CN114806092B - Anticorrosion flexible epoxy composite coiled material and preparation method and application thereof - Google Patents
Anticorrosion flexible epoxy composite coiled material and preparation method and application thereof Download PDFInfo
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/66—Sealings
- E04B1/665—Sheets or foils impervious to water and water vapor
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/18—Separately-laid insulating layers; Other additional insulating measures; Floating floors
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- 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
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- 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
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- 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
- B32B2262/0276—Polyester fibres
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- 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
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- 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
- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
- B32B2307/102—Insulating
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- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/304—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B32B2307/558—Impact strength, toughness
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- B32B2307/70—Other properties
- B32B2307/744—Non-slip, anti-slip
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F2290/00—Specially adapted covering, lining or flooring elements not otherwise provided for
- E04F2290/04—Specially adapted covering, lining or flooring elements not otherwise provided for for insulation or surface protection, e.g. against noise, impact or fire
Abstract
The invention relates to an anti-corrosion flexible epoxy composite coiled material and a preparation method and application thereof, wherein the flexible epoxy composite coiled material comprises a first resin layer, a first reinforcing layer, a second resin layer, a second reinforcing layer and a third resin layer which are sequentially laminated, wherein the first resin layer, the second resin layer and the third resin layer respectively take photo-curing epoxy acrylic resin and photo-curing polyurethane acrylic resin as main raw materials, and the photo-curing epoxy acrylic resin is selected from aliphatic flexible long-chain modified epoxy acrylic resin; the photo-curable urethane acrylic is selected from the group consisting of aliphatic urethane acrylic having multiple functionalities. The three-layer resin layer not only maintains the inherent characteristics of the epoxy resin, but also increases the advantages of the acrylic resin and the polyurethane resin, and simultaneously toughens the film layer from the molecular level to form a reinforced cross-linked network composite film layer structure in the elastomer, so that the composite resin system has weather resistance, flexibility and good mechanical strength.
Description
Technical Field
The invention belongs to the technical field of polymer composite building materials, and particularly relates to an anti-corrosion flexible epoxy composite coiled material, and a preparation method and application thereof.
Background
The epoxy floor is a high-strength and wear-resistant polymer floor, has the advantages of solid texture, good chemical resistance, good barrier property, low maintenance cost and the like, and is a polymer building material with extremely wide application. According to different characteristics of the epoxy terrace, the epoxy resin mortar terrace can be roughly divided into an epoxy resin grinding terrace, an epoxy resin mortar terrace, an epoxy resin color sand pressing terrace, an epoxy resin flat coating terrace, an epoxy resin self-leveling terrace and the like. At present, the epoxy terrace has certain functionality, such as wear resistance, skid resistance, corrosion resistance and the like, and also has decorative effects, and has gradually developed into a universal industrial terrace, and along with the continuous improvement of the living standard of people, the epoxy terrace is popularized and applied in civil household decoration.
The epoxy floor coating is generally composed of two components, including thermosetting epoxy resin, solvent, auxiliary agent, pigment and filler, curing agent, curing accelerator and the like, and is mainly characterized by having high permeability to a concrete base surface, having certain water resistance, corrosion resistance, good physical and mechanical properties of a coating film and the like, and being suitable for ground places such as factories, courts, parking lots, warehouses, markets and the like. The construction steps of the traditional epoxy floor coating mainly comprise basal plane treatment, respectively coating epoxy seal primer, middle coating, top coating and colored paint, and curing and polishing, and the steps are complicated and the construction period is long, mainly because the thermosetting epoxy resin needs to be cured under certain conditions, the construction can be completed generally in5 to 7 days, and meanwhile, a large amount of toxic volatile substances are often accompanied in the construction process, so that the construction method has certain environmental protection and health safety hidden trouble. In order to improve the construction problem of epoxy floor coating, with the continuous development of composite material technology, floor technology and coiled material technology in recent years, the appearance of a novel composite industrial coiled material floor realizes the breakthrough of industrial floor material from the field construction of epoxy resin coating to industrialized preparation. The coiled material floor takes a modified epoxy resin and polymer compound system as a matrix material, special fiber fabrics as reinforcing materials, and the floor is formed by professional automatic production equipment under special curing process conditions. The invention patent [ CN101705744B ] discloses an epoxy terrace material which mainly comprises a polyurethane synthetic leather layer, a glass fiber cloth layer and a terrace coating layer; the invention patent [ CN105462442B ] provides an environment-friendly epoxy resin coating, an environment-friendly coiled material and a preparation method thereof, wherein the coiled material is of a layered structure, and an epoxy resin surface layer, a base paper middle layer, a glass fiber felt layer and an epoxy resin bottom layer are sequentially bonded through the environment-friendly epoxy resin coating from top to bottom; the invention patent [ CN110524985A ] discloses a three-fiber composite reinforced epoxy floor material, which comprises a long-fiber polyester layer, a first epoxy resin layer, a glass fiber layer, a second epoxy resin layer and a short-fiber polyester layer which are sequentially compounded from top to bottom; the invention patent [ CN105711198B ] provides a self-cleaning anti-slip coiled material which is of a layered structure and comprises a self-cleaning anti-slip surface layer, a glass fiber grid cloth layer and a glass fiber cloth layer which are bonded and solidified through self-cleaning anti-slip paint from top to bottom.
However, in the process of preparing and producing the coiled material, the epoxy resin coating or the bonding layer is still in a heat curing mode, so that higher energy consumption is generated, and the development and application of the epoxy coiled material are restricted due to high equipment requirements, large field occupation area, longer production line and production period and the like. Therefore, development of a novel epoxy resin system curing mode to reduce production energy consumption is an important direction for further promoting development of coiled material floor materials. On the other hand, the epoxy resin is high in hardness after being cured, insufficient in flexibility and poor in scratch resistance, and although the modified epoxy resin is adopted in the process and is reinforced by the polyester fiber layer and the glass fiber layer, the problems of bending resistance, difficult coiling and the like still exist. Therefore, how to provide good flexibility through polymer composition and molecular structure design on the premise of not damaging the mechanical properties of the epoxy resin system, and develop a novel epoxy system curing mode is an important technical problem faced by the epoxy resin coiled material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a flexible epoxy composite coiled material which is based on photo-curing and has high flexibility, mechanical strength and other comprehensive properties and a preparation method thereof, and the flexible epoxy composite coiled material is very suitable for floor coiled materials.
The invention also provides application of the flexible epoxy composite coiled material.
In order to achieve the above purpose, the technical scheme adopted is as follows:
the utility model provides a flexible epoxy composite coiled material, includes first resin layer, first enhancement layer, second resin layer, second enhancement layer and the third resin layer that stacks gradually and sets up, the raw materials on first resin layer, second resin layer, third resin layer are independently selected from the formula including following component respectively:
wherein the photo-curable epoxy acrylic resin is selected from aliphatic flexible long chain modified epoxy acrylic resins;
the photo-curable urethane acrylic resin is selected from polyfunctional aliphatic urethane acrylic resins.
Further, the mass ratio of the photo-curing epoxy acrylic resin to the photo-curing polyurethane acrylic resin is 1-8: 1. further preferably, the mass ratio of the photo-curing epoxy acrylic resin to the photo-curing urethane acrylic resin is 1-6.5: 1.
according to some embodiments of the invention, the flexible long chain in the photo-curable epoxy acrylic resin is an aliphatic polyester or polyether oligomer, and the photo-curable epoxy acrylic resin has a viscosity of 5000-55000 cps/25 ℃. Further, the acid value of the photo-curing epoxy acrylic resin is less than or equal to 10mgKOH/g. The flexible long chain is an aliphatic long chain with the number average molecular weight of 400-6000. For example, the photocurable epoxy acrylic resin is selected from L-6136, L-6135, L-6130 of Guangdong blue Ke Lu New Material Co.
According to some embodiments of the invention, the photo-curable urethane acrylic resin has a viscosity of 150 to 4000cps.
Further, the photo-curable urethane acrylic resin is a difunctional or trifunctional photo-curable urethane acrylic resin. For example, the photo-curable urethane acrylic resin is selected from FSP38569 (viscosity 3000-4000 cps/25deg.C, functionality 3), unicryl R7495 (viscosity 2800 cps/25deg.C, functionality 2), unicryl R7350 (viscosity 348 cps/25deg.C, functionality 3), unicryl R7115 (viscosity 162 cps/25deg.C, functionality 3) of Guangzhou chemical materials limited. The use of the photo-curable urethane acrylic resin of low functionality contributes to obtaining a resin layer of better flexibility.
In the invention, the photo-curing epoxy acrylic resin is aliphatic flexible long-chain modified epoxy acrylic resin, has the characteristics of both epoxy resin and acrylic resin, and has the advantages of high curing speed and low curing shrinkage rate; and the molecule contains aliphatic flexible long chains, so that the intramolecular rotation barrier can be reduced, and the flexibility of the resin is increased. In the curing process, due to the difference of the properties of the epoxy group and the acrylic ester group, a micro molecular layer appears on the resin layer, so that the film layer structure has flexibility and good mechanical strength, has excellent water resistance, corrosion resistance and adhesive force, and has certain glossiness and transparency.
The light-cured polyurethane acrylic resin is aliphatic unsaturated resin prepared from polyalcohol, isocyanate, acrylic acid-beta-hydroxyethyl ester and the like through addition reaction, has high curing speed, good flexibility, weather resistance, wear resistance and chemical resistance, and can be compounded with the epoxy acrylic resin to ensure that the film layer structure has the performances of the epoxy resin, the acrylic resin and polyurethane through co-curing, and the film layer is toughened from the molecular level to form a crosslinked network composite film layer structure reinforced in an elastomer.
Further, the diluent is one or more of dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate and acrylic acid ester glycerol derivative, and the mass ratio of the diluent to the epoxy acrylic acid ester reactive diluent is 1-10: 1, and a compound reactive diluent.
Preferably, the epoxy acrylate reactive diluent is selected from one or more of 2, 3-epoxypropyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 1, 2-epoxy-5-hexene, 3, 4-epoxy-1-butene, 1, 2-epoxy-9-decene and isoprene monoxide.
Compared with a single diluent, the single diluent prepared by compounding the acrylic acid ester reactive diluent and the epoxy acrylic acid ester reactive diluent not only can increase the compatibility among different resins and has a compatibilization effect, but also can adjust the mechanical property and the flexibility of a curing system.
Further, the dispersing agent is one or a combination of more of polyether modified siloxane, epoxy modified polydimethylsiloxane, epoxy modified polysiloxane and polydimethylsiloxane. The introduction of the siloxane structure can increase the hydrophobicity of the material and improve the water resistance and self-cleaning capability of the film.
Further, the toughening agent is one or a combination of more of o-benzene type flexible unsaturated resin, polyurethane modified unsaturated resin and nano powder nitrile rubber.
Further, the coupling agent is a silane coupling agent. For example, the coupling agent is selected from one of KH-570, A174, A172, VTES, TEVS, VTMS, vinyltriethoxysilane.
The synergistic compounding effect of the coupling agent and the dispersing agent can promote the compatibilization effect of each resin component in the system, increase the dispersion uniformity and stability of the inorganic component, and simultaneously, the unsaturated bond can participate in the film layer curing process, so that the mechanical strength of the material is further increased.
Further, the photoinitiator is selected from: 2-hydroxy-2-methyl-1-phenyl-1-propanone (e.g., 1173), 1-hydroxycyclohexylphenyl ketone (e.g., 184), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (e.g., 907), 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone (e.g., 369), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (659), benzoin dimethyl ether (e.g., 651), bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene (e.g., 784), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (e.g., 819), benzophenone (BP), diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphine (TPO), ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate (TPO-L), benzoyl Methylbenzoate (MBF), 2, 4-Diethylthiazolone (DETX), and a combination of one or more of the α, ITP.
According to some embodiments of the invention, scratch resistant agent and glass fiber are further added to the raw material of the first resin layer.
Further, the scratch-resistant agent is one or a combination of a plurality of nanoscale silicon dioxide, nanoscale aluminum oxide, ceramic powder and quartz powder, and the hard nano filler can improve the wear resistance and the skid resistance of the film.
Further, the glass fiber is chopped glass fiber, is flame-retardant glass fiber, has the length of 2-4 mm and the diameter of 9.5-10.5 mu m, and can improve the three-dimensional bonding strength in the film layer and the surface friction coefficient.
According to some embodiments of the invention, aerogel powder is further added to the raw material of the second resin layer. The aerogel powder is nano-void silica aerogel powder, has the density of 0.03-0.15 g/mL, the thermal conductivity of 0.01-0.02W/(m.K), and has excellent heat insulation and heat preservation, sound barrier property, flame retardance, waterproofness, weather resistance and corrosion resistance.
According to some embodiments of the invention, the first reinforcing layer is a fiberglass scrim layer. The glass fiber mesh cloth layer adopts electronic grade glass fiber cloth, and the mesh size is one of 3X 3mm, 4X 4mm and 5X 5mm, and the weight per square is 80-160 g.
According to some embodiments of the invention, the second reinforcing layer is a polyester fiber cloth layer with a thickness of 0.5-1.5 mm.
In some preferred aspects of the invention, the epoxy composite coiled material adopts flame-retardant chopped glass fibers to be added in the first resin layer, meanwhile, the first reinforcing layer adopts electronic-grade glass fiber cloth, the second reinforcing layer adopts flame-retardant polyester fiber cloth, a three-dimensional layered structure is established through layer-by-layer bonding, and the epoxy composite coiled material is endowed with good flexibility and flame retardance through selection of different fiber types while reinforcing and toughening. Furthermore, the invention has the advantages of integration innovation through molecular structure design, three-dimensional structure design and formula design of the resin layer, and through synergistic effect among materials from different material angles, the invention has various performances such as flexibility, wear resistance, skid resistance, heat preservation and sound insulation.
According to some embodiments of the invention, the flexible epoxy composite web further includes quartz sand embedded on the third resin layer.
According to some embodiments of the present invention, the raw material formulation of the first resin layer comprises the following components:
according to some embodiments of the present invention, the raw material formulation of the second resin layer comprises the following components:
according to some specific embodiments of the present invention, the raw material formulation of the third resin layer includes the following components:
the invention adopts a second technical scheme that: the preparation method of the flexible epoxy composite coiled material comprises the following steps:
(1) Coating slurry of a first resin layer on one surface of a first reinforcing layer, and forming the first resin layer after ultraviolet irradiation;
(2) Coating the slurry of a second resin layer on the other surface of the first reinforcing layer treated in the step (1), curing by ultraviolet irradiation, coating the slurry of the second resin layer again, attaching the second reinforcing layer, curing by ultraviolet irradiation, coating the slurry of a third resin layer on the second reinforcing layer, spreading quartz sand, and curing by ultraviolet irradiation to obtain the flexible epoxy composite coiled material.
Further, the ultraviolet light irradiation curing conditions in the step (1) and the step (2) are as follows: the wavelength is 310-420 nm, and the maximum light intensity at the irradiation center position is 100+/-10 mW/cm 2 The irradiation time period is 90+/-10 s.
Further, in the step (1), the slurry of the first resin layer is applied in an amount of 300 to 500g/m 2 。
Further, in the step (2), the slurry of the second resin layer coated on the other surface of the first reinforcing layer has a coating amount of 300 to 500g/m 2 The coating amount of the slurry for coating the second resin layer is 100-200 g/m 2 The coating weight of the slurry of the third resin layer is 600-800 g/m 2 。
According to the third technical scheme adopted by the invention, the flexible epoxy composite coiled material or the flexible epoxy composite coiled material prepared by the preparation method is applied to the fields of floor coiled materials, industrial floors or other building materials.
The flexible epoxy composite coiled material is used as the floor coiled material, the first resin layer is used as a surface layer and is used as a modification layer of the epoxy composite coiled material, the main raw materials are compounded by photo-curing epoxy acrylic resin and polyurethane acrylic resin, the flexible epoxy composite coiled material has the performances of the epoxy resin, the acrylic resin and the polyurethane, and meanwhile, the film layer is toughened from the molecular level to form the reinforced cross-linked network composite film layer structure in the elastomer.
The third resin layer is used as a bottom layer and is used as a protective layer of the epoxy composite coiled material, gravel is paved on the surface of the third resin layer, the mechanical biting force of the epoxy composite coiled material and a base material is enhanced, meanwhile, the epoxy acrylic resin and the polyurethane acrylic resin are compounded, the elasticity of the resin layer is enhanced, and water vapor on the surface of the base material can be absorbed, so that the waterproof and moistureproof capacity of the third resin layer is improved.
The flexible epoxy composite coiled material adopts photo-curing epoxy acrylic resin as a polymer matrix, and integrates the performances of high flexibility, scratch resistance, stain resistance, heat preservation, heat insulation, water resistance, flame retardance, corrosion resistance and the like through the functions of elastomer toughening and fiber reinforcement.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the three-layer resin of the flexible epoxy composite coiled material, the epoxy acrylic resin modified by the flexible chains and the flexible aliphatic polyurethane acrylic resin are selected for compounding use, and the polymer alloy prepared by matching with other auxiliary agents not only maintains the inherent characteristics of the epoxy resin, but also increases the advantages of the acrylic resin and the polyurethane resin, and meanwhile, the film layer is toughened from the molecular level to form a reinforced cross-linked network composite film layer structure in the elastomer, so that the composite resin system has weather resistance, flexibility and good mechanical strength.
The flexible epoxy composite coiled material adopts a photo-curing modified epoxy resin system to replace the traditional thermosetting epoxy resin, thereby reducing the process energy consumption, shortening the preparation time, and being a novel composite material with economic and environment-friendly preparation process.
Drawings
FIG. 1 is a schematic structural view of a flexible epoxy composite web of example 1;
1, a first resin layer; 2. a first reinforcing layer; 3. a second resin layer; 4. a second reinforcing layer; 5. and a third resin layer.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention, but is not intended to limit the scope of the present invention. The methods are regarded as conventional methods unless otherwise specified.
Example 1
The flexible epoxy composite coiled material provided in this embodiment, as shown in fig. 1, includes a first resin layer 1, a first reinforcing layer 2, a second resin layer 3, a second reinforcing layer 4 and a third resin layer 5 which are sequentially stacked from top to bottom.
In this example, the first reinforcing layer 2 is a glass fiber mesh cloth layer, and a glass fiber mesh cloth with mesh size of 3×3mm is selected, wherein the weight per square is 100g; the second reinforcing layer 4 adopts a flame-retardant polyester fiber cloth layer with the thickness of 1.2mm.
The raw material formulation of the first resin layer 1 is as follows: 40 parts of light-cured epoxy acrylic resin L-6136, 10 parts of light-cured polyurethane acrylic resin FSP38569, 5 parts of toughening agent o-benzene type flexible unsaturated resin, 20 parts of diluent (a compound diluent of dipropylene glycol diacrylate and glycidyl methacrylate according to a mass ratio of 5:1), 3 parts of dispersant polyether modified siloxane, 1 part of scratch-resistant agent nanoscale silicon dioxide, 2 parts of chopped glass fiber with the length of 3mm, 3 parts of coupling agent KH-570 and 5 parts of photoinitiator 1173.
The raw material formulation of the second resin layer 3 is as follows: 30 parts of light-cured epoxy acrylic resin L-6136, 5 parts of light-cured polyurethane acrylic resin FSP38569, 5 parts of silicon dioxide aerogel powder, 15 parts of diluent (dipropylene glycol diacrylate and glycidyl methacrylate compound diluent according to the mass ratio of 5:1), 2 parts of flexibilizer o-benzene type flexible unsaturated resin, 2 parts of dispersant polyether modified siloxane, 2 parts of coupling agent KH-570 and 3 parts of photoinitiator 1173.
The raw material formulation of the third resin layer 5 is as follows: 30 parts of light-cured epoxy acrylic resin L-6136, 15 parts of light-cured polyurethane acrylic resin FSP38569, 15 parts of diluent (a compound diluent of dipropylene glycol diacrylate and glycidyl methacrylate according to a mass ratio of 5:1), 2 parts of toughening agent o-benzene type flexible unsaturated resin, 2 parts of dispersant polyether modified siloxane, 2 parts of coupling agent KH-570 and 3 parts of photoinitiator 1173.
In this example, the flexible epoxy composite coiled material is prepared by the following method:
(1) Will be the firstMixing all the raw materials of a resin layer 1, stirring uniformly in dark to obtain slurry of the first resin layer 1, and coating the slurry of the first resin layer 1 with the coating weight of 350g/m 2 Uniformly coating on one surface of the first reinforcing layer 2, and irradiating with ultraviolet light for 90s (wavelength is 310-420 nm, maximum light intensity at irradiation center position is 100 mW/cm) 2 ) Forming a first resin layer 1;
(2) Mixing all the raw materials of the second resin layer 3, stirring uniformly in dark to obtain slurry of the second resin layer 3, and coating the slurry of the second resin layer 3 with a coating weight of 300g/m 2 Uniformly coating on the other surface of the first reinforcing layer 2, and irradiating with ultraviolet light for 90s (wavelength of 310-420 nm, maximum light intensity at irradiation center position of 100mW/cm 2 ) Curing and then again applying a coating weight of 100g/m 2 Coating the slurry of the second resin layer 3 and attaching the second reinforcing layer 4, and irradiating with ultraviolet light for 90s (wavelength of 310-420 nm, maximum light intensity at irradiation center position of 100mW/cm 2 ) A second resin layer 3 is formed between the first reinforcing layer 2 and the second reinforcing layer 4, and the second resin layer 3 also has the functions of heat preservation and heat insulation;
(3) Mixing all the raw materials of the third resin layer 5, stirring uniformly in the dark to obtain slurry of the third resin layer 5, and coating the slurry of the third resin layer 5 with a coating weight of 600g/m 2 Coating on the second reinforcing layer 4 treated in step (2), spreading quartz sand grains, and irradiating with ultraviolet light for 90s (wavelength of 310-420 nm, maximum light intensity at irradiation center position of 100 mW/cm) 2 ) And forming a third resin layer 5 with quartz sand grains embedded on the surface, trimming and rolling to obtain the flexible epoxy composite coiled material.
Example 2
The difference between the flexible epoxy composite coiled material provided in this embodiment and the embodiment 1 is that the materials of the first resin layer 1, the second resin layer 3, the third resin layer 5 and the first reinforcing layer 2 are different from each other:
in this example, the raw material formulation of the first resin layer 1 is as follows: 20 parts of photo-curing epoxy acrylic resin L-6135, 15 parts of photo-curing polyurethane acrylic resin Unicryl R7496, 5 parts of toughening agent o-benzene type flexible unsaturated resin, 15 parts of diluent (a compound diluent of acrylic acid ester glycerol derivative and 1, 2-epoxy-5-hexene according to a mass ratio of 2:1), 3 parts of dispersant polyether modified siloxane, 1 part of scratch-resistant agent nanoscale silicon dioxide, 2 parts of chopped glass fiber with the length of 3mm, 3 parts of coupling agent KH-570 and 3 parts of photoinitiator 1173.
In this example, the raw material formulation of the second resin layer 3 is as follows: 25 parts of photo-curing epoxy acrylic resin L-6135, 10 parts of photo-curing polyurethane acrylic resin Unicryl R7496, 10 parts of silicon dioxide aerogel powder, 15 parts of diluent (a compound diluent of acrylic ester glycerol derivative and 1, 2-epoxy-5-hexene according to a mass ratio of 2:1), 2 parts of toughening agent o-benzene type flexible unsaturated resin, 2 parts of dispersing agent polyether modified siloxane, 2 parts of coupling agent KH-570 and 3 parts of photoinitiator 1173.
In this example, the raw material formulation of the third resin layer 5 is as follows: 25 parts of light-cured epoxy acrylic resin L-6135, 20 parts of light-cured polyurethane acrylic resin Unicryl R7496, 10 parts of diluent (a compound diluent of acrylic ester glycerol derivative and 1, 2-epoxy-5-hexene according to a mass ratio of 2:1), 2 parts of toughening agent o-benzene type flexible unsaturated resin, 2 parts of dispersant polyether modified siloxane, 2 parts of coupling agent KH-570 and 3 parts of photoinitiator 1173.
In this example, the first reinforcing layer 2 is a glass fiber mesh cloth having a mesh size of 5×5mm.
Comparative example 1
The epoxy composite coiled material provided in this comparative example is different from example 1 in that: no photoinitiator was added to the raw materials of the first resin layer 1, the second resin layer 3, and the third resin layer 5.
The curing of the three resin layers during the preparation of the epoxy composite coiled material adopts the process of keeping at 120 ℃ for 1h instead of photo-curing.
As a result, it was found that slippage occurred between the first reinforcing layer 2 and the second reinforcing layer 4 of the epoxy composite roll, and the first resin layer 1, the second resin layer 3 and the third resin layer 5 were all tacky, and the reinforcing layer layers were easily peeled off.
Comparative example 2
The epoxy composite coiled material provided in this comparative example is different from example 1 in that: the photo-curable epoxy acrylic resin L-6136 in the raw materials of the first resin layer 1, the second resin layer 3 and the third resin layer 5 is photo-curable pure acrylic resin which is purchased from L-6040 of Lan Kelu.
Comparative example 3
The epoxy composite coiled material provided in this comparative example is different from example 1 in that: the light-cured epoxy acrylic resin L-6136 in the raw materials of the first resin layer 1, the second resin layer 3 and the third resin layer 5 adopts standard high-hardness light-cured epoxy acrylic resin of blue koch road type L-6114.
Comparative example 4
The epoxy composite coiled material provided in this comparative example is different from example 1 in that: the amounts of both the photo-curable epoxy acrylic resin and the photo-curable urethane acrylic resin in the raw materials of the first resin layer 1, the second resin layer 3, and the third resin layer 5 are exchanged.
In this example, the raw material formulation of the first resin layer 1 is as follows: 10 parts of light-cured epoxy acrylic resin L-6136, 40 parts of light-cured polyurethane acrylic resin FSP38569, 5 parts of toughening agent o-benzene type flexible unsaturated resin, 20 parts of diluent (a compound diluent of dipropylene glycol diacrylate and glycidyl methacrylate according to a mass ratio of 5:1), 3 parts of dispersant polyether modified siloxane, 1 part of scratch-resistant agent nanoscale silicon dioxide, 2 parts of chopped glass fiber with the length of 3mm, 3 parts of coupling agent KH-570 and 5 parts of photoinitiator 1173.
The raw material formulation of the second resin layer 3 is as follows: 5 parts of light-cured epoxy acrylic resin L-6136, 30 parts of light-cured polyurethane acrylic resin FSP38569, 5 parts of silicon dioxide aerogel powder, 15 parts of diluent (dipropylene glycol diacrylate and glycidyl methacrylate compound diluent according to the mass ratio of 5:1), 2 parts of toughening agent o-benzene type flexible unsaturated resin, 2 parts of dispersant polyether modified siloxane, 2 parts of coupling agent KH-570 and 3 parts of photoinitiator 1173.
The raw material formulation of the third resin layer 5 is as follows: 15 parts of light-cured epoxy acrylic resin L-6136, 30 parts of light-cured polyurethane acrylic resin FSP38569, 15 parts of diluent (a compound diluent of dipropylene glycol diacrylate and glycidyl methacrylate according to a mass ratio of 5:1), 2 parts of toughening agent o-benzene type flexible unsaturated resin, 2 parts of dispersant polyether modified siloxane, 2 parts of coupling agent KH-570 and 3 parts of photoinitiator 1173.
The epoxy composite rolls of examples 1 to 2 and comparative examples 1 to 4 were tested for surface hardness with reference to GB/T6739, water resistance with reference to GB/T1733, chemical resistance with reference to GB/T9274, and slip resistance with reference to DIN51130, and the results are shown in Table 1.
Table 1 shows the results of the performance test of the epoxy composite coiled materials of examples 1 to 2 and comparative examples 1 to 4
Note that: layer-by-layer delamination refers to delamination between reinforcement layers.
The bending resistance was obtained by bending an epoxy composite web at 90℃for 30 seconds and observing the change in the crease.
Chemical resistance was found to be 60% H 2 SO 4 The surface of the coil was treated with a 50% naoh solution for 30 d.
As can be seen from comparative examples 1 and 1, the light curing process can greatly improve the overall properties of the coil; comparative examples 1 and 2 show that example 1 has better water and chemical resistance and better flexibility; comparative examples 1 and 3 show that example 1 has better flexibility; comparative examples 1 and 4 show that example 1 has better corrosion resistance. From the above table, the properties of example 1 are better than those of comparative example, which shows that the multi-layer flexible epoxy composite coiled material based on photo-cured epoxy acrylic acid prepared by the method provided by the invention has excellent comprehensive properties and wide application prospect.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (10)
1. The utility model provides a flexible epoxy composite coiled material, includes the first resin layer, first enhancement layer, second resin layer, second enhancement layer and the third resin layer that stack gradually and set up, its characterized in that, the raw materials on first resin layer, second resin layer, third resin layer are independently selected from the formula including following component respectively:
20-45 parts of photo-curing epoxy acrylic resin;
5-25 parts of photo-curing polyurethane acrylic resin;
10-30 parts of a diluent;
1-10 parts of a toughening agent;
0.5-5 parts of a dispersing agent;
1-5 parts of a coupling agent;
1-10 parts of a photoinitiator;
the light-cured epoxy acrylic resin is selected from aliphatic flexible long-chain modified epoxy acrylic resin, the light-cured epoxy acrylic resin is provided with an epoxy group, the flexible long chain in the light-cured epoxy acrylic resin is aliphatic polyester or polyether oligomer, and the flexible long chain is an aliphatic long chain with a number average molecular weight of 400-6000;
the photo-curing polyurethane acrylic resin is selected from aliphatic polyurethane acrylic resins with multiple functionalities;
the preparation method of the flexible epoxy composite coiled material comprises the following steps:
(1) Coating slurry of a first resin layer on one surface of a first reinforcing layer, and forming the first resin layer after ultraviolet irradiation;
(2) Coating the slurry of a second resin layer on the other surface of the first reinforcing layer treated in the step (1), curing by ultraviolet irradiation, coating the slurry of the second resin layer again, attaching the second reinforcing layer, curing by ultraviolet irradiation, coating the slurry of a third resin layer on the second reinforcing layer, spreading quartz sand, curing by ultraviolet irradiation, and forming a third resin layer with quartz sand grains embedded on the surface, thus obtaining the flexible epoxy composite coiled material.
2. The flexible epoxy composite web of claim 1, wherein: the viscosity of the photo-curing epoxy acrylic resin is 5000-55000 cps; and/or the viscosity of the photo-curing polyurethane acrylic resin is 150-3000 cps.
3. The flexible epoxy composite web of claim 1, wherein: the mass ratio of the photo-curing epoxy acrylic resin to the photo-curing polyurethane acrylic resin is 1-8: 1, a step of; and/or the photo-curing polyurethane acrylic resin is a bi-functional or tri-functional photo-curing polyurethane acrylic resin.
4. The flexible epoxy composite web of claim 1, wherein: the diluent is one or more of dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate and acrylic acid ester glycerol derivative, and the mass ratio of the diluent to the epoxy acrylic acid ester reactive diluent is 1-10: 1, a compound reactive diluent; and/or the dispersing agent is one or a combination of more of polyether modified siloxane, epoxy modified polysiloxane and polydimethylsiloxane; and/or the toughening agent is one or a combination of a plurality of o-benzene type flexible unsaturated resin, polyurethane modified unsaturated resin and nano powder nitrile rubber; and/or the coupling agent is a silane coupling agent; and/or the photoinitiator is selected from one or more combinations of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinyl) butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, benzoin dimethyl ether, bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, benzophenone, diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphine, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, methyl benzoyl formate, 2, 4-diethylthiazolone, isopropylthioxanthone, alpha' -ethoxyacetophenone.
5. The flexible epoxy composite web of claim 1, wherein: scratch resistant agent and glass fiber are also added into the raw materials of the first resin layer; and/or aerogel powder is also added into the raw materials of the second resin layer.
6. The flexible epoxy composite web of claim 1, wherein: the first reinforcing layer is a glass fiber mesh cloth layer; and/or, the second reinforcing layer is a polyester fiber cloth layer; and/or, the flexible epoxy composite coiled material further comprises quartz sand embedded on the third resin layer.
7. The flexible epoxy composite web of any one of claims 1-6, wherein: the raw material formula of the first resin layer comprises the following components:
20-45 parts of photo-curing epoxy acrylic resin;
10-15 parts of photo-curing polyurethane acrylic resin;
15-30 parts of a diluent;
5-10 parts of a toughening agent;
0.5-5 parts of a dispersing agent;
1-5 parts of a coupling agent;
1-10 parts of a photoinitiator;
1-3 parts of scratch resistant agent;
1-5 parts of glass fiber; and/or the number of the groups of groups,
the raw material formula of the second resin layer comprises the following components:
20-40 parts of photo-curing epoxy acrylic resin;
5-10 parts of photo-curing polyurethane acrylic resin;
10-25 parts of a diluent;
1-5 parts of a toughening agent;
0.5-5 parts of a dispersing agent;
1-5 parts of a coupling agent;
1-5 parts of a photoinitiator;
5-10 parts of aerogel powder; and/or the number of the groups of groups,
the raw material formula of the third resin layer comprises the following components:
20-40 parts of photo-curing epoxy acrylic resin;
10-25 parts of photo-curing polyurethane acrylic resin;
10-25 parts of a diluent;
1-5 parts of a toughening agent;
0.5-5 parts of a dispersing agent;
1-5 parts of a coupling agent;
1-5 parts of a photoinitiator.
8. The flexible epoxy composite web of claim 7, wherein the photo-curable epoxy acrylic resin is a combination of one or more of L-6136, L-6135, L-6130; the photo-curing polyurethane acrylic resin is one or a combination of more of FSP38569, unicryl R7495, unicryl R7350 and Unicryl R7115.
9. A method of producing a flexible epoxy composite web as claimed in any one of claims 1 to 8, characterized in that the method of producing comprises the steps of:
(1) Coating slurry of a first resin layer on one surface of a first reinforcing layer, and forming the first resin layer after ultraviolet irradiation;
(2) Coating the slurry of a second resin layer on the other surface of the first reinforcing layer treated in the step (1), curing by ultraviolet irradiation, coating the slurry of the second resin layer again, attaching the second reinforcing layer, curing by ultraviolet irradiation, coating the slurry of a third resin layer on the second reinforcing layer, spreading quartz sand, and curing by ultraviolet irradiation to obtain the flexible epoxy composite coiled material.
10. Use of the flexible epoxy composite coil material of any one of claims 1 to 8 or the flexible epoxy composite coil material prepared by the preparation method of claim 9 in the field of floor coils, industrial floors or other building materials.
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| US4481258A (en) * | 1982-10-07 | 1984-11-06 | Westinghouse Electric Corp. | UV Curable composition and coil coatings |
| CN102173147A (en) * | 2011-01-01 | 2011-09-07 | 夏良强 | Modified hard bubble polyurethane composite plate and manufacturing method thereof |
| CN104369505A (en) * | 2014-10-27 | 2015-02-25 | 北京兴通力得科技有限公司 | Light-curing heavy corrosion protection roll material and preparation method thereof |
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