阅读说明：本技术 油墨组合物、使用油墨组合物的窗口以及窗口的制造方法 (Ink composition, window using ink composition, and method for producing window ) 是由 崔志源 金东豪 李东云 于 2020-04-29 设计创作，主要内容包括：本公开涉及一种油墨组合物、使用油墨组合物的窗口以及窗口的制造方法,其中,油墨组合物包括：丙烯酸树脂,包括具有羟基的第一单体、具有环氧基的第二单体、具有丙烯酸酯基的第三单体以及具有取代或未取代的苯基的第四单体的聚合产物；具有异氰酸酯基的第一固化剂；以及具有胺基的第二固化剂。可以改善窗口的耐久性和耐磨性。(The present disclosure relates to an ink composition, a window using the ink composition, and a method of manufacturing the window, wherein the ink composition includes: an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group; a first curing agent having an isocyanate group; and a second curing agent having an amine group. The durability and abrasion resistance of the window can be improved.)

1. An ink composition, wherein the ink composition comprises:

an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group;

a first curing agent having an isocyanate group; and

a second curing agent having an amine group.

2. The ink composition of claim 1, wherein the ink composition further comprises an epoxy resin.

3. The ink composition of claim 1, wherein the first monomer is hydroxypropyl acrylate.

4. The ink composition of claim 1, wherein the second monomer is glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, or a combination thereof.

5. The ink composition of claim 1, wherein the third monomer is methyl methacrylate.

6. The ink composition of claim 1, wherein the fourth monomer is benzyl methacrylate, styrene, tert-butyl styrene, or a combination thereof.

7. The ink composition according to claim 1, wherein the ink composition comprises, based on 100 moles of the acrylic resin:

from about 10 moles to about 30 moles of the first monomer;

from about 10 moles to about 20 moles of the second monomer;

from about 20 moles to about 35 moles of the third monomer; and

from about 20 moles to about 35 moles of the fourth monomer.

8. The ink composition according to claim 1, wherein the acrylic resin is represented by formula 1 below:

formula 1

In formula 1

"a", "c" and "d" are each independently integers of 1 to 3,

"b" is 1 or 2,

x is

R₁And R₂Each independently is hydrogen or methyl, and

"n" is an integer of 200 to 400.

9. The ink composition of claim 1, wherein the acrylic resin is a polymer resin having a weight average molecular weight of from about 20000 g/mol to about 40000 g/mol.

10. The ink composition according to claim 1, wherein,

the first curing agent includes two or more isocyanate groups, and

the second curing agent includes two or more amine groups.

11. A window, comprising:

a base substrate comprising a flat region and at least one curved region adjoining the flat region; and

a printing layer disposed on one surface of the base substrate and formed with an ink composition,

wherein the ink composition comprises:

an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group;

a first curing agent having an isocyanate group; and

a second curing agent having an amine group.

12. The window according to claim 11, wherein said ink composition further comprises an epoxy resin.

13. The window according to claim 11,

the first monomer is a hydroxypropyl acrylate,

the second monomer is glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether or a combination thereof,

the third monomer is methyl methacrylate, and

the fourth monomer is benzyl methacrylate, styrene, tert-butyl styrene, or a combination thereof.

14. The window according to claim 13, wherein

The first curing agent includes two or more isocyanate groups, and

the second curing agent includes two or more amine groups.

15. The window according to claim 11, wherein said ink composition comprises, based on 100 moles of said acrylic resin:

from about 10 moles to about 30 moles of the first monomer;

from about 10 moles to about 20 moles of the second monomer;

from about 20 moles to about 35 moles of the third monomer; and

from about 20 moles to about 35 moles of the fourth monomer.

16. The window according to claim 11, wherein said acrylic resin is represented by formula 1 below:

formula 1

In formula 1

"a", "c" and "d" are each independently integers of 1 to 3,

"b" is 1 or 2,

x isOr

R₁And R₂Each independently is hydrogen or methyl, and

"n" is an integer of 200 to 400.

17. A method of manufacturing a window, the method comprising:

providing a base substrate comprising a flat region and at least one curved region adjoining the flat region;

printing an ink composition on a face of the base substrate; and

curing the printed ink composition of the ink composition,

wherein the ink composition comprises:

an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group;

a first curing agent having an isocyanate group; and

a second curing agent having an amine group.

18. The method of manufacturing a window according to claim 17, wherein the ink composition further comprises an epoxy resin.

19. The manufacturing method of a window according to claim 17,

the first monomer is a hydroxypropyl acrylate,

the second monomer is glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, or a combination thereof,

the third monomer is methyl methacrylate, and

the fourth monomer is benzyl methacrylate, styrene, tert-butyl styrene, or a combination thereof.

20. The window manufacturing method according to claim 17, wherein the printing is a process of transcribing the ink composition onto the base substrate using a rubber pad having a convex bottom.

Technical Field

The present disclosure relates to an ink composition printed on a window, a window having the ink composition, and a method of manufacturing the window having the ink composition, and more particularly, to an ink composition having improved printing characteristics, barrier characteristics, chemical resistance, and abrasion resistance, and a window having a printed layer having improved chemical resistance and abrasion resistance.

Background

In order to protect an outer surface of a display panel included in a display device, a window is provided on the display panel. Providing a window on the outer surface of the display device directly affects the design of the display device. Therefore, in order to protect the display panel and add various designs to the display device, the window may be printed with ink and a pattern may be formed. In order to form a pattern on a window of a 3-dimensional structure having a curved shape at its edge, a process of laminating a film printed with ink on the window may be used, but such a laminating method may be complicated and may reduce workability.

Disclosure of Invention

The present disclosure provides an ink composition having improved printing characteristics and reliability.

The present disclosure also provides a window comprising a printed layer having improved chemical and abrasion resistance.

The present disclosure also provides a method of manufacturing a window printed with an ink having improved printing characteristics and reliability.

Embodiments of the inventive concept provide an ink composition including: an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group; a first curing agent having an isocyanate group; and a second curing agent having an amine group.

In an embodiment, the ink composition may further include an epoxy resin.

In an embodiment, the first monomer may be hydroxypropyl acrylate.

In embodiments, the second monomer may be glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, or a combination thereof.

In an embodiment, the third monomer may be methyl methacrylate.

In embodiments, the fourth monomer may be benzyl methacrylate, styrene, tert-butyl styrene, or a combination thereof.

In an embodiment, the acrylic resin may include, based on 100 moles of the acrylic resin: from about 10 moles to about 30 moles of the first monomer; from about 10 moles to about 20 moles of the second monomer; from about 20 moles to about 35 moles of the third monomer; and from about 20 moles to about 35 moles of the fourth monomer.

In an embodiment, the acrylic resin may be represented by formula 1 as follows:

formula 1

In formula 1, a, c and d are each independently an integer of 1 to 3, b is 1 or 2, and X is

Or

R₁And R₂Independently hydrogen or methyl, and n is an integer from 200 to 400.

In an embodiment, the acrylic resin may be a polymer resin having a weight average molecular weight of from about 20000 g/mole to about 40000 g/mole.

In an embodiment, the first curing agent may include two or more isocyanate groups, and the second curing agent may include two or more amine groups.

In an embodiment of the inventive concept, the window includes: a base substrate comprising a flat region and at least one curved region adjacent (i.e., abutting or proximate) the flat region; and a printed layer provided on a face of the base substrate and formed with an ink composition, wherein the ink composition includes: an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group; a first curing agent having an isocyanate group; and a second curing agent having an amine group.

In an embodiment, the ink composition may further include an epoxy resin.

In an embodiment, the first monomer may be hydroxypropyl acrylate, the second monomer may be glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, or a combination thereof, the third monomer may be methyl methacrylate, and the fourth monomer may be benzyl methacrylate, styrene, t-butyl styrene, or a combination thereof.

In an embodiment, the acrylic resin may include, based on 100 moles of the acrylic resin: from about 10 moles to about 30 moles of the first monomer; from about 10 moles to about 20 moles of the second monomer; from about 20 moles to about 35 moles of the third monomer; and from about 20 moles to about 35 moles of the fourth monomer.

In an embodiment, the acrylic resin may be represented by formula 1 as follows:

formula 1

In formula 1, a, c and d are each independently an integer of 1 to 3, b is 1 or 2,

x is

Or

R₁And R₂Independently hydrogen or methyl, and n is an integer from 200 to 400.

In an embodiment of the inventive concept, a method of manufacturing a window includes: providing a base substrate comprising a flat region and at least one curved region adjoining the flat region; printing an ink composition on a face of the base substrate; and curing the printed ink composition, wherein the ink composition comprises: an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group; a first curing agent having an isocyanate group; and a second curing agent having an amine group.

In an embodiment, the ink composition may further include an epoxy resin.

In an embodiment, the first monomer may be hydroxypropyl acrylate, the second monomer may be glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, or a combination thereof, the third monomer may be methyl methacrylate, and the fourth monomer may be benzyl methacrylate, styrene, t-butyl styrene, or a combination thereof.

In an embodiment, the printing may be a process of transcribing the ink composition onto the base substrate using a rubber pad having a raised base.

Drawings

The accompanying drawings are included to provide a further understanding of the inventive concepts, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the inventive concepts and, together with the description, serve to explain the principles of the inventive concepts. In the drawings:

fig. 1 is a perspective view of a display apparatus according to an embodiment of the inventive concept;

fig. 2 is an exploded perspective view of the display device shown in fig. 1;

FIG. 3A is a cross-sectional view taken along line I-I' in FIG. 2;

FIG. 3B is a cross-sectional view taken along line II-II' of FIG. 2;

fig. 4 illustrates a cross-linked state formed after printing of an ink composition according to an embodiment of the inventive concept;

fig. 5 is a flowchart illustrating a method of manufacturing a window according to an embodiment of the inventive concept; and

fig. 6A, 6B, 6C, and 6D illustrate a method of sequentially printing ink compositions according to an embodiment of the inventive concept on a window.

Detailed Description

The present disclosure now will be described more fully hereinafter with reference to the accompanying drawings, in which various embodiments are shown. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. Like reference numerals refer to like elements throughout.

It will be understood that when an element (or region, layer, portion, etc.) is referred to as being "connected" or "coupled" to another element, it can be connected or coupled to the other element or intervening elements or layers may be present. It will also be understood that when an element is referred to as being "on" another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.

Exemplary embodiments are described herein with reference to cross-sectional illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, the embodiments described herein should not be construed as limited to the particular shapes of regions illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region shown or described as flat may generally have rough and/or nonlinear features. Further, the acute angles shown may be rounded/chamfered. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present disclosure. Like numbers refer to like elements throughout. In addition, in the drawings, thicknesses, ratios, and sizes of elements are exaggerated for effectively describing technical contents.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, including "at least one", unless the context clearly indicates otherwise. "at least one" is not to be construed as limited to "a" or "an". "or" means "and/or". As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. For example, a first element discussed below could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the teachings of the present disclosure. Unless a meaning is clearly different in this context, singular expressions include plural expressions.

Additionally, for ease of description, terms such as "below," "above," and "above" may be used herein to describe relative relationships of elements as shown in the figures. These terms have relative concepts and may be interpreted based on the orientation depicted in the figures.

It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof.

In view of the measurements in question and the errors associated with a particular number of measurements (i.e., limitations of the measurement system), the term "about" or "approximately" as used herein includes the recited values and indicates that for a particular value, as determined by one of ordinary skill in the art, it is within an acceptable range of deviation. For example, "about" can mean within one or more standard deviations, or within ± 30%, ± 20%, ± 10% or ± 5% of the stated value.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

In the context of the present disclosure, it is,refers to a location of attachment to an adjacent moiety, and refers to a location of attachment to an adjacent polymeric unit in the present disclosure.

In the present disclosure, monomers are distinguished from oligomers and polymers, and a monomer is a compound having a weight average molecular weight of about 1000 g/mole or less.

Hereinafter, an ink composition, a window printed with the ink composition, and a method of manufacturing the window according to embodiments of the inventive concept will be described.

An ink composition according to an embodiment of the inventive concept may include an acrylic resin, a first curing agent having an isocyanate group, and a second curing agent having an amine group.

In particular, the acrylic resin according to an embodiment of the inventive concept includes a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group. For example, the first monomer may be hydroxypropyl acrylate. The second monomer may be glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, or a combination thereof. The third monomer may be methyl methacrylate. The fourth monomer may be benzyl methacrylate, styrene, t-butyl styrene, or a combination thereof.

In the acrylic resin formed by polymerizing the first to fourth monomers, the hydroxyl group, the epoxy group, the acrylate group, and the substituted or unsubstituted phenyl group may be moieties included in side chains of the first to fourth monomers, respectively.

The first monomer according to an embodiment of the inventive concept may be represented by S1 as follows:

the second monomer according to an embodiment of the inventive concept may be represented by S2-1, S2-2, or S2-3. For example, the second monomer may be glycidyl methacrylate.

The third monomer according to an embodiment of the inventive concept may be represented by S3 as follows:

the fourth monomer according to embodiments of the inventive concept may be represented by S4-1, S4-2, or S4-3. For example, the fourth monomer may be benzyl methacrylate.

The acrylic resin according to an embodiment of the inventive concept may be polymerized by radical polymerization of the first, second, third, and fourth monomers. The acrylic resin included in the ink composition of the embodiment may be an acrylic polymer derived from a repeating unit including a first monomer, a second monomer, then a third monomer and a fourth monomer.

The acrylic resin according to an embodiment of the inventive concept may be formed by polymerizing about 10 to about 30 moles of a first monomer, about 10 to about 20 moles of a second monomer, about 20 to about 35 moles of a third monomer, and about 20 to about 35 moles of a fourth monomer, based on 100 moles of the acrylic resin. For example, the acrylic resin may be polymerized with a molar ratio of the first monomer of about 20, a molar ratio of the second monomer of about 20, a molar ratio of the third monomer of about 30, and a molar ratio of the fourth monomer of about 30 to produce the acrylic resin.

The acrylic resin according to an embodiment of the inventive concept may include a hydroxyl group and an epoxy group. The acrylic resin included in the ink composition according to the embodiment may include both a hydroxyl group and an epoxy group in a side chain. For example, the acrylic resin according to the embodiment may be represented by formula 1 as follows:

formula 1

In formula 1, "a", "c", and "d" are each independently an integer of 1 to 3, and "b" may be 1 or 2. In formula 1, "a" to "d" correspond to the numbers of repeating units of the first monomer, the second monomer, the third monomer, and the fourth monomer, respectively. For example, the acrylic resin may be formed by repeating the first monomer twice, the second monomer twice, the third monomer three times, and the fourth monomer three times.

X may beOr

And for example, X may be

R₁And R₂Each independently is hydrogen or methyl. For example, R₁May be a methyl group. For example, R₂May be a methyl group.

In formula 1, "n" may be an integer of 200 to 400.

The acrylic resin of the ink composition according to an embodiment of the inventive concept may be a polymer resin having a weight average molecular weight of about 20000 g/mol to about 40000 g/mol. For example, the acrylic resin of the ink composition according to embodiments may have a weight average molecular weight of about 20000 g/mole to about 30000 g/mole, such as from about 26000 g/mole to about 29500 g/mole.

The first curing agent of the ink composition according to an embodiment of the inventive concept may be a compound having an isocyanate group. In particular, the first curing agent may have a plurality of isocyanate groups. For example, the first curing agent may be isophorone diisocyanate, toluene diisocyanate, or hexamethylene diisocyanate having two isocyanate groups.

The first curing agent of the ink composition according to an embodiment of the inventive concept may perform a crosslinking reaction with the hydroxyl group of the acrylic resin. The first curing agent may cure the ink composition by binding hydroxyl groups of two first monomers connected to different main chains with each other.

According to the ink composition of the embodiment, the first curing agent may include a blocked isocyanate group in which a reactive group of the isocyanate is protected. The blocked isocyanate is used in order to suppress the reaction between the first curing agent and the second curing agent because the reaction rate between the first curing agent and the second curing agent is greater than the reaction rate between the first curing agent or the second curing agent and the hydroxyl group and the epoxy group of the acrylic resin, respectively.

In particular, hexamethylene diisocyanate may be a blocked isocyanate group first curing agent having a protected reactive group.

For example, according to an embodiment of the inventive concept, if the ink composition is printed on the base substrate BS (fig. 3A and 3B) and cured at a high temperature, the protected group of the first curing agent may be cleaved and the reaction rate of the ink composition may be similar at a high temperature, and thus a crosslinking reaction may occur.

The second curing agent of the ink composition according to an embodiment of the inventive concept may be a curing agent having an amine group. In particular, the second curing agent may have two or more amine groups. For example, the second curing agent may be diethylenetriamine or triethylenetetramine.

The second curing agent of the ink composition according to an embodiment of the inventive concept may perform a crosslinking reaction with the epoxy group of the acrylic resin. The second curing agent may cure the ink composition by reacting with the epoxy groups of two second monomers of two different main chains resulting in cross-linking of the two main chains.

The ink composition according to an embodiment of the inventive concept may include: an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group; a first curing agent having an isocyanate group; and a second curing agent having an amine group.

The ink composition according to an embodiment of the inventive concept may further include an epoxy resin such that the printing layer PL (fig. 3A and 3B) has a high crosslinking density. In particular, the epoxy resin may be a compound comprising one or more epoxidized aromatic rings. For example, the epoxy resin may be a bisphenol a type epoxy resin. In particular, the epoxy resin may be added from about 12.5 parts by weight to about 25 parts by weight based on 100 parts by weight of the acrylic resin. The added epoxy resin controls the crosslinking density in the ink composition to improve the strength, durability and surface hardness of the coating layer after the ink composition is cured, and may also enhance the adhesion.

The ink composition according to an embodiment of the inventive concept may further include a pigment such as carbon black, a carbon black dispersant, an antifoaming agent, an isophorone solvent, and a barium sulfate filler. In particular, the carbon black dispersant functions to uniformly disperse the carbon black pigment in the ink, and may be an amine-based dispersant. The defoaming agent functions to destroy bubbles formed in the composition to prevent appearance defects from being generated during the formation of the coating layer, and may be a silicon-based defoaming agent. The barium sulfate filler controls the viscosity of the ink composition and may prevent cracking during coating formation.

Hereinafter, a window and a method of manufacturing the window according to an embodiment of the inventive concept will be described with reference to the accompanying drawings.

Fig. 1 is a perspective view of a display device DD according to an embodiment of the inventive concept. Fig. 2 is an exploded perspective view of the display device DD shown in fig. 1. Fig. 3A is a sectional view taken along line I-I' in fig. 2. Fig. 3B is a sectional view taken along line II-II' in fig. 2. Fig. 4 schematically illustrates a cross-linked state formed after printing of an ink composition according to an embodiment of the inventive concept.

Fig. 3A is a sectional view taken along line I-I' in fig. 2. The line I-I' is a cutting line corresponding to the non-display area NDA in fig. 2, and the printing layer PL may be disposed on the flat area FA and the curved area BA in the non-display area NDA. Fig. 3B is a sectional view taken along line II-II' in fig. 2. The line II-II' corresponds to a cutting line of a window including the display area DA and the non-display area NDA. In fig. 3B, the printing layer PL is mainly disposed in the non-display area NDA.

In fig. 1, a portable terminal having four edges bent is shown as an embodiment of the display device DD. However, embodiments of the inventive concept are not limited thereto, but may be applied to various display devices, such as a curved display device, a curved type display device, a rollable display device, a foldable display device, and a stretchable display device. In addition, although not separately shown, the display device DD according to the inventive concept may be used in small and medium-sized electronic devices such as a personal computer, a notebook computer, a personal digital terminal, a car navigation unit, a game machine, a portable electronic device, a watch-type electronic device, and a camera, and large-sized electronic devices such as a television and an outdoor signboard. These are suggested for illustrative purposes only and of course allow to apply them to another electronic device without departing from the inventive concept.

The display device DD includes a plurality of areas divided on a display surface. The display device DD may include: a display area DA that displays the image IM; and a non-display area NDA adjacent to the display area DA. The display surface of the display image IM is parallel to a plane defined by the first direction DR1 and the second direction DR2, and the normal direction of the display surface is indicated by the third direction DR 3. Third and fourth directions DR3 and DR4 are base axes defining front and rear surfaces of the member, respectively. In the present disclosure, a plane defined by the first direction DR1 and the second direction DR2 is defined as a plane.

The ink composition according to the embodiment may be provided for forming the printing layer PL disposed on the window WD of the display device DD. The ink composition according to an embodiment of the inventive concept may be printed in the non-display area NDA of the display device DD to form a pattern.

Referring to fig. 2, the display device DD may include a display panel DP, a window WD, and a case CU.

The display panel DP may be employed in various types, such as an organic light emitting display panel, a quantum dot light emitting display panel, a liquid crystal display panel, a plasma display panel, an electrophoretic display panel, and an electrowetting display panel.

The window WD according to an embodiment of the inventive concept may be disposed on the display panel DP. In one embodiment, window WD may comprise a glass substrate.

The case CU according to an embodiment of the inventive concept receives the display panel DP and may be combined with the window WD. The housing CU may be obtained by assembling a plurality of parts or may comprise one injection molded body. The casing CU may comprise glass, plastic or metal.

Referring to fig. 3A and 3B, the window WD includes a base substrate BS including a flat area FA and at least one curved area BA adjacent (i.e., abutting) the flat area FA, and may include a printed layer PL obtained by printing an ink composition on a face of the base substrate BS. For example, the printed layer PL may be formed on the bottom of the base substrate BS.

The base substrate BS may be a glass substrate, a metal substrate, a plastic substrate, or the like. However, embodiments of the inventive concept are not limited thereto, and the base substrate BS may be an inorganic layer, an organic layer, or a composite material layer. In particular, the base substrate BS may be a glass substrate or a reinforced glass substrate.

The printing layer PL may be formed using the ink compositions of the examples. As shown in fig. 4, the ink composition may include: an acrylic resin comprising a polymerization product of a first monomer MN1 having a hydroxyl group, a second monomer MN2 having an epoxy group, a third monomer MN3 having an acrylate group, and a fourth monomer MN4 having a substituted or unsubstituted phenyl group; a first curing agent XL1 having an isocyanate group; and a second curing agent XL2 having an amine group.

The same description can be made for the ink composition for forming the printing layer PL as for the ink composition of the above-described example.

Fig. 4 schematically shows a cross-linked state of the ink composition, and the window WD may include the printing layer PL in a cured state of the ink composition as shown in fig. 4. Referring to fig. 4, a first monomer MN1 including a hydroxyl group may be bonded to an adjacent first monomer MN1 through a first curing agent XL1 to be crosslinked and may function as one or more bonds. The second monomer MN2 comprising an epoxy group can be crosslinked by a second curing agent XL 2. The crosslinked state is shown on the plane of fig. 4, but the crosslink formed by the first curing agent XL1 and the second curing agent XL2 may be formed three-dimensionally. That is, unlike the drawing, the crosslink bond passing through the first curing agent XL1 and the crosslink bond passing through the second curing agent XL2 may intersect with each other, and the structure is not limited to the drawing.

Fig. 5 is a flowchart illustrating a method of manufacturing the window WD according to an embodiment of the inventive concept. Fig. 6A to 6D illustrate a method of sequentially printing the ink compositions P-PL according to an embodiment of the inventive concept on the window WD. Hereinafter, a method of manufacturing the window WD according to an embodiment of the inventive concept will be described with reference to fig. 5 and fig. 6A, 6B, 6C, and 6D.

Referring to fig. 5, a method of manufacturing a window WD according to an embodiment of the inventive concept includes: providing a base substrate BS (S100); printing an ink composition P-PL on one surface of a base substrate BS (S200); and curing the printed ink composition P-PL (S300). In particular, in the step of printing the ink composition P-PL on one side of the base substrate BS (S200), a pattern may be formed on the base substrate BS. In particular, providing the base substrate BS (S100) includes a process of providing the base substrate BS including a flat area FA (fig. 3A) and at least one bent area BA (fig. 3A) adjacent (i.e., abutting) the flat area FA (fig. 3A). Printing the ink composition P-PL on one side of the base substrate BS (S200) may include a process of printing the ink composition P-PL on one side of the base substrate BS by a PAD printing method using a rubber PAD as described in fig. 6A.

Referring to fig. 6A, 6B, 6C, and 6D, on the base substrate BS of the window WD, a printed layer PL may be formed by a pad printing method using the ink composition P-PL. According to fig. 6A and 6B, the ink composition P-PL is transcribed from the ink die MD to the rubber PAD. Referring to fig. 6C and 6D, the ink composition P-PL is transcribed on one face of the base substrate BS using a rubber PAD having a convex bottom to form a printed layer PL. The process of curing the printed ink composition P-PL may include a process of curing the ink composition P-PL at an elevated temperature of about 140 ℃ to about 160 ℃ for about 30 minutes.

Hereinafter, the ink compositions according to the embodiments of the inventive concept will be specifically described with reference to examples and comparative examples. The examples are merely examples to aid understanding of the inventive concepts and the inventive concepts should not be construed as limited to the embodiments set forth herein.

Examples of the invention

1. Polymerization of acrylic resins

The polymerization method of the acrylic resin according to this example will be explained and explained in more detail below. In addition, the polymerization method of the acrylic resin described below is an embodiment, and the polymerization method according to the exemplary embodiment of the inventive concept is not limited to the embodiment described below.

(polymerization example of acrylic resin)

To a round bottom flask (2L), 75g of the solvent Ethyl Carbitol Acetate (ECA) was added and maintained at a temperature of about 80 ℃. Hydroxypropyl acrylate (HPA) was used as the first monomer, Glycidyl Methacrylate (GMA) was used as the second monomer, Methyl Methacrylate (MMA) was used as the third monomer, and Benzyl Methacrylate (BMA) was used as the fourth monomer.

The first to fourth monomers (750 g in total) were mixed in respective ratios shown in table 1, and Azobisisobutyronitrile (AIBN) was added and the mixture was stirred. The amount of AIBN is about 0.2 mole% of the total moles of monomer (theoretical degree of polymerization of 250). The mixture of monomer and initiator was added dropwise to the heated (80 ℃) solvent/flask over about 2 hours. After the entire amount of mixture was added, the reaction was held at 80 ℃ for about 4 hours, then once cooled, the reaction mixture was filtered and the product was collected. The product corresponds to the acrylic resin to be included in the ink compositions of the examples.

In table 1 below, the molar ratio of the monomers and the molecular weight of the acrylic resin formed by the above polymerization method are shown.

TABLE 1

Table 1 shows the results of the molecular weights of the acrylic resins polymerized according to the molar ratios of the first to fourth monomers. The weight average molecular weight of the acrylic resin represented by examples a to D satisfies a range of about 20000 g/mol to about 30000 g/mol.

2. Evaluation of ink composition

Physical properties of the ink composition including the acrylic resin polymerized by the polymerization method of the acrylic resin described above were evaluated. In the ink composition for evaluation, in addition to one of the above-described acrylic resin examples a to D, Hexamethylene Diisocyanate (HDI) was used as the first curing agent, and Diethylenetriamine (DETA) was used as the second curing agent.

In examples 4 to 10 of the ink compositions and comparative example 4 including an epoxy resin in addition to one of the acrylic resins, a bisphenol a type epoxy resin was used as the epoxy resin. The epoxy resin has a weight average molecular weight of about 200 grams/mole.

The physical properties of the ink composition are studied by its usability or processability based on three physical properties of interest of the ink composition including the available time, alcohol wiping, and pad printing properties.

The pot life is a time required for increasing the viscosity after adjusting the initial viscosity to about 600 centipoise (cps) to about 1000cps according to the generation of the curing reaction at room temperature. Ink compositions having a viscosity of about 1000cps or higher are not suitable for printing (not feasible), and ink compositions that retain a viscosity of about 1000cps or lower for about 5 hours or longer are acceptable.

Alcohol wiping is a standard for evaluating the strength and crosslink density of a printed layer formed using the ink composition. Therefore, the ink evaluation was performed by printing the ink composition on a glass substrate, curing at about 150 ℃, standing for about 24 hours, and then measuring the number of rubs required for complete peeling of the printed layer by using an alcohol wiping machine under a load condition of about 1000 g. The decision is acceptable if the number of wipes is 150 or more.

The pad printing characteristics were investigated by performing pad printing in a state where the viscosity of the ink composition was about 600cps, and the definition of the printed outer line was evaluated with the naked eye.

TABLE 2

^aBlocked isocyanates

Referring to the results of table 2, and in view of the three physical properties of interest, each property of the ink compositions was found to be acceptable in example 1(ex.1) to example 10 (ex.10). In contrast, in comparative example 1(CE 1) to comparative example 3(CE 3), alcohol wiping was significantly poor or pad printing characteristics were unsatisfactory. In particular, the ink compositions of example 1(ex.1), example 2(ex.2), and example 3(ex.3) included only an acrylic resin, i.e., included no epoxy resin, and showed a decrease in the usable time as the amount of the second curing agent increased.

Example 4(ex.4) and example 5(ex.5) correspond to ink compositions including an acrylic resin, in which the amount of the second monomer GMA is increased at a 10 molar ratio and the amounts of MMA and BMA are each decreased at a 5 molar ratio, based on 100 moles of the acrylic resin. With increasing GMA, the available time gradually decreases and the number of alcohol wipes increases significantly.

In examples 6(ex.6) to 8(ex.8), physical properties were measured while the amount of GMA (second monomer) was kept stable at about 20 mole ratio based on 100 moles of acrylic resin, and the amount of HPA (first monomer) was changed from 10 mole ratio to 30 mole ratio based on 100 moles of acrylic resin. As a result, since HPA does not react with blocked isocyanate as the first curing agent at room temperature, the pot life is not affected (pot life is determined only by DETA as the second curing agent), and the number of alcohol wipes is acceptable as HPA increases. Furthermore, the pad printing characteristics did not change significantly. In this experiment, evaluation was performed at a ratio of about 30 moles based on 100 moles of the acrylic resin.

In example 9(ex.9) and example 10(ex.10), the physical properties were measured by changing the amount of the epoxy resin. With the increase in epoxy, the number of alcohol wipes increased significantly, but the usable time decreased and the definition of the pad printed decreased. As a result, the amount of epoxy resin was limited to about 25 grams based on 80 grams of acrylic resin (50% solids by weight).

In summary, the amount of HPA in the acrylic resin is suitably about 30 mole ratio or less, the amount of GMA is suitably about 20 mole ratio or less, based on 100 moles of the acrylic resin, and the mixing amount of the epoxy resin is suitably from about 12.5 parts by weight to about 25 parts by weight, based on 100 parts by weight of the acrylic resin (50% by weight of solid content).

In the ink composition according to an embodiment of the inventive concept, a suitable molar ratio of the first monomer is from about 10 to about 30, and a suitable molar ratio of the second monomer is from about 10 to about 20, based on 100 moles of the acrylic resin.

The ink composition according to an embodiment of the inventive concept includes an acrylic resin, a first curing agent having an isocyanate group, and a second curing agent having an amine group, and thus may have improved printing characteristics and reliability. In particular, the acrylic resin according to an embodiment of the inventive concept includes a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group, and a printed layer using the ink composition may have improved chemical resistance and abrasion resistance.

The window according to an embodiment of the inventive concept may include a printed layer having improved chemical resistance and abrasion resistance by using the ink composition.

In addition, the method of manufacturing a window according to an embodiment of the inventive concept may provide a window on which a printed layer having improved chemical resistance and abrasion resistance is formed.

The ink composition according to the embodiment includes: an acrylic resin including a polymerization product of a first monomer having a hydroxyl group, a second monomer having an epoxy group, a third monomer having an acrylate group, and a fourth monomer having a substituted or unsubstituted phenyl group; a first curing agent having an isocyanate group; and a second curing agent having an amine group, and the ink composition may have improved printing characteristics and reliability.

The window according to the embodiment includes a printed layer formed using the ink composition, which may exhibit improved chemical resistance and abrasion resistance.

According to the method of manufacturing a window using the ink composition according to the embodiment, a printed layer having improved printing characteristics and reliability can be realized.

Although exemplary embodiments of the present disclosure have been described, it is to be understood that the present disclosure should not be limited to these exemplary embodiments but various changes and modifications can be made by one of ordinary skill in the art within the spirit and scope of the present disclosure as hereinafter claimed.