KR101254206B1 - Acrylic binders having hydroxy group for color filter - Google Patents

Abstract

상기 화학식 3에서 R₁ ~ R₃ 은 각각 독립적으로 -H 또는 -CH₃ 이고;
R₆은

또는

, 또는 이들의 복수종이며;
x, y, z의 합을 100몰%로 가정할 때, x, y의 합은 50 내지 85몰%이고, z는 15 내지 50몰%이다.
[화학식 4]

상기 화학식 4에서 R₁ ~ R₃ 은 각각 독립적으로 -H 또는 -CH₃ 이고;
R₆은

또는

, 또는 이들의 복수종이며;
x, y, z의 합을 100몰%로 가정할 때, x, y의 합은 50 내지 85몰%이고, z는 15 내지 50몰%이다.
[화학식 5]

상기 화학식 5에서 R₁ ~ R₃ 은 각각 독립적으로 -H 또는 -CH₃ 이고;
R₆은

또는

, 또는 이들의 복수종이며;
x, y, z의 합을 100몰%로 가정할 때, x, y의 합은 50 내지 85몰%이고, z는 15 내지 50몰%이다.The present invention provides a binder resin for producing a color filter comprising a repeating unit represented by the following Chemical Formulas 3 to 5.
(3)

In Formula ₃ R ₁ ~ R 3 are each independently -H or -CH _3, and;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%.
[Chemical Formula 4]

R ₁ to R ₃ in Formula 4 are each independently -H or -CH ₃ ;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%.
[Chemical Formula 5]

R ₁ to R ₃ in Formula 5 are each independently -H or -CH ₃ ;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%.

Description

Acrylic binder resin for color filters having a hydroxyl group {Acrylic binders having hydroxy group for color filter}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder resin used for manufacturing a color filter, which is one of the main components of a liquid crystal display (LCD), and more particularly, to a curable acrylic binder resin added to an inkjet ink for a color filter.

The liquid crystal display (LCD) is transmitted by passing through the secondary polarizer after the white light source irradiated from the backlight passes through the primary polarizer and the liquid crystal layer, and is then colored by a color filter having three colors of red, blue, and green. The three colors are combined to realize the image.

In the liquid crystal display, color filters are one of the key components directly related to image quality.

Conventionally, photolithography has been widely used as a method of manufacturing a color filter, but various problems have occurred, and an inkjet printing method has been developed to replace it.

In the inkjet printing method, ink is injected into a black matrix, which is a pixel space formed on a glass substrate. Unlike the photolithography method, the inkjet printing method eliminates the need for a separate coating, exposure, and development process, thereby reducing the materials required for the process and simplifying the process.

In addition to the red, blue, and green pigments, the color filter inkjet ink includes monomers as reactive diluents, and various chemicals such as initiators, solvents and viscosity modifiers, surfactants, and dispersants. In addition, the binder resin is an indispensable component as a means for adhering the pigment.

When the compatibility between these additives contained in the inkjet ink is inferior to each other (compatibility), it is difficult to manufacture the ink because there is not enough physical properties as ink, there are many product defects. Therefore, the binder resin used in the inkjet ink is not only excellent in affinity with the pigment, but also requires chemical resistance and high mechanical strength, and compatibility with other components such as other monomers, solvents and other additives is prioritized. .

A random copolymer compound of acrylic acid or methacrylic acid is most commonly proposed as a monomer for assigning solvent affinity and acidic radical as benzyl methacrylate or styrene as a pigment affinity monomer used in conventional binder resin production. Examples include Korean Patent Publication Nos. 10-2009-0127232 and 10-2009-119720.

On the other hand, Korean Patent Publication No. 10-2009-0049467 discloses a binder composition containing an acrylic monomer having a hydroxyl group as a specific functional group. In the case of the acrylic monomer having a hydroxyl group, the chemical resistance, heat resistance, water resistance, hardness, and crosslinking density are enhanced to have a sharp synergistic effect on brightness and contrast, suggesting improved optical properties when manufacturing TFT-LCD, OLED, etc. have.

However, among conventional binder resins used in inkjet ink manufacture, pigment affinity or compatibility with other constituents contained in the ink is poor, so that dispersibility is not stable, color characteristics are uneven, heat resistance and chemical resistance are poor. Problems often arise. In addition, the conventional inkjet ink composition may use an excessive amount of a dispersant, a surfactant or other additives to improve the above problems, and an excessive amount of a monomer used as a reactive diluent for viscosity control.

Accordingly, there is a need to develop a binder resin having better compatibility with pigments and solvents contained in inkjet inks and satisfying required physical properties, thereby improving brightness and contrast, which are final properties of consumers.

An object of the present invention is to provide a binder resin having excellent physical properties such as chemical resistance, heat resistance, water resistance, hardness, as well as excellent pigment and solvent affinity.

Still another object of the present invention is an ink for a color filter having excellent reactivity, dispersion stability and color characteristics, chemical and physical durability and flexibility at the same time when the binder resin according to the present invention is used in ink, and which has improved brightness and contrast compared to the prior art. To provide.

In order to achieve the above object, the present invention is characterized in introducing acrylate and methacrylate having both a hydroxy group and a benzene group as monomers of the binder polymer to enhance the physical properties of the binder and increase the pigment miscibility.

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The present invention provides a binder resin for preparing a color filter including a repeating unit represented by the following Chemical Formulas 3 to 5.

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상기 화학식 3에서 R₁ ~ R₃ 은 각각 독립적으로 -H 또는 -CH₃ 이고;
R₆은

또는

, 또는 이들의 복수종이며;
x, y, z의 합을 100몰%로 가정할 때, x, y의 합은 50 내지 85몰%이고, z는 15 내지 50몰%이다.

In Formula ₃ R ₁ ~ R 3 are each independently -H or -CH _3, and;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%.

상기 화학식 4에서 R₁ ~ R₃ 은 각각 독립적으로 -H 또는 -CH₃ 이고;
R₆은

또는

, 또는 이들의 복수종이며;
x, y, z의 합을 100몰%로 가정할 때, x, y의 합은 50 내지 85몰%이고, z는 15 내지 50몰%이다.

R ₁ to R ₃ in Formula 4 are each independently -H or -CH ₃ ;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%.

상기 화학식 5에서 R₁ ~ R₃ 은 각각 독립적으로 -H 또는 -CH₃ 이고;
R₆은

또는

, 또는 이들의 복수종이며;
x, y, z의 합을 100몰%로 가정할 때, x, y의 합은 50 내지 85몰%이고, z는 15 내지 50몰%이다.

R ₁ to R ₃ in Formula 5 are each independently -H or -CH ₃ ;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%.

The present invention further provides an acrylic monomer having a functional group (ether group) similar to a solvent to increase solvent compatibility to increase solubility, thereby providing a binder resin for preparing a color filter including a repeating unit represented by the following Chemical Formula 6.

이고;
(ⅱ) R₆은

또는

, 또는 이들의 복수종이고;
(ⅲ) R₇은

,

,

,

로 이루어진 그룹에서 선택된 1종 또는 2이상의 복수종이고;R ₁ to R ₄ in Formula 6 are each independently -H or -CH ₃ ;
(Iii) R ₅ is

ego;
(Ii) R ₆ is

or

, Or plural kinds thereof;
(Iii) R ₇ is

,

,

,

One or two or more species selected from the group consisting of:

,

,(Iii) R ₈ is

,

,

,

,

,

,

,

,

,

,

,

,

(n=3~20의 정수),

(n=3~20의 정수),

(an integer from n = 3 to 20),

(an integer from n = 3 to 20),

(R₉는 C₂~C₁₄의 알킬 또는 이소알킬),

(R ₉ is C ₂ -C ₁₄ alkyl or isoalkyl),

(R₁₀은 C₂~C₁₄의 알킬 또는 이소알킬),

(R ₁₀ is C ₂ -C ₁₄ alkyl or isoalkyl),

One or two or more species selected from the group consisting of:

Assuming that the sum of x, y, z and w is 100 mol%, the sum of x and y is 50 to 85 mol%, and the sum of z and w is 15 to 50 mol%.

The binder resin according to the present invention has an increased pigment affinity than the conventional binder, and has an effect of increasing physical properties such as heat resistance, chemical resistance, strength and hardness. Moreover, it is excellent in solubility and dispersibility in a solvent, and can be applied to the inkjet ink for color filters.

Inkjet ink using the binder resin according to the present invention can suppress the shrinkage phenomenon after curing, excellent surface strength, excellent ejection properties, color characteristics and color stability is excellent, when applied to the inkjet method color of excellent performance Filters can be prepared.

The present inventors assumed the characteristics required for the binder resin for color filters as follows and synthesized and tested using a functional monomer suitable for the characteristics to complete the present invention.

(A) the affinity of the pigment with benzene or an alkyl group.

(B) mechanical strength and physical properties of the binder.

(C) Affinity with an solvent and giving an acidic radical.

The present invention provides a binder resin polymerized with three or more functional monomers capable of satisfying the above three characteristics alone or in plurality.

The present invention includes benzyl methacrylate (BzMA) or benzyl acrylate (BzA) as a basic monomer as monomer (I) for imparting the pigment affinity of the characteristic (A).

In addition, the present invention is acrylic acid (Acrylic acid), methacrylic acid (Methacrylic acid, MAA), methacrylic acid (Methacrylamide), acrylamide as a monomer (II) for the solvent affinity and acid group assignment of the characteristic (C) It includes as a basic monomer one or a plurality thereof selected from the group consisting of

Meanwhile, the present invention provides 2-hydroxy-3-phenoxypropyl acrylate (2-Hydroxy-) as a monomer (III) for simultaneously satisfying the pigment affinity of the property (A) and the binder properties of the property (B). 3-phenoxypropyl acrylate), 2-hydroxy-3-phenoxypropyl methacrylate (HPPM), 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate [2- (4-benzoil-3- hydroxyphenoxy) ethyl acrylate], 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate, 2-hydroxypropyl-2- (acryloyloxy) ethyl phthalate [2-hydroxy propyl-2- ( acryloxy) ethyl phthalate] or 2-hydroxypropyl-2- (methacryloyloxy) ethyl phthalate [2-hydroxy propyl-2- (methacryloxy) ethyl phthalate], 3- (2H-benzotriazol-2-yl ) -4-hydroxyphenylethyl acrylate [3- (2H-benzotriazol-2-yl) -4-hydroxyphenylethyl acrylate], 3- (2H-benzotrizol-2-yl) -4-hydroxyphenylethyl meta Acrylate It includes a plurality of one or more member selected from the group true.

The monomer (III) forms a chemical structure that satisfies both the properties (A) and (B), and improves the mechanical properties of the binder and at the same time obtains a synergistic effect on the affinity with the pigment.

The above-mentioned monomer (I), monomer (II), and monomer (III) are summarized in Table 1 below.

Monomer
type constitutional formula Chemical name
Monomer (Ⅰ)

,

,

Benzyl methacrylate, benzyl methacrylate

Monomer (II)

,

Methacrylic acid, acrylic acid

,

Methacrylamide, acrylamide













Monomer (III)

,

2-hydroxy-3-phenoxypropyl methacrylate,
2-hydroxy-3-phenoxypropyl acrylate

,

2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate,
2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate,

,

2-hydroxypropyl-2- (methacryloyloxy) ethyl phthalate,
2-hydroxypropyl-2- (acryloyloxy) ethyl phthalate

,

3- (2H-benzotriazol-2-yl) -4-hydroxyphenylethyl methacrylate,
3- (2H-benzotriazol-2-yl) -4-hydroxyphenylethyl acrylate

The binder resin of the present invention is a random polymer containing a repeating unit represented by the following formula (1). The term 'comprising a repeating unit' means that other monomers in addition to the monomers (I), (II) and (III) used in the polymerization of the following Chemical Formula 1 may be added and polymerized.

[Formula 1]

R ₁ to R ₃ in Formula 1 are each independently -H or -CH ₃ ;

이고;(Iii) R ₅ is

ego;

또는

, 또는 이들의 복수종이고;(Ii) R ₆ is

or

, Or plural kinds thereof;

,

,(Iii) R ₇ is

,

,

,

로 이루어진 그룹에서 선택된 1종 또는 2이상의 복수종이다.

,

At least one selected from the group consisting of two or more species.

The use ratio of the functional monomers varies in kind and ratio depending on the purpose of application. The optimum ratio and type should first be adjusted based on the polarity of the pigment to be contained in the ink composition, the desired viscosity, and the properties of the solvent to be used. The monomer containing the carboxyl group of acrylic acid or methacrylic acid in the structure makes it stabilize by having an affinity with an organic solvent. However, the binder resin having a high acid value by the carboxyl group has a low solubility in a solvent used in the introduction of the polymerizable functional group, causing precipitation during polymerization, and thus, a desired molecular weight cannot be obtained. In addition, when the ratio of an acidic monomer is made high, the ratio of the monomer which gives another characteristic becomes comparatively low, and damages another characteristic.

i) Assuming that the sum of each repeating unit x, y, z in Formula 1 is 100 mol%, preferably the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%.

Ii) Assuming that the sum of x and y is 100 mol%, preferably x is 60 to 90 mol%, y is 10 to 40 mol%, more preferably x is 70 to 80 mol%, y Is 20 to 30 mol%.

Recalculating based on the mole% range of each component of i) and ii), assuming that the sum of each repeating unit x, y, z in Formula 1 is 100 mole%, x is 30 to 76.5 mole%, y Is 5 to 34 mol%, z is 15 to 50 mol%.

The binder resin manufacturing method according to the present invention includes a thermal polymerization initiator and a reaction solvent for copolymerizing monomers containing the functional monomers (I), (II) and (III).

The copolymerization method may be performed by a conventional method, and it is preferable to be carried out through a radical reaction. The functional monomers (I), (II), and (III) are mixed in the appropriate molar ratio as described above and dissolved in the reaction solvent, and then a thermal initiator is added thereto to maintain 50 to 120 ° C. in a nitrogen atmosphere, and 5 to 20 It is made to react with time and a binder resin is obtained. In this case, the thermal polymerization initiator is advantageously added dropwise to the mixture of monomers heated under a nitrogen atmosphere for 2 to 3 hours after dissolving separately in the reaction solvent. After the dropping, the total polymerization reaction time is preferably maintained for 5 to 8 hours in the range of 80 to 100 ° C.

Benzoyl peroxide (Benzoyl peroxide, BPO) roneun polymerization initiator (radical initiator) to be used for the radical polymerization, di-tertiary-butyl-peroxide (Di- tert -butyl-peroxide, DTBPO), kyumin-hydro peroxide ( Cumene hydroperoxide, CHPO), tertiary-butyl-hydroperoxide (tert -Butyl-hydroperoxide), tertiary-butyl-peroxy-2-ethyl hexahydro noise benzoate (tert -Butyl-peroxy-2- ethylhexnoate), tertiary -butyl-peroxy-benzoate (tert -Butyl-peroxy-benzoate) , 2,2'- azobis-2,4-dimethylvaleronitrile [2,2'-azobis- (2,4-dimethylvaleronitrile ) acrylonitrile, V-65], and at least one selected from the group consisting of azobisisobutyronitile (AIBN), but is not particularly limited so long as it has a polymerization initiation effect. The polymerization initiator is particularly preferably azobisisobutylonitrile (AIBN). The thermal polymerization initiator is preferably 0.05 to 4% by weight based on 100% by weight of the total reaction composition.

The reaction solvent serves to maintain the solid content and viscosity of the ink composition including the preparation of the binder resin or the like. Examples of the reaction solvent include alcohols such as methanol, ethanol, butyl alcohol and isopropyl alcohol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, and the like, except pro Both tick and aprotic solvents may be used. Among the reaction solvents, the binder synthetic solvent used for the manufacture of the binder for color filters is preferably synthesized in an epitic solvent. In the present invention, dipropylene glycol methyl ether acetate is more preferable in view of solubility, reactivity with each component, compatibility with pigments and initiators, and convenience of coating film formation in ink composition.

The reaction solvent is preferably 60 to 80% by weight based on 100% by weight of the total reaction composition.

The binder resin according to the present invention is a random copolymer as a polymer copolymer, and the synthesized polymer may be included as an ink composition in a state in which a reaction solvent is removed or present. Preferably, it is preferable to remove all of the unreacted monomers by removing the reaction solvent. However, when synthesized in the protic solvent, it may be directly applied without separation of the reaction solvent, which may be advantageous in shortening the process.

The binder resin according to the present invention preferably has a weight average molecular weight of 1,000 to 50,000, and an acid value of 0 to 150. If the molecular weight is less than 1,000, it is difficult to form a thin film, and if it exceeds 50,000, there is a disadvantage in that it is inconvenient to handle the high viscosity. More preferably, the range of 10,000 to 50,000 is preferable.

The molecular weight of the polymer for the binder resin to be synthesized is adjusted according to the concentration and temperature during the reaction and the amount of the initiator used. When the concentration and the reaction temperature are high and the amount of the initiator is used, the molecular weight becomes small, and the reaction concentration is preferably 10 to 40% of the total monomer in the total weight of the reaction composition, more preferably 15 to 30% by weight. Do.

The binder resin according to the present invention may be included in the ink composition for ink jet and used in the manufacture of color filters.

Ink composition comprising a binder resin according to the present invention is 1 to 20% by weight of the binder resin represented by the formula (1), 1 to 20% by weight functional monomer having an ethylenically unsaturated bond, 0.05 to 10% by weight polymerization initiator, and And 50 to 97.95% by weight of a solvent.

It is preferable that the binder resin is contained in an amount of 1 to 20% by weight in the total composition of the ink composition to form a thin film having a thickness of 1 to 100 μm. If it is less than 1% by weight, it is difficult to form a thin film, and if it exceeds 20% by weight, there is a disadvantage in that the viscosity is increased and the thin film is formed too thick.

On the other hand, the present invention can be prepared by further comprising a monomer (IV) having a functional group similar to the solvent, that is, an ether group in order to further increase the compatibility with the solvent in the structure of the formula (1).

The monomer (IV) for the solvent compatibility is diethylene glycol methyl ether acrylate or methacrylate, diethylene glycol ethyl ether acrylate or methacrylate, ethylene Ethylene glycol methyl ether acrylate or methacrylate, ethylene glycol monoethyl ether acrylate or methacrylate, ethylene glycol phenyl ether acrylate or Methacrylate, ethylene glycol dicyclopentenyl ether acrylate or methacrylate, oligo (ethylene glycol) methyl ether methacrylate, oligo (ethylene glycol) methyl ether acrylate, Poly (ethylene glycol) ethyl ether methacrylate, oligo (ethylene glycol) ethyl ether acrylate, diethylene glycol alkyl ether methacrylate, diethylene glycol alkyl ether acrylate, ethylene glycol alkyl ether methacrylate, ethylene glycol alkyl ether It includes one kind or two or more kinds selected from the group consisting of acrylates.

The monomer (IV) described above is summarized in Table 2 below.

Monomer
type constitutional formula Chemical name






















Monomer (IV)
(Continued on next page)

,

,

Diethylene glycol methyl ether methacrylate,
Diethylene glycol methyl ether acrylate

,

Diethylene glycol ethyl ether methacrylate,
Diethylene glycol ethyl ether acrylate

,

Diethylene glycol-2-ethylhexyl ether methacrylate,
Diethylene glycol-2-ethylhexyl ether acrylate

,

Ethylene glycol methyl ether methacrylate,
Ethylene Glycol Methyl Ether Acrylate

,

Ethylene glycol monoethyl ether methacrylate,
Ethylene Glycol Monoethyl Ether Acrylate

,

Ethylene glycol phenyl ether methacrylate,
Ethylene Glycol Phenyl Ether Acrylate

,

Ethylene glycol dicyclopentenyl ether methacrylate,
Ethylene Glycol Dicyclopentenyl Ether Acrylate

,

Oligo (ethylene glycol) methyl ether methacrylate,
Oligo (ethylene glycol) methyl ether acrylate

,

Oligo (ethylene glycol) ethyl ether methacrylate,
Oligo (ethylene glycol) ethyl ether acrylate






Monomer (IV)

,

R ₉ is C ₂ -C ₁₄ alkyl or isoalkyl Diethylene glycol alkyl ether methacrylate,
Diethylene glycol alkyl ether acrylate

,

R ₁₀ is C ₂ to C ₁₄ alkyl or isoalkyl Ethylene Glycol Alkyl Ether Methacrylate
Ethylene Glycol Alkyl Ether Acrylate

The binder resin of the present invention is a random polymer including a repeating unit represented by the following formula (6). The term 'comprising a repeating unit' means that other monomers in addition to the monomers (I), (II), (III), and (IV) used in the polymerization of Chemical Formula 6 may be added and polymerized.

[Formula 6]

In Formula 1, R < 1 _> ˜ R ₃ are each independently —H or —CH ₃ ;

이고;
(ⅱ) R₆은

또는

, 또는 이들의 복수종이고;
(ⅲ) R₇은

,

,

,

로 이루어진 그룹에서 선택된 1종 또는 2이상의 복수종이고;R ₄ in Formula 6 is each independently -H or -CH ₃ ;
(Iii) R ₅ is

ego;
(Ii) R ₆ is

or

, Or plural kinds thereof;
(Iii) R ₇ is

,

,

,

One or two or more species selected from the group consisting of:

,

,(Iii) R ₈ is

,

,

,

,

,

,

,

,

,

,

,

,

(n=3~20의 정수),

(n=3~20의 정수),

(an integer from n = 3 to 20),

(an integer from n = 3 to 20),

(R₉는 C₂~C₁₄의 알킬 또는 이소알킬),

(R ₉ is C ₂ -C ₁₄ alkyl or isoalkyl),

(R₁₀은 C₂~C₁₄의 알킬 또는 이소알킬),

(R ₁₀ is C ₂ -C ₁₄ alkyl or isoalkyl),

At least one selected from the group consisting of two or more kinds.

i) Assuming that the sum of the repeating units x, y, z and w of Formula 1 is 100 mol%, the sum of x and y is 50 to 85 mol%, and the sum of z and w is 15 to 50 mol. %to be.

Ii) Assuming that the sum of x and y is 100 mol%, preferably x is 60 to 90 mol%, y is 10 to 40 mol%, more preferably x is 70 to 80 mol%, y Is 20 to 30 mol%.

I) Assuming that the sum of z and w is 100 mol%, preferably z is 60 to 90 mol%, w is 10 to 40 mol%.

Recalculating based on the mole% range of each component of i), ii) and i), assuming that the sum of each repeating unit x, y, z, w of Formula 1 is 100 mole%, x is from 30 to 76.5 mol%, y is 5 to 34 mol%, z is 9 to 45 mol%, w is 1.5 to 20 mol%.

Hereinafter, the present invention will be described in detail through examples. The following examples are only examples for describing the present invention, but the present invention is not limited thereto.

Example 1 Preparation of Binder Resin 1

Benzyl methacrylate (BzMA) as monomer (I) for pigment affinity,

Methacrylic acid (MAA) as a monomer (II) for solvent affinity and acid group provision,

The binder resin of the present invention was prepared using 2-hydroxy-3-phenoxypropyl methacrylate (HPPM) as a monomer (III) to simultaneously improve pigment affinity and binder physical properties.

The binder production method of the present invention uses a three-necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirrer as a reaction vessel together with a reaction solvent (dipropylene glycol methyl ether acetate, DPMA) with benzyl methacrylate / methacrylic acid / 2-. Hydroxy-3-phenoxypropyl methacrylate was added at a molar ratio of 56/14/30, and then heated to 120 ° C. under a nitrogen atmosphere.

After dissolving 2,2'-azobisisobutylonitrile (AIBN) as a polymerization initiator in the reaction solvent (DPMA), the mixture was slowly and uniformly added to the flask for 2 hours, followed by an additional 4 hours while maintaining the reaction temperature of 120 ° C. To prepare a binder resin 1 represented by the formula (7). The weight average molecular weight (MW) of the prepared binder resin 1 was found to be about 16,500.

Example  2: Preparation of Binder Resin 2

A binder resin was prepared in the same manner as in Example 1, using 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate as a monomer (III) to simultaneously improve pigment affinity and binder properties. It was.

Benzyl methacrylate / methacrylic acid / 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate was reacted at a molar ratio of 56/14/30 to prepare a binder resin 2 represented by the following formula (8). The weight average molecular weight (MW) of the prepared binder resin 2 was found to be about 14,000.

Example  3: Preparation of Binder Resin 3

A binder resin was prepared in the same manner as in Example 1, using 2-hydroxypropyl-2- (methacryloyloxy) ethyl phthalate as the monomer (III) to simultaneously improve pigment affinity and binder properties. .

Benzyl methacrylate / methacrylic acid / 2-hydroxypropyl-2- (methacryloyloxy) ethyl phthalate was reacted at a molar ratio of 56/14/30 to prepare a binder resin 3 represented by the following formula (9). The weight average molecular weight (MW) of the prepared binder resin 3 was found to be about 16,000.

Example  4: Preparation of Binder Resin 4

The same method as in Example 1, except that 3- (2H-benzotrizol-2-yl) -4-hydroxyphenylethyl methacrylate is used as the monomer (III) to simultaneously improve pigment affinity and binder properties. To prepare a binder resin.

A binder resin represented by the following formula (10) by reacting benzyl methacrylate / methacrylic acid / 3- (2H-benzotrizol-2-yl) -4-hydroxyphenylethyl methacrylate in a molar ratio of 56/14/30 4 was prepared. The weight average molecular weight (MW) of the prepared binder resin 4 was found to be about 18,000.

Comparative example  Binder Of resin 5  Produce

A binder resin was prepared in the same manner as in Example 1, using 2-hydroxyethyl methacrylate (2-HEMA), which is a commonly used monomer as a monomer to determine binder physical properties. Benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate was reacted at a molar ratio of 56/14/30 to prepare a binder resin 5 represented by the following formula (11). The weight average molecular weight (MW) of the prepared binder resin 5 was found to be 15,000.

ink Manufacturing example  One

2.5% by weight of the binder resin 1 prepared in Example 1, 13% by weight of polyfunctional monomer 1,6-hexanediol diacrylate (1,6-Hexanediol diacrylate), pigment PB 15: 6 8% by weight, polymerization initiator An ink composition was prepared by adding 1.5% by weight of benzopinacol, 0.02% by weight of surfactant FC-4430, and 75% by weight of a solvent, dipropylene glycol methyl ether acetate (DPMA).

ink Manufacturing example  2

The ink composition was prepared in the same manner as in Ink Preparation Example 1, using the binder resin 2 of Example 2.

ink Manufacturing example  3

The ink composition was prepared in the same manner as in Ink Preparation Example 1, using Binder Resin 3 of Example 3.

ink Manufacturing example  4

The ink composition was prepared in the same manner as in Ink Preparation Example 1, using the binder resin 4 of Example 4.

ink Manufacturing example  5

The ink composition was prepared in the same manner as in Ink Preparation Example 1, using Binder Resin 5 of Comparative Example.

Experimental Example  : Physical property evaluation of ink containing binder resin

The physical properties of the ink compositions prepared using the binder resins 1 to 5 prepared in Examples and Comparative Examples were measured in the following manner.

(1) Dischargeability: The spraying was confirmed by using a single nozzle having a size of 50 μm, and a dot pattern and a line pattern were formed and cured to evaluate the printing state. The discharge time was measured until the discharge amount was reduced by 5%.

(2) Heat resistance evaluation: The color difference of the cured resin layer after leaving the hardened ink coating film at 250 degreeC for 1 hour was measured. The color difference (ΔE _ab ) before and after leaving the cured resin layer was 2 or less was very good, more than 2 and 3 or less was good, and more than 3 was evaluated as poor.

(3) Surface Hardness After Curing: After applying the ink composition including the binder resin prepared above on a substrate, the substrate was prebaked at 80 ° C. for 10 minutes, and then postbaked at 220 ° C. The applied ink was completely cured. The coating surface thus obtained was subjected to scratch experiments with 3H, 4H, and 5H pencils to measure hardness.

(4) Chemical resistance evaluation: The color difference of the cured resin layer was immersed in a solvent of either isopropyl alcohol (IPA) or tetra-methylammonium hydroxide (TMAH) at a solution temperature of 25 ° C. for 1 hour. Measured. The color difference (ΔE _ab ) before and after leaving the cured resin layer was 2 or less was very good, more than 2 and 3 or less was good, and more than 3 was evaluated as poor.

(5) Luminance measurement: After the ink composition containing the binder resin prepared above was applied onto a substrate, prebaking was performed at 80 ° C. for 10 minutes, and post-baking was performed at 220 ° C. to completely cure the applied ink. . The cured ink film was measured for brightness using a spectrophotometer. By changing the measuring point, the average value was expressed after 5 measurements.

(6) Contrast measurement: The ink composition containing the binder resin prepared above was applied onto a substrate and then prebaked at 80 ° C. for 10 minutes, and then post-baked at 220 ° C. to completely cure the applied ink. . The contrast ratio of the cured ink coating was measured using a Contrast tester.

The experimental results are shown in Table 3 below.

Ejectability
(Continuous discharge time up to 5% reduction) Heat resistance
(ΔE _ab change after 250 ° C, 60 minutes) After curing
Surface hardness Chemical resistance
(△ E _ab change after chemical treatment) Luminance Contrast IPA TMAH Example 1
Ink Production Example 1 5 hours 2.62 (good) 4H 2.54 (good) 2.98 (good) 64.85 8600 Example 2
Ink Production Example 2 5 hours 2.28 (good) 5H 2.79 (good) 2.62 (good) 65.82 8866 Example 3
Ink Production Example 3 5.5 hours 2.09 (good) 5H 1.89 (very good) 2.15 (good) 64.38 8772 Example 4
Ink Production Example 4 5.5 hours 1.98 (very good) 5H 1.92 (very good) 2.08 (good) 65.72 8980 Comparative Example
Ink Production Example 5 4 hours 3.85 (bad) 3H 4.95 (bad) 6.54 (bad) 40.96 6760

As shown in Table 3, the binder resin of the present invention was confirmed that the discharge resin, heat resistance, abrasion resistance, chemical resistance is very excellent compared to the comparative example, the brightness and contrast are very improved. Particularly, when 3- (2H-benzotriazol-2-yl) -4-hydroxyphenylethyl methacrylate is used as the monomer (III) for simultaneously improving the pigment affinity and binder properties, Heat resistance, abrasion resistance, chemical resistance, and brightness and contrast were remarkably excellent.

The above description has described one embodiment of the present invention, and those skilled in the art may implement the present invention in a modified form without departing from the essential characteristics of the present invention. Therefore, the scope of the present invention should be interpreted not to be limited to the above-described examples, but to include various embodiments within the scope equivalent to those described in the claims.

Claims (13)

delete delete Binder resin for producing a color filter comprising a repeating unit represented by the formula (3).
(3)

In Formula ₃ R ₁ ~ R 3 are each independently -H or -CH _3, and;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%. Binder resin for manufacturing a color filter comprising a repeating unit represented by the formula (4).
[Chemical Formula 4]

R ₁ to R ₃ in Formula 4 are each independently -H or -CH ₃ ;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%. Binder resin for producing a color filter comprising a repeating unit represented by the formula (5).
[Chemical Formula 5]

R ₁ to R ₃ in Formula 5 are each independently -H or -CH ₃ ;
R ₆ is

or

Or plural kinds thereof;
Assuming that the sum of x, y, z is 100 mol%, the sum of x, y is 50 to 85 mol%, and z is 15 to 50 mol%. The method according to any one of claims 3, 4 or 5,
Assuming that the sum of x and y is 100 mol%, x is 60 to 90 mol%, and y is 10 to 40 mol%.
The method according to any one of claims 3, 4 or 5,
Assuming that the sum of x and y is 100 mol%, x is 70 to 80 mol%, and y is 20 to 30 mol%.
delete The method according to any one of claims 3, 4 or 5,
The binder resin for manufacture for color filters whose acid value is 0-150.
Binder resin for producing a color filter comprising a repeating unit represented by the following formula (6) further comprising an acrylic monomer having an ether group.
[Chemical Formula 6]

R ₁ to R ₄ in Formula 6 are each independently -H or -CH ₃ ;
(Iii) R ₅ is

ego;
(Ii) R ₆ is

or

, Or plural kinds thereof;
(Iii) R ₇ is

,

,

,

One or two or more species selected from the group consisting of:
(Iii) R ₈ is

,

,

,

,

,

,

,

(an integer from n = 3 to 20),

(an integer from n = 3 to 20),

(R ₉ is C ₂ -C ₁₄ alkyl or isoalkyl),

(R ₁₀ is C ₂ -C ₁₄ alkyl or isoalkyl),
One or two or more species selected from the group consisting of:
Assuming that the sum of x, y, z and w is 100 mol%, the sum of x and y is 50 to 85 mol%, and the sum of z and w is 15 to 50 mol%.
The method of claim 10,
Assuming that the sum of x and y is 100 mol%, x is 60 to 90 mol%, and y is 10 to 40 mol%.
The method according to claim 10 or 11,
Assuming that the sum of z and w is 100 mol%, z is 60 to 90 mol%, w is 10 to 40 mol%.
The curable ink for color filters containing the binder resin of any one of Claims 3, 4, 5, or 10.