TWI658130B - Self-repairing material, producing method and application thereof - Google Patents

Abstract

The invention provides a self-healing material that heals in a hydrogen bond manner, and does not require additional exposure to heat, light, or specific sounds, that is, has the ability of self-healing. It is an active self-healing material. Its formula contains: 30 ~ 79 Parts by weight of acrylic monomers; 20 to 60 parts by weight of acrylic acid containing 2-ureido-4-pyrimidinone units; 1 to 10 parts by weight of acrylic acid photoinitiator and 1 to 5 parts by weight of free radical initiator Wherein, the self-healing material generates a photo-curing reaction after being irradiated with ultraviolet light; and the self-healing material has a self-healing property of intermolecular hydrogen bonding.

Description

Self-healing material, its manufacturing method and application

A self-healing material, especially a material that produces self-healing effect by hydrogen bonding polymerization.

Consumer electronics products, such as mobile phones and tablets, have very fragile LCD screens, which can easily cause scratches or damage to the surface due to improper use, which affects the picture quality and aesthetics of LCD screen displays. Therefore, most users will overlay the screen. The protection is attached to the surface of the LCD screen to protect and prevent the LCD screen from being scratched or damaged.

However, when the screen protector is used to a considerable extent, the user must replace the screen protector with a new one, making the screen protector a consumable product. Not only the expensive and obsolete screen protector may cause environmental pollution issues such as garbage pollution.

With the evolution of user needs and technology, a material with self-healing function has been gradually developed, called self-healing material, or self-repairing material (Self-healing material). The self-healing effect is achieved by using the molecules to re-combine the damaged parts due to external forces to the original style.

At present, the self-healing mechanism of self-healing materials is mainly through external stimuli such as heat, light, or specific sounds to re-bond and polymerize molecules to restore damaged areas, although it can solve the problem that existing screen protectors cannot. The problem of self-healing and increasing the use cycle, but this kind of passive self-healing ability that requires external stimuli such as heat, light or specific sounds still has inconvenience in use. At the current stage, there is a lack of self-healing materials that can actively generate self-healing ability.

In order to solve the problem that existing self-healing materials need to pass through heat, light, or external stimuli to receive sound to produce self-healing effects, and lack the ability to actively generate self-healing capabilities, the present invention provides a self-healing material that is hydrogen bonded. The healing material does not require additional exposure to heat, light, or specific sounds, that is, has the ability to self-repair. It is an active self-healing material. Its formula contains: 30 to 79 parts by weight of acrylate monomers; 20 to 60 parts by weight of acrylic acid containing 2-ureido-4-pyrimidinone units; 1 to 10 parts by weight of acrylic photoinitiator and 1 to 5 parts by weight of free radical initiator; wherein the self-healing material generates light after being irradiated with ultraviolet light Curing reaction; and the self-healing material has a self-healing property of intermolecular hydrogen bonding.

The acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-butyl acrylate, n-amyl acrylate, and 2- Amyl, isoamyl acrylate, 2-methylpentyl acrylate, n-hexyl acrylate, 2-hexyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, 2- Heptyl, 2-methylheptyl acrylate, 2-propylheptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, formazan Methyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-butyl methacrylate, n-methacrylate Amyl ester, 2-pentyl methacrylate, isoamyl methacrylate, 2-methylpentyl methacrylate, n-hexyl methacrylate, 2-hexyl methacrylate, 2-methylhexyl methacrylate Ester, 2-ethylhexyl methacrylate, methyl propane N-heptyl acid, 2-heptyl methacrylate, 2-methylheptyl methacrylate, 2-propylheptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, methacrylic acid N-nonyl ester, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, or a mixture of the foregoing monomers; the acrylic photoinitiator contains a propylene bond-containing unsaturated group or methacrylic acid An acetophenone derivative or a benzophenone derivative in which a bond unsaturated group is grafted on a benzene ring; and the free radical initiator includes an azo compound, a difluorene compound, and a dioxane compound , Peroxyester-based compounds, peroxycarbonate-based compounds, peroxydicarbonate-based compounds, or hydrogen peroxide-based compounds.

Wherein, the azo compound includes 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), or 2,2'-azobis (2,4- Dimethylvaleronitrile); the dihydrazone peroxide compound includes dilauric acid peroxide, icosamidine peroxide, or dibenzoyl peroxide; the dioxane compounds include 2,5-dimethyl-2 , 5-tert-butylperoxyhexane, cumene peroxide or 1,3-bis (tert-butylperoxyisopropyl) benzene; the peroxyester compounds include tert-butylperoxypivalate Or 2,5-dimethyl-2,5-bis (2-ethylhexanol peroxy) hexane; the percarbonate compounds include 2-ethylhexyl tert-pentyl peroxycarbonate or 2- Ethylhexyl tert-butyl peroxycarbonate; the peroxydicarbonate-based compounds include dimyristoyl peroxydicarbonate or bis (4-tert-butylcyclohexyl) peroxydicarbonate; the peroxydicarbonate The carbonate-based compound includes dimyristoylperoxydicarbonate or bis (4-tert-butylcyclohexyl) peroxydicarbonate; and the hydrogen peroxide-based compound includes tert-butylhydroperoxide or isopropyl isopropyl Propyl Hydrogen Peroxide

Wherein, the reactive diluent includes n-butyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, Acrylic ester with cyclic structure or methacrylic ester with cyclic structure.

The present invention further provides a method for manufacturing the self-healing material, the steps include: a thermal polymerization step: sequentially 79 to 30 parts by weight of an acrylate monomer, and 20 to 60 parts by weight of 2-ureido-4-pyrimidine The acrylic acid of the ketone unit and the photoinitiator of 1 to 10 parts by weight of acrylic acid were placed in the reaction container, and then 1 to 5 parts by weight of the free radical initiator was added to the reaction container and stirred uniformly. ^o C and react for about 3 to 6 hours. After the temperature is lowered, the acrylate prepolymer is obtained; and the photocuring step: the obtained acrylate prepolymer is coated on a substrate, and then cured by ultraviolet light to form a film. The self-healing material has the self-healing property of intermolecular hydrogen bonding.

Wherein, the acrylate monomer is a methacrylate monomer; the acrylic acid containing a 2-ureido-4-pyrimidone unit is a methacrylic acid containing a 2-ureido-4-pyrimidone unit; the acrylic acid The photoinitiator is a methacrylic photoinitiator; and the substrate includes a polyethylene terephthalate substrate.

In addition, the present invention further provides a self-healing protective film, comprising: a substrate, the substrate is a flat sheet, and has an upper surface and a lower surface; a self-healing layer, the self-healing layer is disposed on the substrate The upper surface of the material; an adhesive layer disposed on the lower surface of the substrate; wherein: the self-healing layer is coated with a self-healing material on the substrate and cured by irradiation with ultraviolet light Formed; the self-healing material formula contains: 79-30 parts by weight of acrylic monomers, 20-60 parts by weight of acrylic acid containing 2-ureido-4-pyrimidinone units, and 1-10 parts by weight of acrylic light An initiator and a free-radical initiator of 1 to 5 parts by weight, and the self-healing material has a self-healing property of intermolecular hydrogen bonding.

Wherein, the acrylate monomer is a methacrylate monomer; the acrylic acid containing a 2-ureido-4-pyrimidone unit is a methacrylic acid containing a 2-ureido-4-pyrimidone unit; the acrylic acid The photoinitiator is a methacrylic photoinitiator; and the self-healing layer includes an antistatic agent particle or a reactive diluent.

Wherein, the adhesive layer is disposed on the other side of the substrate, and a release layer is further provided.

According to the above description, the present invention has the following effects:

1. The self-healing mechanism of the present invention is through intermolecular 2-ureido-4-pyrimidinone groups to generate hydrogen bond polymerization with each other. This reaction mechanism occurs automatically in the natural state without additional exposure to specific light or heat sources. , Can produce self-healing effect, is an active self-healing material. When the present invention is used as a screen protective film or a protective film for an electrical appliance shell, the service life of the current protective film or the protective film can be increased, and the life time of the protective film can be improved.

2. Further, the present invention modifies the polymerization monomers of 2-ureido-4-pyrimidinone, photoinitiator and reactive diluent with acrylic or methacrylic functional groups, so that these components and acrylates When monomers or methacrylic monomers are polymerized, no organic solvent is needed to produce a high-efficiency polymerization effect, which is relatively environmentally friendly and environmentally friendly, and can further improve the subsequent photo-curing efficiency. The preparation process of the invention is short and transparent Good fluidity, good chemical resistance, and excellent self-healing properties.

The invention is a self-healing material, and its formula comprises: 30 to 79 parts by weight of an acrylate monomer, 20 to 60 parts by weight of acrylic acid containing a 2-ureido-4-pyrimidone unit, and 1 to 10 parts by weight of acrylic acid. A photoinitiator and a free-radical initiator of 1 to 5 parts by weight, wherein the self-healing material produces a photo-curing reaction after being irradiated with ultraviolet light, and the self-healing material has a self-healing property of intermolecular hydrogen bonding. Further, the self-healing material can be added as an additive for adjusting viscosity by adding 1 to 20 parts by weight of an active diluent.

The aforementioned method for manufacturing the self-healing material includes the following steps:

1. Thermal polymerization step: sequentially put acrylate monomers, acrylic acid containing 2-ureido-4-pyrimidone units and acrylic photoinitiator into the reaction vessel, and then add a free radical initiator into the reaction vessel and Stir well, raise the reactor temperature to 70 ~ 90 ^o C and react for about 3 ~ 6 hours. After the temperature is lowered, the acrylate prepolymer is obtained.

2. Photo-curing step: the acrylate prepolymer obtained in step 1 is coated on a substrate, such as a polyethylene terephthalate (PET) substrate, and is photo-cured by UV light The film is a self-healing material of the present invention.

Further, a reactive diluent may be added during the photo-curing step as a viscosity adjuster for adjusting the coating of the acrylate prepolymer on the substrate.

The above-mentioned acrylate monomer preferably includes a methyl alkyl acrylate to a dodecyl acrylate (C1-C12), and more preferably a methyl alkyl acrylate to an octyl acrylate (C1-8). For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-butyl acrylate, n-amyl acrylate, 2-pentyl acrylate, isoamyl acrylate, 2-methylpentyl acrylate, n-hexyl acrylate, 2-hexyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, 2-heptyl acrylate, 2-methyl acrylate Heptyl, 2-propylheptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate and mixtures of these monomers.

The acrylate monomer may also be a methacrylate monomer, such as a methyl methacrylate to a dodecyl methacrylate (C1-C12), preferably a methyl methacrylate Within the range of octyl methacrylate (C1-8). For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-butyl methacrylate, methyl N-pentyl acrylate, 2-pentyl methacrylate, isoamyl methacrylate, 2-methylpentyl methacrylate, n-hexyl methacrylate, 2-hexyl methacrylate, 2-methyl methacrylate Hexyl ester, 2-ethylhexyl methacrylate, n-heptyl methacrylate, 2-heptyl methacrylate, 2-methylheptyl methacrylate, 2-propylheptyl methacrylate, methyl formate N-octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate and mixtures of these monomers.

Wherein, the 2-ureido-4-pyrimidinone unit-containing acrylic acid is grafted onto the acrylate monomer, as shown in the following formula 1.

Formula 1

In Formula 1, R1 is a hydrogen atom or a methyl group, and when R1 is a hydrogen atom, the acrylate monomer is polymerized; if R1 is a methyl group, the methacrylate monomer is polymerized; R2 is a polymer having at least 2 ~ 10 carbon atoms, preferably 4 ~ 6 carbon atoms.

Among them, the acrylic photoinitiator preferably contains a propylene bond unsaturated group or a methacrylic bond unsaturated group which can be directly connected to the acetophenone derivative or benzophenone derivative. Benzene ring.

The free radical initiator can also be called a thermal initiator. Its characteristics are preferably a free radical initiator with a 10-hour half-life temperature of 40 to 120 ° C, and more preferably 50 to 90 ° C. The type of material may include azo compounds. For example: 2,2'-azobisisobutyronitrile (2,2'-Azobis- (isobutyronitrile), abbreviated as AIBN), 2,2'-azobis (2-methylbutyronitrile) (2, 2'-Azobis- (2-methylbutyronitrile), abbreviated as AMBN), 2,2'-azobis (2,4-dimethylvaleronitrile) (2,2'-Azobis- (2,4-dimethylvaleronitrile) (Referred to as ADVN), etc .; Diacyl peroxides compounds, such as: Dilauroyl peroxide, Decanoyl peroxide, Dibenzoyl peroxide, Abbreviated as BPO), etc .; Dialkyl peroxides compounds, such as: 2,5-dimethyl-2,5-tert-butylperoxyhexane (2,5-Dimethyl-2,5-di -(t-butylperoxy) hexane), Dicumyl peroxide, 1,3-Bis- (t-butyl peroxyisopropyl) benzene) Etc; Peroxyesters , Such as: t-butylperoxypivalate (t-butylperoxypivalate), 2,5-dimethyl-2,5-bis (2-ethylhexanol peroxy) hexane (2,5-Dimethyl- 2,5-di (2-ethylhexanoylperoxy) hexane), etc .; Peroxycarbonates compounds, for example: 2-ethylhexyl-tert-amyloxycarbonate (tert-Amylperoxy 2-ethylhexyl carbonate), 2- Tert-Butylperoxy 2-ethylhexyl carbonate, etc .; peroxydicarbonates, for example: Dimyristylperoxydicarbonate, di (4 -Di (4-tert-butylcyclohexyl) peroxydicarbonate, etc .; Hydroperoxides, for example: t-Butyl hydroperoxide, isopropyl Isopropylcumylhydroperoxide and the like. .

The reactive diluent comprises methyl alkyl acrylate to dodecyl acrylate (C1-C12), preferably butyl to dodecyl acrylate (C4-12), for example: n-butyl acrylate (BA ), Isooctyl acrylate (2-EHA), isodecyl acrylate (IDA), lauryl acrylate (LA), hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate Acrylate with cyclic structure or methacrylate with cyclic structure.

In the present invention, by modifying the polymerization monomers of 2-ureido-4-pyrimidone, a photoinitiator, and a reactive diluent to carry an acrylic functional group or a methacrylic functional group, these components can be combined with an acrylic monomer or When methacrylate monomers are polymerized, it does not require the use of organic solvents to produce a high-efficiency polymerization effect, and can further improve the subsequent photo-curing performance.

Please refer to the following formula 2. The self-healing mechanism of the present invention is through intermolecular 2-ureido-4-pyrimidinone groups to generate hydrogen bond polymerization with each other (hydrogen bonds are shown by the dashed lines in formula 2). This reaction mechanism is natural. It will be generated automatically under the condition without additional exposure to specific light or heat source.

Equation 2

Among them, in Formula 2, R1 is a hydrogen atom or a methyl group, and when R1 is a hydrogen atom, the acrylate monomer is polymerized; if R1 is a methyl group, the methacrylate monomer is polymerized; R2 is At least 2 to 10 carbon atoms, preferably 4 to 6 carbon atoms; R3 has at least 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms.

A preferred embodiment of the material formulation and manufacturing method of the present invention: 60 parts of methacrylate monomers, 35 parts of methacrylic acid monomers containing 2-ureido-4-pyrimidone units, and 5 parts The photoinitiator of methacrylic acid was added to a 500 mL round bottom reactor, and after stirring well, 3 parts of the free radical initiator was added and heated to 90 ° C. After 6 hours of reaction in nitrogen, it was left to cool to 40 ° C, and then gradually add 15 parts of the active diluent and stir well. This reaction process is preferably performed under nitrogen. Finally, the reaction product is coated on a PET substrate having an area of 5 cm * 5 cm, and then placed in an ultraviolet light box to perform a photo-solidification reaction to obtain a protective layer of a self-healing material with a thickness of about 25 μm.

Please refer to FIG. 1 (a) to FIG. 1 (b), which are the protective layer of the self-healing material prepared in this embodiment. The surface is scratched with a blade, and then observed with an optical microscope (SEM) and photographed. Fig. 1 (a) and Fig. 1 (b) are the repair conditions of the cuts at different repair time. Figures 1 (a) and 1 (b) are the photos of the cuts on the sample surface when the repair time is 0 minutes and 10 minutes, respectively. Compared with the unrepaired photo shown in Fig. 1 (a), when the repair time is 10 minutes, as shown in Fig. 1 (b), the cuts on the surface of the sample are obviously repaired, showing the excellent and rapid self-repair of the present invention Effect, without the need to irradiate any heat, light source or specific sound, it has a self-healing effect.

Please refer to FIG. 2, the present invention further provides a self-healing protective film 10. The first preferred embodiment includes a substrate 11, a self-healing layer 13 and an adhesive layer 15 formed of the self-healing material. The substrate 11 is planar and has an upper surface 111 and a lower surface 113. The self-healing layer 13 is disposed on the upper surface 111 of the substrate 11, and the adhesive layer 15 is disposed on the substrate 11. Lower surface 113.

In addition, please refer to Figure 3, because general plastic materials have electrical insulation (except conductive polymers), if they are in contact with or rubbed with other materials, static electricity will accumulate. If the accumulated static electricity is not eliminated in time, it may cause electrostatic adsorption, dust collection, Cremation and discharge, etc., cause combustion and explosion. Therefore, the second preferred embodiment of the self-healing protective film 10 of the present invention is based on the self-healing layer 20, and further adds 1 to 6 parts by weight of antistatic agent particles 131 to reduce or accelerate the elimination of accumulated static electricity.

Please refer to FIG. 3, the adhesive layer 15 can be made of silicon material or adhesive, so that the self-healing protective film 10 can be adhered to any surface. Further, for convenience, an adhesive layer 15 can be provided with a The release layer 17 is used for temporary covering and blocking adhesion. After the release layer 17 is peeled off during use, the present invention can be adhered to any surface.

Please refer to FIG. 4, the adhesive layer 15 is adhered to the screen of an electronic product 20, and the self-healing layer 13 is disposed at the outermost layer to contact the outside world. The self-healing protective film 10 of the present invention can be used as the screen of the electronic product 20 The protective patch, when any mechanical external force is applied to the self-healing layer 13 to cause damage to the brackets, the self-healing layer 13 can recover and repair the damaged brackets through its self-repairing ability, which not only can increase the life cycle of the screen protector, It can reduce waste generation and achieve environmental protection and environmental friendliness.

The electronic product 20 according to the present invention may be a mobile phone, a tablet computer, a camera, etc., but in addition to being applied to the electronic product 20, it may also be used in the casing of an electrical product.

The above are merely preferred embodiments of the present invention, and are not intended to limit the scope of the claims of the present invention. Any other equivalent changes or modifications made without departing from the spirit of the present invention should be included in the claims of the present invention Within range.

10‧‧‧ Self-healing protective film

11‧‧‧ Substrate

111‧‧‧ top surface

113‧‧‧ lower surface

13‧‧‧Self-healing layer

131‧‧‧Antistatic agent particles

15‧‧‧Viscose

20‧‧‧Electronic products

FIG. 1 (a) and FIG. 1 (b) are optical microscope photographs (SEM) of the cuts on the surface of the preferred embodiment of the present invention when the repair time is 0 minutes and 10 minutes, respectively. FIG. 2 is a schematic diagram of a first preferred embodiment of the self-healing protective film of the present invention. 3 is a cross-sectional view of a second preferred embodiment of the self-healing protective film of the present invention. FIG. 4 is a schematic diagram and a partially enlarged view of the self-healing protective film of the present invention.

Claims (8)

A self-healing material whose formula comprises: 30 to 79 parts by weight of an acrylate monomer; 20 to 60 parts by weight of acrylic acid containing a 2-ureido-4-pyrimidone unit; and 1 to 10 parts by weight of an acrylic photoinitiator And 1 to 5 parts by weight of a free radical initiator; 1 to 20 parts by weight of a reactive diluent, the reactive diluent includes n-butyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl acrylate, Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylate with a cyclic structure or methacrylate with a cyclic structure; wherein the self-healing material is generated after irradiating ultraviolet light Photo-curing reaction; and the self-healing material has self-healing properties of intermolecular hydrogen bonding. For example, the self-healing material of the first patent application scope, wherein the acrylate monomer includes methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and acrylic acid 2 -Butyl, n-pentyl acrylate, 2-pentyl acrylate, isoamyl acrylate, 2-methylpentyl acrylate, n-hexyl acrylate, 2-hexyl acrylate, 2-methylhexyl acrylate, 2-ethyl acrylate Hexyl hexyl, n-heptyl acrylate, 2-heptyl acrylate, 2-methylheptyl acrylate, 2-propylheptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate , N-decyl acrylate, isodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-butyl methacrylate, n-pentyl methacrylate, 2-pentyl methacrylate, isoamyl methacrylate, 2-methylpentyl methacrylate, n-hexyl methacrylate, methacrylic acid 2 -Hexyl ester, 2-methylhexyl methacrylate 2-ethylhexyl methacrylate, n-heptyl methacrylate, 2-heptyl methacrylate, 2-methylheptyl methacrylate, 2-propylheptyl methacrylate, n-octyl methacrylate Ester, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate or a mixture of the foregoing monomers; the photoinitiator of acrylic acid comprises An acetophenone derivative or a benzophenone derivative containing a propylene bond unsaturated group or a methacrylic bond unsaturated group grafted on a benzene ring; and the radical initiator includes an azo compound, Dioxin peroxide compounds, dioxane peroxide compounds, peroxide ester compounds, peroxide carbonate compounds, peroxide dicarbonate compounds, or hydrogen peroxide compounds. For example, the self-healing material in the second scope of the patent application, wherein: the azo compound contains 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) or 2 , 2'-Azobis (2,4-dimethylvaleronitrile); the difluorene peroxide compound comprises dilauric acid peroxide, icosamidine peroxide, or dibenzofluorene peroxide; the dioxane peroxide Compounds include 2,5-dimethyl-2,5-tert-butylperoxyhexane, cumene peroxide or 1,3-bis (tert-butylperoxyisopropyl) benzene; the peroxide ester The compounds include tert-butyl peroxypivalate or 2,5-dimethyl-2,5-bis (2-ethylhexanol peroxy) hexane; the percarbonate compounds include 2-ethyl Hexyl tert-pentyl peroxycarbonate or 2-ethylhexyl tert-butyl peroxycarbonate; the peroxydicarbonate compounds include dimyristoyl peroxydicarbonate or bis (4-tert-butyl ring) Hexyl) dicarbonate; and the hydrogen peroxide-based compound includes tert-butyl hydroperoxide or cumyl cumyl hydroperoxide. A method for manufacturing a self-healing material, the steps include: a thermal polymerization step: sequentially 79 to 30 parts by weight of an acrylate monomer and 20 to 60 parts by weight of acrylic acid containing a 2-ureido-4-pyrimidone unit Put 1 ~ 10 parts by weight of acrylic photoinitiator into the reaction container, and then add 1 ~ 5 parts by weight of free radical initiator into the reaction container and stir evenly, raise the reactor temperature to 70 ~ 90 ℃ and react for about 3 to 6 hours, the acrylate prepolymer is obtained after the temperature is lowered; and the photocuring step: the obtained acrylate prepolymer is coated on a substrate, and is photocured into a film after ultraviolet irradiation to obtain the self-healing material, The self-healing material has the self-healing property of intermolecular hydrogen bonding. For example, the method for manufacturing a self-healing material according to item 4 of the application, wherein: the acrylate monomer is a methacrylate monomer; the acrylic acid containing 2-ureido-4-pyrimidinone unit contains 2- Methacrylic acid of a ureido-4-pyrimidinone unit; the acrylic photoinitiator is a methacrylic photoinitiator; and the substrate comprises a polyethylene terephthalate substrate. A self-healing protective film includes: a substrate, the substrate is a flat sheet, and has an upper surface and a lower surface; a self-healing layer, the self-healing layer is disposed on the upper surface of the substrate; Adhesive layer, the adhesive layer is disposed on the lower surface of the substrate; wherein: the self-healing layer is formed by coating a self-healing material on the substrate and curing by irradiating ultraviolet light; the self-healing material formula Contains: 79 ~ 30 parts by weight of acrylate monomer, 20 ~ 60 parts by weight of acrylic acid containing 2-ureido-4-pyrimidone unit, 1 ~ 10 parts by weight of acrylic acid photoinitiator, 1 ~ 20 parts by weight A reactive diluent containing n-butyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and methacrylic acid Hydroxypropyl ester, acrylate with cyclic structure or methacrylate with cyclic structure, and 1 to 5 parts by weight of a free radical initiator, and the self-healing material has an intermolecular hydrogen bonding bond. Healing properties. For example, the self-healing protective film according to item 6 of the application, wherein: the acrylate monomer is a methacrylate monomer; the acrylic acid containing a 2-ureido-4-pyrimidone unit is a 2-urea group Methacrylic acid of a 4-pyrimidinone unit; the acrylic photoinitiator is a methacrylic photoinitiator; and the self-healing layer contains an antistatic agent particle or a reactive diluent. For example, if the self-healing protective film of item 6 or 7 is applied for, the adhesive layer is disposed on the other side of the substrate, and a release layer is further provided.