KR20240102114A - Decorating material and method for manufacturing the same - Google Patents

Abstract

This application selects polyurethane dispersion (PUD), the particle size of which is controlled to a specific range, as a material for the adhesion enhancement layer, and provides a method for manufacturing decorative materials and decorative materials with excellent adhesion performance and aesthetics, and when forming a printed layer, A decorative material with excellent printer output and resolution can be provided by using an ink composition that does not contain binder resin.
Additionally, an adhesion enhancement layer coating composition that can be used to form the adhesion enhancement layer can be provided.

Description

Decorating material and method for manufacturing the same}

This application relates to a decorative material with excellent adhesion properties and aesthetics and a method of manufacturing the decorative material.

Recently, as interest in interior design has increased, the demand for decorative materials with excellent design is increasing, and the demand for manufacturing decorative materials using digital printing to realize various and delicate designs is rapidly increasing. The existing digital printing method used a lot of oil-based types, but the use of ink compositions using water-based solvents has recently been increasing. The ink composition is environmentally friendly due to the low risk of VOC (volatile organic compound) emissions, but has a problem in that the decorative material is easily peeled off due to poor adhesion to the substrate. In particular, in the process of manufacturing decorative materials, a transparent layer made of PVC (polyvinyl chloride) or the like is laminated on the printed layer to protect the printed layer. The transparent layer has low adhesion to the printed layer, so it often peels off from the decorative material. Occurs. To solve these problems, research is being conducted to improve adhesion performance by adding adhesive resin to the ink composition. For example, as disclosed in Patent Document 1, a method of adding a binder resin to water-based ink to improve adhesion may be considered. However, when binder resin is included in the ink composition, the longer it is used due to hardening of the resin, the more sludge is generated in the ink reservoir and the viscosity and particle size of the composition increase, making it difficult to jet by the nozzle of the inkjet printer head, and the print head is damaged, causing damage to parts. This may cause replacement.

Therefore, in the industry, there is a demand for the development of various types of film layers that can be laminated on the printing layer to secure the desired adhesion performance, instead of including the binder resin in the ink composition. In addition, even when the film layer is added on the print layer, the transparency of the film layer needs to be high so that the pattern or patterns formed on the print layer are clearly visible. For example, as disclosed in Prior Document 2, it may be considered to introduce an adhesive layer containing an acrylate-based resin on the printing layer.

Patent Document 1: US Patent No. 11401719 Patent Document 2: Korean Patent No. 10-1161369

This application provides a decorative material with excellent printer output and adhesion performance and a method for manufacturing the decorative material.

One purpose of this application is to provide a method of manufacturing a decorative material and decorative material with excellent adhesion performance and aesthetics by selecting polyurethane dispersion (PUD), the particle size of which is controlled to a specific range, as a material for the adhesion enhancement layer.

In addition, one purpose of this application is to provide a decorative material with excellent printer output and resolution by using an ink composition that does not contain a binder resin when forming a printing layer.

Among the physical properties mentioned in this specification, in cases where the measured temperature and/or pressure affects the physical properties, unless specifically stated otherwise, the physical properties refer to the physical properties measured at room temperature and/or pressure.

In this application, the term room temperature refers to a natural temperature that is not heated or reduced, and may mean, for example, any temperature in the range of about 10°C to 30°C, or a temperature of about 25°C or 23°C.

In this application, the term normal pressure refers to pressure when not specifically reduced or increased, and may mean a pressure within the range of about 1 atmosphere, such as ordinary atmospheric pressure, for example, about 740 to 780 mmHg.

Among the physical properties mentioned in this specification, in cases where the measured humidity affects the physical properties, unless otherwise specified, the physical properties refer to the physical properties measured at natural humidity without special adjustment at the measured temperature and pressure. do.

In this specification, the formation of any configuration on or additionally including an arbitrary configuration “on” a substrate means that the arbitrary configuration is formed in contact with the upper surface of the substrate, but also means that the configuration is formed on the substrate. It is interpreted that other configurations can be included between arbitrary configurations.

In this specification, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

In this specification, terms such as “located” between any two components not only mean existing in contact with any two components, but are also interpreted to mean that other components may be included and exist between the two components.

Since the present invention can make various changes and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description.

However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

In this application, “adhesion enhancement layer” refers to a layer formed on the printed layer to improve the adhesion between the base layer and/or the transparent layer.

In this application, “average particle size” means the D50 particle size of the particles according to ISO 13320-1.

In this application, “content” of a specific material means the weight percent of the specific material relative to the total weight of the specific layer.

In the present application, “resin dispersion” means that resin particles are dispersed in an aqueous solvent and/or an organic solvent, and the resin can be interpreted as existing in various forms such as an emulsion or dispersion.

In this application, “solids content” means the weight percent of the solid material remaining when all the moisture in the entire composition is evaporated.

Hereinafter, the decorative material of this application will be described in detail.

The decorative material of this application includes a printing layer; Adhesion enhancing layer; And it may include a transparent layer, and the adhesion enhancement layer may include resin particles having an average particle diameter of 1000 nm or less. The lower limit of the average particle diameter of the resin particles is not particularly limited, and may be, for example, 1 nm or more. In other examples, the ratio is 950 nm or less, 900 nm or less, 850 nm or less, 800 nm or less, 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less. , may be 200 nm or less, 180 nm or less, or 170 nm or less.

Additionally, the adhesion enhancement layer may include ester-based polyurethane resin particles having an average particle diameter of 1000 nm or less. The ester-based polyurethane resin may refer to a polyurethane resin containing an ester group. The adhesion enhancement layer containing polyurethane resin particles having an ester group (hereinafter “ester-based polyurethane resin particles”) having an average particle size in the above range can exhibit the best adhesion strength to the base layer and/or transparent layer, The above results can be confirmed by referring to Table 1 below.

Polyurethane is a type of polymer in which urethane bonds are formed repeatedly in a three-dimensional form, and can be manufactured from polyols containing various functional groups. For example, the polyurethane may include polyurethane having a specific type of functional group, such as ether-based polyurethane, polycarbonate-based polyurethane, or ester-based polyurethane. In this application, as can be confirmed from the experimental results below, it was confirmed that when ester-based polyurethane is used for the purpose of adhesion within a decorative material, the related physical properties can be excellent. The ester group in polyurethane exists mixed with components such as resin, inorganic particles, or pigment particles in the decorative material. The ester group has excellent compatibility with other materials, so the adhesion performance in the decorative material can be improved. It is estimated. Therefore, in the present invention, by using ester-based polyurethane particles as a material for the adhesion enhancement layer, the appearance of the decorative material can be protected and durability improved by securing excellent adhesion without excessively increasing the resin content.

An exemplary structure of the decorative material 10 of the present invention is schematized in FIG. 2.

Referring to FIG. 2, in the decorative material 10 of the present application, the adhesion enhancement layer 300 may be located on the printing layer 400. By positioning the adhesion enhancing layer 300 on the printing layer 400, it can serve to improve the adhesion of the printing layer 400. Additionally, a transparent layer 600 may be located on the adhesion enhancing layer 300. Therefore, in the decorative material of the present application, the laminated structure is a structure in which the printed layer 400, the adhesion enhancement layer 300, and the transparent layer 600 are laminated in that order, or the adhesion enhancement layer 300, the printed layer 400, and the transparent layer. It may be a structure that is stacked in the order of (600). By including the adhesion enhancement layer in the decorative material in the above order, the adhesion with the transparent layer and/or the base layer can be improved. The printing layer 400 and the ink receiving layer 500 adjacent to the adhesion enhancement layer 300 have a substantially thin layer thickness and there are many pores between the layers, so the adhesion enhancement layer 300 Even without direct contact with the transparent layer 600, the adhesion strength between the printed layer and the transparent layer can be sufficiently improved by the adhesion enhancement layer 300.

The decorative material 10 is, for example, laminated in the following order: base layer 100, white layer 200, adhesion enhancing layer 300, printing layer 400, ink receiving layer 500, and transparent layer 600. However, it is not limited to this stacking order, and decorative materials in the form of some components omitted from the above configuration are not excluded.

Meanwhile, in the decorative material of the present application, the printing layer may be formed by drying the ink composition, and the printing layer may include pigment. Pigments included in the printing layer may include all common pigments that can be used in ink compositions in the relevant field, and their type and content are not particularly limited.

For example, the pigment may be an organic pigment or an inorganic pigment, and a pigment of any color may be used. Examples of organic pigments include colorants such as azo-based, phthalocyanine-based, dye-based, condensed polycyclic, quinacridone-based, nitro-based and nitroso-based, black-based carbon black, lamp black, acetylene black and channel black, and inorganic pigments. Pigments may include, for example, metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, and nickel, metal oxides, and sulfides.

The pigment may preferably include one or more of cyan pigment, magenta pigment, yellow pigment, or black pigment. When such pigment is used, the quality of the print layer formed by the ink composition can be printed more clearly.

The pigment included in the ink composition of the present application may exist in the form of a pigment that does not contain a dispersant, or may exist as an aqueous pigment dispersion or an oil-based pigment dispersion in which the pigment is dispersed with a dispersant.

The pigment dispersant is used to improve the dispersibility of the pigment, that is, the storage stability of the ink composition of the present application, and any conventionally used dispersant can be used without particular limitation. Among them, it is preferable to use a polymer dispersant. Examples of such pigment dispersants include carbodiimide-based dispersants, polyesteramine-based dispersants, fatty acid amine-based dispersants, modified polyacrylate-based dispersants, modified polyurethane-based dispersants, multi-chain polymer nonionic dispersants, polymer ion activators, etc. . These pigment dispersants can be used individually or in mixture of two or more types.

The printing layer of the present application may include a binder resin content of 1% by weight or less. In other examples, the ratio may be 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, 0.3 wt% or less, 0.2 wt% or less, 0.1 wt% or less or substantially the binder. It may not contain resin. The content is determined by the content of the binder resin in the ink composition forming the printing layer. The print layer having the content of the binder resin in the above range can save process costs by lengthening the cleaning cycle of the surface of the print head or the replacement cycle of the print head because there is no fear of contaminating the print head during the manufacturing process. Since nozzle clogging rarely occurs, diagonal spraying or nozzle fall-off occurs rarely during the printing process. In addition, the ink composition containing the binder resin in the above range can be used without fear of nozzle clogging even when the nozzle diameter of the print head is small, so it is possible to increase resolution and improve print quality by spraying a small amount of ink composition. You can. In other words, if a printing layer containing little binder resin is introduced as described above, an increase in overall process speed and printing quality can be expected.

In the present application, the type of the binder resin is not particularly limited and includes adhesive resins that can be commonly used in the relevant field. For example, the binder resin may include one or more selected from the group consisting of acrylic resin, polyurethane resin, silicone resin, rubber resin, and vinyl resin.

Meanwhile, in the decorative material of the present application, the ester-based polyurethane resin particles included in the adhesion enhancement layer may have an average particle diameter in the range of 50 nm to 200 nm. In other examples, the ratio is 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, or 190 nm or more, 190 nm or less, 180 nm or less, 170 nm or less, 160 nm or less, 150 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, 80 nm or less, or 60 nm or less It may be nm or less. Additionally, the resin particles included in the adhesion enhancement layer of the present application may have a maximum particle diameter of 300 nm or less. In other examples, the ratio may be 280 nm or less, 260 nm or less, 240 nm or less, 220 nm or less, 200 nm or less, 180 nm or less, 160 nm or less, 140 nm or less, 120 nm or less, or 100 nm or less, The upper limit of the maximum particle size is not particularly limited, and may be, for example, 1 nm or more. In this particle size range, the empty space between the adhesion enhancing layer and the interface of the layer to which it is attached (e.g., base layer or transparent layer) is reduced, and the resin particles can be densely distributed in the layer to be attached to the adjacent layer. The adhesion performance of the liver can be significantly increased. In addition, by controlling the size of the resin particles below a certain range, the transparency of the adhesion promotion layer is maintained at a high level, making it possible to provide a decorative material with excellent visibility of patterns or patterns formed on the printed layer. On the other hand, for example, when the particle size of the resin particles is 1000 nm or more, an empty space is created between the formed adhesion promotion layers, which causes bubbles between the interfaces to be created, or the surface area of the contact surface is reduced, so the adhesion strength decreases. Results may appear. In addition, if the particle size of the resin particles is large, the transparency of the adhesion enhancement layer may decrease, which may cause the clarity and visibility of the pattern or pattern of the printed layer to decrease. Figure 1 below shows the surface of an adhesion enhancement layer (left, Example 1) containing resin particles having an average particle diameter of about 100 nm and a maximum particle diameter of about 300 nm, and an average particle diameter of about 2700 nm and a maximum particle size of about 30 μm. This is an SEM image showing the surface of the adhesion enhancement layer (right, Comparative Example 1) containing resin particles having a particle size. Referring to Figure 1, it can be seen that when the particle size of the resin particles is small, the surface of the adhesion enhancement layer is formed smoothly, and the surface area of the contact surface is large without empty spaces between particles, resulting in improved adhesion. In addition, Figures 3 and 4 below are graphs showing the particle size distribution of the resin particles in Example 1 and Comparative Example 1, respectively, according to the present invention. The average particle diameter and maximum particle diameter values of the resin particles can be confirmed with reference to Figures 3 and 4 below.

Meanwhile, in the decorative material of the present application, the average particle diameter of the resin particles included in the adhesion enhancement layer may be smaller than the thickness of the adhesion enhancement layer. When the average particle diameter of the resin particles and the thickness of the adhesion enhancement layer satisfy the above relationship, several layers of resin particles are closely arranged within the adhesion enhancement layer, and when a compression process is performed after contacting the layer to which the adhesion is to be applied, the resin particles It can be placed between the gaps of layers to be attached, and in particular, due to the excellent compatibility of the ester group present in the polyurethane resin particles, more bonding reactions with adjacent layers can be generated, improving the adhesion between decorative layers. You can contribute. In addition, when the transparent layer in the decoration material is made of PVC, the adhesion may be significantly increased due to the high chemical affinity with the PVC.

Additionally, the thickness of the adhesion enhancement layer in the decorative material of the present application may be in the range of 1 μm to 50 μm. In other examples, the ratio is 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, 6 μm or more, 7 μm or more, 9 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more , can be 30 μm or greater, 35 μm or greater, or 40 μm or greater, or 45 μm or less, 40 μm or less, 35 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, or 5 μm or less. there is. When the adhesion promotion layer having the above thickness range is included in the decorative material, the desired adhesion strength with the layer to which it is attached can be secured, and the thickness range in which the adhesion promotion layer is uniformly coated on the printing layer can be satisfied. .

Meanwhile, in the decorative material of the present application, the transparent layer includes polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polycarbonate film, ethylene vinyl acetate (EVA) film, polyethylene film, polypropylene film, and polyvinyl chloride ( It may be made of one or more selected from the group consisting of PVC) films. However, the material of the transparent layer is not limited to the materials listed above, and the type is not particularly limited as long as it can achieve the purpose of protecting the appearance of the decoration material and improving the durability of the printing layer.

Preferably, in the present invention, the transparent layer may include a PVC film. When the transparent layer includes a PVC film, the adhesion with the adhesion promotion layer containing ester-based polyurethane resin particles may be particularly excellent, so that the purpose While achieving the desired adhesion strength, the exterior of the decorative material can be effectively protected and the durability of the decorative material can be sufficiently strengthened.

Additionally, in the present application, the thickness of the transparent layer may be in the range of 0.1 mm to 5 mm. In other examples, the ratio is 0.3 mm or more, 0.5 mm or more, 0.7 mm or more, 0.9 mm or more, 1.0 mm or more, 1.5 mm or more, 2.0 mm or more, 2.5 mm or more, 3.0 mm or more, 3.5 mm or more, 4.0 mm or more Or it may be 4.5 mm or more, 4.5 mm or less, 4.0 mm or less, 3.5 mm or less, 3.0 mm or less, 2.5 mm or less, 2.0 mm or less, 1.5 mm or less, 1.0 mm or less, or 0.5 mm or less. The transparent layer having a thickness in the above range effectively protects the printing layer, which has weak durability, from external shock or deterioration, and can maintain the pattern or pattern formed on the decorative material clearly for a long time.

Meanwhile, the decorative material of the present application may have a peeling strength of 3.5 kgf/2.0cm or more with respect to the transparent layer of the printed layer. The upper limit of the peel strength is not particularly limited, and for example, if peeling does not occur as a result of peeling through a tensile tester described below, it can be evaluated as “no peeling.” In other examples, the ratio is 3.7 kgf/2.0cm or more, 3.9 kgf/2.0cm or more, 4.0 kgf/2.0cm or more, 4.1 kgf/2.0cm or more, 4.3 kgf/2.0cm or more, 4.5 kgf/2.0cm or more, 5.0 kgf /2.0cm or more, 5.5 kgf/2.0cm or more, 6.0 kgf/2.0cm or more, 7.0 kgf/2.0cm or more, 8.0 kgf/2.0cm or more, 9.0 kgf/2.0cm or more, or 10.0 kgf/2.0cm or more. In the present invention, the peel strength as described above can be achieved by applying an adhesion enhancement layer containing ester-based polyurethane resin particles whose particle size is controlled.

In the present application, for one purpose, an adhesion enhancement layer coating composition that can be used in the production of an adhesion enhancement layer can be provided.

The adhesion enhancement layer coating composition of the present application may include a resin dispersion and a surface control agent. The resin dispersion may use an aqueous solvent and/or an oil-based solvent as a solvent, and may be in the form of a dispersion in which the resin component is dispersed in a solvent or an emulsion in which fine particles are colloidally and stably dispersed. It can be manufactured by dissolving or dispersing the solid resin in a solvent. In addition, the surface control agent is a type of additive that changes the physical and chemical properties of the resin dispersion. It can change the surface tension of the resin component and forms a film surrounding the resin particles to improve the adhesion to the layer to which it is attached. Enhancing effects may occur. In other words, the surface control agent is an additive that can contribute to improving performance such as adhesion by changing the physical properties of the coating composition.

In the present application, the adhesion enhancement layer coating composition includes a resin dispersion; and a surface control agent, wherein the resin dispersion is an ester-based polyurethane dispersion (PUD) whose average particle diameter of the resin particles is in the range of 50 mm to 200 mm, and the content of the surface control agent is in the range of 0.1 to 0.9% by weight. It may be a layer coating composition. In other examples, the ratio of the average particle size range of the resin particles is 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, or 190 nm or more, or 190 nm or less, 180 nm or less, 170 nm or less, 160 nm or less, 150 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, 100 It may be less than 80 nm or less than 60 nm. In addition, in other examples, the surface control agent content ratio is 0.2% by weight or more, 0.3% by weight or more, 0.4% by weight or more, 0.5% by weight or more, 0.6% by weight or more, 0.7% by weight or more, or 0.8% by weight or more, or 0.8% by weight. % or less, 0.7 weight% or less, 0.6 weight% or less, 0.5 weight% or less, 0.4 weight% or less, 0.3 weight% or less, or 0.2 weight% or less. When the adhesion enhancement layer coating composition includes polyurethane dispersion (PUD) and a surface control agent in the above range, the printed layer formed from this coating composition may exhibit excellent adhesion performance to the transparent layer and/or the base layer.

In addition, the adhesion enhancement layer coating composition of the present application may have a solid content of ester-based polyurethane resin in the range of 5 to 30% by weight. In other examples, the ratio is 7% by weight or more, 9% by weight or more, 11% by weight or more, 13% by weight or more, 15% by weight or more, 17% by weight or more, 19% by weight or more, 21% by weight or more, 23% by weight. or more than 25% by weight, more than 27% by weight or more than 29% by weight, or less than 28% by weight, less than 26% by weight, less than 24% by weight, less than 22% by weight, less than 20% by weight, less than 18% by weight, or less than 16% by weight. % or less, 14 weight% or less, 12 weight% or less, 10 weight% or less, 8 weight% or less, 6 weight% or less, or 4 weight% or less. The adhesion enhancement layer coating composition having the above-mentioned resin solid content range can secure the desired adhesion performance and maintain appropriate viscosity so that it can be uniformly coated on the printing layer. If a coating composition exceeding the above range is used, for example, if the content is too low, the desired adhesion performance may not be secured, and if the content is too high, the viscosity will be high, making it difficult to adhere well to the printing layer using the gravure coating method. Application may not occur.

Additionally, the surface control agent may be one or more selected from the group consisting of silicone-based surface control agents, hydrocarbon-based surface control agents, and fluorine-based surface control agents. However, the type of surface control agent is not limited to the range listed above, and the type is not particularly limited as long as it is a material that can improve adhesion by appropriately adjusting the physical properties of the adhesion enhancement layer coating composition. Preferably, the surface control agent may include a hydrocarbon-based surface control agent, and the hydrocarbon-based surface control agent may include an acetylene diol component. In this application, it was confirmed that when a hydrocarbon-based surface control agent containing the above components was used, better adhesion performance occurred when combined with the ester-based polyurethane resin component. The results can be seen in Table 1. According to Table 1, it can be seen that when a hydrocarbon-based surface control agent was used, the peel strength increased by about 0.5 to 0.8 kgf/2.0cm.

The present application may, for one purpose, provide a method of manufacturing the above-described decorative material.

The method of manufacturing a decorative material includes a printed layer and a transparent layer, and includes forming an adhesion-promoting layer on the printed layer, wherein the adhesion-promoting layer includes a resin dispersion; and a surface control agent.

Additionally, the printing layer forming step may include forming the ink composition by spraying an ink composition on one surface of the ink receiving layer through a print head nozzle. In the present application, since the binder resin particles are contained in a trace amount of 1% by weight or less or are substantially not contained in the ink composition, there is little concern that the print head of the inkjet printer will be contaminated even if the ink composition is sprayed using an inkjet method, There is also a low possibility of clogging of the nozzle of the inkjet head or diagonal spraying. Therefore, an inkjet printer with a small nozzle diameter can be used, which makes it possible to provide a decorative material with excellent printing quality and resolution.

Additionally, the average diameter of the resin particles used in the decoration material manufacturing method may be in the range of 50 nm to 200 nm. In other examples, the ratio is 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more. or 190 nm or more, 190 nm or less, 180 nm or less, 170 nm or less, 160 nm or less, 150 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, 80 nm or less, or It may be 60 nm or less. The effects that can be expected by using a coating composition having a resin particle diameter in the above range are the same as those described above.

내지 160

의 온도 조건 및 0.5 Mpa 내지 2.5 Mpa 의 압력 조건에서 약 1 분 내지 30 분간 압착 공정을 수행하는 단계를 더 포함할 수 있다. In addition, the method of manufacturing the decorative material includes forming a transparent layer on the ink receiving layer; and 100 by heating press.

to 160

It may further include performing a compression process for about 1 minute to 30 minutes under temperature conditions and pressure conditions of 0.5 Mpa to 2.5 Mpa.

The step of forming a transparent layer on the ink receiving layer includes contacting one side of the adhesion enhancement layer with one side of the white layer, followed by heat laminating at about 100°C to 150°C for about 20 seconds, forming a base layer on the white layer. It may include the step of laminating.

이상, 130

이상, 140

이상, 150

이상 또는 160

이상이거나, 150

이하, 140

이하, 130

이하, 120

이하, 110

이하 또는 100

이하일 수 있고, 압력 조건은 1.0 Mpa 이상, 1.5 Mpa 이상, 2.0 Mpa 이상 또는 2.5 Mpa 이상이거나, 2.0 Mpa 이하, 1.5 Mpa 이하, 1.0 Mpa 이하 또는 0.5 Mpa 이하일 수 있다. 또한, 압착 시간은 다른 예시에서 5분 이상, 10분 이상, 15분 이상, 20분 이상 또는 25분 이상이거나, 25분 이하, 20분 이하, 15분 이하 또는 10분 이하일 수 있다. 본 출원에서는 장식재 제조 시에, 상기와 같은 온도, 압력 조건에서 압착 공정을 수행하여, 부착증진층의 수지 입자가 투명층 및/또는 기재층 내부에 침투하여 고온/고압 조건에서 상기 층들과 화학적 결합이 강화됨으로써 인쇄층과 투명층 및/또는 기재층 사이에 부착 성능이 우수한 장식재를 완성할 수 있다.In addition, the conditions for performing the pressing process are, in another example, the temperature condition is 120

over 130

Over 140

Over 150

More than or 160

greater than or equal to 150

Below, 140

Below, 130

Below, 120

Hereafter, 110

less than or 100

It may be less than or equal to 1.0 Mpa, more than 1.5 Mpa, more than 2.0 Mpa or more than 2.5 Mpa, or less than 2.0 Mpa, less than 1.5 Mpa, less than 1.0 Mpa or less than 0.5 Mpa. Additionally, the compression time may be 5 minutes or more, 10 minutes or more, 15 minutes or more, 20 minutes or more, or 25 minutes or more, or 25 minutes or less, 20 minutes or less, 15 minutes or less, or 10 minutes or less in other examples. In this application, when manufacturing a decorative material, a compression process is performed under the above temperature and pressure conditions, so that the resin particles of the adhesion enhancement layer penetrate into the transparent layer and/or the base layer and chemically bond with the layers under high temperature/high pressure conditions. By being strengthened, a decorative material with excellent adhesion performance between the printed layer and the transparent layer and/or the base layer can be completed.

This application can provide a decorative material and a method of manufacturing the decorative material with excellent printer output, adhesion performance, and aesthetics.

The present application selects polyurethane dispersion (PUD), the particle size of which is controlled to a specific range, as a material for the adhesion enhancement layer, and provides a method of manufacturing a decorative material and decorative material with excellent adhesion performance and aesthetics, and the printing layer is formed. A decorative material with excellent printer output and resolution can be provided by using an ink composition that does not contain a binder resin.

Figure 1 shows an adhesion-promoting layer containing ester-based polyurethane with an average particle diameter of about 100 nm in Example 1 of the present invention and an adhesion-promoting layer containing ester-based polyurethane with an average particle diameter of about 2670 nm in Comparative Example 1. This is an image taken of the surface of the layer using a scanning electron microscope (SEM).
Figure 2 is a schematic diagram showing the structure of the decorative material of the present invention.
Figure 3 is a graph showing the particle size distribution of resin particles in Example 1 according to the present invention.
Figure 4 is a graph showing the particle size distribution of resin particles in Comparative Example 1 according to the present invention.
Figure 5 is a diagram showing the process of measuring peel strength.

The contents of the present application will be described in detail through examples below, but the scope of the present application is not limited by the examples below.

Example 1 .

Manufacture of adhesion enhancement layer coating composition

An adhesion enhancement layer coating composition used to form the adhesion enhancement layer of the present invention was prepared. An ester-based polyurethane prepolymer was prepared by polymerizing a polyol having an ester group and a compound having an isocyanate group, and water and a dispersant were added to prepare an ester-based polyurethane dispersion (PUD, Polyurethane dispersion) with a solid concentration of about 35% by weight. did. Thereafter, the resin content of the adhesion enhancement layer coating composition was adjusted by adding water to the coating composition and stirring it so that the solid content of the ester-based polyurethane dispersion (PUD, solids concentration 35% by weight) was about 20% by weight. Afterwards, a surface control agent was added in an amount of about 0.5% by weight based on the total weight of the prepared adhesion enhancement layer coating composition and further stirred. As the surface control agent, a hydrocarbon-based surface control agent containing acetylene diol was used, and the coating composition was An adhesion enhancement layer coating composition was obtained by adjusting the amount of dispersant so that the average particle diameter of the included resin particles was about 108 nm.

Decorative material manufacturing

에서 약 3분 간 건조하여 인쇄층을 형성하였다. 상기 인쇄층이 형성된 면에 앞서 제조한 부착증진층 코팅 조성물로 그라비어 코팅 처리하였다. 이후 약 130

에서 약 2분 간 건조하여 두께가 약 20 μm인 부착증진층을 형성하였다. 이후, 상기 부착증진층의 일면을 백색층의 일면에 접촉시키고, 약 130

에서 약 20 초간 열 라미네이팅 처리하여 전사 방식을 통해 전사하였다. 이후, 상기 백색층을 기재층 상에 적층시키고, 상기 캐리어 필름을 제거한 후에 두께가 약 500 μm인 투명층을 적층시켰다. 투명층은 투명한 PVC 필름을 사용하였다. 이후, 열 프레스(heating press)를 사용하여 약 140℃ 의 온도 및 1.5 MPa 의 압력 조건에서 약 10 분간 압착 공정을 수행하여 장식재를 제조하였다.A decorative material including an adhesion enhancement layer formed from the adhesion enhancement layer coating composition was manufactured. A commercially available product (manufactured by LX Hausys) containing PVC (poly(vinyl chloride)) was used as the base layer, a typical PVC white layer was used as the white layer, and the ink receiving layer contained a PVC resin component and a wetting agent. Film was used. First, an ink-receiving layer is formed on a carrier film, and the ink composition is sprayed and printed on one side of the ink-receiving layer through a print head nozzle of an inkjet printer, and then printed at approximately 130° C.

was dried for about 3 minutes to form a printed layer. The surface on which the printing layer was formed was gravure coated with the previously prepared adhesion enhancement layer coating composition. After about 130

was dried for about 2 minutes to form an adhesion enhancing layer with a thickness of about 20 μm. Afterwards, one side of the adhesion enhancing layer is brought into contact with one side of the white layer, and about 130

It was transferred using a transfer method by heat laminating for about 20 seconds. Thereafter, the white layer was laminated on the base layer, and after removing the carrier film, a transparent layer with a thickness of about 500 μm was laminated. The transparent layer used a transparent PVC film. Afterwards, a decorative material was manufactured by performing a pressing process for about 10 minutes at a temperature of about 140°C and a pressure of 1.5 MPa using a heating press.

The average particle diameter of the resin particles present in the adhesion enhancement layer prepared above was approximately 108 nm, and the maximum particle size was measured to be approximately 300 nm.

Example 2.

When preparing the adhesion enhancement layer coating composition, the coating composition and decoration material were prepared in the same manner as in Example 1, except that a silicone-based surface control agent was used as the surface control agent.

Example 3 .

When preparing the adhesion enhancement layer coating composition, the coating composition and decoration material were prepared in the same manner as in Example 1, except that a fluorine-based surface control agent was used as a surface control agent.

Example 4.

The coating composition and decoration material were prepared in the same manner as in Example 1, except that the amount of water was adjusted so that the solids concentration of the resin in the coating composition was about 15% by weight when preparing the adhesion enhancement layer coating composition.

Example 5.

The coating composition and decoration material were prepared in the same manner as in Example 1, except that the amount of water was adjusted so that the solids concentration of the resin in the coating composition was about 10% by weight when preparing the adhesion enhancement layer coating composition.

Example 6.

The coating composition and decoration material were prepared in the same manner as in Example 1, except that the amount of water was adjusted so that the solids concentration of the resin in the coating composition was about 5% by weight when preparing the adhesion enhancement layer coating composition.

Comparative Example 1.

When preparing the adhesion enhancement layer coating composition, the coating composition and decoration material were prepared in the same manner as in Example 1, except that the amount of dispersant was adjusted so that the average particle diameter of the resin particles was 2670 nm.

Comparative Example 2.

When preparing the adhesion enhancement layer coating composition, the coating composition and decoration material were prepared in the same manner as in Example 1, except that ether-based polyurethane was used as the resin composition.

Comparative Example 3.

When preparing the adhesion enhancement layer coating composition, the coating composition and decoration material were prepared in the same manner as in Example 1, except that carbonate-based polyurethane was used as the resin composition.

Comparative Example 4.

When preparing the adhesion enhancement layer coating composition, the coating composition and decoration material were prepared in the same manner as in Example 1, except that an acrylic emulsion was used as the resin composition.

Comparative Example 5.

When preparing the adhesion enhancement layer coating composition, the coating composition and decoration material were prepared in the same manner as in Example 1, except that the resin composition and surface control agent were not added.

Test Example 1. Peel strength evaluation

First, a specimen was manufactured by cutting the decorative material into a rectangular shape with a width of 20 mm and a length of 250 mm. The specimen was then fixed to a tensile tester, peeled at a peeling speed of approximately 200 mm/min and a peeling angle of 180 degrees, and measured by a peel off test in which the load was divided by the width of the specimen. Figure 5 is a diagram showing the process of measuring the peel strength. When fixing the specimen above, the base layer and the printing layer of the decoration material were fixed to the bottom of the device, and the transparent layer of the decoration material was fixed to the top of the device.

INSTRON's 5969 model was used as the tensile tester used in the above process, and a 1kN load cell was used as the load cell.

Using the above method, the peeling strength of the decorative material was measured while peeling the transparent layer from the printed layer.

Test Example 2. Measurement of particle size distribution and average particle size

The particle size distribution and average particle diameter (D50) of the resin particles forming the adhesion enhancing layer of the decorative material were measured using a particle size analyzer (PSA). The particle size distribution of each adhesion enhancing layer (Example 1, Comparative Example 1) prepared by the above-described manufacturing method was measured using a particle size analyzer. Figure 3 is a graph showing the particle size distribution of the resin particles in Example 1, and Figure 4 is a graph showing the particle size distribution of the resin particles in Comparative Example 1. In Example 1, the average particle size (D50) of the particles was measured to be about 107.5 nm, and the maximum particle size was measured to be about 300 nm. In Comparative Example 1, the average particle size (D50) of the particles was approximately 2670 nm, and the maximum particle size was measured to be approximately 30 μm.

Test Example 3. Evaluation of transparency of adhesion enhancement layer

As mentioned above, since the adhesion enhancement layer is formed on the printed layer, transparency of the adhesion enhancement layer is required to maintain visibility of the printed layer. In the decorative material of the present invention, when the visibility of the pattern or pattern of the printed layer is excellent even after forming the adhesion enhancement layer on the printed layer on which a specific pattern or pattern is formed, transparency is indicated as OK, and the formed adhesion enhancement layer allows the printed layer to be If the clarity of the pattern or pattern decreases and visibility deteriorates, it is marked as transparency NG.

Adhesion enhancement layer coating composition Peel strength (kgf/2cm) Adhesion enhancement layer
transparency Composition type Particle average particle size (nm) surface conditioner
(Wetting agent) Resin solids concentration (%) Example 1 Ester-based PUD 108 hydrocarbon system 20 4.54 OK Comparative Example 1 Ester-based PUD 2670 hydrocarbon system 2.26 NG Comparative Example 2 Ethereum PUD 100~150 hydrocarbon system 3.14 OK Comparative Example 3 Carbonate-based PUD hydrocarbon system 2.47 OK Comparative Example 4 Acrylic emulsion hydrocarbon system 2.32 OK Example 2 Ester-based PUD silicone type 3.98 OK Example 3 Ester-based PUD Fluorine type 3.76 OK Comparative Example 5 Unapplied 1.21 OK

Adhesion enhancing coating composition Peel strength (kgf/2cm) Adhesion enhancement layer
transparency Composition type Average particle size (nm) surface conditioner
(Wetting agent) Resin solids concentration (%) Example 1 Ester-based PUD 108 hydrocarbon system 20 4.54 OK Example 4 Ester-based PUD 100~150 15 3.27 OK Example 5 Ester-based PUD 10 2.87 OK Example 6 Ester-based PUD 5 2.14 OK

According to Table 1, it can be seen that more improved peel strength can be secured when polyurethane dispersion (PUD) is applied as a resin component of the adhesion enhancement layer coating composition compared to an acrylic emulsion. That is, compared to Comparative Example 4 using an acrylic emulsion, the peel strength was measured to be high in Example 1, Comparative Example 2, and Comparative Example 3 using polyurethane dispersion (PUD).

Additionally, it can be seen that peel strength varies depending on the type of polyurethane dispersion (PUD). Specifically, comparing Example 1, Comparative Example 2, and Comparative Example 3, when the ester-based polyurethane dispersion (PUD) of Example 1 was used as the resin component, the best peel strength (about 4.54 kgf/2.0cm) was obtained. You can see that it can be secured. In other words, it can be confirmed that the ester-based functional group contained in polyurethane shows the best effect in improving the adhesion with a transparent layer made of PVC, etc.

Meanwhile, even if the same polyurethane dispersion (PUD) is used, adhesion and transparency may vary depending on the size of the resin particles. The adhesion enhancement layer formed of resin particles with an average particle diameter of about 2670 nm has a lower adhesion with the transparent layer. It may be unsuitable as a material for decoration due to decreased transparency. On the other hand, when the average particle diameter of the particles is about 100 nm, not only does it show high adhesion performance, but it also has excellent transparency, which can improve both the durability and aesthetics of the decorative material.

In addition, in this application, peel strength was measured using different types of surface control agents, and among them, the highest peel strength was secured when a hydrocarbon-based surface control agent was used. Additionally, in Examples 1, 4, 5, and 6 of Table 2, the peel strength of the decorative material was evaluated while varying the resin solid concentration in the coating composition. Referring to the above examples, it was confirmed that as the solid concentration increased, the peel strength also increased, and it was found that excellent adhesion strength could be secured when the solid concentration was about 20% by weight. However, as a result of the experiment, there was a problem that if the solid concentration was excessively high, the viscosity of the coating composition became too high, making it difficult to perform gravure coating treatment on the printing layer. Therefore, on the premise that the desired adhesion strength is secured, it would be desirable to manufacture the decorative material with the concentration of the solid content to a minimum.

100: base layer
200: white layer
300: Adhesion enhancement layer
400: Printing layer
500: Ink receiving layer
600: transparent layer

Claims (20)

printed layer; Adhesion enhancing layer; And a transparent layer,
The adhesion enhancement layer is a decorative material comprising ester-based polyurethane resin particles having an average particle diameter of 1000 nm or less. The decorative material according to claim 1, wherein the adhesion enhancing layer is located on the printing layer. 2. The printing layer of claim 1, wherein the printing layer comprises a pigment,
The pigment is a decorative material comprising at least one selected from the group consisting of cyan pigment, magenta pigment, yellow pigment, and black pigment. The decorative material according to claim 1, wherein the printed layer contains a binder resin content of 1% by weight or less. The decorative material according to claim 1, wherein the printed layer contains a binder resin content of 0.1% by weight or less. The decorative material according to claim 4 or 5, wherein the binder resin includes at least one selected from the group consisting of acrylic resin, polyurethane resin, silicone resin, rubber resin, and vinyl resin. The decorative material according to claim 1, wherein the average particle diameter of the resin particles is in the range of 50 nm to 200 nm. The decorative material according to claim 1, wherein the resin particles have a maximum particle diameter of 300 nm or less. The decorative material according to claim 1, wherein the average particle diameter of the resin particles is smaller than the thickness of the adhesion promotion layer. The decorative material according to claim 1, wherein the thickness of the adhesion enhancing layer is in the range of 1 μm to 50 μm. The method of claim 1, wherein the transparent layer is a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polycarbonate film, an ethylene vinyl acetate (EVA) film, a polyethylene film, a polypropylene film, and a polyvinyl chloride (PVC) film. ) A decorative material consisting of one or more selected from the group consisting of films. The decorative material according to claim 1, wherein the thickness of the transparent layer is in the range of 0.1 mm to 5 mm. The decorative material according to claim 1, wherein the peeling strength of the printed layer with respect to the transparent layer is 3.5 kgf/2.0 cm or more. Resin dispersion; and a surface modifier,
The resin dispersion is an ester-based polyurethane dispersion (PUD) whose average particle diameter of resin particles is in the range of 50 mm to 200 mm,
An adhesion enhancement layer coating composition wherein the content of the surface control agent is in the range of 0.1 to 0.9% by weight. The adhesion enhancement layer coating composition according to claim 14, wherein the solid content of the ester-based polyurethane resin is in the range of 5 to 30% by weight. The coating composition for an adhesion enhancement layer according to claim 14, wherein the surface control agent is at least one selected from the group consisting of a silicone-based surface control agent, a hydrocarbon-based surface control agent, and a fluorine-based surface control agent. A method of manufacturing a decorative material comprising a printed layer and a transparent layer,
Comprising the step of forming an adhesion enhancing layer on the printing layer,
The adhesion enhancing layer is a resin dispersion; and an adhesion enhancement layer coating composition comprising a surface control agent,
The resin dispersion is an ester-based polyurethane dispersion (PUD) in which the average particle diameter of the resin particles is smaller than the thickness of the adhesion enhancing layer. The method of claim 17, wherein the printing layer forming step includes forming the ink composition by spraying an ink composition on one surface of the ink receiving layer through a print head nozzle. The method of manufacturing a decorative material according to claim 17, wherein the average particle diameter of the resin particles is in the range of 50 nm to 200 nm. 18. The method of claim 17, further comprising: forming a transparent layer on the ink receiving layer; and
100 by heating press

to 160

A method of manufacturing a decorative material further comprising performing a pressing process for about 1 minute to 30 minutes under temperature conditions and pressure conditions of 0.5 Mpa to 2.5 Mpa.