KR20210122433A - Coating composite and Laminate using the same and improved elongation property - Google Patents

Abstract

The objective of the present invention is to provide a coating composition that shows the effect of implementing an excellent elongation rate while remaining constant over a certain level of surface properties, and a laminate comprising the same. To this end, a laminate according to the present invention comprises: a base material layer; and a coating layer positioned on one surface of the base material layer, wherein the coating layer is a cured layer of a coating composition including a monomer having a nitrogen-containing functional group and a urethane acrylate-based oligomer, and it may exhibit an elongation rate of 40% or more.

Description

Coating composition and laminate using the same and improved elongation properties {Coating composite and Laminate using the same and improved elongation property}

The present invention relates to a coating composition and a laminate including the same, and to a laminate having improved elongation properties.

In general, in order to impart predetermined physical properties to the surface of a material such as a resin, a hard coating layer may be formed. In particular, the hard coating layer may impart surface properties such as surface hardness, abrasion resistance, solvent resistance, chemical resistance, and weather resistance to the exterior of the substrate. A laminate including such a hard coating layer is required in a field in which various plastic products such as automobile exterior materials, building materials, furniture, and various display devices are used.

On the other hand, the exterior material may be required to have a curved portion according to the need for its shape or structure, and the curved portion may be formed by a press molding process of the exterior material. In this case, the exterior material may be made of a laminate including a coating layer to further improve surface properties, and the coating layer formed on the outermost surface of the exterior material must essentially satisfy an appropriate level of hardness. However, when a laminate including a coating layer exhibiting excellent hardness as described above has excessive hardness characteristics, the workability of the laminate is very poor. Process difficulties may arise.

That is, if the elongation rate of the coating layer is improved to improve workability, the surface properties of the final product are not secured to the same level as in the prior art, but may be deteriorated. Accordingly, surface properties such as elongation and hardness have a trade-off relationship, so that the final product maintains the surface properties, ie, hardness, at a level equal to or higher than that of the existing product, while the existing laminate having a coating layer It is necessary to realize the excellent elongation rate that the sieve did not have at the same time.

In order to solve the above problems, the problem to be solved by the present invention is to provide a coating composition and a laminate including the same. The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

The present invention may provide a coating composition comprising a monomer (A) having a nitrogen-containing functional group and a urethane acrylate-based oligomer component (Y). The monomer (A) having the nitrogen-containing functional group may be a monomer including at least one of an amide group, an amine group, an imine group, and an imide group. The monomer (A) having the nitrogen-containing functional group may include acrylamide, acryloylmorpholine, acrylonitrile or a derivative thereof. The monomer (A) having the nitrogen-containing functional group may be included in an amount of 25 parts by weight or more based on 100 parts by weight of the total coating composition. The urethane acrylate-based oligomer component (Y) may include at least one selected from the group consisting of a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a pentafunctional oligomer. The coating composition may further include a polyfunctional acrylate-based monomer component (B). The polyfunctional acrylate-based monomer component (B) may include at least one selected from the group consisting of a difunctional monomer, a trifunctional monomer, a tetrafunctional monomer, and a pentafunctional oligomer. The polyfunctional acrylate-based monomer component (B) may be included in an amount of 9 parts by weight or less based on 100 parts by weight of the total coating composition.

In addition, the present invention is a substrate layer; And it is located on one surface of the base layer and includes a coating layer that is a cured layer of the coating composition according to claim 1, and exhibiting an elongation of 40% or more, it is possible to provide a laminate. The base layer may include polycarbonate. At least one of a printing layer and an adhesive layer may be further included on the other surface of the base layer.

As described above, the laminate according to the present invention can exhibit the effect of implementing excellent elongation while maintaining surface properties above a certain level. However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a cross-sectional view showing a laminate according to an embodiment of the present invention.
2 is a cross-sectional view illustrating a laminate according to an embodiment of the present invention.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In this application, when an element, such as a layer, region, or substrate, is referred to as being “on” another component, it may be directly on the other element or intervening elements may be present in between. You will understand.

In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

In the present application, "acrylate-based" means not only acrylates, but also methacrylates, or derivatives in which substituents are introduced into acrylates or methacrylates. In addition, "alkyl (group)" refers to an aliphatic hydrocarbon group, and may be a saturated alkyl group not containing multiple bonds or an unsaturated alkyl group containing at least one multiple bond. The alkyl group, whether saturated or unsaturated, may be branched, straight-chain or cyclic.

In the present application, the term "monofunctional acrylate monomer" refers to an acrylate-based monomer including one substituted or unsubstituted acrylate group as a polymerizable functional group. In addition, in the present application, the term “polyfunctional acrylate-based monomer” refers to an acrylate-based monomer including two or more substituted or unsubstituted acrylate groups as polymerizable functional groups. Specifically, the monomer may be unsubstituted or substituted with any one or more of the hydrogen included in the acrylate group.

Furthermore, in the present application, the description of a numerical range such as "x to y" or "x to carbon number y" should be interpreted as describing not only x and y but also all numbers in between.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise.

Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In an example related to the present application, the present application provides a coating composition.

The coating composition may include a monomer (A) having a nitrogen-containing functional group. A monomer is a material having one or more polymerizable functional groups and having reactivity, and may refer to a compound having a relatively low molecular weight of about 1,000 or less, and a weight average molecular weight (Mw). Here, the weight average molecular weight may mean a value converted to standard polystyrene measured by GPC. The nitrogen-containing functional group may include at least one of an amide group, an amine group, an imine group, an imide group, and a nitril group, if the functional group contains nitrogen However, the present invention is not limited thereto.

As an example, the monomer (A) having a nitrogen-containing functional group may be acrylamide, N-acryloyl morpholine, acryloyl morpholine, acrylonitrile or a derivative thereof, and as another example, a monomer having a nitrogen-containing functional group ( A) may be, but is not limited to, 2-aminoethyl acrylate, 3-aminoethyl acrylate, N,N-dimethylaminoethyl acrylate or N,N-dimethylaminopropyl acrylate acrylonitrile.

Preferably, it may be acrylamide or a derivative thereof. The acrylamide may be an alkyl acrylamide or a derivative thereof, and more specifically, N-hydroxyethyl acrylamide, N,N-dimethylacrylamide, DMAA ), N-methylacrylamide (N-methylacrylamide), N-butoxymethyl acrylamide (N-(Butoxymethyl)acrylamide) or N-isopropyl acrylamide (N-isopropyl acrylamide).

Furthermore, the monomer (A) having a nitrogen-containing functional group may be included in an amount of 25 parts by weight or more, 28 parts by weight or more, 41 parts by weight or more, 44 parts by weight or more based on 100 parts by weight of the total coating composition. When the monomer (A) having a nitrogen-containing functional group is used together with other components in the above content range, in particular, surface properties such as abrasion resistance and hardness are excellent, and further, excellent elongation while maintaining excellent surface properties As a result, both physical properties can be secured at an appropriate level or higher.

The coating composition may include a urethane acrylate-based oligomer component (Y). An oligomer is an oligomer in which several to tens of monomers are linked, and may be a reactive material. The urethane acrylate may act advantageously to secure the flexibility of the coating layer through the elasticity of the urethane bond while securing the strength of the coating layer by including the urethane bond.

The urethane acrylate may be prepared by polymerizing a compound such as an isocyanate-based compound, a polyol, and an acrylate according to a known method to satisfy the following functional number. For example, a polyisocyanate having 3 or more isocyanate groups is reacted with an acrylate having a hydroxyl group in a molecule and containing 3 or more acrylic groups under a metal catalyst and a radical polymerization inhibitor until the isocyanate (NCO) disappears. , urethane acrylate may be prepared by adding 5 to 30% by weight of an ultraviolet curable monomer. Alternatively, a urethane acrylate satisfying the following functional number may be selected from among commercially available products. In particular, in the present application, an aliphatic urethane acrylate-based oligomer may be used.

The urethane acrylate-based oligomer may be a polyfunctional oligomer including two or more photopolymerizable functional groups. Specifically, the urethane acrylate-based oligomer component (Y) may include at least one selected from the group consisting of a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a pentafunctional oligomer oligomer. By selecting an oligomer having a functional group satisfying the above specific number, it exhibits improved elongation while maintaining excellent surface properties, and both physical properties can be secured at an appropriate level or higher. Accordingly, the laminate according to the present invention may have a three-dimensional curved portion without being damaged during the press forming process. On the other hand, in the case of using an oligomer including a functional group of 6 or more functional groups, only the hardness is excellent, and the elongation is relatively very low.

As an example, the urethane acrylate-based oligomer component (Y) may be included in two or more types having different numbers of functional groups in the coating composition. Specifically, the composition may use a combination of a bifunctional oligomer and a trifunctional oligomer as the urethane acrylate-based oligomer component (Y). In particular, the bifunctional oligomer may have a molecular weight of 8,000 g/mol to 11,000 g/mol, and the trifunctional oligomer may have a molecular weight of 1,000 g/mol to 1,500 g/mol.

Furthermore, the urethane acrylate-based oligomer component (Y) may be included in an amount of 40 to 70 parts by weight based on 100 parts by weight of the total coating composition. Specifically, the lower limit of the urethane acrylate-based oligomer component (Y) may be 42 parts by weight or more, 44 parts by weight or more, 46 parts by weight or more, 48 parts by weight or more, or 50 parts by weight or more, and the upper limit is 70 parts by weight or less. , 68 parts by weight or less, 66 parts by weight or less, 64 parts by weight or less, 62 parts by weight or less, 60 parts by weight or less, 58 parts by weight or less, or 56 parts by weight or less. When the urethane acrylate-based oligomer component (Y) is used in the above content range along with other components, the surface properties of the coating layer may be sufficiently secured.

The coating composition may further include a polyfunctional acrylate-based monomer component (B). The polyfunctional acrylate-based monomer may have excellent crosslinking properties compared to the monofunctional monomer. The cured layer of the coating composition further includes a polyfunctional acrylate-based monomer, thereby improving the crosslinking density of the coating layer including the same, and the coating layer may exhibit excellent physical properties such as abrasion resistance, weather resistance, and chemical resistance.

The polyfunctional acrylate-based monomer component (B) may include at least one selected from the group consisting of a difunctional monomer, a trifunctional monomer, a tetrafunctional monomer, and a pentafunctional monomer. As an example, the polyfunctional acrylate-based monomer component (B) may include at least one of a bifunctional acrylate-based monomer or a trifunctional acrylate-based monomer. In contrast to the case of using a polyfunctional acrylate-based monomer containing a functional group of six or more functional groups as used in the existing coating composition, the coating layer according to the present invention is a polyfunctional acrylate-based monomer component (B) containing a monomer having less than or equal to five functions. As it is used, excellent elongation may be exhibited, and workability of the laminate obtained therefrom, specifically, curvature molding may be easier.

The bifunctional acrylate-based monomer is, for example, tricyclodecane dimethanol diacrylate (TCDDA), cyclohexane dimethanol diacrylate, hexanediol diacrylate (hexanediol diacrylate) , triethylene glycol diacrylate, tetra ethylene glycol diacrylate, butylene glycol diacrylate, polyethylene glycol diacrylate, or It may be polypropylene glycol diacrylate. The trifunctional acrylate-based monomer is, for example, trimethylolpropane triacrylate (TMPTA), glycerine triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propylated trimethylolpropane triacrylate, glycerylpropylated triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate. The tetrafunctional acrylate-based monomer may be, for example, pentaerythritol tetraacrylate or ditrimethylolpropane tetraacrylate. The pentafunctional acrylate-based monomer may be, for example, dipentaerythritol pentaacrylate or dipentaerythritol hydroxypentaacrylate.

The polyfunctional acrylate-based monomer component (B) is included in an amount greater than 0 parts by weight based on 100 parts by weight of the total coating composition, and further, 9 parts by weight or less, 8.5 parts by weight or less, 8 parts by weight or less, 7.5 parts by weight or less, 7 parts by weight or less It may be included in parts by weight or less, 6.5 parts by weight or less, and 6 parts by weight or less. When the polyfunctional acrylate-based monomer component (B) is used in excess beyond the above range, the curing density may be excessive and the elongation rate may be reduced.

Furthermore, the polyfunctional acrylate-based monomer component may include a bifunctional acrylate-based monomer and a trifunctional acrylate-based monomer, and in this case, the bifunctional acrylate-based monomer has more weight than the trifunctional acrylate-based monomer By being included, it may be to implement a more excellent elongation rate.

In addition, additives such as an initiator, a light stabilizer, a UV absorber, a smoothing agent, a dispersant, and an antistatic agent may be further mixed with the coating composition.

In another example related to the present application, the present application provides a laminate including a coating layer.

1 is a cross-sectional view showing a laminate according to an embodiment of the present invention.

Referring to FIG. 1 , the laminate includes a base layer 10 . The base layer 10 may include polycarbonate (PC), polyvinylchloride (PVC), polyethylene (PE), polypropylene (PP), and polystyrene (PS). It is not limited. In particular, the base layer may be polycarbonate (PC).

In addition, the laminate may include a coating layer 20 that is positioned on one surface of the base layer and is a cured layer of the coating composition according to the above. The cured layer may be obtained by photo-curing or thermal curing the coating composition.

The laminate may exhibit an elongation of 40% or more, specifically, an elongation of 50% or more. The elongation rate was evaluated using a universal testing machine. The laminate was prepared as a dog-bone type specimen with a length of 120 mm and a width of 10 mm, and stretched at a tensile rate of 100 mm/min, elongation at the point where cracks occur. will be measured

2 is a cross-sectional view illustrating a laminate according to an embodiment of the present invention.

Referring to FIG. 2 , the laminate may include a substrate layer 10 and a coating layer 20 positioned on one surface of the substrate layer, and a printed layer 30 or an adhesive layer ( 40) may be further included. In addition to this, if necessary, the laminate according to the present invention may further include a layer that can be used in the art.

For example, the sheet may have a structure in which an adhesive layer, a base layer, a printing layer, and a coating layer are sequentially stacked, and in some cases, an adhesive layer, a base layer, and a coating layer may have a structure in which the coating layer is sequentially stacked. In addition, the substrate layer, the printing layer, and the coating layer may have a sequentially stacked structure, but is not limited thereto. Components described in FIG. 1 will be omitted.

The adhesive layer is a layer in contact with the laminate and other materials, and may have a function of imparting adhesive force to the laminate. Therefore, as long as a material capable of imparting adhesive strength is used, it may be used without limitation.

The printing layer may perform a function of directly realizing an aesthetic feeling such as color and shape of the laminate, and may include patterns formed through various raw materials and printing methods as necessary. The printing method may be a method commonly applied in the art, and specifically may be using a method such as gravure printing, flexographic printing, or rotary screen printing.

The use of the laminate having the above configuration and characteristics is not particularly limited. For example, the laminate may be used as a film or sheet for supplementing surface properties of articles such as furniture. Alternatively, the laminate may be used as an exterior material used in a building or automobile.

In one example, the laminate may be used as an exterior material of an article having a shape such as a curved surface or an inclined portion. Specifically, the laminate is a laminate that can be combined or attached to an article having a shape such as a curved surface or an inclined portion through engagement of the shape or through an adhesive, etc., and is press-molded to have the same shape as the article. It may be manufactured through Since press forming is an operation to give a shape such as a curved surface or an inclined portion, elongation is important. In addition, in the application of the exterior material, since it has a predetermined elongation, the laminate formed to have a curved portion or an inclined portion is required to have excellent surface hardness. As described above, since the laminate of the above-described configuration can provide both excellent elongation and surface hardness, it is suitable for use as an exterior material formed through press molding.

In another example related to the present application, the present application relates to an exterior material having a curved portion or an inclined portion. For example, the exterior material may be an automobile pillar. An automobile pillar means a pillar that is located between the door and the ceiling of the vehicle and adds strength to the vehicle. Specifically, it may be a front pillar (A pillar), a center pillar (B pillar), or a rear pillar (C pillar). have. The automobile pillar may have a shape of a curved portion with severe curvature.

In another example related to the present application, the present application may relate to a laminate for press molding. Press molding may be molding to have a predetermined curved surface by applying pressure.

Hereinafter, a preferred experimental example (example) is presented to help the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited by the following experimental examples.

<Production Example>

Example

Based on 100 parts by weight of the total coating composition, N-hydroxyethylacrylamide (N-hydroxyethylacrylamide, HEAA), tricyclodecane dimethanol diacrylate (TCDDA), trimethylpropane triacrylate (TMPTA) ) and the urethane acrylate-based oligomer component to include as much as parts by weight described in the column according to the Examples of Table 1 below, and they were sufficiently mixed to prepare a coating composition.

5 parts by weight of a photoinitiator (Irgacure 184) is further added to the coating composition based on the total weight of the coating composition, and the mixture is sufficiently mixed, and then the mixture is applied on the surface of a polycarbonate (PC) film, and UV irradiation to cure the coating layer Thus, a laminate was obtained.

Comparative Examples 1 to 3

A laminate was obtained by using the same method as in the above Example, except that the amount of the coating composition was included in the amount of Comparative Examples 1 to 3 described in Comparative Examples 1 to 3 based on 100 parts by weight of the total coating composition.

Table 1 below summarizes some of the components constituting the coating composition according to Examples and Comparative Examples of the present invention and the corresponding content (in detail, parts by weight of the component relative to 100 parts by weight of the total coating composition) .

[Table 1]

<Experimental example>

elongation rate evaluation

A laminate obtained by applying a coating composition on a polycarbonate film and curing it by UV was prepared as a dog-bone type specimen having a length and width of 120 mm and 10 mm, respectively. At room temperature, the elongation rate was evaluated using a universal testing machine. The tensioner jig maintains a distance of 100mm, fixes 10mm at both ends of the prepared specimen, and stretches it at a tensile speed of 100mm/min. The point at which cracks occur in the coating layer was measured. That is, if cracks started to occur in the coating layer at the point where the 100 mm specimen was stretched by 10 mm, the elongation of the specimen was evaluated as 10%.

Pencil hardness evaluation

Using a pencil hardness tester and a pencil for measuring hardness, the pencil hardness was measured and evaluated.

Wear-resistance evaluation

According to ASTM D1044-05 test method, the abrasion resistance of the coating layer was evaluated. A coating composition was applied on a polycarbonate film and UV cured to obtain a laminate. The surface of the laminate was scratched under the conditions of a load of 500 g, a speed of 60 rpm, and 100 cycles using a CS10F wear wheel, and gloss retention was evaluated by comparing the gloss of 60° before and after treatment.

Table 2 below shows the results obtained according to each of the above evaluations.

[Table 2]

Referring to Tables 1 and 2, it can be confirmed that the coating layer according to the Examples compared to Comparative Examples exhibits pencil hardness of HB or more and has excellent gloss retention, while sufficiently securing excellent surface properties, and exhibiting improved elongation. .

10: base layer
20: coating layer
30: print layer
40: adhesive layer

Claims (11)

A coating composition comprising a monomer having a nitrogen-containing functional group (A) and a urethane acrylate-based oligomer component (Y). The method according to claim 1,
The monomer (A) having the nitrogen-containing functional group is a coating composition comprising at least one of an amide group, an amine group, an imine group, or an imide group. The method according to claim 1,
The monomer (A) having a nitrogen-containing functional group is a coating composition comprising acrylamide, acryloylmorpholine, acrylonitrile or a derivative thereof. The method according to claim 1,
The monomer (A) having the nitrogen-containing functional group is a coating composition comprising 25 parts by weight or more based on 100 parts by weight of the total coating composition. The method according to claim 1,
The urethane acrylate-based oligomer component (Y) is a coating composition comprising at least one selected from the group consisting of a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a pentafunctional oligomer. The method according to claim 1,
The coating composition further comprises a polyfunctional acrylate-based monomer component (B). 7. The method of claim 6,
The polyfunctional acrylate-based monomer component (B) is a coating composition comprising at least one selected from the group consisting of a bifunctional monomer, a trifunctional monomer, a tetrafunctional monomer, and a pentafunctional oligomer. 7. The method of claim 6,
The polyfunctional acrylate-based monomer component (B) is included in an amount of 9 parts by weight or less based on 100 parts by weight of the total coating composition. base layer; and a coating layer that is located on one surface of the base layer and is a cured layer of the coating composition according to claim 1,
A laminate exhibiting an elongation of 40% or more. 10. The method of claim 9,
The base layer includes a polycarbonate (polycarbonate), the laminate. 10. The method of claim 9,
The laminate further comprising at least one of a printed layer or an adhesive layer on the other surface of the base layer.

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