CN117603487A - High-hardness bio-based nylon film and preparation method thereof - Google Patents

High-hardness bio-based nylon film and preparation method thereof Download PDF

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CN117603487A
CN117603487A CN202311769912.0A CN202311769912A CN117603487A CN 117603487 A CN117603487 A CN 117603487A CN 202311769912 A CN202311769912 A CN 202311769912A CN 117603487 A CN117603487 A CN 117603487A
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bio
coating
parts
nylon
based nylon
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曹丽军
冉江渝
任月璋
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Suzhou Omay Optical Materials Co ltd
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Suzhou Omay Optical Materials Co ltd
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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
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/06—Unsaturated polyesters
    • 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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Abstract

The invention provides a high-hardness bio-based nylon film and a preparation method thereof, wherein the bio-based nylon film comprises a bio-based nylon substrate and a coating arranged on one side surface of the bio-based nylon substrate, the preparation raw materials of the coating comprise a film forming substance, an adhesion promoter and a photoinitiator, and the film forming substance comprises nano hybridized modified acrylic ester with the functionality of more than 2 and/or other acrylic compounds with the functionality of more than 5 except the nano hybridized modified acrylic ester; the specific film forming substances are adopted to enable the coating to have higher crosslinking density, and then the adhesion promoter and the photoinitiator are matched to enable the coating to have excellent film forming property and higher adhesion with the bio-based nylon base material, so that the bio-based nylon film with excellent mechanical property, optical property and high hardness is finally obtained.

Description

High-hardness bio-based nylon film and preparation method thereof
Technical Field
The invention belongs to the technical field of biological base materials, and particularly relates to a high-hardness biological base nylon film and a preparation method thereof.
Background
With the increasing energy crisis, the over-exploitation and over-use of petroleum exacerbates the greenhouse gas effect, thereby making the use of petroleum-based polymeric materials more careful. In order to solve the problems, researchers have proposed and developed bio-based polymer materials to replace oil-based polymer materials, which are polymer materials obtained by extracting chemical monomers from non-petroleum sources such as animals or plants and polymerizing the chemical monomers.
The bio-based polymer materials can be classified according to the product attributes into products prepared from bio-based plastics, bio-based chemical fibers, bio-based rubbers, bio-based coatings, bio-based materials auxiliary agents, bio-based composite materials and various bio-based materials; with the wide acceptance of bio-based polymers and the increasing demand of the actual market, more bio-based polymer materials are emerging, such as poly (3-light-butyrate) (PHB), poly (3-hexanoic acid) (PHH) and poly (3-hexanoic acid) (PHV), which are currently in wide use in various places as packaging materials, fibers, biocompatible and biodegradable materials, and drug delivery materials; although the above bio-based polymer materials have been developed to some extent, the current sources are mostly crops such as corn and soybean, which cause competition with human grains, thereby limiting the development.
To solve this problem, researchers developed a bio-based nylon, nylon 11, which is a polymer of monomers extracted from castor, and has the structural formulaCompared with conventional nylon, the polymer material is superior in optical and mechanical properties, but has lower surface hardness and is not scratch-resistant, so that the wide application of the material is greatly limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-hardness bio-based nylon film and a preparation method thereof, wherein a coating is arranged on one side surface of a bio-based nylon substrate, and the coating has high crosslinking density due to the selection of a film forming substance with high functionality, and is matched with a photoinitiator and an adhesion promoter, so that the obtained bio-based nylon film has high hardness and excellent optical performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a high hardness bio-based nylon film comprising a bio-based nylon substrate and a coating;
the coating is prepared from the following raw materials in parts by weight:
20-70 parts by weight of film forming substances;
2-10 parts by weight of an adhesion promoter;
3-6 parts by weight of a photoinitiator;
the film-forming materials include nano-hybrid modified acrylates having a functionality > 2 (e.g., 3, 4, 5, or 6, etc.) and/or other acrylic compounds other than the nano-hybrid modified acrylates having a functionality > 5 (e.g., 6, 7, 8, 9, or 10, etc.).
Wherein the film forming material is 20 to 70 parts by weight, for example, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts or 70 parts, etc.
The adhesion promoter is 2 to 10 parts by weight, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or the like.
The weight part of the photoinitiator is 3-6 parts, for example 3 parts, 4 parts, 5 parts or 6 parts, etc.
The high-hardness bio-based nylon film provided by the invention comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate, wherein the high-hardness refers to the surface hardness of the side, with the coating layer, of the bio-based nylon film is more than 2H; according to the invention, the nano hybridized modified acrylic ester with the functionality more than 2 and/or other acrylic compounds with the functionality more than 5 except the nano hybridized modified acrylic ester are selected as film forming substances of the coating, so that the coating has higher crosslinking density and does not influence the high light transmittance of the bio-based nylon base material, and then the adhesion promoter and the photoinitiator are added in a matching way, so that the finally obtained bio-based nylon film has high hardness, excellent optical performance and mechanical performance.
Preferably, the bio-based nylon film has a hardness > 2H, such as 3H, 4H, or 5H, etc.
Preferably, the bio-based nylon substrate is a nylon 11 film.
Preferably, the bio-based nylon substrate has a thickness of 5 to 6000 μm, for example, 10 μm, 50 μm, 100 μm, 500 μm, 1000 μm, 5000 μm, or the like.
Preferably, the thickness of the coating is 1 to 20. Mu.m, for example 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm or 18 μm, etc., more preferably 5 to 20. Mu.m
Preferably, the other acrylic compound comprises any one or a combination of at least two of aliphatic urethane acrylate oligomer, aromatic urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate oligomer, polyether acrylate oligomer, ethoxylated trimethylolpropane triacrylate epoxidized soybean oil acrylate oligomer, modified epoxy acrylate oligomer, epoxy methacrylate oligomer, aliphatic silicone acrylate oligomer, acidic functional acrylate oligomer, silicone urethane acrylate oligomer, polybutadiene dimethacrylate oligomer, polybutadiene diacrylate oligomer, polyester acrylate oligomer, acrylate polyester oligomer or chlorinated polyester acrylate oligomer.
Preferably, the adhesion promoter comprises any one or a combination of at least two of a silane coupling agent, a titanate coupling agent, a zirconium-based coupling agent, or a chromium complex-based coupling agent.
In the invention, the adhesion promoter can improve the binding force between the bio-based nylon base material and the coating, so that the coating has strong adhesion on the bio-based nylon base material and can be applied to actual places; including but not limited to the trade name: coatOSil 1770,CoatOSil 2287,CoatOSil DRI,CoatiOSil MP 200,Silquest A-1170, silquest A-171, silquest A-187, silquest A-1110, silquest A-1100, silquest A-186, silquest A-1871, silquest A-2120, silquest A-Link 597, silquest A-9627, silquest Y-Y9669, BYK-4509, BYK-4510, BYK-4511, BYK-4512, BYK-C8000, BYK-4513.
Preferably, the photoinitiator is any one or a mixture of at least two of 2-hydroxy-2-methyl-1-phenylpropion, 2,4, 6-trimethylbenzoyl phenylphosphonate ethyl ester, methyl benzoate, 1-hydroxycyclohexylphenyl ketone, diethoxy-phenylacetophenone, diethoxy acetophenone, dimethoxy phenyl acetophenone, 2, 4-dihydroxybenzophenone, 2,4, 6-trimethylbenzoyl ethoxy phenyl phosphine oxide, 2-di-sec-butoxyacetophenone, alpha-hydroxy ketone, hydroxycyclohexylphenyl ketone, hydroxy methylphenyl acetone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide.
Preferably, the coating is prepared from raw materials including other auxiliary agents, including but not limited to: rheology auxiliaries, defoamers or viscosity reducers.
In the invention, the compatibility and stability of each component can be improved by adding the rheological auxiliary agent, and the coating film forming property can be improved; the rheology aid includes a wetting agent and/or a leveling agent, for example, the rheology aid includes 0.1 to 3 parts by weight of a wetting agent and 0.1 to 3 parts by weight of a leveling agent;
wherein, the wetting agent is an auxiliary agent capable of reducing interfacial tension between solid and liquid to enable liquid substances to wet the solid surface more easily, and comprises the following marks but not limited to: anti-Terra-203, anti-Terra-204, anti-Terra-2005, anti-Terra-210, anti-Terra-250, BYK-151, BYK-1162, BYK-1165, BYK-synergy 2100, BYKUMEN, disperbyk, disperbyk-163, dynol 360, dynol 604, dynol 607, dynol 800, dynol 810, dynol 960, dynol 980, surfynol AD01, surfynol 82, surfynol 104, surfynol420, surfynol 440, surfynol 465, surfynol 485, surfynol 2502, TEGO Wet 245 KL, TEGO Wet 250, TEGO Wet 260, TEGO Wet 270, TEGO Wet 280, TEGO Wet 500, TEGO 510, TEGO 4000, TETWIn 0, TEK 342, BYK345, BYK 346; the leveling agent is a substance which can effectively reduce the surface tension of a coating film, obtain a uniform, flat and smooth coating in the coating film forming process and improve the film forming property, and comprises the following marks: TEGO Glide 440, TEGO Glide110, TEGO Flow 425, TEGO Glide 482, TEGO Glide 410, EASYTECHST-5050, BYK333, BYK341, BYK349, TERIC 320, BYK348, N-2218, BYK306, BYK307.
In a second aspect, the present invention provides a method for preparing the bio-based nylon film according to the first aspect, the method comprising the steps of:
(1) Mixing a film forming substance, an adhesion promoter, a photoinitiator and optionally an auxiliary agent in a solvent to obtain a coating;
(2) And (3) coating the coating obtained in the step (1) on the surface of the bio-based nylon substrate, and drying and curing to obtain the bio-based nylon film.
Preferably, the solvent of step (1) comprises any one or a combination of at least two of ethanol, isopropanol, ethyl acetate, butyl acetate, methyl isobutyl ketone or butanone.
Preferably, the curing in step (2) is ultraviolet light curing.
Preferably, the radiation intensity of the ultraviolet light curing is 100-600J/m 2 For example 100J/m 2 、150J/m 2 、200J/m 2 、250J/m 2 、300J/m 2 、350J/m 2 、400J/m 2 、450J/m 2 、500J/m 2 、550J/m 2 Or 600J/m 2 Etc.
Compared with the prior art, the invention has the beneficial effects that:
the high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate, wherein the preparation raw materials of the coating layer comprise a film forming substance, an adhesion promoter and a photoinitiator in specific parts, and the film forming substance comprises nano hybrid modified polyurethane acrylate with the functionality of more than 2 and/or other acrylic compounds with the functionality of more than 5 except the nano hybrid modified acrylate; by adopting the specific film forming substances, the coating has higher crosslinking density, and is matched with the adhesion promoter and the photoinitiator, so that the coating also has excellent film forming property, and simultaneously has higher adhesion with the bio-based nylon base material, so that the finally obtained coating has excellent mechanical property and optical property and also has high hardness.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The technical scheme of the invention is further described by the following specific embodiments.
The various starting materials of the present invention are commercially available, or may be prepared according to methods conventional in the art, unless specifically indicated. Wherein, in the following examples and comparative examples, film-forming materials were purchased from Satomer company and Allnex company; adhesion promoters are available from Dow and Chemours; the photoinitiator was purchased from BASF, and the auxiliaries (wetting and leveling agents) were purchased from BYK, evonik, dow Corning, momentive and 3M; the bio-based nylon substrate, namely nylon 11 substrate, is from Acinamar, and the ultraviolet curing equipment adopts a Heraeus F600S ultraviolet curing system
Example 1
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with the thickness of 5 μm;
the thickness of the coating is 5 mu m, and the preparation raw materials comprise the following components in parts by weight: 20 parts by weight of nano hybrid modified urethane acrylate (functionality 9, CR 90727-2), 2 parts by weight of adhesion promoter (Silquest A-171), 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone and 2 parts by weight of wetting agent (Dynol 800);
the preparation method of the bio-based nylon film provided by the embodiment comprises the following steps:
(1) Mixing the components in the raw materials for preparing the coating in ethanol according to the proportion, and uniformly stirring to obtain the coating with the solid content of 20%;
(2) Uniformly coating the coating obtained in the step (1) on one side surface of a nylon 11 substrate by using a wire rod, drying at 100 ℃ for 2min, and finally completing the curing process in an ultraviolet curing system, wherein the radiation intensity of ultraviolet curing is 100J/m 2 。
Example 2
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with the thickness of 10 μm;
the thickness of the coating is 10 mu m, and the preparation raw materials comprise the following components in parts by weight: 50 parts by weight of a nanohybrid modified acrylate (functionality 3,c150) 4 parts by weight of adhesion promoter (Coatosil 2287), 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone and 2 parts by weight of wetting agent (BYK 342);
the preparation method of the bio-based nylon film provided by the embodiment comprises the following steps:
(1) Mixing the components in the raw materials for preparing the coating in ethanol according to the proportion, and uniformly stirring to obtain the coating with the solid content of 40%;
(2) Uniformly coating the coating obtained in the step (1) on one side surface of a nylon 11 substrate by using a wire rod, drying at 100 ℃ for 2min, and finally completing the curing process in an ultraviolet curing system, wherein the radiation intensity of ultraviolet curing is 300J/m 2 。
Example 3
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with the thickness of 50 μm;
the thickness of the coating is 20 mu m, and the preparation raw materials comprise the following components in parts by weight: 60 parts by weight of nano hybrid modified urethane acrylate (functionality 9, CR 90822-1), 6 parts by weight of adhesion promoter (Silquest Y-Y9669), 6 parts by weight of 2-hydroxy-2-methyl-1-phenylpropion and 2 parts by weight of wetting agent (TEGO Wet KL 245);
the preparation method of the bio-based nylon film provided by the embodiment comprises the following steps:
(1) Mixing the components in the preparation raw materials of the coating in ethyl acetate according to the proportion, and uniformly stirring to obtain the coating with 70% of solid content;
(2) Uniformly coating the coating obtained in the step (1) on one side surface of a nylon 11 substrate by using a wire rod, drying at 100 ℃ for 2min, and finally completing the curing process in an ultraviolet curing system, wherein the radiation intensity of ultraviolet curing is 300J/m 2 。
Example 4
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with thickness of 100 μm;
the thickness of the coating is 5 mu m, and the preparation raw materials comprise the following components in parts by weight: 70 parts by weight of a silicone modified urethane acrylate (functionality 6, cr 90223), 10 parts by weight of an adhesion promoter (BYK-4511), 6 parts by weight of diethoxyacetophenone and 6 parts by weight of a wetting agent (EASYTECHST-5050);
the preparation method of the bio-based nylon film provided in this example is the same as that of example 3.
Example 5
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with thickness of 200 μm;
the thickness of the coating is 20 mu m, and the preparation raw materials comprise the following components in parts by weight: 60 parts by weight of polyester acrylate (functionality 8, HT7602), 5 parts by weight of adhesion promoter (XIAMEER) TM OFS-6011), 3 parts by weight of 2-hydroxy-2-methyl-1-phenylpropion and 8 parts by weight of wetting agent (TEGO Glide 482);
the preparation method of the bio-based nylon film provided by the embodiment comprises the following steps:
(1) Mixing the components in the preparation raw materials of the coating in butanone according to the proportion, and uniformly stirring to obtain the coating with the solid content of 20%;
(2) Uniformly coating the coating obtained in the step (1) on one side surface of a nylon 11 substrate by using a wire rod, drying at 100 ℃ for 2min, and finally completing the curing process in an ultraviolet curing system, wherein the radiation intensity of ultraviolet curing is 300J/m 2 。
Example 6
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with thickness of 200 μm;
the thickness of the coating is 20 mu m, and the preparation raw materials comprise the following components in parts by weight: 60 parts by weight of aliphatic urethane acrylate (functionality 6, CR 90898), 5 parts by weight of adhesion promoter (BYKUMEN), 4 parts by weight of 2, 2-di-sec-butoxyacetophenone and 3 parts by weight of auxiliary agent (TEGO Glide 110);
the preparation method of the bio-based nylon film provided by the embodiment comprises the following steps:
(1) Mixing the components in the preparation raw materials of the coating in ethyl acetate according to the proportion, and uniformly stirring to obtain the coating with the solid content of 40%;
(2) Uniformly coating the coating obtained in the step (1) on one side surface of a nylon 11 substrate by using a wire rod, drying at 100 ℃ for 2min, and finally completing the curing process in an ultraviolet curing system, wherein the radiation intensity of ultraviolet curing is 600J/m 2 。
Example 7
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with the thickness of 2000 μm;
the thickness of the coating is 15 mu m, and the preparation raw materials comprise the following components in parts by weight: 60 parts by weight of urethane acrylate (functionality 3, CN972), 6 parts by weight of adhesion promoter (BYK-4509), 4 parts by weight of ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate and 3 parts by weight of auxiliary agent (BYK-1165);
the preparation method of the bio-based nylon film provided by the embodiment comprises the following steps:
(1) Mixing the components in the preparation raw materials of the coating in methyl isobutyl ketone according to the proportion, and uniformly stirring to obtain the coating with the solid content of 40%;
(2) Uniformly coating the coating obtained in the step (1) on one side surface of a nylon 11 substrate by using a wire rod, drying at 100 ℃ for 2min, and finally completing the curing process in an ultraviolet curing system, wherein the radiation intensity of ultraviolet curing is 300J/m 2 。
Example 8
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with thickness of 4000 μm;
the thickness of the coating is 15 mu m, and the preparation raw materials comprise the following components in parts by weight: 60 parts by weight of an aliphatic urethane acrylate (functionality 15, CR 90492), 6 parts by weight of an adhesion promoter (DOWSI TREFIL E-606), 3 parts by weight of hydroxycyclohexyl phenyl ketone and 3 parts by weight of an auxiliary agent (BYK-1165);
the preparation method of the bio-based nylon film provided by the embodiment comprises the following steps:
(1) Mixing the components in the preparation raw materials of the coating in ethyl acetate according to the proportion, and uniformly stirring to obtain the coating with the solid content of 40%;
(2) Uniformly coating the coating obtained in the step (1) on one side surface of a nylon 11 substrate by using a wire rod, drying at 100 ℃ for 2min, and finally completing the curing process in an ultraviolet curing system, wherein the radiation intensity of ultraviolet curing is 300J/m 2 。
Example 9
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with thickness of 4000 μm;
the thickness of the coating is 15 mu m, and the preparation raw materials comprise the following components in parts by weight: 50 parts by weight of an aliphatic urethane acrylate (functionality 9, HP6919), 8 parts by weight of an adhesion promoter (Anti-Terra-203), 3 parts by weight of hydroxycyclohexyl phenyl ketone and 3 parts by weight of an auxiliary agent (BYK-1165);
the preparation method of the bio-based nylon film provided in this example is the same as that of example 8.
Example 10
A high-hardness bio-based nylon film comprises a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
wherein the bio-based nylon substrate is nylon 11 substrate with thickness of 4000 μm;
the thickness of the coating is 15 mu m, and the preparation raw materials comprise the following components in parts by weight: 50 parts by weight of aromatic urethane acrylate (functionality 9, CR 90843), 6 parts by weight of adhesion promoter (DOWSIL Z-6121), 4 parts by weight of hydroxycyclohexyl phenyl ketone and 10 parts by weight of auxiliary agent (Disperbyk-163);
the preparation method of the bio-based nylon film provided in this example is the same as that of example 8.
Comparative example 1
A high-hardness bio-based nylon film is different from example 1 in that an acrylic resin CN8004 NS (with a functionality of 1) is used for replacing nano hybrid modified polyurethane acrylate (CR 90727-2), and other components, amounts and preparation methods are the same as in example 1.
Comparative example 2
A high-hardness bio-based nylon film is different from example 1 in that an adhesion promoter is not added to the preparation raw material of the coating, and the reduced amount of the adhesion promoter is proportionally increased to other components so as to ensure that the dosage ratio of the other components is kept unchanged, and the preparation method is the same as that of example 1.
Comparative example 3
A high-hardness bio-based nylon film is different from example 1 in that no photoinitiator is added to the raw materials for preparing the coating, and the amount of the reduced photoinitiator is increased to other components according to a proportion so as to ensure that the ratio of the other components is kept unchanged, and the preparation method is the same as that of example 1.
Comparative example 4
A nylon film was different from example 1 in that a polyethylene terephthalate (PET) (thickness 5 μm) substrate was used instead of the nylon 11 substrate, and the other components and amounts were the same as in example 1.
The nylon films prepared in examples 1 to 10 and comparative examples 1 to 4 were subjected to performance test in which pencil hardness was measured by the method of ASTM D3363, adhesion was measured by the method of ASTM D3359, appearance was visually observed, and test data are shown in table 1.
TABLE 1
As can be seen from the data in table 1, the high-hardness bio-based nylon film provided by the invention has higher hardness and smooth appearance, and the coating and the bio-based nylon substrate have excellent adhesion properties;
specifically:
the bio-based nylon films provided in examples 1-10 had hardness of 3H-5H, and were very smooth in appearance, with adhesion between the coating and the bio-based nylon substrate as high as 5B;
compared with example 1, the film forming substance in the coating layer of the bio-based nylon film provided in comparative example 1 has lower functionality, resulting in a cross-linking density angle of the coating layer, and thus lower hardness of the bio-based nylon film;
compared with the example 1, the coating of the bio-based nylon film provided in the comparative example 2 is not added with the adhesion promoter, so that the adhesion between the coating and the bio-based nylon substrate is only 1B, and the adhesion performance is poor;
in comparison with example 1, the coating of the bio-based nylon film provided in comparative example 3 was not added with a photoinitiator, and the coating was not cured;
in comparative example 4, the non-bio-based nylon material was used as a PET film, resulting in a decrease in adhesion and mechanical properties, as compared with example 1.
The present invention is described by way of the above examples as a bio-based nylon film with high hardness and a method for preparing the same, but the present invention is not limited to the above detailed process equipment and process flow, i.e., it does not mean that the present invention must be implemented depending on the above detailed process equipment and process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (10)

1. The high-hardness bio-based nylon film is characterized by comprising a bio-based nylon substrate and a coating layer arranged on one side surface of the bio-based nylon substrate;
the coating is prepared from the following raw materials in parts by weight:
20-70 parts by weight of film forming substances;
2-10 parts by weight of an adhesion promoter;
3-6 parts by weight of a photoinitiator;
the film-forming material comprises a nano-hybrid modified acrylate having a functionality > 2 and/or other acrylic compounds other than the nano-hybrid modified acrylate having a functionality > 5.
2. The biobased nylon film of claim 1, wherein the biobased nylon film has a hardness > 2H.
3. The biobased nylon film of claim 1 or 2, wherein the biobased nylon substrate is a nylon 11 substrate;
preferably, the thickness of the bio-based nylon base material is 5-6000 μm;
preferably, the thickness of the coating is 1 to 20 μm.
4. A biobased nylon film according to any of claims 1-3, wherein the other acrylic compound comprises any one or a combination of at least two of aliphatic urethane acrylate oligomers, aromatic urethane acrylate oligomers, epoxy acrylate oligomers, polyester acrylate oligomers, polyether acrylate oligomers, ethoxylated trimethylol propane triacrylate epoxidized soybean oil acrylate oligomers, modified epoxy acrylate oligomers, epoxy methacrylate oligomers, aliphatic silicone acrylate oligomers, acidic functional acrylate oligomers, silicone urethane acrylate oligomers, polybutadiene dimethacrylate oligomers, polybutadiene diacrylate oligomers, polyester acrylate oligomers, acrylate polyester oligomers, or chlorinated polyester acrylate oligomers.
5. The biobased nylon film of any one of claims 1-4, wherein the adhesion promoter comprises any one or a combination of at least two of a silane coupling agent, a titanate coupling agent, a zirconium-based coupling agent, or a chromium complex-based coupling agent.
6. The biobased nylon film of any of claims 1-5, wherein the photoinitiator comprises at least one of 2-hydroxy-2-methyl-1-phenylpropion, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, methyl benzoylformate, 1-hydroxycyclohexylphenyl ketone, diethoxy-phenylacetophenone, diethoxy acetophenone, dimethoxy phenylacetophenone, 2, 4-dihydroxybenzophenone, 2,4, 6-trimethylbenzoyl ethoxy phenyl phosphine oxide, 2-di-sec-butoxyacetophenone, α -hydroxy ketone, hydroxycyclohexylphenyl ketone, hydroxy methylphenyl acetone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylphosphine oxide, or a combination thereof.
7. The biobased nylon film of any one of claims 1-6, wherein the raw materials for the preparation of the coating further comprise other adjuvants;
preferably, the other auxiliary comprises any one or a combination of at least two of a rheology auxiliary, an antifoaming agent or a viscosity reducer.
8. A method for preparing the bio-based nylon film according to any one of claims 1 to 7, comprising the steps of:
(1) Mixing a film forming substance, an adhesion promoter, a photoinitiator and optionally an auxiliary agent in a solvent to obtain a coating;
(2) And (3) coating the coating obtained in the step (1) on the surface of the bio-based nylon substrate, and drying and curing to obtain the bio-based nylon film.
9. The method of claim 8, wherein the curing in step (2) is ultraviolet light curing.
10. The method according to claim 9, wherein the energy of ultraviolet light curing is 100-600J/m 2 。
CN202311769912.0A 2023-12-21 2023-12-21 High-hardness bio-based nylon film and preparation method thereof Pending CN117603487A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104177885A (en) * 2014-08-18 2014-12-03 张家港康得新光电材料有限公司 Hardening paint and preparation method thereof, and automobile window film
CN110527388A (en) * 2019-09-27 2019-12-03 广东鼎立森新材料有限公司 A kind of silicone glass liquid ultraviolet-curing paint
CN116042078A (en) * 2022-11-30 2023-05-02 张家港保税区康得菲尔实业有限公司 UV gloss oil, preparation method and use method thereof and packaging film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104177885A (en) * 2014-08-18 2014-12-03 张家港康得新光电材料有限公司 Hardening paint and preparation method thereof, and automobile window film
CN110527388A (en) * 2019-09-27 2019-12-03 广东鼎立森新材料有限公司 A kind of silicone glass liquid ultraviolet-curing paint
CN116042078A (en) * 2022-11-30 2023-05-02 张家港保税区康得菲尔实业有限公司 UV gloss oil, preparation method and use method thereof and packaging film

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