Table 1 (weight portions)
Examples 10 to 12
Examples 10 to 12 of the infant mouth-biting silicone automobile leather according to the present invention differ from example 2 only in the type of methyl silicone resin used in the preparation raw material of the silicone top layer, methyl silicone resin-2 was used in example 10, methyl silicone resin-3 was used in example 11, and methyl silicone resin-4 was used in example 12.
Examples 13 to 18
Examples 13 to 18 of the infant mouth-biting silicone automobile leather of the present invention were different from example 2 only in that the silicone reinforcing layer was prepared from different materials from example 2, as shown in table 2.
Table 2 (weight portions)
The performance of the silicone automotive leather described in the examples and comparative examples was tested according to the standard outline of automotive interior by Zhejiang zero running technologies, inc.:
1. abrasion resistance test: the wear-resistant color and texture change slightly after 5000 revolutions of wear resistance is required by using a Taber wear-resistant instrument and a CS-10 grinding wheel with a weight of 1000 g.
2. Fastness to folding at normal temperature: tests are carried out according to the specification of QB/T2714, and the surface is required to be free from whitening and cracks after 10 ten thousands of times of folding resistance;
3. low temperature fold fastness: the surface is required to be free from whitening and cracking after being folded for 3 ten thousand times according to the specification of QB/T2714 and tested at the temperature of minus 20 ℃;
4. joint fatigue: stitch spacing sets (5+ -0.5) mm sewn samples. And fixing the sewn sample on a joint fatigue testing machine, wherein the load of the two ends is 3kg, the reciprocating motion distance of the testing machine is 150mm, and the testing times are 2500. And after the test is finished, measuring the size of the pinhole spacing under the condition of keeping the load, wherein the pinhole spacing is required to be less than 2mm.
5. Anti-sticking properties: the surfaces of the two sample blocks are adhered together, a weight of 30N is placed on the test sample and heated at the temperature of 80+/-2 ℃, the test sample is taken out after 24 hours, the weight is removed and cooled for 1 hour in the room temperature environment, and after the test sample is stripped, the surface is required to be free from adhesion, lines and color change.
6. Jean blue stain resistance test: the results were determined after 1000 rubs using EMPA 128-1 standard denim as a contaminant according to ISO 26082-1 specifications. The sample was repeatedly wiped clean using a neutral soap (2.5%) with a force of about 10N, and the results were evaluated according to GB/T250. The cleaning is required to be more than or equal to 4 grades before cleaning and more than or equal to 4 grades after cleaning.
7. Conventional stain resistance test: the surface of leather is polluted by using sewing machine oil, lubricating oil, instant coffee, tomato sauce, cola, soy sauce and other stains for 30min, then the surface of leather is dipped with neutral soap solution by using wiping cloth conforming to ISO 105-F09, and then the change of the surface of leather is judged according to the standard shown in Table 3, and the required result is more than or equal to grade 6.
TABLE 3 Table 3
Grade 10 No change
Level 8 Slightly changed, with a small amount of visible blemish, not easily visible
Grade 6 Medium change, little smudge, easy to see
Grade 4 Large variation in
Level 2 Severe changes with a large amount of stains
8. Light color fastness testing: the test was performed using method A-1 of GB/T32088 with a total test time set to 500h. And after the test is finished, judging the fading degree of the sample according to the GB/T250 standard, wherein the test result is required to be more than or equal to level 4.
9. Atomization test: the atomization value is required to be less than or equal to 2.5mg according to the ISO 6452 standard test.
10. Cytotoxicity test: tested according to ISO 10993-5.
11. Antiallergic test: tested according to ISO 10993-10.
12. Occlusion experimental test: according to the 16CFR 1500.53C standard test, the test load of 100+/-0.5 LBS is uniformly increased within 5 seconds, and after the load is kept for 10 seconds, the sample piece is free of safety defects such as breakage, side benefit, corner benefit and the like, and the safety defects such as easy mistaken swallowing are qualified.
The above test results are recorded in table 4.
TABLE 4 Table 4
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From the above test results, it is known that the organosilicon automobile leather capable of being bitten by an infant in embodiments 1 to 18 can meet the basic requirements of automobile interior parts, has good performances of wear resistance, folding resistance, stain resistance, seam fatigue and the like, can pass the bite test, is suitable for being bitten by an infant, and can be used for preparing automobile interior parts such as infant seats and the like.
The surface layer of the organic silicon automobile leather in comparative example 1 does not contain methyl silicone resin, and the abrasion resistance and folding resistance of the organic silicon automobile leather are obviously poorer, so that the basic requirements of automobile interior trim parts cannot be met. The organic silicon automobile leather described in comparative example 2 has too high methyl silicone resin content in the surface layer, and has poor folding endurance, and cannot meet the basic requirements. The silicone automobile leather of comparative example 3 has too little silicone masterbatch in the top layer, and has poor abrasion resistance and folding resistance.
In addition, the performance test results of comparative examples 1 to 9 show that when three molecular weight vinyl MT silicone resins are selected for compounding in the surface layer, the joint fatigue performance is better; it is further preferred that when the mass ratio of the vinyl MT silicone resin having a weight average molecular weight of 2000 to 5000, the vinyl MT silicone resin having a weight average molecular weight of 10000 to 15000, and the vinyl MT silicone resin having a weight average molecular weight of 20000 to 25000 is 3: (1.5-2.5): (4-6) in the case of the silicone automobile leather, the abrasion resistance, folding endurance, seam fatigue resistance and stain resistance can be further improved.
The test results of comparative examples 13 to 18 show that the addition of high hydroxyl silicone resin to the reinforcing layer of the silicone automobile leather can significantly improve the joint fatigue properties of the silicone automobile leather.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (7)

1. The organic silicon automobile leather capable of being bitten by a baby is characterized by comprising an organic silicon surface layer, an organic silicon reinforcing layer and a base layer, wherein the organic silicon surface layer, the organic silicon reinforcing layer and the base layer are sequentially arranged;
the organic silicon surface layer comprises the following preparation raw materials in parts by weight: 10-40 parts of vinyl polydimethylsiloxane, 30-60 parts of vinyl MT silicon resin, 1-10 parts of methyl silicon resin, 1-15 parts of hydrogen-containing polysiloxane, 5-20 parts of silicone master batch, 0.1-10 parts of platinum catalyst and 0.1-5 parts of inhibitor; the vinyl MT silicone resin comprises vinyl MT silicone resin-1, vinyl MT silicone resin-2 and vinyl MT silicone resin-3; the weight average molecular weight of the vinyl MT silicon resin-1 is 2000-5000, the weight average molecular weight of the vinyl MT silicon resin-2 is 10000-15000, and the weight average molecular weight of the vinyl MT silicon resin-3 is 20000-25000; the mass fraction of vinyl in the vinyl MT silicon resin is 2% -5%;
the organic silicon reinforcing layer comprises the following preparation raw materials in parts by weight: 15-50 parts of vinyl polydimethylsiloxane, 15-30 parts of vinyl MT silicone resin, 1-15 parts of hydrogen-containing polysiloxane, 2-8 parts of chain extender, 3-10 parts of high-hydroxyl silicone resin, 30-50 parts of filler, 2-8 parts of silicone master batch, 2-15 parts of color paste, 0.1-10 parts of platinum catalyst and 0.1-5 parts of inhibitor, wherein the mass fraction of hydroxyl in the Gao Qiangji silicone resin is 1-3%.
2. The infant mouth-biting silicone automotive leather of claim 1, wherein said methyl silicone resin has a weight average molecular weight of 2500 to 10000.
3. The infant bite organosilicon car leather according to claim 1, wherein the mass ratio of the vinyl MT silicone resin-1, the vinyl MT silicone resin-2 and the vinyl MT silicone resin-3 is vinyl MT silicone resin-1: vinyl MT silicone-2: vinyl MT silicone-3=3: (1.5-2.5): (4-6).
4. The infant bite organosilicon automotive leather of claim 1, wherein the organosilicon facing is prepared from a material that meets at least one of the following conditions:
(a) The vinyl polydimethylsiloxane is vinyl-terminated polydimethylsiloxane;
(b) The mass fraction of active hydrogen in the hydrogen-containing polysiloxane is 0.18% -1.2%;
(c) The organic silicon surface layer also contains 0-10 parts of color paste;
(d) The platinum catalyst is at least one of chloroplatinic acid, platinum black, octanol solution of chloroplatinic acid, complex of platinum and tetramethyl divinyl disiloxane and platinum and tetramethyl tetravinyl cyclotetrasiloxane, and the effective platinum content of the platinum catalyst is 100-20000ppm;
(e) The inhibitor is at least one of alkynol compounds, amide compounds and vinyl-containing siloxane compounds.
5. The infant bite organosilicon automotive leather of claim 1, wherein the organosilicon reinforcing layer is prepared from a material satisfying at least one of the following conditions:
(I) The mass fraction of active hydrogen in the hydrogen-containing polysiloxane is 0.18% -1.2%;
(II) the chain extender is polydimethylsiloxane having active hydrogen end caps at both ends;
the filler (III) is at least one of fumed silica, precipitated silica, quartz powder, calcium carbonate, mica powder, kaolin and alumina.
6. The infant mouth-biting organosilicon automobile leather according to claim 1, wherein the base layer is at least one of knitted fabric, woven fabric, non-woven fabric, microfiber and dermis, and the base layer is at least one of terylene, spandex, chinlon, aramid, viscose and natural cotton fiber.
7. The method for preparing the organosilicon automobile leather capable of being bitten by infants according to any one of claims 1-6, which is characterized by comprising at least one of the following steps:
(1) Mixing the preparation raw materials of the organic silicon surface layer according to a proportion, and uniformly stirring to obtain mixed slurry-1; mixing the raw materials of the organic silicon enhancement layer according to a proportion, and uniformly stirring to obtain mixed slurry-2;
(2) Coating the mixed slurry-1 on release paper, coating the paper with 3-10 filaments, and curing to obtain the organic silicon surface layer;
(3) And (3) coating the mixed slurry-2 on the organic silicon surface layer, wherein the coating thickness is 10-50 filaments, solidifying, and stripping the release paper to obtain the organic silicon automobile leather capable of being bitten by the baby mouth.
CN202310682475.2A 2023-06-09 2023-06-09 Organosilicon automobile leather capable of being bitten by baby mouth and preparation method thereof Active CN117002117B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353821A (en) * 2017-07-27 2017-11-17 宁波瑞世达新材料有限公司 A kind of bi-component organosilicon coating of hydro-oleophobicity
CN108998988A (en) * 2018-06-22 2018-12-14 安徽索亚装饰材料有限公司 A kind of degradable PVC decorative artificial leather of Environment-friendlywear-resistant wear-resistant
CN111172778A (en) * 2020-01-17 2020-05-19 江西赛欧特科新材料有限公司 Organic silicon synthetic leather and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353821A (en) * 2017-07-27 2017-11-17 宁波瑞世达新材料有限公司 A kind of bi-component organosilicon coating of hydro-oleophobicity
CN108998988A (en) * 2018-06-22 2018-12-14 安徽索亚装饰材料有限公司 A kind of degradable PVC decorative artificial leather of Environment-friendlywear-resistant wear-resistant
CN111172778A (en) * 2020-01-17 2020-05-19 江西赛欧特科新材料有限公司 Organic silicon synthetic leather and manufacturing method thereof

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