CN112029429A - Shock-absorbing protective film and preparation method thereof - Google Patents
Shock-absorbing protective film and preparation method thereof Download PDFInfo
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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
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- C08J5/18—Manufacture of films or sheets
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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- 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
- 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
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- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/00—Use of organic ingredients
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- C08K5/10—Esters; Ether-esters
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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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
- C09J2483/00—Presence of polysiloxane
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- Wood Science & Technology (AREA)
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Abstract
The utility model provides a shock attenuation protection film, includes the four layers, and the first layer is self-repairing coating, and the second floor is the polyethylene terephthalate film layer, and the third layer is gluing agent layer, and the fourth layer is the separation and reunion rete. The shock absorption protective film has excellent shock absorption and scratch resilience, can effectively buffer impact, prevent screen bursting, or prevent glass or plastic panels from being broken and scattered due to careless impact, reduce hidden damage of the glass panels, has a self-repairing function on fine scratches generated by hard objects to ensure the safety of users, and also has good fingerprint and hydrophobicity prevention and can keep the special luster and texture of the glass of the screen panels.
Description
Technical Field
The invention belongs to the technical field of plastic processing, and particularly relates to a damping protective film and a preparation method thereof.
Background
The shock-absorbing protective film is a high-molecular protective film adhered to the front and back screens (glass or plastic) of a mobile phone, and the material has excellent shock absorption and scratch resilience, so that the shock-absorbing protective film can effectively buffer impact, prevent the screen from bursting, or prevent the glass or plastic panel from being broken and scattered due to accidental impact, reduce the hidden damage of the glass panel, and has the self-repairing function of fine scratch on hard objects to ensure the safety of users.
Chinese patent CN 201711397946.6 discloses an automatic repairing and shock-absorbing protective film, which comprises a substrate layer, a silica gel layer, an adsorption layer, a carbon nanotube layer, a shock-absorbing coating and a scratch-proof layer, wherein the adsorption layer is arranged behind the substrate layer; the upper surface of the substrate layer is attached with a carbon nanotube layer; a silica gel layer is attached to the upper layer of the carbon nanotube layer; the silica gel layer is 0.1-0.3 mm; and the upper surface of the silica gel layer is adhered with a damping coating. The automatic repairing and damping protective film realizes the sticking function of the protective film through the adsorption layer; the scratch-resistant layer realizes the scratch-resistant function; the strength of the protective film is enhanced through the carbon nanotube layer, so that the protective capability to glass is enhanced; the damping function of the protective film is realized through the damping coating; through the OCA glue film, the automatic repairing function of the protective film is realized. This automatic restoration shock attenuation protection film convenient to use, protection are effectual, the protection function is stronger. The patent is provided with 6 layers in total, and the production method is complex and high in cost.
Disclosure of Invention
The invention aims to provide a shock absorption protective film and a preparation method thereof, wherein the shock absorption protective film has excellent shock absorption and scratch resilience, can effectively buffer impact, prevent a screen from bursting, or prevent glass or plastic panels from being broken and scattered due to careless impact, reduce hidden damage of the glass panels, has a self-repairing function on fine scratches generated on hard objects so as to ensure the safety of users, and also has good fingerprint prevention and hydrophobicity, and can keep the special luster and texture of the glass of the screen panels.
The shock absorption protective film comprises four layers, wherein the first layer is a self-repairing coating, the second layer is a polyethylene terephthalate film layer, the third layer is an adhesive layer, and the fourth layer is a clutch film layer.
The self-repairing coating is prepared from the following components in parts by weight:
40-60 parts of acrylic acid modified polyurethane, 10-15 parts of curing agent, 0.005-0.010 part of defoaming agent, 0.01-0.05 part of flatting agent, 5-10 parts of fluotitanic acid, 50-60 parts of solvent and 0.05-0.06 part of surfactant.
Wherein the acrylic modified polyurethane is prepared by the following method:
adding 50-100 parts of epoxy resin, 10-20 parts of acrylic acid and 0.2-0.5 part of triethylamine into a reactor, reacting at 90-110 ℃ for 1-3 hours, adding 5-10 parts of hexamethylene diisocyanate, reacting at 80-90 ℃ for 1-3 hours, and finally adding tripropylene glycol diacrylate to obtain the acrylic modified polyurethane.
The curing agent is hexamethylene diisocyanate.
The defoaming agent is BYK-012.
The leveling agent is an acrylic leveling agent.
The surfactant is sodium dodecyl sulfate.
The solvent is compounded by water and ethyl acetate, the weight ratio of the compound is 1:7-10, if the water content is too much, the surface of the obtained coating is uneven, the water content is too little, and the fluotitanic acid cannot play a role in resisting fingerprints.
The preparation method of the self-repairing coating comprises the following steps:
(1) 1/2 solvent is added into the stirring kettle, the defoamer and the acrylic acid modified polyurethane are sequentially added under the stirring state, and the mixture is stirred for 1 to 2 hours at the speed of 2500-.
(2) Mixing and stirring the solvent 1/2, the leveling agent, the fluotitanic acid and the surfactant uniformly to obtain a component B;
(3) adding the curing agent and the component B into the component A, stirring and feeding, and dispersing at 3000 rpm for 1-2 hours at 2000-.
The polyethylene terephthalate film layer is prepared from the following components in parts by weight: 100 parts of polyethylene terephthalate, 1-2 parts of antioxidant, 2-5 parts of titanate coupling agent, 0.5-1 part of nucleating agent and 0.5-1 part of ultraviolet light aging resistant agent.
The preparation method of the polyethylene terephthalate film layer comprises the following steps:
(1) weighing the materials in proportion, putting the materials into a high-speed mixer for uniformly mixing for 5-10 minutes at the mixing speed of 1000-;
(2) and (3) putting the mixed materials into a double-screw extruder to extrude sheets, then carrying out four-roll calendering at the calendering temperature of 195-265 ℃, and then carrying out bidirectional stretching at the temperature of 180-200 ℃ to obtain the polyethylene terephthalate film layer.
The adhesive layer is dimethyl silicone oil.
The clutch film layer is a polyethylene or PVC film.
In the technical scheme, the thickness of the shock absorption protective film is 50-60 micrometers, the thickness of the polyethylene terephthalate film layer is 10-15 micrometers, the thickness of the self-repairing coating is 20-25 micrometers, the thickness of the adhesive layer is 5-10 micrometers, and the thickness of the clutch film layer is 10-15 micrometers.
The preparation method of the damping protective film comprises the following steps:
(1) coating the self-repairing coating on a machine, wherein the substrate is a polyethylene terephthalate film layer;
(2) then gluing and attaching a separation film.
The invention has the following beneficial effects: the shock absorption protective film has excellent shock absorption and scratch resilience, can effectively buffer impact, prevent screen bursting, or prevent glass or plastic panels from being broken and scattered due to careless impact, reduce hidden damage of the glass panels, has a self-repairing function on fine scratches generated by hard objects to ensure the safety of users, and also has good fingerprint and hydrophobicity prevention and can keep the special luster and texture of the glass of the screen panels.
Detailed Description
Example 1
Self-healing coating formulation:
45 parts of acrylic modified polyurethane, 12 parts of hexamethylene diisocyanate, BYK-0120.009 parts of a defoaming agent, 1570.04 parts of an acrylic flatting agent KEPERSURF-1570.04 parts, 6 parts of fluotitanic acid, 50 parts of a solvent and 0.05 part of sodium dodecyl sulfate, wherein the compounding weight ratio of water to ethyl acetate in the solvent is 1: 9.
The preparation method of the acrylic acid modified polyurethane comprises the following steps:
adding epoxy resin E5170 parts, acrylic acid 15 parts and triethylamine 0.4 part into a reactor, reacting at 95 ℃ for 2 hours, adding hexamethylene diisocyanate 6 parts, reacting at 85 ℃ for 2 hours, and finally adding tripropylene glycol diacrylate to obtain acrylic acid modified polyurethane.
The preparation method of the self-repairing coating comprises the following steps:
(1) 1/2 solvent is added into the stirring kettle, the defoamer and the acrylic acid modified polyurethane are sequentially added under the stirring state, and the mixture is stirred for 1 to 2 hours at the speed of 2500-.
(2) And mixing and stirring the solvent 1/2, the leveling agent, the fluotitanic acid and the surfactant uniformly to obtain a component B.
(3) Adding the curing agent and the component B into the component A, stirring and feeding, and dispersing at 3000 rpm for 1-2 hours at 2000-.
The formula of the polyethylene terephthalate film layer is as follows:
100 parts of polyethylene terephthalate, 10101 parts of antioxidant and 3 parts of titanate coupling agent; 0.6 part of nucleating agent silicon dioxide and 5710.5 parts of ultraviolet light aging resistant agent UV.
The preparation method of the polyethylene terephthalate film layer comprises the following steps:
(1) weighing the materials in proportion, putting the materials into a high-speed mixer, uniformly mixing the materials for 7 minutes at a mixing speed of 1100 r/min, and then discharging the materials;
(2) and (3) putting the mixed materials into a double-screw extruder to extrude sheets, then carrying out four-roll calendering at the calendering temperature of 250 ℃, and then carrying out bidirectional stretching within the range of 190 ℃ to obtain the polyethylene terephthalate film layer with the film thickness of 15 microns.
The preparation method of the damping protective film comprises the following steps:
(1) coating the self-repairing coating on a machine, wherein the substrate is a polyethylene terephthalate film layer;
(2) then gluing and attaching a separation film.
The thickness of the polyethylene terephthalate film layer is 15 micrometers, the thickness of the self-repairing coating layer is 20 micrometers, the thickness of the adhesive layer is 10 micrometers, and the thickness of the clutch film layer is 10 micrometers.
The technical performance criteria of example 1 are as follows:
1) peeling force: not less than 80-120 gf/25 mm;
2) thickness: 90 +/-2 um;
3) light transmittance: more than or equal to 90 percent;
4) haze: less than or equal to 1.0;
5) self-repairability: 2S (750gf special copper wire brush);
6) the contact angle of water drops is more than or equal to 105 degrees;
7) odor: none;
8) fingerprint resistance: for fingerprint prints, wiping is easy.
Comparative example 1
The only difference from example 1 is that the solvent of the coating was all water, and the resulting coating had an uneven surface.
Comparative example 2
The only difference from example 1 is that the solvent of the coating was all ethyl acetate, and the coating obtained had poor fingerprint resistance and could not be rubbed off.
Claims (10)
1. The utility model provides a shock attenuation protection film, its characterized in that includes the four layers, and the first layer is self-repairing coating, and the second floor is the polyethylene terephthalate film layer, and the third layer is gluing agent layer, and the fourth layer is separation and reunion rete.
2. The shock absorbing protective film according to claim 1, wherein said self-healing coating is made of the following components in parts by weight:
40-60 parts of acrylic acid modified polyurethane, 10-15 parts of curing agent, 0.005-0.010 part of defoaming agent, 0.01-0.05 part of flatting agent, 5-10 parts of fluotitanic acid, 50-60 parts of solvent and 0.05-0.06 part of surfactant.
3. The shock absorbing protective film according to claim 2, wherein said acrylic modified polyurethane is prepared by a method comprising:
adding 50-100 parts of epoxy resin, 10-20 parts of acrylic acid and 0.2-0.5 part of triethylamine into a reactor, reacting at 90-110 ℃ for 1-3 hours, adding 5-10 parts of hexamethylene diisocyanate, reacting at 80-90 ℃ for 1-3 hours, and finally adding tripropylene glycol diacrylate to obtain the acrylic modified polyurethane.
4. The shock-absorbing protective film according to claim 2, wherein the curing agent is hexamethylene diisocyanate, the defoaming agent is BYK-012, the leveling agent is an acrylic leveling agent, and the surfactant is sodium dodecyl sulfate.
5. The shock-absorbing protective film according to claim 2, wherein the solvent is a mixture of water and ethyl acetate, and the weight ratio of the mixture is 1: 7-10.
6. The shock absorbing protective film according to claim 2, wherein said self-healing coating is prepared by the following method:
(1) adding 1/2 solvent into a stirring kettle, sequentially adding defoamer and acrylic acid modified polyurethane under the stirring state, and stirring at 2500-;
(2) mixing and stirring the solvent 1/2, the leveling agent, the fluotitanic acid and the surfactant uniformly to obtain a component B;
(3) adding the curing agent and the component B into the component A, stirring and feeding, and dispersing at 3000 rpm for 1-2 hours at 2000-.
7. The shock-absorbing protective film according to claim 1, wherein the polyethylene terephthalate film layer is made of the following components in parts by weight: 100 parts of polyethylene terephthalate, 1-2 parts of antioxidant, 2-5 parts of titanate coupling agent, 0.5-1 part of nucleating agent and 0.5-1 part of ultraviolet light aging resistant agent.
8. The shock absorbing protective film according to claim 7, wherein the polyethylene terephthalate film layer is prepared by the following method:
(1) weighing the materials in proportion, putting the materials into a high-speed mixer for uniformly mixing for 5-10 minutes at the mixing speed of 1000-;
(2) and (3) putting the mixed materials into a double-screw extruder to extrude sheets, then carrying out four-roll calendering at the calendering temperature of 195-265 ℃, and then carrying out bidirectional stretching at the temperature of 180-200 ℃ to obtain the polyethylene terephthalate film layer.
9. The shock-absorbing protective film according to claim 1, wherein the adhesive layer is dimethicone, and the clutch film layer is a polyethylene or PVC film.
10. The method for preparing a shock absorbing protective film according to claim 1, comprising the steps of:
(1) coating the self-repairing coating on a machine, wherein the substrate is a polyethylene terephthalate film layer;
(2) then gluing and attaching a separation film.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010786458.XA CN112029429A (en) | 2020-08-07 | 2020-08-07 | Shock-absorbing protective film and preparation method thereof |
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| CN202010786458.XA CN112029429A (en) | 2020-08-07 | 2020-08-07 | Shock-absorbing protective film and preparation method thereof |
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| CN1320669A (en) * | 2000-04-27 | 2001-11-07 | 山东工业大学 | Process for preparing epoxy modified acrylic acid-polyurethane emulsion and water-soluble polyurethane paint |
| CN1438257A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
| JP2012096946A (en) * | 2010-10-29 | 2012-05-24 | Mitsubishi Materials Corp | Titanium-based black powder, method for producing the same and use of the same |
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| CN106118314A (en) * | 2016-06-28 | 2016-11-16 | 詹俊英 | Modified urethane acrylate water-borne wood latex and preparation method thereof |
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| CN111363488A (en) * | 2020-04-23 | 2020-07-03 | 广东邦固薄膜涂料创新研究院有限公司 | 3D curved screen self-repairing TPU protective film and preparation method thereof |
-
2020
- 2020-08-07 CN CN202010786458.XA patent/CN112029429A/en active Pending
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| JP2012096946A (en) * | 2010-10-29 | 2012-05-24 | Mitsubishi Materials Corp | Titanium-based black powder, method for producing the same and use of the same |
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| CN106118314A (en) * | 2016-06-28 | 2016-11-16 | 詹俊英 | Modified urethane acrylate water-borne wood latex and preparation method thereof |
| CN110628350A (en) * | 2018-06-25 | 2019-12-31 | 上海海优威新材料股份有限公司 | Protective film for protecting workpieces in a processing state and use thereof |
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| CN111363488A (en) * | 2020-04-23 | 2020-07-03 | 广东邦固薄膜涂料创新研究院有限公司 | 3D curved screen self-repairing TPU protective film and preparation method thereof |
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| 涂志刚等: "《塑料软包装材料》", 31 July 2018, 文化发展出版社 * |
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Application publication date: 20201204 |
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