CN111548750B - Surface protection film for vacuum forming part - Google Patents

Surface protection film for vacuum forming part Download PDF

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CN111548750B
CN111548750B CN202010508787.8A CN202010508787A CN111548750B CN 111548750 B CN111548750 B CN 111548750B CN 202010508787 A CN202010508787 A CN 202010508787A CN 111548750 B CN111548750 B CN 111548750B
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layer
base
vacuum
matrix
forming part
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CN111548750A (en
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严兵
张可可
吴世超
祁震
张德胜
张永喜
张继维
唐许
施刘生
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Jiangsu Aosheng Composite Materials Hi Tech Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • 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
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
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    • B32B2264/10—Inorganic particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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Abstract

The invention discloses a surface protection film for a vacuum forming part, which comprises a base layer and an adhesive layer positioned on one side of the base layer, wherein the base layer is formed by alternately accumulating a base A layer and a base B layer, and the constituent component of the base A layer is different from that of the base B layer. The surface protection film has good aging resistance, and can prolong the service life of a vacuum forming part used outdoors for a long time. In addition, the surface protection film can be attached to the surface of the vacuum forming part in the forming process of the vacuum forming part, and the vacuum forming part does not need to be coated after the vacuum forming part is formed, so that the production time is shortened compared with a coating technology.

Description

Surface protection film for vacuum forming part
Technical Field
The invention belongs to the technical field of thin film materials, and particularly relates to a surface protection thin film for a vacuum forming part.
Background
Devices used outdoors are often vacuum molded parts of thermosetting resins. The material has simple forming method, is easy to prepare into various shapes, has relatively good mechanical property and aging resistance, and can be applied to various aspects of human life.
However, for devices requiring long-term, high-strength outdoor use, such as devices used in electrical equipment and transportation equipment, better aging resistance is required than general outdoor use devices due to longer exposure to light and rain. In general, it is a common practice to apply coatings to vacuum moldings in order to increase their resistance to aging.
For example, CN201610406953.7 discloses a weather-resistant and ultraviolet-resistant epoxy resin powder coating, which is composed of hydrogenated bisphenol a epoxy resin, novolac epoxy resin, barite powder, and curing agent. CN201510335727.X discloses an anti-ultraviolet aging coating material for pump valve components, which consists of silane modified fine-mesh corundum, epoxy resin, styrene and the like. CN201410475744.9 discloses a water-based fluorine-containing coating with excellent weather resistance, acid and alkali corrosion resistance, low friction, low contamination and ultraviolet ray resistance and aging resistance, which is composed of water-based fluorine-containing epoxy resin, zinc powder, water and an auxiliary agent.
However, the coating paint has problems that it must be coated after the vacuum forming part is formed, the production time is prolonged, and the coating method is limited, the structural design of the paint cannot be performed, the aging resistance of the paint can be improved only by the formulation technology, and finally, the performance improvement is not obvious, or the cost is high.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a surface protective film for a vacuum formed part. The surface protection film has good aging resistance, and can prolong the service life of a vacuum forming part used outdoors for a long time. In addition, the surface protection film can be attached to the surface of the vacuum forming part in the forming process of the vacuum forming part, and the vacuum forming part does not need to be coated after the vacuum forming part is formed, so that the production time is shortened compared with a coating technology.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a surface protection film for vacuum formed parts comprises a base layer and an adhesive layer positioned on one side of the base layer, wherein the base layer is formed by alternately accumulating a base A layer and a base B layer, and the constituent component of the base A layer is different from that of the base B layer.
Further, the substrate layer is formed by alternately accumulating M layers of substrate A layers and N layers of substrate B layers, and M + N is more than or equal to 10; the large number of the total layers is beneficial to refraction of more light rays at the interface, and the durability is improved. However, the number of layers is too large, and the processing difficulty and cost of the film are increased. Preferably, the total number of the base body layer A and the base body layer B is 12-20.
Further, the base A layer and the base B layer respectively contain a resin main agent, and the resin main agents of the base A layer and the base B layer are respectively one or a combination of two or more of polyurethane resin, polyamide resin, polyester resin, polycarbonate resin, polyacrylic resin, polyolefin resin, fluorine resin and silicone resin.
Further, the resin main agent in the base A layer and the base B layer is preferably polyurethane resin; polyurethane resins are polymers containing urethane groups in the main chain and can be obtained by copolymerizing polyesters, polyethers or polyurethane oligomers with di-or polyisocyanates. Compared with other polymers, the polyurethane has good aging resistance, contains no fluorine and has little harmful effect on the environment.
Polyurethanes can be classified according to their chemical structure into aliphatic polyurethanes, which do not contain aromatic groups, and aromatic polyurethanes, which contain aromatic groups. The aliphatic polyurethane and the aromatic polyurethane have different aging resistance, and the aliphatic polyurethane has relatively good aging resistance. One of the substrate A layer and the substrate B layer contains an aliphatic polyurethane; preferably, the base a layer contains an aliphatic polyurethane resin and the base B layer contains an aromatic polyurethane resin, and the base layer thus formed has better aging resistance than a base layer in which both the base a layer and the base B layer contain an aliphatic polyurethane resin.
Further, the aliphatic polyurethane resin contains an alicyclic ring.
Further, the aliphatic polyurethane resin has a structure represented by formula I:
Figure BDA0002527612500000031
wherein R is1And R1' each independently represents a hydrogen atom or an optional substituent.
Further, the aromatic polyurethane resin contains a structure shown in a chemical formula II:
Figure BDA0002527612500000032
Figure BDA0002527612500000041
wherein R is2And R2' each independently represents a hydrogen atom or an optional substituent.
Further, the base A layer and the base B layer both contain a curing agent, and the weight ratio of the resin main agent to the curing agent is 100: 5 to 15.
In order to further improve the durability, at least one of the matrix a layer and the matrix B layer contains an inorganic filler comprising one or more of titanium dioxide, silica, barium sulfate, magnesium sulfate, calcium carbonate, talc, carbon fiber.
Furthermore, at least one of the substrate A layer and the substrate B layer contains 0-40% of inorganic filler; most preferably, the substrate A layer contains 5-20% of inorganic filler, and the substrate B layer contains 10-40% of inorganic filler; the inorganic filler in the layer A of the matrix is preferably titanium dioxide, and the inorganic filler in the layer B of the matrix is preferably talcum powder.
Further, the thickness of the substrate layer is 100-400 microns, and the thickness of each layer of substrate A layer and each layer of substrate B layer is 1-20 microns. If the thickness of the base layer is less than 100 μm, the durability is insufficient. If the thickness of the substrate layer is greater than 400 microns, the film is too thick and the cost is too high. More preferably, the thickness of the substrate layer is 110 to 200 micrometers. If the thickness of the base a layer or the base B layer is less than 1 μm, the light-blocking ability is greatly weakened, resulting in a decrease in aging resistance. If the thickness of the substrate A layer or the substrate B layer is greater than 20 μm, the performance advantage due to the alternate lamination is not significant. More preferably, the thickness of each layer of the substrate A layer and the thickness of each layer of the substrate B layer are respectively 4-15 micrometers.
The adhesive layer fixes the base layer to the vacuum-formed body by forming a chemical bond with the vacuum-formed body and a physical anchoring effect at the time of vacuum-forming.
Furthermore, the thickness of the bonding layer is 1-30 micrometers. When the thickness of the adhesive layer is less than 1 μm, the adhesive force between the base layer and the vacuum molded body is insufficient. When the thickness is more than 30 μm, the adhesion between the base layer and the vacuum-molded article may be insufficient, and the adhesive layer may be broken when the film is subjected to an external force. More preferably, the thickness of the bonding layer is 4-20 micrometers.
Further, the adhesive layer contains a urethane resin, and the urethane resin has an isocyanate group. The bonding layer contains polyurethane resin, which is beneficial to improving the bonding force between the bonding layer and the substrate layer, so that the layering phenomenon does not occur between the bonding layer and the substrate layer in the use process. The urethane resin has an isocyanate group, and contributes to improvement of chemical bonding with a vacuum molded body during vacuum molding, thereby improving bonding force between a film and the vacuum molded body.
Further, the adhesive layer contains a curing agent.
The invention has the beneficial effects that:
the surface protection film can be attached to the surface of a vacuum forming part in the forming process of the vacuum forming part. That is, before vacuum molding, a surface protective film is laid on a mold, and vacuum molding of a vacuum molded article is performed on the adhesive layer side, and the surface of the obtained vacuum molded article has the surface protective film. Therefore, the surface protection film of the invention does not need to coat the vacuum formed part after the vacuum formed part is formed, and compared with a coating technology, the production time is shortened.
According to the surface protection film, the substrate layer is formed by alternately accumulating the substrate A layer and the substrate B layer and is matched with the bonding layer, so that the surface protection film has good aging resistance, and the service life of a vacuum forming part used outdoors for a long time can be prolonged.
The surface protection film can be applied to various vacuum forming parts, including various devices in the fields of electric power, transportation and transportation.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the following examples and comparative examples are as follows:
1. polyurethane resin main agent
Resin main agent a 1: 116g of cyclohexanediol, 100g of polyethylene glycol having a molecular weight of 1000, 200g of hydroxyl-terminated polybutylene adipate having a molecular weight of 2000, 6g of methyldiethanolamine, 236g of dicyclohexylmethane diisocyanate, and an appropriate amount of butanone were reacted at 72 ℃ for 2 hours to obtain a resin main agent 1 having a solid content of 80% by weight.
Resin main agent a2: 198g of dicyclohexyl alcohol, 100g of polyethylene glycol with the molecular weight of 1000, 200g of hydroxyl-terminated polybutylene adipate with the molecular weight of 2000, 6g of methyldiethanolamine, 236g of dicyclohexylmethane diisocyanate and a proper amount of butanone are reacted at 72 ℃ for 2 hours to obtain a main agent with the solid content of 80 weight percent. The resin main agent 2 contains a structure shown in a chemical formula I:
Figure BDA0002527612500000061
resin main agent a3: 186g of dihydroxybiphenyl, 100g of polyethylene glycol having a molecular weight of 1000, 200g of hydroxyl-terminated polybutylene adipate having a molecular weight of 2000, 6g of methyldiethanolamine, 329g of phenylmethane diisocyanate, and an appropriate amount of butanone were reacted at 72 ℃ for 2 hours to obtain a resin main agent 3 having a solid content of 80% by weight. The resin main agent 3 contains a structure shown in a chemical formula II:
Figure BDA0002527612500000071
2. curing agent
Curing agent B1: dicyclohexylmethane diisocyanate.
Curing agent B2: diphenylmethane diisocyanate.
3. Inorganic filler
F1: titanium dioxide, available from Shanghai Chaowei nanotechnology, Inc.
F2: talcum powder, produced by Shanghai Yangjiang chemical Co., Ltd.
The raw materials and the formulation of the base layer of the surface protective films of examples 1 to 16 are shown in table 1, and the raw materials and the formulation of the adhesive layer of the surface protective films of examples 1 to 16 are shown in table 2.
TABLE 1
Figure BDA0002527612500000072
Figure BDA0002527612500000081
Remarking: no isocyanate group was detected on the surface of the adhesive layer of example 2, and no isocyanate group was detected on the surface of the adhesive layer of the other examples.
TABLE 2
Figure BDA0002527612500000082
As shown in tables 1 and 2, the resin main agent, the curing agent, and the inorganic filler for forming the substrate a layer, the resin main agent, the curing agent, and the inorganic filler for forming the substrate B layer, and the resin main agent and the curing agent for forming the adhesive layer were mixed in a ratio, respectively, and subjected to vacuum defoaming to obtain a substrate a layer coating solution, a substrate B layer coating solution, and an adhesive layer coating solution.
The coating liquid of the substrate layer A is coated on a biaxially oriented polypropylene film (BOPP) with the thickness of 30 microns by using a coating machine, and after drying at 80 ℃, the composite film with the substrate layer A/BOPP structure is formed. And (3) coating the coating liquid of the base body B layer on a biaxially oriented polyethylene terephthalate film (BOPET) with the thickness of 30 micrometers, and drying at 80 ℃ to form a composite film of a base body B layer/BOPET structure.
And (3) compounding the two composite films by using a compound machine to obtain the composite film with a BOPP/substrate A layer/substrate B layer/BOPET structure.
And then, taking two rolls of the composite film, peeling off the BOPET film on the substrate B layer of one roll and the BOPP film on the substrate A layer of the other roll, and then compounding to obtain the composite film with a structure of BOPP/substrate A layer/substrate B layer/BOPET.
And repeating the steps to obtain the BOPP/matrix layer/BOPET structure composite film with the required number of layers and structure.
And (3) coating the bonding layer coating liquid on a biaxially oriented polypropylene (BOPP) film with the thickness of 30 micrometers by using a coating machine, and drying at 80 ℃ to form the bonding layer/BOPP structure composite film. And (3) stripping off the BOPP layer of the composite film with the BOPP/substrate layer/BOPET structure, and compounding the BOPP layer with the composite film with the bonding layer/BOPP structure to obtain the composite film with the BOPP/bonding layer/substrate layer/BOPET structure.
Finally, curing was carried out at 70 ℃ for 3 days. Removing the BOPP and the BOPET to obtain the surface protection film.
And taking a surface protection film with a proper size, attaching one side of the substrate layer to the surface of a metal plate (vacuum forming die), enabling one side of the bonding layer to face upwards, and carrying out vacuum forming on epoxy resin on the surface of the bonding layer. The epoxy resin used for vacuum forming is GEKR378 type glycidyl ether epoxy resin produced by Hongchang electronic material GmbH, and the epoxy equivalent is 180 g/eq; the curing agent is a GERH2031 amine curing agent produced by Hongchang electronic material GmbH, and the amine value is 600 mgKOH/g; the resin and the curing agent are mixed in an equivalent ratio of epoxy resin/amine curing agent. The reinforcing material is 10 layers of 0.8mm thick glass fiber cloth. The molding temperature was 80 ℃ and the time was 5 hours. The thickness of the molded article was about 10 cm. After molding, the molded article was cooled to room temperature and taken out. Observing the adhesion condition of the surface protection film on the formed product, and testing the adhesion force of the coating. The test results are shown in table 3.
Subjecting the molded product to wet heat treatment at 85 deg.C and 85% RH for 1000 hr. Another part of the molded product is put under an UVA-340 ultraviolet lamp with the ultraviolet intensity of 0.85W/m2Under irradiation 1440 hr. And then observing the appearance of the side of the formed product attached with the surface protection film on the sample subjected to the damp heat treatment and the ultraviolet irradiation, and testing the coating adhesion. The test results are shown in table 3.
Comparative example 1
After a release agent was applied to the surface of a metal plate (vacuum forming mold) without using a surface protective film, vacuum forming of an epoxy resin was performed by the vacuum forming method described in examples, and the performance was tested.
Comparative examples 2 to 3
The main agent, the curing agent and the inorganic filler which form the surface protection film are mixed according to the following proportion and defoamed in vacuum to obtain the coating liquid.
Comparative example 2 resin base a2, curing agent B1, inorganic filler F1 (weight ratio) 100:10: 9.
Comparative example 3 resin base a3, curing agent B2, inorganic filler F1 (weight ratio) 100:12: 23.
The coating liquid was applied to a biaxially oriented polypropylene film (BOPP) having a thickness of 30 μm using a coater, and dried at 80 ℃ to form a composite film having a base layer/BOPP structure, wherein the base layer had a thickness of 160 μm.
Curing at 70 ℃ for 3 days. And removing the BOPP to obtain the surface protection film.
The surface protection film was vacuum formed with epoxy resin and tested for performance as described in the examples. The test results are shown in table 3.
The examples and comparative examples have the following performance test criteria:
appearance of molded article: the appearance of the molded article with the surface protective film was observed. The surface protective film is preferably free from delamination from the molded article, and free from defects such as cracks and voids. The surface protection film has slight delamination with the molded product, or the surface protection film has fine cracks, pores and other defects. The surface protective film is inferior to the molded article in that the surface protective film is largely delaminated, the surface protective film is peeled off, or the surface protective film has a large defect such as cracking or voids.
Coating or film adhesion: measured by using a pull force tester according to GB/T5210-2006. The average value of the pulling force was determined at random 5 places on the sample.
Identification of isocyanate groups: the surface reflection FT-IR test was carried out on the test surface of the sample using an infrared spectrometer, and the presence of a peak characteristic to the-NCO group at a wave number of 2270. + -. 5cm-1 was considered to contain an isocyanate group.
TABLE 3
Figure BDA0002527612500000121
As can be seen from table 3, the surface protective film of the present invention has good aging resistance and can improve the service life of a vacuum molded article used outdoors for a long time. Comparative example 1 no surface protective film was used, and the epoxy resin showed a crack phenomenon on the surface during the aging test. In contrast, comparative examples 2 and 3, in which the surface protective film of the present invention was not used, had poor aging resistance.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents made by the contents of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (7)

1. A surface protection film for a vacuum forming part is characterized by comprising a base layer and an adhesive layer positioned on one side of the base layer, wherein the base layer is formed by alternately accumulating a base A layer and a base B layer, and the constituent composition of the base A layer is different from that of the base B layer; the base A layer contains aliphatic polyurethane resin, and the base B layer contains aromatic polyurethane resin; the thickness of the substrate layer is 100-400 microns, and the thickness of the substrate layer A and the substrate layer B is 1-20 microns; the aliphatic polyurethane resin contains an alicyclic ring.
2. The surface protective film for vacuum formed articles as claimed in claim 1, wherein said matrix layer is formed by alternately accumulating M matrix A layers and N matrix B layers, M + N.gtoreq.10.
3. The surface protective film for vacuum formed parts according to claim 1, wherein the aliphatic polyurethane resin has a structure represented by formula i:
Figure DEST_PATH_IMAGE002
chemical formula I
Wherein R is1And R1' each independently represents a hydrogen atom or an optional substituent.
4. The surface protective film for vacuum-formed articles as claimed in claim 1, wherein the aromatic polyurethane resin has a structure represented by formula ii:
Figure DEST_PATH_IMAGE004
chemical formula II
Wherein R is2And R2' each independently represents a hydrogen atom or an optional substituent.
5. The surface protective film for a vacuum formed article according to claim 1, wherein the base a layer and the base B layer each contain a curing agent, and the weight ratio between the resin main agent and the curing agent is 100: 5 to 15.
6. The surface protective film for a vacuum formed article according to claim 1, wherein the matrix A layer and/or the matrix B layer contains an inorganic filler, and the content of the inorganic filler in the matrix A layer or the matrix B layer is 0 to 40%.
7. The surface protective film for a vacuum-formed article according to claim 1, wherein the adhesive layer contains a urethane resin having an isocyanate group.
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CN1827367A (en) * 2005-02-23 2006-09-06 日东电工株式会社 Multilayer sheet, production method thereof and adhesive sheet using the multilayer sheet
CN204472013U (en) * 2014-12-26 2015-07-15 东莞市纳利光学材料有限公司 A kind of antivibration diaphragm
CN105307863A (en) * 2013-06-04 2016-02-03 东丽株式会社 Decorative moulding film, and decorative moulded article
CN108025538A (en) * 2015-09-17 2018-05-11 株式会社可乐丽 Multilayer structure making and its manufacture method, the packaging material obtained using it and the protection sheet material of product and electronic equipment

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CN1827367A (en) * 2005-02-23 2006-09-06 日东电工株式会社 Multilayer sheet, production method thereof and adhesive sheet using the multilayer sheet
CN105307863A (en) * 2013-06-04 2016-02-03 东丽株式会社 Decorative moulding film, and decorative moulded article
CN204472013U (en) * 2014-12-26 2015-07-15 东莞市纳利光学材料有限公司 A kind of antivibration diaphragm
CN108025538A (en) * 2015-09-17 2018-05-11 株式会社可乐丽 Multilayer structure making and its manufacture method, the packaging material obtained using it and the protection sheet material of product and electronic equipment

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