Composition for printing and high resistance surface printed pearlescent film label

Abstract

The present application belongs to the technical field of printing materials, and relates to a composition for printing and a high-resistance surface-printed pearlescent film label. The present application directly adopts a surface printing process of a film (for example, a pearlescent film), that is, a special high-resistance ink and a varnish are directly printed on the film, and the printed film can be cut and used after printing, thereby achieving energy saving and emission reduction and greatly reducing the manufacturing time. The surface-printed label prepared by the present application can effectively replace a composite label, and the label material is single, which is a green, energy-saving and emission-reducing beverage label. As a surface-printed label, the surface ink has high resistance and can withstand the harsh environmental fluctuations in the flow process, has the characteristics of resistance to sunlight and weather, wear resistance, water boiling resistance, water soaking resistance, high temperature adhesion resistance, and improves the use experience of consumers.

Description

Technical Field

[0001] This invention belongs to the field of printing materials technology, and relates to compositions for printing and high-durability pearlescent film labels. Background Technology

[0002] Product labels are brief labels used to indicate the name, weight, volume, and purpose of an item. As a pre-packaged liquid food, beverages require accurate and clear labeling of the product name, net content, ingredient list, nutritional information, production date and shelf life, and manufacturer information to provide consumers with accurate and clear beverage information. Sweat and cosmetics can be corrosive to the ink on beverage labels. Currently used single-layer pearlescent film surface-printed labels are prone to large-area ink peeling when exposed to sweat or chemical solvents in summer, affecting the consumer experience. Therefore, most beverage labels use composite film reverse printing or transparent material reverse printing processes.

[0003] Currently, most high-durability beverage labels on the market are manufactured using a composite process. This involves printing ink onto a polypropylene (or polyester) film, then applying a layer of adhesive to bond it to another film layer. Finally, the adhesive is baked at 50°C for over 24 hours to cure, resulting in a composite label structure with ink in the middle layer and both inner and outer layers made of plastic film. Because the outer layer is entirely plastic film, the ink does not come into contact with the external environment, exhibiting good resistance to external substances, high temperatures, and high humidity.

[0004] Composite printing and coating processes result in high VOC emissions, high energy consumption during baking and curing, and long label manufacturing cycles, which are detrimental to energy conservation, emission reduction, and improved manufacturing efficiency. While surface printing is also used for labels, the inks, varnishes, and printing processes used are inadequate, making these labels unable to withstand the erosion of artificial sebum and sunscreen. They are prone to fading in harsh environments, frequently leading to consumer complaints and damaging brand image. Summary of the Invention

[0005] This invention discloses a highly durable surface-printed pearlescent film beverage label. The label uses a pearlescent film as the substrate, with a specially formulated one-component ink and one-component varnish printed on the surface. The finished label is resistant to artificial sebum and sunscreen, and also possesses properties of sun and weather resistance, abrasion resistance, boiling water resistance, immersion resistance, and high-temperature adhesion resistance. This surface-printed label can replace composite labels in the beverage labeling field. Its manufacturing process is green, energy-saving, and emission-reducing, while also exhibiting excellent properties.

[0006] In a first aspect, this application provides a composition for printing, comprising an ink composition and a varnish composition, wherein the ink composition and the varnish composition are present separately from each other before use;

[0007] The ink composition comprises, by weight percentage, the following components:

[0008]

[0009] The latent crosslinking agent is selected from one or more of butanol-etherified amino resins, zirconate chelates, and titanate chelates.

[0010] The organic solvent is selected from one or more of ethyl acetate, n-propyl acetate, butyl acetate, isopropanol, and anhydrous ethanol;

[0011] The varnish composition comprises the following components by weight percentage:

[0012]

[0013] The resin modifier is selected from tetraisopropyl titanate, hexamethylene diisocyanate, or a combination of both.

[0014] The latent crosslinking agent is selected from one or more of butanol-etherified amino resins, zirconate chelates, and titanate chelates.

[0015] The organic solvent is selected from one or more of ethyl acetate, n-propyl acetate, butyl acetate, isopropanol, and anhydrous ethanol.

[0016] The ink of this invention is a specially formulated single-component ink with self-crosslinking properties. It primarily consists of nitrocellulose, hydroxyl acrylic resin, polyester polyol, lightfast pigments, and a latent crosslinking agent as film-forming substances, supplemented by organic solvents mainly composed of ethyl acetate, n-propyl acetate, butyl acetate, isopropanol, and / or anhydrous ethanol. This ink can be used as a gravure printing ink.

[0017] Nitrocellulose, also known as nitrocellulose, cellulose nitrate, or nitrocellulose cotton, is an organic polymer compound with the chemical formula (C6H7N3O). 11 ) nFiber nitrate is a product of the esterification reaction of cellulose with nitric acid. It is white or slightly yellow and cottony in appearance, insoluble in water but soluble in organic solvents such as esters and acetone. Because cellulose nitrate is flammable in air and highly flammable and explosive when exposed to open flames or high heat, it can be dissolved in solvents such as alcohols, ethers, or esters to obtain a viscous liquid for easier transportation and storage. The viscosity of industrial cellulose nitrate solutions can be determined according to ISO 14446-1999, "Binders for paints and varnishes—Determination of the viscosity of industrial cellulose nitrate solutions and classification of such solutions," or by following the methods recommended by the supplier.

[0018] In some embodiments, the nitrocellulose used in the ink composition of the present invention is an H-type nitrocellulose (nitrocellulose) resin with a viscosity of 1 / 8 second or 1 / 16 second. In some embodiments, the nitrocellulose used in the ink composition of the present invention is sourced from Sichuan Northern Nitrocellulose Co., Ltd.

[0019] In some embodiments, nitrocellulose accounts for 1%-5%, 5%-8%, 8%-10%, 10%-12%, or 12%-15% of the mass percentage of the ink composition.

[0020] Hydroxyacrylate resin is an acrylic resin prepared by free radical polymerization using hard monomers such as styrene or methyl methacrylate, soft monomers such as ethyl acrylate, butyl acrylate, or butyl methacrylate, and hydroxyl-containing functional monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, or hydroxypropyl methacrylate as raw materials, under the action of a molecular chain regulator. It can be compounded with a crosslinking agent and cured to form a crosslinked network structure. The hydroxyl value of hydroxyacrylate resin refers to the amount of hydroxyl groups in 100g of resin. Industrially, the hydroxyl value is usually expressed as the number of milligrams of potassium hydroxide (KOH) equivalent to the hydroxyl groups in 1g of sample, expressed as mgKOH / g.

[0021] In some embodiments, the hydroxyl acrylic resin used in the ink composition of the present invention is a copolymer of methyl methacrylate, butyl methacrylate, and hydroxypropyl methacrylate. In some embodiments, the hydroxyl value of the hydroxyl acrylic resin is 50-60 mg KOH / g. In some embodiments, the molecular weight of the hydroxyl acrylic resin is 20k-30k.

[0022] The hydroxyl value and molecular weight of hydroxyl acrylic resins can be determined according to conventional methods in the art, or according to methods recommended by the supplier.

[0023] In some embodiments, the hydroxyl acrylic resin accounts for 1%-6%, 6%-8%, 8%-10%, 10%-12%, 12%-16%, or 16%-20% of the ink composition by mass.

[0024] Polyester polyols are copolymers obtained by polycondensation reaction of dicarboxylic acids and diols. In some embodiments, the polyester polyol used in the ink compositions of the present invention is 1,4-butanediol adipate. In some embodiments, the molecular weight of the polyester polyol is 4k-5k. The molecular weight of the polyester polyol can be determined according to conventional methods in the art or according to methods recommended by the supplier.

[0025] In some embodiments, the polyester polyol accounts for 1%-3%, 3%-4%, 4%-5%, 5%-10%, 10%-15%, or 15%-20% of the mass percentage of the ink composition.

[0026] The pigments used in this invention can be lightfast pigments, such as Pigment Red 122, Pigment Blue 15:4, or Pigment Yellow 180, or they can be carbon black pigments. Lightfast pigments refer to pigments with a certain degree of lightfastness. Lightfastness refers to the ability of an ink or coating colored with pigment to maintain its color within a specific time frame under sunlight. Pigments with a certain degree of lightfastness can be used to improve the lightfastness of the ink and reduce discoloration of printed materials under light.

[0027] In some embodiments, the pigment accounts for 1%-3%, 3%-5%, 5%-10%, 10%-12%, 12%-15%, or 15%-20% of the ink composition by mass.

[0028] In this invention, a latent crosslinking agent refers to a compound that does not react with the polymer to be crosslinked under normal temperature conditions, or reacts very slowly, but can rapidly undergo a crosslinking reaction with the polymer upon heating. The latent crosslinking agent used in the ink composition of this invention is selected from one or more of butanol-etherified amino resins, zirconate chelates, and titanate chelates. The latent crosslinking agent used in this invention undergoes a crosslinking reaction with hydroxyl-containing resins during the ink printing heating and drying process, greatly increasing the molecular weight of the dried ink resin and significantly improving the label's high-temperature resistance and anti-adhesion properties.

[0029] In some embodiments, the latent crosslinking agent used in the ink composition of the present invention is a composition of butanol-etherified amino resin, zirconate chelate and titanate chelate in a 1:4:2 (mass ratio).

[0030] In some embodiments, the latent crosslinking agent used in the ink composition of the present invention is a composition of zirconate chelate and titanate chelate in a 1:1 (mass ratio).

[0031] In some embodiments, the latent crosslinking agent used in the ink composition of the present invention is a composition of butanol-etherified amino resin and titanate chelate 1:7 (mass ratio).

[0032] In some embodiments, the latent crosslinking agent used in the ink compositions of the present invention is a zirconate chelate.

[0033] In some embodiments, the latent crosslinking agent accounts for 1%-3%, 3%-5%, 5%-6%, 6%-7%, 7%-8%, 8%-10%, 10%-12%, or 12%-15% of the mass percentage of the ink composition.

[0034] The organic solvent used in the ink composition of the present invention may be selected from one or more of ethyl acetate, n-propyl acetate, butyl acetate, isopropanol and anhydrous ethanol.

[0035] In some embodiments, the ink compositions of the present invention, by weight percentage, comprise the following organic solvents:

[0036] Ethyl acetate 5%-20% (e.g., 5%-10%, 10%-15%, 15%-18%, or 18%-20%),

[0037] Propyl acetate 1%-35% (e.g., 1%-5%, 5%-9%, 9%-10%, 10%-15%, 15%-20%, 20%-22%, 22%-24%, 24%-30%, or 30%-35%),

[0038] Butyl acetate 1%-30% (e.g., 1%-5%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, or 25%-30%),

[0039] and / or

[0040] Isopropanol or anhydrous ethanol 1%-15% (e.g., 1%-5%, 5%-6%, 6%-7%, 7%-8%, 8%-10%, 10%-12% or 12%-15%).

[0041] In some embodiments, the ink compositions of the present invention, by weight percentage, comprise the following organic solvents:

[0042] Isopropanol (5% by mass), ethyl acetate (18% by mass), n-propyl acetate (10% by mass), and butyl acetate (25% by mass).

[0043] Anhydrous ethanol (6% by mass), ethyl acetate (20% by mass), n-propyl acetate (9% by mass), and butyl acetate (25% by mass).

[0044] Anhydrous ethanol (7% by mass), ethyl acetate (10% by mass), n-propyl acetate (24% by mass), and butyl acetate (15% by mass).

[0045] or

[0046] Isopropanol (8% by mass), ethyl acetate (15% by mass), n-propyl acetate (22% by mass) and butyl acetate (15% by mass).

[0047] The ink composition of the present invention can be prepared by a method comprising the following steps:

[0048] 1. Nitrocellulose, hydroxyl acrylic resin, and polyester polyol are dissolved in a portion of an organic solvent to form a clear and transparent resin solution, and then pigments are added.

[0049] 2. After dispersing the resin liquid with added pigment, grind the maximum particle size of the pigment to below 25 micrometers (e.g., 1-5 micrometers, 5-10 micrometers, 10-15 micrometers, 15-20 micrometers or 20-25 micrometers), while ensuring that the median particle size (D50) is below 5 micrometers (e.g., 1-2 micrometers, 2-3 micrometers, 3-4 micrometers or 4-5 micrometers);

[0050] 3. Add the remaining organic solvents and latent crosslinking agents to obtain the ink composition of the present invention.

[0051] When the ink composition of the present invention contains different kinds of organic solvents, the organic solvents can be added in a certain order. In some embodiments, the ink composition of the present invention contains butyl acetate and other organic solvents. In such embodiments, other organic solvents besides butyl acetate are added in step 1, and butyl acetate is added in step 3.

[0052] In some embodiments, step 2 may involve high-speed dispersion of the pigmented resin liquid at a rate of 1500 rpm or higher for a certain period of time (e.g., 1 hour or longer) to ensure complete dispersion of the components. In some embodiments, step 2 may involve grinding using a sand mill.

[0053] The ink composition of the present invention can be used for printing on labels and other printed materials. To improve the durability of printed materials, a top coat can be printed after the ink is printed. This forms a new coating on the ink coating, protecting the surface of the printed material and giving it better durability and abrasion resistance. It can also present gloss, matte, tactile, and patterned effects, thus finishing and decorating the printed material.

[0054] The varnish of this invention is a specially formulated single-component varnish with self-crosslinking properties. It primarily uses nitrocellulose, cellulose acetate butyrate, hydroxyl acrylic resin, and polyethylene wax powder, supplemented with resin modifiers and latent crosslinking agents, as film-forming substances, and adds ethyl acetate, n-propyl acetate, butyl acetate, isopropanol, and / or anhydrous ethanol as main organic solvents. The varnish of this invention can be used as a printing varnish.

[0055] In some embodiments, the nitrocellulose used in the varnish composition of the present invention is an H-type nitrocellulose resin with a viscosity of 1 / 8 second.

[0056] In some embodiments, nitrocellulose accounts for 1%-5%, 5%-8%, 8%-10%, 10%-12%, or 12%-15% of the mass percentage of the varnish composition.

[0057] Cellulose acetate butyrate (CAB) is the product of the esterification reaction of cellulose with butyric acid (anhydride) and acetic acid (anhydride). In some embodiments, the cellulose acetate butyrate used in the varnish compositions of the present invention is CAB381.05. In some embodiments, the supplier of said cellulose acetate butyrate is Eastman Chemical.

[0058] In some embodiments, cellulose acetate butyrate constitutes 1%-3%, 3%-5%, 5%-10%, 10%-13%, or 13%-15% of the varnish composition by mass.

[0059] In some embodiments, the hydroxyl acrylic resin used in the varnish composition of the present invention is a copolymer of methyl methacrylate, butyl methacrylate, and hydroxypropyl methacrylate. In some embodiments, the hydroxyl value of the hydroxyl acrylic resin is 35-50 mg KOH / g. In some embodiments, the molecular weight of the hydroxyl acrylic resin is 20k-24k.

[0060] In some embodiments, the hydroxyl acrylic resin accounts for 1%-6%, 6%-10%, 10%-16%, 16%-18%, 18%-21%, or 21%-30% of the weight of the varnish composition.

[0061] In some embodiments, the polyethylene wax powder accounts for 1%-2%, 2%-3%, 3%-4%, or 4%-5% of the weight of the varnish composition.

[0062] The resin modifier used in the varnish of this invention is selected from tetraisopropyl titanate, hexamethylene diisocyanate, or a combination of the two.

[0063] In some embodiments, the resin modifier used in the varnish of the present invention is a combination of tetraisopropyl titanate and hexamethylene diisocyanate in a mass ratio of 2:1.

[0064] In some embodiments, the resin modifier comprises tetraisopropyl titanate, and the tetraisopropyl titanate accounts for 1% of the mass percentage of the varnish composition.

[0065] In some embodiments, the resin modifier comprises hexamethylene diisocyanate, and the hexamethylene diisocyanate accounts for 0.5% of the mass percentage of the varnish composition.

[0066] In some embodiments, the resin modifier accounts for 0.5%-1%, 1%-1.5%, or 1.5%-2% of the mass of the varnish composition.

[0067] The latent crosslinking agent used in the varnish of this invention is selected from one or more of butanol-etherified amino resins, zirconate chelates, and titanate chelates.

[0068] In some embodiments, the latent crosslinking agent accounts for 1%-1.5%, 1.5%-2%, 2%-2.5%, 2.5%-3%, 3%-4%, or 4%-5% of the mass of the varnish composition.

[0069] The organic solvent used in the varnish composition of the present invention may be selected from one or more of ethyl acetate, n-propyl acetate, butyl acetate, isopropanol and anhydrous ethanol.

[0070] In some embodiments, the varnish composition of the present invention comprises, by weight percentage, the following organic solvents:

[0071] Ethyl acetate 5%-30% (e.g., 5%-10%, 10%-15%, 15%-18%, 18%-20%, 20%-25%, or 25%-30%),

[0072] Propyl acetate 1%-35% (e.g., 1%-5%, 5%-10%, 10%-13.5%, 13%-15%, 15%-20%, 20%-22.5%, 22.5%-23.5%, 23.5%-30%, or 30%-35%),

[0073] Butyl acetate 1%-20% (e.g., 1%-5%, 5%-8%, 8%-9.5%, 9.5%-10%, 10%-15% or 15%-20%),

[0074] and / or

[0075] Isopropanol or anhydrous ethanol 1%-15% (e.g., 1%-5%, 5%-6%, 6%-7%, 7%-8%, 8%-10%, 10%-12% or 12%-15%).

[0076] In some embodiments, the varnish composition of the present invention comprises, by weight percentage, the following organic solvents:

[0077] Ethyl acetate (30% by mass), n-propyl acetate (15% by mass), butyl acetate (9.5% by mass), and isopropanol (5% by mass).

[0078] Ethyl acetate (30% by mass), n-propyl acetate (13.5% by mass), butyl acetate (5% by mass), anhydrous ethanol (10% by mass).

[0079] Ethyl acetate (25% by mass), n-propyl acetate (22.5% by mass), butyl acetate (8% by mass), anhydrous ethanol (5% by mass),

[0080] or

[0081] Ethyl acetate (15% by mass), n-propyl acetate (23.5% by mass), butyl acetate (10% by mass), and isopropanol (10% by mass).

[0082] The varnish composition of the present invention can be prepared by a method comprising the following steps:

[0083] 1. Dissolve cellulose acetate butyrate and hydroxyl acrylic resin in a partial organic solvent, add resin modifier to modify the resin, stir evenly and store at room temperature to ensure complete resin modification.

[0084] 2. Add nitrocellulose, polyethylene wax powder and other organic solvents, and add a latent crosslinking agent. Stir at high speed until homogeneous to obtain the varnish composition of the present invention.

[0085] When the varnish composition of the present invention contains different kinds of organic solvents, the organic solvents can be added in a certain order. In some embodiments, the varnish composition of the present invention contains ethyl acetate and other organic solvents. In such embodiments, ethyl acetate is added in step 1, and other organic solvents other than ethyl acetate are added in step 2.

[0086] In some implementations, the product is stored at room temperature for 5 hours or more, or for 20 hours or more. In some implementations, the first step involves low-speed stirring, and the second step involves high-speed stirring.

[0087] Optionally, the ink composition, varnish composition, or printing composition used in this invention may further comprise one or more additives commonly used in the art, such as driers, diluents, thinners, antioxidants, anti-gelling agents, defoamers, surfactants, anti-pinhole agents, slip agents, plasticizers, preservatives, and fragrances.

[0088] In a second aspect, this application also provides a printing method comprising using the printing composition of the present invention.

[0089] In some embodiments, the printing method employs gravure printing. In some embodiments, the ink coating amount reaches 4 g / m². 2 (wet basis) or higher (e.g., 4-5 g / m²) 2 (wet basis), 5-6 g / m 2 (wet basis), 6-7 g / m 2 (wet basis) or 7-8 g / m 2 (Wet substrate) The topcoat application rate needs to reach 6 g / m². 2 (wet basis) or higher (e.g., 6-7 g / m²) 2 (wet basis), 7-8 g / m 2 (wet basis), 8-9 g / m 2 (wet basis) or 9-10 g / m 2 (Wet basis)). In some embodiments, the topcoat application rate (dry basis) is 1-2 g / m². 2 (e.g., 1.5g / m 2 A color ink electro-engraving gravure plate or a varnish electro-engraving gravure plate can be used. In some embodiments, the depth of the color ink electro-engraving gravure plate is set to 42-45 micrometers (e.g., 43 or 44 micrometers). In some embodiments, the depth of the varnish electro-engraving gravure plate is set to 50-52 micrometers (e.g., 51 micrometers).

[0090] In some embodiments, the printing method includes the following steps: printing color ink, drying in an oven at 65-75°C (e.g., 70°C), and then printing a top coat, which is also dried at 65-75°C (e.g., 70°C).

[0091] In a third aspect, this application provides a printed article comprising a substrate and a printing composition of the present invention applied to said substrate.

[0092] In some embodiments, the substrate comprises one or more materials selected from polyethylene terephthalate, crystalline polyethylene terephthalate, polyethylene, and polypropylene.

[0093] In some embodiments, the substrate comprises polypropylene. In some embodiments, the substrate is a polypropylene (PP) pearlescent film.

[0094] In some embodiments, the substrate has a content of 0.65-0.8 g / cm³. 3 The density.

[0095] In some embodiments, the substrate has a thickness of 30-40 micrometers (e.g., 38 micrometers).

[0096] In some embodiments, the printing surface of the substrate may be corona treated to achieve a certain surface tension. In some embodiments, the printing surface of the substrate has a surface tension of 38 dyn / cm or higher.

[0097] In some implementations, the printed material is a label.

[0098] In a fourth aspect, this application provides a packaging material comprising a container and a printed article of the third aspect. In some embodiments, the container is a bottle. In some embodiments, the container comprises one or more materials selected from high-density polyethylene, polyethylene terephthalate, and polypropylene.

[0099] In a fifth aspect, this application provides the use of the composition for printing described in the first aspect, the printed article described in the third aspect, and the packaging material described in the fourth aspect for packaging (e.g., beverage packaging).

[0100] In a sixth aspect, this application provides a product comprising the printed articles described in the third aspect or the packaging materials described in the fourth aspect. In some embodiments, the product is a beverage.

[0101] Beneficial effects of the invention

[0102] This invention directly employs a thin film (e.g., pearlescent film) surface printing process, that is, printing specially made high-durability inks and varnishes directly onto the film. After printing, the film can be slit and used, saving energy and reducing emissions while greatly reducing manufacturing time.

[0103] The surface-printed label prepared by this invention can effectively replace composite labels, making the label material more uniform. It is a green, energy-saving, and emission-reducing beverage label. As a surface-printed label, the surface ink has high durability and can withstand the harsh environmental fluctuations during circulation. It has the characteristics of being sun-resistant, weather-resistant, wear-resistant, water-resistant, water-resistant, and high-temperature resistant, thus improving the consumer experience. Attached Figure Description

[0104] Figure 1 This is a schematic diagram of the longitudinal cross-sectional structure of a printed label according to the present invention. Detailed Implementation

[0105] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0106] Example 1

[0107] Ink Preparation: Nitrocellulose (H-type nitrocellulose resin with a viscosity of 1 / 8 second, 8% by mass, supplied by Sichuan Northern Nitrocellulose Co., Ltd.), hydroxyl acrylic resin (hydroxyl value of 50 mg KOH / g, molecular weight of 20000, copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate, 12% by mass), polyester polyol (1,4-butanediol adipate with a molecular weight of 4000, 5% by mass), dissolved in isopropanol (5% by mass), ethyl acetate (18% by mass) and n-propyl acetate (10% by mass) to form a clear and transparent resin solution, then lightfast pigment (Pigment Red) is added. 122 (10% by mass) was dispersed at 1500 rpm for 1 hour and then ground to a maximum particle size of less than 25 micrometers using a sand mill, while ensuring that the median particle size (D50) was less than 5 micrometers. Then, butyl acetate (25% by mass) and a latent crosslinking agent (a composition of butanol-etherified amino resin, zirconate chelate and titanate chelate in a 1:4:2 (mass ratio) composition, 7% by mass) were added.

[0108] Preparation of the varnish: Cellulose acetate butyrate (CAB381.05, 5% by mass, supplied by Eastman Chemical Company), hydroxyl acrylic resin (hydroxyl value 35 mg KOH / g, molecular weight 24000, copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate 21% by mass), are dissolved in ethyl acetate (30% by mass). Tetraisopropyl titanate (1% by mass) and hexamethylene diisocyanate (0.5% by mass) are added for resin modification. The mixture needs to be stirred at low speed until homogeneous and stored at room temperature for at least 20 hours to ensure complete resin modification. Then, nitrocellulose (H-type nitrocellulose resin with a viscosity of 1 / 8 second, 10% by mass), polyethylene wax powder (1% by mass), n-propyl acetate (15% by mass), butyl acetate (9.5% by mass), isopropanol (5% by mass), and a latent crosslinking agent (zirconate chelate, 2% by mass) are added. The mixture is stirred at high speed until homogeneous.

[0109] Example 2

[0110] Ink Preparation: Nitrocellulose (H-type nitrocellulose resin with a viscosity of 1 / 16 seconds, 10% by mass, supplied by Sichuan Northern Nitrocellulose Co., Ltd.), hydroxyl acrylic resin (hydroxyl value of 50 mg KOH / g, molecular weight of 20000, copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate, 10% by mass), and polyester polyol (1,4-butanediol adipate with a molecular weight of 4000, 3% by mass) were dissolved in anhydrous ethanol (6% by mass), ethyl acetate (20% by mass), and n-propyl acetate (9% by mass) to form a clear and transparent resin solution. Then, a lightfast pigment (Pigment Blue) was added. The pigment was dispersed at a high speed of 1500 rpm for 1 hour in a 15:4 ratio (12% by mass). The maximum particle size of the pigment was then ground to below 25 micrometers using a sand mill, while ensuring that the median particle size (D50) was below 5 micrometers. Butyl acetate (25% by mass) and a latent crosslinking agent (a 1:1 composition of zirconate chelate and titanate chelate, 5% by mass) were then added.

[0111] Preparation of the varnish: Cellulose acetate butyrate (CAB381.05, 3% by mass, supplied by Eastman Chemical Company), hydroxyl acrylic resin (hydroxyl value 35 mg KOH / g, molecular weight 24000, copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate, 18% by mass), are dissolved in ethyl acetate (30% by mass). Tetraisopropyl titanate (1% by mass) is added for resin modification. The mixture needs to be stirred at low speed until homogeneous and stored at room temperature for at least 5 hours to ensure complete resin modification. Then, nitrocellulose (H-type nitrocellulose resin with a viscosity of 1 / 8 second, 15% by mass), polyethylene wax powder (2% by mass), n-propyl acetate (13.5% by mass), butyl acetate (5% by mass), anhydrous ethanol (10% by mass), and a latent crosslinking agent (titanium ester chelate, 2.5% by mass) are added. The mixture is stirred at high speed until homogeneous.

[0112] Example 3

[0113] Ink preparation: Nitrocellulose (H-type nitrocellulose resin with a viscosity of 1 / 16 seconds, 12% by mass, supplied by Sichuan Northern Nitrocellulose Co., Ltd.), hydroxyl acrylic resin (hydroxyl value of 50 mg KOH / g, molecular weight of 20000, copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate, 8% by mass), and polyester polyol (1,4-butanediol adipate with a molecular weight of 4000, 4% by mass) were dissolved in anhydrous ethanol (7% by mass), ethyl acetate (10% by mass) and n-propyl acetate (24% by mass) to form a clear and transparent resin liquid. Then, carbon black pigment (12% by mass) was added, and the mixture was dispersed at a high speed of 1500 rpm for 1 hour. The maximum particle size of the pigment was then ground to below 25 micrometers using a sand mill, while ensuring that the median particle size (D50) was below 5 micrometers. Finally, butyl acetate (15% by mass) and a latent crosslinking agent (a 1:7 composition of butanol-etherified amino resin and titanate chelate ester, 8% by mass) were added.

[0114] Preparation of the varnish: Cellulose acetate butyrate (CAB381.05, 10% by mass, supplied by Eastman Chemical Company), hydroxyl acrylic resin (hydroxyl value 35 mg KOH / g, molecular weight 24000, copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate, 16% by mass), are dissolved in ethyl acetate (25% by mass). Hexamethylene diisocyanate (0.5% by mass) is added for resin modification. The mixture must be stirred at low speed until homogeneous and stored at room temperature for at least 20 hours to ensure complete resin modification. Then, nitrocellulose (H-type nitrocellulose resin with a viscosity of 1 / 8 second, 10% by mass), polyethylene wax powder (1% by mass), n-propyl acetate (22.5% by mass), butyl acetate (8% by mass), anhydrous ethanol (5% by mass), and a latent crosslinking agent (zirconate chelate, 2% by mass) are added. The mixture is stirred at high speed until homogeneous.

[0115] Example 4

[0116] Ink preparation: Nitrocellulose (H-type nitrocellulose resin with a viscosity of 1 / 16 seconds, 15% by mass, supplied by Sichuan Northern Nitrocellulose Co., Ltd.), hydroxyl acrylic resin (hydroxyl value of 50 mg KOH / g, molecular weight of 20000, copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate, 6% by mass), and polyester polyol (1,4-butanediol adipate with a molecular weight of 4000, 3% by mass) were dissolved in isopropanol (8% by mass), ethyl acetate (15% by mass) and n-propyl acetate (22% by mass) to form a clear and transparent resin liquid. Then, a lightfast pigment (Pigment Yellow 180, 10% by mass) was added. After high-speed dispersion at 1500 rpm for 1 hour, the maximum particle size of the pigment was ground to below 25 micrometers using a sand mill, while ensuring that the median particle size (D50) was below 5 micrometers. Then, butyl acetate (15% by mass) and a latent crosslinking agent (zirconate chelate, 6% by mass) were added.

[0117] Preparation of the varnish: Cellulose acetate butyrate (CAB381.05, 13% by mass, supplied by Eastman Chemical Company), hydroxyl acrylic resin (hydroxyl value 35 mg KOH / g, molecular weight 24000, copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate, 15% by mass), are dissolved in ethyl acetate (15% by mass). Tetraisopropyl titanate (1% by mass) is added for resin modification. The mixture needs to be stirred at low speed until homogeneous and stored at room temperature for at least 5 hours to ensure complete resin modification. Then, nitrocellulose (H-type nitrocellulose resin with a viscosity of 1 / 8 second, 8% by mass), polyethylene wax powder (2% by mass), n-propyl acetate (23.5% by mass), butyl acetate (10% by mass), isopropanol (10% by mass), and a latent crosslinking agent (titanium ester chelate, 2.5% by mass) are added. The mixture is stirred at high speed until homogeneous.

[0118] Printing conditions for Examples 1-4: The depth of the color ink electro-engraved gravure plate was set to 42-45 micrometers, the depth of the varnish electro-engraved gravure plate was set to 50-52 micrometers, and the varnish coating amount was controlled to be maintained at 1.5 g / m² (dry basis). 2 Left and right. The printing sequence is as follows: first print the color ink, dry it in a 70℃ oven, then print the varnish, and dry it at the same 70℃.

[0119] Test and evaluation methods:

[0120] Test Method 1:

[0121] 1) Scope of application: Pearl film printed labels

[0122] 2) Equipment used: paper towels, 4kg weight, artificial sebum, drying oven, ruler, utility knife, measuring cup, cotton swabs

[0123] 3) Operating steps: Cut out 6 samples containing all graphic and text areas according to the label size; based on the actual label area, take a certain amount of artificial sebum and evenly apply it to the printed surface of the sample; lay the sample with the artificial sebum applied, printed side up, inside the oven, set the temperature to 45℃, and keep it warm for 60 minutes; after removing the sample, cover it with a paper towel, apply 4 kg of pressure vertically to its surface, and rub it back and forth horizontally 10 times. Perform 6 parallel tests.

[0124] 4) Result judgment: Under natural light or fluorescent light, there is no obvious ink peeling on the paper towel, and there is no exposed substrate in the printed area of ​​the sample.

[0125] Test Method 2:

[0126] 1) Scope of application: Pearl film printed labels

[0127] 2) Equipment used: paper towels, 4kg compressed sunscreen, Maxam sunscreen (SPF30), drying oven, ruler, utility knife, measuring cup, cotton swabs

[0128] 3) Operating steps: Cut out 6 samples containing all graphic and text areas according to the label size; based on the actual label area, apply a certain amount of Meijiajing sunscreen (SPF30) evenly to the printed surface of the sample; lay the sample with the Meijiajing sunscreen (SPF30) applied on the printed side up inside the oven, set the temperature to 45℃, and keep it warm for 5 minutes; after removing the sample, cover it with a paper towel, apply 4kg of pressure vertically to its surface, and rub it back and forth horizontally 10 times. Perform 6 parallel tests.

[0129] 4) Result Judgment: Under natural light or fluorescent light, visual inspection reveals no obvious ink peeling on the paper towel, and no exposed ink in the printed area of ​​the sample. Test Method 3:

[0130] 1) Scope of application: Pearl film printed labels

[0131] 2) Equipment used: aging chamber, ruler, utility knife

[0132] 3) Operating steps: Cut out 6 sets of samples containing all the text and image areas according to the label size; place the cut sample labels into the aging chamber in sequence, referring to GB / T 16422.2-2022 Cycle 1 (Filter: Sunlight filter (artificial climate aging); Irradiance: (0.51±0.02)W / (m²) 2 •nm)@340nm; Black mark temperature (65±3)℃; Chamber temperature (38±3)℃; Relative humidity (50±10)%; Exposure cycle: 102min drying + 18min light spray); After placing the sample under the above exposure conditions for 48h, it was taken out, and 6 parallel tests were conducted.

[0133] 4) Result Judgment: The label ink must not peel off, and the degree of discoloration of the substrate background color and printing ink should be controlled within ΔE00≤7.0.

[0134] Test Method 4:

[0135] 1) Scope of application: Pearl film printed labels

[0136] 2) Tools needed: 3M 600 tape, ruler, utility knife

[0137] 3) Operating Procedures: Cut 18 samples containing all graphic and text areas according to the label size; apply 25mm wide 3M 600 adhesive tape to the printed surface of the sample, press with your finger 3 times to avoid wrinkling the tape and label, and peel off the tape at a speed of 150mm / s and a reverse angle of 120°-150°. Perform 6 parallel tests; immerse the sample in cold water for 30 minutes, wipe it dry, apply 3M 600 adhesive tape to the printed surface, press with your finger 3 times to avoid wrinkling the tape and label, and peel off the tape at a speed of 150mm / s and a reverse angle of 120°-150°. Perform 6 parallel tests; boil the sample in boiling water for 1 minute, and wipe it with your fingertips. Perform 6 parallel tests.

[0138] Result determination: The ink on the sample must not peel off, and the degree of discoloration of the substrate background color and the printing ink should be controlled within ΔE00 ≤ 7.0.

[0139] Example Result Evaluation Table:

[0140]

[0141] Notes:

[0142] 1. Evaluation results are divided into 1-5 levels, with 1 being the worst, 5 being the best, 3 and above being qualified, and below 3 being unqualified.

[0143] 2. The printing substrate in the above embodiments was evaluated as PP pearlescent film with a density of 0.8 g / cm³. 3 Thickness 38μm, surface tension 38dyn / cm

[0144] Comparative Example

[0145] Labels were prepared using ordinary ink plus the varnish of the present invention, or using the ink of the present invention plus ordinary varnish, according to the printing conditions of Examples 1-4. The performance of the labels was tested according to the above test methods. It was found that the prepared labels did not meet the requirements of high durability and were inferior to those using the ink of the present invention plus the varnish of the present invention in terms of sun and weather resistance, abrasion resistance, water boiling resistance, water immersion resistance, and / or high temperature adhesion resistance.

[0146] It is understood that the above specific description of the present invention is only for illustrating the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention to achieve the same technical effect; as long as the use needs are met, they are all within the protection scope of the present invention.

Claims

1. A composition for printing, comprising an ink composition and a varnish composition, wherein the ink composition and the varnish composition are present separately from each other before use; in, The ink composition comprises the following components by weight percentage: Nitrocellulose 1%-15% Hydroxyacrylate resin 1%-20% Polyester polyols 1%-20% Pigment 1%-20% Latent crosslinking agent 1%-15% The rest are organic solvents. The latent crosslinking agent is selected from one or more of butanol-etherified amino resins, zirconate chelates, and titanate chelates. The organic solvent is selected from one or more of ethyl acetate, n-propyl acetate, butyl acetate, isopropanol, and anhydrous ethanol; The varnish composition comprises the following components by weight percentage: Nitrocellulose 1%-15% Cellulose acetate butyrate 1%-15% Hydroxyacrylate resin 1%-30% Polyethylene wax powder 1%-5% Resin modifier 0.5%-2% Latent crosslinking agent 1%-5% The rest are organic solvents. The resin modifier is selected from tetraisopropyl titanate, hexamethylene diisocyanate, or a combination of both. The latent crosslinking agent is selected from one or more of butanol-etherified amino resins, zirconate chelates, and titanate chelates. The organic solvent is selected from one or more of ethyl acetate, n-propyl acetate, butyl acetate, isopropanol, and anhydrous ethanol.

2. The composition for printing according to claim 1, wherein, The ink composition has one or more of the following characteristics: (1) The nitrocellulose is an H-type nitrocellulose resin with a viscosity of 1 / 8 second or an H-type nitrocellulose resin with a viscosity of 1 / 16 second; (2) The hydroxy acrylic resin is a copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate; (3) The polyester polyol is 1,4-butanediol adipate; (4) The pigment is a lightfast pigment.

3. The composition for printing according to claim 1, wherein, The ink composition has one of the following characteristics: (1) The latent crosslinking agent is a composition of butanol-etherified amino resin, zirconate chelate and titanate chelate in a mass ratio of 1:4:2; (2) The latent crosslinking agent is a composition of zirconate chelate and titanate chelate in a mass ratio of 1:1; (3) The latent crosslinking agent is a composition of butanol-etherified amino resin and titanate chelate in a mass ratio of 1:7; (4) The latent crosslinking agent is a zirconate chelate.

4. The composition for printing according to claim 1, wherein, The ink composition contains the following organic solvents: Ethyl acetate 5%-20%, propyl acetate 1%-35%, Butyl acetate 1%-30%, and / or 1%-15% isopropanol or anhydrous ethanol.

5. The composition for printing according to claim 1, wherein, The ink composition is prepared by a method comprising the following steps: (1) Nitrocellulose, hydroxyl acrylic resin and polyester polyol are dissolved in a portion of an organic solvent to form a clear and transparent resin liquid, and then pigments are added; (2) After dispersing the resin liquid with added pigment, grind the maximum particle size of the pigment to below 25 micrometers, while ensuring that the median particle size is below 5 micrometers; (3) Add the remaining organic solvents and latent crosslinking agents to obtain the ink composition.

6. The composition for printing according to claim 1, wherein, The varnish composition has one or more of the following characteristics: (1) The nitrocellulose is an H-type nitrocellulose resin with a viscosity of 1 / 8 second; (2) The cellulose acetate butyrate is CAB-381-0.5; (3) The hydroxy acrylic resin is a copolymer of methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate.

7. The composition for printing according to claim 1, wherein, The varnish composition contains the following organic solvents: Ethyl acetate 5%-30%, propyl acetate 1%-35%, Butyl acetate 1%-20%, and / or Isopropanol or anhydrous ethanol 1%-15%.

8. The composition for printing according to claim 1, wherein, The varnish composition is prepared by a method comprising the following steps: (1) Cellulose acetate butyrate and hydroxyl acrylic resin are dissolved in a partial organic solvent, and resin modifier is added to modify the resin. After stirring evenly, the resin is stored at room temperature to ensure complete resin modification. (2) Add nitrocellulose, polyethylene wax powder and other organic solvents, and add a latent crosslinking agent, stir at high speed until uniform, and obtain the varnish composition.

9. The composition for printing according to claim 1 further comprises one or more commonly used additives.

10. The composition for printing according to claim 9, wherein the additive is selected from driers, diluents, thickeners, thinners, antioxidants, anti-gelling agents, defoamers, surfactants, anti-pinhole agents, slip agents, plasticizers, preservatives, and fragrances.

11. A printing method comprising using the printing composition of any one of claims 1-10.

12. The printing method according to claim 11, wherein the printing method employs gravure printing technology.

13. The printing method according to claim 12, wherein, The coating weight of the ink composition reaches 4 g / m². 2 The coating amount of the varnish composition reaches 6 g / m². 2 above.

14. The printing method according to claim 12, wherein, The coating amount of the varnish is 1.5 g / m². 2 .

15. The printing method according to claim 12, wherein, Use colored ink electro-engraving gravure or varnish electro-engraving gravure.

16. The printing method according to claim 15, wherein, The depth of the color ink electro-engraving gravure plate is set to 42-45 micrometers.

17. The printing method according to claim 15, wherein, The depth of the electro-engraved gravure plate is set to 50-52 micrometers.

18. The printing method according to any one of claims 11-17, wherein the printing method comprises the following steps: After printing the ink and drying it in an oven at 65-75℃, print the top coat and dry it at the same 65-75℃.

19. A printed article comprising a substrate and a printing composition according to any one of claims 1-10 applied to said substrate.

20. The printed article of claim 19, wherein the substrate comprises one or more materials selected from polyethylene terephthalate, polyethylene, and polypropylene.

21. The printed article according to claim 19, wherein the substrate comprises a material selected from crystalline polyethylene terephthalate.

22. The printed article of claim 19, wherein the substrate comprises polypropylene.

23. The printed article according to claim 19, wherein the substrate is a polypropylene pearlescent film.

24. The printed article according to claim 19, wherein the substrate has a content of 0.65-0.8 g / cm³. 3 The density.

25. The printed article according to claim 19, wherein the substrate has a thickness of 30-40 micrometers.

26. The printed article according to claim 19, wherein the substrate has a thickness of 38 micrometers.

27. The printed article according to claim 19, wherein the printing surface of the substrate is corona treated.

28. The printed article according to claim 19, wherein the printed surface of the substrate has a surface tension of 38 dyn / cm or more.

29. The printed article according to claim 19, wherein the printed article is a label.

30. A packaging material comprising a container and a printed article as described in any one of claims 19-29.

31. The packaging material according to claim 30, wherein the container is a bottle.

32. The packaging material of claim 30, wherein the container comprises one or more materials selected from high-density polyethylene, polyethylene terephthalate, and polypropylene.

33. Use of the composition for printing according to any one of claims 1-10, the printed article according to any one of claims 19-29, and the packaging material according to any one of claims 30-32 for packaging.

34. The use according to claim 33, wherein the packaging is beverage packaging.

35. A beverage comprising the printed article as described in any one of claims 19-29 or the packaging material as described in any one of claims 30-32.

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