WO2019213990A1 - 一种硅橡胶弹性体/纤维复合材料及其制备方法和应用 - Google Patents

一种硅橡胶弹性体/纤维复合材料及其制备方法和应用 Download PDF

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WO2019213990A1
WO2019213990A1 PCT/CN2018/087782 CN2018087782W WO2019213990A1 WO 2019213990 A1 WO2019213990 A1 WO 2019213990A1 CN 2018087782 W CN2018087782 W CN 2018087782W WO 2019213990 A1 WO2019213990 A1 WO 2019213990A1
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silicone rubber
fiber
rubber elastomer
elastomer
fiber composite
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PCT/CN2018/087782
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English (en)
French (fr)
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马汉永
吴超
陈有斌
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广东聚合科技股份有限公司
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • the invention relates to the technical field of polymer materials, in particular to a silicone rubber elastomer/fiber composite material and a preparation method and application thereof.
  • fiber products prepared by chemical fiber or natural fiber as raw materials such as wool products made of natural wool, camel hair and the like; and polyester fiber as raw material by compression molding.
  • These products are lightweight, soft, and breathable, and have a wide range of applications.
  • fiber products due to its own material properties and structural characteristics, fiber products usually have the disadvantage of poor resilience. After the product is compressed and deformed, it takes a long time to restore the original shape. Even after long-term compression, the original product cannot be restored. Some shapes lose their use value.
  • Silicone rubber refers to a polymer elastomer material in which a main chain is composed of silicon atoms and oxygen atoms alternately. Silicone rubber has the advantages of non-toxic, tasteless, high temperature resistance, weather resistance and good physiological compatibility. It is widely used in daily necessities, chemicals, automobiles, machinery, medical and health fields. In particular, silicone rubber has excellent resilience performance and can be used in a high compression state for a long time, and can quickly restore its original shape and function.
  • the patent CN102561047A is coated on the reticulated chemical fiber fabric by liquid silicone rubber, and the excess liquid silicone rubber is blown out by air injection method, and the cured coating mesh has good release property and anti-slip property, and is used for steaming plated food.
  • the lining also failed to improve the resilience of the chemical fiber fabric. Since thicker articles cannot be blown out of the excess liquid silicone rubber by air injection, the method is only suitable for thinner mesh fabrics and is not suitable for thicker fibrous products.
  • Patent CN105696352B discloses a silicon silk cotton product in which the inner and outer fiber surfaces of the chemical fiber cotton are coated with a silicone rubber layer to form two layers of completely synchronous mesh elastic structure, which improves the resilience of the chemical fiber cotton.
  • the resilience of the silicon silk cotton product is mainly provided by a thin layer of a continuously distributed silicone rubber layer on the surface of the fiber, it is limited by the thickness factor of the silicone rubber layer, and the resilience performance of the modified fiber product is particularly The fast resilience and rebound durability are not optimal. If the proportion of the silicone rubber is simply increased to increase the thickness of the silicone rubber layer, the softness and gas permeability of the fiber product are affected.
  • the object of the present invention is to overcome the above technical drawbacks and provide a silicone rubber elastomer/fiber composite material which has the advantages of good resilience, good gas permeability and good flexibility.
  • Another object of the present invention is to provide a method and application for the preparation of the above composite material.
  • the present invention has been achieved by the following technical solutions.
  • a silicone rubber elastomer/fiber composite material comprising: a fiber product made of chemical fiber and/or natural fiber, the fiber surface of the fiber product has a particle shape of a silicone rubber elastomer attached, and the silicone rubber elastomer has a packing density of 0.005. -0.200g/cm 3 .
  • the filling density of the silicone rubber elastomer in the composite material is less than 0.005 g/cm 3 , the filling amount of the silicone rubber elastomer is insufficient to provide sufficient resilience performance; the silicone rubber elastomer has a packing density of more than 0.200 g/cm 3 in the composite material. At the time, the filling amount of the silicone rubber is too large, and it is easy to block the pores of the product, and the composite material loses flexibility and gas permeability.
  • Some of the fiber surfaces of the fibrous article are also coated with a silicone rubber elastomer layer.
  • the fiber product has a fiber fineness of 1-8D, and the mass ratio of the silicone rubber elastomer layer distributed in the fiber product to the particle shape silicone rubber elastomer is (0.05-1):1.
  • the particle-shaped silicone rubber elastomer has a spherical shape, a hemispherical shape, an ellipsoidal shape, a multi-spherical shape in which a plurality of hemispheres are agglomerated, and other irregular shapes that are compatible with the shape of the slit of the fiber.
  • the chemical fiber material refers to a fiber material obtained by a spinning process using a synthetic polymer compound or a artificially modified natural polymer material as a raw material; a synthetic polymer compound fiber material such as polyester fiber, polyamide fiber, polypropylene Nitrile fiber, polyvinyl formal fiber, poly(p-phenylene terephthalate) fiber, polyvinyl chloride fiber, polyurethane fiber, polypropylene fiber, polyethylene fiber, etc.; artificially modified natural polymer fiber material such as man-made cellulose Fiber, artificial starch fiber, artificial protein fiber, copper ammonia fiber, viscose fiber, chitin fiber, and the like.
  • a synthetic polymer compound fiber material such as polyester fiber, polyamide fiber, polypropylene Nitrile fiber, polyvinyl formal fiber, poly(p-phenylene terephthalate) fiber, polyvinyl chloride fiber, polyurethane fiber, polypropylene fiber, polyethylene fiber, etc.
  • artificially modified natural polymer fiber material such as man-made
  • Natural fibers mainly include animal fiber, plant fiber and inorganic mineral fiber; animal fiber such as wool, rabbit hair, camel hair, yak hair, silk, etc.; plant fiber such as cotton, kapok, coir, sisal, ramie, Flax, hemp, etc.; inorganic mineral fibers are mainly silicate minerals, such as asbestos fibers.
  • the fibers in the silicone rubber elastomer/fiber composite material of the present invention may be used singly or in combination of two or more kinds, or may be used in combination of different types of fiber materials.
  • the fibrous product is woven for the fibrous material by a nonwoven process.
  • the non-woven process refers to a process in which the filaments are oriented or randomly arranged without a textile process to form a network structure, and then reinforced by mechanical, thermal bonding or chemical methods.
  • Nonwoven processes include vertical web forming, spunbonding, meltblowing, and the like.
  • the fiber material products prepared by the non-woven process are commercially available in dozens of varieties such as hard cotton, imitation silk cotton, down cotton, filled cotton, erect cotton, hollow cotton, and the like.
  • the silicone rubber elastomer has a Sauer hardness (type A) of from 1 to 70 degrees; preferably, the silicone rubber elastomer has a Sauer hardness (type A) of from 5 to 50 degrees.
  • the elasticity is mainly provided by the particle-shaped silicone rubber elastomer.
  • the silicone rubber elastomer has an average particle diameter ranging from 1 to 1000 ⁇ m; preferably, the silicone rubber elastomer has an average particle diameter ranging from 5 to 200 ⁇ m.
  • the distribution silicone rubber elastomer has an average particle diameter ranging from 1 to 1000 ⁇ m.
  • the silicone rubber elastomer is selected from one or more of an elastomer material formed by crosslinking a peroxide vulcanized rubber, an elastomer material formed by crosslinking a condensation type silicone rubber, and an elastomer material formed by crosslinking a modified silicone rubber.
  • it is selected from an elastomeric material formed by crosslinking of an addition silicone rubber.
  • the fibrous article has a density of from 0.008 to 20.20 g/cm 3 .
  • density of the fiber product is less than 0.008 g/cm 3 , the strength of the fiber product itself is very weak, and the silicone rubber composite modification has no practical value; when the density of the fiber product is more than 0.20 g/cm 3 , the void of the fiber product structure The structure is too small, and the silicone rubber easily blocks the pores of the product, losing flexibility and gas permeability.
  • the length of the fiber is 35-150 mm.
  • the fiber matrix used in the present invention is a fiber prepared by a nonwoven process, which is different from the fiber product of the conventional weaving process.
  • the fiber products of the weaving process are all prepared by a two-step process of spinning and weaving using long fibers, and the fiber length is usually more than 150 mm; the non-woven fiber products are generally made of a short fiber in a non-woven process.
  • the mechanical strength of the fiber product of the nonwoven process is related to the fiber length, and the longer the fiber length, the greater the strength of the fiber product.
  • the fiber length is greater than 150 mm, the strength growth of the fiber product is not obvious, and it is not conducive to the processing process of the nonwoven process; when the fiber length is less than 35 mm, the fiber product itself is insufficient in elasticity.
  • the structure of the fibrous product is three-dimensional network; the thickness of the silicone rubber elastomer/fiber composite is in the range of 3 to 80 mm.
  • the thickness of the fiber product is less than 3 mm, the requirement for resilience is not strong, and the improvement of the silicone rubber after compounding is not obvious; when the thickness of the fiber product is more than 80 mm, the application surface is narrow, and the preparation of the composite material is difficult.
  • the thickness of the fiber product is more than 80 mm, by compounding the two materials by one-time manufacturing, the composite uniformity of the product is deteriorated, and the energy consumption is also improved. The goal can be achieved by fitting the two thicknesses of composite material.
  • the preparation method of the above silicone rubber elastomer/fiber composite material comprises the following steps: preparing a silicone rubber emulsion: preparing a silicone rubber emulsion, uniformly wetting the fiber product therein, and then extruding excess silicon in the fiber product by extrusion. The rubber emulsion is discharged, and then the fibrous product is heated to volatilize the solvent, and after cross-linking and solidification, a silicone rubber elastomer/fiber composite material is obtained; in the silicone rubber emulsion, the average particle diameter of the silicone rubber distributed in the solution is 0.01-100 ⁇ m.
  • the silicone rubber emulsion is volatilized by heating, and the silicone rubber droplets in the emulsion gradually agglomerate and solidify and crosslink into a granular silicone rubber elastomer of a certain particle size.
  • the particle size of the silicone rubber in the emulsion is too small, it is not conducive to the formation of a granular silicone rubber elastomer of a certain particle size, which affects the resilience performance of the final composite material; when the particle size of the silicone rubber in the emulsion is too large, the emulsion is a kind of Stable state, it is easy to produce sedimentation stratification quickly, which is not conducive to the preparation operation of composite materials.
  • the application of the silicone rubber elastomer/fiber composite material is mainly used in the fields of clothing, furniture, passenger tools and the like. Specifically, it can be applied to underwear cups, mattresses, insoles, various cushions, and the like.
  • the silicone rubber elastomer/fiber composite material of the invention has the advantages of good elasticity, good flexibility, good ventilation and the like. Moreover, the preparation method was optimized, and the particle size range of the silicone rubber droplets in the silicone rubber emulsion was screened, and the production stability was good.
  • Figure 1 Schematic diagram of the cross-sectional structure of one of the fibrous products
  • Figure 2 Schematic diagram of the three-dimensional network structure of the fiber product
  • Reference numeral 1 is a fiber
  • reference numeral 2 is a fiber product
  • reference numeral 3 is a granular silicone rubber elastomer.
  • the raw materials used in the examples and comparative experiments were the following raw materials, but were not limited to the following raw materials:
  • Polyester fiber materials are prepared by a vertical web forming process, and the fineness of the fibers is 4D.
  • Silicone rubber A Addition molding silicone rubber, Guangdong Polymer Technology Co., Ltd. produces JH-6000 series addition molding silicone rubber, the series products have different hardness, AB two-component formula, the AB components are mixed in a 1:1 ratio before use. After uniformity, it is used during the operation period, and the curing condition is 150 ° C / 5 min, and the silicone rubber elastomer A is obtained after curing.
  • Silicone rubber B peroxide vulcanized rubber, produced by Guangdong Polymer Technology Co., Ltd., commercial brand No. JH-1035, hardness Sauer hardness (type A) 35 degrees, one-component formula, curing condition is 130 ° C / 3 min, obtained after curing Silicone rubber elastomer B.
  • Silicone rubber C condensed silicone rubber; Guangdong Polymer Technology Co., Ltd., manufacturer brand number JH-3035, hardness Sauer hardness (type A) 35 degrees, one-component formula, curing conditions are room temperature or slightly heated moisture Curing, the curing time is related to the ambient humidity, and the silicone rubber elastomer C is obtained after curing.
  • the remaining raw materials are derived from commercially available products.
  • Examples 1-18 and Comparative Example 1-10 Preparation of Silicone Rubber Elastomer/Fiber Composite Material: Prepare a silicone rubber emulsion, uniformly infiltrate the fiber product therein, and then extrude the excess in the fiber product. The silicone rubber emulsion is discharged, and the fiber product is heated to volatilize the solvent, and after cross-linking and curing, a silicone rubber elastomer/fiber composite material is obtained.
  • Embodiment 19 Preparation method of silicone rubber elastomer/fiber composite material: preparing a solventless silicone rubber, uniformly wetting the fiber product therein, and then extruding excess solventless silicone rubber in the fiber product by extrusion , cross-linking curing, to obtain a silicone rubber elastomer / fiber composite.
  • Rapid resilience test The rapid resilience can be expressed by compressing the sample for a period of time and removing the compression set from 1 min after compression.
  • the samples were tested after standing at room temperature (25 ° C) for 72 h. If the sample thickness exceeds 25 mm, test it directly, the sample thickness is less than 25 mm, and stack multiple layers to a thickness exceeding 25 mm.
  • the sample was compressed to 50% of the original thickness with a jig at room temperature. After being placed for 22 hours, the jig was removed, and the final thickness was measured immediately after standing for 1 min.
  • Fast resilience performance (initial thickness of sample - final thickness of sample) ⁇ initial thickness of sample ⁇ 100%. Among them, the smaller the value of the fast resilience energy, the better.
  • Mass ratio of silicone rubber elastomer layer to granular silicone rubber elastomer Weigh the original fiber material sample mass m 0 and the obtained composite sample mass m 1 , and pulverize the composite material sample into 1 mm by a pulverizer After the granules, the granules were placed in purified water, mechanically stirred for 30 min, and then allowed to stand for 24 h, and the lower layer of the settled granular silicone rubber elastomer was collected. After drying at 120 ° C, the weighing mass was m 2 , the silicone rubber elastomer layer and the granular silicone rubber. The mass ratio of the elastomer is: (m 1 - m 0 - m 2 ): m 2 .

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Abstract

公开了一种硅橡胶弹性体/纤维复合材料及其制备方法和应用。硅橡胶弹性体/纤维复合材料包括：化学纤维和/或天然纤维制成的纤维制品，有颗粒形状的硅橡胶弹性体分布于纤维制品，硅橡胶弹性体的填充密度为0.005-0.200g/cm3。硅橡胶弹性体/纤维复合材料具有弹性好、柔软性好、透气好等优点。同时对硅橡胶弹性体/纤维复合材料的制备方法进行了优化，工艺稳定，由此工艺制备的硅橡胶弹性体/纤维复合材料回弹力好、透气性强。

Description

一种硅橡胶弹性体/纤维复合材料及其制备方法和应用 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种硅橡胶弹性体/纤维复合材料及其制备方法和应用。
背景技术
当前市场上存在大量以化学纤维或天然纤维为原料，经非织造工艺制备的纤维制品，如以天然羊毛、骆驼毛等动物纤维制成的毛毡制品；以聚酯纤维为原料通过压缩定型而成的内衣罩杯等；以及其它如鞋垫、各类坐垫、靠枕等。这些产品具有轻便、柔软、透气性好等优点，应用范围非常广泛。但纤维制品由于其自身的材料性质以及结构特点，通常有回弹性差的缺点，即制品经过压缩变形后，需要较长时间才能恢复原有的形状，甚至在长时间压缩使用后，无法恢复原有的形状，失去使用价值。
硅橡胶是指主链由硅原子和氧原子交替构成的高分子弹性体材料。硅橡胶具有无毒无味、耐高温、耐候、生理相容性好等优点，在日用品、化工、汽车、机械、医疗卫生等领域都有广泛的应用。特别是硅橡胶的回弹性能优异，长期以高压缩状态使用，也能很快恢复原有的形状和功能。
专利CN102561047A利用液体硅橡胶涂覆在网状化纤织物上，并使用空气注射方法吹出多余液体硅橡胶，固化后的涂布网状物具有良好的释放性和防滑性能，用于蒸盘装食品的衬里，也未能改善化纤织物的回弹性能。因为较厚的制品无法用空气注射的的方法吹出多余的液体硅橡胶，该方法只适用于较薄的网状织物，并不适用于较厚的纤维制品。
专利CN105696352B公开了一种硅丝棉产品，其化纤棉内、外部的纤维表面包覆着硅橡胶层，形成两层完全同步的网状弹性结构，提高了化纤棉的回弹性。但是，由于该硅丝棉产品的回弹力主要由纤维表面薄薄一层连续分布的的硅橡胶层提供，受限于硅橡胶层的厚度因素影响，改性后纤维制品的回弹性能，特别是快速回弹性能和回弹耐久性并未达到最佳效果。如果单纯增加硅橡胶的比例，以增加硅橡胶层的厚度，则会影响纤维制品的柔软性和透气性。
发明内容
本发明的目的在于，克服以上技术缺陷，提供一种硅橡胶弹性体/纤维复合材料，具有回弹性好、透气性好、柔软性好等优点。
本发明的另一目的在于，提供上述复合材料的制备方法和应用。
本发明是通过以下技术方案实现的。
一种硅橡胶弹性体/纤维复合材料，包括：化学纤维和/或天然纤维制成的纤维制品，纤维制品的纤维表面有颗粒形状的硅橡胶弹性体附着，硅橡胶弹性体的填充密度为0.005-0.200g/cm 3。
硅橡胶弹性体在复合材料中填充密度小于0.005g/cm 3时，硅橡胶弹性体的填充量不足以提供足够的回弹性能；硅橡胶弹性体在复合材料中填充密度大于0.200g/cm 3时，硅橡胶的填充量过多，容易堵塞制品的孔隙，复合材料失去柔软性和透气性。
纤维制品的一些纤维表面还包覆硅橡胶弹性体层。
所述的纤维制品选用的纤维细度为1-8D，纤维制品中分布的硅橡胶弹性体层与颗粒形状的硅橡胶弹性体的质量比为(0.05-1):1。颗粒形状的硅橡胶弹性体外观为球形、半球形、椭球形、多个半球团聚成的多球面形、与纤维丝缝隙形状相适应的其它无规则形状。
化学纤维材料是指以人工合成的高分子化合物或人工改造过的天然高分子材料为原料经过纺丝工艺得到的纤维材料；人工合成高分子化合物纤维材料如聚酯纤维、聚酰胺纤维、聚丙烯腈纤维、聚乙烯醇缩甲醛纤维、聚对苯二甲酸对苯二胺纤维、聚氯乙烯纤维、聚氨酯纤维、聚丙烯纤维、聚乙烯纤维等；人工改造的天然高分子纤维材料如人造纤维素纤维、人造淀粉纤维、人造蛋白纤维、铜氨纤维、粘胶纤维、甲壳素纤维等。天然纤维主要有动物纤维、植物纤维和无机矿物纤维三大类；动物纤维如羊毛、兔毛、骆驼毛、牦牛毛、蚕丝等；植物纤维如棉花、木棉、椰壳纤维、剑麻、苎麻、亚麻、大麻等；无机矿物纤维主要为硅酸盐类矿物，如石棉纤维等。本发明的硅橡胶弹性体/纤维复合材料中纤维可以单独选用一种或选用两种及以上混合使用，也可不同类别的纤维材料混合使用。
纤维制品为纤维材料通过非织造工艺织造。非织造工艺是指不需要经过纺织过程，将纤维丝进行定向或随机排列，形成网状结构，然后通过机械、热粘或化学方法加固的工艺过程。非织造工艺包括垂直成网、纺粘法、熔喷法等方法。非织造工艺制备的纤维材料制品在商业上现已有硬质棉、仿丝棉、羽绒棉、填充棉、直立棉、中空棉等几十个品种。
所述的硅橡胶弹性体的绍尔硬度(A型)为1-70度；优选的，所述的硅橡胶弹性体的绍尔硬度(A型)为5-50度。硅橡胶弹性体/纤维复合材料中，弹性主要由颗粒形状的硅橡胶弹性体提供的。硅橡胶弹性体的硬度小于1度时，弹性体自身的机械强度不能支持较好的回弹性能；硅橡胶弹性体的硬度大于70度时，则会影响纤维制品的柔软性。
所述的硅橡胶弹性体的平均粒径范围是1-1000μm；优选的，所述的硅橡胶弹性体的平均粒径范围是5-200μm。无溶剂型硅橡胶或硅橡胶乳液在固化过程中，会发生部分颗粒 的团聚粘结现象。最终得到的硅橡胶弹性体/纤维复合材料中，分布硅橡胶弹性体的平均粒径范围为1～1000μm。硅橡胶弹性体的粒径过小时，对复合材料的回弹性增强不明显，粒径过大时，堵塞纤维网孔，影响复合材料的柔软性和透气性。
所述的硅橡胶弹性体选自过氧化物硫化橡胶交联形成的弹性体材料、缩合型硅橡胶交联形成的弹性体材料、加成型硅橡胶交联形成的弹性体材料中的一种或多种；优选的，选自加成型硅橡胶交联形成的弹性体材料。
所述纤维制品的密度为0.008-0.20g/cm 3。当纤维制品的密度小于0.008g/cm 3时，纤维制品自身的强度非常弱，硅橡胶复合改性后也无实用价值；当纤维制品的密度大于0.20g/cm 3时，纤维制品结构的空隙结构过小，硅橡胶容易堵塞制品的孔隙，失去柔软性和透气性。
所述的纤维制品中，纤维的长度为35-150mm。本发明使用的纤维基体为纤维通过非织造工艺制备而成，与传统的织造工艺的纤维产品不同。织造工艺的纤维制品都是选用长纤维通过纺纱和编织两步工艺制备，纤维长度通常大于150mm；而非织造纤维制品一般选用短纤维以非织造工艺一步制成。在一定范围内，非织造工艺的纤维制品机械强度和纤维长度有关，纤维长度越长，纤维制品的强度越大。但纤维长度大于150mm时，纤维制品的强度增长不明显，而且不利于非织造工艺的加工工艺；纤维长度小于35mm时，纤维制品自身弹性不足。
所述纤维制品的结构为三维网络状；所述的硅橡胶弹性体/纤维复合材料的厚度范围是3-80mm。当纤维制品的厚度小于3mm时，对于回弹性需求不强，且硅橡胶复合后改进不明显；当纤维制品的厚度大于80mm时，应用面较窄，且复合材料的制备难度较大。通过叠加的方式使复合材料的厚度超过80mm，也在本发明的保护范围内。当纤维制品厚度大于80mm时，通过一次性制造来复合两种材料，则产品的复合均匀度变差，能耗也提升。可以通过两种厚度的复合材料进行贴合来达成目标。
上述硅橡胶弹性体/纤维复合材料的制备方法，包括以下步骤：以硅橡胶乳液制备：制备好硅橡胶乳液，再将纤维制品均匀浸润其中，然后通过挤压的方式将纤维制品中多余的硅橡胶乳液排出，再将纤维制品进行加热挥发溶剂，交联固化后，得到硅橡胶弹性体/纤维复合材料；所述的硅橡胶乳液中，硅橡胶在溶液中分布的平均粒径为0.01-100μm；优选0.5-20μm；通过加热方式让硅橡胶乳液水分挥发，乳液中硅橡胶液滴逐渐团聚并固化交联成一定粒径的颗粒状硅橡胶弹性体。当乳液中硅橡胶粒径过小时，不利于形成一定粒径的颗粒状硅橡胶弹性体，影响最后复合材料的回弹性能；当乳液中硅橡胶的粒径过大时，乳液为 一种不稳定状态，容易很快产生沉降分层现象，不利于复合材料的制备操作。
以无溶剂型硅橡胶制备：制备好无溶剂型硅橡胶，再将纤维制品均匀浸润其中，然后通过挤压的方式将纤维制品中多余的无溶剂型硅橡胶挤出，交联固化，得到硅橡胶弹性体/纤维复合材料。无溶剂型硅橡胶再浸入纤维制品后，逐渐收缩成非连续分布的硅橡胶液滴，并在硅橡胶的固化条件下交联固化，形成颗粒状硅橡胶弹性体。
所述的硅橡胶弹性体/纤维复合材料的应用，主要用于衣物、家具、乘用工具等领域。具体的，可以应用与内衣罩杯、床垫、鞋垫、各类坐垫靠枕等。
本发明具有如下有益效果：
本发明的硅橡胶弹性体/纤维复合材料具有弹性好、柔软性好、透气好等优点。并且对制备方法进行了优化，筛选了硅橡胶乳液中硅橡胶液滴的粒径范围，生产稳定性好。
附图说明
图1：纤维制品中其中一层的剖面结构示意图，
图2：纤维制品的三维网状结构示意图，
附图标记1为纤维，附图标记2为纤维制品，附图标记3为颗粒状的硅橡胶弹性体。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较能体现发明思路的实施方式，但是本发明并不受下述实施例的限制。
实施例与对比例实验所用的原料为以下原料，但不限于以下原料：
纤维制品：聚酯纤维材料通过垂直成网工艺制备而成，纤维的细度为4D。
硅橡胶A：加成型硅橡胶，广东聚合科技股份有限公司生产JH-6000系列加成型硅橡胶，系列产品具有不同的硬度，AB双组分配方，使用前将AB组分以1:1比例混合均匀后在操作期内使用，固化条件为150℃/5min，固化后得到硅橡胶弹性体A。
硅橡胶B：过氧化物硫化橡胶，广东聚合科技股份有限公司生产，商品牌号JH-1035，硬度绍尔硬度(A型)35度，单组份配方，固化条件为130℃/3min，固化后得到硅橡胶弹性体B。
硅橡胶C：缩合型硅橡胶；广东聚合科技股份有限公司生产，商品牌号JH-3035，硬度绍尔硬度(A型)35度，单组份配方，固化条件为室温或稍加热条件下湿气固化，固化时间与环境湿度有关，固化后得到硅橡胶弹性体C。
其余原料来源于市售产品。
实施例1-18的和对比例1-10硅橡胶弹性体/纤维复合材料的制备方法：制备好硅橡胶 乳液，再将纤维制品均匀浸润其中，然后通过挤压的方式将纤维制品中多余的硅橡胶乳液排出，再将纤维制品进行加热挥发溶剂，交联固化后，得到硅橡胶弹性体/纤维复合材料。
实施例19硅橡胶弹性体/纤维复合材料的制备方法：制备好无溶剂型硅橡胶，再将纤维制品均匀浸润其中，然后通过挤压的方式将纤维制品中多余的无溶剂型硅橡胶挤出，交联固化，得到硅橡胶弹性体/纤维复合材料。
各性能测试方法
(1)快速回弹性能测试：快速回弹性能以样品被压缩一段时间，撤去压缩后1min内测试的压缩永久形变率来表示。参考国标GB/T 6669-2008的方法，样品在室温(25℃)放置72h后进行测试。如果样品厚度超过25mm，直接测试，样品厚度不足25mm，叠加多层至厚度超过25mm。样品在室温下用夹具压缩至原有厚度的50％，放置22h后撤去夹具，静置1min后立刻测量其最终厚度。快速回弹性能＝(样品初始厚度－样品最终厚度)÷样品初始厚度×100％。其中，快速回弹性能数值越小越好。
(2)回弹耐久性测试：回弹耐久性以样品被反复压缩5000次后的压缩永久形变率来表示。参考国标GB/T 6669-2008的方法，样品在室温(25℃)放置72h后进行测试。如果样品厚度超过25mm，直接测试；样品厚度不足25mm，叠加多层至厚度超过25mm，测量其初始厚度。样品在室温下重复被机械装置压缩至原有厚度的50％后立刻撤去压缩，2s循环一次，循环压缩5000次后，撤去装置。静置30min后测量其最终厚度。回弹耐久性＝(样品初始厚度－样品最终厚度)÷样品初始厚度×100％。其中，回弹耐久性数值越小越好。
(3)手感测试：测试员以手触样品的方式进行直接评价，柔软到硬由分数1-5逐渐上升，分数越高越硬。
(4)绍尔硬度(A型)：参考国标GB/T 531-1999的方法，将硅橡胶单独在模具中固化为硅橡胶弹性体后，使用袖珍硬度计进行测量。
(5)硅橡胶弹性体填充密度：称量原始纤维材料样品质量m 0和制得的复合材料样品质量m 1，测量复合材料的长度、宽度、厚度，计算出复合材料的体积V，填充密度＝(m 1-m 0)/V。
(6)颗粒状的硅橡胶弹性体平均粒径的测量：将复合材料切片成1mm厚的样品，利用视频图象测量仪(尼康NEXIV VMR-H3030)随机选取样品中一块5mm×5mm区域内所有可见的颗粒状的硅橡胶弹性体，测量其粒径，选取50个以上，计算平均值，如果区域内颗粒状的硅橡胶弹性体数不足50个，可另外选取一个区域叠加统计。
(7)透气性测试：参考国标GB/T 5453-1997的方法，使用全自动织物透气性测试仪(温州际高生产，型号YG461E-II)进行检测，实验面积为20cm 2，压降为200Pa。
(8)硅橡胶弹性体层与颗粒状硅橡胶弹性体的质量比：称量原始纤维材料样品质量m 0和制得的复合材料样品质量m 1，将复合材料样品用粉碎机粉碎成1mm的颗粒后，将颗粒至于纯净水中，机械搅拌30min后静置24h，收集下层沉降的颗粒状硅橡胶弹性体，120℃烘干后称量质量为m 2，硅橡胶弹性体层与颗粒状硅橡胶弹性体的质量比为：(m 1-m 0-m 2):m 2。
表1：实施例1-13、18/19和对比例1-9的数据
Figure PCTCN2018087782-appb-000001
续表1
Figure PCTCN2018087782-appb-000002
续表1
Figure PCTCN2018087782-appb-000003
表2：实施例14-17和对比例10数据
Figure PCTCN2018087782-appb-000004
从实施例1-13和对比例1-8可以看出，随着填充密度、硅橡胶弹性体硬度、颗粒状硅橡胶弹性体平均粒径、纤维密度的上升，快速回弹性、回弹耐久性上升，透气性下降，手感会逐渐变硬；当填充密度为0.25g/cm 3时，手感达到4，太硬使手感不佳，而且透气性差；当硬度达到80度时，手感达到5，太硬使手感不佳；当平均粒径为1200μm时，手感为5级，太硬使手感不佳，而且透气性差；当纤维密度为0.25g/cm 3时，手感达到4，太硬使手感不佳，而且透气性太差。从实施例14-17和对比例10可以看出，随着硅橡胶弹性体层与颗粒状硅橡胶弹性体的质量比的上升，快速回弹性、回弹耐久性下降，手感几乎不变，透气性缓慢上升，质量比在(0.05-1):1的范围内，快速回弹性、回弹耐久性保持优良，但是，当质量比为1.1:1时，快速回弹性、回弹耐久性下降较多，不能满足产品性能需求。

Claims (10)

  1. 一种硅橡胶弹性体/纤维复合材料，包括：化学纤维和/或天然纤维制成的纤维制品，其特征在于，有颗粒形状的硅橡胶弹性体分布于纤维制品，硅橡胶弹性体的填充密度为0.005-0.200g/cm 3。
  2. 根据权利要求1所述的硅橡胶弹性体/纤维复合材料，其特征在于，纤维制品的纤维表面还包覆硅橡胶弹性体层。
  3. 根据权利要求2所述的硅橡胶弹性体/纤维复合材料，其特征在于，所述的纤维制品选用的纤维细度为1-8D，纤维制品中分布的硅橡胶弹性体层与颗粒形状的硅橡胶弹性体的质量比为(0.05-1):1。
  4. 根据权利要求1或2任一项所述的硅橡胶弹性体/纤维复合材料，其特征在于，所述的硅橡胶弹性体的平均粒径范围是1-1000μm；优选的，所述的硅橡胶弹性体的平均粒径范围是5-200μm。
  5. 根据权利要求1或2任一项所述的硅橡胶弹性体/纤维复合材料，其特征在于，所述的硅橡胶弹性体选自过氧化物硫化橡胶交联形成的弹性体材料、缩合型硅橡胶交联形成的弹性体材料、加成型硅橡胶交联形成的弹性体材料中的一种或多种；优选的，选自加成型硅橡胶交联形成的弹性体材料。
  6. 根据权利要求1或2所述的硅橡胶弹性体/纤维复合材料，其特征在于，所述的硅橡胶弹性体的绍尔硬度(A型)为1-70度；优选的，所述的硅橡胶弹性体的绍尔硬度(A型)为5-50度。
  7. 根据权利要求1或2任一项所述的硅橡胶弹性体/纤维复合材料，其特征在于，所述纤维制品的密度为0.008-0.20g/cm 3；所述的纤维制品中，纤维的长度为35-150mm。
  8. 根据权利要求1或2任一项所述的硅橡胶弹性体/纤维复合材料，其特征在于，所述纤维制品的结构为三维网络状；所述的硅橡胶弹性体/纤维复合材料的厚度范围是3-80mm。
  9. 权利要求8所述的硅橡胶弹性体/纤维复合材料的制备方法，其特征在于，包括以下步骤：以硅橡胶乳液制备：制备好硅橡胶乳液，再将纤维制品均匀浸润其中，然后通过挤压的方式将纤维制品中多余的硅橡胶乳液排出，再将纤维制品进行加热挥发溶剂，交联固化后，得到硅橡胶弹性体/纤维复合材料；所述的硅橡胶乳液中，硅橡胶在溶液中分布的平均粒径为0.01-100μm；优选0.5-20μm；
    以无溶剂型硅橡胶制备：制备好无溶剂型硅橡胶，再将纤维制品均匀浸润其中，然后通过挤压的方式将纤维制品中多余的无溶剂型硅橡胶挤出，交联固化，得到硅橡胶弹性体/纤维复合材料。
  10. 权利要求1-8任一项所述的硅橡胶弹性体/纤维复合材料的应用，其特征在于，用于衣物、家具、乘用工具等领域。
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