KR20210036630A - A sheet having wrinkle surface - Google Patents

Abstract

The present application relates to a laminate that can be used as an interior material for automobiles. The laminate includes a substrate layer and a cured layer formed on the substrate layer and having a wrinkled surface.

Description

Laminate having a wrinkled surface {A sheet having wrinkle surface}

The present application relates to a laminate having a corrugated surface.

In addition to functionality such as durability and antifouling properties, aesthetics such as color, touch, and luxury are required for automobile interior materials. Accordingly, in the field of automotive interior materials, surface treatment technology capable of imparting both functionality and aesthetics has been developed. For example, so-called functional coatings can be considered, such as using a curing agent on the substrate. As such, when using a curing treatment agent, there is an advantageous advantage in securing durability by increasing curing density.

In recent years, the interior materials of differential vehicles with matte characteristics are in the spotlight. Accordingly, a curing agent containing a matting agent (eg, silica) is used. However, since the matting agent is porous and has a low apparent specific gravity, it may rise to the surface when the treatment agent is used. Accordingly, as the content of the matting agent for realizing the matte property increases, there is a problem that the appearance of the interior material of the vehicle is deteriorated as fine dust, moisture, or oil stains are adhered to the matting agent. In addition, when prescribing a curing agent containing an excessive amount of a matting agent, the solvent resistance is not good, so when the solvent contacts the surface of the interior material, the glossiness is rather increased. Therefore, there is a need for a technology capable of realizing matte properties without using a matting agent or using a small amount.

On the other hand, as an example of a vehicle interior material in which the functional coating is used, artificial leather for a car seat may be mentioned. A considerable tension is applied to the artificial leather mounted as a vehicle interior material in consideration of the aesthetics of the exterior, the fit and the feeling of seating. In addition, because the artificial leather is sewn, a considerable pull is applied. However, when a curing agent is used, when the curing density is increased to improve durability, there is a problem that the elongation decreases. In the case of artificial leather containing a coating layer derived from a curing agent with a reduced elongation, tearing or battering occurs, and aesthetics (eg, matte properties) deteriorate.

Accordingly, there is a need for a vehicle interior material capable of simultaneously satisfying the aesthetic feeling including the matte characteristics, functionality including durability, and elongation characteristics described above.

One object of the present application is to solve the problems of the prior art described above.

Another object of the present application is to provide a vehicle interior material that can simultaneously satisfy aesthetics including matte characteristics, functionality including durability, and elongation characteristics.

Another object of the present application is to provide a vehicle interior material that can simultaneously satisfy aesthetics including matte properties and functionality including durability even when tension is applied during manufacturing and during use after manufacturing.

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

In an example related to the present application, the present application relates to a laminate comprising a base layer and a cured layer. The cured layer has a wrinkled surface.

The surface on which the wrinkles are formed is one surface opposite to one surface of the cured layer facing the substrate layer. The wrinkled surface may impart a predetermined surface characteristic (eg, surface roughness and/or gloss) to the laminate to be described below.

In the present application, the term "surface on which wrinkles are formed" (hereinafter, referred to as S _wrinkle ) means that the cured layer includes wrinkles on at least one surface thereof, and the cured layer has three-dimensional surface irregularities due to the wrinkles. Means (see Fig. 1). For example, the surface (S _wrinkle ) has a large and small ridge (ridge), a valley (valley), and irregularities including wrinkles (wrinkle) formed from these and can be visually recognized in a predetermined shape. Each of the ridges, valleys, and corrugations may have a regular or irregular shape. Such a wrinkled surface may also be referred to as a surface having a fine folding structure.

_{When observing the surface of the cured layer (S wrinkle} ) in which wrinkles are formed in the normal direction of the cured layer, ridges, valleys, wrinkles, and irregularities formed therefrom are, for example, the surface (S _{wrinkle) while undergoing the curing process described below.} ) Is observed over the entire area. The fact that the wrinkles or surface irregularities described in the present application are observed in the entire area of the surface of the cured layer can be expressed as satisfying the matte characteristics and elongation described below at the same time.

The wrinkles may be observed in a form including a line shape (eg, straight line, curved line) having a directionality. In one example, the wrinkles of the surface formed while repeating the straight and curved shapes may impart a curvature such as a mountain range shape to the surface of the cured layer.

The surface uneven structure formed by corrugations having a line shape as described above is a so-called point-wise uneven shape (Fig. 2a).

In one example, the surface (S _{wrinkle ) may include a} wrinkle (W a) that can be visually recognized in a predetermined size and shape. Specifically, the wrinkles may have a line (straight line or curved) shape extending to a length ranging from several to tens of μm while having a width in the range of several to tens of μm. For example, the wrinkles may have a width of 15 μm or less and a length of several 300 μm or less.

The width of the wrinkles and the length of the wrinkles can be confirmed from an image (eg, SEM) photographing the wrinkled surface as shown in the accompanying drawings. At this time, the length in the extending direction is greater than the width (see Fig. 3).

_{Specifically, the ends of the wrinkles (W a} ) extending in a straight or curved shape form an inclination of gradually decreasing in height and may be incorporated into the hardened layer. _{In some cases, the end of any one wrinkle (W a} ) having the size and shape may be a starting point of another wrinkle or a connection portion with another wrinkle. In addition, when observing the cross-sectional curve near the wrinkle in the direction perpendicular to the extension direction of the wrinkle (W _a ), the width of the wrinkle is in both directions from the point or part (e.g., ridge) forming the height of the wrinkle. It forms a slope that gradually decreases in height and may be incorporated into the hardened layer. On the other hand, when a ridge and a valley adjacent thereto form a wrinkle or a part thereof, the area of the shape recognized including the valley may be viewed as the width _{of the wrinkle W a.}

In one example, the _{width of the wrinkles (W a} ) may be 15 µm or less, for example, 14 µm or less, 13 µm or less, 12 µm or less, 11 µm or less, or 10 µm or less. Specifically, the upper limit of the width of the wrinkles may be, for example, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, or 300 nm or less. The lower limit of the width of the wrinkles (W _a ) may be, for example, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 400 nm or more, or 500 nm or more, and specifically, for example, 1 It may be µm or more, 2 µm or more, or 3 µm or more. If the above range is satisfied, it may be advantageous for the surface formed by the wrinkles to have matte properties and stain resistance.

In one example, the _{length of the wrinkles (W a} ) extending may be 5 μm or more or 10 μm or more, and specifically, for example, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, It may be 60 µm or more, 70 µm or more, 80 µm or more, or 90 µm or more. And, the upper limit may be, for example, 300 µm or less, 250 µm or less, 200 µm or less, or 100 µm or less, and more specifically, 90 µm or less, 80 µm or less, 70 µm or less, 60 µm or less, or 50 µm or less. I can. If the above range is satisfied, it may be advantageous for the surface formed by the wrinkles to have matte properties and stain resistance. According to an exemplary embodiment of the present application, the _{length of the wrinkles (W a} ) extending may be in the range of 20 to 80 µm, 30 to 70 µm, 40 to 60 µm, or 45 to 55 µm.

The wrinkles (W _a ) may have a predetermined height in most of the extending length. For example, the wrinkles (W _a ) may have a height of 1 μm or more. Specifically, when observing the cross-sectional curve of the wrinkle in the direction perpendicular to the extension direction of the wrinkle, the point or part that forms the height of the wrinkle (e.g., ridge) and the point or part of the hardened layer where the width of the wrinkle is mixed ( Example: Valley) may have a height difference of at least 1 μm or more. At this time, the most of the length at which the height is observed means 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95 of the length that _{the wrinkle (W a) continuously extends along its shape.} It means a length that is greater than or equal to %. When the height difference gradually decreases in the extension direction of the wrinkles, and the height is less than or equal to 1 μm, a shape in which the ends of the wrinkles are mixed into the hardened layer can be observed, or the size or shape of the wrinkles (W _a ) A shape in which the contact with other wrinkles different from the is started may be observed. In the latter case, a more complex wrinkle structure may form the unevenness of the _{surface (S wrinkle).}

The wrinkle (W _a ) is observed over the entire area of the surface (S _wrinkle ), while showing a regular or irregular distribution may form a surface wrinkle or surface irregularities. The fact that the wrinkles or surface irregularities described in the present application are observed in the entire area of the surface of the cured layer can be expressed as satisfying the matte characteristics and elongation described below at the same time.

For example, in the surface (S _wrinkle ), the wrinkle (W _a ) can form surface irregularities while having a shape in which _a plurality of wrinkles (W a) are branched in different directions from one specific point. have.

For example, in the surface (S wrinkle), the wrinkle (W <sub>a ) may have a shape similar to ``</sub> Y'' or ``<'' (that is, the wrinkle may be recognized as a shape similar to ``Y'' or ``<''). Can). At this time, wrinkles having a shape similar to "Y" or "<" may be densely arranged to form surface irregularities.

For example, in the surface (S _wrinkle ), the wrinkles (W _a ) may form surface irregularities in a form in which branches in other directions are suppressed and are distributed while extending generally in one direction.

The shape and arrangement of _{the wrinkles (W a} ) forming the surface irregularities as described above are exemplary. In addition, one or more wrinkles of the shape or form described above may be observed on the surface having irregularities (S _wrinkle).

Examples of the shape of the surface wrinkles as described above can be found in FIGS. 1, 3, 4 and 5, and the like.

In one example, the surface (S _wrinkle ) may include a wrinkle (W _b ) different in size and/or shape from the wrinkle (W _{a ).} For example, it may be that the folds (W _a) crease (W _b) of wrinkles that do not meet one or more of the width, length and height. Preferably, the number of one or more of the width, length and height to be defined by the folds (W _b) to be smaller than that of the folds (W _a) defined as above. _{When a} large number of wrinkles larger than the wrinkle (W a) are observed on the surface, it may become an obstacle to securing the surface properties.

In one example, the wrinkle (W _b ) is observed over the entire area of the surface (S _wrinkle ), it may form a surface irregularities while showing a regular or irregular distribution. For reference, that wrinkles or surface irregularities described in the present application are observed in all areas of the surface of the cured layer may be expressed as satisfying the matte characteristics and elongation described below at the same time.

For example, in the surface (S _wrinkle ), the wrinkle (W _b ) can form surface irregularities while having a shape in which a plurality of wrinkles (W _{b) are branched in different directions from one specific point.} have.

For example, in the surface (S wrinkle), the wrinkle (W <sub>b ) may have a shape similar to ``</sub> Y'' or ``<'' (that is, the wrinkle may be recognized as a shape similar to ``Y'' or ``<''). Can). At this time, wrinkles having a shape similar to "Y" or "<" may be densely arranged to form surface irregularities.

For example, in the surface (S _wrinkle ), the wrinkles (W _b ) may form surface irregularities in a form in which branches in other directions are suppressed and are distributed while extending generally in one direction.

_{The shape of the wrinkles (W b} ) forming the surface irregularities as described above is exemplary. In addition, one or more wrinkles of the shape or form described above may be observed on the surface having irregularities (S _wrinkle).

Examples of the shape of the surface wrinkles as described above can be found in FIGS. 1, 3, 4 and 5, and the like.

In one example, the _{unevenness of the surface (S wrinkle} ) may be formed by the wrinkles (W _a , W _{b ).}

In one example, the wrinkle (W _b ) may form a cured layer surface (S _wrinkle ) in a state located adjacent to the wrinkle (W _{a ).} For example, when observed from the normal direction of the hardened layer, valleys or ridges may exist between _{the wrinkles (W a} ) and the wrinkles (W _{b ).}

In another example, the folds (W _b) are the folds (W _a) and physically connected to the state, e.g., the pleats (W _a) from which the height is low and the width is less wrinkled branched (W _b) It may have a shape or form, and these wrinkles (W _a , W _b ) may form a cured layer surface (S _wrinkle ). The direction or length of the wrinkles (W _b ) branching from the wrinkles (W _{a) is not particularly limited.}

Examples of the shape of the surface wrinkles as described above can be found in FIGS. 1, 3, 4 and 5, and the like.

In one example, the shape of the wrinkles on the surface of the cured layer may have the same or similar shape as shown in FIG. 5. For example, the surface of the cured layer may be a surface in which only one of the wrinkles of a specific shape exemplified below is observed, or two or more of the wrinkles of a specific shape exemplified below may be observed at the same time, otherwise the following In addition to the exemplified specific shape wrinkles, other shapes of wrinkles may also be the surfaces observed (at a level that does not impair the desired surface properties).

For example, the surface may be a radially corrugated surface (see FIG. 5A). The radial shape may be a shape in which a plurality of wrinkles having the same or different directions extend from a certain point (center portion). The wrinkles forming the radial shape may include wrinkles (Wa). In addition, the wrinkles forming the radial shape may include wrinkles (Wb). Such wrinkles may be observed over the entire area of the surface of the cured layer, and may be distributed on the surface to an extent that, for example, satisfies the following surface properties while undergoing a curing process described below. In addition, in some cases, the wrinkles extending from the center with directionality may have a shape that gradually decreases in height as they move away from the center.

For example, the surface may be a Y-shaped (Y-tie or Y-tile pattern) corrugated surface (see FIG. 5B). The Y-shape may have a shape in which a plurality of wrinkles having three different directions extend from a certain point (central portion). In the case of Y-type, it is sufficient if the Y-shaped curvature is observed in most of the surface area when observing the surface of the cured layer, and three corrugations with directionality must be observed from a certain point so that only the curvature with the Y-shaped shape is observed. It doesn't have to have a shape that stretches out. The wrinkles forming the Y-shape may include wrinkles Wa. In addition, the wrinkles forming the Y-shape may include wrinkles (Wb). Such wrinkles may be observed over the entire area of the surface of the cured layer, and may be distributed on the surface to an extent that, for example, satisfies the following surface properties while undergoing a curing process described below. In addition, in some cases, the wrinkles extending from the center with directionality may have a shape that gradually decreases in height as they move away from the center.

For example, the surface may be a sand wave type corrugated surface (see FIG. 5C). The sand wave type has a lower depth (height) and is more evenly distributed when compared to other shapes of surface wrinkles. The wrinkles forming the sand wave shape may include wrinkles Wa. In addition, the wrinkles forming the sand wave shape may include wrinkles (Wb). Such wrinkles may be observed over the entire area of the surface of the cured layer, and may be distributed on the surface to an extent that, for example, satisfies the following surface properties while undergoing a curing process described below.

For example, the surface may be a tensioned-web corrugated surface (see FIG. 5D). In the tensioned-web type, there are wrinkles formed to be arranged in one direction, which is generally the same, and other wrinkles arranged in a direction intersecting with respect to them (they are also arranged in one direction which is generally the same. It may be in the same shape as the web (web) to be formed. At this time, the crossing angle is not particularly limited. In the case of the tensioned-web type, it can be recognized that the corrugations formed to be generally arranged in one direction extend over the entire surface area. The wrinkles forming the tensioned-web shape may include wrinkles Wa. In addition, the wrinkles forming the tensioned-web type may include wrinkles (Wb). Such wrinkles may be observed over the entire area of the surface of the cured layer, and may be distributed on the surface to an extent that, for example, satisfies the following surface properties while undergoing a curing process described below.

In one example, the surface may have irregularities formed by randomly dispersing radial or Y-shaped corrugated structures.

The laminate of the present application including a cured layer having a wrinkled surface (S _{wrinkle) as described above may have the following characteristics.}

Specifically, a laminate including a substrate layer and a cured layer having a wrinkled surface may have an elongation of 100% or more. The elongation of 100% or more means that when the laminate is stretched in a predetermined direction (when pulled), the laminate can be stretched by at least the original size. In other words, an elongation of 100% or more can be at least twice the size of the original laminate in the tensile direction (that is, the length in the tensile direction during tensioning can be at least twice the original length). Means. In this case, the elongation is the elongation when the lengthwise direction or the width direction and the tensile direction of the laminate having a predetermined size (length x width) (however, the length is greater than the width) in the normal direction to the surface of the laminate are matched. I can.

Specifically, in the present application, the "elongation" may be measured while stretching the laminated body cut in the form of a dogbone at a speed of 200 mm/min, as in the following experimental examples. In one example, when cutting the dogbone, the longitudinal direction may be matched with the width direction of a specimen wound in a roll type, and the width direction of the specimen may be a TD direction among so-called MD and TD directions. With regard to the elongation measurement, each thickness of the base layer and the cured layer may be in the same range as described below. In addition, the thickness of the laminate depends on the thickness of the base layer and the cured layer.

In one example, the elongation of the laminate may be 110% or more, 120% or more, 130% or more, 140% or more, or 150% or more. In addition, the upper limit of the elongation of the laminate may be 250% or less, specifically 200% or less, 190% or less, 180% or less, 170% or less, 160% or less, or 150% or less. When the elongation within the above range is satisfied, it can be seen that the workability of the laminate is excellent.

In addition, the laminate may have ultra-matt properties. Specifically, the laminate may have a glossiness of 60° measured before and after 100% stretching may satisfy 1.0 or less, respectively. That is, in the laminate, the wrinkled surface may be a surface that satisfies each of 1.0 or less with a 60° gloss measured before and after 100% elongation measurement.

In the present application, the "60° glossiness" can be measured using a gloss meter according to ASTM D2457, and is a numerical value representing the glossiness of the surface (GU: gloss unit). The lower the gloss, the closer to matte.

In addition, the term ``glossiness after 100% elongation measurement'' in the present application means that the elongation is measured as in the following experimental example, but the specimen is stretched by its original length in the tensile direction (compared to the original specimen length before stretching) twice as long. It means that after making it to be, the glossiness is measured.

In one example, the glossiness (G1) before 100% elongation measurement may be 1.0 or less, specifically 0.9 or less, 0.8 or less, or 0.7 or less. The upper limit of the glossiness G1 may be, for example, 0.5.

In one example, the glossiness (G2) after 100% elongation measurement may be 1.0 or less, specifically 0.9 or less, 0.8 or less, or 0.7 or less. The upper limit of the glossiness G2 may be, for example, 0.5.

In one example, the laminate may be a laminate having a rate of change (%) between 60° gloss (G1, G2) measured before and after 100% stretching, respectively, of 20% or less. That is, in the laminate, the surface on which the wrinkles are formed may be a surface in which a rate of change of 60° gloss measured before and after 100% elongation measurement satisfies 20% or less. For example, the change rate (%) of the 60° gloss may be 15% or less, 10% or less, or 5% or less. The lower limit of the rate of change is not particularly limited, and may be, for example, 1% or more, 2% or more, 3% or more, 4% or more, or 5% or more.

As described above, the laminate of the present application can maintain a considerable level of matte properties even after stretching. Accordingly, the laminate is matte without change even when a significant tension is applied to the laminate during a process for use in automobile interior materials such as artificial leather, and even when a significant tension is applied to the laminate during use as an automobile interior material. Can maintain the characteristics. The above characteristics can be secured through curing through a predetermined step for a composition having a predetermined composition (curing agent). The specific configuration and curing process of the composition will be described in detail below.

In one example, the composition may be a solvent type. That is, it may be a composition containing a solvent.

In another example, the composition may be a solvent-free composition. That is, the composition may not contain a solvent, for example, an organic solvent or an aqueous solvent. When a solvent-free composition is used, the drying process for the solvent may be omitted, thereby increasing the process efficiency. In addition, through the use of the solvent-free composition, it is possible to prevent deterioration of the surface properties required in the laminate of the present application due to air bubbles generated when the solvent volatilizes during the solvent drying process. Specifically, the composition may be a photocurable solvent-free composition.

In one example, the cured layer may include a composition comprising a reactive oligomer component (A) and a reactive monomer component (B). That is, the cured layer may be formed from a composition comprising a reactive oligomer component (A) and a reactive monomer component (B). For example, after the photocuring treatment described below is performed on a resin composition having a predetermined configuration described below, a cured layer having a wrinkled surface as described above may be prepared.

In one example, the reactive oligomer may be urethane (meth)acrylate. The urethane acrylate oligomer may function advantageously in securing the strength of the cured layer and securing the flexibility of the cured layer through the elasticity peculiar to urethane bonding. For convenience, urethane (meth)acrylate is referred to as urethane acrylate.

The urethane acrylate usable in the present application may be prepared to satisfy the following functionalities and/or molecular weights by polymerizing compounds such as isocyanate, alcohol, and acrylate according to a known method. For example, in a polyisocyanate having three or more isocyanate groups, an acrylate containing three or more acrylic groups having a hydroxyl group in the molecule is reacted under a metal catalyst and a radical polymerization inhibitor until the isocyanate (NCO) disappears, and then , Urethane acrylate may be prepared by adding 5 to 30% by weight of an ultraviolet curable monomer. Alternatively, a urethane acrylate that satisfies the following functionalities and/or molecular weights may be selected and used from among commercially available products.

In one example, the urethane acrylate oligomer may be a multifunctional oligomer including two or more photopolymerizable functional groups. Specifically, the urethane acrylate oligomer may be a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, a 5functional oligomer, or a 6functional or higher oligomer.

In one example, the composition may include two or more different urethane acrylate oligomers having different numbers of functional groups. For example, the composition may include two or more urethane acrylate oligomers having different numbers of functional groups among 2 to 10 functional urethane acrylate oligomers. That is, the composition may contain two or more polyfunctional urethane acrylate oligomers.

In one example, the urethane acrylate oligomer may have a weight average molecular weight (Mw) of 30,000 or less. Specifically, the upper limit of the molecular weight of the oligomer may be, for example, 25,000 or less or 20,000 or less, and more specifically, for example, 19,000 or less, 18,000 or less, 17,000 or less, 16,000 or less, 15,000 or less, 14,000 or less, 13,000 or less, It may be 12,000 or less, 11,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, or 5,000 or less. In addition, the lower limit of the urethane acrylate oligomer weight average molecular weight (Mw) is, for example, 1,000 or more, 2,000 or more, 3,000 or more, 4,000 or more, 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more, or 10,000 or more. I can. When the molecular weight as described above is satisfied, it may be advantageous for the laminate to have an appropriate level of durability and elongation.

When the number and/or molecular weight of the above functional groups are satisfied, the specific structure of the urethane acrylate oligomer is not particularly limited.

In one example, the urethane acrylate may be an aliphatic urethane acrylate. In the case of an aliphatic urethane acrylate, the yellowing resistance may be excellent.

In another example, the urethane acrylate may be an aromatic urethane acrylate. In the case of aromatic urethane acrylates, odor issues may not occur.

In one example, the urethane acrylate used as the oligomer component (A) may include a urethane acrylate (a-1) having units derived from hydrogenated polydiene polyols. The hydrogenated polydiene polyol may be, for example, a hydrogenated polydiene diol.

Polydiene diols can be prepared, for example, from dienes having 4 to 24 carbons, 4 to 20 carbons, 4 to 16 carbons, 4 to 12 carbons or 4 to 8 carbons. Examples of such dienes include butadiene and isoprene. That is, in a specific example, polybutadiene diol and polyisoprene diol may be used as the polydiene diol.

Hydrogenation of the polydiene diol may be performed in the presence of, for example, a catalyst such as Raney nickel, a noble metal catalyst (eg, platinum), or a titanium catalyst or a transition metal catalyst. In this regard, the hydrogenation of a polydiene diol in the present application relates to hydrogenation of a double bond in a polydiene diol, that is, a hydrogenation product resulting from the reaction of hydrogen and an alkene group. In addition, the hydrogenation is complete hydrogenation of all double bonds in the polydiene diol, or hydrogenation of the majority of double bonds (at least a significant amount of double bonds, about 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol%). Or more, 90 mol% or more, or 95 mol% or more).

In one example, as the hydrogenated polydiene diol as described above, hydrogenated polybutadiene diol may be used, and the hydrogenated polybutadiene diol may be represented by Formula 1 below. In Formula 1, n is an arbitrary number and may have a value sufficient to satisfy the molecular weight of the urethane acrylate described above. For example, n may be a number ranging from 1 to 100,000.

<Formula 1>

Since the hydrogenated polydiene polyol has a long main chain without a side branch, it can provide hydrophobicity and flexibility. Accordingly, the cured layer can be advantageously operated to secure a smooth and matte property, and to provide an appropriate level of flexibility required in the present application.

The urethane acrylate (a-1) having a unit derived from the hydrogenated polydiene polyol may also be expressed as a hydrophobic oligomer.

In one example, the urethane acrylate (a-1) having a unit derived from the hydrogenated polydiene polyol may have a weight average molecular weight of 15,000 or less. Specifically, the weight average molecular weight of the urethane acrylate (a-1) may be 14,000 or less, 13,000 or less, 12,000 or less, 11,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, or 5,000 or less. And the lower limit may be, for example, 4,000 or more, 4,500 or more, or 5,000 or more. If the above range is satisfied, the cured layer may be smooth and may function advantageously in securing matte properties.

In one example, the composition is a urethane acrylate that is an oligomer component, in addition to the urethane acrylate (a-1) having a unit derived from the hydrated polydiene polyol, a urethane acrylic that does not satisfy the definition of hydrogenation mentioned above. It may further include a rate (a-2). The urethane acrylate (a-2), as a concept corresponding to (a-1) urethane acrylate, is a non-hydrogenated (non-hydrogenated) urethane acrylate (a-2), a polar urethane acrylate (a-2). ), or a hydrophilic urethane acrylate (a-2).

The molecular weight of the urethane acrylate (a-2) may be the same as or different from that of the urethane acrylate (a-1).

In one example, the urethane acrylate (a-2) may have a weight average molecular weight (Mw) in the same range as described above, for example, 1,000 to 30,000.

In one example, the composition may contain a urethane acrylate, which is an oligomer component (A), in the range of 20 to 70 parts by weight, based on 100 parts by weight of the total (excluding additives such as matting agents (eg, filler) components). have. Specifically, the urethane acrylate, in the total composition, for example, 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 or 65 parts by weight or more may be used, and the upper limit of the content may be, for example, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, or 45 parts by weight or less. If the above range is satisfied, it may act advantageously in securing the durability and flexibility of the cured layer.

In one example, the composition may contain at least 5 parts by weight or more of urethane acrylate (a-1) relative to 100 parts by weight of the total composition (excluding additive components such as a matting agent). For example, the content of (a-1) may be 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more. In addition, the upper limit of the content of (a-1) may be, for example, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less.

The content of urethane acrylate (a-2) in the composition may be appropriately adjusted according to the content of the total urethane acrylate and the content of urethane acrylate (a-1) described above.

In one example, the content ratio (w1/w2) between the weight (w1) of the urethane acrylate (a-1) and the weight (w2) of the urethane acrylate (a-2) may range from 0.4 to 2.5. . Specifically, the lower limit of the content ratio (w1/w2) is, for example, 0.4 or more, 0.6 or more, 0.8 or more, 1.0 or more, 1.2 or more, 1.4 or more, 1.6 or more, 1.8 or more, 2.0 or more, 2.2 or more, or 2.4 or more. The upper limit may be, for example, 2.4 or less, 2.2 or less, 2.0 or less, 1.8 or less, 1.6 or less, 1.4 or less, 1.2 or less, 1.0 or less, 0.8 or less, 0.6 or less, or 0.4 or less. The weight ratio may be appropriately adjusted in consideration of durability, elongation, and gloss required in the laminate of the present application.

When the cured layer is formed mainly by photocuring of oligomers, flexibility may be insufficient, and it may be disadvantageous in forming the above-described wrinkles. Accordingly, the composition comprises a reactive monomer component (B) in addition to the oligomer. In addition, the reactive monomer component can function like a solvent to lower the viscosity of the composition (rather than when only the oligomer component is included), thereby improving the coating processability for the substrate layer.

In one example, a monofunctional or polyfunctional monomer may be used as the reactive monomer component. For example, the composition may include a monofunctional monomer as a reactive monomer in a range of 15 to 70 parts by weight, based on 100 parts by weight of the total composition (excluding additive components such as a quencher). Specifically, the composition contains 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, or 55 parts by weight or more of a monofunctional monomer The upper limit is 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight It may contain less than or equal to 20 parts by weight.

In one example, the monofunctional monomer may be a (meth)acrylic monomer.

In one example, the composition may include a polar (or hydrophilic) monomer (b-1) having a hydroxy group, a nitrogen-containing functional group, or a functional group such as alkylene oxide.

In one example, the monomer (b-1) may be a monofunctional monomer.

In one example, the monomer (b-1) may be used in a range of 10 to 60 parts by weight based on 100 parts by weight of the total composition. For example, it may be 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, or 40 parts by weight or more, and the upper limit thereof is, for example, 55 parts by weight or less, 50 parts by weight. It may be parts by weight or less, 45 parts by weight or less, or 40 parts by weight or less.

Although not particularly limited, examples of the hydroxy group-containing (meth) acrylic monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6- Hydroxyalkyl (meth)acrylates such as hydroxyhexyl (meth)acrylate or 8-hydroxyoxyl (meth)acrylate may be used.

In the case of a nitrogen-containing functional group, as a functional group containing nitrogen in the molecule, for example, an amine group, an imine group, an amide group, a nitrile group, a nitro group, an azo group, an imide group, or an azide group may be exemplified, but are limited thereto. It is not. In one example, when a (meth) acrylic monomer having a nitrogen-containing functional group is used, the specific type is not particularly limited, but, for example, (meth) acrylonitrile, N-methyl acrylamide, (meth) acryl Amide, alkyl (meth)acrylamide, dialkyl (meth)acrylamide, hydroxyalkyl (meth)acrylamide, N-butoxy methyl (meth)acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, 2-aminoethyl (meth)acrylate, 3-aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate or N,N-dimethylaminopropyl (meth)acrylate, etc. may be used. .

In the case of a monomer having an alkylene oxide, for example, an alkoxy alkylene glycol (meth)acrylic acid ester, an alkoxy dialkylene glycol (meth)acrylic acid ester or an alkoxy polyethylene glycol (meth)acrylic acid ester may be used. It is not limited.

In one example, the composition may include an alkyl (meth) acrylate monomer (b-2) having an alkyl group having 6 to 20 carbon atoms. These monomers having a relatively long chain provide a soft and dry touch and contribute to securing flexibility.

In one example, the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 6 to 20 carbon atoms may be a monofunctional monomer.

The type of the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 6 to 20 carbon atoms is not particularly limited, but, for example, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth) Acrylate, undecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate , Stearyl (meth)acrylate, octyldecyl (meth)acrylate, nonadecyl (meth)acrylate, and the like may be used. One or more of those listed above may be used.

In one example, the monomer (b-2) may be used in a range of 5 to 40 parts by weight based on 100 parts by weight of the total composition. For example, it may be 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more, and the upper limit thereof is, for example, 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight It may be less than or equal to 20 parts by weight.

In one example, the monomer (b-1) and the monomer (b-2) may be used simultaneously in the composition. Although not particularly limited, in consideration of curability or coatability, the content of the monomer (b-1) may be greater than the content of the monomer (b-2). For example, the content ratio (w3/w4) of the weight (w3) of the monomer (b-1) and the weight (w4) of the monomer (b-2) may range from 1 to 3.5. Specifically, the lower limit of the ratio (w3/w4) is, for example, 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2.0 or more, 2.1 or more, It may be 2.2 or more, 2.3 or more, 2.4 or more, or 2.5 or more, and its upper limit is, for example, 3.5 or less, 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less , 2.5 or less, 2.4 or less, 2.3 or less, 2.3 or less, 2.2 or less, 2.1 or less, or 2.0 or less.

In one example, the composition may further include a polyfunctional monomer (C). Specifically, in the composition, a monomer having two or more reactive functional groups may be used. For example, a polyfunctional (meth)acrylate monomer having two or more functional groups may be used. The polyfunctional monomer increases the curing strength and imparts durability to the cured layer.

Although not particularly limited, the polyfunctional (meth)acrylate monomers include cyclohexane dimethanol di(meth)acrylate, hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and tri 2, such as ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. Functional (meth)acrylate monomers; Trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propylated trimethylolpropane tri(meth) ) Trifunctional (meth)acrylate monomers such as acrylate, glycerylpropylated tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, etc.; Tetrafunctional (meth)acrylate monomers such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; 5-functional (meth)acrylate monomers such as dipentaerythritol penta(meth)acrylate and dipentaerythritol hydroxypenta(meth)acrylate; 5-functional (meth)acrylate monomers such as dipentaerythritol hexa(meth)acrylate and the like may be used.

In one example, the number of functional groups of the polyfunctional monomer component (C) may be in the range of 2 to 5 or 2 to 4.

In one example, the composition may contain 15 parts by weight or less of the polyfunctional monomer (C). For example, the polyfunctional monomer may be used in an amount of 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, or 10 parts by weight or less, and the lower limit thereof is, for example, 1 part by weight or more, It may be 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, or 5 parts by weight or more. If it is less than the above range, durability after curing may be poor, and if it exceeds the above range, the elongation may be poor.

The composition may further include an initiator (D). As long as it is an initiator that can be used in the curing process described below, the type of the initiator is not particularly limited, and a known commercial product may be used.

In one example, the composition may include 10 parts by weight or less of an initiator based on 100 parts by weight of the total composition (excluding additive components such as a matting agent). Specifically, the content of the initiator may be 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. And, the lower limit of the content may be, for example, 0.1 parts by weight or 0.5 parts by weight. As described below, in the present application, since the stepwise curing is performed when curing the cured layer, the curing efficiency is excellent even when a small amount of an initiator is used.

In one example, the composition for forming the cured layer may not contain an additive component such as a matting agent or may be used in a small amount.

Specifically, the matting agent has a particle shape, and can impart a matte effect to the laminate by increasing the scattering rate of light on the surface of the laminate. However, the use of a matting agent brings the problem of increased fouling resistance, as described above. However, since the cured layer of the present application has the above-described surface characteristics, it can effectively implement matte characteristics. Accordingly, sufficient matte properties can be implemented in the laminate of the present application without using the matting agent used to implement the matte effect in the prior art. In addition, according to the present application, even if a matting agent is used (in the case of excluding an additive component such as a matting agent, for example, based on the combined composition of the components (A) to (D)), based on the total composition of 100 parts by weight, 5 parts by weight or less, specifically 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less, such that the matting agent is used, the content of the matting agent can be significantly reduced compared to the prior art. Accordingly, the laminate of the present application has the advantage of preventing contamination resistance problems caused by the use of a matting agent.

In one example, the composition for forming a cured layer that does not contain a particle-shaped matting agent, which is an additive, or uses as little as the above content, may have a low viscosity, for example, a viscosity of 550 cps or less at room temperature. Specifically, when an excessive amount of an additive in the form of particles is used for realizing the matte effect, the viscosity of the composition increases, and thus the coating workability for the substrate layer is not good. However, since the present application does not use a matting agent or can be used significantly less than the prior art as described above, the composition for forming a cured layer is 500 cps or less, 450 cps or less, 400 cps or less, 350 cps or less, 300 cps or less at room temperature. It may have a viscosity of cps or less or 250 cps or less. The lower limit of the viscosity of the composition may be, for example, 50 cps or more, 100 cps or more, 150 cps or more, or 200 cps or more. At this time, room temperature refers to a temperature in the range of about 18 to 32 °C, specifically, a temperature in the range of 22 to 28 °C, a temperature in the range of 23 to 27 °C, or about 25 °C. It can mean the temperature of. In addition, the viscosity can be measured according to a known method using a Brookfield viscometer.

The substrate layer on which the cured layer having the above characteristics is formed may be a fibrous layer including natural leather or synthetic leather. In the case of synthetic leather, it may be synthetic leather including polyvinyl chloride (PVC), polyurethane (PU) and polyester.

In one example, the base layer may be a fibrous layer in which a pattern is formed in advance. The method of forming the pattern on the substrate layer is not particularly limited, and may be imprinting using, for example, a rubber or metal roller engraved with a predetermined shape.

In another example, the base layer may be a fibrous layer in which a pattern is not formed. In this case, as described below, after the cured layer is formed on the base layer, imprinting for pattern formation may be performed.

In one example, the laminate including the cured layer and the base layer may be used for automobile interior materials. Specifically, the automobile interior material includes a fiber material, and may be, for example, a car seat (car seat). The fibrous material includes the above-described fibrous layer (substrate layer) and a cured layer.

In another example related to the present application, the present application relates to a method of providing the laminate. The method may include a process of first and second curing after applying a photocurable composition including a photocurable oligomer component (A) and a reactive monomer component (B) directly on a substrate layer.

The first curing and the second curing may be referred to as a first light irradiation step and a second light irradiation step, respectively, and these curings may be performed in different ways in which the wavelength of the irradiated light, the amount of light irradiation, and/or the time of light irradiation I can. At this time, the first curing is performed under conditions capable of forming wrinkles while shrinking the surface of the cured layer applied on the substrate layer. Specific conditions are described below.

The specific configuration of the composition applied on the substrate layer is as described above. In addition, the types and characteristics of the base layer are the same as described above.

The method of applying the composition on the base layer is not particularly limited. For example, Mayer, D-bar, rubber roll, G/V roll, air knife, slot die, etc. The composition may be applied on the substrate layer using a known method.

The method includes a first light irradiation step of irradiating _{light (L 1} ) having a relatively short wavelength to the composition applied on the substrate layer under inert gas conditions; And a second light irradiation step of curing the composition by irradiating light (L ₂ ) having a longer wavelength than the light (L _{1) under air conditions.} Specifically, the method includes a first light irradiation step of irradiating a composition coated on a substrate layer with light (L ₁ ) of a predetermined wavelength under an inert gas condition to form wrinkles on the surface of the applied composition; And a second light irradiation step of forming a cured layer that is a cured product of the composition by irradiating light (L ₂ ) having a longer wavelength than the light (L _{1) under air conditions.}

The device for irradiating light in each step is not particularly limited, for example, when irradiating light with a wavelength of less than 300 nm in the first irradiation step, and irradiating light with a wavelength of 400 nm or less in the second irradiation step, A known mercury or metal halide lamp may be used.

In the first light irradiation step, the composition applied on the substrate layer is irradiated with light, and the surface of the composition (or the composition cured by light irradiation) to which the excimer generated by the irradiated light is applied is contracted. This is a step to form wrinkles. The wrinkled surface increases scattering of light incident on the surface so that a matte property can be imparted. The wrinkled surface may have the same surface characteristics as described above. Accordingly, in the present application, the matting agent may not be used, or even if the matting agent is used, it may be used in a significantly smaller amount compared to the prior art to achieve a matte effect. Accordingly, problems associated with the use of the matting agent can be solved.

In one example, in the first light irradiation step, light having a high energy of less than 300 nm, for example, light having a wavelength of 200 nm or less may be irradiated. Specifically, light having a wavelength of 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, or 170 nm or more may be irradiated at the first light irradiation stage. In one example, the upper limit of the wavelength of light irradiated in the first light irradiation step may be, for example, 200 nm or less, 190 nm or less, or 180 nm or less.

The first light irradiation step may be performed in an inert atmosphere. The gas used to create an inert atmosphere may be, for example, He, Ne, Ar, and/or N ₂ .

In one example, the inert atmosphere in which the first light irradiation step is performed may be an atmosphere in which _{the concentration of oxygen (O 2} ) is about 4,000 ppm or less. Specifically, the upper limit of the concentration of oxygen in the inert atmosphere may be 3,000 ppm or less, 2,500 or less, 2,000 ppm or less, 1,500 ppm or less, or 1,000 ppm or less, and more specifically 900 ppm or less, 800 ppm or less, 700 ppm or less, 600 ppm It may be less than, 500 ppm or less, 400 ppm or less, or 300 ppm or less. And the lower limit is, for example, 50 ppm or more, 100 ppm or more, 200 ppm or more, 300 ppm or more, 400 ppm or more, 500 ppm or more, 600 ppm or more, 700 ppm or more, 800 ppm or more, 900 ppm or more, or 1,000 ppm It can be more than that.

In one example, the inert atmosphere may be formed such that the concentration of oxygen in the _{nitrogen gas N 2 satisfies the above range.}

When the first light irradiation is performed under the inert atmosphere conditions as described above, it is advantageous in securing the above-described wrinkles and surface characteristics. For example, when the first light irradiation is performed in an inert atmosphere in which the concentration of oxygen exceeds the above range, the size of the wrinkles is excessively increased and the surface characteristics as described above cannot be provided.

In one example, when performing the first light irradiation step, the distance between the composition and the light source, that is, the distance from the surface of the composition applied on the base layer to the light source may be 5 mm or more. Specifically, the lower limit of the distance may be, for example, 10 mm or more, 15 mm or more, 20 mm or more, 25 mm or more, 30 mm or more, 35 mm or more, 40 mm or more, 45 mm or more, or 50 mm or more, The upper limit may be, for example, 90 mm or less, 85 mm or less, 80 mm or less, 75 mm or less, 70 mm or less, 65 mm or less, 60 mm or less, 55 mm or less, or 50 mm or less. In the first light irradiation step, when the distance between the composition and the light source is adjusted within the above range, it is advantageous to form a wrinkled surface of the above-described shape and size, and to secure surface characteristics of the above-described degree.

In one example, the irradiation amount of light irradiated in the first light irradiation step may be 1 mJ/cm2 or 5 mJ/cm2 or more. Specifically, the lower limit of the light irradiation amount in the first light irradiation step may be, for example, 10 mJ/cm 2 or more, 15 mJ/cm 2 or more, 20 mJ/cm 2 or more, 25 mJ/cm 2 or more, or 30 mJ/cm 2 or more, and And the upper limit is, for example, 100 mJ/cm2 or less, 90 mJ/cm2 or less, 80 mJ/cm2 or less, 70 mJ/cm2 or less, 60 mJ/cm2 or less, 50 mJ/cm2 or less, 40 mJ/cm2 or less , 30 mJ/cm 2 or less or 25 mJ/cm 2 or less. In the first light irradiation step, when the amount of light irradiation is adjusted within the above range, it is advantageous to form a corrugated surface of the above-described shape and size, and to secure surface characteristics of the above-described degree.

In one example, the time that the light is irradiated in the first light irradiation step may be at the level of several seconds, for example, the upper limit may be 10 seconds or less or 5 seconds or less, and the lower limit is, for example, 0.5 seconds or more or 1 second. It can be more than that. In the first light irradiation step, when adjusting the irradiation time in the above range, it is advantageous to form a wrinkled surface of the shape and size described above, and to secure the surface roughness and glossiness of the above-described degree. .

In this case, the light control time may be controlled in a manner of adjusting the moving speed of the resin composition to be irradiated with light. For example, when the device as shown in FIG. 6 is used, the light irradiation time can be controlled while appropriately adjusting the moving speed of the substrate layer coated with the composition on the conveyor belt within the range of 1 to 50 m/min.

In the second light irradiation step, the coating composition is coated on the substrate layer and wrinkled on the surface through the first light irradiation step, and light energy of a wavelength different from that of the first light irradiation step is applied to cure the coating composition and cure. This is the step of forming a layer.

In one example, in the second light irradiation step, light having a wavelength within a range of 200 to 400 nm may be irradiated. Specifically, the second light irradiation step includes a wavelength of 210 nm or more, 220 nm or more, 230 nm or more, 240 nm or more, 250 nm or more, 260 nm or more, 270 nm or more, 280 nm or more, 290 nm or more, or 300 nm or more. It may be a step to investigate. The upper limit of the light wavelength irradiated in the second light irradiation step may be, for example, 350 nm or less, 340 nm or less, 330 nm or less, 320 nm or less, 310 nm or less, or 300 nm or less. The coated resin composition in which wrinkles are formed on the surface with slight curing in the first light irradiation step may be cured in the thickness direction (applied) while being irradiated with light of the wavelength through the second light irradiation step.

In one example, the second irradiation step may be a step of irradiating light having a higher wavelength than the first irradiation step in the above-described wavelength range.

When performing the second light irradiation step, the temperature of the surface of the composition in which wrinkles are formed on the surface through the first light irradiation step may be 100° C. or less. That is, the composition in which wrinkles are formed on the surface through the first light irradiation step may be subjected to the second light irradiation step under the condition that the temperature of the surface is maintained at 100° C. or less. The corresponding temperature condition may be appropriately performed by a person skilled in the related art.

The second light irradiation step is performed in an air atmosphere. The curing rate of the composition may be improved through an air atmosphere, and the surface of the cured layer may be cleaned _{while oxygen molecules (O 2} ) are converted to ozone (O _{3) during the irradiation process.}

In one example, when performing the second light irradiation step, the distance between the composition and the light source, that is, the distance from the surface of the composition applied on the base layer to the light source may be 20 mm or less. Specifically, the upper limit of the distance is, for example, 19 mm or less, 18 mm or less, 17 mm or less, 16 mm or less, 15 mm or less, 14 mm or less, 13 mm or less, 12 mm or less, 11 mm or less, or 10 mm It may be less than or equal to, and its lower limit may be, for example, 0.5 mm or more, 1 mm or more, 2 mm or more, 3 mm or more, 4 mm or more, or 5 mm or more. In another example, when the second light irradiation step is performed, a distance between the composition and the light source may be smaller than that at the first light irradiation step. During the second light irradiation, when the distance between the composition and the light source is adjusted within the above range, it is advantageous to form a corrugated surface of the above-described shape and size, and to secure surface properties of the above-described degree.

In one example, an irradiation amount of light irradiated in the second light irradiation step may be greater than an irradiation amount of light irradiated in the second light irradiation step. For example, the irradiation amount of light irradiated in the second light irradiation step is 150 mJ/cm 2 or more, specifically 160 mJ/cm 2 or more, 170 mJ/cm 2 or more, 180 mJ/cm 2 or more, 190 mJ/cm 2 or more, 200 It may be mJ/cm2 or more, 210 mJ/cm2 or more, 220 mJ/cm2 or more, 230 mJ/cm2 or more, 240 mJ/cm2 or more, or 250 mJ/cm2 or more. And the upper limit may be, for example, 350 mJ/cm2 or less, 340 mJ/cm2 or less, 320 mJ/cm2 or less, 310 mJ/cm2 or less, or 300 mJ/cm2 or less. At the time of the second light irradiation, when the amount of light irradiation is adjusted to the above range, it is advantageous to form a corrugated surface of the above-described shape and size, and to secure surface characteristics of the above-described degree.

In one example, the time when light is irradiated in the second light irradiation step may be the same as or different from the time when light is irradiated in the first light irradiation step described above. Specifically, the light irradiation time in the second light irradiation step may be at the level of several seconds, for example, the upper limit may be 10 seconds or less or 5 seconds or less, and the lower limit may be, for example, 0.5 seconds or more or 1 second or more. have.

When the first light irradiation and the second light irradiation are performed as described above, the surface of the hardened layer may have a relatively dense hardening density. Specifically, at the time of the first light irradiation, light having a relatively high energy short wavelength (light of about 200 nm or less) acts in the vicinity of several hundred nm near the surface of the coated cured layer, and after that, the second light irradiation is performed and the cured layer Although the surface of the cured layer has a dense curing density, the curing density inside the cured layer may be relatively low because the short wavelength light used for the first light irradiation does not affect the inside of the cured layer. Accordingly, the inside of the cured layer having a relatively low curing density can contribute to securing the elongation, and the surface of the cured layer having a dense cured state can maintain distinct wrinkles. In addition, since the surface of the dense cured layer is less damaged even after 100% elongation evaluation (or even after stretching is made), the above-described surface properties can be maintained. In addition, the densely cured surface contributes to improvement of stain resistance and solvent resistance.

In one example, after the first light irradiation and the second light irradiation, the total curing rate of the cured layer may be 60% or more.

In the FT-IR analysis, the curing rate is calculated as a value comparing the area of ^{1650 to 1620 cm -1} based on the area of ^{the 1637 cm -1 peak corresponding to the double bond between (aliphatic) carbons.} I can. For example, when comparing the FT-IR analysis result of the UV treatment agent, which is a liquid before curing, and the FT-IR analysis result of the surface after curing, when the area is reduced by 80%, the curing rate may be 80%.

For example, the curing rate may be 65% or more, 70% or more, 75% or more, or 80% or more of the curing rate calculated by Equation 1. In addition, the degree of curing may be 85% or less, 80% or less, 75% or less, 70% or less, or 65% or less. If the curing rate of the cured layer is greater than the above range, it may be difficult to secure flexibility, and if it is less than the above range, durability may not be sufficient.

According to the manufacturing method of the present application described above, an excimer is generated through a first light irradiation step of irradiating light of a short wavelength such as less than 200 nm, and the excimer generates a short wavelength UV to form a composition (or composition It accelerates the surface hardening of the applied coating layer), and as a result, a fine wrinkle (curvature) structure corresponding to the aforementioned surface wrinkles due to shrinkage may be formed on the surface of the composition (or the coating layer on which the composition is applied). By adjusting the composition of the composition or the above-described performance conditions in the first light irradiation step of forming such wrinkles, it is possible to control the shape or frequency of an appropriate fine curved structure to simultaneously satisfy durability, elongation and matte properties. have. That is, the sheet manufactured according to the present application, that is, the fibrous material, does not contain a matting agent or has low gloss even if it is used in a very small amount, and quality deterioration such as cracking of the surface after stretching may not occur. In addition, through the subsequent second light irradiation, not only the interior of the coated composition may be cured, but the cured structure of the surface of the cured layer may become more dense, so that the contamination resistance, chemical resistance and durability of the surface of the laminate may also increase. I can.

In one example, the method may further include a step of forming a pattern on the wrinkled surface after the second light irradiation step. The method of forming the pattern is not particularly limited, and may be, for example, an imprinting method using a rubber or metal roller engraved with a predetermined shape. Even after imprinting for pattern formation is performed, since the laminate manufactured according to the present application has a dense cured surface, the surface characteristics described above may be satisfied.

In another example related to the present application, the present application relates to an automobile interior material. The vehicle interior material may be a car seat (car seat). In addition, the vehicle interior material may include the laminate described above.

In another example related to the present application, the present application relates to a treatment agent that may have the above properties. The specific composition of the treatment agent is as described above.

According to an example of the present application, it is possible to provide a vehicle interior material that can simultaneously satisfy aesthetics including matte characteristics, functionality including durability, and elongation characteristics. In particular, the present application may provide a vehicle interior material capable of simultaneously satisfying aesthetics including matte properties and functionality including durability even when tension is applied during use in a manufacturing process and in an appropriate use after manufacturing.

1 is an image photographing the surface of a matte laminate manufactured according to an example of the present application.
2 is an image photographing the surface of a matte laminate manufactured according to the prior art. Specifically, FIG. 2(a) is a photograph of the surface of a matte laminate manufactured using a matting agent, and FIG. 2(b) is a photograph of the surface of a matte laminate manufactured using a transfer method.
3 is for explaining the wrinkles formed on the surface of the matte laminate manufactured according to an example of the present application. In FIG. 3, colored dotted lines are marks for visually explaining wrinkles Wa and/or Wb.
4 is a photograph of various surface shapes that a matte laminate manufactured according to an example of the present application may have.
5 illustrates some of the typical irregularities on the surface of the hardened layer formed according to an example of the present application. Fig. 5(a) is a corrugation of a radial structure, Fig. 5(b) is a corrugation of a Y-shaped structure, Fig. 5(c) is a corrugation of a sand wave type structure, and Fig. 5(d) is The corrugation of a tensioned-web type structure is shown.
6 schematically shows an apparatus that can be used to perform the method for manufacturing a laminate of the present application.
7 is an image photographed of the surface of a cured layer of an example laminate.
8 is an image photographing the surface of a cured layer of a laminate of a comparative example.
9 is an image for explaining the standard and shape of a specimen for measuring the elongation.

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

<Production of laminate>

Examples 1 to 3

Of the oligomer component 44 parts by weight ((a-1) of urethane acrylate (weight average molecular weight: about 6,000) (a-1) and non-hydrogenated urethane acrylate (a-2) having units derived from hydrogenated polydiene polyol The content was adjusted to 5 to 20 parts by weight); 34 parts by weight of a polar monomer component including dimethyl acrylamide (N,N-Dimethyl acrylamide); 10 parts by weight of an alkyl (meth)acrylate component having an alkyl group having 6 to 20 carbon atoms including lauryl acrylate and stearyl acrylate; 7 parts by weight of polyfunctional (meth)acrylate; And an initiator (1-Hydroxycyclohexyl phenyl ketone) 5 parts by weight to prepare a composition.

After the composition was applied to a fiber sheet made of polyvinyl chloride (PVC) having a width of 30 cm by a length of 20 cm, it was fixed to a photocuring device as shown in FIG. 6.

Thereafter, as shown in Table 1 below, light irradiation was performed step by step while moving the fiber sheet at a moving speed of 20±1 m/min to prepare a fiber material (laminate). At this time, the average thickness of the coating layer was 8 ± 5㎛. Table 1 shows the specific filler content and the curing process for each example.

[Table 1]

Comparative Examples 1 to 3

A fiber material was prepared by performing the same conditions and method as in Example 1, except that the composition was cured under the curing conditions in Table 2 below. In the case of Comparative Example 3, it was confirmed that the viscosity of the acrylic resin composition was high, so when the composition was applied to the fiber layer, it was difficult to uniformly apply the composition to the surface, so that the workability was significantly deteriorated.

[Table 2]

<Experimental Example 1: Surface structure confirmation>

In order to confirm the surface structure/shape of the cured layer on which wrinkles were formed of the fibrous material, a scanning electron microscope (SEM) analysis was performed on the fibrous materials prepared in Examples and Comparative Examples. The results are shown in FIGS. 7 to 8.

As shown in FIG. 7, in the fibrous materials of Examples 1 to 3, the surface of the cured layer in which wrinkles were uniformly formed was observed. Specifically, when the SEM analysis is performed at an arbitrary location, _{the length of the wrinkle (W a} ) extending is 5 μm or more or 10 μm or more, and in particular, the size of the wrinkle (W _a ) is at a length of 100 μm or less. The case at the level of about 50 μm was mainly observed.

On the contrary, referring to FIG. 8, it was confirmed that the coating layer of the fiber material of Comparative Example 1, which was not subjected to the first light irradiation (first photocuring), did not have a fine wrinkle structure on the surface. In addition, in the _{fiber material of Comparative Example 2 in which the concentration of oxygen gas (O 2} ) in nitrogen gas was significantly high, a simpler wrinkle structure was observed compared to the example. Specifically, in the case of Comparative Example 2, ^{not only the frequency of wrinkles decreased within an arbitrary 100 μm 2} area (confirmed in the same manner as in Example), and the direction of the observed wrinkles (when compared with the results of Example) was more clearly visible. Became. More specifically, in Comparative Example 2, a length level of 100 μm was mainly observed, and a large number of wrinkles having a length of 150 μm or more were observed, such that substantially long wrinkles were observed. The fibrous material of Comparative Example 3 containing an excessive amount of filler showed a more dense structure than the wrinkles of Example, and, for example, wrinkles of about 20 μm in length were mainly observed.

<Experimental Example 2: Measurement of physical properties>

The physical properties of the laminate having the surface wrinkle characteristics identified in Experimental Example 1 were measured. Specifically, the surface gloss and elongation of the fiber materials prepared in Examples and Comparative Examples were evaluated. The results are shown in Table 3.

* Elongation evaluation

Tensile elongation of the fiber material was measured for each of the fiber materials prepared in Examples and Comparative Examples. Specifically, a specimen was prepared in the shape and size (unit: mm) as shown in FIG. 9, and the clamp interval of UTM was set to 150 mm, and the clamp interval corresponding to 100% elongation, which was 300, was pulled at a tensile speed of 200 mm/min. When mm reached, the test was terminated and the specimen was recovered. It was evaluated whether or not the material was sufficiently elongated at the corresponding elongation by checking whether there was spatter or cracking in the surface layer of the specimen.

* Gloss evaluation

Using a gloss meter (Gloss Meter) the 60 ° gloss (gloss 60 ° condition) of the fiber material according to ASTM D2457 was measured both before and after the elongation evaluation. After elongation evaluation, the glossiness was measured in parallel to the stretching direction at the center position of the specimen. For reference, when the measured glossiness is 1.0 or less, ultra-matte, matte in the range of 1.0 to 2.0, and matte properties gradually lose after exceeding 2.0.

[Table 3]

As shown in Table 3, it was confirmed that the fibrous materials of Examples 1 to 3 had a glossiness of 1.0 or less under a gloss 60° condition and a change in gloss of 20% or less even when a small amount of the matting agent was used. That is, not only the gloss itself was low, but also surface cracking did not occur even after stretching, and no gloss degradation was observed with the naked eye even after measuring the elongation.

However, in the case of Comparative Example 1, it showed a gloss property instead of a matte property before stretching. The reason why the glossiness after stretching in Comparative Example 1 was lowered was that the surface was cracked and damaged during stretching. Specifically, the lowered glossiness of Comparative Example 1 did not reach the matte property. In addition, the cracking of the surface by stretching means a decrease in the touch, the lack of a luxurious external feel, and a decrease in stain resistance. In the case of Comparative Example 2, it can be seen that it has a matte characteristic, but it did not implement the ultra matte characteristic of a luxurious appearance required in the present application. It is thought that fine control of the oxygen concentration during the first light irradiation step affects the ultra-matt properties. In the case of Comparative Example 3, in the case of Comparative Example 3, a whitening phenomenon due to the matting agent appeared after stretching due to the use of an excessive amount of the matting agent, and the gloss was greatly increased, resulting in loss of ultra-matt properties.

100: light curing device
110: light irradiation room
111: first light irradiator
112: second light irradiator
120: light irradiated
130: conveyor belt
140: gas diaphragm
150: Psalm

Claims (15)

Base layer; And a cured layer positioned on at least one surface of the base layer and having a wrinkled surface,
The laminate has an elongation of 100% or more,
The laminate is a laminate that satisfies each of 1.0 or less of 60˚ gloss measured before and after 100% stretching. The laminate according to claim 1, wherein the rate of change between the 60° gloss measured before and after 100% stretching is 20% or less. The laminate according to claim 1, wherein the cured layer comprises a cured product of a composition comprising a reactive oligomer component (A) and a reactive monomer component (B). The laminate according to claim 3, wherein the reactive oligomer component (A) comprises urethane acrylate. The laminate according to claim 3, wherein the reactive oligomer component (A) contains a urethane acrylate having a weight average molecular weight (Mw) of 30,000 or less. The laminate of claim 4, wherein the composition comprises a urethane acrylate in the range of 20 to 70 parts by weight, based on 100 parts by weight of the total composition. The laminate according to claim 6, wherein the urethane acrylate contains a urethane acrylate (a-1) having a unit derived from a hydrogenated polydiene polyol. The laminate according to claim 7, wherein the urethane acrylate contains 5 parts by weight or more of urethane acrylate (a-1) having units derived from hydrogenated polydiene polyol, based on 100 parts by weight of the total composition. The laminate according to claim 3, wherein the composition comprises a polar monomer (b-1) having a hydroxy group, a nitrogen-containing functional group, or an alkylene oxide group. The laminate according to claim 3, wherein the composition comprises an alkyl (meth)acrylate (b-2) having an alkyl group having 6 to 20 carbon atoms. The laminate according to claim 3, wherein the composition further comprises a multifunctional (meth)acrylate (C). The laminate according to claim 1, wherein the base layer comprises natural or synthetic leather. Automobile interior material comprising the laminate according to claim 1. A first light irradiation step of irradiating the composition coated on the substrate layer with light (L ₁ ) of a predetermined wavelength under inert gas conditions to form wrinkles on the surface of the applied composition; And
Including a second light irradiation step of forming a cured layer that is a cured product of the composition by irradiating light (L ₂ ) of a longer wavelength than the light (L _{1) under air conditions,}
A method of manufacturing a laminate according to claim 1 including a base layer and a cured layer. The method of claim 14, wherein the light (L ₂ ) has a wavelength in the range of 200 to 400 nm, including a base layer and a cured layer.

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