KR102196127B1 - Toner composition comprising poly(styrene-co-maleimide) copolymer dispersants and preparation method thereof - Google Patents

Abstract

The present invention relates to a toner composition comprising a poly(styrene-co-maleimide)-based dispersant, and to a production method thereof. Specifically, the poly(styrene-co-maleimide)-based dispersant is an amide imide-based copolymer mixture produced by ring-opening a poly(styrene-co-maleic anhydride) copolymer with methoxy polyalkylene glycol amine and an N,N-dimethylpropylamine compound. When the same is used as a dispersant for a toner composition, it is possible to provide a toner composition having good compatibility and no color separation by simultaneously applying the same to various resins due to improved fluidity of the toner.

Description

Toner composition comprising poly(styrene-co-maleimide) copolymer dispersants and preparation method thereof

It relates to a toner composition and a manufacturing method comprising a poly(styrene-co-maleimide)-based copolymer dispersant.

We can make the world in which we live even more beautiful by coloring things that are precious to us or by applying paints and coatings to protect them. In paints and coatings, solid particles such as pigments and fillers are important components, and solid particles must be well dispersed and stabilized in the liquid medium to ensure consistent color, quality and durability. Special additives, dispersants, are required to wet, disperse and stabilize solid particles in a liquid medium. In addition, energy is required so that the dispersing power is lowered by mechanical force and the solid particles can be easily dissociated, and the total energy needs to be minimized. And in order to minimize the dispersing time, it is preferable to use an optimal dispersant. In addition, a mixture of grinding action and mechanical shearing force is required to achieve optimal dispersion, and during this process the surface of the pigment particles is wetted and stabilized by the dispersant absorbed on the particle surface. After the dispersing operation, it is known that after the agglomerated solid particles have been completely peptized into the primary fine particles, re-aggregation takes place to partially or completely eliminate the effort entering the dispersion. As a result of inadequate dispersion and/or re-aggregation, undesirable side effects such as increased liquid viscosity, shade drift and loss of gloss in paints and coatings and reduced mechanical strength of plastics appear. Therefore, the particle dispersion process is one of the most difficult and time/energy consuming parts of the paint production process. These dispersants are composed of anionic surfactants, cationic surfactants, or neutral surfactants depending on their ionic charge, and can be classified into low molecular weight dispersants, oligomeric dispersants, and polymer dispersants according to their molecular weight. By using a dispersant, there are various advantages such as short dispersing time, enhanced gloss, increased color strength and hiding power, decreased viscosity, improved tone development, prevented immersion and flotation, prevented aggregation and prevented pigment and filler precipitation.

The polymer type dispersant is as follows,

Poly(ethylene-co-vinyl acetate) (poly(ethylene-co-vinyl acetate), EVA), poly(ethylene-co-butene) (poly(ethylene-co-butene), PEB), polyoctadecyl acrylate ( polyoctadecyl acrylate), polytetradecyl/hexadecyl/octadecyl methacrylate (polytetradecyl/hexadecyl/octadecyl methacrylate), poly(octadecene-co-octadecyl maleamic acid) (poly(octadecene-co-octadecyl maleamic acid)) , Poly(ethyl vinyl ether-co-docosanyl maleamic acid)), poly(N,N-diallyl-N-octadecylamine-alt-(maleic acid) ) (poly(N,N-diallyl-N-octadecylamine-alt-(maleic acid))), poly(vinyl acetate-codocosanylfumarate) (poly(vinyl acetate-codocosanylfumarate)), dodecylphenol resin ( dodecylphenolic resin), poly(alkyl acrylate-acrylic acid)), poly(alkylacrylate-acrylic acid-styrene) (poly(alkylacrylate-acrylic acid-styrene)), poly(alkyl acrylate) -Acrylic acid-1-vinyl-2-pyrrolidone (poly(alkyl acrylate-acrylic acid-1-vinyl-2-pyrrolidone)), poly(alkyl acrylate-styrene-1-vinyl-2-pyrrolidone (poly (alkylacrylate-styrene-1-vinyl-2-pyrrolidone)), poly(styrene-alt-octadecyl maleimide) (Poly(styrene-alt-octadecyl maleimide)), etc. have been used (Non-Patent Document 1, NIHON GAZO GAKKAISHI (Journal of the Imaging Society of Japan ), 2005 Volume 44 Issue 5 Pages 332-341, Use of amphiphilic copolymer as a polymeric dispersant for Disperse-Dye-Inkjet Ink printed on polyester fabric).

In addition, as a dispersant for preparing pigment dispersions in many companies, (meth)acrylic acid-based (co)polymer polyflow various Solspers dispersants (manufactured by Avisia), various dispervic dispersants (manufactured by Vicchemi), various Adispa dispersants ( Ajinomoto Fine Techno Co., Ltd.) and the like have been shown to be used. Polymers and copolymers having a functional group having pigment affinity depending on the structural form of the polymeric dispersant, alkyl ammonium salts of polymers and copolymers, polymers and copolymers having acid functional groups, combs and block copolymers (e.g., Block copolymers having basic groups, in particular with pigment affinity), unmodified or modified acrylate block copolymers, unmodified or modified polyurethanes, unmodified or modified and/or unchlorinated or chlorinated polyamines, epoxides -Amine adducts, in particular, phosphate esters of polyethers, polyesters and polyether-esters, basic or acidic ethoxylates such as alkoxylated monoamines or polyamines, or acidic 1,2-dicarboxyls of alkoxylated monoalcohols Acid anhydride monoesters, reaction products of unsaturated fatty acids with monoamines, diamines and polyamines, amino alcohols and unsaturated 1,2-dicarboxylic acids and their anhydrides and salts thereof, and of unsaturated fatty acids with alcohols and/or amines Reaction product; Polymers and copolymers of fatty acid radicals, unmodified or modified polyacrylates (e.g., transesterified polyacrylates), unmodified or modified polyesters (e.g., acid-functional and/or amino-functional Polyester), polyphosphates, and mixtures thereof. The polyisocyanate-based polymer dispersant is a monohydroxy compound, a diisocyanate functional compound, and an addition reaction of a compound having a tertiary amino group with an excess of NCO groups of a polyisocyanate containing an isocyanurate, biuret, urethane and/or allophanate group. It is manufactured by

However, even if the polymer dispersant mentioned above is used, it is insufficient to maintain the dispersion stability of the finely divided solid particles, and there are still problems such as thickening due to re-aggregation and a decrease in contrast due to time-lapse aggregation. .

The present invention is a result of using a poly(styrene-co-maleimide)-based copolymer dispersant within a specific numerical range for the purpose of overcoming the problems of the toner as described above, and has good compatibility and good physical properties when applied to various resins. And, it was confirmed that a toner composition (colorant composition) without color separation was secured, and the present invention was completed.

Non-Patent Document 1, NIHON GAZO GAKKAISHI (Journal of the Imaging Society of Japan), 2005 Volume 44 Issue 5 Pages 332-341, Use of amphiphilic copolymer as a polymeric dispersant for Disperse-Dye-Inkjet Ink printed on polyester fabric

Objects in one aspect of the present invention,

Urea-aldehyde resin, phenol-aldehyde resin, acrylic resin, polyester resin, acrylic urethane resin, epoxy resin, alkyd resin, polyvinylpyrrolidone (PVP) resin, polyvinylbutyral (PVB) resin, It is to provide a toner composition including a dispersant having excellent dispersibility and fluidity, which can realize vivid colors without color separation by applying to various resins such as methyl cellulose resin, or a mixed resin thereof.

Another object of the present invention is to provide a method of manufacturing a toner composition. In addition, another object of the present invention is to provide a toner composition comprising the dispersant, a resin, a colorant, and a solvent.

Another object of the present invention is to provide an ink cartridge for an inkjet printer, comprising the toner composition and a toner receiving portion accommodating the toner composition. In addition, another object of the present invention is to provide an inkjet printer including the ink cartridge for the inkjet printer. Further, an object of another aspect of the present invention is to provide an inkjet recording method in which the toner composition is ejected from an inkjet recording head to record an image on a recording medium.

To achieve the above object,

An aspect of the present invention provides a toner composition comprising 8 to 14% by weight of a dispersant including a copolymer represented by the following formula (1) and a copolymer represented by the following formula (2).

[Formula 1]

In Formula 1,

m and n are independently an integer of 4 to 18,

l and p are independently integers from 2 to 40; And

[Formula 2]

In Chemical Formula 2,

m and n are independently integers of 4 to 18.

In addition, another aspect of the present invention,

Dissolving a poly(styrene-co-maleic anhydride) copolymer represented by the following formula (i);

Adding a compound represented by the following formula (ii) and a compound represented by the following formula (iii);

Inducing an imidation reaction to prepare a dispersant including the copolymer represented by Formula 1 and the copolymer represented by Formula 2;

Adjusting a dispersant content of 8 to 14% by weight in the total 100% by weight of the toner composition; It provides a method for producing a toner composition comprising a.

[Formula i]

The number average molecular weight (M _n ) of the compound of Formula i is 500 to 10,000 g/mol,

the mole ratio of m and n is 1:0.3 to 1;

[Formula ii]

The weight average molecular weight (M _w ) of the compound of Formula ii is 500 to 1,200 g/mol,

) 부분인 l과, 에틸렌 옥사이드(

) 부분인 p의 몰 비율(PO/EO mole ratio)은 1 : 4 내지 8이거나, 또는 7 내지 11 : 1이다;Propylene oxide (

) Part of l and ethylene oxide (

) The molar ratio of the part p (PO/EO mole ratio) is 1: 4 to 8, or 7 to 11: 1;

[Formula iii]

.

.

Furthermore, another aspect of the present invention,

As a toner composition comprising (a) a resin, (b) a dispersant, (c) a colorant, and (d) a solvent,

The (b) dispersant comprises a copolymer represented by the following formula (1) and a copolymer represented by the following formula (2), and comprises 8 to 14% by weight of the total 100% by weight of the toner composition. to provide.

[Formula 1]

In Formula 1,

m and n are independently an integer of 4 to 18,

l and p are independently integers from 2 to 40; And

[Formula 2]

In Chemical Formula 2,

m and n are independently integers of 4 to 18.

In addition, another aspect of the present invention provides an ink cartridge for an inkjet printer including the toner composition and a toner receiving portion accommodating the toner composition, and an inkjet printer including the same. Further, another aspect of the present invention provides an inkjet recording method for recording an image on a recording medium by discharging the toner composition from an inkjet recording head.

When the poly(styrene-co-maleimide) dispersant according to the present invention is included in the toner composition in a specific numerical range, the solid particles of high concentration in the toner composition exhibit excellent dispersibility in organic solvents, and compatibility when applied to various resins It is possible to provide this good and color separation phenomenon-free toner composition. Moreover, due to the finer dispersion procedure, the color intensity of the toner composition prepared according to the present invention is superior to that prepared according to the prior art, so that the same amount of toner is used to display a more vivid color or maintain color. It makes it possible to make it possible, and at the same time, there is an effect of enabling material reduction and thus cost reduction.

Hereinafter, the present invention will be described in detail.

Meanwhile, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, embodiments of the present invention are provided in order to more completely explain the present invention to those having average knowledge in the art.

Furthermore, "including" a certain component throughout the specification means that other components may be further included, rather than excluding other components unless specifically stated to the contrary.

An aspect of the present invention provides a toner composition comprising 8 to 14% by weight of a dispersant including a copolymer represented by the following formula (1) and a copolymer represented by the following formula (2).

[Formula 1]

In Formula 1,

m and n are independently an integer of 4 to 18,

l and p are independently integers from 2 to 40; And

[Formula 2]

In Chemical Formula 2,

m and n are independently integers of 4 to 18.

The dispersant is preferably included in an amount of 9 to 13% by weight, more preferably 10 to 12% by weight, and most preferably 11% by weight of the total 100% by weight of the toner composition. If the dispersant is contained in an amount of less than 8% by weight or more than 14% by weight of the total 100% by weight of the toner composition, the Brookfield viscosity (cP) is high, as demonstrated in Experimental Example 1 to be described later, and the color difference (ΔE *ab) The value is also high, and the storage stability is poor, so it is difficult to secure desirable physical properties required as a toner composition.

The copolymer represented by Formula 1 and the copolymer represented by Formula 2 may be included in the dispersant at a molar ratio of 1: 0.3 to 1.2, and are preferably included in the dispersant at a molar ratio of 1: 0.5 to 1.2, It is more preferable to be contained in the dispersant in a molar ratio of 1: 0.8 to 1.2, and even more preferably contained in the dispersant in a molar ratio of 1: 0.9 to 1.1, as in Example 2 (including dispersant 2) described below, 1: It is most preferably contained in the dispersant in a molar ratio of 1.

The dispersant contains a copolymer consisting of a styrene unit having a solvent property (the m unit) and an amide imide unit having a functional group containing a nitrogen atom (the n unit), and the amine value (TBN) is calculated as an effective solid content. It is 10 mgKOH/g or more and 80 mgKOH/g or less. If the amine value (TBN) is too low, the adsorption power of the dispersant molecules to the pigment surface is insufficient, and sufficient dispersion stability cannot be obtained. On the other hand, when the amine value is too high, the molecular weight of the A block becomes relatively small, resulting in insufficient dispersion stability. In other words, in order to express optimal dispersibility, the amine value (TBN) must be in the above range. The presence or absence of an amine value (TBN) in the dispersant according to the present invention is due to the use of the N,N-dimethylaminopropylamine (DMAPA, N,N-dimethylaminopropylamine) compound and the degree of reaction. When the amount is used, the amine value (TBN) is high. The amine values (TBN) of the dispersants 1 to 6 described later are 16.00 mgKOH/g, 34.78 mgKOH/g, 21.36 mgKOH/g, 27.95 mgKOH/g, 13.90 mgKOH/g, and 13.14 mgKOH/g, respectively, Since the example having the lowest color difference (ΔE*ab) and excellent compatibility is Example 2 using a dispersant 2, the amine number (TBN) of the preferred dispersant based on Example 2 is 25 to 45 mgKOH/g, 30 to 45 mgKOH/g, 34 to 45 mgKOH/g, 25 to 40 mgKOH/g, 25 to 35 mgKOH/g, 30 to 40 mgKOH/g, 33 to 35 mgKOH/g.

In addition, the acid value of the copolymer in the dispersant varies depending on the presence and type of the acidic group that is the basis of the acid value, but generally, the lower one is preferred, and usually 1 to 20 mgKOH/g or less, preferably 1 To 10 mgKOH/g or less, more preferably 1 to 5 mgKOH/g or less. The reason why the acid value appears in the dispersant of the present invention is that when the ring of maleic anhydride is opened, it exists in the form of an amide-carboxylic acid salt, and the imidation reaction occurs at a certain temperature or higher, but when the imidation reaction occurs 100%, the acid value hardly appears.

Another aspect of the present invention,

(Step 1) dissolving a poly(styrene-co-maleic anhydride) copolymer represented by the following formula (i);

(Step 2) adding a compound represented by the following formula (ii) and a compound represented by the following formula (iii);

(Step 3) inducing an imidation reaction to prepare a dispersant including the copolymer represented by Formula 1 and the copolymer represented by Formula 2;

(Step 4) adjusting a dispersant content of 8 to 14% by weight in the total 100% by weight of the toner composition; It provides a method for producing a toner composition comprising a.

[Formula i]

The number average molecular weight (M _n ) of the compound of Formula i is 500 to 10,000 g/mol,

the mole ratio of m and n is 1:0.3 to 1;

[Formula ii]

The weight average molecular weight (M _w ) of the compound of Formula ii is 500 to 1,200 g/mol,

) 부분인 l과, 에틸렌 옥사이드(

) 부분인 p의 몰 비율(PO/EO mole ratio)은 1 : 4 내지 8이거나, 또는 7 내지 11 : 1이다;Propylene oxide (

) Part of l and ethylene oxide (

) The molar ratio of the part p (PO/EO mole ratio) is 1: 4 to 8, or 7 to 11: 1;

[Formula iii]

.

.

Hereinafter, a method of manufacturing a toner composition provided in another aspect of the present invention will be described in detail step by step.

(Step 1) In the method for preparing a toner composition provided in another aspect of the present invention, Step 1 is a step of dissolving a poly(styrene-co-maleic anhydride) copolymer. At this time, the chemical structure of the poly(styrene-co-maleic anhydride) copolymer may be represented by the following formula.

[Formula i, structure of poly(styrene-co-maleic anhydride) copolymer]

m and n are independently as described above.

At this time, butyl acetate may be used as a solvent used to dissolve the poly(styrene-co-maleic anhydride) copolymer, but any solvent capable of dissolving the poly(styrene-co-maleic anhydride) copolymer may be used without limitation. Can be used. Some non-limiting examples are as follows: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Glycolalkyl ether acetates such as mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate, Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, alkyl acetates such as cyclohexanol acetate, acetone, methyl ethyl ketone, methyl amyl ketone, methyl Isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy methyl pentanone and Same ketone solvent. In addition, the amount of the solvent may be 100 to 300 parts by weight based on 100 parts by weight of the poly(styrene-co-maleic anhydride) copolymer compound. Further, the n unit representing the maleic anhydride unit is preferably smaller than or equal to the m unit which is a styrene unit. In other words, the m unit is preferably greater than or equal to the n unit. More specifically, the n unit may be present in a molar ratio of 0.3 to 1.0 based on 1.0 mol of the m unit. Here, considering that the mole ratio of m and n is 1: 0.3 to 1, the above-defined "m and n are independently 4 to 18" is preferably, if m is 13, n is 4 (more specifically Is from 3.9) to 13; When m is 18, n may be 5 (more specifically, 5.4) to 18. That is, m may be 13 to 18, and n may be 4 to 18. In addition, the number average molecular weight (M _n ) of the poly(styrene-co-maleic anhydride) copolymer may be 500 to 10,000 g/mol. In another aspect, it is preferably in the range of 1,000 to 5,000, more preferably in the range of 1,000 to 4,000, even more preferably in the range of 1,000 to 3,000, and most preferably in the range of 1,500 to 2,500.

(Step 2) In the method of manufacturing a toner composition provided in another aspect of the present invention, step 2 is a step of adding a compound represented by the following formula (ii) and a compound represented by the following formula (iii).

[Formula ii]

[Formula iii]

) 부분인 l과, 에틸렌 옥사이드(

) 부분인 p의 몰 비율(PO/EO mole ratio)은 1 : 4 내지 8이거나, 또는 7 내지 11 : 1일 수 있다. 다른 측면에서는 1 : 5 내지 7이거나, 또는 8 내지 10 : 1일 수 있다. 참조로, 후술하는 실험예 2에서는 Jeffamine^® M-1000을 사용할 경우와 Jeffamine^® M-2070을 사용할 경우 제조되는 토너 조성물의 물성을 비교하였으며, 그 결과 분자량(M_w)이 2,000이고 PO/EO 몰 비율이 10/31인 Jeffamine^® M-2070를 사용할 경우 브룩필드 점도는 60, 색차는 3.50, 저장안정성은 나쁨으로 평가되어 토너 조성물로서 요구되는 물성이 달성될 수 없는 반면, 분자량(M_w)이 1,000이고 PO/EO 몰 비율이 3/19인 Jeffamine^® M-1000을 사용할 경우는 우수한 물성이 확보됨을 입증하였다. At this time, the weight average molecular weight of the methoxy alkylene glycol amine represented by Formula ii may be in the range of 400 to 2,000, more preferably in the range of 450 to 1,500, even more preferably in the range of 500 to 1,200, and 600 to 1,000. It is most preferred that it is a range. In addition, propylene oxide (

) Part of l and ethylene oxide (

) The molar ratio of the part p (PO/EO mole ratio) may be 1: 4 to 8, or 7 to 11: 1. In another aspect, it may be 1: 5 to 7 or 8 to 10: 1. For reference, in Experimental Example 2 to be described later, the physical properties of the toner composition produced when using Jeffamine ^® M-1000 and Jeffamine ^® M-2070 were compared. As a result, the molecular weight (M _w ) is 2,000 and PO/EO mole If Jeffamine ^® M-2070 with a ratio of 10/31 is used, the Brookfield viscosity is 60, the color difference is 3.50, and the storage stability is evaluated as poor, so that the physical properties required as a toner composition cannot be achieved, whereas the molecular weight (M _w ) is When using Jeffamine ^® M-1000 with 1,000 and PO/EO mole ratio of 3/19, it has been proven that excellent physical properties are secured.

(Step 3) In the method for preparing a toner composition provided in another aspect of the present invention, step 3 includes a copolymer represented by Formula 1 and a copolymer represented by Formula 2 by inducing an imidation reaction. This is the step of preparing a dispersant. At this time, the poly(styrene-co-maleic anhydride) copolymer compound represented by Formula i in the ring opening reaction, the methoxy alkylene glycol amine represented by Formula ii, and N,N- represented by Formula iii. The amount of dimethylaminopropyl amine used is a methoxy alkylene glycol amine represented by formula ii and an N,N-dimethylaminopropyl amine represented by formula iii per 1 mol of the poly(styrene-co-maleic anhydride) copolymer compound. It is preferred to use 0.5 to 1.1 moles of the compound. More preferably, it is 0.7 to 0.95 mol. When the methoxy alkylene glycol amine represented by Formula ii and the N,N-dimethylaminopropyl amine compound represented by Formula iii are less than 0.5 mol, there is a problem in pigment dispersibility, and when it is more than 1.1 mol, the pigment's printability and economical efficiency Since there is a phosphorus problem, it is preferable to use it within the above range. The amine compound of Formula iii is preferably used in an amount of 0.5 to 1.0 mol% based on the amine compound of Formula ii.

In addition, the ring opening reaction is preferably carried out for 4 to 10 hours at a temperature of 130 to 220 ℃. In order to induce more imide products than amide products in the reaction product, the lower limit of the temperature is preferably 130°C, and for coloration and economy of the product, the upper limit of the temperature is more preferably 220°C. In addition, when the reaction is carried out in a nitrogen stream, one with little coloration is obtained.

In this step 3, by the ring opening reaction of the poly(styrene-co-maleic anhydride) copolymer compound of formula i, the polyalkylene glycol amine of formula ii, and the N,N-dimethylaminopropyl amine of formula iii, An amide-imide-based dispersant comprising a copolymer represented by Formula 1 and a copolymer represented by Formula 2 is synthesized.

(Step 4) In the method of manufacturing a toner composition provided in another aspect of the present invention, step 4 is a step of adjusting the content of the dispersant to be contained in 8 to 14% by weight of the total 100% by weight of the toner composition. At this time, preferably, the content of the dispersant may be adjusted to be 9 to 13% by weight, more preferably, the content of the dispersant may be adjusted to be 10 to 12% by weight, and most preferably the content of the dispersant is 11% by weight. Can be adjusted to include. If the dispersant is contained in an amount of less than 8% by weight or more than 14% by weight of the total 100% by weight of the toner composition, the Brookfield viscosity (cP) is high, as demonstrated in Experimental Example 1 to be described later, and the color difference (ΔE *ab) The value is also high, and the storage stability is poor, so it is difficult to secure desirable physical properties required as a toner composition.

Another aspect of the present invention,

As a toner composition comprising (a) a resin, (b) a dispersant, (c) a colorant, and (d) a solvent,

The (b) dispersant comprises a copolymer represented by the following formula (1) and a copolymer represented by the following formula (2), and comprises 8 to 14% by weight of the total 100% by weight of the toner composition. to provide.

[Formula 1]

In Formula 1,

m and n are independently an integer of 4 to 18,

l and p are independently integers from 2 to 40; And

[Formula 2]

In Chemical Formula 2,

m and n are independently integers of 4 to 18.

The poly(styrene-co-maleimide)-based dispersant according to the present invention disperses well-designed formulations with a high pigment content, so that when producing paints of various colors, the desired color can be easily worked using them in the field. When used in a toner product, it improves the dispersibility of the pigment in the high concentration toner in the organic solvent. In particular, it is possible to provide a toner with little change in color tone by improving the adhesion and long-term storage performance of the toner by using a pigment and a dispersant by selecting a resin that is well compatible with all resins used in paints.

More specifically, the toner composition in the present invention comprises (a) 20 to 30% by weight of a polymer resin, (b) 8 to 14% by weight of a dispersant, (c) 10 to 60% by weight of a colorant, and (d) 20 to 75% by weight of an organic solvent. It may contain weight percent.

(a) Polymeric resin

The (a) polymer resin is used to improve toner printability and adhesion, and is added to prevent yarn-like sagging while maintaining adhesiveness, and to increase ink strength and chemical resistance after toner is printed on a printing film.

The (a) polymer resin is urea-aldehyde resin, phenol-aldehyde resin, acrylic resin, polyester resin, petroleum resin, vinyl resin, urethane resin, acrylic urethane resin, epoxy resin, alkyd resin, polyvinylpyrrolidone , PVP) resin, polyvinylbutyral (PVB) resin, methyl cellulose resin, or a mixed resin thereof may include at least one selected from the group consisting of. Here, the urea-aldehyde resin means urea and aliphatic aldehyde polymers, and as one specific example, BASF's Laropal A81 may be used.

(a) The polymer resin is preferably contained in an amount of 20 to 30% by weight based on the total weight of the toner composition, which is difficult to expect printability and adhesion when (a) the polymeric resin is less than 20% by weight, and exceeds 30% by weight. In the case of, it is preferable to use it within the above range because of poor drying, insufficient adjustment of coating amount, difficulty in adjusting viscosity, and not economical.

(b) dispersant

(b) The dispersant plays a role of uniformly dispersing pigment particles in the toner composition to improve printability, adhesion, and workability, and the poly(styrene-co-maleic anhydride) copolymer compound of Formula (i) is, the formula (ii) And an amide-imide-based compound produced by a ring-opening reaction with the amine compound of iii. That is, a copolymer represented by Formula 1 and a copolymer represented by Formula 2 are included.

(b) The dispersant is preferably contained in an amount of 8 to 14% by weight based on the total weight of the toner composition, which (b) has a dispersibility problem when the dispersant is less than 8% by weight, and is not economical when it exceeds 14% by weight There is. In addition, as described above, when included in an amount of less than 8% by weight or more than 14% by weight, the Brookfield viscosity (cP) is high and color difference (ΔE*ab) as demonstrated in Experimental Example 1 to be described later. The value is also high, and storage stability is poor, causing a problem in which it is difficult to secure desirable physical properties required as a toner composition. Therefore, it is preferable to use it within the above range.

(c) colorant

(c) The colorant may be selected from the group consisting of dyes, pigments, or mixtures thereof.

In one embodiment, the pigment may be carbon black, red iron oxide, yellow iron oxide, black iron oxide, titanium oxide, green pigment, blue pigment, violet pigment, orange pigment, and red pigment, and the content is 100 It is 10 to 60% by weight of the weight%. (C) If the content of the colorant is less than 10% by weight, there is a problem that the coloration strength is weakened, and if it exceeds 60% by weight, the toner (colorant) decreases the glossiness of the applied paint, decreases the dispersibility of the pigment in the colorant, and forms a precipitate. There is a problem that the storage of the product is poor. Based on the embodiment (c) the colorant may be 10 to 30% by weight.

(d) organic solvent

(d) Organic solvent is added to prevent the toner ink from smearing on the printed object by forming a film on the ink film due to volatilization of the solvent after printing the toner ink on the printing film. For example, xylene, xylene, or Kocosol 100 may be used. In this case, the organic solvent is used in an amount of 20 to 75% by weight of the total 100% by weight of the toner composition. If the organic solvent is less than 20% by weight, the mesh of the printing screen is clogged during printing, making continuous printing impossible, and the gelation of the ink is fast, making it difficult to obtain. It is preferable to use within. Based on the embodiment (d) the organic solvent may be 20 to 40% by weight.

In addition to the above-described composition, an antifoaming agent or an anti-settling agent may be additionally added as necessary in an ordinary amount.

When the poly(styrene-co-maleimide) dispersant according to the present invention is included in the toner composition in a specific numerical range, the solid particles of high concentration in the toner composition exhibit excellent dispersibility in organic solvents, and compatibility when applied to various resins It is possible to provide this good and color separation phenomenon-free toner composition. Moreover, due to the finer dispersion procedure, the color intensity of the toner composition prepared according to the present invention is superior to that prepared according to the prior art, so that the same amount of toner is used to display a more vivid color or maintain color. It makes it possible to do so, and at the same time, there is an effect of enabling material reduction and thus cost reduction, which is supported by Examples and Experimental Examples described later.

Hereinafter, the present invention will be described in detail through examples and experimental examples.

However, the examples and experimental examples to be described later are only to specifically illustrate the present invention in one aspect, and the present invention is not limited thereto.

Preparation for Experiment 1. Preparation of poly(styrene-co-maleic anhydride) copolymer

The poly(styrene-co-maleic anhydride) copolymer represented by the following formula was prepared by purchasing the SMA ^® product of CRAY VALLEY. The SMA ^® product is a copolymer in which styrene and maleic anhydride are polymerized in a ratio of 1:1 to 8:1, and in examples, SMA 1000, SMA 2000, and SMA 3000 were used.

-SMA 1000: styrene unit (m unit) and maleic anhydride unit (n unit) mole ratio (mole ratio) of 1:1 SMA ^® product.

-SMA 2000: SMA ^® product with a styrene unit (m unit) and maleic anhydride unit (n unit) mole ratio of 2:1.

-SMA 3000: SMA ^® product with a styrene unit (m unit) and maleic anhydride unit (n unit) mole ratio of 3:1.

Preparation for experiment 2. Preparation of methoxy alkylene glycol

Jeffamine ^® (Aldrich Co.) represented by the following formula was purchased and prepared.

Representative Jeffamine ^® types classified according to the molar ratio of propylene oxide (PO) and ethylene oxide (EO) and molecular weight are shown below.

(R=CH₃)

(R=CH ₃ )

<Production Example 1> Poly(styrene-co-maleimide) copolymer dispersant 1

To a 500 mL 4-neck round flask equipped with a stirrer, condenser, nitrogen injector, and temperature sensor, 100 mL of butyl acetate was added, and poly(styrene-co-maleic anhydride) copolymer SMA 1000 (number average molecular weight 2,000 g/mol) 30.3 g (0.15 equivalent) ) Was dissolved. For reference, since SMA 1000 is composed of a unit of styrene and maleic anhydride in a 1:1 molar ratio, as described above, 0.15 equivalent is derived by calculating the equivalent by converting styrene and maleic acid rings to 202 g/mol. When the dissolution was sufficiently completed, Jeffamine ^® M-1000 (molecular weight 1,000 g/mol) 94.5 g (0.0945 equivalent) of methoxy alkylene glycol was slowly added dropwise. Then, 4.1 g (0.0405 equivalent, 102.2 g/mol) of N,N-dimethylaminopropyl amine (DMAPA) was slowly added dropwise. The temperature of the reactant was raised to 120° C. and maintained for 2 hours. Thereafter, the temperature of the reactant was slowly increased from 140 to 160 to 180° C. to remove the butyl acetate solvent and reacted for 4 hours. Thereafter, the reaction mixture was heated to 200° C. to proceed with an imidization reaction for 2 hours, and the reaction mixture was cooled to 120° C. to terminate the reaction. The dispersant product exhibited 4.625 mgKOH/g TAN and 16.00 mgKOH/g TBN. FT-IR (KBr, cm ^-1 ): 1700, 1771 cm ^-1 (Imide C=O stretching) and 1110 cm ^-1 (CO stretching).

<Production Example 2> Poly(styrene-co-maleimide) copolymer dispersant 2

Poly(styrene-co-maleic anhydride) copolymer SMA 1000 (number average molecular weight 2,000 g/mol) 30.3 g (0.15 equivalent), methoxy alkylene glycol Jeffamine ^® M-1000 (molecular weight 1,000 g/mol) 67.5 g ( 0.0675 equivalents) and DMAPA 6.9g (0.0675 equivalents, 102.2 g/mol) were prepared as in Example 1. The dispersant product exhibited 5.048 mgKOH/g of TAN and 34.78 mgKOH/g of TBN. FT-IR (KBr, cm ^-1 ): 1701, 1770 cm ^-1 (Imide C=O stretching) and 1111 cm ^-1 (CO stretching).

<Production Example 3> Poly(styrene-co-maleimide) copolymer dispersant 3

Poly(styrene-co-maleic anhydride) copolymer SMA 1000 (number average molecular weight 2,000 g/mol) 30.3 g (0.15 equivalent), methoxy alkylene glycol (molecular weight 800 g/mol) 75.6 g (0.0945 equivalent), DMAPA 4.6 It was prepared as in Example 1 except that g (0.045 equivalent, 102.2 g/mol) was used. For reference, the methoxy alkylene glycol used in Preparation Example 3 was made by mixing Jeffamine ^® M-600 and Jeffamine ^® M-1000 1:1. The dispersant product exhibited 5.472 mgKOH/g TAN and 21.36 mgKOH/g TBN. FT-IR (KBr, cm ^-1 ): 1701, 1770 cm ^-1 (Imide C=O stretching) and 1110 cm ^-1 (CO stretching).

<Production Example 4> Poly(styrene-co-maleimide) copolymer dispersant 4

Poly(styrene-co-maleic anhydride) copolymer SMA 1000 (number average molecular weight 2,000 g/mol) 35.4 g (0.175 equivalent), methoxy alkylene glycol Jeffamine ^® M-600 (molecular weight 600 g/mol) 66.2 g ( 0.11025 equivalents) and 4.8 g of DMAPA (0.04275 equivalents, 102.2 g/mol) were prepared as in Example 1. The dispersant product exhibited TAN 13.472 mgKOH/g, TBN 27.95 mgKOH/g. FT-IR (KBr, cm ^-1 ): 1699, 1771 cm ^-1 (Imide C=O stretching) and 1109 cm ^-1 (CO stretching).

<Production Example 5> Poly(styrene-co-maleimide) copolymer dispersant 5

Poly(styrene-co-maleic anhydride) copolymer SMA 2000 (number average molecular weight 3,000 g/mol) 36.7 g (0.12 equivalent), methoxy alkylene glycol Jeffamine ^® M-1000 (molecular weight 1,000 g/mol) 75.6 g ( 0.0756 equivalent), DMAPA 3.3g (0.0324 equivalent, 102.2g / mol) was prepared as in Example 1, except for using. For reference, as described above, since SMA 2000 is composed of a unit of styrene and maleic anhydride in a 2:1 molar ratio, 0.12 equivalent is derived when the equivalent is calculated by converting the styrene and maleic acid rings to 306 g/mol. The dispersant product exhibited TAN 7.733 mgKOH/g and TBN 13.9 mgKOH/g. FT-IR (KBr, cm ^-1 ): 1696, 1771 cm ^-1 (Imide C=O stretching) and 1110 cm ^-1 (CO stretching).

<Production Example 6> Poly(styrene-co-maleimide) copolymer dispersant 6

Poly(styrene-co-maleic anhydride) copolymer SMA 3000 (number average molecular weight 3,800 g/mol) 41.0 g (0.10 equivalent), methoxy alkylene glycol Jeffamine ^® M-1000 (molecular weight 1,000 g/mol) 63.0 g ( 0.063 equivalent), DMAPA 2.8g (0.027 equivalent, 102.2g/mol) was prepared as in Example 1, except that. For reference, as described above, SMA 3000 is composed of a unit of styrene and maleic anhydride in a 3:1 molar ratio, and thus 0.10 equivalent is derived when the equivalent is calculated by converting the styrene and maleic acid ring to 410 g/mol. The dispersant product exhibited TAN 9.758 mgKOH/g, TBN 13.14 mgKOH/g. FT-IR (KBr, cm ^-1 ): 1700, 1771 cm ^-1 (Imide C=O stretching) and 1109 cm ^-1 (CO stretching).

<Production Example 7> Poly(styrene-co-maleimide) copolymer dispersant 7

Poly(styrene-co-maleic anhydride) copolymer (number average molecular weight 2,000 g/mol) 20.2 g (0.15 equivalent), methoxy alkylene glycol Jeffamine ^® M-1000 (molecular weight 1,000 g/mol) 90.0 g (0.09 equivalent) ) Was prepared through the same process as in Example 1, except for using. The dispersant product exhibited TAN 9.004 mgKOH/g. FT-IR (KBr, cm ^-1 ): 1701, 1769 cm ^-1 (Imide C=O stretching) and 1110 cm ^-1 (CO stretching).

The amounts and molecular weights of the starting materials used in preparing the dispersants of Preparation Examples 1 to 7 are summarized and shown in Table 1 below.

Poly(styrene-ball-
Maleic anhydride) copolymer Methoxy alkylene glycol
(Jeffamine ^® ) N,N-dimethylaminopropyl amine
(DMAPA) Molecular Weight
(g/mol) equivalent weight Molecular Weight
(g/mol) equivalent weight equivalent weight Manufacturing Example 1 2,000 0.15 1,000 0.0945 0.0405 Manufacturing Example 2 2,000 0.15 1,000 0.0675 0.0675 Manufacturing Example 3 2,000 0.15 800 0.0945 0.045 Manufacturing Example 4 2,000 0.175 600 0.11025 0.04275 Manufacturing Example 5 3,000 0.12 1,000 0.0756 0.0324 Manufacturing Example 6 3,800 0.10 1,000 0.063 0.027 Manufacturing Example 7 2,000 0.15 1,000 0.09 0.0405

Thus, in the dispersants of Preparation Examples 1 to 7, the polymer compounds represented by the following Formulas 1 and 2 are present together, and the mixing ratio of the polymer compounds of Formulas 1 and 2 is methoxy alkylene glycol ( Jeffamine ^® ) and N,N-dimethylaminopropyl amine (DMAPA).

[Formula 1]

[Formula 2]

The molecular weights of the dispersants prepared in Preparation Examples 1 to 7 are shown in the following table.

Dispersant Number average molecular weight (g/mol) Weight average molecular weight (g/mol) Manufacturing Example 1 9,000 25,000 Manufacturing Example 2 7,000 19,600 Manufacturing Example 3 7,600 20,500 Manufacturing Example 4 6,200 17,000 Manufacturing Example 5 10,000 28,000 Manufacturing Example 6 11,000 29,000 Manufacturing Example 7 7,200 21,000

<Example 1-6, Comparative Example 1-2> Preparation of toner composition

After adding 11.0 g of the dispersant prepared in Preparation Example, 27.0 g of a polymerization resin (Laropal A81), and 38.0 g of a solvent Kocosol-100, stirred for 10 minutes at 1,500 rpm in a high speed dissolver, and then used as a pigment. Green pigment 24.0g was added. After stirring at 1,500 rpm for 30 minutes, the particles were dispersed to a particle size of 5 μm using a disperser, and then a small amount of an antifoaming agent and an anti-settling agent were added and finished to prepare a toner composition. The toner compositions prepared according to Examples 1 to 6 and Comparative Examples 1 to 2 were added to KSM5703 white paint to measure paint properties.

<Experimental Example 1> Evaluation of physical properties

1-1: Evaluation of the viscosity of the toner composition

Brookfield viscosity is a value that measures the torque value generated when a spindle is immersed in the fluid to be measured and rotated at a constant speed, and the shear rate is the rotational speed of the Brookfield viscometer. , It is a value determined by the type of spindle. Shear stress depends on the internal resistance of the fluid, that is, the torque value of the Brookfield viscometer.

Viscosity was measured by the method of ASTM D 1986-14 at room temperature using a Brookfield LVT 230 viscometer.

1-2: Compatibility evaluation method

Prepare white paint for each resin. White paint and toner are mixed at a weight ratio of 100/3 (all toners have the same mixing ratio). After thoroughly mixing the white paint and toner, paint on a glass plate or concealed paper using a 10 Mil Applicator with a standard sample. After painting with an applicator, check the compatibility of the paint by rubbing the wet paint with your finger. The more the color of the part rubbed with the finger and the part not rubbed the same, the better the compatibility between the toner and the paint, and the different the color difference, the worse the compatibility. Poor compatibility between paint and toner also means that the dispersant has poor performance. Of course, it is possible to improve compatibility with solvents or other auxiliary agents, but it is fundamentally important to select a dispersant. The color deviation was evaluated by measuring the L value of the part rubbed with the finger and the part not rubbed using a color difference meter. The color coordinates in ASTM E313 CIELAB are expressed as L*a*b*, where L* represents the brightness, a* represents the degree of red and green, and b* represents the degree of yellow and blue. The distance between the positions of the two colors within the color coordinate is expressed as △E, which is called'color difference' and evaluated as △E*ab value.

1-3: Storage stability test of toner composition

Storage stability was evaluated using the prepared sample when evaluating compatibility. Storage stability was evaluated by the STEMTM-Technology (Space- and Time-resolved Extinction Profiles) technique using a LUMiSizer ^® LS610 Dispersion Analyzer (LUM GmbH, Berlin Germany) tester. By using the sample for evaluation, by setting the rotation speed (4,000 rpm) of the rotor and the chamber temperature (room temperature), and measuring the change in the transmittance% for the position of the sample cell over one hour. The stability of the toner (coloring agent) composition was evaluated, and storage stability was determined as follows. As a result of the test, when the permeability change range before and after the test was less than 20%, it was evaluated as'excellent storage stability', less than 40% as'normal storage stability', and more than 40% as'poor storage stability'.

The experimental results are shown in Table 3 below.

Example (thread)
Comparative Example (Rain) Thread 1 Thread 2 Thread 3 Thread 4 Thread 5 Thread 6 Rain 1 Rain 2 Rain 3 Toner manufacture, wt% Polymerization resin 27 27 27 27 27 27 27 27 27 Dispersant Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 1 Manufacturing Example 3 Manufacturing Example 5 11wt% 11wt% 11wt% 11wt% 11wt% 11wt% 1wt% 1wt% 1wt% Pigment
Green 24 24 24 24 24 24 24 24 24 Antifoam 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sedimentation
Inhibitor 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 solvent 38 38 38 38 38 38 48 48 48 Brookfield
Viscosity, cP 19.80 17.40 13.80 18.60 32.40 25.20 265.9 68.80 36.20 Compatibility
(Color difference, △E*ab) 0.63 0.25 0.57 0.75 0.73 0.71 4.26 4.01 1.20 Storage stability Great Great Great Great Great Great Bad Bad Bad

* The total sum of the polymerization resin, dispersant, pigment Green, and solvent is 100% by weight,

It means that the antifoaming agent and the anti-settling agent are added in an amount of 0.1 or 0.2 parts by weight based on 100 parts by weight of the toner composition.

As shown in Table 3 above,

Compared to Comparative Examples 1 to 3 including 1% by weight of the dispersant according to the preparation example among the total 100% by weight of the toner composition, the toner compositions of Examples 1 to 6 including 11% by weight of the dispersant have lower viscosity, and It was found to have high compatibility with and excellent storage stability. Among them, in particular, in the case of the toner composition of Example 2 using the dispersant of Preparation Example 2, the color difference (ΔE*ab) value was the lowest at 0.25, and it was found that the compatibility with the paint was very good.

From this, the toner composition containing the dispersant of the present invention in a specific numerical range is used for manufacturing conductive nano ink, manufacturing electronic printer material, flexible printing material, coloring paint, printing ink, ink for color filter, resist for color filter, and inkjet. It can be seen that it can be used in various ways such as ink, toner for copying, and carbon-polymer composite materials.

<Experimental Example 2> Jeffamine used in preparing a dispersant ^® Evaluation of differences in physical properties by type

To prepare a toner composition according to Example 2 of the present invention, but instead of Jeffamine ^® M-1000 used to prepare a dispersant 2 included in Example 2 toner composition, a toner composition was prepared through the same process using Jeffamine ^® M-2070 I did. Then, the physical properties of the toner composition were evaluated in the same manner as in Experimental Example 1.

As a result, the toner composition prepared using Jeffamine M-2070 could not implement the physical properties as the toner composition according to Example 2. More specifically, the Brookfield viscosity was evaluated as 60, the color difference was 3.50, and the storage stability was evaluated as poor.

From this, it can be seen that only when SMA and Jeffamine ^® used in the examples of the present invention are adopted, the physical properties required as a toner composition can be easily achieved.

Claims (15)

A toner composition comprising 8 to 14% by weight of a dispersant including a copolymer represented by the following formula 1 and a copolymer represented by the following formula 2:
[Formula 1]

In Formula 1,
m and n are independently an integer of 4 to 18,
l and p are independently integers from 2 to 40; And

[Formula 2]

In Chemical Formula 2,
m and n are independently integers of 4 to 18.
The method of claim 1,
The toner composition, characterized in that contained in 9 to 13% by weight of the total 100% by weight of the toner composition.
The method of claim 1,
The toner composition, wherein m is greater than or equal to n.
The method of claim 3,
The toner composition, characterized in that the mole ratio of m and n is 1: 0.3 to 1.
The method of claim 1,
In the copolymer represented by Formula 1,
Propylene oxide (

) Part of l and ethylene oxide (

) The molar ratio of the part p (PO/EO mole ratio) is 1: 4 to 8, or 7 to 11: 1, characterized in that the toner composition.
The method of claim 1,
The toner composition, wherein the copolymer represented by Formula 1 and the copolymer represented by Formula 2 are contained in a dispersant in a molar ratio of 1:0.3 to 1.2.
The method of claim 1,
The toner composition, wherein the dispersant has a total base number (TBN) of 10 to 80 mgKOH/g.
Dissolving a poly(styrene-co-maleic anhydride) copolymer represented by the following formula (i);
Adding a compound represented by the following formula (ii) and a compound represented by the following formula (iii);
Inducing an imidation reaction to prepare a dispersant comprising a copolymer represented by Formula 1 and a copolymer represented by Formula 2;
Adjusting a dispersant content of 8 to 14% by weight in the total 100% by weight of the toner composition; A method for producing a toner composition comprising:
[Formula i]

The number average molecular weight (M _n ) of the compound of Formula i is 500 to 10,000 g/mol,
the mole ratio of m and n is 1:0.3 to 1;

[Formula ii]

The weight average molecular weight (M _w ) of the compound of Formula ii is 500 to 1,200 g/mol,
Propylene oxide (

) Part of l and ethylene oxide (

) The molar ratio of the part p (PO/EO mole ratio) is 1: 4 to 8, or 7 to 11: 1;

[Formula iii]

;

[Formula 1]

In Formula 1,
m and n are as defined in Formula i,
l and p are as defined in Formula ii;

[Formula 2]

In Chemical Formula 2,
m and n are as defined in Formula i.
The method of claim 8,
The weight average molecular weight (M _w ) of the compound of Formula ii is 600 to 1,000 g/mol,
Propylene oxide (

) Part of l and ethylene oxide (

) The molar ratio of the part p (PO / EO mole ratio) is 1: 5 to 7, or 8 to 10: 1, characterized in that the manufacturing method.
As a toner composition comprising (a) a resin, (b) a dispersant, (c) a colorant, and (d) a solvent,
The (b) dispersant comprises a copolymer represented by the following formula (1) and a copolymer represented by the following formula (2), and is contained in an amount of 8 to 14% by weight based on a total of 100% by weight of the toner composition:
[Formula 1]

In Formula 1,
m and n are independently an integer of 4 to 18,
l and p are independently integers from 2 to 40; And

[Formula 2]

In Chemical Formula 2,
m and n are independently integers of 4 to 18.
The method of claim 10,
The resin (a) is urea-aldehyde resin, phenol-aldehyde resin, acrylic resin, polyester resin, petroleum resin, vinyl resin, urethane resin, acrylic urethane resin, epoxy resin, alkyd resin, polyvinylpyrrolidone, PVP) resin, polyvinylbutyral (PVB) resin, methyl cellulose (methyl cellulose) resin, or a mixture thereof, characterized in that selected from the group consisting of a toner composition.
The method of claim 10,
The (c) colorant, characterized in that selected from the group consisting of dyes, pigments, or mixtures thereof.
The toner composition of claim 1; And
Containing, a toner accommodating part for accommodating the toner composition.
An inkjet printer comprising the ink cartridge for an inkjet printer of claim 13.
An inkjet recording method for recording an image on a recording medium by discharging the toner composition of claim 1 from an inkjet recording head.