WO2021071206A1 - Laminate, pattern laminate, decorative material, and method for producing same - Google Patents

Abstract

The present application relates to a laminate for a decorative material, comprising: a base layer (A) having recessed portions and protruding portions; a cured layer (B) formed on the base layer and having recessed portions and protruding portions having the same shapes as those of the base layer. The laminate has excellent reality on the surface thereof, excellent durability, and fouling resistance.

Description

Laminate, pattern laminate, decorative material, and manufacturing method thereof

The present application relates to a decorative laminate and a pattern laminate. Specifically, the present application relates to a decorative material including the laminate or pattern laminate and having a texture similar to a natural material, and a method of manufacturing the same.

Demand for decorative materials with a three-dimensional appearance, especially floor decorative materials, is increasing. Accordingly, the development of decorative materials in which reality close to natural materials such as wood, stone or fabric is implemented is being actively developed. For example, products with so-called tuning embossing characteristics in which the irregularities on the surface of the decorative material and the main pattern of the printing layer included in the decorative material are matched are being released.

Conventional products have been manufactured in such a way that embossing formed in irregularities is applied to a sheet such as PVC (polyvinylchloride), and the surface of the embossed sheet is finished with a UV curing agent. However, there is a limit to realizing a sense of realism close to that of natural materials using only the embossed PVC sheet.

One object of the present application is to provide a decorative material having excellent surface realism so as to be close to natural texture.

Another object of the present application is to provide a decorative material excellent in durability and stain resistance.

Another object of the present application is to provide a laminate and a pattern laminate used to form a decorative material excellent in realism, durability and stain resistance.

Another object of the present application is to provide a flooring material having excellent realism as well as durability and stain resistance.

All of the above and other objects of the present application can be solved by the present application described in detail below.

In one example related to the present application, the present application relates to a patterned laminate. The pattern of the laminate provides the user with a sense of realism close to the natural texture.At least on the surface side of the laminate, specifically, on one side of the layer close to the user's viewing side among two or more layers constituting the laminate. Can be formed.

The patterned laminate according to the present application may be manufactured while applying a pattern to the substrate layer and the cured layer having the configuration or characteristics described below through a predetermined method. Accordingly, compared with the prior art, the patterned laminate of the present application can provide a decorative material having excellent pattern reality. In addition, the patterned laminate may provide durability and stain resistance equivalent to or higher than those of the prior art.

A pattern that provides the user with a sense of realism similar to the natural texture is formed by concave parts and convex parts. That is, the pattern includes a concave portion and a convex portion. Unless otherwise defined, the pattern formed by the concave portion and the convex portion may be mixed with terms such as unevenness or embossing. According to the pattern design, the concave portion and the convex portion can be visually recognized by the user as having a predetermined width. Depending on the shape of the pattern and its height, the concave portion or the convex portion may be called relatively.

Regarding the realism of the pattern, in the case of a conventional product manufactured to realize a natural-like texture, an emboss design is first formed on the substrate layer through a pressure roller, and thereafter, a method of performing a curing agent treatment to protect the emboss design (composition It was prepared by curing after application). In the case of the manufactured product, the surface texture is not luxurious because the curing agent coating the base layer embossing does not sufficiently reflect the embossing of the base layer, and there is a problem that the realism of natural similarity is not sufficiently delivered to the user. The inventor of the present application invented the present application as a result of studying the problems of such conventional products.

Specifically, the inventor of the present application first formed a cured layer on the base layer and then embossed the surface of the laminate (ie, a process for forming surface irregularities) to manufacture a laminate for decorative materials. It focused on the advantage of securing similar texture. Furthermore, in the case of a cured layer formed through curing treatment after the composition is applied on the substrate layer, the problem of being damaged during the pressing/heating process for forming irregularities due to an increase in hardness due to curing (e.g., cured layer Or cracking of the base layer), and the inventor of the present application has come to complete the present invention of the present application that can compensate for such problems.

Hereinafter, the present application will be described in detail with reference to the accompanying drawings. For convenience of explanation of the present application, a process for forming concave portions and convex portions is referred to as embossing. In addition, the base layer and the cured layer before the embossing treatment is performed are referred to as a base layer (A') and a cured layer (B'), respectively, and a base layer and a cured layer having concave portions and convex portions by embossing are formed. They are referred to as a base layer (A) and a cured layer (B), respectively. In addition, in order to distinguish between before and after the embossing treatment, the laminate including the substrate layer (A) and the cured layer (B) in which concave portions and convex portions are formed through embossing is referred to as a pattern laminate, and the substrate layer (A') and When the cured layer (B') is included, it is referred to as a laminated body or a non-patterned laminated body.

The pattern laminate of the present application includes a base layer (A) in which concave portions and convex portions are formed; And a cured layer (B) positioned on the substrate layer and having a concave portion and a convex portion having the same shape as the substrate layer. Specifically, in the present application, a cured layer (B') is first formed on the base layer (A'), and the laminate of the base layer (A') and the cured layer (B') is integrally embossed. Therefore, it is advantageous for the base layer (A) and the cured layer (B) to have concave portions and convex portions of the same shape.

For example, in the case of curing treatment after applying a curing agent (curing composition) to the surface of the'embossed base layer', the cured layer is the base layer in the thickness direction due to the thickness variation of the cured layer as shown in FIG. 1A. There is a problem that the shape of the concave portion and the convex portion is not sufficiently reflected. In particular, in the case of the laminate manufactured according to this method, the cured layer is formed thinly on the convex portion of the base layer, and the cured layer is easily formed thickly on the concave portion of the base layer. It is difficult for the user to feel the realism of the pattern due to the severe thickness deviation of the concave portion and the convex portion.

However, according to the specific example of the present application, when the laminate of the base layer (A') and the cured layer (B') is integrally embossed after forming the cured layer on the base layer, the cured layer is Since the thickness variation in the thickness direction is significantly reduced, the cured layer is also advantageous in having an emboss of the same shape as that of the base layer (see, for example, FIG. 1B). For reference, this difference can also be confirmed through the pattern surface image of Comparative Examples and Examples.

In an example related to the present application, a feature in which the cured layer (B) and the base layer (A) have concave portions and convex portions having the same shape may be expressed as a value related to thickness variation. For example, the cured layer (B) having a concave portion and a convex portion may have a thickness variation within 2 μm. That is, the pattern stack of the present application includes a base layer (A) in which concave portions and convex portions are formed; And a cured layer located on the substrate layer, having a concave portion and a convex portion having the same shape as the substrate layer, and having a thickness deviation (or thickness deviation between the concave portion and the convex portion) of the concave portion and the convex portion within 2 µm. It may be a pattern laminate including (B).

Specifically, the thickness of the cured layer measured toward the user's viewing side from a certain point of the base layer or cured layer that forms the interface between the base layer (A) and the cured layer (B) is different in all areas forming the pattern. It may be within 2 μm. For example, the cured layer (B) may have a thickness variation within 2 μm in all areas of the cured layer including concave portions and convex portions.

The upper limit of the thickness deviation may be, for example, 1.5 µm or less or 1.0 µm or less. Specifically, the upper limit may be, for example, 0.9 µm or less, 0.8 µm or less, 0.7 µm or less, 0.6 µm or less, or 0.5 µm or less. Since the smaller the deviation of the cured layer thickness, the more excellent the realism of the natural texture by the pattern may be, so the lower limit of the thickness deviation is not particularly limited, but the deviation may be substantially 0 μm or closer, for example, It may be 0.01 μm or more or 0.1 μm or more.

For the pattern of the same shape and thickness variation of the base layer (A) and the cured layer (B) described above, reference may be made to FIG. 4B according to a specific example of the present application.

On the other hand, just by performing the embossing treatment after forming the cured layer, the cured layer and the base layer have the same embossing, and the realism of the pattern cannot be improved. Specifically, not only must the cured layer have a characteristic that is rigid enough to protect the pattern of the substrate layer, but in addition, the cured layer is flexible enough not to break even under high temperature and high pressure applied to the surface during embossing. Should have. In other words, in order to improve the realism of the pattern, it is possible to simultaneously satisfy the appropriate level of softness and hardness required for the embossing process performed integrally with the base layer (A') and the cured layer (B'). The cured layer (B, B') or a material forming it (eg, curing agent) must be used.

The cured layer (B, B') or the material (treatment agent) forming the same, having an appropriate level of flexibility and rigidity required for the embossing process according to the present application can be expressed through dynamic viscoelastic properties. The viscoelastic properties may be achieved using a known dynamic mechanical analysis, for example, an Advanced Rheometric Expansion System (ARS) device. The viscoelastic property is the viscoelasticity when dynamic viscoelasticity is measured from -25°C to 125°C at a temperature increase rate in the range of 5 to 10°C/min at a strain in the range of 0.1 to 100%, a frequency in the range of 0.01 to 100 rad/s. It can be a characteristic. Although not particularly limited, a plate of 8 to 25 mmΦ may be used when measuring rheological properties.

In one example, the hardened layers (B, B') may have a tanδ peak value (or a maximum value) of 0.5 or more as determined by dynamic viscoelasticity measurement.

For example, the tanδ peak value may be 0.55 or more, 0.60 or more, or 0.65 or more, and the upper limit thereof may be, for example, 0.80 or less, 0.75 or less, or 0.70 or less. That is, the cured layer (B) and/or the cured layer (B') may satisfy the tanδ peak value. The tanδ peak value means a value obtained by dividing a loss modulus (G") by a dynamic storage modulus (G'). The fact that the cured layer satisfies the tanδ peak value in the above range means that the treatment agent cured after application or the cured layer including the same satisfies the tanδ peak value in the range, and the cured layer has an appropriate level of rigidity and flexibility. .

In one example, the hardened layer (B, B') has a tanδ peak value (or maximum value) of 0.5 or more, as determined by dynamic viscoelasticity measurement, and a glass transition temperature (Tg) defined as a temperature for the peak value. It may be 10 ℃ or less. For example, the glass transition temperature (Tg) may be 5°C or less or 0°C or less, and its lower limit is, for example, -35°C or more, -20°C or more, -15°C or more, -10°C or more, or- It may be 5 ℃ or more. That is, the cured layer (B) and/or the cured layer (B′) may satisfy the tanδ peak value and the glass transition temperature (Tg). That the cured layer satisfies the glass transition temperature in the above range means that the treatment agent cured after application or the cured layer including the same satisfies the glass transition temperature in the above range. Compared with the case where the glass transition temperature is exceeded, according to the present application, even if the embossing process described below is performed, an elongation sufficient to clearly accommodate the emboss without breaking the laminate is secured, and the cured layer is used as the substrate. It can be advantageous to have a state of adhesion to the layer.

In one example, the cured layers (B, B') may have a storage modulus (G') value of 3.0 x 10 ⁶ Pa or less measured at a temperature of 90 °C or higher. That is, the cured layer (B) and/or the cured layer (B') may satisfy the storage modulus (G') value. Specifically, the upper limit of the storage modulus (G') value may be 2.5 x 10 ⁶ Pa or less, 2.0 x 10 ⁶ Pa or less, or 1.5 x 10 ⁶ Pa or less, and the lower limit is, for example, 1.0 x 10 ⁵ Pa or more. , 5.0 x 10 ⁵ Pa or more, 8.0 x 10 ⁵ Pa or more, or 1.0 x 10 ⁶ Pa or more. The fact that the cured layer satisfies the storage modulus in the above range means that the treatment agent cured after application or the cured layer including the same can not only secure the tanδ peak value in the above range, but also have an appropriate hardness at a predetermined temperature. it means. The temperature at which the storage modulus (G') in the above range is measured may be, for example, in the range of 90° C. or more and 140° C. or less, which is in contact with the high-temperature roller on which the pattern is formed during the embossing process according to the present application described below. While the cured layer may have a surface temperature.

In the case of using the curing agent or cured layer having dynamic viscoelastic properties as described above, a cured layer is formed on the base layer as described above with reference to FIG. 1B, and then the base layer (A') and the cured layer (B') Even if embossing is performed as an integral part of the laminate having ), there is no cracking of the cured layer or the base layer, and the cured layer and the base layer may have the same embossing shape.

With respect to the above-described viscoelastic properties, reference may be made to FIG. 2 regarding a result of measuring viscoelasticity according to a specific example of the present application.

Physical properties of the cured layer such as the viscoelastic properties described below may be physical properties after curing for the curing treatment agent of the present application described below, or of the cured layer (B and/or B′) cured after being applied on the substrate layer. It may be a physical property when obtained by collecting a part.

In this regard, unless specifically stated otherwise, the expression “curing” used in connection with forming a cured layer using a curing agent in the present application refers to the treatment agent or composition for forming the cured layer (B') as the base layer (A '), and refers to a treatment of irradiating ultraviolet rays at a level of 250 to 350 mJ/cm ² (eg, about 300 mJ/cm ² ), or subsequently in the range of 90 to 110° C. for several minutes to several tens of minutes. It may mean a treatment including heating (for example, about 5 minutes at about 100°C). Curing layers (B, B') may be formed while the curing treatment agent described below undergoes such a curing process. In other words, the cured layers (B, B') may include or be a cured product of the curing agent as described above in physical properties after curing.

In one example, the base layer (A' and/or A) may have a thickness within a range of 200 to 1,000 μm. For example, the lower limit of the thickness of the base layer may be 250 µm or more, 300 µm or more, 350 µm or more, 450 µm or more, 500 µm or more, or 550 µm or more, and the upper limit is, for example, 900 µm or less, 800 µm Hereinafter, it may be 700 µm or less, 600 µm or less, or 500 µm or less. When the thickness of the substrate layer is less than the above range, there is a problem in that the uneven pattern is not sufficiently engraved on the substrate layer. In addition, when the thickness exceeds the above range, when a laminate manufactured for forming a decorative material is laminated with another configuration, a difference in hardness between the laminated layers may increase and warpage may occur.

In one example, the cured layer (B' and/or B) may have a thickness within a range of 5 to 50 μm. For example, the lower limit of the thickness of the cured layer is 6 µm or more, 7 µm or more, 8 µm or more, 9 µm or more, 10 µm or more, 11 µm or more, 12 µm or more, 13 µm or more, 14 µm or more, or 15 µm or more. I can. And, the upper limit may be, for example, 45 µm or less, 40 µm or less, 35 µm or less, 30 µm or less, 25 µm or less, 20 µm or less, or 15 µm or less. When the thickness of the cured layer is less than the above range, it is difficult for the cured layer and a laminate or decorative material including the cured layer to have sufficient mechanical strength. In addition, when the thickness exceeds the above, there is a problem that the price increases and hardening is difficult.

As described above, the embossing treatment for manufacturing the patterned laminate of the present application is performed integrally with the base layer (A') and the cured layer (B') at the same time. For example, the embossing treatment may be performed by pressing and heating a pattern including a concave portion and a convex portion by a mechanism (eg, a roller) formed on the surface thereof.

In this regard, in order to increase the realism of the pattern to be recognized, a substrate layer having a thickness of at least 200 µm or more, specifically 300 µm or more, 400 µm or more, or 500 µm or more is used so that the uneven pattern can be sufficiently deeply engraved on the base layer. It is desirable. In addition, in order to form a pattern on the substrate layer having the thickness, an embossing treatment at a high temperature is required. For example, the embossing treatment may be performed under a temperature condition of at least 150° C. or higher, specifically, using a roller having a surface temperature of 150° C. or higher.

When a roller is used as a device for embossing, a metal roller may be used for high-temperature embossing. For example, the metal roller may be a SUS roller known as stainless steel. Accordingly, the embossing treatment can be performed at a higher temperature than when using a roller made of a rubber material. In the prior art, embossing was performed at a temperature of about 150° C. or less, specifically about 120 to 150° C. using a rubber roller, but in the case of performing the embossing using a metal roller, a temperature of about 150° C. or higher, eg For example, high-temperature pressurization on the surface of the laminate may be performed at a temperature of 150 to 180°C. Accordingly, a clear pattern can be formed on the substrate layer.

When the embossing is performed at a temperature of 150° C. or higher, the surface of the laminate in contact with the roller may have a temperature of 90° C. or higher. Specifically, the surface of the laminate in contact with the roller may have a temperature of, for example, 150° C. or less or 140° C. or less, and may have a temperature of about 90° C. or more, 95° C. or more, or 100° C. or more. Accordingly, the laminate, in particular, the cured layer and the base layer forming the laminate should have a degree of flexibility to clearly accommodate the pattern of the roller without being broken even by the high-temperature pressure as described above. In this regard, the laminate may include a base layer and a cured layer having excellent elongation at a temperature of at least 90 °C.

In one example, the embossed laminate may include a cured layer (B') having an elongation of 20% or more at a temperature of 90° C. or more. That is, the patterned laminate may include a base layer (A'); And a cured layer (B') formed on the base layer and having an elongation of 20% or more at a temperature of 90° C. or higher. In the present application, the elongation of 20% or more means that, for example, when the hardened layer is stretched in a predetermined direction (if pulled), the hardened layer can be increased by at least 20% of its original size. At this time, the elongation is when the lengthwise direction or the width direction and the tensile direction of the cured layer having a predetermined size (e.g., length X width) (however, the length is greater than the width) are matched in the normal direction to the surface of the laminate. It can be elongation.

The lower limit of the elongation may be, for example, 25% or 30%, and the upper limit may be, for example, 50% or less, 40% or less, or 30% or less. When the elongation of the cured layer B′ is less than the above range, the cured layer B′ may be broken during embossing. In addition, when the flexibility is too large, such as when the elongation exceeds 50%, the cured structure of the cured layer is not dense, and contamination resistance, chemical resistance, and durability may be poor.

In the present application, the elongation is 100 mm/min for the substrate layer (A, A'), the cured layer (B, B'), the laminated body or the patterned laminate cut in a dogbone shape at a predetermined temperature as in the following experimental example. It may be measured while stretching at a speed. At this time, each thickness of the base layer and the cured layer may be in the same range as described above. In addition, the thickness of the laminate and the pattern laminate depends on the thickness of the base layer and the cured layer.

In one example, the base layer (A') may have a higher elongation at a temperature of 90° C. or higher than that of the cured layer (B'). For example, the base layer (A') may have an elongation of 20% or more, 30% or more, 40% or more, 50% or more, and, for example, 100% or more at a temperature of 90°C or more. Specifically, the elongation of the base layer (A') may be 200% or more, 300% or more, 400% or more, 500% or more, 600% or more, 700% or more, 800% or more, 900% or more, or 1,000% or more, and , May be greater than or equal to 1,500%, or greater than or equal to 2,000%. When the elongation of the base layer A'is less than the above range, it may be difficult to form a pattern due to insufficient flexibility. Although not particularly limited, the lower limit of the elongation of the base layer (A') may be, for example, 3,000% or less, 2,500% or less, or 2,000% or less.

In one example, the cured layer (B′) formed on the base layer (A′) using the curing agent may satisfy 70% or less of the curing degree defined by the following [Equation 1]. That is, the formation of the cured layer (B'), specifically, curing of the curing agent may be performed at a level that satisfies the degree of curing specified by the following [Equation 1] of 70% or less.

[Equation 1]

Hardness (%) = {1-(Wi-Wf)/Wi} X 100

In Equation 1, Wi refers to the weight of the sample obtained by cutting the cured sample into a certain size before immersing it in the solvent, and Wf is the sample left after immersing the sample in a solvent and leaving it for a certain period of time, followed by filtering using a strainer. Means the weight of.

For example, the cured layer (B') may have a degree of curing calculated by Equation 1 of 70% or less, 65% or less, 60% or less, 55% or less, or 50% or less. In addition, the degree of curing may be 45% or more, 50% or more, 55% or more, 60% or more, or 65% or more. When the curing degree of the cured layer B'is larger than the above range, it is difficult to secure flexibility, and when it is less than the above range, the hardness is insufficient.

The solvent for measuring the degree of curing according to Formula 1 is not particularly limited, but may be, for example, an alkyl acetate solvent, a ketone solvent, an aromatic solvent, a halocarbon oil solvent, or the like. For the calculation of Equation 1, the period in which the specimen is immersed in a solvent and left to stand is not particularly limited, and may be, for example, several hours or more, several days or more, or 1 day (24 hours) to 7 days.

As described above, in the present application, embossing is performed after forming the cured layer (B') having excellent elongation properties. The embossing treatment as described above increases the density of the cured layer (B') formed by curing. Specifically, a cured layer (B) in which a pattern having a physical/chemical crosslinking degree higher than that of the cured layer (B′) may be provided through high temperature/pressure embossing treatment on the cured layer (B′) already formed. Due to the hardened layer (B), which has a higher degree of density after embossing, the patterned laminate increases mechanical strength and durability, and reduces the possibility of contaminants penetrating into the hardened tissue. have.

The description of the patterned cured layer (B) in which the degree of physical/chemical crosslinking was higher than that of the cured layer (B′) through the embossing treatment was confirmed through Experimental Example 2 below. For example, the degree of curing that can be compared by the fluorescence intensity is lowered after the embossing treatment, and the elongation of the cured layer B'may also decrease by 5% or more or 10% or more.

The material for forming the base layer (A') and the cured layer (B') is not particularly limited as long as the above-described properties can be satisfied.

In one example, the base layer (A') is a polyvinylchloride (PVC) film, a polylactic acid (PLA) film, a styrene film, a stryen/butadiene/styrene (SBS) film, or a Styrene Ethylene/Butylene Styrene (SEBS) film. ) It may include a film.

The cured layers (B, B') may be or may include a cured product of a curing agent containing a predetermined component.

In one example, the curing agent includes polyurethane (meth) acrylate and a reactive monomer. For convenience, polyurethane (meta) acrylate is referred to as polyurethane acrylate, and components of the curing agent are indicated by polyurethane acrylate component (A) and reactive monomer component (B), respectively.

Polyurethane acrylate component (A) is a component that contributes to the cured layer (B and/or B') having the aforementioned flexibility (e.g., elongation), and has a weight average molecular weight (Mw) of 10,000 or more. I can. Specifically, the lower limit of the weight average molecular weight of the polyurethane acrylate may be, for example, 11,000 or more, 12,000 or more, 13,000 or more, 14,000 or more, 15,000 or more, 16,000 or more, 17,000 or more, 18,000 or more, 19,000 or more, or 20,000 or more. . In addition, the upper limit of the weight average molecular weight of the polyurethane acrylate may be, for example, 30,000 or less, 29,000 or less, 28,000 or less, 27,000 or less, 26,000 or less, 25,000 or less, 24,000 or less, 23,000 or less, 22,000 or less, 21,000 or less, or 20,000 or less. have. The weight average molecular weight is measured by GPC and may be a value converted by standard styrene.

As long as the weight average molecular weight is satisfied, the specific type or structure of the polyurethane acrylate component is not particularly limited.

In one example, the curing agent may include two or more polyurethane acrylates having different weight average molecular weights. For example, the polyurethane acrylate component (A) is a first polyurethane acrylate (A1) having a weight average molecular weight (Mw) of 10,000 or more and less than 15,000 and a second polyurethane having a weight average molecular weight (Mw) of 15,000 or more and 30,000 or less. It may contain acrylate (A2). Specifically, the weight average molecular weight (Mw) of the first polyurethane acrylate (A1) may be 14,000 or less, 13,500 or less, 13,000 or less, 12,500 or less, 12,000 or less, 11,500 or less, or 11,000 or less. In addition, the weight average molecular weight (Mw) of the second polyurethane acrylate (A2) may be 16,000 or more, 17,000 or more, 18,000 or more, 19,000 or more, or 20,000 or more, and 25,000 or less, 24,000 or less, 23,000 or less, 22,000 or less, 21,000 or less , 20,000 or less, 19,000 or less, 18,000 or less, or 17,000 or less. When the first polyurethane acrylate (A1) and the second polyurethane acrylate (A2) are used together, it is advantageous to provide a cured layer having both flexibility and rigidity suitable for the present application.

In the polyurethane acrylate component (A), the content (weight ratio) between the first polyurethane acrylate (A1) and the second polyurethane acrylate (A2) may be appropriately adjusted to satisfy the characteristics of the cured layer described above. .

In one example, the content of the first polyurethane acrylate (A1) in the polyurethane acrylate component (A) may be equal to or greater than the content of the second polyurethane acrylate (A2). For example, based on the total content of the polyurethane acrylate component (A) (100 parts by weight), 50 to 90 parts by weight of the first polyurethane acrylate (A1) and 10 to 50 parts by weight of the second polyurethane acrylate (A2) Additional can be used. Specifically, the content of the first polyurethane acrylate (A1) within the above range is, for example, 55 parts by weight or more, 60 parts by weight or more, 65 parts by weight or more, 70 parts by weight or more, 65 parts by weight or more, 70 parts by weight Or more, or 75 parts by weight or more, and may be 85 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, or 65 parts by weight or less. The content of the second polyurethane acrylate (A2) may be appropriately adjusted according to the content of the first polyurethane acrylate (A1) to be used.

In another example, the content of the second polyurethane acrylate (A2) in the polyurethane acrylate component (A) may be equal to or greater than the content of the first polyurethane acrylate (A1). For example, based on the total content of the polyurethane acrylate component (A) (100 parts by weight), 50 to 90 parts by weight of the second polyurethane acrylate (A2) and 10 to 50 parts by weight of the first polyurethane acrylate (A1) Additional can be used. Specifically, the content of the second polyurethane acrylate (A2) within the above range is, for example, 55 parts by weight or more, 60 parts by weight or more, 65 parts by weight or more, 70 parts by weight or more, 65 parts by weight or more, 70 parts by weight Or more, or 75 parts by weight or more, and may be 85 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, or 65 parts by weight or less. The content of the first polyurethane acrylate (A2) may be appropriately adjusted according to the content of the second polyurethane acrylate (A1) to be used.

The reactive monomer component (B) refers to a monomer component containing a curable functional group, and its specific type is not particularly limited. For example, the reactive monomer component may be a monomer having a double bond between carbons as a polymerizable functional group.

In one example, the reactive monomer component (B) may be a monofunctional monomer having one curable functional group. In another example, the reactive monomer component (B) may be a functional monomer having two or more curable functional groups.

In one example, the reactive monomer component (B) may be a (meth)acrylate-based monomer.

In one example, the curing agent may include a reactive monomer component (B) in the range of 40 to 80 parts by weight based on 100 parts by weight of the polyurethane acrylate component (A). If the above range is satisfied, flexibility and rigidity suitable for achieving the technical task of the present application can be secured.

In one example, the reactive monomer component (B) may include a reactive monomer (B1) having a glass transition temperature (Tg) of 0° C. or less of the homopolymer. Reactive monomers with a glass transition temperature of 0 ℃ or less of the homopolymer impart flexibility to the cured layer (B') to more effectively prevent cracking of the base layer (A') or the cured layer (B') during the embossing process by high temperature pressurization. Can be prevented. The glass transition temperature (Tg) at this time may be confirmed by a differential scanning calorimetry (DSC) method. For example, while the sample is heated at a heating rate of 10° C./min under a nitrogen atmosphere, it can be confirmed by checking the temperature at which the base line of the obtained DSC curve and the tangent line at the inflection point intersect.

As long as the glass transition temperature (Tg) of the homopolymer satisfies 0° C. or less, the specific type of the reactive monomer component is not particularly limited. For example, caprolactone acrylate (CA), lauryl acrylate (LA), isodecyl acrylate (IDA), tetrahydrofuryl acrylate (THFA), or alkyl An acrylate having a renoxide unit can be used. The alkylene oxide may be, for example, ethylene oxide (EO, ethylene oxide) or propylene oxide (PO, propylene oxide), and as an acrylate having such an alkylene oxide unit, for example, PHEA-2 (phenol ( EO) ₂ acrylate), PHEA-4(phenol (EO) ₄ acrylate), NP(EO) ₄ A(nonyl phenol (EO) ₄ acrylate), NP(EO) ₈ A(nonyl phenol (EO) ₈ acrylate), EOEOEA (ethoxy ethoxy ethyl acrylate), or NP(PO) ₂ A (nonyl phenol (PO) ₂ acrylate) may be used.

In one example, an acrylate having an aromatic ring may be used as the reactive monomer (B1) having a glass transition temperature (Tg) of 0° C. or less of the homopolymer. For example, the reactive monomer (B1) having a glass transition temperature (Tg) of 0 °C or less of the homopolymer is at least PHEA-2 (phenol (EO) ₂ acrylate), PHEA-4 (phenol (EO) ₄ acrylate), NP ( EO) ₄ A (nonyl phenol (EO) ₄ acrylate), NP(EO) ₈ A (nonyl phenol (EO) ₈ acrylate), or NP(PO) ₂ A (nonyl phenol (PO) ₂ acrylate) have. When a monomer having an aromatic ring is used as one component of the reactive monomer, there is an advantage of suppressing an unpleasant odor that may occur in a product.

In one example, based on the total content (100 parts by weight) of the reactive monomer component (B), the content of the reactive monomer (B1) having a glass transition temperature (Tg) of 0 °C or less of the homopolymer is 10 parts by weight to 100 parts by weight. It can be a minor range. More specifically, the lower limit of the content of the reactive monomer (B1) having a glass transition temperature (Tg) of 0° C. or less within the above range is, for example, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, 50 parts by weight or more, 55 parts by weight or more, 60 parts by weight or more, 65 parts by weight or more, 70 parts by weight or more, 75 parts by weight or more, It may be 80 parts by weight or more, 85 parts by weight or more, or 90 parts by weight or more, and its upper limit is, for example, 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, 70 It may be less than or equal to 65 parts by weight, or less than or equal to 60 parts by weight. When the content range is satisfied, it is advantageous in imparting to the cured layer the hardness and flexibility suitable for achieving the technical problem of the present application.

In one example, the reactive monomer component (B) may further include a reactive monomer (B2) having a functional group such as a hydroxy group or an amide group. Specifically, the monomer (B2) having a functional group such as a hydroxy group or an amide group may be a (meth)acrylic monomer having a functional group such as a hydroxy group or an amide group.

In another example, the monomer (B2) may be a monofunctional (meta) acrylic monomer.

Although not particularly limited, examples of the monofunctional (meth) acrylic monomer containing a hydroxy group include hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, and hydroxy butyl (meth) acrylate. Roxyalkyl(meth)acrylate can be used.

The specific type of the monofunctional (meth) acrylic monomer containing an amide group is also not particularly limited, but, for example, (meth)acrylamide, alkyl (meth)acrylamide, dialkyl (meth)acrylamide, or hydroxyalkyl (meth) ) Acrylamide and the like may be used. Specifically, methacrylamide, dimethyl acrylamide, 2-hydroxy propyl methacrylamide, or N-isopropyl acrylamide may be used, but is not limited thereto.

As described above, when the reactive monomer component (B) further contains a reactive monomer (B2) having a functional group such as a hydroxy group or an amide group in addition to the reactive monomer (B1) having a glass transition temperature (Tg) of 0° C. or less of the homopolymer, The content of the monomer (B2) component having a functional group such as a hydroxy group or an amide group may be appropriately adjusted according to the content of the reactive monomer (B1) having a glass transition temperature (Tg) of 0° C. or less of the homopolymer described above. For example, based on the total content (100 parts by weight) of the reactive monomer component (B), the content of the monomer (B2) component having a functional group such as a hydroxy group or an amide group may range from 0 to 90 parts by weight.

The curing treatment agent may include an initiator component (C). The initiator may be appropriately selected from known materials or commercially available products, but when considering the change in the degree of curing through the measurement of fluorescence intensity measured in the following experimental examples, since it has an aromatic ring such as benzene or a unit derived from it, it may emit fluorescence after curing. Initiators that become capable of being used can be used.

In one example, the curing agent may include the initiator component (C) in a range of 1 to 20 parts by weight based on 100 parts by weight of the polyurethane acrylate component (A).

The curing agent may include a curing agent component (D). Specifically, a curing agent component having a number of functional groups of 2 or more may be used so that the curing agent for securing flexibility can secure even strength.

In one example, as the curing agent component (D), a polyfunctional (meth)acrylate having a number of functional groups of 2 or more may be used. As such a curing agent component (D), cyclohexane dimethanol di(meth)acrylate, hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, triethylene glycol di(meth)acrylate, Bifunctional (meth)acrylates such as tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and the like; Trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propylated trimethylolpropane tri(meth) ) Trifunctional (meth)acrylates such as acrylate, glycerylpropylated tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, etc.; Tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; 5-functional (meth)acrylates such as dipentaerythritol penta (meth)acrylate and dipentaerythritol hydroxypenta (meth)acrylate; 6-functional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate may be used.

In one example, the curing agent component (D) may include at least trifunctional (meth)acrylate. It is advantageous for securing strength when using a curing agent component with three or more functionalities. Specifically, the curing agent component (D) may include 3 to 6 functionality, 3 to 5 functionality, or 3 to 4 functionality (meth)acrylate.

In one example, the curing agent may include a curing agent component (D) in the range of 10 to 45 parts by weight based on 100 parts by weight of the polyurethane acrylate component (A). When the above range is satisfied, it is advantageous in securing rigidity without compromising the flexibility appropriate for achieving the technical task of the present application.

In one example, the curing agent having the component may have a viscosity in the range of 300 to 800 cps. When it has the above viscosity, coating processability is excellent. Specifically, since the polyurethane acrylate component (A) has a higher molecular weight than other components forming the curing agent, the viscosity may be high.In consideration of this, components such as (B), (C) and (D) are appropriate. By mixing in an amount, the viscosity of the treatment agent can be lowered and coating processability can be secured.

In another example related to the present application, the present application relates to a decorative material. The decorative material includes a patterned laminate of the characteristics or configurations described above. Detailed description of the patterned laminate will be omitted.

The decorative material may be a film having a tuned pattern. Specifically, the decorative material may further include, on the lower surface of the substrate layer, a printed layer with a tuning pattern having the same or substantially similar shape as the main pattern formed by the concave portions and the convex portions of the pattern stack. In this case, the lower surface of the base layer may mean one surface opposite to the surface of the base layer in contact with the cured layer (B') close to the user viewing side in the patterned laminate.

The printing layer may be a white sheet, specifically a white vinyl chloride resin sheet. The printing method is not particularly limited, and, for example, gravure printing or transfer printing may be used.

The print layer may have a thickness of about 1 μm to about 10 μm, but is not limited thereto.

In one example, the decorative material may further include a transparent layer. The transparent layer is a layer capable of protecting the print pattern of the printing layer. The transparent layer may be a cured product such as a binder resin. When a transparent layer is used, the decorative material may include a pattern laminate, a transparent layer, and a printing layer from the user viewing side.

The transparent layer may have a thickness of about 0.05mm to about 2.0mm, but is not limited thereto.

In one example, the decorative material may further include a dimension reinforcing layer. The dimensional reinforcing layer may provide excellent dimensional stability by reducing the dimensional strain of the decorative material even under high temperature and high humidity conditions, and at the same time, increase the durability of the film by increasing adhesion with other layers to be laminated together.

The dimension reinforcing layer may be formed of a composite material in which a filler or the like is impregnated with a binder resin. The kind of binder resin is not particularly limited. As the filler, for example, TiO ₂ , CaCO ₃ , wood flour, mica, glass fiber, starch, natural fiber, rice husk, rosin or talc, etc. may be used, preferably glass Fibers can be used. Although not particularly limited, the dimensional reinforcing layer may be a layer formed by impregnating a glass fiber sheet prepared by appropriately mixing glass fiber and pulp with a binder with a vinyl chloride sol, followed by gelling.

When the dimension reinforcing layer is used, the decorative material may include a pattern laminate, a printing layer, and a dimension reinforcing layer in an order close to the user's viewing side.

The thickness of the dimension reinforcing layer may range from about 0.1 mm to about 2.0 mm, but is not limited thereto.

In one example, the decorative material may further include a base layer. The base layer may serve to support other layer configurations and absorb shocks from the top or bottom.

The base layer may include a binder resin. The type of resin used to form the base layer is not particularly limited.

When the base layer is used, the decorative material may include a pattern laminate, a printing layer, and a base layer in an order close to the user's viewing side.

The thickness of the base layer may be about 1.0 mm to about 3.0 mm, but is not limited thereto.

In one example, the decorative material may further include a balance layer. The balance layer is a part that is bonded to the floor surface during construction, and functions to protect the decorative material from the external environment.

The balance layer may be formed by curing a binder resin. The kind of resin used to form the balance layer is not particularly limited. As the filler, for example, TiO ₂ , CaCO ₃ , wood flour, mica, glass fiber, starch, natural fiber, rice husk, rosin or talc, and the like may be used.

When the balance layer is used, the decorative material may include a pattern laminate, a printing layer, and a balance layer in an order close to the user's viewing side.

The balance layer may have a thickness of about 1.0mm to about 3.0mm, but is not limited thereto.

In one example, the decorative material of the above configuration may be used as a flooring material.

In another example related to the present application, the present application relates to a laminate used to manufacture the pattern laminate or the decorative material. The laminate includes a base layer (A') and a cured layer (B'). Specific properties and configurations of the laminate, the base layer (A'), and the cured layer (B') are as described above.

In another example of the present application, the present application relates to a curing agent that can be used to form the cured layer (B') of the laminate or the cured layer (B) of the patterned laminate. Description of the components contained in the curing agent is the same as described above, and thus will be omitted.

In another example related to the present application, the present application relates to a method of manufacturing a patterned laminate.

In one example, the method includes: preparing a laminate including a base layer (A') and a cured layer (B') in sequence; And forming concave portions and convex portions having the same shape in the base layer (A') and the cured layer (B') by pressing the surface of the cured layer (B') at a temperature of 150° C. or higher. The configuration and characteristics of the base layer (A') and the cured layer (B') are the same as described above, and thus are omitted.

The pressing may be performed using a pattern forming apparatus having a temperature of 150° C. or higher. As described above, the roller may be a metal roller. Further, the substrate layer (A') and the cured layer (B') having concave portions and convex portions by pressing may be referred to as a substrate layer (A) and a cured layer (B), respectively.

In one example, pressing of the pattern forming mechanism may be performed such that a difference in fluorescence intensity before and after pressing may be 50 or more. Fluorescence intensity is a value measured by focusing on the change of a photopolymerization initiator into a substance that emits fluorescence while reacting with other components of the treatment agent, as described in the following experimental examples. UV excitation light is irradiated to the cured product and then in the cured layer. Emission can be measured in a way that detects fluorescence. The measurement can be made using the UV curing sensor OL series (Sentech Co., Ltd.). The difference in fluorescence intensity may be 150 or less or 100 or less.

The measurement of fluorescence intensity can be used as a means of comparing the degree of curing before and after pressing. It can be seen that the lower the fluorescence intensity, the higher the degree of curing. For example, the fluorescence intensity of the cured layer (B') in the range of 300 to 600 may be measured in the range of 250 to 550 through pressurization by the pattern forming mechanism. That is, the cured layer (B) may have a higher degree of curing through the embossing treatment by high temperature/high pressure. The cured layer (B) having a dense structure by increasing the degree of curing after the embossing treatment may have higher durability, stain resistance and strength characteristics.

In one example, the method may further include forming a cured layer (B') on the base layer (A'). The cured layer may be formed by applying and curing the curing agent having the above-described configuration. The degree of curing and curing conditions are also the same as described above.

According to the present application, there is provided a laminate having excellent surface reality and excellent durability and stain resistance, and a decorative material (eg, flooring) including the same.

1 is a schematic diagram for comparing the uneven cross-section of the decorative material manufactured according to the prior art and the decorative material manufactured according to the present application. Specifically, FIG. 1 (a) is a schematic diagram of a cross-section of a pattern stacked body in which embossing is formed according to the prior art, and FIG. 1 (b) is a schematic diagram of a cross-section of a pattern stacked body in which embossing is formed according to the present application.

2 is a measurement of viscoelastic properties of the cured layer (B') of Example 1 according to a specific example of the present application.

3 is a comparison of images taken with microscopes of 50 magnification and 100 magnification of the surface of the laminate manufactured according to Comparative Example 1 and Example 1. FIG.

4 is a check of the thickness of the cured layer in the laminates prepared according to Comparative Example 1 and Example 1. Specifically, comparing 4a of Comparative Example 1 and FIG. 4B of Example 1, it can be seen that Example 1 significantly improved the large thickness deviation in the convex and concave portions that Comparative Example 1 shows. .

5 schematically shows a laminated configuration of a decorative material according to an example of the present application.

Hereinafter, the present application will be described in detail using an experimental example. However, the scope of protection of the present application is not limited by the experimental examples described below.

<Experimental Example 1: Comparison of cross-sectional shape>

Example 1

Step 1 (Formation of a cured layer) : A curing system in which a length of 1 M in the moving direction is divided into one zone was used. Specifically, a curing agent of the following composition was applied on one side of the PVC substrate layer (A') having a thickness of about 500 µm located in a line moving at a speed of 6 M/min, and irradiated with UV light of 300 mj/cm 2 to increase the thickness. A cured layer (B') of about 13 μm was formed. The components of the curing agent are shown in Table 1.

Step 2 ( embossing ) : Thereafter, using a heating drum (SUS drum) having a predetermined pattern, one side opposite to the side of the cured layer (B') in contact with the base layer (A') is pressed, A patterned laminate was formed. The high temperature pressurization conditions related to the embossing treatment were maintained at the levels shown in Table 2.

Comparative Example 1

The same curing system and the same pattern formation process as in Example 1 were used, and the same curing treatment agent and the same base layer (A') were used. However, in Comparative Example 1, the embossing treatment was first performed on the base layer (A'), and a cured layer was formed on the base layer (A) on which the pattern was formed.

[Table 1]

[Table 2]

In Example 1 and Comparative Example 1, the visually recognized surface shape of the patterned laminate is as shown in FIG. 3. As can be seen from the drawings, it can be seen that more vivid irregularities were formed on the surface of the laminate of Example 1, and a significantly smaller thickness deviation was observed in the cured layer of Example 1.

For reference, the reference example shown in FIG. 2 is an image showing that the embossing process of step 2 is performed without forming a UV coating on the base layer (A') used in the examples and comparative examples. That is, the reference example in which the pattern is formed through direct embossing on the substrate and the example 1 having a small difference in appearance means that a desired pattern (design) can be realized with a sense of realism.

<Experimental Example 2: Confirmation of Strength Increase>

The embossing treatment after the formation of the cured layer (B') (UV treatment after application of the treatment agent) increases the strength of the cured layer (B) having concave portions and convex portions, and as a result, the surface properties of the patterned laminate, for example, mechanical strength. An experiment was conducted to confirm that it can be higher.

Specifically, in the process of manufacturing the laminate of Example 1, the fluorescence hardness and high-temperature elongation of the cured layer (B') were measured before step 2 (before embossing, that is, when the cured layer was formed through step 1). I did. In addition, after performing step 2 (after embossing), the fluorescence hardness and high-temperature elongation of the cured layer (B) were measured. The results are shown in Table 3. At this time, the thickness of the laminate or pattern laminate in which the corresponding experiment was performed was about 500 µm and about 300 µm, respectively.

* Fluorescence intensity (Comparison of change in curing degree): When the treatment agent is cured, the photopolymerization initiator reacts with other components of the treatment agent and changes into a substance that emits fluorescence, and UV excitation light is irradiated to detect fluorescence emitted from the cured layer. In this way, the change in the degree of curing was confirmed. Specifically, a device sold under the name "UV curing sensor OL series (Sentech Co., Ltd.)" was used. The operating principle of the device can be found in Japanese Patent Publication No. 2007-248244, and detailed information on the device can be found on the web page http://www.sentech.jp/seihin/seihin02.html or http://www. Available at .sentech.jp/images/uvkoukasennsa-katarogu2.pdf . For reference, the lower the fluorescence intensity, the more curing was performed.

* 90 °C elongation: The pattern laminate cut in the form of a dogbone was stored in a chamber at 90 °C, and measured while stretching at a rate of 100 mm/min. At this time, the total length of the dogbone shape was 10 cm, and the length and width of the elongation measurement excluding the handle were about 6 cm and 1 cm, respectively.

[Table 3]

As shown in Table 3, it can be seen that the fluorescence intensity measured after step 2 is lower than that before step 2 is performed, and the elongation measured after step 2 is also lower than that before step 2 is performed.

This is because the surface of the cured layer (B') undergoes additional chemical crosslinking and/or physical crosslinking through high-temperature/pressurization embossing on the cured layer (B'), so that the cured layer (B) is a cured layer before embossing. (B') It means that it can have a finer surface property. This contributes to further enhancing the surface properties of the patterned laminate, such as durability and stain resistance.

<Experimental Example 3: Comparison of physical properties of patterned laminates>

A pattern laminate of Example 2 was manufactured through the same process as in Example 1 (steps 1 and 2), except that the components of the curing treatment agent were different as shown in Table 4 below. In the case of Comparative Examples 2 and 3, the components of the treatment agent were different from those of the Examples as shown in Table 4. The method of measuring physical properties is as follows, and the results are shown in Table 5.

* High-temperature elongation: In the same manner as in Experimental Example 2, the cured layer (B') was measured.

* Clear function: Contamination was formed on the surface of the hardened layer (B) with oily magic, removed with a tissue paper after 30 seconds, and then visually determined according to the following criteria. If it is 3 or more, it can be considered excellent.

1 point: removed

2 points: traces and smears

3 points: No smearing, but traces remain

4 points: a few traces remain

5 points: completely removed

[Table 4]

[Table 5]

As shown in Table 5, it can be seen that Comparative Examples 2 and 3, which do not satisfy the high-temperature elongation, are unsuitable for embossing by high-temperature pressurization.

[Explanation of code]

A: a base layer having a concave portion and a convex portion

B: Hardened layer having concave portions and convex portions

100, 100', 1000, 1000': flooring

110, 1100: pattern laminate

120, 1200: transparent layer

130, 1300: printed layer

140, 1400: base layer

150, 1500: balance layer

160, 1600: dimensionally stable layer

Claims (15)

1. A base layer (A) in which concave portions and convex portions are formed; And

   A pattern laminate comprising a cured layer (B) positioned on the substrate layer, having a concave portion and a convex portion having the same shape as that of the substrate layer, and having a thickness deviation of the concave portion and the convex portion within 2 μm.
2. The method of claim 1, further comprising: a base layer (A'); And a pattern forming mechanism having a temperature of 150° C. or higher to a laminate comprising a cured layer (B') positioned on the base layer (A').
3. The patterned laminate according to claim 2, wherein the cured layer (B') has a peak value of tan δ determined by dynamic viscoelasticity measurement of 0.5 or more.
4. The patterned laminate according to claim 3, wherein the cured layer (B') has a glass transition temperature (Tg) of 5° C. or less, defined as a temperature with respect to the peak value.
5. The patterned laminate according to claim 2, wherein the cured layer (B') has a storage modulus (G') value of 3 x 10 ⁶ Pa or less measured at a temperature of 90° C. or higher.
6. The patterned laminate according to claim 2, wherein the cured layer (B') has an elongation of 20% or more at a temperature of 90°C or more.
7. The patterned laminate according to claim 2, wherein the base layer (A') has an elongation at a temperature of 90°C or higher at a temperature of 90°C or higher that the cured layer (B') has.
8. The method of claim 2, wherein the base layer (A') is a polyvinylchloride (PVC) film, a polylactic acid (PLA) film, a styrene film, a stryen/butadiene/styrene (SBS) film, and a Styrene Ethylene/Butylene (SEBS) film. Styrene) comprising at least one of the film, a patterned laminate.
9. The patterned laminate according to claim 2, wherein the base layer (A') has a thickness in the range of 200 to 1,000 μm.
10. The patterned laminate according to claim 2, wherein the cured layer (B') has a thickness in the range of 5 to 50 μm.
11. The patterned laminate according to claim 1, wherein the cured layer (B) comprises a cured product of a curing agent containing polyurethane acrylate having a weight average molecular weight (Mw) of 10,000 or more.
12. The patterned laminate according to claim 11, wherein the curing treatment agent contains a reactive monomer having a glass transition temperature (Tg) of 0° C. or less of the homopolymer.
13. The patterned laminate according to claim 11, wherein the curing treatment agent further contains a reactive monomer containing a hydroxy group or an amide group.
14. A decorative material comprising the patterned laminate according to claim 1.
15. 15. The decorative material according to claim 14, further comprising a printed layer on the lower surface side of the substrate layer, on which a tuning pattern having the same shape as those of the concave portions and the convex portions of the pattern laminate is printed.

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