[go: up one dir, main page]

WO2017140124A1 - Interlayer reinforced fiber composite material having diversion layer, and method for manufacture thereof - Google Patents

Interlayer reinforced fiber composite material having diversion layer, and method for manufacture thereof Download PDF

Info

Publication number
WO2017140124A1
WO2017140124A1 PCT/CN2016/103786 CN2016103786W WO2017140124A1 WO 2017140124 A1 WO2017140124 A1 WO 2017140124A1 CN 2016103786 W CN2016103786 W CN 2016103786W WO 2017140124 A1 WO2017140124 A1 WO 2017140124A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
interlayer
composite material
flow guiding
cloth
Prior art date
Application number
PCT/CN2016/103786
Other languages
French (fr)
Chinese (zh)
Inventor
梅天诚
Original Assignee
苏州振瑞昌材料科技有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 苏州振瑞昌材料科技有限公司 filed Critical 苏州振瑞昌材料科技有限公司
Publication of WO2017140124A1 publication Critical patent/WO2017140124A1/en

Links

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
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • 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
    • 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
    • B32B5/06—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 characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
    • 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
    • B32B5/08—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 the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • 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
    • B32B5/10—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 characterised by a fibrous or filamentary layer reinforced with filaments
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/18—Fabrics, textiles
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/38—Meshes, lattices or nets
    • 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
    • B32B2307/58—Cuttability
    • 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
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
    • B32B2315/085—Glass fiber cloth or fabric
    • 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
    • B32B2323/00—Polyalkenes
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene

Definitions

  • the present invention relates to the field of reinforcing materials, and in particular to an interlayer reinforcing fiber composite material and a method for manufacturing the same, and more particularly, a design is suitable for An interlayer reinforcing fiber pre-woven fabric of a pultrusion process and a method of manufacturing the same.
  • Glass fiber reinforced plastics with glass fiber as a reinforcing material has the advantages of light weight, high strength, corrosion resistance, moisture absorption, heat resistance, low temperature resistance, etc., and is widely used in the construction field, and has been applied to green industrial buildings, industrial energy-saving windows and doors, shopping malls, The stadiums and exhibition halls are mainly used for roofing panels, lighting belts, partition boards, wall panels, flooring, industrial profiles and so on.
  • the pultrusion process is a main molding process applied to building composite materials. The basic process is that the fiber reinforced material is subjected to external force traction, dipped, preformed template guide, and hot mold cured to obtain profile products. And cut into a certain length according to the requirements of use.
  • the most used are glass fiber roving, glass fiber continuous felt and glass fiber surface felt.
  • the composite material prepared by the molding process not only has good mechanical properties, but also can be continuously produced, and has been widely used in the production and manufacture of composite materials such as FRP.
  • this composite material has anisotropy and is prone to interlayer delamination, resulting in a significant decrease in interlaminar shear strength. How to improve the interlaminar shear strength of the pultrusion forming sheet is an urgent problem to be solved.
  • the technical problem to be solved by the present invention is to overcome the above-mentioned drawbacks of the prior art, and to provide a layered reinforcing fiber pre-woven fabric with a flow guiding layer suitable for a pultrusion process and a manufacturing method thereof, so that the cost can be reduced.
  • the interlaminar shear strength of the composite material is increased, and the resin can be uniformly impregnated into the fiber pre-woven fabric.
  • An interlayer reinforcing fiber composite material with a flow guiding layer comprising an interlayer reinforced fiber pre-woven fabric and a matrix resin, the interlayer reinforced fiber pre-woven fabric comprising a layered glass mat and a drainage layer fiber cloth And an interlayer continuous fiber, wherein the drainage layer fiber cloth is located at an intermediate layer position of the layered glass mat, and the layer of the laid glass mat and the drainage layer fiber cloth pass through the interlayer
  • the continuous fibers are stitched together.
  • the flow guiding layer fiber cloth is flexibly set to 1-3 layers in accordance with the thickness variation of the interlayer-reinforced fiber pre-woven fabric.
  • the baffle fiber cloth is a polyolefin fiber unidirectional cloth.
  • the baffle fiber cloth is a polypropylene fiber unidirectional cloth.
  • the baffle fiber cloth is a carbon fiber unidirectional cloth or a high molecular weight polyolefin mesh cloth.
  • the glass mat is a mixed fabric of pure glass fibers and chopped glass fibers.
  • the glass mat is a mixed fabric of glass fibers, basalt fibers, and carbon fibers.
  • the continuous fibers of the interlayer are made of high-strength glass fiber, carbon fiber or basalt fiber.
  • the matrix resin is an unsaturated resin, a vinyl resin, and a phenol resin. One or several.
  • the present invention also provides a method for manufacturing an interlayer reinforcing fiber composite material as described above, firstly laminating a glass mat, and then adding a wind guiding layer fiber cloth to an intermediate layer position of the layered glass mat. Then, using the sewing technique, the layered glass felt and the drainage layer fiber cloth are stitched together by continuous fibers of the interlayer, and the stitched glass felt is formed by a pultrusion process using a matrix resin. The interlayer reinforcing fiber composite material is obtained.
  • the present invention has the following significant advantages and beneficial effects:
  • the pre-woven fabric of the present invention adopts a reinforcing fiber cloth as a flow guiding layer, and can uniformly penetrate the fiber mat during the resin dipping process, so that the obtained composite material has stable performance.
  • the pre-wovens are layered with continuous fiber mats such as glass mats, the sewing technology used is simple, easy to handle, and can be continuously produced, and the cost of the prepared inter-layer reinforced pre-wovens does not increase too much.
  • the composite material obtained from the interlayer reinforced fiber pre-woven material of the present invention by the pultrusion process has a markedly improved mechanical property compared with the conventional pultrusion composite material, and the interlaminar shear strength is increased by 50% or more. .
  • Figure 1 is a structural view of an interlayer reinforced fiber pre-woven fabric of the present invention.
  • the interlayer reinforcing fiber composite material disclosed by the present invention comprises an interlayer-reinforced fiber pre-woven fabric and a matrix resin, wherein the interlayer-reinforced fiber pre-woven fabric comprises a layered glass mat 1 and a drainage layer
  • the interlayer-reinforced fiber pre-woven fabric comprises a layered glass mat 1 and a drainage layer
  • the fiber cloth 2 and the interlayer continuous fiber 3 and the layered glass mat 1 and the drainage layer fiber cloth 2 are sewn together by the inter-layer continuous fibers 3.
  • a composite material can be obtained by forming a layer-reinforced fiber pre-woven fabric by a pultrusion process using an unsaturated resin, a vinyl resin, a phenol resin or the like as a matrix.
  • the processing of the unsaturated resin, vinyl resin and phenolic resin used meets the needs of the pultrusion process.
  • the glass mat can be made of a mixture of pure glass fiber and chopped glass fiber, or a continuous fiber fabric can be prepared by mixing fibers such as glass fiber, basalt fiber, and carbon fiber; glass woven from pure glass fiber and chopped glass fiber is preferred. felt.
  • the continuous fiber for stitching is made of high-strength glass fiber, carbon fiber and basalt fiber; glass fiber and basalt fiber are preferably used.
  • the base resin can be a conventional unsaturated resin resin, a vinyl resin, and a phenolic tree suitable for the pultrusion process.
  • the drainage layer can be made of a polyolefin fiber unidirectional cloth, such as a polypropylene fiber unidirectional cloth or a polyethylene fiber unidirectional cloth.
  • the fiber has a smooth surface rod-like structure, is light in weight, high in strength, and has good wear resistance. Polypropylene fiber unidirectional cloth is preferred.
  • the baffle may also be a carbon fiber unidirectional cloth, which means that there is a large amount of carbon fiber filaments in one direction (usually warp direction) and only a small amount and usually fine carbon fiber filaments in the other direction.
  • the flow directing layer can also employ extruded high molecular weight polyolefin mesh having high permeability which facilitates the flow and penetration of the resin.
  • a diversion cloth having a different square gram weight may be selected, or a layered laying structure of the multi-layer guide cloth may be designed according to the structure of the product to be molded, thereby realizing effective control of the flow state of the resin. Thereby improving the reliability and product quality of the complex product forming process.
  • the woven continuous glass mat is layered.
  • the drainage layer with enhanced osmosis is introduced into the layer of continuous fiber mat in a certain layering manner, and the width of the continuous glass felt is layered. It can be 20-2000 mm, preferably 1000-1500 mm, and the number of layers can be selected according to the needs of the product, that is, the thickness of the layer can be controlled.
  • the diversion layer is placed in the middle of the layer, and the number of layers of the diversion layer can be increased according to the thickness of the layer. 2.
  • the layered continuous glass mat was stitched.

Landscapes

  • Laminated Bodies (AREA)
  • Road Paving Structures (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Woven Fabrics (AREA)

Abstract

Provided is an interlayer reinforced fiber composite material having a diversion layer, comprising an interlayer reinforced fiber pre-woven element and a matrix resin; the interlayer reinforced fiber pre-woven element contains a laid layer of glass felt, a diversion-layer fiber fabric, and an interlayer continuous fiber; the diversion-layer fiber fabric is located at the position of the intermediate layer of the laid layer of glass felt, and the laid layer of glass felt and the diversion-layer fiber fabric are stitched together by means of the interlayer continuous fiber. The interlayer reinforced fiber composite material not only reduces costs and increases the interlayer shear strength of the reinforced fiber composite material, but also ensures that the resin uniformly permeates the fiber pre-woven element.

Description

一种带导流层的层间增强纤维复合材料及其制造方法 技术领域 本发明涉及增强材料领域， 具体涉及一种层间增强纤维复合材料及其 制造方法， 更具体地， 设计一种适用于拉挤成型工艺的层间增强纤维预织 件及其制造方法。 背景技术 以玻璃纤维为增强材料的玻璃钢具有轻质高强、耐腐防渗、隔热吸音、 耐低温等综合优点， 在建筑领域被大量利用， 已经应用到绿色工业建筑、 工业节能门窗、 商场、 体育馆、 展览馆， 其应用产品主要为屋面板、 采光 带、 隔断板、 墙板、 地板、 工业型材等。 拉挤成型工艺是一种应用于建筑 复合材料的主要成型工艺， 其基本工艺过程是， 纤维增强材料， 在外力的 牵引下， 经浸胶、 预成型模板导向、 热模固化， 得到型材制品， 并按使用 要求切成一定长度的过程。  TECHNICAL FIELD The present invention relates to the field of reinforcing materials, and in particular to an interlayer reinforcing fiber composite material and a method for manufacturing the same, and more particularly, a design is suitable for An interlayer reinforcing fiber pre-woven fabric of a pultrusion process and a method of manufacturing the same. BACKGROUND OF THE INVENTION Glass fiber reinforced plastics with glass fiber as a reinforcing material has the advantages of light weight, high strength, corrosion resistance, moisture absorption, heat resistance, low temperature resistance, etc., and is widely used in the construction field, and has been applied to green industrial buildings, industrial energy-saving windows and doors, shopping malls, The stadiums and exhibition halls are mainly used for roofing panels, lighting belts, partition boards, wall panels, flooring, industrial profiles and so on. The pultrusion process is a main molding process applied to building composite materials. The basic process is that the fiber reinforced material is subjected to external force traction, dipped, preformed template guide, and hot mold cured to obtain profile products. And cut into a certain length according to the requirements of use.
在拉挤成型工艺中， 应用最多的是玻璃纤维无捻粗纱、 玻璃纤维连续 毡及玻璃纤维表面毡等。 这种成型工艺制备的复合材料， 不仅具有良好的 力学性能， 而且可以连续化生产， 已经广泛应用于玻璃钢等复合材料的生 产与制造。 然而这种复合材料具有各向异性， 易出现层间分层， 使其层间 剪切强度明显下降。如何提高拉挤工艺成型板材的层间剪切强度是目前急 需解决的难题。  In the pultrusion process, the most used are glass fiber roving, glass fiber continuous felt and glass fiber surface felt. The composite material prepared by the molding process not only has good mechanical properties, but also can be continuously produced, and has been widely used in the production and manufacture of composite materials such as FRP. However, this composite material has anisotropy and is prone to interlayer delamination, resulting in a significant decrease in interlaminar shear strength. How to improve the interlaminar shear strength of the pultrusion forming sheet is an urgent problem to be solved.
通过三维编织以及缝合技术，虽然完美的解决复合材料的层间剪切强 度与断裂韧性问题， 但是对设备的要求高， 而且成本昂贵， 仅限于航空航 天等高端领域。 对于建筑等民用领域来说， 其复杂的结构和高昂的制造成 本， 限制了该技术的发展。  Through the three-dimensional weaving and stitching technology, although the interlaminar shear strength and fracture toughness of the composite material are perfectly solved, the equipment is highly demanded and expensive, and is limited to high-end fields such as aerospace. For civilian applications such as construction, its complex structure and high manufacturing costs limit the development of this technology.
此外， 随着现代工业的发展， 拉挤成型的复合材料越来越大型化， 不 仅厚度明显增加， 而且尺寸也大幅提升。 因此在拉挤成型加工过程中， 由 于纤维预制件的厚度较大， 且各向异性， 树脂很难均匀浸透纤维预织件， 容易造成拉挤成型后复合材料的缺胶等缺陷。 In addition, with the development of modern industry, pultrusion composite materials are becoming larger and larger, not Only the thickness is significantly increased, and the size is also greatly increased. Therefore, in the pultrusion processing process, due to the large thickness of the fiber preform and the anisotropy, it is difficult for the resin to uniformly impregnate the fiber pre-woven fabric, which is liable to cause defects such as lack of glue of the composite material after pultrusion.
因此， 在现有的玻璃钢复合材料中， 如何在降低成本的同时提高纤维 增强复合材料的层间剪切结构，且保证树脂能够均匀浸透纤维预织件， 是 目前建筑用纤维增强复合材料领域急需解决的问题。 发明内容  Therefore, in the existing FRP composite materials, how to improve the interlayer shear structure of the fiber reinforced composite material while reducing the cost, and to ensure that the resin can uniformly impregnate the fiber pre-woven fabric, is urgently needed in the field of fiber reinforced composite materials for construction. solved problem. Summary of the invention
本发明所要解决的技术问题在于克服前述技术存在的上述缺陷，提供 一种适用于拉挤成型工艺的带导流层的层间增强纤维预织件及其制造方 法， 使得既能够在降低成本的同时增加复合材料的层间剪切强度， 又可以 保证树脂能够均匀浸透纤维预织件。  The technical problem to be solved by the present invention is to overcome the above-mentioned drawbacks of the prior art, and to provide a layered reinforcing fiber pre-woven fabric with a flow guiding layer suitable for a pultrusion process and a manufacturing method thereof, so that the cost can be reduced. At the same time, the interlaminar shear strength of the composite material is increased, and the resin can be uniformly impregnated into the fiber pre-woven fabric.
为解决上述技术问题， 本发明采取的技术方案如下：  In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:
一种带导流层的层间增强纤维复合材料，包括层间增强的纤维预织件 和基体树脂， 所述层间增强的纤维预织件包含层铺好的玻璃毡、 导流层纤 维布和层间连续纤维， 其中， 所述导流层纤维布位于所述层铺好的玻璃毡 的中间层位置，所述层铺好的玻璃毡和所述导流层纤维布通过所述层间连 续纤维缝合在一起。  An interlayer reinforcing fiber composite material with a flow guiding layer comprising an interlayer reinforced fiber pre-woven fabric and a matrix resin, the interlayer reinforced fiber pre-woven fabric comprising a layered glass mat and a drainage layer fiber cloth And an interlayer continuous fiber, wherein the drainage layer fiber cloth is located at an intermediate layer position of the layered glass mat, and the layer of the laid glass mat and the drainage layer fiber cloth pass through the interlayer The continuous fibers are stitched together.
进一歩地，所述导流层纤维布根据所述层间增强的纤维预织件的厚度 变化灵活设置为 1-3层。  Further, the flow guiding layer fiber cloth is flexibly set to 1-3 layers in accordance with the thickness variation of the interlayer-reinforced fiber pre-woven fabric.
进一歩地， 所述导流层纤维布为聚烯烃纤维单向布。  Further, the baffle fiber cloth is a polyolefin fiber unidirectional cloth.
进一歩地， 所述导流层纤维布为聚丙烯纤维单向布。  Further, the baffle fiber cloth is a polypropylene fiber unidirectional cloth.
进一歩地，所述导流层纤维布为碳纤维单向布或高分子量聚烯烃网格 布。  Further, the baffle fiber cloth is a carbon fiber unidirectional cloth or a high molecular weight polyolefin mesh cloth.
进一歩地， 所述玻璃毡为纯玻璃纤维与短切玻璃纤维的混织物。  Further, the glass mat is a mixed fabric of pure glass fibers and chopped glass fibers.
进一歩地，所述玻璃毡为玻璃纤维、玄武岩纤维以及碳纤维的混织物。 进一歩地， 所述层间连续纤维采用高强玻璃纤维、 碳纤维或玄武岩纤 维。  Further, the glass mat is a mixed fabric of glass fibers, basalt fibers, and carbon fibers. Further, the continuous fibers of the interlayer are made of high-strength glass fiber, carbon fiber or basalt fiber.
进一歩地， 所述基体树脂是不饱和树脂、 乙烯基树脂以及酚醛树脂中 的一种或几种。 Further, the matrix resin is an unsaturated resin, a vinyl resin, and a phenol resin. One or several.
同时，本发明还提供了一种如上所述的层间增强纤维复合材料的制造 方法， 先将玻璃毡进行层铺， 再将导流层纤维布加入层铺好的玻璃毡的中 间层位置， 然后运用缝纫技术， 通过层间连续纤维将所述层铺好的玻璃毡 和所述导流层纤维布缝合在一起，再利用基体树脂将缝合后的玻璃毡通过 拉挤工艺成型， 即可制得所述层间增强纤维复合材料。  Meanwhile, the present invention also provides a method for manufacturing an interlayer reinforcing fiber composite material as described above, firstly laminating a glass mat, and then adding a wind guiding layer fiber cloth to an intermediate layer position of the layered glass mat. Then, using the sewing technique, the layered glass felt and the drainage layer fiber cloth are stitched together by continuous fibers of the interlayer, and the stitched glass felt is formed by a pultrusion process using a matrix resin. The interlayer reinforcing fiber composite material is obtained.
本发明与现有技术相比具有如下显著的优点和有益效果：  Compared with the prior art, the present invention has the following significant advantages and beneficial effects:
1. 本发明预织件采用了具有增强作用的纤维布作为导流层，在树脂浸 渍过程中， 能够均匀浸透纤维毡， 使获得的复合材料性能稳定。  1. The pre-woven fabric of the present invention adopts a reinforcing fiber cloth as a flow guiding layer, and can uniformly penetrate the fiber mat during the resin dipping process, so that the obtained composite material has stable performance.
2. 由于预织件采用了玻璃毡等连续纤维毡进行层铺，运用的缝纫技术 设备简单， 易于操作， 且可以连续化生产， 制备的层间增强预织件的成本 不会增加太高。  2. Since the pre-wovens are layered with continuous fiber mats such as glass mats, the sewing technology used is simple, easy to handle, and can be continuously produced, and the cost of the prepared inter-layer reinforced pre-wovens does not increase too much.
3. 通过拉挤成型工艺由本发明的层间增强的纤维预织件制得的复合 材料， 相对于传统的拉挤成型的复合材料， 其力学性能明显提高， 层间剪 切强度提高 50%以上。 附图说明  3. The composite material obtained from the interlayer reinforced fiber pre-woven material of the present invention by the pultrusion process has a markedly improved mechanical property compared with the conventional pultrusion composite material, and the interlaminar shear strength is increased by 50% or more. . DRAWINGS
图 1为本发明的层间增强的纤维预织件的结构图。  BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a structural view of an interlayer reinforced fiber pre-woven fabric of the present invention.
附图标记说明：  Description of the reference signs:
1、 玻璃毡， 2、 导流层纤维布，  1. Glass felt, 2. Diversion layer fiber cloth,
3、 层间连续纤维。 具体实施方式  3. Inter-layer continuous fibers. detailed description
为充分公开的目的， 以下将结合实施例对本发明做进一歩详细说明。 应当理解， 以下所述的具体实施例仅用于解释本发明， 并非用于限定本发 明的保护范围。  For the purpose of full disclosure, the present invention will be described in detail below with reference to the embodiments. It is understood that the specific embodiments described below are merely illustrative of the invention and are not intended to limit the scope of the invention.
本发明公开的层间增强纤维复合材料包括层间增强的纤维预织件和 基体树脂， 其中， 层间增强的纤维预织件包含层铺好的玻璃毡 1、 导流层 纤维布 2和层间连续纤维 3， 并且层铺好的玻璃毡 1和导流层纤维布 2通 过层间连续纤维 3缝合在一起。 The interlayer reinforcing fiber composite material disclosed by the present invention comprises an interlayer-reinforced fiber pre-woven fabric and a matrix resin, wherein the interlayer-reinforced fiber pre-woven fabric comprises a layered glass mat 1 and a drainage layer The fiber cloth 2 and the interlayer continuous fiber 3, and the layered glass mat 1 and the drainage layer fiber cloth 2 are sewn together by the inter-layer continuous fibers 3.
以不饱和树脂、 乙烯基树脂以及酚醛树脂等为基体， 层间增强的纤维 预织件通过拉挤工艺成型， 即可制得复合材料。 所用的不饱和树脂、 乙烯 基树脂以及酚醛树脂的加工工艺满足拉挤成型工艺的需要。  A composite material can be obtained by forming a layer-reinforced fiber pre-woven fabric by a pultrusion process using an unsaturated resin, a vinyl resin, a phenol resin or the like as a matrix. The processing of the unsaturated resin, vinyl resin and phenolic resin used meets the needs of the pultrusion process.
玻璃毡可以用纯玻璃纤维与短切玻璃纤维的混织物， 也可以采用玻璃 纤维、 玄武岩纤维、 以及碳纤维等混织纤维制备连续纤维织物； 优选采用 纯玻璃纤维与短切玻璃纤维织成的玻璃毡。缝合用连续纤维采用高强玻璃 纤维、 碳纤维以及玄武岩纤维； 优选采用玻璃纤维和玄武岩纤维。 基体树 脂可以采用常规的适用于拉挤成型工艺的不饱和脂树脂、 乙烯基树脂以及 酚醛树。  The glass mat can be made of a mixture of pure glass fiber and chopped glass fiber, or a continuous fiber fabric can be prepared by mixing fibers such as glass fiber, basalt fiber, and carbon fiber; glass woven from pure glass fiber and chopped glass fiber is preferred. felt. The continuous fiber for stitching is made of high-strength glass fiber, carbon fiber and basalt fiber; glass fiber and basalt fiber are preferably used. The base resin can be a conventional unsaturated resin resin, a vinyl resin, and a phenolic tree suitable for the pultrusion process.
导流层可以采用聚烯烃纤维单向布， 如聚丙烯纤维单向布、 聚乙烯纤 维单向布，这种纤维具有光滑表面的棒状结构，轻质高强，耐磨性能良好。 优先采用聚丙烯纤维单向布。  The drainage layer can be made of a polyolefin fiber unidirectional cloth, such as a polypropylene fiber unidirectional cloth or a polyethylene fiber unidirectional cloth. The fiber has a smooth surface rod-like structure, is light in weight, high in strength, and has good wear resistance. Polypropylene fiber unidirectional cloth is preferred.
导流层也可以采用碳纤维单向布， 碳纤维单向布是指在一个方向 （通 常是经向）具有大量的碳纤维丝， 在另一方向只有少量并且通常是细的碳 纤维丝。  The baffle may also be a carbon fiber unidirectional cloth, which means that there is a large amount of carbon fiber filaments in one direction (usually warp direction) and only a small amount and usually fine carbon fiber filaments in the other direction.
导流层还可以采用挤出的具有高渗透性的高分子量聚烯烃网格布， 其 有利于树脂的流动和渗透。  The flow directing layer can also employ extruded high molecular weight polyolefin mesh having high permeability which facilitates the flow and penetration of the resin.
可根据被成型制品的所需流速， 选用不同平方克重的导流布， 也可根 据被成型制品的结构， 设计多层导流布层叠的铺放结构， 实现对树脂流动 状态的有效控制， 从而提高复杂制品成型工艺的可靠性和产品质量。  According to the required flow rate of the product to be molded, a diversion cloth having a different square gram weight may be selected, or a layered laying structure of the multi-layer guide cloth may be designed according to the structure of the product to be molded, thereby realizing effective control of the flow state of the resin. Thereby improving the reliability and product quality of the complex product forming process.
具体的预织件制造歩骤如下：  The specific pre-woven manufacturing steps are as follows:
1.连续玻璃毡的层铺  1. Layering of continuous glass felt
将编织好的连续玻璃毡进行层铺， 在连续纤维层铺过程中， 引入增强 渗透作用的导流层以一定的铺层方式加入连续纤维毡的层铺中，层铺的连 续玻璃毡的宽度可以为 20-2000mm，优选 1000-1500mm，层数根据产品的 需要进行选择， 即层铺的厚度可以进行控制。 导流层置于层铺中间位置， 根据层铺厚度需求， 导流层的层数可以增加。 2.层间缝合 The woven continuous glass mat is layered. During the continuous fiber layer laying process, the drainage layer with enhanced osmosis is introduced into the layer of continuous fiber mat in a certain layering manner, and the width of the continuous glass felt is layered. It can be 20-2000 mm, preferably 1000-1500 mm, and the number of layers can be selected according to the needs of the product, that is, the thickness of the layer can be controlled. The diversion layer is placed in the middle of the layer, and the number of layers of the diversion layer can be increased according to the thickness of the layer. 2. Interlayer stitching
将层铺好的连续玻璃毡进行缝合。  The layered continuous glass mat was stitched.
以上所述实施例仅表达了本发明的实施方式， 其描述较为具体和详 细， 但并不能因此而理解为对本发明专利范围的限制。 应当指出的是， 对 于本领域的普通技术人员来说， 在不脱离本发明构思的前提下， 还可以做 出若干变形和改进， 这些都属于本发明的保护范围。 因此， 本发明专利的 保护范围应以所附权利要求为准。  The above-mentioned embodiments are merely illustrative of the embodiments of the present invention, and the description thereof is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims

权 利 要 求 书 Claim
1. 一种带导流层的层间增强纤维复合材料，包括层间增强的纤维预织 件和基体树脂， 其特征在于： 所述层间增强的纤维预织件包含层铺好的玻 璃毡、 导流层纤维布和层间连续纤维， 其中， 所述导流层纤维布位于所述 层铺好的玻璃毡的中间层位置，所述层铺好的玻璃毡和所述导流层纤维布 通过所述层间连续纤维缝合在一起。 An interlayer reinforcing fiber composite material with a flow guiding layer comprising an interlayer reinforced fiber pre-woven member and a matrix resin, characterized in that: the interlayer-reinforced fiber pre-woven member comprises a layered glass felt a drainage layer fiber cloth and an interlayer continuous fiber, wherein the drainage layer fiber cloth is located at an intermediate layer position of the layered glass mat, the layer laid glass felt and the drainage layer fiber The cloth is stitched together by the continuous fibers of the layers.
2. 根据权利要求 1所述的带导流层的层间增强纤维复合材料，其特征 在于，所述导流层纤维布根据所述层间增强的纤维预织件的厚度变化灵活 设置为 1-3层。  The interlayer reinforcing fiber composite material with a flow guiding layer according to claim 1, wherein the flow guiding layer fiber cloth is flexibly set to 1 according to a thickness variation of the interlayer-reinforced fiber pre-woven fabric. - 3 floors.
3. 根据权利要求 1所述的带导流层的层间增强纤维复合材料，其特征 在于， 所述导流层纤维布为聚烯烃纤维单向布。  The interlayer reinforcing fiber composite material with a flow guiding layer according to claim 1, wherein the flow guiding layer fiber cloth is a polyolefin fiber unidirectional cloth.
4. 根据权利要求 2所述的带导流层的层间增强纤维复合材料， 其特 征在于， 所述导流层纤维布为聚丙烯纤维单向布。  The interlayer reinforcing fiber composite material with a flow guiding layer according to claim 2, wherein the flow guiding layer fiber cloth is a polypropylene fiber unidirectional cloth.
5. 根据权利要求 1所述的带导流层的层间增强纤维复合材料， 其特 征在于， 所述导流层纤维布为碳纤维单向布或高分子量聚烯烃网格布。  The inter-layer reinforcing fiber composite material with a flow guiding layer according to claim 1, wherein the flow guiding layer fiber cloth is a carbon fiber unidirectional cloth or a high molecular weight polyolefin mesh cloth.
6. 根据权利要求 1所述的带导流层的层间增强纤维复合材料，其特征 在于： 所述玻璃毡为纯玻璃纤维与短切玻璃纤维的混织物。  The interlayer reinforcing fiber composite material with a flow guiding layer according to claim 1, wherein the glass mat is a mixed fabric of pure glass fibers and chopped glass fibers.
7. 根据权利要求 1所述的带导流层的层间增强纤维复合材料，其特征 在于： 所述玻璃毡为玻璃纤维、 玄武岩纤维以及碳纤维的混织物。  The interlayer reinforcing fiber composite material with a flow guiding layer according to claim 1, wherein the glass mat is a mixed fabric of glass fibers, basalt fibers, and carbon fibers.
8. 根据权利要求 1所述的带导流层的层间增强纤维复合材料，其特征 在于， 所述层间连续纤维采用高强玻璃纤维、 碳纤维或玄武岩纤维。  The interlayer reinforcing fiber composite material with a flow guiding layer according to claim 1, wherein the interlayer continuous fiber is made of high-strength glass fiber, carbon fiber or basalt fiber.
9. 根据权利要求 1所述的带导流层的层间增强纤维复合材料，其特征 在于： 所述基体树脂是不饱和树脂、 乙烯基树脂以及酚醛树脂中的一种或 几种。  The interlayer reinforcing fiber composite material with a flow guiding layer according to claim 1, wherein the matrix resin is one or more of an unsaturated resin, a vinyl resin, and a phenol resin.
10. 一种如权利要求 1所述的带导流层的层间增强纤维复合材料的制 造方法， 其特征在于， 先将玻璃毡进行层铺， 再将导流层纤维布加入层铺 好的玻璃毡的中间层位置， 然后运用缝纫技术， 通过层间连续纤维将所述 层铺好的玻璃毡和所述导流层纤维布缝合在一起，再利用基体树脂将缝合 后的玻璃毡通过拉挤工艺成型， 即可制得所述层间增强纤维复合材料。  10. A method of manufacturing an interlayer reinforcing fiber composite material with a flow guiding layer according to claim 1, wherein the glass mat is first layered, and the drainage layer fiber cloth is layered. The position of the intermediate layer of the glass mat, and then using the sewing technique, the layered glass mat and the baffle fiber cloth are stitched together by the continuous fibers of the interlayer, and the stitched glass mat is pulled by the base resin. The interlayer reinforcing fiber composite material can be obtained by extrusion molding.
PCT/CN2016/103786 2016-02-19 2016-10-28 Interlayer reinforced fiber composite material having diversion layer, and method for manufacture thereof WO2017140124A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610093554.XA CN105711214A (en) 2016-02-19 2016-02-19 Interlamination reinforced fiber composite material with flow guiding layer and preparation method thereof
CN201610093554.X 2016-02-19

Publications (1)

Publication Number Publication Date
WO2017140124A1 true WO2017140124A1 (en) 2017-08-24

Family

ID=56156898

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/103786 WO2017140124A1 (en) 2016-02-19 2016-10-28 Interlayer reinforced fiber composite material having diversion layer, and method for manufacture thereof

Country Status (2)

Country Link
CN (1) CN105711214A (en)
WO (1) WO2017140124A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105711214A (en) * 2016-02-19 2016-06-29 苏州振瑞昌材料科技有限公司 Interlamination reinforced fiber composite material with flow guiding layer and preparation method thereof
CN109109407B (en) * 2018-08-01 2019-09-06 中材科技股份有限公司 A kind of insulating composite material and preparation method thereof
CN110039792B (en) * 2018-11-22 2025-01-07 阜宁云逸航空复合材料有限公司 Method and device for manufacturing honeycomb with continuous fiber reinforced sidewalls
CN113524716A (en) * 2021-07-26 2021-10-22 常州天马集团有限公司（原建材二五三厂） Fiber-reinforced preformed composite structure

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201567440U (en) * 2009-11-12 2010-09-01 江苏九鼎新材料股份有限公司 One-way fabric composite surface felt
CN102632663A (en) * 2012-04-01 2012-08-15 常州市华乐玻纤新材料有限公司 Composite fiber material capable of being used for RTM (resin transfer molding) and vacuum guide stream manufacture technology
CN102777708A (en) * 2012-07-25 2012-11-14 广东宝通玻璃钢有限公司 Fiber-woven pultrusion pipeline and production method
CN105694354A (en) * 2016-02-19 2016-06-22 苏州振瑞昌材料科技有限公司 Bakelite corrugated board made of preliminarily woven components with flow guide layers and method for manufacturing bakelite corrugated board
CN105711199A (en) * 2016-02-19 2016-06-29 苏州振瑞昌材料科技有限公司 Manufacturing method of non-metal anti-corrosion daylighting plate manufactured from pre-weaving part with flow guide layer
CN105711214A (en) * 2016-02-19 2016-06-29 苏州振瑞昌材料科技有限公司 Interlamination reinforced fiber composite material with flow guiding layer and preparation method thereof
CN105733175A (en) * 2016-02-19 2016-07-06 苏州振瑞昌材料科技有限公司 Bakelite purline manufactured by pre-fabricated member with flow guide layer and manufacturing method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201567440U (en) * 2009-11-12 2010-09-01 江苏九鼎新材料股份有限公司 One-way fabric composite surface felt
CN102632663A (en) * 2012-04-01 2012-08-15 常州市华乐玻纤新材料有限公司 Composite fiber material capable of being used for RTM (resin transfer molding) and vacuum guide stream manufacture technology
CN102777708A (en) * 2012-07-25 2012-11-14 广东宝通玻璃钢有限公司 Fiber-woven pultrusion pipeline and production method
CN105694354A (en) * 2016-02-19 2016-06-22 苏州振瑞昌材料科技有限公司 Bakelite corrugated board made of preliminarily woven components with flow guide layers and method for manufacturing bakelite corrugated board
CN105711199A (en) * 2016-02-19 2016-06-29 苏州振瑞昌材料科技有限公司 Manufacturing method of non-metal anti-corrosion daylighting plate manufactured from pre-weaving part with flow guide layer
CN105711214A (en) * 2016-02-19 2016-06-29 苏州振瑞昌材料科技有限公司 Interlamination reinforced fiber composite material with flow guiding layer and preparation method thereof
CN105733175A (en) * 2016-02-19 2016-07-06 苏州振瑞昌材料科技有限公司 Bakelite purline manufactured by pre-fabricated member with flow guide layer and manufacturing method thereof

Also Published As

Publication number Publication date
CN105711214A (en) 2016-06-29

Similar Documents

Publication Publication Date Title
US20210114333A1 (en) Prepregs, cores, composites and articles including repellent materials
CA2713204C (en) Fiber reinforced core panel
CN103589127A (en) High-transverse-strength pultrusion structural sheet material and manufacturing method thereof
WO2017140124A1 (en) Interlayer reinforced fiber composite material having diversion layer, and method for manufacture thereof
CN111421926B (en) Continuous fiber cloth three-dimensional reinforced wood-plastic composite material and production method and equipment thereof
CN102991046A (en) Light-weight and high-strength plastic steel sandwich board and its making method
KR20130121858A (en) Uni-directional fibre preform having slivers and consisting of reinforcing fibre bundles, and a composite material component
Nelyub Technologies of production of components of electric transmission line supports from epoxy binders by the winding method
CN105835481A (en) Interlaminar reinforced fiber composite material and manufacturing method thereof
US20170218635A1 (en) Stucco support structures and stucco walls
US20140170361A1 (en) FRP Plate and Manufacturing Method Thereof
US10208177B2 (en) Fiber reinforced cellular PVC
CN202192817U (en) Dedicated reinforcing compound felt for pultrusion sectional material
WO2017140125A1 (en) Manufacturing method for anticorrosive nonmetal skylight panel made of pre-woven element having diversion layer
EP1690968B1 (en) Method for producing a reinforced polyester non-woven material
KR100933929B1 (en) Thermoplastic Molding Material for Water Tank Manufacturing and Method for Manufacturing Water Tank Panel Using the Same
CN103612453A (en) Thermosetting-resin-base reinforcing material preform for metal surface decoration
CN107662253A (en) A kind of fiber reinforcement orients wood-plastic composite particleboard
CN101871556A (en) Pultruded bamboo fiber reinforce plastic wrapped inorganic core composite plate and molding method thereof
CA3103551A1 (en) Ultra-thin pre-preg sheets and composite materials thereof
CN103967267A (en) Ultra-high molecular weight polyethylene composite formwork and manufacturing method and device thereof
CN101871569A (en) Pultruded wood glass fabric fiber reinforce plastic tube and molding method thereof
CN103410308B (en) Plastic formwork of LFT material strip fabric reinforcing core layer and producing method thereof
WO2010022547A1 (en) A paper-based composite material
JPH074880B2 (en) Resin impregnated fiber base material and method for producing fiber reinforced plastic

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16890350

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16890350

Country of ref document: EP

Kind code of ref document: A1