WO2017117724A1

WO2017117724A1 - Composition, pre-coating film and preparation method therefor

Info

Publication number: WO2017117724A1
Application number: PCT/CN2016/070187
Authority: WO
Inventors: 曹华
Original assignee: 江苏康得新复合材料股份有限公司
Priority date: 2016-01-05
Filing date: 2016-01-05
Publication date: 2017-07-13

Abstract

Provided are a composition, a pre-coating film and a preparation method therefor. The composition contains a water-based self-crosslinked acrylate, a fluorine-silicon-modified resin, a polyurethane dispersion, a curing agent and auxiliaries. The pre-coating film contains a substrate layer composed of a base material layer and a flexible coating; an intermediate layer arranged on the substrate layer; a hot melt adhesive layer arranged on the intermediate layer; and a tackifying layer placed on the hot melt adhesive layer.

Description

Composition, precoat film and preparation method thereof

Technical field

The present disclosure relates to the field of printed film technology, and in particular to a composition, a precoat film, and a method of preparing the same.

Background technique

Print film is an important means of post-press processing, which determines the final value of the printed product. The film coating process of the printed matter refers to covering the paper printed matter with a plastic film, and using an adhesive in the middle, after heat and pressure treatment, the two different properties of the plastic film and the paper are bonded together to form a paper/plastic combination. A surface decoration processing technology. It protects and decorates prints and is widely used in the field of packaging and printing, such as book covers, brochures, maps, advertising gift bags, and advanced packaging.

Pre-coated film can be called environmentally friendly or clean laminating technology, which can protect the environment, protect health and safe production, so it is more and more popular in the market.

However, with the development and progress of the society, people's requirements for the quality of the printed matter and the surface decoration effect are also constantly improving. The film products with "soft feeling" and "scratch resistance" can express warmth, beauty and velvety. The unique appearance of the effect, but also conveys a unique touch of the texture. However, when people touch the soft feeling, they also leave unsightly fingerprint marks on the oil and sweat on their hands. Therefore, it has become a popular research to develop a film material that meets people's needs and has fingerprint resistance. direction. In addition, the existing soft surface precoating film on the market gradually precipitates due to the extension of the small molecules on the surface of the flexible coating layer over time, and migrates to the surface of the adhesive layer, which affects the adhesion effect of the precoat film on paper and the like, so development A flexible coating with anti-migration and anti-pollution is also necessary.

At present, the domestic pre-coated film products are ordinary EVA type pre-coated films. For low-speed manual film coating processes and products that do not need to be rolled and embossed, ordinary pre-coated films can meet the requirements. However, for the use of an increasingly wide-automatic high-speed laminating process, as well as products for rolling and embossing after lamination, ordinary pre-coated films will exhibit quality problems such as blistering and delamination, which will seriously affect the yield and work of the film. Efficiency, so the pre-coating film can be thickened to meet the needs of more customers.

Summary of the invention

The present disclosure is intended to address at least one of the technical problems existing in the prior art. The application provides a composition, a precoat film and a preparation method thereof to solve the above technical problems.

Embodiments of one aspect of the present disclosure provide a composition comprising: an aqueous self-crosslinking acrylate, a fluorosilicone modified resin, a polyurethane dispersion, a curing agent, and an adjuvant.

In one embodiment of the present disclosure, based on the total weight of the composition,

The content of the aqueous self-crosslinking acrylate is from 0.1% by weight to 1% by weight;

The content of the fluorosilicon modified resin is from 1% by weight to 5% by weight;

The content of the polyurethane dispersion is from 10% by weight to 29% by weight;

The content of the curing agent is 50% by weight or less,

Optionally,

The content of the aqueous self-crosslinking acrylate is from 0.1% by weight to 0.5% by weight;

The content of the fluorosilicone modified resin is from 1% by weight to 3% by weight;

The content of the polyurethane dispersion is from 25% to 28% by weight;

The curing agent is contained in an amount of from 30% by weight to 40% by weight.

In one embodiment of the present disclosure, wherein the curing agent is aziridine or an isocyanate.

In one embodiment of the present disclosure, the auxiliary agent comprises a first leveling agent, and the first leveling agent is a polyurethane emulsion type or an acrylic emulsion leveling agent.

In one embodiment of the present disclosure, the first leveling agent is present in an amount of from 0.01% by weight to 1% by weight, alternatively from 0.1% by weight to 0.5% by weight, based on the total weight of the composition.

In one embodiment of the present disclosure, the adjuvant further comprises an antifoaming agent, and the antifoaming agent is contained in an amount of 0.01% by weight to 1% by weight.

In one embodiment of the present disclosure, the polyurethane dispersion contains a second leveling agent, a film former, a thickener, and a diluent.

In one embodiment of the present disclosure, the second leveling agent is a silicone-based leveling agent.

In one embodiment of the present disclosure, the film forming agent is a glycol ether, a glycol ether ester or an ester alcohol.

In one embodiment of the present disclosure, the thickener comprises an acrylate and/or methacrylate copolymer.

In one embodiment of the present disclosure, the diluent is deionized water.

An embodiment of another aspect of the present disclosure provides a precoat film comprising:

a substrate layer comprising a substrate layer and a flexible coating;

An intermediate layer disposed on the substrate layer;

a layer of hot melt adhesive disposed on the intermediate layer;

An adhesion promoting layer disposed on the hot melt adhesive layer,

Wherein the flexible coating is formed on the first side of the substrate layer and is formed from the above composition.

In one embodiment of the present disclosure, the substrate layer is a biaxially oriented polyester layer, a biaxially oriented nylon layer, or a biaxially oriented polypropylene layer.

In one embodiment of the present disclosure, the thickness of the substrate layer is from 8 μm to 50 μm.

In one embodiment of the present disclosure,

When the substrate layer is a biaxially stretched polyester layer, the substrate layer has a thickness of 9 μm to 12 μm, or

When the substrate layer is a biaxially stretched nylon layer, the substrate layer has a thickness of 12 μm to 20 μm, or

When the substrate layer is a biaxially oriented polypropylene layer, the substrate layer has a thickness of from 12 μm to 15 μm.

In one embodiment of the present disclosure, the flexible coating has a thickness of from 4 μm to 10 μm, alternatively from 4 μm to 6 μm.

In one embodiment of the present disclosure, the adhesion promoting layer has a thickness of from 0.1 μm to 0.5 μm, alternatively from 0.2 μm to 0.4 μm.

In one embodiment of the present disclosure, the hot melt adhesive layer has a thickness of from 6 μm to 30 μm, alternatively from 12 μm to 19 μm.

In one embodiment of the present disclosure, the adhesion promoting layer is formed of a modified acrylic emulsion or a modified urethane acid emulsion and an adhesion promoter.

In one embodiment of the present disclosure, the adhesion promoting layer has a coating dry weight of from 0.05 g/m ² to 0.5 g/m ² , alternatively from 0.1 g/m ² to 0.4 g/m ² .

In one embodiment of the present disclosure, the adhesion promoter is included in an amount of from 0.1% by weight to 10% by weight, alternatively from 0.5% by weight to 5% by weight, based on the total weight of the adhesion-promoting layer.

In one embodiment of the present disclosure, the modified acrylic emulsion or the modified urethane acid emulsion has a solid content of 50% or less.

In one embodiment of the present disclosure, the adhesion promoter is a terpene phenol resin, a silane coupling agent, or an ethylene-acrylic emulsion.

In one embodiment of the present disclosure, the adhesion promoter is an ethylene-acrylic emulsion having a solid content of 10% to 40%.

In one embodiment of the present disclosure, the intermediate layer is formed of an aqueous solution of polyethyleneimine.

In one embodiment of the present disclosure, the polyethyleneimine has a solid content of from 0.4% to 2.5%.

In one embodiment of the present disclosure, the polyethyleneimine has a coating dry weight of from 0.007 g/m ² to 0.03 g/m ² , alternatively from 0.009 g/m ² to 0.011 g/m ² .

In one embodiment of the present disclosure, the polyethyleneimine has a molecular formula of (CH ₂ CH ₂ NH) _n and an average molecular weight of between 1,000 and 10,000.

In one embodiment of the present disclosure, the hot melt adhesive layer is composed of an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, or an ethylene-methacrylic acid copolymer.

In one embodiment of the present disclosure, when the hot melt adhesive layer is formed of an ethylene-vinyl acetate copolymer, the content of vinyl acetate is 10% by weight to 30% by weight based on the total weight of the hot melt adhesive layer. The melt index is 10g/10min-25g/10min,

Alternatively, the vinyl acetate content is from 15% by weight to 20% by weight, and the melt index is from 10 g/10 min to 20 g/10 min.

In one embodiment of the present disclosure, the composition further comprises a colorant, based on the total weight of the composition, The content of the color paste is from 0.5% by weight to 3% by weight.

In one embodiment of the present disclosure, the precoat film further includes a printed layer formed on the second side of the substrate layer.

In one embodiment of the present disclosure, the printed layer has a thickness of from 0.5 μm to 4 μm, alternatively from 0.5 μm to 1 μm.

An embodiment of still another aspect of the present disclosure provides a method of preparing the above precoated film, comprising the steps of:

Providing a substrate layer;

Spraying a mixture of a polyurethane dispersion, a fluorosilicone modified resin, a curing agent, a self-crosslinking acrylate, and a color paste on the first side of the substrate layer to form a flexible layer;

Coating a polyethyleneimine aqueous solution on the second side of the substrate layer to form an intermediate layer;

Coating an ethylene-vinyl acetate copolymer, an ethylene-acetic acid propylene copolymer, an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer on the intermediate layer to form a hot melt adhesive layer;

A modified acrylic emulsion or a mixture of a modified urethane acid emulsion and an adhesion promoter is coated on the hot melt adhesive layer to form an adhesion promoting layer.

Providing a substrate layer;

Spraying a mixture of a polyurethane dispersion, a fluorosilicon modified resin, a self-crosslinking acrylate, and a curing agent on the first side of the substrate layer to form a flexible layer;

Printing ink on the second side of the substrate layer to form a printed layer;

Applying an aqueous solution of polyethyleneimine on the printed layer to form an intermediate layer;

In one embodiment of the present disclosure, the ink is printed on the second side of the substrate layer using gravure printing techniques.

In one embodiment of the present disclosure, the step of coating an aqueous solution of polyethyleneimine on the second side of the substrate layer or the step of coating an aqueous solution of polyethyleneimine on the printed layer further comprises:

Performing a first corona treatment on the second surface of the substrate layer or the surface on the printing layer, so that the surface value of the substrate layer or the printed layer reaches 36 or more;

Coating the aqueous solution of polyethyleneimine on the second side of the first corona-treated substrate layer or on the upper surface of the printed layer;

Drying is carried out at a temperature of 85 degrees Celsius to 95 degrees Celsius.

In one embodiment of the present disclosure, the step of coating the modified acrylic emulsion or the mixture of the modified urethane acid emulsion and the adhesion promoter on the hot melt adhesive layer further comprises:

Performing a second corona treatment on the surface of the hot melt adhesive layer to achieve a dyne value of 50-54 on the surface of the hot melt adhesive layer;

Coating the mixture of the modified acrylic emulsion or the modified urethane acid emulsion and the adhesion promoter on the surface of the hot-melt adhesive layer subjected to the second corona treatment;

Drying is carried out at a temperature of 70 degrees Celsius to 95 degrees Celsius.

In one embodiment of the present disclosure, the modified acrylic emulsion or the mixture of the modified urethane acid emulsion and the adhesion promoter is previously subjected to a high-speed dispersion treatment before the coating step.

In one embodiment of the present disclosure, the high speed dispersion treatment takes 10 minutes to 20 minutes.

The beneficial effects of the above technical solutions of the present disclosure are as follows:

First, the fluorosilicone modified resin allows the film layer formed by the composition to have fingerprint-resistance characteristics; and the aqueous self-crosslinking acrylate can form a self-crosslinking molecular layer, thereby effectively preventing the formation of the composition. The film layer affects the surface tension of the film layer due to precipitation and migration of small molecules;

Secondly, the film layer (flexible coating layer) formed by the composition according to the embodiment of the present disclosure has fingerprint-resistance and migration resistance characteristics, and can gradually self-repair slight scratches on the surface while ensuring a soft touch of the surface. That is, the film layer formed by the composition can resist slight abrasion or scratching, and does not leave a fingerprint mark after being touched by the finger, thereby ensuring the appearance after being touched;

Thirdly, the pre-coated film of the present disclosure not only has a soft touch, is resistant to fingerprints, and has a layer of adhesive layer which is stable in surface tension and which is not attenuated, and its adhesion effect with a printed matter is much higher than that of a conventional pre-coated film;

Further, the adhesion-promoting layer as a surface of the pre-coated film according to the embodiment of the present disclosure which is heat-compressed with the printed matter not only provides a better adhesion of the pre-coated film of the embodiment of the present invention, but also enhances the same with the printed matter. The adhesion between the two to meet the requirements of the subsequent processing technology; and can be composited on the surface of a variety of textures to be coated, suitable for subsequent processing of rolling lines, bumps, etc. and automatic high-speed coating process, will not Problems such as bubble generation or delamination, expanding the scope of application;

And, the method of preparing a precoat film according to an embodiment of the present disclosure is not only simple in operation but also makes full use of the existing precoat film production line, thereby effectively reducing the cost of precoat film preparation.

The additional aspects and advantages of the present disclosure will be set forth in part in the description which follows.

DRAWINGS

The above and/or additional aspects and advantages of the present disclosure will become apparent from the description of the embodiments in conjunction with the accompanying drawings Obvious and easy to understand, where:

1 is a schematic structural view of a precoat film according to an embodiment of the present disclosure;

2 is a schematic structural view of a substrate layer in a precoat film according to an embodiment of the present disclosure;

3 is a schematic structural view of a substrate layer in a precoat film according to another embodiment of the present disclosure;

4 is a flow chart of a method of preparing a precoat film according to an embodiment of the present disclosure;

FIG. 5 is a flow chart of a method of preparing a precoat film according to another embodiment of the present disclosure.

Detailed description of the invention

The embodiments of the present disclosure are described in detail below, and the examples of the embodiments are illustrated in the drawings, wherein the same or similar reference numerals are used to refer to the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are intended to be illustrative only, and are not to be construed as limiting.

In the description of the present disclosure, it is to be understood that the terms "center", "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", The orientation or positional relationship of the "top", "bottom", "inside", "outside" and the like is based on the orientation or positional relationship shown in the drawings, and is merely for the convenience of describing the present disclosure and the simplified description, rather than indicating or implying The device or component referred to must have a particular orientation, is constructed and operated in a particular orientation, and thus is not to be construed as limiting the disclosure.

It should be noted that the terms "first" and "second" are used for descriptive purposes only, and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, features defining "first" and "second" may include one or more of the features either explicitly or implicitly. Further, in the description of the present disclosure, "a plurality of" means two or more unless otherwise stated.

combination

An embodiment of one aspect of the present disclosure provides a composition comprising: an aqueous self-crosslinking acrylate, a fluorosilicone modified resin, a polyurethane dispersion, a curing agent, and an adjuvant. The fluorosilicone modified resin makes the film layer formed by the composition have fingerprint resistance characteristics; and the aqueous self-crosslinking acrylate can form a self-crosslinking molecular layer, thereby effectively preventing the film formed by the composition The layer affects the surface tension of the film layer due to precipitation and migration of small molecules.

According to some embodiments of the present disclosure, the content of the aqueous self-crosslinking acrylate is from 0.1% by weight to 1% by weight based on the total weight of the composition; and the content of the fluorosilicon modified resin is from 1% by weight to 5 parts by weight The content of the polyurethane dispersion is from 10% by weight to 29% by weight; and the content of the curing agent is 50% by weight or less. According to further embodiments of the present disclosure, the content of the aqueous self-crosslinking acrylate is from 0.1% by weight to 0.5% by weight based on the total weight of the composition; and the content of the fluorosilicon modified resin is from 1% by weight to 3 % by weight; the content of the polyurethane dispersion is from 25% by weight to 28% by weight; and the content of the curing agent is from 30% by weight to 40% by weight. Some real according to the present disclosure In one embodiment, the curing agent is aziridine or an isocyanate. According to some embodiments of the present disclosure, the adjuvant comprises a first leveling agent, the first leveling agent being a polyurethane emulsion or an acrylic emulsion leveling agent. According to some embodiments of the present disclosure, the first leveling agent is present in an amount of from 0.01% by weight to 1% by weight, alternatively from 0.1% by weight to 0.5% by weight, based on the total weight of the composition. According to further embodiments of the present disclosure, the adjuvant further comprises an antifoaming agent which can be various blowing agents commonly used in the art. According to some embodiments of the present disclosure, the antifoaming agent is present in an amount of from 0.01% by weight to 1% by weight. According to some embodiments of the present disclosure, the polyurethane dispersion contains a second leveling agent, a film former, a thickener, and a diluent. In some embodiments of the present disclosure, the second leveling agent is a silicone-based leveling agent. In some embodiments of the present disclosure, the film former is a glycol ether, a glycol ether ester, or an ester alcohol. In some embodiments of the present disclosure, the thickener comprises an acrylate and/or methacrylate copolymer. In some embodiments of the present disclosure, the diluent is deionized water.

The film layer formed by the composition according to an embodiment of the present disclosure has fingerprint-resistant and migration-resistant properties, and while ensuring a soft touch on the surface, it is also possible to gradually self-repair slight scratches on the surface, that is, by the combination The film forming layer can resist slight abrasion or scratching, and does not leave a fingerprint mark after being touched by the finger, thereby ensuring the appearance after being touched.

Precoat film

The precoat film according to an embodiment of the present disclosure will be described in detail below with reference to FIGS. 1-3.

An embodiment of another aspect of the present disclosure provides a precoat film comprising: a substrate layer 1 comprising a substrate layer 11 and a flexible coating 12; an intermediate layer 2 disposed on the substrate layer 1; a glue layer 3 disposed on the intermediate layer 2; and an adhesion promoting layer 4 disposed on the layer of the hot melt adhesive 3, wherein the flexible coating layer 12 is formed on the first layer of the substrate layer Face 111 is formed from the above composition.

As described above, the flexible coating 12 formed of the above composition has fingerprint-resistant and migration-resistant properties, and while ensuring a soft touch on the surface, it is also possible to gradually self-repair slight scratches on the surface, that is, by the The composition forms a film layer which is resistant to slight abrasion or scratching, and does not leave a fingerprint mark after being touched by a finger, thereby ensuring the aesthetic appearance after being touched.

The adhesion-promoting layer as a surface of the pre-coated film and the printed article according to the embodiment of the present disclosure is not only provided with a better adhesion of the pre-coated film of the embodiment of the present invention, but also enhanced between the adhesion-promoting layer and the printed matter. Adhesive force to meet the requirements of subsequent processing technology; and can be combined on the surface of a variety of textures to be coated, suitable for subsequent processing of rolling lines, bumps, etc. and automatic high-speed coating process, no bubbles Or delamination and other issues, expanding the scope of application.

Therefore, the precoat film of the present disclosure not only has a soft touch, is resistant to fingerprints, and has a rubber layer which is stable in surface tension and is not attenuated, and its adhesion effect with a printed matter is much higher than that of a conventional precoat film.

In some embodiments of the present disclosure, the substrate layer is a biaxially stretched polyester layer (BOPET), a biaxially stretched nylon layer (BOPA), or a biaxially oriented polypropylene layer (BOPP). In some embodiments of the present disclosure, the substrate layer 11 has a thickness of 8 μm to 50 μm. In some embodiments of the present disclosure, when the substrate layer 11 is a biaxially stretched polyester layer, the substrate layer 11 has a thickness of 9 μm to 12 μm, or when the substrate layer 11 is a biaxially stretched nylon. The layer, the substrate layer 11 has a thickness of 12 μm to 20 μm, or when the substrate layer 11 is a biaxially oriented polypropylene layer, the substrate layer 11 has a thickness of 12 μm to 15 μm. In some embodiments of the present disclosure, the flexible coating 12 has a thickness of from 4 μm to 10 μm, alternatively from 4 μm to 6 μm. In some embodiments of the present disclosure, the adhesion promoting layer 4 has a thickness of from 0.1 μm to 0.5 μm, alternatively from 0.2 μm to 0.4 μm. In some embodiments of the present disclosure, the hot melt adhesive layer 3 has a thickness of from 6 μm to 30 μm, alternatively from 12 μm to 19 μm. In some embodiments of the present disclosure, the adhesion promoting layer 4 is formed of a modified acrylic emulsion or a modified urethane acid emulsion and an adhesion promoter. In some embodiments of the present disclosure, the adhesion promoting layer 4 has a coating dry weight of from 0.05 g/m ² to 0.5 g/m ² , alternatively from 0.1 g/m ² to 0.4 g/m ² . In some embodiments of the present disclosure, the adhesion promoter is present in an amount of from 0.1% by weight to 10% by weight, alternatively from 0.5% by weight to 5% by weight, based on the total weight of the adhesion promoting layer 4. In some embodiments of the present disclosure, the modified acrylic emulsion or modified urethane acid emulsion has a solid content of 50% or less. In some embodiments of the present disclosure, the adhesion promoter is a terpene phenolic resin, a silane coupling agent, or an ethylene-acrylic emulsion. In some embodiments of the present disclosure, the adhesion promoter is an ethylene-acrylic emulsion having a solids content of from 10% to 40%. In some embodiments of the present disclosure, the intermediate layer 2 is formed from an aqueous solution of polyethyleneimine. In some embodiments of the present disclosure, the polyethyleneimine has a solids content of from 0.4% to 2.5%. In some embodiments of the present disclosure, the polyethyleneimine has a coating dry weight of from 0.007 g/m ² to 0.03 g/m ² , alternatively from 0.009 g/m ² to 0.011 g/m ² . In some embodiments of the present disclosure, the polyethyleneimine has a molecular formula of (CH ₂ CH ₂ NH) _n and an average molecular weight of between 1000 and 10,000. In some embodiments of the present disclosure, the hot melt adhesive layer 3 is composed of an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, or an ethylene-methacrylic acid copolymer. In some embodiments of the present disclosure, when the hot melt adhesive layer is formed of an ethylene-vinyl acetate copolymer, the content of vinyl acetate is 10% by weight to 30% by weight based on the total weight of the hot melt adhesive layer. The melt index is from 10 g/10 min to 25 g/10 min, and optionally, the vinyl acetate content is from 15% by weight to 20% by weight, and the melt index is from 10 g/10 min to 20 g/10 min.

In some embodiments of the present disclosure, the composition further comprises a colorant, the colorant being present in an amount from 0.5% to 3% by weight, based on the total weight of the composition. When no colorant is added to the composition, a printed layer may be provided on the second side 112 of the substrate layer to form a surface printing effect of a different color or pattern by printing techniques. In some embodiments of the present disclosure, when no colorant is added to the flexible coating 12, a printed layer 13 may be disposed on the second side 112 of the substrate layer. In some embodiments of the present disclosure, the printed layer has a thickness of from 0.5 μm to 4 μm, alternatively from 0.5 μm to 1 μm. By adding a color paste or setting a printed layer to the composition, surface effects of different colors and patterns can be formed, thereby increasing the beauty and the diversity of choice.

Method for preparing precoated film

A further aspect of the present disclosure provides a method of preparing the above precoated film.

In some embodiments of the present disclosure, the method comprises:

Providing a substrate layer, which is a biaxially stretched polyester layer, a biaxially stretched nylon layer or a biaxially oriented polypropylene layer;

Spraying a mixture of a polyurethane dispersion, a fluorosilicone modified resin, a curing agent, a self-crosslinking acrylate, and a color paste onto a first side of the substrate layer by a spraying process to form a color flexible layer, a substrate layer and the flexible coating form a substrate layer;

Applying an aqueous solution of polyethyleneimine on the second side of the substrate layer, and drying to form an intermediate layer;

A mixture of a modified acrylic emulsion or a modified urethane acid emulsion and an adhesion promoter is applied onto the hot melt adhesive layer to form an adhesion promoting layer after drying.

In some other embodiments of the present disclosure, the method comprises:

Spraying a mixture of a polyurethane dispersion, a fluorosilicon modified resin, a self-crosslinking acrylate, and a curing agent onto the first side of the substrate layer by a spraying process to form a fingerprint-resistant flexible layer;

Printing ink of different colors or patterns on the second side of the substrate layer by gravure printing technology to form a printed layer having a color, the substrate layer being composed of the substrate layer, the flexible coating layer and the printed layer;

Applying an aqueous solution of polyethyleneimine on the printed layer, and drying to form an intermediate layer;

The method of preparing a precoat film according to an embodiment of the present disclosure is not only simple in operation but also makes full use of the existing precoat film production line, thereby effectively reducing the cost of precoat film preparation.

In some embodiments of the present disclosure, the step of coating an aqueous solution of polyethyleneimine on the second side of the substrate layer or coating the aqueous solution of polyethyleneimine on the printed layer further comprises: Performing a first corona treatment on the second surface of the substrate layer or the surface on the printing layer, such that the surface of the substrate layer or the printed layer reaches a value of 36 or more; the polyethyleneimine The aqueous solution is coated on the second side of the substrate layer subjected to the first corona treatment or on the upper surface of the printed layer; and dried at a temperature of 85 degrees Celsius to 95 degrees Celsius.

In some embodiments of the present disclosure, the step of coating the modified acrylic emulsion or the mixture of the modified urethane acid emulsion and the adhesion promoter on the hot melt adhesive layer further comprises: the hot melt adhesive layer Performing a second corona treatment on the surface to achieve a dyne value of 50-54 on the surface of the hot melt adhesive layer; applying the modified acrylic emulsion or modified polyurethane acid A mixture of the emulsion and the adhesion promoter is coated on the surface of the hot-melt adhesive layer subjected to the second corona treatment; and the drying treatment is performed at a temperature of 70 degrees Celsius to 95 degrees Celsius. In some embodiments of the present disclosure, the modified acrylic emulsion or the mixture of the modified urethane acid emulsion and the adhesion promoter is previously subjected to a high speed dispersion treatment before the coating step. In some embodiments of the present disclosure, the high speed dispersion treatment takes 10 minutes to 20 minutes. Thereby, each substance in the adhesion-promoting layer can be sufficiently mixed, so that the adhesion-promoting layer has a uniform adhesive force, and the bonding effect between the pre-coating film and the printed matter of the embodiment of the present invention is ensured.

Example 1

Referring to Figure 4, a method of preparing a precoat film comprises the following steps.

Step 1: A biaxially stretched polyester layer or a biaxially stretched nylon layer is provided as the substrate layer 11.

Step 2: applying a flexible coating 12 comprising a mixture of a polyurethane dispersion, a fluorosilicone modified resin, a self-crosslinking acrylate, a curing agent and a colorant onto the first side 111 of the substrate layer 11 by means of a spraying device, To form the substrate 1.

Step 3: Applying an aqueous polyethyleneimine solution prepared according to the above ratio on the second surface 112 of the substrate layer 11 and drying it with a drying device to cure the polyvinyl chloride to form the intermediate layer 2.

Prior to the implementation of step three, the substrate layer 11 is first subjected to a first corona treatment to obtain a certain amount of a polar group such as a carbonyl group. The dyne value of the surface of the second surface 112 of the substrate layer 11 after the corona treatment can reach 36 or more.

Step 4: The EVA hot melt layer 3 is thermocompression-bonded to the intermediate layer 2 by an extrusion composite apparatus.

Specifically, the substrate 1 carrying the cured intermediate layer 2 is fed to the composite position through a guide roll of an extrusion compounding line while the extruder extrudes the hot melt adhesive layer 3. An ozone generator is arranged at a composite position adjacent to the extrusion compounding line, and ozone generated by the ozone generator is sprayed onto the EVA casting film extruded by the extruder, the concentration of ozone is 40%, the power is 800 W, and the gas flow rate is For 3.5 SCXFM, ozone causes some of the polar groups on the cast surface of the resin, and then the substrate 1 is combined with the extrusion of the intermeshing rolls that are cast through the composite position of the extrusion composite line to form a composite film.

After stretching, cooling, and trimming, the thickness of the hot melt adhesive layer was 16 μm.

Step 5: coating the modified acrylic emulsion or the mixture of the modified urethane acid emulsion and the adhesion promoter on the hot melt adhesive layer 3 by a coating device and drying to form the adhesion promoting layer 4. Thereby a preliminary film is obtained.

In addition, considering that the polarity of the hot melt adhesive layer 3 is weak, in order to make the product have good adhesion in the application (ie, the pre-coating film of the embodiment of the invention and the printed matter process), as shown in FIG. 4, Before the adhesion promoting layer 4 is coated on the hot melt adhesive layer 3, the surface of the hot melt adhesive layer 3 in contact with the adhesion promoting layer 4 is subjected to a second corona treatment to obtain a certain amount of polar groups. The degree of corona treatment is indicated by the wetting tension (i.e., the dyne value), and the dyne value of the surface of the hot melt adhesive layer 4 after the corona treatment is between 50 and 54.

Before the coating, the mixture of the modified acrylic emulsion or the modified urethane emulsion constituting the adhesion-promoting layer 4 and the adhesion promoter is subjected to high-speed dispersion treatment for 10-20 minutes, and the substances in the adhesion-promoting layer 4 can be sufficiently mixed. The adhesion-promoting layer 4 has a uniform adhesive force to ensure the bonding effect between the pre-coated film and the printed matter of the embodiment of the present invention.

On the surface of the corona-treated hot-melt adhesive layer 4, a high-speed dispersion-treated modified acrylic emulsion or a mixture of a modified urethane acid emulsion and an adhesion promoter is coated and dried, and the drying temperature is 70 ° C - After drying at 95 ° C, the thickness of the adhesion-promoting layer 4 is from 0.2 μm to 0.4 μm, and the dry weight of the coating is from 0.1 to 0.4 g/m ² .

Thus, the precoat film preparation method according to the embodiment of the present invention is not only simple in operation, but also effectively reduces the cost of precoat film preparation because the existing precoat film production line is fully utilized. In addition, the precoat film prepared by the precoat film preparation method according to the embodiment of the present invention not only has a soft touch, but also can enhance the adhesion between the precoat film and the printed matter, and satisfies the requirements of the subsequent processing steps.

Example 2

Referring to Figure 5, a method of preparing a precoat film comprises the following steps.

Step 2: A flexible coating 12 comprising a mixture of a polyurethane dispersion, a fluorosilicone modified resin, a self-crosslinking acrylate and a curing agent is applied to the first side 111 of the substrate layer 11 by means of a spraying device.

Step 3: Coating the plastic composite gravure ink on the second side 112 of the substrate layer 11 using a gravure printing technique to form a printed or coated coating 13 of color or pattern. The substrate layer 11, the flexible coating 12 and the printed layer 13 form the substrate 1.

Step 4: coating the upper surface of the printed layer 13 after the first corona treatment with the polyethyleneimine aqueous solution prepared according to the above ratio and drying it with a drying device to cure the polyvinyl chloride imide in printing The upper surface of layer 13 is formed to form intermediate layer 2.

Prior to the implementation of step four, the upper surface of the printed layer 13 is subjected to a second corona treatment to obtain a certain amount of a polar group such as a carbonyl group. The dyne value of the surface of the printed layer 13 after the corona treatment can reach 36 or more.

The other steps in the embodiment 2 are the same as the corresponding steps in the embodiment 1, and are not described herein again.

Embodiment 2 of the present invention is different from Embodiment 1 in that a printed layer 13 is provided on the second surface 112 of the substrate layer 11 to obtain a surface printing pattern effect.

Although specific embodiments of the present disclosure have been described in detail, those skilled in the art will understand. Various modifications and alterations of the details are possible in light of the teachings of the invention. The full scope of the disclosure is given by the appended claims and any equivalents thereof.

In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiment", "example", "specific example", or "some examples", etc. Particular features, structures, materials or features described in the examples or examples are included in at least one embodiment or example of the present disclosure. In the present specification, the schematic representation of the above terms does not necessarily mean the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

Claims

A composition comprising:

Aqueous self-crosslinking acrylate, fluorosilicone modified resin, polyurethane dispersion, curing agent and auxiliary agent.
The composition of claim 1 wherein, based on the total weight of the composition,

The content of the aqueous self-crosslinking acrylate is from 0.1% by weight to 1% by weight;

The content of the fluorosilicon modified resin is from 1% by weight to 5% by weight;

The content of the polyurethane dispersion is from 10% by weight to 29% by weight;

The content of the curing agent is 50% by weight or less,

Optionally,

The content of the aqueous self-crosslinking acrylate is from 0.1% by weight to 0.5% by weight;

The content of the fluorosilicone modified resin is from 1% by weight to 3% by weight;

The content of the polyurethane dispersion is from 25% to 28% by weight;

The curing agent is contained in an amount of from 30% by weight to 40% by weight.
The composition according to claim 1 or 2, wherein the curing agent is aziridine or an isocyanate.
The composition according to any one of claims 1 to 3, wherein the auxiliary agent comprises a first leveling agent, and the first leveling agent is a polyurethane emulsion type or an acrylic emulsion type leveling agent.
The composition according to claim 4, wherein the content of the first leveling agent is from 0.01% by weight to 1% by weight, alternatively from 0.1% by weight to 0.5% by weight, based on the total weight of the composition.
The composition according to any one of claims 1 to 5, wherein the adjuvant further comprises an antifoaming agent, and the antifoaming agent is contained in an amount of from 0.01% by weight to 1% by weight.
The composition according to any one of claims 1 to 6, wherein the polyurethane dispersion contains a second leveling agent, a film former, a thickener and a diluent.
The composition of claim 7 wherein said second leveling agent is a silicone leveling agent.
The composition according to claim 7 or 8, wherein the film former is a glycol ether, a glycol ether ester or an ester alcohol.
The composition according to any one of claims 7 to 9, wherein the thickener comprises an acrylate and/or methacrylate copolymer.
A composition according to any one of claims 7 to 10 wherein the diluent is deionized water.
A precoat film comprising:

a substrate layer comprising a substrate layer and a flexible coating;

An intermediate layer disposed on the substrate layer;

a layer of hot melt adhesive disposed on the intermediate layer;

An adhesion promoting layer disposed on the hot melt adhesive layer,

Wherein the flexible coating is formed on the first side of the substrate layer and is formed from the composition of any of claims 1-11.
The precoated film according to claim 12, wherein the substrate layer is a biaxially oriented polyester layer, a biaxially oriented nylon layer or a biaxially oriented polypropylene layer.
The precoated film according to claim 12 or 13, wherein the substrate layer has a thickness of from 8 μm to 50 μm.
The precoated film according to any one of claims 12 to 14, wherein

When the substrate layer is a biaxially stretched polyester layer, the substrate layer has a thickness of 9 μm to 12 μm, or

When the substrate layer is a biaxially stretched nylon layer, the substrate layer has a thickness of 12 μm to 20 μm, or

When the substrate layer is a biaxially oriented polypropylene layer, the substrate layer has a thickness of from 12 μm to 15 μm.
The precoat film according to any one of claims 12 to 15, wherein the flexible coating layer has a thickness of from 4 μm to 10 μm, alternatively from 4 μm to 6 μm.
The precoat film according to any one of claims 12 to 16, wherein the adhesion promoting layer has a thickness of from 0.1 μm to 0.5 μm, alternatively from 0.2 μm to 0.4 μm.
The precoated film according to any one of claims 12 to 17, wherein the hot melt adhesive layer has a thickness of from 6 μm to 30 μm, alternatively from 12 μm to 19 μm.
The precoat film according to any one of claims 12 to 18, wherein the adhesion promoting layer is formed of a modified acrylic emulsion or a modified urethane acid emulsion and an adhesion promoter.
The precoated film according to claim 19, wherein said adhesion promoting layer has a coating dry weight of from 0.05 g/m 2 to 0.5 g/m 2 , alternatively from 0.1 g/m 2 to 0.4 g/m 2 .
The precoated film according to claim 19 or 20, wherein the adhesion promoter is contained in an amount of from 0.1% by weight to 10% by weight, based on the total weight of the tackifying layer, optionally from 0.5% by weight to 5 weight%.
The precoat film according to any one of claims 19 to 21, wherein the modified acrylic emulsion or the modified urethane acid emulsion has a solid content of 50% or less.
The precoat film according to any one of claims 19 to 22, wherein the adhesion promoter is a terpene phenol resin, a silane coupling agent or an ethylene-acrylic emulsion.
The precoat film according to any one of claims 19 to 23, wherein the adhesion promoter is an ethylene-acrylic emulsion having a solid content of 10% to 40%.
The precoated film according to any one of claims 12 to 24, wherein the intermediate layer is formed of an aqueous solution of polyethyleneimine.
The precoated film according to claim 25, wherein the polyethyleneimine has a solid content of from 0.4% to 2.5%.
The precoated film according to claim 25 or 26, wherein the polyethyleneimine has a coating dry weight of from 0.007 g/m 2 to 0.03 g/m 2 , alternatively from 0.009 g/m 2 to 0.011 g. /m 2 .
The precoated film according to any one of claims 25 to 27, wherein the polyethyleneimine has a molecular formula of (CH 2 CH 2 NH) n and an average molecular weight of from 1,000 to 10,000.
The precoat film according to any one of claims 12 to 28, wherein the hot melt adhesive layer is composed of an ethylene-vinyl acetate copolymer, an ethylene-acetic acid propylene copolymer, an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer. Things.
The precoat film according to claim 29, wherein when the hot melt adhesive layer is formed of an ethylene-vinyl acetate copolymer, the content of vinyl acetate is 10% by weight based on the total weight of the hot melt adhesive layer % by weight, melt index is 10g/10min-25g/10min,

Alternatively, the vinyl acetate content is from 15% by weight to 20% by weight, and the melt index is from 10 g/10 min to 20 g/10 min.
The precoat film according to any one of claims 12 to 30, wherein the composition further contains a color paste, and the color paste is contained in an amount of from 0.5% by weight to 3% by weight based on the total mass of the composition.
A precoat film according to any one of claims 12 to 30, further comprising a printed layer formed on the second side of the substrate layer.
The precoated film according to claim 32, wherein the printed layer has a thickness of from 0.5 μm to 4 μm, alternatively from 0.5 μm to 1 μm.
A method of preparing a precoat film according to any one of claims 12 to 31, comprising the steps of:

Providing a substrate layer;

Spraying a mixture of a polyurethane dispersion, a fluorosilicone modified resin, a curing agent, a self-crosslinking acrylate, and a color paste on the first side of the substrate layer to form a flexible layer;

Coating a polyethyleneimine aqueous solution on the second side of the substrate layer to form an intermediate layer;

Coating an ethylene-vinyl acetate copolymer, an ethylene-acetic acid propylene copolymer, an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer on the intermediate layer to form a hot melt adhesive layer;

A modified acrylic emulsion or a mixture of a modified urethane acid emulsion and an adhesion promoter is coated on the hot melt adhesive layer to form an adhesion promoting layer.
A method of preparing a precoat film according to any one of claims 12-30, 32 and 33, comprising the steps of:

Providing a substrate layer;

Spraying a mixture of a polyurethane dispersion, a fluorosilicon modified resin, a self-crosslinking acrylate, and a curing agent on the first side of the substrate layer to form a flexible layer;

Printing ink on the second side of the substrate layer to form a printed layer;

Applying an aqueous solution of polyethyleneimine on the printed layer to form an intermediate layer;

Coating an ethylene-vinyl acetate copolymer, an ethylene-acetic acid propylene copolymer, an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer on the intermediate layer to form a hot melt adhesive layer;

A modified acrylic emulsion or a mixture of a modified urethane acid emulsion and an adhesion promoter is coated on the hot melt adhesive layer to form an adhesion promoting layer.
The method of claim 35 wherein said ink is printed on the second side of said substrate layer using a gravure printing technique.
The method according to any one of claims 34 to 36, wherein a step of coating an aqueous solution of polyethyleneimine on the second side of the substrate layer or coating an aqueous solution of polyethyleneimine on the printing layer The above steps further include:

Performing a first corona treatment on the second surface of the substrate layer or the surface on the printing layer, so that the surface value of the substrate layer or the printed layer reaches 36 or more;

Coating the aqueous solution of polyethyleneimine on the second side of the first corona-treated substrate layer or on the upper surface of the printed layer;

Drying is carried out at a temperature of 85 degrees Celsius to 95 degrees Celsius.
The method according to any one of claims 34 to 37, wherein the step of coating the modified acrylic emulsion or the mixture of the modified urethane acid emulsion and the adhesion promoter on the hot melt adhesive layer further comprises:

Performing a second corona treatment on the surface of the hot melt adhesive layer to achieve a dyne value of 50-54 on the surface of the hot melt adhesive layer;

Coating the mixture of the modified acrylic emulsion or the modified urethane acid emulsion and the adhesion promoter on the surface of the hot-melt adhesive layer subjected to the second corona treatment;

Drying is carried out at a temperature of 70 degrees Celsius to 95 degrees Celsius.
The method according to claim 38, wherein the modified acrylic emulsion or the mixture of the modified urethane acid emulsion and the adhesion promoter is previously subjected to a high-speed dispersion treatment before the coating step.
The method according to claim 39, wherein said high-speed dispersion treatment has a time of from 10 minutes to 20 minutes.