CN111303689B - Non-solvent type photocuring composition, film layer and wire - Google Patents

Non-solvent type photocuring composition, film layer and wire Download PDF

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Publication number
CN111303689B
CN111303689B CN202010164192.5A CN202010164192A CN111303689B CN 111303689 B CN111303689 B CN 111303689B CN 202010164192 A CN202010164192 A CN 202010164192A CN 111303689 B CN111303689 B CN 111303689B
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photoinitiators
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photoinitiator
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CN111303689A (en
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周孟博
张郭
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Shanghai Jin Dun Industrial Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
    • 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
    • C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • 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
    • 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
    • C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

A non-solvent type photo-curing composition, a film layer and a wire belong to the field of printing ink. The solvent-free photocurable composition comprises the following components in percentage by mass: 20-65% of hydrophobic acrylate oligomer, 10-40% of high-functionality acrylate oligomer with functionality of more than or equal to 5%, 20-55% of acrylate monomer, 0.3-3% of adhesion promoter, 1-6% of photoinitiator, 0.5-5% of antioxidant polymerization inhibitor and 1-10% of toner. The photocurable compositions of the examples are solvent free and therefore more environmentally friendly.

Description

Non-solvent type photocuring composition, film layer and wire
Technical Field
The application relates to the field of printing ink, in particular to a non-solvent type photocuring composition, a film layer and a wire.
Background
Metallic yarns are one of the important raw materials in the textile industry, and can enable fabrics to present metallic luster when added into the fabrics. The method comprises the steps of coating ink and protective coating on a film roll of a PET film after vacuum aluminizing, and forming lines after wide cutting and fine cutting.
In the metallic yarn industry, besides the metallic yarn and the silver yarn which are used in the largest amount, other varieties with smaller color consumption, such as red, blue, green, and the like, also exist.
Except that the silver wire does not need the ink layer to change the color, other varieties all need to be coated with the ink layer to obtain the required color. And the quality of the color layer directly influences the quality of the metallic yarn fabric. Generally, the color layer needs to have good adhesion fastness, rubbing resistance, and resistance to organic solvents. Meanwhile, in consideration of the subsequent fabric processing process, the ink layer also needs to have the boiling resistance.
At present, the ink layer of the metallic yarn products on the market still adopts a solvent type thermosetting double-component ink system to meet the use requirements. However, since the coating and drying temperature exceeds 180 degrees and the drying time is long, there are problems of high energy consumption and low production efficiency, and a serious problem of large organic solvent emission (VOC). Therefore, solvent-free ink materials are the direction of their future development.
In view of this, the present application is specifically made.
Disclosure of Invention
Based on the defects, the application provides a non-solvent type photocuring composition, a film layer and a wire rod so as to partially or completely improve and even solve the problems of environmental protection and performance of the ink.
The application is realized as follows:
in a first aspect, examples of the present application provide a non-solvent based photocurable composition.
The following components in percentage by mass are included:
20-65% of hydrophobic acrylate oligomer, 10-40% of high-functionality acrylate oligomer with functionality of more than or equal to 5%, 20-55% of acrylate monomer, 0.3-3% of adhesion promoter, 1-6% of photoinitiator, 0.5-5% of antioxidant polymerization inhibitor and 1-10% of toner.
The composition is a non-solvent based composition because it is formulated without the use of solvents. Overall, it belongs to a solventless, free radical curing acrylate system. Among them, the acrylate monomer has low viscosity, can serve as a diluting action, and plays a role in dispersing and mixing various substances. And the composition has good water boiling resistance after curing by the hydrophobic acrylate oligomer and the high functionality acrylate oligomer with the functionality of more than or equal to 5. And the anti-oxidation polymerization inhibitor can prevent the oxygen inhibition of the obvious thin coating from being blocked.
In a second aspect, the present disclosure provides a film layer that is photocured from the above-described non-solvent-based photocurable composition.
The film layer has a relatively thin structural dimension and can still have a good resistance to hot water impingement.
In a third aspect, the present examples propose a wire. The method comprises the following steps: PET basement membrane, aluminium membrane and color film. Wherein the aluminum film is formed in a plating manner and wraps the surface of the PET base film. Wherein, the color film is formed in a coating mode and wraps the surface of the aluminum film. The color film is formed by photocuring the non-solvent type photocuring composition.
Has the advantages that:
the compositions of the examples have at least the following advantages:
1) the printing ink has no solvent, does not have solvent discharge, and can essentially solve the problem of environmental protection;
2) the ink is a solvent-free ultraviolet curing system, does not need drying of a drying tunnel, and is energy-saving, efficient and high in yield;
3) the printing ink is convenient to prepare and good in storage stability;
4) the prepared metallic yarn back ink layer has excellent rubbing resistance, good organic solvent wiping resistance and good boiling resistance.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the textile industry, the dosage of the metallic yarns is huge. The quality of the textile fabric is directly affected by the quality of the textile fabric. One of the main manufacturing raw materials of the metallic yarns is printing ink or paint. At present, the metallic yarns are generally made of solvent-based ink. However, the general coating and drying temperature reaches 180 ℃ or higher, which results in long drying time, high energy consumption, low efficiency, and large volatilization of solvents (organic solvents such as VOC).
In view of the above, it is considered to provide a non-solvent type ink, and to selectively lower the drying temperature of a solvent type ink. However, both solutions have certain problems.
In view of the above, the present application proposes a solvent-free ink, and also realizes photocuring by the inventive design of the formulation. Thus, it is essentially a non-solvent type ink that can be cured by light. In addition, the ink obtained by the method also has the following advantages when applied to the metallic yarns: high adhesion strength, rubbing resistance, organic solvent corrosion resistance, boiling resistance and the like. Moreover, the ink can be controlled to be relatively thin (such as below 4 microns), so that the diameter of the metallic yarns can be reduced.
The inks of the examples will be described in more detail below.
The ink in the present example is a composition that is free of solvent and is capable of being cured by photo-initiation, and thus may also be referred to as a non-solvent-based photocurable composition.
The solvent-free photocurable composition comprises the following components in percentage by mass: 20-65% of hydrophobic acrylate oligomer, 10-40% of high-functionality acrylate oligomer with functionality of more than or equal to 5%, 20-55% of acrylate monomer, 0.3-3% of adhesion promoter, 1-6% of photoinitiator, 0.5-5% of antioxidant polymerization inhibitor and 1-10% of toner.
Optionally, the non-solvent type photo-curing composition comprises the following components in percentage by mass: 30-45% of hydrophobic acrylate oligomer, 15-30% of high-functionality acrylate oligomer with functionality of more than or equal to 5%, 30-40% of acrylate monomer, 1-2% of adhesion promoter, 3-4% of photoinitiator, 1-4% of antioxidant polymerization inhibitor and 4-7% of toner.
Optionally, the non-solvent type photo-curing composition comprises the following components in percentage by mass: 35-50% of hydrophobic acrylate oligomer, 20-28% of high-functionality acrylate oligomer with the functionality of more than or equal to 5, 20-30% of acrylate monomer, 2-3% of adhesion promoter, 2-5% of photoinitiator, 2-3% of antioxidant polymerization inhibitor and 4-7% of toner.
In addition, some auxiliary agents can be selected according to the requirements of the manufacturing process so as to improve the processing performance and the performance of the finished product. For example, the solvent-free photocurable composition further comprises an auxiliary agent in an amount of not more than 5% by mass.
Therefore, the non-solvent type light-cured composition comprises the following components in percentage by mass: 35-50% of hydrophobic acrylate oligomer, 20-28% of high-functionality acrylate oligomer with the functionality of more than or equal to 5, 20-30% of acrylate monomer, 2-3% of adhesion promoter, 2-5% of photoinitiator, 2-3% of antioxidant polymerization inhibitor, 2-3% of toner and 1-2% of auxiliary agent.
According to different processing requirements, different kinds or types of additives can be selected, for example, the additives include but are not limited to any one of defoaming agent, leveling agent, wetting dispersant and storage stabilizer; alternatively, the adjuvant is a combination of a plurality of different types of substances, e.g., a defoamer and a leveling agent; or leveling agents and wetting and dispersing agents; or defoamers, leveling agents, and storage stabilizers, among others. When the auxiliary agent has a plurality of different types of substances, the dosage proportion of the different substances can be selected according to the shape in the actual blending process, and the application does not limit the dosage proportion.
Since the solvent-free photocurable composition in the present application is a mixture of organic substances mainly composed of acrylic acid esters, it is easy to disperse toner and is solvent-free. Therefore, an acrylate monomer having a low viscosity is selected. Such acrylate monomers may act as diluents to dissolve and disperse the various components. However, since the low viscosity monomer is relatively poor in boiling resistance, a high-functionality acrylate oligomer having a functionality of 5 or more and a hydrophobic acrylate oligomer are also selected.
Exemplary acrylate monomers include, but are not limited to, one or more combinations including 1,6 hexanediol diacrylate (HDDA), 1,6 hexanediol methoxy monoacrylate (EOTMPTA), neopentyl glycol diacrylate (NPGDA), propoxylated neopentyl glycol diacrylate (PONPGDA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (EOTMPTA), propoxylated trimethylolpropane triacrylate (pottmpta), pentaerythritol triacrylate (PET 3A).
Wherein the hydrophobic acrylate oligomer comprises: any one or a combination of a plurality of organic/inorganic hybrid acrylate, organic/inorganic hybrid methacrylate, organic silicon modified acrylate, polybutadiene methacrylate, polybutadiene acrylate and hydrophobic polyurethane acrylate. These hydrophobic polymers achieve more hydrophobic properties than conventional acrylate oligomers by introducing hydrophobic structures such as silicone segments, polybutadiene segments, inorganic structures, and the like. Wherein the organic/inorganic hybrid acrylate and the organic/inorganic hybrid methacrylate can be 601A-35, 601B-35, 601C-35, 604C-35 and 604X-35 of Changxing company, PO9026 of Pasteur company and the like. Silicone-modified acrylates such as 6225 by changxing corporation, ETERSLIP 90, Zhan New EB1360, DSP-3324 by Jeshda, etc.; polybutadiene methacrylate and polybutadiene acrylates such as CN307 by Saedoma, 3100, 3500 by Ricon Resins Inc, etc.; hydrophobic urethane acrylate such as CN9017 of sartomer.
Wherein the high functionality acrylate oligomer comprises: any one or combination of more of epoxy acrylate, polyurethane acrylate, polyester acrylate and hyperbranched acrylate. Hydrophobic acrylate oligomers and high functionality acrylate oligomers can solve the problem of resistance to boiling. Epoxy acrylates such as 188 double bond chemical, Changxing G908, etc.; urethane acrylates such as 5812, 850, 87A, 88A, 89A of double bond chemical industry, Youxing U591, U095, U185, U076, 6161, 6126, 6196-100, 6145-100, etc., polyester acrylates such as 2015, 287, 220, 245 of double bond chemical industry, Youxing 6311-100, 6312-1000, etc., hyperbranched acrylates such as CN2303, CN2302 of Sadoma, Youxing 6361-100, 6362-100, 6363, E522, etc.
Further, the above-mentioned non-solvent type photocurable composition is generally present in a relatively thin coating layer in view of use as metallic silks. However, the inventors have found that this very easily results in significant oxygen inhibition occurring due to contact with oxygen. Based on this recognition, the use of antioxidant polymerization inhibitors is chosen in the present application to avoid significant oxygen inhibition of thin coatings. Optionally, the antioxidant polymerization inhibitor in the non-solvent based photocurable composition comprises any one or combination of thiol or tertiary amine compounds. Examples of the thiol compound include Zhan-Xin LED01 and Rong 7302. Tertiary amine compounds such as Freon 5142, 5271, 5275, MDEA, etc. The antioxidant polymerization inhibitor can generate sulfur free radical and nitrogen free radical which are difficult to be stopped by oxygen and can continuously initiate photocuring reaction, thereby achieving the purpose of resisting oxygen and inhibiting polymerization.
In order to improve the durability of adhesion, an adhesion promoter is also added to the composition, and includes but is not limited to: phosphate adhesion promoters or modified acid ester adhesion promoters; or a mixture of a phosphate ester adhesion promoter and a modified acid ester adhesion promoter. The industrial product brands of the adhesion promoters comprise SR9050, SR9051, SR9009 and SR9016 of Sartomer company, EB111, EB112, EB1039, EB168 and EB17, Freon 7151 and the like.
As a curing condition, the composition contemplated herein is a photo-initiated material that achieves curing by free radicals. Thus, the photoinitiator may optionally include a cleavage type photoinitiator or a hydrogen abstraction type photoinitiator. Wherein, the cracking type photoinitiator comprises any one of benzoin photoinitiators, benzil photoinitiators, acetophenones photoinitiators, alpha-hydroxyketones photoinitiators, alpha-aminoketones photoinitiators, benzoylformate photoinitiators and acylphosphine oxide photoinitiators; wherein, the hydrogen abstraction photoinitiator comprises any one of benzophenone type, thioxanthone type and anthraquinone type photoinitiators.
Toners may be selected differently in different textile products, for example toners including pigments or metal chelating dyes. Such as victorious Permanent Yellow pigment G and pigment 2G, blue toners such as phthalocyanine blue B, phthalocyanine blue BS of yuhong. These toners not only impart selected colors to the finished product, but also provide corresponding lightfastness, acid and alkali resistance.
The composition is prepared by uniformly mixing the various raw materials.
The solvent-free photocurable composition may have various application prospects due to its characteristics. For example, it may have a selected color according to the selected toner. It can therefore act as a pigmented coating. It can be used as anticorrosive paint because of its resistance to boiling and rubbing. Thus, a film layer can be provided which is photocured from the solvent-free photocurable composition and which can be adhered to a surface to be protected. And, in particular, its thickness can be less, can avoid introducing and arousing thickness, height and too big, can avoid the occupation of too big space of coating. In some examples, the thickness of the film layer is no greater than 4 microns, such as 3 microns, 2 microns, and the like. Further, various woven fabrics or knitted fabrics such as gloves, scarves, clothes, and the like can be manufactured by using the above-mentioned thread material.
The following description is made with reference to specific examples.
Example 1
The solvent-free photocuring composition for coloring the metallic yarns is prepared by the following steps:
the preparation method comprises the following steps of taking various raw materials according to the formula shown in the following table 1, and uniformly mixing the raw materials.
The components of the solvent-free photocurable compositions of examples 1 to 3 are shown in table 1, and the preparation methods are the same.
TABLE 1 composition Components (percentage amounts)
Figure T_220527155537229_229172001
Note: in Table 1, "-" indicates "none".
The ink prepared from the solvent-free photocuring composition in each example is used for preparing metallic silks.
Among them, the ink of example 1 has good coating adaptability to an aluminum-plated PET film with a thickness of 12 μm, and the coating amount is 1 to 2g/m2And the thickness is 1 to 2 μm. After being cured by a UV lamp, the coating is not sticky when being rolled, and has good adhesive force and good dimensional stability of an aluminum-plated film. The gold and silver thread product made by cutting the film has good rubbing resistance and is resistant to wiping by organic solventExcellent performance and water boiling resistance.
Among them, the ink of example 2 has good coating adaptability to an aluminum-plated PET film with a thickness of 12 μm, and the coating amount is 1 to 2g/m2And the thickness is 1 to 2 μm. After being cured by a UV lamp, the aluminum-plated film is not sticky when being rolled, has good adhesive force and good dimensional stability of the aluminum-plated film. The metallic yarn product cut by the film has good resistance to rubbing, organic solvent wiping and boiling.
Among them, the ink of example 3 has good coating suitability for an aluminum-plated PET film with a thickness of 12 μm, and the coating amount is 1 to 2g/m2And the thickness is 1 to 2 μm. After being cured by a UV lamp, the aluminum-plated film is not sticky when being rolled, has good adhesive force and good dimensional stability of the aluminum-plated film. The metallic yarn product cut by the film has good rubbing resistance, excellent organic solvent wiping resistance and excellent water boiling resistance.
Comparative example
The solvent-free photocuring composition for coloring the metallic yarns is prepared by the following method:
the ink is prepared by weighing the raw materials according to the formula given in the following table 2 and then mixing the components uniformly.
The components of the solvent-free photocurable compositions in comparative examples 1 to 4 are shown in Table 2, and the production methods are the same.
TABLE 2 composition Components (percentage amounts)
Figure T_220527155537670_670587002
Note: in Table 2, "-" indicates "none".
The ink prepared from the solvent-free photocurable composition of each of the above comparative examples was used to prepare metallic filigrees and tested, and the test results and the corresponding test methods are summarized below.
Wherein the ink of comparative example 1 is used for coating an aluminized PET film with a thickness of 12 μm, and the coating amount is 1-2 g/m2And the thickness is 1 to 2 μm. After being cured by a UV lamp, the aluminum-plated film is not sticky when being rolled, has poor adhesive force and is collectedShrinkage is severe and dimensional stability is poor. The metallic yarn product cut by the film has poor rubbing resistance, poor organic solvent wiping resistance and poor water boiling resistance.
Wherein the aluminum-plated PET film of comparative example 2 having a thickness of 12 μm is coated in an amount of 1 to 2g/m2And the thickness is 1 to 2 μm. After being cured by a UV lamp, the adhesive tape is not sticky when being rolled, has poor adhesive force, and has poor dimensional stability when the aluminizer shrinks seriously. The metallic yarn product cut by the film has poor rubbing resistance, poor organic solvent wiping resistance and poor water boiling resistance.
Wherein the ink of comparative example 3 is used for coating an aluminized PET film with a thickness of 12 μm, and the coating amount is 1-2 g/m2And the thickness is 1 to 2 μm. After being cured by a UV lamp, the adhesive tape is not sticky when being rolled, has poor adhesive force, and has poor dimensional stability when the aluminizer shrinks seriously. The metallic yarn product cut by the film has poor rubbing resistance, poor organic solvent wiping resistance and poor water boiling resistance.
Wherein the ink of comparative example 4 is used for coating an aluminum-plated PET film with a thickness of 12 μm, and the coating amount is 1-2 g/m2And the thickness is 1 to 2 μm. After being cured by a UV lamp, the aluminum-plated film is rolled, anti-sticky, poor in adhesive force, and poor in dimensional stability due to severe shrinkage of the aluminum-plated film. The metallic yarn product cut by the film has poor rubbing resistance, poor organic solvent wiping resistance and poor water boiling resistance.
The test method is described below.
Solvent resistance test
And (4) testing standard: determination of the solvent resistance of paints, GB/T23989-. The present standard specifies a test method for determining the resistance to solvent rub of a single-coat or composite-coat system of a paint, varnish or related product.
The test method is suitable for evaluating the solvent wiping resistance of coatings which chemically react when cured. The method comprises a method A and a method B, wherein the method A is a manual wiping method, and the method B is an instrument wiping method. The manual wiping method comprises the following steps: three drops of acetone and ethanol solvent are dropped on the horizontal plane of the sprayed paint sample, the paint film is kept in contact for two minutes, a cotton swab is used for wiping the surface for 10 times, and the color and luster of the paint film are observed by naked eyes. If the color and the gloss are not changed, the test is regarded as passed.
Second, Water boiling test
And (4) testing standard: water resistance test method of paint film, GB/T1733-93.
And (3) putting the coated product into a pressure cooker, and boiling for 30 minutes. And after the film is taken out, observing whether the surface is obviously fallen off or not, and judging that the color and the luster are unchanged, wherein if the surface is not judged to pass the test.
And thirdly, carrying out a rubbing resistance test.
And cutting the coated product into proper sizes, forcibly rubbing for 10 times by hands, observing whether the surface has obvious shedding, paint falling and gloss change, and if the surface does not obviously drop, judging that the test is passed.
TABLE 3 test results
Group of Solvent resistance test Boil resistance test Rub resistance test
S1 Surface unchanged by Does not fall off, pass through Does not fall off powder, is passed
S2 The surface is unchanged by Does not fall off, through Does not fall off powder through
S3 Surface unchanged by Does not fall off, pass through Does not fall off powder, is passed
D1 Change color on the surface without passing through Most of them fall off and do not pass through The powder fall is serious and does not pass
D2 Change color on the surface without passing through Almost fall off and do not pass through Powder fall is not serious, through
D3 Surface does not change color by Most of them fall off and do not pass through The powder fall is serious and does not pass
D4 Surface does not change color by A small part falls off, passes The powder fall is serious and does not pass
Note S1 represents example 1, and so on; d1 represents comparative example 1, and so on.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (7)

1. A wire rod, characterized by comprising:
PET basal membrane;
an aluminum film formed in a plating manner and wrapping the surface of the PET base film;
the color film is formed in a coating mode and wraps the surface of the aluminum film, and the color film is formed by photocuring a non-solvent type photocuring composition;
the non-solvent type light-cured composition comprises the following components in percentage by mass:
20-65% of hydrophobic acrylate oligomer, 10-40% of high-functionality acrylate oligomer with functionality of more than or equal to 5%, 20-55% of acrylate monomer, 0.3-3% of adhesion promoter, 1-6% of photoinitiator, 0.5-5% of antioxidant polymerization inhibitor and 1-10% of toner.
2. The wire of claim 1, wherein the hydrophobic acrylate oligomer comprises: any one or combination of more of organic/inorganic hybrid acrylate, organic/inorganic hybrid methacrylate, organic silicon modified acrylate, polybutadiene methacrylate, polybutadiene acrylate and hydrophobic polyurethane acrylate;
and/or, the high functionality acrylate oligomer comprises: any one or combination of more of epoxy acrylate, polyurethane acrylate, polyester acrylate and hyperbranched acrylate.
3. The wire of claim 1, wherein the acrylate monomer comprises:
1,6 hexanediol diacrylate, 1,6 hexanediol methoxy monoacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate.
4. The wire rod according to claim 1, wherein the adhesion promoter comprises:
phosphate adhesion promoters and/or modified acid ester adhesion promoters.
5. The wire of claim 1, wherein the photoinitiator comprises:
a cleavage type photoinitiator or a hydrogen abstraction type photoinitiator;
wherein, the cracking type photoinitiator comprises any one of benzoin photoinitiators, benzil photoinitiators, acetophenones photoinitiators, alpha-hydroxyketones photoinitiators, alpha-aminoketones photoinitiators, benzoylformate photoinitiators and acylphosphine oxide photoinitiators;
wherein, the hydrogen abstraction photoinitiator comprises any one of benzophenone type, thioxanthone type and anthraquinone type photoinitiators.
6. The wire rod of claim 1, wherein the antioxidant polymerization inhibitor comprises any one or combination of thiol or tertiary amine compounds.
7. The wire rod according to any one of claims 1 to 6, wherein the solvent-free photocurable composition further comprises an auxiliary agent with a mass percentage content of no more than 5%, and the auxiliary agent comprises any one or more of a defoaming agent, a leveling agent, a wetting dispersant and a storage stabilizer;
alternatively, the toner includes a pigment or a metal chelate type dye.
CN202010164192.5A 2020-03-10 2020-03-10 Non-solvent type photocuring composition, film layer and wire Active CN111303689B (en)

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