CN118927748B - Thermoplastic polyolefin elastomer plastic steel tile and preparation method thereof - Google Patents

Thermoplastic polyolefin elastomer plastic steel tile and preparation method thereof Download PDF

Info

Publication number
CN118927748B
CN118927748B CN202411281181.XA CN202411281181A CN118927748B CN 118927748 B CN118927748 B CN 118927748B CN 202411281181 A CN202411281181 A CN 202411281181A CN 118927748 B CN118927748 B CN 118927748B
Authority
CN
China
Prior art keywords
parts
adhesive layer
thermoplastic polyolefin
modified polyethylene
steel tile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202411281181.XA
Other languages
Chinese (zh)
Other versions
CN118927748A (en
Inventor
丁竹
胡全超
黄海亮
曹昌义
高二林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Keshun Waterproof Technology Co Ltd
Original Assignee
Keshun Waterproof Technology Co Ltd
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 Keshun Waterproof Technology Co Ltd filed Critical Keshun Waterproof Technology Co Ltd
Priority to CN202411281181.XA priority Critical patent/CN118927748B/en
Publication of CN118927748A publication Critical patent/CN118927748A/en
Application granted granted Critical
Publication of CN118927748B publication Critical patent/CN118927748B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • 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
    • B32B2262/0276—Polyester 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

本申请提供一种热塑性聚烯烃弹性体塑钢瓦及其制备方法。该塑钢瓦包括热塑性聚烯烃弹性体塑钢瓦包括层叠设置的热塑性聚烯烃防水卷材、热熔胶膜和金属板；热熔胶膜至少包括层叠设置的第一胶层、过渡胶层和第二胶层，第一胶层中包括第一聚烯烃树脂及添加剂；过渡胶层和第二胶层中均包括改性聚乙烯、第一聚烯烃树脂、增粘树脂及添加剂；过渡胶层中改性聚乙烯的重量百分比为a％，第二胶层中改性聚乙烯的重量百分比为b％，其中，15≤a＜b，24≤b≤50。本申请在热塑性聚烯烃防水卷材和金属板之间设有包括三层结构的热熔胶膜，调整三层膜结构的组分及配比，提高塑钢瓦在高温下的剥离强度。

The present application provides a thermoplastic polyolefin elastomer plastic steel tile and a preparation method thereof. The plastic steel tile comprises a thermoplastic polyolefin elastomer plastic steel tile comprising a laminated thermoplastic polyolefin waterproofing coil, a hot melt adhesive film and a metal plate; the hot melt adhesive film at least comprises a laminated first adhesive layer, a transition adhesive layer and a second adhesive layer, the first adhesive layer comprising a first polyolefin resin and an additive; the transition adhesive layer and the second adhesive layer both comprise modified polyethylene, a first polyolefin resin, a tackifying resin and an additive; the weight percentage of the modified polyethylene in the transition adhesive layer is a%, and the weight percentage of the modified polyethylene in the second adhesive layer is b%, wherein 15≤a＜b, 24≤b≤50. The present application provides a hot melt adhesive film having a three-layer structure between the thermoplastic polyolefin waterproofing coil and the metal plate, adjusts the components and proportions of the three-layer film structure, and improves the peel strength of the plastic steel tile at high temperatures.

Description

Thermoplastic polyolefin elastomer plastic steel tile and preparation method thereof
Technical Field
The application belongs to the technical field of plastic steel tiles, and particularly relates to a thermoplastic polyolefin elastomer plastic steel tile and a preparation method thereof.
Background
The service life of the thermoplastic polyolefin elastomer (Thermoplastic polyolefin, TPO) waterproof coiled material is up to 30 years, and the waterproof coiled material can effectively prevent the metal roof from corroding and leaking by compounding the waterproof coiled material with the metal plate of the metal roof.
The mode of compounding the thermoplastic polyolefin elastomer waterproof coiled material and the metal plate to prepare the plastic steel tile mainly comprises two modes of mechanical fixing and chemical bonding. The thermoplastic polyolefin elastomer waterproof coiled material is fixed on the metal plate in a mechanical fixing mode, the full-sticking effect cannot be achieved, the thermoplastic polyolefin elastomer waterproof coiled material is prone to hollowing and water channeling, particularly when the temperature is high, the possibility and the area of hollowing and water channeling of the thermoplastic polyolefin elastomer waterproof coiled material are larger, and the corrosion prevention effect on the metal plate is greatly reduced.
The method for compounding the thermoplastic polyolefin elastomer waterproof coiled material and the metal plate into the plastic steel tile through hot-press bonding is a common method in chemical bonding, and the method is simple and convenient to operate, can save construction cost and improve construction quality. However, because the thermoplastic polyolefin elastomer waterproof coiled material and the metal plate have large material property difference, the thermoplastic polyolefin elastomer waterproof coiled material and the metal plate are difficult to bond together well, and particularly, the plastic steel tile is easy to peel at high temperature, so that the peeling strength of the plastic steel tile at high temperature is not ideal.
Disclosure of Invention
The application provides a thermoplastic polyolefin elastomer plastic steel tile and a preparation method thereof, aiming at improving the peeling strength of the thermoplastic polyolefin elastomer plastic steel tile at high temperature.
The first aspect of the application provides a thermoplastic polyolefin elastomer plastic-steel tile, which comprises a thermoplastic polyolefin waterproof coiled material, a hot melt adhesive film and a metal plate which are arranged in a laminated manner;
The hot melt adhesive film at least comprises a first adhesive layer, a transition adhesive layer and a second adhesive layer which are arranged in a laminated mode, wherein the first adhesive layer comprises first polyolefin resin and additives, the transition adhesive layer and the second adhesive layer both comprise modified polyethylene, first polyolefin resin, tackifying resin and additives, the weight percentage of the modified polyethylene in the transition adhesive layer is a%, the weight percentage of the modified polyethylene in the second adhesive layer is b%, wherein a is more than or equal to 15 and less than or equal to 50, and b is more than or equal to 24 and less than or equal to 50.
In a possible embodiment of the first aspect of the present application, the hot melt adhesive film satisfies at least one of the following conditions:
a. the weight percentage of the modified polyethylene in the transition adhesive layer is a percent, and the weight percentage of the modified polyethylene in the second adhesive layer is b percent, wherein b/a=1.2-1.6;
b. the weight percentage of the modified polyethylene in the transition glue layer is a percent, and a=15-30.
In a possible embodiment of the first aspect of the present application, the melt index (MFR) of the first polyolefin resin is 6g/10min to 11g/10min (under test conditions of 230 ℃ C./2.16 kg).
In a possible embodiment of the first aspect of the present application, the first polyolefin resin comprises one or several of CA10A, CA a and NS 06.
In a possible embodiment of the first aspect of the present application, the first polyolefin resin comprises a combination of CA10A and CA60A in a weight ratio of 1 (1.0 to 2.2).
In a possible embodiment of the first aspect of the present application, the grafting ratio of the modified polyethylene is 1.2% -2.3%.
In a possible embodiment of the first aspect of the present application, the grafting agent of the modified polyethylene comprises one or more of Maleic Anhydride (MAH), 2-hydroxyethyl methacrylate (HEMA), and acrylic acid.
In a possible embodiment of the first aspect of the present application, the hot melt adhesive film satisfies at least one of the following conditions:
c. The second adhesive layer comprises, by weight, 60 parts of a first polyolefin resin, 30-85 parts of modified polyethylene based on 60 parts of the first polyolefin resin, 20-50 parts of a tackifying resin based on 60 parts of the first polyolefin resin, and 1-8.5 parts of an additive based on 60 parts of the first polyolefin resin;
optionally, 30-50 parts of modified polyethylene based on 60 parts of the first polyolefin resin;
optionally, 20-30 parts of tackifying resin based on 60 parts of the first polyolefin resin;
d. the transition adhesive layer comprises, by weight, 80 parts of a first polyolefin resin, 15-44 parts of modified polyethylene based on 80 parts of the first polyolefin resin, 10-20 parts of tackifying resin based on 80 parts of the first polyolefin resin, and 1-5 parts of an additive based on 80 parts of the first polyolefin resin;
Optionally, 15-30 parts of modified polyethylene based on 80 parts of the first polyolefin resin;
Optionally, 10-15 parts of tackifying resin based on 80 parts of the first polyolefin resin;
e. The first adhesive layer comprises, by weight, 90 parts of a first polyolefin resin, 10-20 parts of a tackifying resin based on 90 parts of the first polyolefin resin, and 1-5 parts of an additive based on 90 parts of the first polyolefin resin;
optionally, 10-15 parts of tackifying resin based on 90 parts of the first polyolefin resin.
In a possible embodiment of the first aspect of the application, the thermoplastic polyolefin elastomer plastic-steel tile satisfies at least one of the following characteristics:
f. the total thickness of the hot melt adhesive film is 0.05 mm-0.06 mm;
g. the thickness of the first adhesive layer, the transition adhesive layer and the second adhesive layer in the hot melt adhesive film are respectively and independently 0.015 mm-0.020mm;
h. The metal of the plating layer in the metal plate is 60g/m 2～150g/m2, and the metal plate can be one or more of an aluminum-zinc plated steel plate, a zinc-plated steel plate, an aluminum-magnesium-manganese plated steel plate, a zinc-magnesium plated steel plate and an aluminum-magnesium plated steel plate.
In a possible embodiment of the first aspect of the present application, the thermoplastic polyolefin waterproof roll comprises:
80 parts of a second polyolefin resin, comprising a combination of CA10A and CA60A in a weight ratio of 1 (0.1-0.5);
16-40 parts of an additive based on 80 parts of the second polyolefin resin.
In a possible embodiment of the first aspect of the application, the additive comprises one or more of an antioxidant material, a flame retardant material and a pigment.
In a feasible embodiment of the first aspect of the application, the antioxidant material comprises antioxidant master batches, wherein the antioxidant in the antioxidant master batches comprises 20% -25% of the components of the antioxidant, and optionally, the antioxidant comprises one or more of hindered phenol antioxidants and phosphite antioxidants.
In a possible embodiment of the first aspect of the application, the flame retardant material comprises a composite flame retardant of metal hydroxide and phosphorus-nitrogen flame retardant master batch in a weight ratio of 3:1, wherein the flame retardant in the phosphorus-nitrogen flame retardant master batch accounts for 75% -85% of the total weight of the phosphorus-nitrogen flame retardant master batch.
In a possible embodiment of the first aspect of the application, the pigment comprises one or more of titanium white, iron yellow, chrome oxide green and ultramarine blue (the main component being sodium aluminosilicate).
The second aspect of the present application provides a method for preparing the thermoplastic polyolefin elastomer plastic steel tile according to the first aspect of the present application, comprising:
Compounding the thermoplastic polyolefin waterproof coiled material with a hot melt adhesive film under a first condition to obtain a coated thermoplastic polyolefin waterproof coiled material; and compounding the coated thermoplastic polyolefin waterproof coiled material with a metal plate under a second condition to obtain the thermoplastic polyolefin elastomer plastic steel tile.
In a possible implementation manner of the second aspect of the present application, in the step of compounding the thermoplastic polyolefin waterproof roll with the hot melt adhesive film under the first condition to obtain the thermoplastic polyolefin waterproof roll of the coating film, the compounding temperature under the first condition is 140 ℃ to 160 ℃, the compounding pressure under the first condition is 0.4mpa to 0.6mpa, and the compounding linear speed under the first condition is 10m/min to 15m/min.
In a feasible implementation mode of the second aspect of the application, in the step of compounding the thermoplastic polyolefin waterproof coiled material of the coating film with the metal plate under the second condition to obtain the thermoplastic polyolefin elastomer plastic steel tile, the compounding temperature under the second condition is 190-220 ℃, the compounding pressure under the second condition is 0.6-0.8 MPa, and the compounding linear speed under the second condition is 5-10 m/min.
The application is provided with the hot melt adhesive film with at least three layers between the thermoplastic polyolefin waterproof coiled material and the metal plate, on one hand, the composition and the proportion of the polyolefin resin, the modified polyethylene and the tackifying resin in the second adhesive layer, which is close to the metal plate, in the hot melt adhesive film are controlled, so that the hot melt adhesive film has better cohesiveness with the metal plate and better compatibility with the transition adhesive layer at high temperature. On the other hand, the polarity of the hot melt adhesive film can be gradually increased by controlling the content of the modified polyethylene in each layer of the hot melt adhesive film, for example, the content of the modified polyethylene in the first adhesive layer is zero, the weight percentage of the modified polyethylene in the transition adhesive layer is smaller than that of the modified polyethylene in the second adhesive layer, and the like, so that the first adhesive layer, the transition adhesive layer and the second adhesive layer are well bonded, the difference between three-layer structures in the hot melt adhesive film at high temperature can be reduced, the integrity and the compatibility of the hot melt adhesive film are improved, and the peeling strength of the plastic steel tile at high temperature is integrally improved.
Drawings
FIG. 1 is a block diagram of a TPO plastic steel tile shown in example 1;
The TPO waterproof roll comprises a TPO waterproof roll body 1, a hot melt adhesive film 2, a first adhesive layer in the hot melt adhesive film 21, a transition adhesive layer in the hot melt adhesive film 22, a second adhesive layer in the hot melt adhesive film 23 and a metal plate 3.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present application clearer, the present application will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the application only and are not intended to limit the application.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited, and any lower limit may be combined with any other lower limit to form a range not explicitly recited, as may any upper limit combined with any other upper limit. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, when a composition is described as containing, comprising or including a particular component, or when a process is described as containing, comprising or including a particular process step, it is contemplated that the composition of the application also consists essentially of or consists of that component, and that the process of the application also consists essentially of or consists of that process step.
The use of the terms "comprising," "including," "containing," and "having" are generally to be construed as open-ended and not limiting, unless expressly stated otherwise.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, and the meaning of "multiple" in "one or more" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.
The thermoplastic polyolefin elastomer waterproof coiled material and the metal plate are compounded by arranging the hot melt adhesive film between the two, so that the method is simple and convenient to operate, the construction cost can be saved, and the construction quality can be improved. However, due to the large difference in properties between the thermoplastic polyolefin elastomer waterproof coiled material and the metal plate, the common hot melt adhesive film is difficult to bond together well, and the common hot melt adhesive film is often good in bonding performance with the polyolefin elastomer waterproof coiled material or good in bonding performance with the metal plate, and especially the difference in bonding performance between the two materials at high temperature is enlarged, so that the peeling strength of the plastic steel tile is low.
CN 115570864A discloses a multifunctional film-coated plate and a preparation method thereof, wherein the film-coated plate comprises an anti-corrosion bottom film, a metal plate, a hot melt adhesive film and a high-molecular waterproof roll which are sequentially arranged, silicon micropowder is respectively added into the high-molecular waterproof roll and the hot melt adhesive film, the anti-corrosion bottom film comprises a first bottom film layer and a second bottom film layer, raw materials of the first bottom film layer comprise maleic anhydride grafted polyethylene, tackifying resin, silicon micropowder and graphene oxide, and raw materials of the second bottom film layer comprise matrix resin, silicon micropowder and graphene oxide. The whole film-coated plate has heat conducting property and heat radiating property, so that heat generated during welding of the exposed high-polymer waterproof coiled material can be quickly diffused, and welding failure caused by hot wrinkling easily occurring during welding of the high-polymer waterproof coiled material with thinner thickness, such as TPO, is avoided. It does not mention what the peel strength at high temperatures is.
In order to improve the peeling strength of the thermoplastic polyolefin elastomer plastic steel tile at high temperature, the inventor provides a thermoplastic polyolefin elastomer plastic steel tile and a preparation method thereof through a great deal of experimental study and demonstration. The application is provided with the hot melt adhesive film with at least three layers between the thermoplastic polyolefin waterproof coiled material and the metal plate, on one hand, the composition and the proportion of the polyolefin resin, the modified polyethylene and the tackifying resin in the second adhesive layer, which is close to the metal plate, in the hot melt adhesive film are controlled, so that the hot melt adhesive film has better cohesiveness with the metal plate and better compatibility with the transition adhesive layer at high temperature. On the other hand, the polarity of the hot melt adhesive film can be gradually increased by controlling the content of the modified polyethylene in each layer of the hot melt adhesive film, for example, the content of the modified polyethylene in the first adhesive layer is zero, the weight percentage of the modified polyethylene in the transition adhesive layer is smaller than that of the modified polyethylene in the second adhesive layer, and the like, so that the first adhesive layer, the transition adhesive layer and the second adhesive layer are well bonded, the difference between three-layer structures in the hot melt adhesive film at high temperature can be reduced, the integrity and the compatibility of the hot melt adhesive film are improved, and the peeling strength of the plastic steel tile at high temperature is integrally improved.
In an embodiment of the first aspect of the application, the thermoplastic polyolefin elastomer plastic-steel tile comprises a thermoplastic polyolefin waterproof coiled material, a hot melt adhesive film and a metal plate which are stacked, wherein the hot melt adhesive film at least comprises a first adhesive layer, a transition adhesive layer and a second adhesive layer which are stacked, the first adhesive layer comprises a first polyolefin resin and an additive, the transition adhesive layer and the second adhesive layer comprise modified polyethylene, the first polyolefin resin, a tackifying resin and the additive, the weight percentage of the modified polyethylene in the transition adhesive layer is a%, the weight percentage of the modified polyethylene in the second adhesive layer is b%, and the weight percentage of the modified polyethylene in the transition adhesive layer is 15-50 (for example, the weight percentage of the modified polyethylene in the transition adhesive layer is 24-25, 30, 35, 40, 45, 50 or any value in the interval of 24-50).
The polarity of the metal plate is stronger, the content of the modified polyethylene in the second adhesive layer film structure close to the metal plate in the hot melt adhesive film can be increased, but the inventor discovers through a great deal of experimental study and demonstration that the weight percentage of the modified polyethylene needs to be controlled to be less than or equal to 50 percent, and although the weight percentage of the modified polyethylene is higher than 50 percent, the adhesive property of the modified polyethylene and the metal plate can be enhanced, but through experimental study, when the plastic steel tile with the weight percentage of the modified polyethylene being less than or equal to 50 percent is peeled at high temperature, the peeling strength is better.
The inventor considers that the reason probably is that the thermoplastic polyolefin waterproof coiled material of the TPO plastic steel tile is made of nonpolar material, the metal plate is made of material with stronger polarity, the polarity of the modified polyethylene is increased when the plastic steel tile is at high temperature, and the bonding performance of the plastic steel tile and the metal plate is enhanced, but the first adhesive layer structure near one side of the TPO waterproof coiled material usually does not contain the modified polyethylene, the polarization degree of the nonpolar or polar first adhesive layer is slightly changed along with the increase of the temperature, the polarity in the second adhesive layer is obviously increased, so that the compatibility with other layers is poor, the cohesive force of the material is reduced, and the stripping is easier to occur. Also, too high a modified polyethylene content may raise the melting point of the TPO, resulting in a higher processing temperature being required and further in a greater tendency to thermally degrade during processing at high temperatures.
Therefore, if the peeling strength of the plastic steel tile at high temperature is required to be achieved, the hot melt adhesive film between the waterproof coiled material and the metal plate and the hot melt adhesive film between the waterproof coiled material and the metal plate are required to have good bonding performance, and the hot melt adhesive film is required to have good compatibility and stability, and has good bonding performance under the high temperature condition. When the weight percentage of the modified polyethylene in the second adhesive layer structure in the hot melt adhesive film is lower than 50 percent (which can comprise 50 percent), the adhesive has better adhesive property with a metal plate, and has better compatibility with the transition adhesive layer, the first adhesive layer and the nonpolar TPO waterproof coiled material which are sequentially reduced in weight percentage.
The inventor also found that under the high temperature condition, since the hot melt adhesive film comprises a 3-layer structure, molecules between layers are easy to displace, cohesive force is reduced, and the hot melt adhesive film is easy to peel, especially in order to improve the compatibility of the three-layer film structure in the hot melt adhesive film, the weight percentage of the modified polyethylene is relatively not high, although the compatibility between the film layers is better, the flow is easier, and the adhesive property is poor, so that in order to improve the adhesive property between the film layers in the hot melt adhesive film at the high temperature, a proper amount of tackifying resin is needed to be added, the fluidity and the thermal degradation at the high temperature are reduced, and all substances in the hot melt adhesive film are not easy to move, so that the stability of the hot melt adhesive film is improved, and the peeling strength of the plastic steel tile at the high temperature is improved as a whole.
Moreover, the plastic steel tile has high-temperature peel strength (60 ℃) and good ageing resistance, and the peel strength of the plastic steel tile after ageing for 720 hours at 80 ℃ can reach 8N/mm.
In addition, when the weight percentage difference of the transition adhesive layer and the modified polyethylene in the second adhesive layer and the first adhesive layer is controlled within a certain range, the compatibility and the overall stability of the hot melt adhesive film are better, the peeling strength of the plastic steel tile at high temperature can be improved, the peeling strength and the high-temperature aging resistance at normal temperature (23 ℃) and low temperature (-40 ℃) can be greatly improved, and the plastic steel tile with better comprehensive performance can be obtained.
In some embodiments, the hot melt adhesive film satisfies at least one of a. The weight percent of the modified polyethylene in the transition adhesive layer is a%, and the weight percent of the modified polyethylene in the second adhesive layer is b%, wherein b/a = 1.2 to 1.6 (e.g., may be any value within the interval 1.2, 1.3, 1.4, 1.5, 1.6, or 1.2 to 1.6), b. The weight percent of the modified polyethylene in the transition adhesive layer is a%, and a = 15 to 30 (e.g., may be any value within the interval 15, 16, 18, 20, 22, 24, 26, 28, 30, or 15 to 30).
Further, plastic steel tiles with higher peel strength at high temperature and excellent aging resistance can be selected by adjusting specific compositions and proportions of three layers in the hot melt adhesive film. In some embodiments, the hot melt adhesive film satisfies at least one of the following conditions:
c. The second adhesive layer comprises, by weight, 60 parts of a first polyolefin resin, 30-85 parts of modified polyethylene based on 60 parts of the first polyolefin resin, 20-50 parts of a tackifying resin based on 60 parts of the first polyolefin resin, and 1-8.5 parts of an additive based on 60 parts of the first polyolefin resin;
optionally, 30-50 parts of modified polyethylene based on 60 parts of the first polyolefin resin;
optionally, 20-30 parts of tackifying resin based on 60 parts of the first polyolefin resin;
d. the transition adhesive layer comprises, by weight, 80 parts of a first polyolefin resin, 15-44 parts of modified polyethylene based on 80 parts of the first polyolefin resin, 10-20 parts of tackifying resin based on 80 parts of the first polyolefin resin, and 1-5 parts of an additive based on 80 parts of the first polyolefin resin;
Optionally, 15-30 parts of modified polyethylene based on 80 parts of the first polyolefin resin;
Optionally, 10-15 parts of tackifying resin based on 80 parts of the first polyolefin resin;
e. The first adhesive layer comprises, by weight, 90 parts of a first polyolefin resin, 10-20 parts of a tackifying resin based on 90 parts of the first polyolefin resin, and 1-5 parts of an additive based on 90 parts of the first polyolefin resin;
optionally, 10-15 parts of tackifying resin based on 90 parts of the first polyolefin resin.
In the course of studying improvement of peel strength of plastic steel tiles, the inventors found that selection of polyolefin resins was also important. When polyolefin resin with the melt index of 6g/10 min-11 g/10min is in the adhesive layer of the hot melt adhesive film, and is matched with the modified polyethylene and the tackifying resin, the material has better fluidity in the hot pressing process, can be helpful for sufficiently wetting the bonded material, penetrating into microscopic pores of the bonded material, filling uneven bonding interface, and improving bonding strength of bonding surface contacted with the bonding uniformity. In some embodiments, the first polyolefin resin has a melt index (MFR) of 6g/10min to 11g/10min (under test conditions of 230 ℃ C./2.16 kg), for example, may be 6, 6.5, 7.0, 7.3, 7.5, 8, 8.5, 9.0, 9.5, 9.8, 10, 10.5, 11, or any value within the interval 6 to 11.
Wherein, the material in the hot melt adhesive film can be better in fluidity and better in dispersity in the hot pressing process by selecting one or more of CA10A, CA A and NS06, and the stability of the hot melt adhesive film can be improved so as to improve the peeling strength of the plastic steel tile at high temperature. In some embodiments, the first polyolefin resin comprises one or more of CA10A, CA a and NS 06. Optionally, the first polyolefin resin comprises a combination of CA10A and CA60A in a weight ratio of 1 (1.0-2.2), for example, may be any value within the interval 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2 or 1.0-2.2.
The modified polyethylene of the application can be obtained by introducing polar groups or functional side chains on the molecular chain of the polyethylene. In some embodiments, the modified polyethylene has a grafting ratio of 1.2% -2.3% (e.g., may be 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.3, or any value within the interval 1.2-2.3). When the grafting rate of the modified polyethylene is controlled within the range, the hot melt adhesive film has better adhesive property and compatibility. In some embodiments, the grafting agent of the modified polyethylene may include one or more of Maleic Anhydride (MAH), 2-hydroxyethyl methacrylate (HEMA), acrylic acid.
The proper hot melt adhesive film, the metal plate and the thermoplastic polyolefin waterproof coiled material are selected for matching, so that the overall peeling strength of the plastic steel tile can be improved. The thermoplastic polyolefin elastomer plastic-steel tile at least meets one of the following conditions that f. The total thickness of the hot melt adhesive film is 0.05 mm-0.06 mm, g. The thicknesses of the first adhesive layer, the transition adhesive layer and the second adhesive layer in the hot melt adhesive film are respectively and independently 0.015 mm-0.020mm, h. The metal of a plating layer in a metal plate is 60g/m 2～150g/m2, and the metal plate can be one or more of an aluminum-zinc plated steel plate, a zinc-magnesium-manganese plated steel plate, a zinc-magnesium plated steel plate and an aluminum-magnesium plated steel plate.
In some embodiments, the thermoplastic polyolefin waterproof roll comprises 80 parts of a second polyolefin resin, and 16-40 parts of an additive based on 80 parts of the second polyolefin resin, wherein the additive comprises a combination of CA10A and CA60A (for example, the combination can be any value in the interval of 0.1, 0.2, 0.3, 0.4, 0.5 or 0.1-0.5) with the weight ratio of (0.1-0.5).
Meanwhile, proper tackifying resin and additives can be selected for matching according to requirements so as to obtain different plastic-steel tiles. In some embodiments, the tackifying resin may be one or more of petroleum resin, C5 resin, C9 resin, terpene resin. In some embodiments, the additive may include one or more of an antioxidant material, a flame retardant material, and a pigment.
The antioxidant material can comprise antioxidant master batches, wherein the antioxidant in the antioxidant master batches comprises 20% -25% of the components, and optionally, the antioxidant comprises one or more of hindered phenol antioxidants and phosphite antioxidants. The flame retardant material can comprise a composite flame retardant of metal hydroxide and phosphorus-nitrogen flame retardant master batch with the weight ratio of 3:1, wherein the flame retardant in the phosphorus-nitrogen flame retardant master batch accounts for 75% -85% of the total weight of the phosphorus-nitrogen flame retardant master batch. The pigment may include one or more of titanium white, iron yellow, chrome oxide green and ultramarine blue (the main component is sodium aluminosilicate). Pigments may also include materials formed by compounding titanium dioxide with a resin, such as white master.
The second aspect of the present application provides a method for preparing the thermoplastic polyolefin elastomer plastic steel tile according to the first aspect of the present application, comprising:
Compounding the thermoplastic polyolefin waterproof coiled material with a hot melt adhesive film under a first condition to obtain a coated thermoplastic polyolefin waterproof coiled material; and compounding the coated thermoplastic polyolefin waterproof coiled material with a metal plate under a second condition to obtain the thermoplastic polyolefin elastomer plastic steel tile.
In the step of compounding the thermoplastic polyolefin waterproof coiled material with the hot melt adhesive film under the first condition to obtain the thermoplastic polyolefin waterproof coiled material of the coating film, controlling some parameters within a certain range to obtain the plastic steel tile with better performance. Optionally, in some embodiments, in the step of compounding the thermoplastic polyolefin waterproof coiled material with the hot melt adhesive film under the first condition to obtain the thermoplastic polyolefin waterproof coiled material of the coating, the compounding temperature under the first condition is 140 ℃ to 160 ℃, the compounding pressure under the first condition is 0.4MPa to 0.6MPa, and the compounding linear speed under the first condition is 10m/min to 15m/min.
And in the step of compounding the thermoplastic polyolefin waterproof coiled material with the metal plate under the second condition to obtain the thermoplastic polyolefin elastomer plastic steel tile, controlling some parameters within a certain range to obtain the plastic steel tile with better performance. Optionally, in some embodiments, in the step of compounding the coated thermoplastic polyolefin waterproof coiled material with the metal plate under the second condition to obtain the thermoplastic polyolefin elastomer plastic steel tile, the compounding temperature under the second condition is 190-220 ℃, the compounding pressure under the second condition is 0.6-0.8 MPa, and the compounding linear speed under the second condition is 5-10 m/min.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
The TPO waterproof coiled material comprises (1) thermoplastic polyolefin resin, namely CA10A, CA A purchased from Lian Debarsel industrial company, NS06 purchased from China petrochemical industry Co., ltd, (2) composite flame retardant, namely 5250M purchased from Guangdong forward same-path new materials Co., ltd, magnesium hydroxide purchased from Dandong Tianci flame retardant materials science and technology Co., ltd, (3) composite antioxidant master batch, namely composite antioxidant master batch of Buddha Bikun plastics Co., ltd, and (4) white master batch, namely HT84997 purchased from Heshan Han color master Co., ltd.
The hot melt adhesive film raw materials include (1) thermoplastic polyolefin resin CA10A, CA A from Lian Debarsel industry Co., ltd., (2) polyethylene 7042 from China petrochemical industry Co., ltd., (3) tackifying resin 41E755 from Dow chemical company, (4) grafting agent maleic anhydride A010576 from Anhui Hirskin and 2-hydroxyethyl methacrylate MS4248 from Jinan Ming chemical industry Co., ltd., (5) initiator benzoyl peroxide from Li Erming commercial industry Co., ltd.).
The metal plate used was an aluminum-zinc-plated steel sheet with no surface treatment, and was purchased from Baoshan Steel Co., ltd.
Example 1
The thermoplastic polyolefin elastomer plastic-steel tile comprises a TPO waterproof coiled material, a hot melt adhesive film and a metal plate which are arranged in a laminated mode, and the preparation method comprises the following steps:
(1) The TPO waterproof coiled material is prepared by uniformly mixing 70 parts by weight of CA10A and 10 parts by weight of CA60A thermoplastic polyolefin resin, 20 parts by weight of composite flame retardant (magnesium hydroxide: phosphorus-nitrogen flame retardant master batch=3:1), 3 parts by weight of composite antioxidant master batch and 3 parts by weight of white master batch, and then performing melt extrusion by a single screw extruder, three-roll shaping, cooling and rolling to form the TPO waterproof coiled material.
(2) Preparing a hot melt adhesive film, namely respectively providing a first adhesive layer raw material, namely 30 parts of thermoplastic polyolefin resin CA10A, 60 parts of CA60A, 10 parts of tackifying resin and 3 parts of composite antioxidant master batch; the transition adhesive layer comprises, by weight, 25 parts of thermoplastic polyolefin resin CA10A, 55 parts of CA60A, 15 parts of maleic anhydride modified polyethylene, 10 parts of tackifying resin and 3 parts of composite antioxidant master batch, and the second adhesive layer comprises, by weight, 20 parts of thermoplastic polyolefin resin CA10A, 40 parts of CA60A, 30 parts of maleic anhydride modified polyethylene, 20 parts of tackifying resin and 3 parts of composite antioxidant master batch;
And respectively adding the uniformly mixed first adhesive layer raw material, transition adhesive layer raw material and second adhesive layer raw material into a hopper of a three-layer coextrusion film blowing machine, heating and melting the raw materials through a screw at 200 ℃, then merging the first adhesive layer molten raw material, the transition adhesive layer molten raw material and the second adhesive layer molten raw material at a die head, coextruding the composite film blowing, and cooling to form the three-layer superposed hot melt adhesive film.
Wherein the grafting rate of the maleic anhydride modified polyethylene is 1.2% -2.3%. The weight percentage of the maleic anhydride modified polyethylene in the transition glue layer is 13.9 percent. The weight percent of maleic anhydride modified polyethylene in the second tie layer was 26.5%. The weight percent of the maleic anhydride modified polyethylene in the second tie layer is 1.91 times the weight percent of the maleic anhydride modified polyethylene in the transition glue layer. The difference between the weight percent of maleic anhydride modified polyethylene in the transition gum layer and the weight percent of maleic anhydride modified polyethylene in the first tie layer was 13.9%.
The thermoplastic polyolefin resin has a melt index (MFR) of 7-10 g/10min (at 230 ℃ C./2.16 kg), and the weight ratio of CA10A to CA60A used in the thermoplastic polyolefin resin is 1 (2-2.2).
Preparation of modified polyethylene, 100 parts of polyethylene, 6 parts of modifier (grafting agent, maleic anhydride A010576), 1.5 parts of styrene and 0.2 part of initiator (benzoyl peroxide) are uniformly mixed, and then added into a double-screw extruder, and melt extrusion is carried out under certain conditions to obtain the modified polyethylene.
(3) The TPO plastic steel tile is prepared by coating a TPO waterproof coiled material and a hot melt adhesive film by a press roller under the conditions of 150 ℃ and 0.5MPa of pressure and 12m/min of linear speed, coating the TPO waterproof coiled material coated with the hot melt adhesive film and a previously heated aluminum-zinc plated steel plate by the press roller under the conditions of 200 ℃ and 0.7MPa of pressure and 8m/min of linear speed, and finally shaping by the press roller, cooling and rolling.
Example 2
(1) TPO waterproof coiled material was prepared in the same manner as in example 1.
(2) The hot melt adhesive film is prepared by respectively providing a first adhesive layer raw material, a transition adhesive layer raw material, a second adhesive layer raw material and a bonding layer raw material, wherein the first adhesive layer raw material comprises, by weight, 45 parts of thermoplastic polyolefin resin CA10A, 45 parts of CA60A, 10 parts of tackifying resin, 3 parts of composite antioxidant master batch, the transition adhesive layer raw material comprises, by weight, 40 parts of thermoplastic polyolefin resin CA10A, 40 parts of CA60A, 15 parts of maleic anhydride modified polyethylene, 10 parts of tackifying resin, 3 parts of composite antioxidant master batch, and the second adhesive layer raw material comprises, by weight, 30 parts of thermoplastic polyolefin resin CA10A, 30 parts of CA60A, 30 parts of maleic anhydride modified polyethylene, 20 parts of tackifying resin and 3 parts of composite antioxidant master batch;
And respectively adding the first adhesive layer raw material, the transition adhesive layer raw material and the second adhesive layer raw material into three extruders of a co-extrusion film blowing machine, heating and melting the raw materials at 200 ℃, then sequentially converging the first adhesive layer molten raw material, the transition adhesive layer molten raw material and the second adhesive layer molten raw material at a die head, co-extruding the composite film blowing, and cooling to form the three-layer overlapped hot melt adhesive film.
The difference compared to example 1 is that the thermoplastic polyolefin resin used in the hot melt adhesive film has a weight ratio of CA10A to CA60A of 1:1.
(3) TPO plastic steel tiles were prepared as in example 1.
Example 3
(1) TPO waterproof coiled material was prepared in the same manner as in example 1.
(2) Preparing a hot melt adhesive film, namely respectively providing a first adhesive layer raw material, namely 30 parts of thermoplastic polyolefin resin CA10A, 60 parts of CA60A, 15 parts of tackifying resin and 3 parts of composite antioxidant master batch; the transition adhesive layer comprises, by weight, 25 parts of thermoplastic polyolefin resin CA10A, 55 parts of CA60A, 15 parts of maleic anhydride modified polyethylene, 15 parts of tackifying resin and 3 parts of composite antioxidant master batch, and the second adhesive layer comprises, by weight, 20 parts of thermoplastic polyolefin resin CA10A, 40 parts of CA60A, 30 parts of maleic anhydride modified polyethylene, 30 parts of tackifying resin and 3 parts of composite antioxidant master batch;
And respectively adding the first adhesive layer raw material, the transition adhesive layer raw material and the second adhesive layer raw material into three extruders of a co-extrusion film blowing machine, heating and melting the raw materials at 200 ℃, then sequentially converging the first adhesive layer molten raw material, the transition adhesive layer molten raw material and the second adhesive layer molten raw material at a die head, co-extruding the composite film blowing, and cooling to form the three-layer overlapped hot melt adhesive film.
The difference compared with example 1 is the proportion of tackifying resin in the hot melt adhesive film.
(3) TPO plastic steel tiles were prepared as in example 1.
Example 4
(1) TPO waterproof coiled material was prepared in the same manner as in example 1.
(2) Preparing a hot melt adhesive film, namely respectively providing a first adhesive layer raw material, namely, 30 parts of thermoplastic polyolefin resin CA10A, 60 parts of CA60A, 10 parts of tackifying resin and 3 parts of composite antioxidant master batch; the transition adhesive layer comprises, by weight, 25 parts of thermoplastic polyolefin resin CA10A, 55 parts of CA60A, 30 parts of maleic anhydride modified polyethylene, 10 parts of tackifying resin and 3 parts of composite antioxidant master batch, and the second adhesive layer comprises, by weight, 20 parts of thermoplastic polyolefin resin CA10A, 40 parts of CA60A, 50 parts of maleic anhydride modified polyethylene, 20 parts of tackifying resin and 3 parts of composite antioxidant master batch;
And respectively adding the first adhesive layer raw material, the transition adhesive layer raw material and the second adhesive layer raw material into three extruders of a co-extrusion film blowing machine, heating and melting the raw materials at 200 ℃, then sequentially converging the first adhesive layer molten raw material, the transition adhesive layer molten raw material and the second adhesive layer molten raw material at a die head, co-extruding the composite film blowing, and cooling to form the three-layer overlapped hot melt adhesive film.
The difference compared to example 1 is that the weight percentage of modified polyethylene in the hot melt adhesive film transition glue layer and the second adhesive layer is increased. Wherein the weight percent of maleic anhydride modified polyethylene in the transition gum layer in example 4 was 24.4%. The weight percent of maleic anhydride modified polyethylene in the second tie layer was 37.5%. The weight percent of the maleic anhydride modified polyethylene in the second tie layer is 1.54 times the weight percent of the maleic anhydride modified polyethylene in the transition glue layer. The difference between the weight percent of maleic anhydride modified polyethylene in the transition gum layer and the weight percent of maleic anhydride modified polyethylene in the first tie layer was 24.4%.
(3) TPO plastic steel tiles were prepared as in example 1.
Example 5
(1) TPO waterproof coiled material was prepared in the same manner as in example 1.
(2) Preparing a hot melt adhesive film, namely respectively providing a first adhesive layer raw material, namely, 30 parts of thermoplastic polyolefin resin CA10A, 60 parts of CA60A, 10 parts of tackifying resin and 3 parts of composite antioxidant master batch; the transition adhesive layer comprises, by weight, 25 parts of thermoplastic polyolefin resin CA10A, 55 parts of CA60A, 15 parts of methacrylic acid-2-hydroxyethyl modified polyethylene, 10 parts of tackifying resin and 3 parts of composite antioxidant master batch, and the second adhesive layer comprises, by weight, 20 parts of thermoplastic polyolefin resin CA10A, 40 parts of CA60A, 30 parts of methacrylic acid-2-hydroxyethyl modified polyethylene, 20 parts of tackifying resin and 3 parts of composite antioxidant master batch;
And respectively adding the first adhesive layer raw material, the transition adhesive layer raw material and the second adhesive layer raw material into three extruders of a co-extrusion film blowing machine, heating and melting the raw materials at 200 ℃, then sequentially converging the first adhesive layer molten raw material, the transition adhesive layer molten raw material and the second adhesive layer molten raw material at a die head, co-extruding the composite film blowing, and cooling to form the three-layer overlapped hot melt adhesive film.
Compared with example 1, the difference is that methacrylic acid-2-hydroxyethyl modified polyethylene is used, and the grafting rate is 1.2% -2.3%.
(3) TPO plastic steel tiles were prepared as in example 1.
Example 6
(1) Preparing TPO waterproof coiled material, namely 40 parts by weight of CA10A and 40 parts by weight of NS06 thermoplastic polyolefin resin and 20 parts by weight of composite flame retardant (magnesium hydroxide: phosphorus-nitrogen flame retardant master batch)
=3:1), 3 Parts of composite antioxidant master batch and 3 parts of white master batch are uniformly mixed, and then are subjected to melt extrusion by a single screw extruder, three-roll shaping, cooling and rolling.
The difference compared to example 1 is that the thermoplastic polyolefin resin has a different composition.
(2) A hot melt adhesive film was prepared in the same manner as in example 1.
(3) TPO plastic steel tiles were prepared as in example 1.
Examples 7 to 8
Example 7 differs from example 4 in that the weight percentage of maleic anhydride modified polyethylene in the transition gum layer in example 4 is 31.25%. The weight percent of maleic anhydride modified polyethylene in the second tie layer was 37.5%. The weight percent of the maleic anhydride modified polyethylene in the second tie layer is 1.2 times the weight percent of the maleic anhydride modified polyethylene in the transition glue layer. The difference between the weight percent of maleic anhydride modified polyethylene in the transition gum layer and the weight percent of maleic anhydride modified polyethylene in the first tie layer was 31.25%.
Example 8 is different from example 1 in that the polyolefin resin used in the hot-melt adhesive film was POE having a melt index (MFR) of about 1.4g/10min under test conditions of 230℃per 2.16 kg.
Comparative examples 1 to 3
Comparative example 1 is different from example 1 in that the second adhesive layer structure in the hot melt adhesive film used includes 90 parts by weight of the modified polyethylene.
The weight percentage of maleic anhydride modified polyethylene in the second tie layer was 52.0%. The weight percent of the maleic anhydride modified polyethylene in the second tie layer is 3.7 times the weight percent of the maleic anhydride modified polyethylene in the transition glue layer. The difference between the weight percent of maleic anhydride modified polyethylene in the transition gum layer and the weight percent of maleic anhydride modified polyethylene in the first tie layer was 13.9%.
Comparative example 2 is different from example 1 in that the second adhesive layer structure in the hot melt adhesive film used comprises 25 parts by weight of modified polyethylene.
The weight percentage of maleic anhydride modified polyethylene in the second tie layer was 23.1%. The weight percent of the maleic anhydride modified polyethylene in the second tie layer is 1.9 times the weight percent of the maleic anhydride modified polyethylene in the transition glue layer. The difference between the weight percent of maleic anhydride modified polyethylene in the transition gum layer and the weight percent of maleic anhydride modified polyethylene in the first tie layer was 13.9%.
Comparative example 3 is different from example 1 in that the hot melt adhesive film used does not contain a tackifying resin.
Test method
Sample size: plastic steel tile 50 mm. 200mm
Heat aging treatment the test specimen was put into an oven and heat aged at 80 ℃ for 720 hours.
Peel strength test was performed according to GB2792-2014 test method for peel strength of adhesive tape.
Table 1 performance testing of each of the examples and comparative examples
As can be seen from the analysis of Table 1, the peel strength of the plastic steel tiles of examples 1-8 of the present application at a high temperature of 60 ℃ is higher than that of comparative examples 1-3, and it can be seen that the design of the hot melt adhesive film of the present application can improve the peel strength of the plastic steel tiles at a high temperature.
As can be seen from further analysis of Table 1, the design of the three-layer film structure in the hot-melt adhesive film of the present application can significantly improve the peel strength of the plastic steel tile at a high temperature of 60 ℃ when the composition and the proportion of the first polyolefin resin, the modified polyethylene and the tackifying resin in the second adhesive layer are all within a proper range, as can be seen from the comparison of the plastic steel tiles of examples 1 to 8 and comparative examples 1 to 3.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (15)

1. The thermoplastic polyolefin elastomer plastic-steel tile is characterized by comprising a thermoplastic polyolefin waterproof coiled material, a hot melt adhesive film and a metal plate which are arranged in a laminated manner;
The hot melt adhesive film at least comprises a first adhesive layer, a transition adhesive layer and a second adhesive layer which are arranged in a stacked manner, wherein the first adhesive layer comprises first polyolefin resin and an additive;
the weight percentage of the modified polyethylene in the transition adhesive layer is a percent, and the weight percentage of the modified polyethylene in the second adhesive layer is b percent, wherein a is more than or equal to 15 and less than or equal to b, and b is more than or equal to 24 and less than or equal to 50;
the first adhesive layer comprises, by weight, 90 parts of a first polyolefin resin, 10-20 parts of a tackifying resin based on 90 parts of the first polyolefin resin, 1-5 parts of an additive based on 90 parts of the first polyolefin resin, and no modified polyethylene.
2. The thermoplastic polyolefin elastomer steel tile according to claim 1, wherein the hot melt adhesive film satisfies at least one of the following characteristics:
a. the weight percentage of the modified polyethylene in the transition adhesive layer is a percent, and the weight percentage of the modified polyethylene in the second adhesive layer is b percent, wherein b/a=1.2-1.6;
b. The weight percentage of the modified polyethylene in the transition glue layer is a percent, and a=15-30.
3. The thermoplastic polyolefin elastomer plastic steel tile according to claim 1, wherein the first polyolefin resin has a melt index of 6 g/10 min to 11 g/10 min under test conditions of a load of 2.16kg at 230 ℃.
4. The thermoplastic polyolefin elastomer plastic steel tile according to claim 3, wherein the first polyolefin resin comprises a combination of CA10A and CA60A in a weight ratio of 1 (1.0 to 2.2).
5. The thermoplastic polyolefin elastomer plastic steel tile according to claim 1, wherein the grafting ratio of the modified polyethylene is 1.2% -2.3%.
6. The thermoplastic polyolefin elastomer plastic steel tile according to claim 4, wherein the grafting agent of the modified polyethylene comprises one or more of maleic anhydride, 2-hydroxyethyl methacrylate, and acrylic acid.
7. The thermoplastic polyolefin elastomer steel tile according to claim 1, wherein the hot melt adhesive film satisfies at least one of the following characteristics:
c. The second adhesive layer comprises, by weight, 60 parts of a first polyolefin resin, 30-85 parts of modified polyethylene based on 60 parts of the first polyolefin resin, 20-50 parts of a tackifying resin based on 60 parts of the first polyolefin resin, and 1-8.5 parts of an additive based on 60 parts of the first polyolefin resin;
d. The transition adhesive layer comprises, by weight, 80 parts of a first polyolefin resin, 15-44 parts of modified polyethylene based on 80 parts of the first polyolefin resin, 10-20 parts of a tackifying resin based on 80 parts of the first polyolefin resin, and 1-5 parts of an additive based on 80 parts of the first polyolefin resin.
8. The thermoplastic polyolefin elastomer plastic steel tile according to claim 7, wherein the second adhesive layer comprises 30-50 parts of modified polyethylene and 20-30 parts of tackifying resin, based on 60 parts of the first polyolefin resin.
9. The thermoplastic polyolefin elastomer plastic steel tile according to claim 7, wherein the transition glue layer comprises 15-30 parts of modified polyethylene and 10-15 parts of tackifying resin, based on 80 parts of the first polyolefin resin.
10. The thermoplastic polyolefin elastomer plastic steel tile according to claim 1, wherein the first adhesive layer comprises 10 to 15 parts of tackifying resin based on 90 parts of the first polyolefin resin.
11. The thermoplastic polyolefin elastomer plastic steel tile according to claim 1, wherein the thermoplastic polyolefin elastomer plastic steel tile satisfies at least one of the following characteristics:
f. The total thickness of the hot melt adhesive film is 0.05 mm-0.06 mm;
g. The thickness of the first adhesive layer, the transition adhesive layer and the second adhesive layer in the hot melt adhesive film are respectively and independently 0.015 mm-0.020 mm;
h. The metal of the plating layer in the metal plate is 60 g/m 2~150 g/m2, and the metal plate can be one or more of an aluminum-zinc plated steel plate, a zinc-plated steel plate, an aluminum-magnesium-manganese plated steel plate, a zinc-magnesium plated steel plate and an aluminum-magnesium plated steel plate.
12. The thermoplastic polyolefin elastomer plastic steel tile according to claim 1, wherein the thermoplastic polyolefin waterproof roll comprises:
80 parts of a second polyolefin resin, comprising a combination of CA10A and CA60A in a weight ratio of 1 (0.1-0.5);
16-40 parts of an additive based on 80 parts of the second polyolefin resin.
13. The thermoplastic polyolefin elastomer steel tile according to claim 1, wherein the additive comprises one or more of an antioxidant material, a flame retardant material and a pigment.
14. The method for preparing the thermoplastic polyolefin elastomer plastic steel tile according to any one of claims 1 to 13, comprising the steps of:
compounding the thermoplastic polyolefin waterproof coiled material with the hot melt adhesive film under a first condition to obtain a coated thermoplastic polyolefin waterproof coiled material;
and compounding the thermoplastic polyolefin waterproof coiled material with the metal plate under a second condition to obtain the thermoplastic polyolefin elastomer plastic steel tile.
15. The method for producing a thermoplastic polyolefin elastomer plastic steel tile according to claim 14, wherein in the step of compounding the thermoplastic polyolefin waterproof roll with a hot melt adhesive film under a first condition to obtain a thermoplastic polyolefin waterproof roll of a coating film, the compounding temperature under the first condition is 140 ℃ to 160 ℃, the compounding pressure under the first condition is 0.4 MPa to 0.6MPa, the compounding linear velocity under the first condition is 10 m/min to 15m/min, and/or,
In the step of compounding the thermoplastic polyolefin waterproof coiled material with the metal plate under the second condition to obtain the thermoplastic polyolefin elastomer plastic steel tile, the compounding temperature under the second condition is 190-220 ℃, the compounding pressure under the second condition is 0.6-MPa-0.8 MPa, and the compounding linear speed under the second condition is 5-m/min-10 m/min.
CN202411281181.XA 2024-09-12 2024-09-12 Thermoplastic polyolefin elastomer plastic steel tile and preparation method thereof Active CN118927748B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202411281181.XA CN118927748B (en) 2024-09-12 2024-09-12 Thermoplastic polyolefin elastomer plastic steel tile and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202411281181.XA CN118927748B (en) 2024-09-12 2024-09-12 Thermoplastic polyolefin elastomer plastic steel tile and preparation method thereof

Publications (2)

Publication Number Publication Date
CN118927748A CN118927748A (en) 2024-11-12
CN118927748B true CN118927748B (en) 2025-01-24

Family

ID=93354789

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202411281181.XA Active CN118927748B (en) 2024-09-12 2024-09-12 Thermoplastic polyolefin elastomer plastic steel tile and preparation method thereof

Country Status (1)

Country Link
CN (1) CN118927748B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109207073A (en) * 2018-08-30 2019-01-15 上海邦中高分子材料股份有限公司 A kind of three layers of composite hot melt adhesive film and its processing technology for metal and polar functionalities plastic bonding

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3821143A (en) * 1973-03-22 1974-06-28 Du Pont Hot melt adhesive composition containing a branched elastomeric copolymer
US5382615A (en) * 1993-10-01 1995-01-17 Eastman Chemical Company Modified polyethylene based hot-melt adhesives for use in packaging
CN1772462A (en) * 2005-10-24 2006-05-17 广州市鹿山化工材料有限公司 Three-layer co-extruded composite film for athesion of metal plate and non-metal plate
CN114672257B (en) * 2022-05-26 2022-09-02 江苏凯伦建材股份有限公司 Anti-grid-scratching poached hot-melt adhesive film, preparation method thereof and film laminated plate
CN115044311B (en) * 2022-08-17 2022-11-29 江苏凯伦建材股份有限公司 High-temperature-resistant hot-melt adhesive film, preparation method thereof and film-coated plate
CN115570864B (en) * 2022-11-24 2023-03-31 江苏凯伦建材股份有限公司 Multifunctional film-coated plate and preparation method thereof
CN117567956B (en) * 2023-09-28 2025-06-27 江苏凯伦建材股份有限公司 High-barrier hot melt adhesive film, preparation method thereof and composite board
CN117801711A (en) * 2023-12-27 2024-04-02 广州鹿山新材料股份有限公司 Hot melt adhesive film for water boiling resistant ASA/metal composite, and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109207073A (en) * 2018-08-30 2019-01-15 上海邦中高分子材料股份有限公司 A kind of three layers of composite hot melt adhesive film and its processing technology for metal and polar functionalities plastic bonding

Also Published As

Publication number Publication date
CN118927748A (en) 2024-11-12

Similar Documents

Publication Publication Date Title
CN103205210B (en) High-temperature-resistant hot melt adhesive membrane for aluminum honeycomb boards, and preparation method thereof
EP0174044B1 (en) High heat metal-polymer laminate
EP2610305B1 (en) Thermoplastic polymer composition and molded article
EP2592115B1 (en) Thermoplastic polymer composition and molded article
KR100743355B1 (en) Low temperature activated adhesive composition with high peel strength and high cohesive failure
EP2803701A1 (en) Thermoplastic polymer composition and molded article
KR20170047194A (en) Low dielectric adhesive composition
EP2599833B1 (en) Thermoplastic polymer composition and molded article
MX2011004078A (en) Biaxially oriented film.
CN117801711A (en) Hot melt adhesive film for water boiling resistant ASA/metal composite, and preparation method and application thereof
JP7727904B2 (en) Heat-sealable laminated film
CN118927748B (en) Thermoplastic polyolefin elastomer plastic steel tile and preparation method thereof
CN115873519B (en) Adhesive film for aluminum honeycomb plate, preparation method of adhesive film, aluminum honeycomb plate and application of adhesive film
JP2018020487A (en) Multilayer film and molded body
TW202003607A (en) Resin having a catalyst for reactive adhesion to a polyester
WO2022270468A1 (en) Multilayer sheet and production method therefor
CN113817105A (en) Preparation method of high-bonding-strength EVA (ethylene-vinyl acetate) film for glass fiber reinforced plastic interlayer
CN114456726A (en) A kind of BOPP digital pre-coating film for low temperature embossing and preparation method thereof
JP5744607B2 (en) Adhesive film
CN114702818B (en) A kind of masking film for automobile spray paint protection and preparation method thereof
JP7727905B2 (en) Heat-sealable laminated film
JP2505022B2 (en) Polymer composition and laminate using this polymer composition
KR20150037584A (en) Film for steel plate laminate
WO2024113168A1 (en) Building panel
JP4453388B2 (en) Resin coated metal plate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20241112

Assignee: FOSHAN KESHUN BUILDING MATERIAL Co.,Ltd.

Assignor: KESHUN WATERPROOF TECHNOLOGY Co.,Ltd.

Contract record no.: X2025980035296

Denomination of invention: Thermoplastic Olefin Elastomer Plastic Steel Tile and Its Preparation Method

Granted publication date: 20250124

License type: Common License

Record date: 20251117