TW201531536A - Thermosetting ink composition - Google Patents

Abstract

Disclosed is an ink composition including a binder resin having a hydroxyl group, a hardener represented by Formula 1, a poly-functional monomer having an ethylentically unsaturated double-bond, and a solvent. The ink composition of the present invention may be hardened even at lower temperatures and applied to a flexible display or the like, which uses a polymer resin film as a substrate, thereby enabling formation of a pattern without deterioration of the film.

Description

Thermosetting ink composition

The invention relates to a thermoset ink composition that is heat curable at lower temperature conditions.

Conventionally, photolithography has been used to form image patterns of image display devices and semiconductor circuit elements applied to, for example, liquid crystal display devices, plasma display devices, and the like by photolithography.

Photolithography has the advantage of providing subtle and desired patterns while requiring very expensive devices, high resolution masks or the like to maximize photoresist effects. In addition, since a large amount of photoresist is consumed during processing, it also involves cost inefficiency. In addition, photolithography includes multi-step processes such as exposure, post-exposure bake, post-bake development, etching, rinsing, etc., which in turn require long-term processing, and the process must be repeated several times, thus resulting in productivity The reduction.

In recent years, as a method for replacing photolithography, a printing method using an application method of a nozzle such as lithography, reverse lithography, roll-to-roll, or the like has been proposed.

Using the above method, the resin composition is applied to the substrate, and the substrate is heated and hardened so that a desired pattern is formed on the substrate. In general, this thermosetting process is carried out at a high temperature of about 230 °C.

At the same time, as the display field continues to move toward flexible displays, flexible substrates are needed. In this regard, the glass substrate conventionally used in the related art is now replaced by a polymer resin film such as a polyimide or polyethylene terephthalate film or the like. When forming a pattern on a glass substrate, there are no specific problems associated with high temperature processes. However, when a polymer resin film is used as the substrate, shrinkage or deterioration due to high-temperature heat or the like may occur.
Therefore, there is a need for a resin composition capable of hardening even under low temperature conditions for a flexible substrate or the like, which is not deteriorated.

A thermosetting protective film resin composition is disclosed in Korean Patent Publication No. 2008-68286.

Accordingly, it is an object of the present invention to provide an ink composition which is heat curable at lower temperature conditions.

The above objects of the present invention are achieved by the following features:

(1) An ink composition comprising a binder resin having a hydroxyl group, a hardener represented by the following formula 1, a polyfunctional monomer having an ethylenically unsaturated double bond, and a solvent:

[Molecular Formula 1]

(wherein R ₁ is an alkyl group having 1 to 5 carbon atoms,

or ;

R ₂ is an alkylene group having 1 to 10 carbon atoms;

R ₃ and R _{4 are} each independently an alkyl group having 1 to 5 carbon atoms;

n is an integer ranging from 1 to 3.)

(2) The composition according to the above (1), wherein the hardener is included in an amount of 0.1 to 5 wt.% based on the total weight of the composition.

(3) The composition according to the above (1), wherein the binder resin is a novolak resin.

(4) The composition according to the above (1), wherein the binder resin is included in an amount of 10 to 20 wt.% based on the total weight of the composition.

(5) A pattern formed using the composition according to any one of the above (1) to (4).

(6) The pattern according to (5) above, wherein the pattern includes a pattern for a color filter, a black matrix pattern, a black column spacer pattern, a thin film transistor pattern, and an image display device. Electrode pattern or barrier pattern.

The ink composition of the present invention can be hardened even at a relatively low temperature. Therefore, it can be applied to a flexible display using a polymer resin film as a substrate or the like, whereby a pattern can be formed without deterioration of the film.

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The present invention discloses an ink composition comprising a binder resin having a hydroxyl group, a hardener represented by Formula 1, a polyfunctional monomer having an ethylenically unsaturated double bond, and a solvent. The ink composition of the present invention can be hardened even at a lower temperature, and is applied to a flexible display using a polymer resin film as a substrate or the like, whereby a pattern can be formed without deterioration of the film.

Hereinafter, the present invention will be described in more detail.

Thermosetting ink composition

The thermosetting ink composition of the present invention may include a binder resin having a hydroxyl group, a hardener, a polyfunctional monomer having an unsaturated double bond, and a solvent.

Adhesive resin

The binder resin according to the present invention is a binder resin which can react with a hardener to be described below, and may include any resin which is typically used in the related art without any particular limitation as long as it has a hydroxyl group. For example, a novolak resin can be used.
The novolak resin is a novolac type phenol resin obtained by copolymerization of at least one phenol compound and an aldehyde compound.
The phenol compound is not particularly limited, but may include, for example, phenol; cresols such as p-cresol, m-cresol, o-cresol, etc.; xylenols such as 3,5-xylenol, 2 , 5-xylenol, 2,3-xylenol, 3,4-xylenol, etc.; dimethylphenols, such as 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, etc.; trimethylphenols, such as 2, 3, 4 -trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, etc.; tert-butylphenols, such as 2- Tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, etc.; chlorophenols such as o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, etc.; methoxy Phenolics such as m-methoxyphenol, p-methoxyphenol, o-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxy Alkylphenols, etc.; ethylphenols such as butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, 3 , 5-diethylphenol, 2,3,5-triethylphenol, 3,4,5-triethylphenol, etc. Resorcinol, such as resorcinol, 2-methyl resorcinol, 4-methyl resorcinol, 5-methyl resorcinol, etc.; p-isopropylphenol; naphthols, For example, α-naphthol, β-naphthol, etc.; methylene bisphenol, methyl bis-p-cresol, catechol, 4-methyl resorcinol or the like. These compounds may be used singly or in combination of two or more thereof.

The aldehyde compound is also not particularly limited, but may include, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylaldehyde, α-phenylpropanal, β-phenylpropanal, O-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, glutaraldehyde, glyoxal, o-methylbenzaldehyde, p-methylbenzaldehyde or the like. These compounds may be used singly or in combination of two or more thereof.

The binder resin may be included in an amount of 10 to 20 wt.% of the total of 100 wt.% of the ink composition. Within the above range of contents, the binder resin can play a role in supporting the pattern and increasing the transcription rate of the pattern, thereby improving yield and process efficiency. Hardener The hardener according to the present invention can be represented by the following formula 1:

[Molecular Formula 1]

(wherein R ₁ is an alkyl group having 1 to 5 carbon atoms,

or ;

R ₂ is an alkylene group having 1 to 10 carbon atoms;

R ₃ and R _{4 are} each independently an alkyl group having 1 to 5 carbon atoms;

n is an integer ranging from 1 to 3.

The isocyanate group (-NCO) reacts with a hydroxyl group (-OH), and when a hardener having an isocyanate group is used in the ink composition, the reactivity can be extremely excellent, so that the hardener is even The binder resin having a hydroxyl group is reacted at room temperature before the heat curing process, and the ink composition is partially hardened. Therefore, it is difficult to uniformly coat and it is difficult to form a micropattern.

Therefore, a conventional ink composition including a polymer compound, a thermal initiator, a decane compound, or the like is used at a high temperature hardening process at about 230 ° C to form a pattern.

However, the ink composition according to the present invention includes a hardener protected by an alternative substituent, and the carbon atom of the isocyanate group does not form a double bond with the nitrogen atom.

The hardener according to the present invention may not react with a hydroxyl group at room temperature due to the above-mentioned protective substituent, and if a heat at a certain temperature (about 120 ° C) or higher is applied, the protective substituent is dissociated, and therefore, isocyanic acid The salt group becomes activated and reacts with the binder resin to crosslink the binder resin, thereby hardening the ink composition.

In other words, the ink composition of the present invention comprising the above-mentioned hardener can be hardened even at a relatively low temperature of about 120 ° C, and thus can be used to form a pattern applied to a flexible display or the like.

The hardener may be included in an amount of from 0.1 to 5 wt.% of the total 100 wt.% of the ink composition. If the content is less than 0.1 wt.%, the crosslinking is not remarkable, and the hardness of the pattern can be lowered. When the content exceeds 5 wt.%, the storage stability of the composition can be lowered.
Polyfunctional monomer having an ethylenically unsaturated double bond The polyfunctional monomer having an ethylenically unsaturated double bond is a component that enhances the strength of the pattern and may include a single to a hexafunctional monomer. Specific examples thereof may include: a monofunctional monomer such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyl Ethyl acrylate, N-vinyl pyrrolidone, etc.; difunctional monomers such as 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl Alcohol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylic acid Esters and the like; trifunctional monomers such as trimethylolpropane tri(meth)acrylate, neopentyltriol tri(meth)acrylate, etc.; tetrafunctional monomers such as neopentyltetraol tetra(methyl) An acrylate; a pentafunctional monomer such as dipentaerythritol penta (meth) acrylate; a hexafunctional monomer such as dipentaerythritol hexa(meth) acrylate, either alone or in a di- or More combinations are used.
The ethylenically unsaturated double bond polyfunctional monomer may be included in an amount of from 1 to 10 wt.% of the total 100 wt.% of the ink composition. Within the above content range, the desired pattern strength can be achieved.

The solvent may take into consideration the solubility, dispersibility or coating characteristics of the colorant, etc., and the solvent may include, for example, an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , ethylene glycol monobutyl ether, etc.; diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Etc.; ethylene glycol alkyl ether acetate, such as methoxyethyl acetate, ethoxyethyl acetate, etc.; alkylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexyl Ketones and the like; alcohols such as ethanol, methanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc.; cyclic esters such as γ-butyrolactone, etc., which are used alone or in their Used in combination of two or more.

The solvent may be included in an amount of from 75 to 90 wt.% of the total of 100 wt.% of the ink composition. If the content is less than 75 wt.%, the solid content and viscosity increase, and the coating properties (coatability) may be deteriorated. When the content exceeds 90 wt.%, the solid content is too small, and it is difficult to apply, while increasing the amount of solvent to be dried, and therefore, a treatment viewpoint is not desirable.

Colorant The ink composition of the present invention may further include a coloring agent known in the related art.

The colorant may include, for example, an organic colorant such as a pigment, a dye, a synthetic or natural pigment; or an inorganic colorant such as a metal oxide, a metal complex, barium sulfate (potentiator pigment) or the like. As the coloring agent, compounds classified as pigments and dyes according to the Society of Dyers and Colourists may be used singly or in combination of two or more thereof.

Specific examples of the pigment may include: CI Pigment Yellow Nos. 1, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 , 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185; CI Pigment Orange 13, 13, 36, 38, 40, 42, 43, 51, 55, 59, No. 61, 64, 65, 71, 73; CI Pigment Red No. 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254 , 255, 264, 265; CI Pigment Blue No. 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet No. 1, 14, 19, 23, 29, 32, 33, 36, 37 No. 38; CI Pigment Green Nos. 7, 10, 15, 25, 36, 47; CI Pigment Brown No. 23, 25, 28; CI Pigment Black No. 1, No. 7, carbon black or the like.

Specific examples of the dye may include: CI Solvent Yellow Nos. 2, 14, 16, 33, 34, 44, 56, 82, 93, 94, 98, 116, 135; CI Solvent Orange Nos. 1, 3, 7, 63 CI Solvent Red 1, 2, 3, 8, 18, 23, 24, 27, 35, 43, 45, 48, 49, 91:1, 119, 135, 140, 196, 197; CI Solvent Violet 8, 9, 13, 26, 28, 31, 59; CI Solvent Blue Nos. 4, 5, 25, 35, 36, 38, 70; CI Solvent Green Nos. 3, 5, 7 or the like.

The content of the colorant may be controlled depending on the desired color characteristics, and may be included in an amount of 5 to 20 wt.% of the total 100 wt.% of the ink composition.

The ink composition in which the additive includes the above components may further include at least one additive such as an adhesion enhancer, an antioxidant, a dispersant, a surfactant, or the like.

In addition, the present invention provides a pattern prepared using the above ink composition.

The pattern of the present invention may include a pattern for a color filter, a black matrix pattern, a black column spacer pattern, a thin film transistor pattern, an electrode pattern for a image display device, or a barrier pattern.

The pattern can be formed from a coated ink composition and a thermally hardened ink composition.
The method of coating the ink composition is not particularly limited, but may include, for example, lithography, reverse lithography, screen printing, gravure printing, dispensing, spraying, casting, bar coating, die casting coating, rotation Coating or the like.

The formation of the pattern can be accomplished by hardening the applied coating film.

The ink composition of the present invention can be hardened even at a relatively low temperature, and therefore, a pattern can be formed under milder conditions. For example, the hardening may be performed at a temperature ranging from 120 to 150 ° C for 10 to 30 minutes to form a pattern, however, the conditions for hardening are not particularly limited thereto.

Hereinafter, preferred embodiments are presented to more specifically describe the present invention. However, the following examples are given to illustrate the invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the invention. Such changes and modifications are fully included in the scope of the appended claims.

Sample example 1

A color paste was prepared by mixing 30 wt.% of carbon black as a pigment and 3 wt.% of Diperbyk-2010 (BYK Co.) as a polyethylene dispersant.

Then, a total of 100 wt.% of the composition of 12 wt.% of the binder resin having an average molecular weight of 5,000 wt. (by a polymerization ratio of m-cresol and p-cresol of 6:4 wt. ratio (formaldehyde copolymerization) () obtained), 8 wt.% dipentaerythritol hexaacrylate (Toagoesi Co.), 1.5 wt. % BI-7963 (Baxenden Co.) as hardener, 0.2 wt. % TF-1535 (DIC Co .) as a surfactant, and the remainder is propylene glycol monomethyl acetate mixed and added to the prepared color paste while stirring the color paste.

Next, the above mixture was stirred for 3 hours to finally produce an ink composition.
Examples 2 and 3, Comparative Examples 1 to 3

The same procedure as described in Example 1 was carried out except that the type and composition of the binder resin and the hardener were changed as described in Table 1 below.
【Table 1】

Experimental example

(1) Evaluation of pattern adhesion

Each of the ink compositions prepared in the examples and comparative examples was applied to a glass substrate using a spin coater, and heated at 120 ° C for 30 minutes to harden. The hardened coating film was subjected to a viscose peeling test using JSK K5400 to examine the selection of 100 crystal lattices, and the inspection results are shown in Table 2 below.

(2) Evaluation of chemical resistance

The coating film prepared in the experimental example (1) was respectively immersed in a 1% potassium hydroxide solution (anti-alkaline) at 50 ° C, MA-So 2 (Dongwoo Fine Chem Etchant) (anti-acidic), and SAM-19 (anti-stripping) In 2 minutes, the change in adhesion before and after soaking was determined to evaluate its chemical resistance.

<Evaluation criteria>

○: There are 90 to 100 lattice patterns (good)

△: There are 80 at least 90 lattice patterns (normal)

×: There are less than 80 lattice patterns (poor)

(3) Evaluation of storage stability

After measuring the initial viscosity of each ink composition prepared in the examples and comparative examples, it was stored at 5 ° C for 1 month. After that, the viscosity of the ink composition was measured and the change in viscosity was monitored. The viscosity was measured at 25 ° C using a Brookfield viscometer (DVI+, manufactured by BROOKFIELD Co.). The measurement results are shown in Table 2 below.

◎: 3% or less viscosity change

○: viscosity change of more than 3% to 5% or less

△: more than 5% to 10% viscosity change

×: more than 10% viscosity change

【Table 2】

Referring to Table 2 above, although the pattern was formed under a low temperature hardening process at 120 ° C, the pattern formed using the ink compositions prepared in Examples 1 to 4 had excellent adhesion to the substrate and desired chemical resistance.

In contrast, the pattern formed using the compositions prepared in Comparative Examples 1 to 3 had poor adhesion to the substrate and poor chemical resistance.

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Claims (6)

[Item 1]
An ink composition comprising a binder resin having a hydroxyl group, a hardener represented by the following formula 1, a polyfunctional monomer having an ethylenically unsaturated double bond, and a solvent:
[Molecular Formula 1]

(wherein R ₁ is an alkyl group having 1 to 5 carbon atoms,
or ;
R ₂ is a monoalkylene group having 1 to 10 carbon atoms;
R ₃ and R _{4 are} each independently an alkyl group having 1 to 5 carbon atoms;
n is an integer ranging from 1 to 3. [Item 2]
The composition of claim 1, wherein the hardener is included in an amount of 0.1 to 5 wt.% based on a total weight of the composition. [Item 3]
The composition of claim 1, wherein the binder resin is a novolak resin. [Item 4]
The composition of claim 1, wherein the binder resin is included in an amount of 10 to 20 wt.% based on a total weight of the composition. [Item 5]
A pattern formed using the composition according to any one of claims 1 to 4. [Item 6]
The pattern of claim 5, wherein the pattern comprises a pattern for a color filter, a black matrix pattern, a black column spacer pattern, a thin film transistor pattern, An electrode pattern or a barrier pattern for an image display device.