Uv adhesion reducing protective film

Abstract

The application discloses a UV tack-reducing protective film, which comprises a substrate layer, a glue layer and a release layer which are sequentially arranged in layers, the glue layer is obtained by coating a UV tack-reducing glue on the substrate layer and then drying and curing; the UV tack-reducing glue comprises the following raw material components in parts by weight: 80-120 parts of acrylic resin polymer, 7.5-30 parts of multifunctional monomer, 1-4 parts of surface energy reducing substance, 1-4 parts of plasticizer, 0.5-2 parts of curing agent, 1-4 parts of photoinitiator and 30-70 parts of organic solvent. The UV tack-reducing protective film is prepared by using the acrylic resin polymer with a large molecular weight, adding the light-curing resin, the surface energy reducing substance and the plasticizer for softening the glue layer. After the UV tack-reducing protective film product is subjected to UV tack-reducing, the silicon dioxide can reduce the surface energy of the product, the plasticizer can soften the glue layer, the product is more convenient to tear off the film, and the problems of difficulty in tearing off the film of the protective film after etching and tack-reducing of the UTG glass and low yield are solved by mutual complementation.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of protective film, in particular to a UV adhesion-reducing protective film. BACKGROUND

[0002] The glass used for the bendable mobile phone is a 30-40 mu m thick UTG glass, which is thinned from thick glass through etching processes such as pickling, alkali washing, and water washing to the existing thickness. In this process, a UV adhesion-reducing film is needed for process protection. The UV adhesion-reducing film has no problem in the etching section, but when tearing the film after adhesion reduction under ultraviolet light, the UTG glass is very thin, and although the weight of the adhesion-reducing film is very small, it is easy to tear the glass when tearing the film, or the film is torn very slowly, and the operation efficiency is very low.

[0003] In summary, the protective film has the following problems in actual application: (1) The adhesion-reducing film has a large weight, and when tearing the film, the glass directly follows the adhesion-reducing film, and when the UTG glass is forced to separate, it is easy to break; (2) Although the weight of the adhesion-reducing film is small, after adding a multi-tube resin to the UV adhesive layer to reduce adhesion, the polarity is strong, and the affinity with the UTG glass is good. At a certain tearing speed, the tearing force is multiplied, and it is also easy to tear the glass and difficult to operate. SUMMARY

[0004] The technical problem to be solved by the present application is to provide a UV adhesion-reducing protective film to solve the above problems in the prior art.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is: a UV adhesion-reducing protective film, comprising a substrate layer, a glue layer and a release layer which are sequentially stacked, the glue layer is obtained by coating UV adhesion-reducing glue on the substrate layer and then drying and curing.

[0006] The UV adhesion-reducing glue comprises the following raw material components by weight: 80-120 parts of acrylic resin polymer, 7.5-30 parts of multifunctional monomer, 1-4 parts of surface energy reducing material, 1-4 parts of plasticizer, 0.5-2 parts of curing agent, 1-4 parts of photoinitiator, and 30-70 parts of organic solvent.

[0007] Preferably, the acrylic resin polymer is obtained by polymerization reaction of the following raw materials by weight:

[0008] 10-30 parts of isooctyl acrylate, 10-50 parts of methyl acrylate, 10-50 parts of n-butyl acrylate, 3-10 parts of morpholine acrylate, 1-15 parts of hydroxyethyl acrylate, 1-10 parts of beta-hydroxyethyl acrylate, and 20-70 parts of ethyl acetate.

[0009] Preferably, the acrylic resin polymer is prepared by the following method:

[0010] Put acrylic acid isopropyl ester 10-30 parts, methyl acrylate 10-50 parts, n-butyl acrylate 10-50 parts, acrylic acid morpholine 3-10 parts, hydroxyethyl acrylate 1-15 parts, beta-hydroxyethyl acrylate 1-10 parts, ethyl acetate 20-70 parts into the reaction kettle, after 0.5-2 hours of N2 gas, add initiator, and react at 65-75℃ for 5-9 hours to obtain the acrylic resin polymer.

[0011] Preferably, the multi-functional monomer is one or more of unsaturated polyester resin, polyurethane resin, epoxy acrylic resin, polyether acrylic resin.

[0012] Preferably, the surface energy reducing material is one or more of silica microspheres, polyethylene microspheres, polypropylene microspheres, fluorine-containing auxiliary agent.

[0013] Preferably, the plasticizer is one or more of dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, dioctyl sebacate, tributyl citrate.

[0014] Preferably, the curing agent is an isocyanate curing agent selected from one or more of toluene diisocyanate (TDI), diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI).

[0015] Preferably, the photoinitiator is one or more of 184 (1-hydroxy cyclohexyl phenyl ketone), 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone), TPO (diphenyl-(2,4,6-trimethyl benzoyl) phosphine oxide), IHT-PI (2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-1-butanone);

[0016] The organic solvent is one or more of ethyl acetate, toluene, butanone, methyl isobutyl ketone.

[0017] Preferably, the UV adhesion-reducing adhesive comprises the following raw material components by weight parts: acrylic resin polymer 80-120 parts, polyurethane resin 7.5-30 parts, silica 1-4 parts, tributyl citrate 1-4 parts, toluene diisocyanate 0.5-2 parts, initiator TPO 1-4 parts, ethyl acetate 30-70 parts;

[0018] The mass ratio of silica to tributyl citrate is 1:1.

[0019] Preferably, the thickness of the substrate layer is 50-300μm, the thickness of the adhesive layer is 10-80μm, and the thickness of the release layer is 25-100μm.

[0020] The beneficial effects of the present application are:

[0021] The application adopts an acrylic resin polymer with a large molecular weight, adds a photocuring resin and a plasticizer for reducing surface material and softening the adhesive layer, and thus a UV tack-reducing protective film is prepared. After the UV tack-reducing protective film product, the silica can reduce the surface energy of the product, the plasticizer can soften the adhesive layer, the product is more convenient to tear off the film, and the problems of difficult tearing off the film and low yield of the protective film after etching and tack reduction of the UTG glass are solved by mutual complementation. DETAILED DESCRIPTION

[0022] The application will be further described in detail below with reference to examples, so that those skilled in the art can implement the application according to the description.

[0023] It should be understood that the terms such as "have", "contain" and "include" used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0024] The test methods used in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples can be obtained commercially unless otherwise specified. The specific conditions not specified in the following examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be obtained by commercial purchase.

[0025] The application provides a UV tack-reducing protective film, comprising a substrate layer, an adhesive layer and a release layer which are sequentially stacked, the adhesive layer is obtained by coating a UV tack-reducing adhesive on the substrate layer and then drying and curing.

[0026] The UV tack-reducing adhesive comprises the following raw material components by weight: acrylic resin polymer 80-120 parts, multifunctional monomer 7.5-30 parts, surface energy reducing material 1-4 parts, plasticizer 1-4 parts, curing agent 0.5-2 parts, photoinitiator 1-4 parts, organic solvent 30-70 parts.

[0027] In a preferred embodiment, the acrylic resin polymer is prepared by the following method:

[0028] Isocetyl acrylate 10-30 parts, methyl acrylate 10-50 parts, n-butyl acrylate 10-50 parts, morpholine acrylate 3-10 parts, hydroxyethyl acrylate 1-15 parts, beta-hydroxyethyl acrylate 1-10 parts, ethyl acetate 20-70 parts are added to a reaction kettle, N2 gas is introduced for 0.5-2 hours, then an initiator is added, and the reaction is carried out at 65-75℃ for 5-9 hours to obtain an acrylic resin polymer.

[0029] In a preferred embodiment, the multifunctional monomer is one or more of unsaturated polyester resin, polyurethane resin, epoxy-acrylic resin, polyether-acrylic resin, more preferably polyurethane resin.

[0030] In a preferred embodiment, the surface energy reducing substance is one or more of silica microspheres, polyethylene microspheres, polypropylene microspheres, fluorine-containing auxiliary agent, more preferably silica microspheres.

[0031] In a preferred embodiment, the plasticizer is one or more of dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, dioctyl sebacate, tributyl citrate, more preferably tributyl citrate.

[0032] In a preferred embodiment, the curing agent is an isocyanate-based curing agent selected from one or more of toluene diisocyanate (TDI), diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), more preferably TDI.

[0033] In a preferred embodiment, the photoinitiator is one or more of 184 (1-hydroxycyclohexyl phenyl ketone), 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone), TPO (diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide), IHT-PI (2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone), more preferably TPO.

[0034] In a preferred embodiment, the organic solvent is one or more of ethyl acetate, toluene, butanone, methyl isobutyl ketone, more preferably ethyl acetate.

[0035] In a preferred embodiment, the UV adhesion-reducing adhesive comprises the following raw material components by weight parts: acrylic resin polymer 80-120 parts, polyurethane resin 7.5-30 parts, silica 1-4 parts, tributyl citrate 1-4 parts, toluene diisocyanate 0.5-2 parts, initiator TPO 1-4 parts, ethyl acetate 30-70 parts.

[0036] In a preferred embodiment, the UV adhesion-reducing adhesive comprises the following raw material components by weight parts: acrylic resin polymer 80-120 parts, polyurethane resin 7.5-30 parts, silica 1-4 parts, tributyl citrate 1-4 parts, toluene diisocyanate 0.5-2 parts, initiator TPO 1-4 parts, ethyl acetate 30-70 parts.

[0037] The substrate layer is a supporting substrate of the adhesive layer, and the soft substrate material such as PO, PE, CPP, PVC, etc. is selected according to the application requirements. The thickness of the substrate layer is usually 300 μm or less, preferably 50-300 μm, more preferably about 80-100 μm, but is not limited thereto. The substrate layer is usually first subjected to conventional surface treatment such as corona, Plasma, coating treatment, etc. to increase the adhesion between the adhesive layer and the substrate layer.

[0038] In a preferred embodiment, the thickness of the adhesive layer is 10-80 μm, more preferably 10-30 μm.

[0039] The release layer 3 is a release layer for the adhesive layer, and is generally a release film with a PET substrate, and the thickness is usually below 200 μm, preferably 25-100 μm, more preferably 50 μm.

[0040] The above is the general idea of the present application, and the following provides detailed examples and comparative examples based on the general idea.

[0041] The acrylic resin polymer involved in the following examples is prepared by the following method:

[0042] Isocetyl acrylate 15 parts, methyl acrylate 10 parts, n-butyl acrylate 25 parts, morpholine acrylate 5 parts, hydroxyethyl acrylate 8 parts, β-hydroxyethyl acrylate 3 parts, and ethyl acetate 50 parts are added to a reaction kettle, N2 gas is introduced for 1 hour, then an initiator (azobisisobutyronitrile AIBN) is added, and the reaction is carried out at 72°C for 7 hours to obtain an acrylic resin polymer.

[0043] Example 1

[0044] A UV adhesion-reducing protective film, comprising a substrate layer, an adhesive layer and a release layer which are sequentially stacked,

[0045] The adhesive layer is obtained by coating a UV adhesion-reducing adhesive on the substrate layer and drying and curing, and the UV adhesion-reducing adhesive comprises the following raw material components by weight: acrylic resin polymer 100 parts, polyurethane resin 15 parts, silicon dioxide 2 parts, tributyl citrate 2 parts, toluene diisocyanate 1 part, initiator TPO 2 parts, and ethyl acetate 50 parts.

[0046] The preparation method of the UV adhesion-reducing protective film is as follows:

[0047] S1, uniformly mix the acrylic resin polymer, polyurethane resin, silicon dioxide, tributyl citrate, toluene diisocyanate, initiator TPO and ethyl acetate to obtain a UV adhesion-reducing adhesive;

[0048] S2, uniformly coat the UV adhesion-reducing adhesive on the corona surface of the substrate layer, and dry at 120°C for 3 min to obtain an adhesive layer with a thickness of 20 μm;

[0049] S3, adhere a release film to the surface of the adhesive layer to obtain a UV adhesion-reducing protective film.

[0050] The substrate layer is a PO substrate with a thickness of 100 μm, and the release layer is a PET release film with a thickness of 50 μm.

[0051] Example 2

[0052] A UV adhesion-reducing protective film, comprising a substrate layer, a glue layer and a release layer arranged in sequence,

[0053] The glue layer is obtained by coating a UV adhesion-reducing glue on the substrate layer and then drying and curing, wherein the UV adhesion-reducing glue comprises the following raw material components by weight: 100 parts of acrylic resin polymer, 15 parts of polyurethane resin, 2 parts of silicon dioxide, 8 parts of tributyl citrate, 1 part of toluene diisocyanate, 2 parts of initiator TPO, and 50 parts of ethyl acetate.

[0054] The preparation method of the UV adhesion-reducing protective film is as follows:

[0055] S1, uniformly mix acrylic resin polymer, polyurethane resin, silicon dioxide, tributyl citrate, toluene diisocyanate, initiator TPO and ethyl acetate to obtain a UV adhesion-reducing glue;

[0056] S2, uniformly coat the UV adhesion-reducing glue on the corona surface of the substrate layer, and dry at 120 DEG C for 3 minutes to obtain a glue layer with a thickness of 20 microns;

[0057] S3, adhere a release film to the surface of the glue layer to obtain a UV adhesion-reducing protective film.

[0058] The substrate layer is a PO substrate with a thickness of 100 microns, and the release layer is a PET release film with a thickness of 50 microns.

[0059] Example 3

[0060] A UV adhesion-reducing protective film, comprising a substrate layer, a glue layer and a release layer arranged in sequence,

[0061] The glue layer is obtained by coating a UV adhesion-reducing glue on the substrate layer and then drying and curing, wherein the UV adhesion-reducing glue comprises the following raw material components by weight: 100 parts of acrylic resin polymer, 15 parts of polyurethane resin, 2 parts of silicon dioxide, 8 parts of tributyl citrate, 1 part of toluene diisocyanate, 2 parts of initiator TPO, and 50 parts of ethyl acetate.

[0062] The preparation method of the UV adhesion-reducing protective film is as follows:

[0063] S1, uniformly mix acrylic resin polymer, polyurethane resin, silicon dioxide, tributyl citrate, toluene diisocyanate, initiator TPO and ethyl acetate to obtain a UV adhesion-reducing glue;

[0064] S2, uniformly coat the UV adhesion-reducing glue on the corona surface of the substrate layer, and dry at 120 DEG C for 3 minutes to obtain a glue layer with a thickness of 20 microns;

[0065] S3, adhere a release film to the surface of the glue layer to obtain a UV adhesion-reducing protective film.

[0066] The base material layer is a PO base material with a thickness of 100 μm, and the release layer is a PET release film with a thickness of 50 μm.

[0067] Comparative Example 1

[0068] A UV adhesion-reducing protective film includes, in sequence, a base material layer, a glue layer, and a release layer,

[0069] The glue layer is obtained by coating a UV adhesion-reducing glue on the base material layer and then drying and curing, and the UV adhesion-reducing glue includes the following raw material components by weight: 100 parts of an acrylic resin polymer, 15 parts of a polyurethane resin, 2 parts of silicon dioxide, 1 part of toluene diisocyanate, 2 parts of an initiator TPO, and 50 parts of ethyl acetate.

[0070] The preparation method of the UV adhesion-reducing protective film is as follows:

[0071] S1, uniformly mix the acrylic resin polymer, the polyurethane resin, the silicon dioxide, the tributyl citrate, the toluene diisocyanate, the initiator TPO, and the ethyl acetate to obtain a UV adhesion-reducing glue;

[0072] S2, uniformly coat the UV adhesion-reducing glue on the corona surface of the base material layer, dry at 120°C for 3 min, and obtain a glue layer with a thickness of 20 μm;

[0073] S3, adhere the release film to the surface of the glue layer to obtain a UV adhesion-reducing protective film.

[0074] The base material layer is a PO base material with a thickness of 100 μm, and the release layer is a PET release film with a thickness of 50 μm.

[0075] Comparative Example 2

[0076] A UV adhesion-reducing protective film includes, in sequence, a base material layer, a glue layer, and a release layer,

[0077] The glue layer is obtained by coating a UV adhesion-reducing glue on the base material layer and then drying and curing, and the UV adhesion-reducing glue includes the following raw material components by weight: 100 parts of an acrylic resin polymer, 15 parts of a polyurethane resin, 2 parts of tributyl citrate, 1 part of toluene diisocyanate, 2 parts of an initiator TPO, and 50 parts of ethyl acetate.

[0078] The preparation method of the UV adhesion-reducing protective film is as follows:

[0079] S1, uniformly mix the acrylic resin polymer, the polyurethane resin, the silicon dioxide, the tributyl citrate, the toluene diisocyanate, the initiator TPO, and the ethyl acetate to obtain a UV adhesion-reducing glue;

[0080] S2, uniformly coat the UV adhesion-reducing glue on the corona surface of the base material layer, dry at 120°C for 3 min, and obtain a glue layer with a thickness of 20 μm;

[0081] S3, laminating a release film on the surface of the glue layer to obtain the UV debonding protective film.

[0082] The substrate layer is a PO substrate with a thickness of 100 μm, and the release layer is a PET release film with a thickness of 50 μm.

[0083] Comparative Example 3

[0084] The UV debonding protective film comprises a substrate layer, a glue layer and a release layer which are sequentially stacked,

[0085] The glue layer is obtained by coating a UV debonding glue on the substrate layer and drying and curing, wherein the UV debonding glue comprises the following components by weight: 100 parts of acrylic resin polymer, 15 parts of polyurethane resin, 2 parts of silicon dioxide, 0.5 parts of tributyl citrate, 1 part of toluene diisocyanate, 2 parts of initiator TPO, and 50 parts of ethyl acetate.

[0086] The preparation method of the UV debonding protective film is as follows:

[0087] S1, uniformly mixing acrylic resin polymer, polyurethane resin, silicon dioxide, tributyl citrate, toluene diisocyanate, initiator TPO and ethyl acetate to obtain a UV debonding glue;

[0088] S2, uniformly coating the UV debonding glue on the corona surface of the substrate layer, drying at 120°C for 3 min to obtain a glue layer with a thickness of 20 μm;

[0089] S3, laminating a release film on the surface of the glue layer to obtain the UV debonding protective film.

[0090] The substrate layer is a PO substrate with a thickness of 100 μm, and the release layer is a PET release film with a thickness of 50 μm.

[0091] The UV debonding protective films prepared in Examples 1-3 and Comparative Examples 1-3 are tested as follows:

[0092] (1) Molecular weight test: GPC (gel chromatography) method;

[0093] (2) Peel strength test: ASTM-D3330 method (test speed is 300 mm / min and 6000 mm / min respectively)

[0094] (2) UTG glass film tearing method: the UV debonding film is attached to one side of a thick glass with a ratio of 1:1. After etching process (acid washing, alkali washing, water washing) and drying, the product is subjected to UV debonding in a UV curing equipment. After debonding, the product is placed on a fixed operation platform and mechanically torn, with a tearing speed of 8 m / min.

[0095] The test results are shown in Table 1 below:

[0096] Table 1

[0097]

[0098] As can be seen from the test results, the UV adhesion-reducing protective films prepared in Examples 1-3 and Comparative Examples 1-3 all exhibit good UV adhesion-reducing performance, and Examples 1-3 exhibit better performance; and the UTG glass yield after film tearing of Examples 1-3 is significantly higher than that of Comparative Examples 1-3. In actual application, the overall film tearing yield is improved due to the addition of silica and plasticizer tributyl citrate in proper proportions in the examples, the silica is a low surface energy substance that can reduce the surface energy of the adhesive surface, the plasticizer tributyl citrate can soften the adhesive layer, and the combination of the two makes the frictional shear under high-speed film tearing after UV adhesion reduction smaller, and the peeling force also smaller, thereby improving the yield.

[0099] Although the embodiments of the present application have been disclosed as above, it is not limited to the use listed in the specification and embodiments, and can be fully applied to various fields suitable for the present application, and additional modifications can be easily made by those skilled in the art, and therefore the present application is not limited to specific details, but within the general concept defined by the claims and equivalent scope.

Claims

1. A UV-resistant anti-adhesion protective film, characterized in that, It includes a substrate layer, an adhesive layer and a release layer stacked in sequence, wherein the adhesive layer is obtained by coating the substrate layer with UV anti-tack adhesive and then drying and curing it; The UV-resistant adhesive comprises the following raw material components by weight: 80-120 parts acrylic resin polymer, 7.5-30 parts polyurethane resin, 1-4 parts silica microspheres, 1-4 parts plasticizer, 0.5-2 parts curing agent, 1-4 parts photoinitiator, and 30-70 parts organic solvent. The acrylic resin polymer is obtained by polymerization reaction of the following raw materials in parts by weight: 10-30 parts of isooctyl acrylate, 10-50 parts of methyl acrylate, 10-50 parts of n-butyl acrylate, 3-10 parts of morpholine acrylate, 1-15 parts of hydroxyethyl acrylate, 1-10 parts of β-hydroxyethyl acrylate, and 20-70 parts of ethyl acetate. The plasticizer is tributyl citrate.

2. The UV anti-adhesion protective film according to claim 1, characterized in that, The acrylic resin polymer is prepared by the following method: 10-30 parts of isooctyl acrylate, 10-50 parts of methyl acrylate, 10-50 parts of n-butyl acrylate, 3-10 parts of morpholine acrylate, 1-15 parts of hydroxyethyl acrylate, 1-10 parts of β-hydroxyethyl acrylate, and 20-70 parts of ethyl acetate are added to a reaction vessel. After purging with N2 gas for 0.5-2 hours, an initiator is added, and the reaction is carried out at 65-75°C for 5-9 hours to obtain the acrylic resin polymer.

3. The UV anti-adhesion protective film according to claim 1, characterized in that, The curing agent is an isocyanate curing agent, selected from one or more of toluene diisocyanate, isoflurone diisocyanate, and hexamethylene diisocyanate.

4. The UV anti-adhesion protective film according to claim 1, characterized in that, The photoinitiator is one or more of 184, 1173, TPO, and IHT-PI; The organic solvent is one or more of ethyl acetate, toluene, butanone, and methyl isobutyl ketone.

5. The UV anti-adhesion protective film according to claim 1, characterized in that, The UV-resistant adhesive comprises the following raw material components by weight: 80-120 parts acrylic resin polymer, 7.5-30 parts polyurethane resin, 1-4 parts silica microspheres, 1-4 parts tributyl citrate, 0.5-2 parts toluene diisocyanate, 1-4 parts initiator TPO, and 30-70 parts ethyl acetate. The mass ratio of silica microspheres to tributyl citrate is 1:

1.

6. The UV anti-adhesion protective film according to any one of claims 1-5, characterized in that, The thickness of the substrate layer is 50-300 μm, the thickness of the adhesive layer is 10-80 μm, and the thickness of the release layer is 25-100 μm.

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