JP2007112932A - Block resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a block resin that has high pigment dispersibility, excellent alkali development and compatibility with a photosensitive resin. <P>SOLUTION: The block resin is a resin composed only of a block having an acid group, comprises a block (A) having 0.1-90mgKOH/g acid value and a block (B) having ≥100mgKOH/g acid value and is obtained by living polymerization. The block resin is preferably a block resin characterized by modifying a hydroxy group-containing resin obtained by living polymerization of a hydroxy group-containing monomer with a compound (c) to make an acid group exist by reaction with the hydroxy group. Especially the living polymerization is preferably an atom transfer radical polymerization. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a block resin. More specifically, the present invention relates to the fields of pigment dispersion resins, resin-type dispersants, pigment compositions containing the same, and pigment dispersions that require proper use of printing inks and paints.

Printing inks, paints, hue materials for flat screen panels, and the like are required to have high transparency and contrast, and thus pigment dispersions require high pigment dispersibility and stability over time.
In order to solve these problems, proposals have been made to improve the dispersibility of the pigment by providing the resin with a substituent capable of adsorbing with the pigment or the pigment dispersant. However, according to this method, since the adsorption group with the pigment is randomly introduced into the resin, the affinity between the resin part and the dispersion medium is weakened, and it becomes difficult to secure an adsorption layer sufficient for dispersion stabilization, In addition, when the amount of the pigment adsorbing group introduced into the resin is increased, the solubility in the dispersion medium is decreased, and thus there is a problem that an adsorbing layer sufficient for stabilizing the dispersion cannot be secured.

Furthermore, in order to solve this problem, a block type pigment dispersion composition using a resin having a block which becomes a pigment adsorbing group and a block having solvent solubility in the resin has been proposed (Patent Documents 1 and 2). In addition, a block copolymer in which acid groups are localized in a resin has been proposed to improve adhesion to a substrate, background contamination during development, and film residue (Patent Document 3).
However, block resins or gradient resins with localized acid groups provide good pigment dispersibility or good alkali developability of the dried coating film, but good compatibility with the photosensitive resin in the hue material. In some cases, the light transmittance of the coating film after post-baking may be reduced.
JP 2002-534542 A JP 2004-66235 A Japanese Patent No. 3094403

  An object of the present invention is to provide a block resin having high pigment dispersibility and having good alkali development and compatibility with a photosensitive resin.

The present invention is a resin comprising only a block having an acid group, comprising a block (A) having an acid value of 0.1 to 90 mgKOH / g and a block (B) having an acid value of 100 mgKOH / g or more. Provided is a block resin obtainable by polymerization.
The block resin is a block resin characterized in that a hydroxyl group-containing resin obtained by living polymerization of a monomer having a hydroxyl group is modified with a compound (c) capable of causing an acid group to react with the hydroxyl group. It is preferable that the living polymerization is atom transfer radical polymerization. It is also desirable that the compound (c) is a cyclic polycarboxylic acid anhydride. Further, together with the compound (c), it can react with a hydroxyl group and can react with a compound (d) having a curable unsaturated double bond or an acid group or a hydroxyl group possessed by a block resin. It is also desirable to react the compound (e) having a heavy bond.
In the block resin of the present invention, the number average molecular weight of the block resin is preferably 1000 to 50000. Moreover, it is preferable that the mass ratio of a block (A) and a block (B) is (A) 60-99.9 weight% and (B) 0.1-40 weight%.
A suitable pigment dispersion can be obtained by dispersing the block resin of the present invention in an organic solvent or water together with a pigment and, if necessary, a pigment derivative having a basic group and / or a resin other than the block resin of the present invention. Obtainable.

Next, the present invention provides a block resin having a block (A ′) having a repeating unit having a hydroxyl group of 70 wt% or less and a block (B ′) having a repeating unit having a hydroxyl group of 80 wt% or more obtained by living polymerization. The present invention relates to a method for producing a block resin, which comprises reacting a compound (c) capable of causing an acid group to exist by reacting with the hydroxyl group.
The production method further comprises a compound (d) capable of reacting with a hydroxyl group and having a curable unsaturated double bond and / or a compound capable of reacting with an acid group or a hydroxyl group and having a curable unsaturated double bond. A method for producing a block resin characterized by reacting (e) is preferred, and the living polymerization is particularly preferably atom transfer radical polymerization.

  According to the present invention, in pigment dispersions such as inks and paints, the applicability such as non-aggregability and fluidity, the sharpness of the color tone of the coated material, the gloss and the like are remarkably improved, and good alkali developability and photosensitivity are also achieved. It is possible to provide a block resin having good compatibility with the functional resin.

The block resin of the present invention is a block resin having a block (A) having an acid value of 0.1 to 90 mgKOH / g and a block (B) having an acid value of 100 mgKOH / g or more. The block resin of the present invention is an acrylic block resin, and living polymerization is used for its synthesis.
The block (A) is composed of a monomer having an acid group and a monomer having no acid group, and the block (B) does not have to have a single repeating unit. Therefore, the resin of the present invention consists only of blocks having acid groups. The block of the present invention is defined as a chain of monomers having a polymerization degree of 5 or more.

  In the living polymerization, side reactions occurring in general radical polymerization are suppressed, and further, the growth of the polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.

Among them, the atom transfer radical polymerization method using organic halides and sulfonyl halide compounds as initiators and transition metal complexes as catalysts can be applied to a wide range of monomers, and the polymerization temperature can be applied to existing equipment. It is preferable in that it can be adopted. An atom transfer radical polymerization method can be performed by the method described in the following references 1-8.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329.
(Reference 2) Matyjaszewski et al., Chem. R ev. 2001, 101, 2921.
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614.
(Reference 4) Macromolecules 1995, 28, 7901, Science 1996, 272, 866
(Reference 5) Pamphlet of International Publication No. 96/30421 (Reference 6) Pamphlet of International Publication No. 97/18247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-411117

  In the block resin of the present invention, the relatively low acid value block (A) contributes to the developability and compatibility with the photosensitive resin, and the high acid value block (B) having dense acid groups is the pigment or It becomes an adsorption site on the pigment derivative surface.

  When the acid value of the block (A) of the block resin of the present invention is less than 0.1, the compatibility with the photosensitive resin is reduced. On the other hand, when the acid value exceeds 90 mgKOH / g, the compatibility with the photosensitive resin is caused. In addition to block (B), not only block (B) but also block (A) will be adsorbed to the pigment or pigment derivative, and a resin adsorbing layer contributing to dispersion stabilization will not be formed, and dispersion stability will be impaired. . On the other hand, when the acid value of the block (B) is less than 100 mgKOH / g, sufficient adsorption power of the resin to the pigment or pigment derivative cannot be obtained, and the dispersion stability is impaired.

  The block (A) of the block resin of the present invention contributes to the improvement of the compatibility with the solvent and the resin, the stabilization of dispersion by steric repulsion, and the effect of alkali developability. The monomer constituting the block (A) is a monomer having a low interaction with the pigment and the pigment derivative, and can be appropriately selected according to the organic solvent or water solvent used.

When the resin of the present invention is synthesized by atom transfer radical polymerization, it is difficult to use a monomer having a carboxyl group directly because the carboxyl group becomes a catalyst poison.
For this reason, after polymerizing with an acrylic monomer containing a hydroxyl group and polymerizing a resin comprising a block (A ′) having a loose hydroxyl group and a block (B ′) having a dense hydroxyl group, an acid anhydride is added to the hydroxyl group of each block. It is preferable to react the product to form the block resin of the present invention.

The polymer synthesized by such a method has blocks having acid groups loosely and blocks having densely in the resin, due to the characteristics of living polymerization. For this reason, the block resin of this invention does not contain the block which does not have an acid group.

In addition, when the block resin of the present invention is synthesized by atom transfer radical polymerization, a monomer having no hydroxyl group and a monomer having a small amount of hydroxyl group are randomly copolymerized to form a block (A ′), It is preferable to form a block (B ′) by adding a monomer having a hydroxyl group to the polymerization reaction product.
Naturally, a block (B ′) having a repeating unit having a hydroxyl group of 80 wt% or more is sandwiched between blocks (A ′) having a repeating unit having a hydroxyl group of 70 wt% or less, that is, an A′B′A ′ triblock is formed. It may be a thing.

Examples of monomers having no hydroxyl group include dienes such as ethylene, buta-1,3-diene, 2-methylbuta-1,3-diene, 2-chlorobuta-1,3-diene;
Styrenes such as styrene and α-methylstyrene;
Methyl acrylate, normal butyl acrylate, tertiary butyl acrylate, benzyl acrylate, ethyl hexyl acrylate, paracumylphenol EO modified acrylate, nonylphenol EO modified acrylate, 2-vinyloxyethyl acrylate, 2- (2'-vinyl) Roxyethoxy) ethyl, acrylic acid esters such as lauryl acrylate, glyceryl acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate;
Methyl methacrylate, ethyl methacrylate, normal butyl methacrylate, tertiary butyl methacrylate, stearyl methacrylate, ethyl hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, lauryl methacrylate, glyceryl methacrylate, methoxypolyethylene glycol methacrylate, methacrylic acid Methacrylic acid esters such as acid phenoxypolyethylene glycol, glycidyl methacrylate, dimethylaminoethyl methacrylate, 2-vinyloxyethyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl methacrylate, cyclopentadienyl methacrylate;
(Meth) acrylic acid derivatives such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate;
Vinyl ethers such as vinyl methyl ether and vinyl ethyl ether;
N-vinyl compounds such as vinyl methyl ketone, vinyl hexyl ketone, vinyl ketones, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone;
Allyl compounds such as allyl alcohol, allyl chloride, allyl acetate, vinyl chloride, vinylidene chloride;
Examples thereof include (meth) acrylic acid esters having a fluorine alkyl group such as vinyl fluoride and vinylidene fluoride. These may be used alone or in combination of two or more.

  Although it does not specifically limit as an example of the acrylic monomer containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4- Examples thereof include hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers. These may be used alone or in combination of two or more.

The hydroxyl group of the block (B ′) is modified to a carboxylic acid group. At this time, the compound (c) which can react with a hydroxyl group and can make a carboxylic acid group exist after the reaction is used.
The compound (c) has a functional group capable of reacting with a hydroxyl group. Examples of such functional groups include carboxylic acid anhydride groups, carboxylic acid groups, carboxylic acid ester groups, carboxylic acid amide groups, carboxylic acid halogen groups, epoxy groups, isocyanate groups, carbodiimide groups, vinyloxy groups, and halogen groups. .
Furthermore, the compound (c) must be capable of allowing a carboxyl group to exist after the reaction with the hydroxyl group of the block (B ′). For this purpose, the compound (c) must have a carboxyl group in addition to a functional group capable of reacting with a hydroxyl group, or must generate a carboxylic acid upon reaction with the hydroxyl group.

Examples of the compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group include epoxy compounds having a carboxylic acid group, carbonyl chlorides having a carboxylic acid group, sulfonyl chlorides having a carboxylic acid group, and carboxylic acid Examples thereof include isocyanates having a group and chlorotriazines having a carboxylic acid group.
Moreover, the compound which can introduce | transduce a carboxylic acid group after reaction with a hydroxyl group has a substituent which produces | generates carboxylic acid by the hydrolysis by an acid. For example, it is a compound having in the same molecule a substituent capable of reacting with the hydroxyl group such as a polycarboxylic acid anhydride group or a t-butyl ester group.

  A functional group that generates a carboxylic acid by reaction with a hydroxyl group includes a polycarboxylic acid anhydride group, and a compound having the functional group includes a cyclic polycarboxylic acid anhydride. Cyclic polycarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, succinic anhydride, trimellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, het anhydride Tetrabromophthalic anhydride, hymic anhydride and derivatives thereof, and the like may be used alone or in combination. The reaction between the hydroxyl group and the polycarboxylic anhydride group can be performed according to known conditions.

  As for the mass ratio of the block (A) and the block (B) of the block resin of the present invention, the block (A) is 60 to 99.9% by weight and the block (B) is 0.1 to 40% by weight. Is preferred. If the block (B) exceeds 40% by weight, the solubility of the resin in the dispersion solvent decreases, leading to poor dispersion. Further, when the mass ratio of the block (B) is less than 0.1% by weight, there are few adsorption sites between the resin and the pigment, and thus aggregation of the pigment cannot be prevented.

  Moreover, the pigment dispersion of this invention can be thermosetted by reaction with a well-known thermosetting agent and the carboxyl group and hydroxyl group in the block resin of this invention.

The block resin of the present invention can react with a hydroxyl group and can react with a compound (d) having a curable unsaturated double bond and / or a carboxyl group or a hydroxyl group, and has a curable unsaturated double bond. The block resin can be made to have photocuring property or thermosetting property by reacting the compound (e).
For example, the compound (d) may be reacted with the hydroxyl group of the block (B ′) before the reaction of the compound (c).
Moreover, you may use a compound (d) with a compound (c).
Further, the compound (e) may be reacted with the block resin after the reaction with the compound (c). In this case, the amount of curable unsaturated double bonds introduced is preferably 20 to 60 mol% of the total hydroxyl groups of the resin.
Examples of the functional group capable of reacting with a hydroxyl group of the compound (d) or the compound (e) are the same as those of the compound (c). Moreover, as a functional group which can react with a carboxyl group of a compound (e), an isocyanate group, a glycidyl group, a vinyloxy group, an amino group, a carboxylic acid halogen group, an oxazoline group, an isothiocyanate group, a carbodiimide group etc. are mentioned.

Examples of the compound (d) and the compound (e) include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-vinyl-1-cyclohexene 1,2 epoxide, glycidyl cinnamate, 1,3-butadiene monoepoxide, Celoxide 2000 (manufactured by Daicel Chemical Industries, Ltd.) Can be mentioned.
Examples of the compound having a functional group capable of reacting with a hydroxyl group and a polymerizable double bond include methacryloyloxyethyl isocyanate (MOI), acryloyloxyethyl isocyanate (AOI), methacryloyloxyethyl isothiocyanate, acryloyloxyethyl isothiocyanate, methacryloyl isotope. Examples include thiocyanate, acryloyl isothiocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate (MAI), and isopropenyl-α, α-dimethylbenzyl isocyanate (TMI). 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate. A compound obtained by reacting a diisocyanate ester compound such as dimer acid diisocyanate with a hydroxyl group, carboxyl group, or amide group-containing vinyl monomer in an equimolar amount is also used as the isocyanate ester compound in the compounds (d) and (e). be able to.
Furthermore, acid halides of (meth) acrylic acid, halopropionic acids, or acid halides thereof can be used for compound (d) and compound (e). When halopropionic acids or acid halides thereof are used, the resulting halopropionic acid ester compound is dehalogenated to produce a (meth) acrylic acid ester compound, thereby increasing the hardness after curing. be able to.

  Among the above compounds, cyclic polycarboxylic acid anhydrides having unsaturated double bonds are desirable. For example, maleic anhydride, tetrahydrophthalic acid anhydride, or those having an acrylate group and a cyclic polycarboxylic acid structure in the molecule are used. It is preferable to do this.

  In the atom transfer radical polymerization used in the present invention, in order to suppress side reactions that occur during general radical polymerization, depending on the charging ratio of the initiator of the atom transfer radical polymerization added during polymerization and the radical polymerizable monomer, Resin molecular weight and block (A) or (B) ratio can be freely controlled.

  The number average molecular weight (Mn) of the block resin of the present invention is usually preferably 1000 to 50000, more preferably 3000 to 30000. When the number average molecular weight (Mn) is less than 1000, the effect of steric repulsion by the block (A), the solvent solubility or the compatibility with the resin is small, and it becomes difficult to prevent the aggregation of the pigment. Will increase in viscosity. On the other hand, if Mn exceeds 50,000, the amount of the resin block resin necessary for dispersion increases, resulting in a decrease in the pigment concentration in the coating film.

  Since the block resin in the present invention is produced by a living polymerization method, its molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is usually 2.0 or less, preferably 1.5 or less.

  Also in the living polymerization, the atom transfer radical polymerization method is carried out using a transition metal complex such as copper, ruthenium, iron and nickel as a redox catalyst. Specific examples of the transition metal complex include low-valent halogenated transition metals such as copper (I) chloride and copper (I) bromide. In order to control the polymerization rate, a well-known method is used. High valent transition metals such as copper (II) chloride and copper (II) bromide may be added to the polymerization system.

  An organic ligand is used for the metal complex. Organic ligands are used to allow reversible changes in solubility in the polymerization solvent and redox conjugated complexes. Examples of the metal coordination atom include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom, and a nitrogen atom or a phosphorus atom is preferable. Specific examples of organic ligands include sparteine, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, triphenyl Examples include phosphine and tributylphosphine.

  The transition metal and the organic ligand may be added separately to form a metal complex in the polymer, or the metal complex may be synthesized in advance and added to the polymerization system. In particular, the former method is preferable when the transition metal is copper, and the latter method is preferable for ruthenium, iron, and nickel.

Specific examples of ruthenium, iron and nickel complexes synthesized in advance include tristriphenylphosphinoniruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ), bistrisphenylphosphinoniiron chloride (FeCl ₂ (PPh ₃ ) ₂ ), Nickel bistrisphenylphosphinonichloride (NiCl ₂ (PPh ₃ ) ₂ ), nickel bistributylphosphinonibromide (NiBr ₂ (PBu ₃ ) ₂ ), and the like.

  As the initiator used in the atom transfer radical polymerization method, known initiators can be used, and organic halides and sulfonyl halide compounds having a highly reactive carbon halogen bond are mainly used. Specific examples include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, paratoluenesulfonic acid chloride, bromoethylbenzene, chloroethylbenzene, and the like. These are used alone or in combination.

In the atom transfer radical polymerization, the atom transfer radical polymerization initiator is used in a proportion of 0.01 to 10 mol%, preferably 0.1 to 2 mol%, based on the total amount of the radical polymerizable monomer.
Moreover, the usage-amount of a transition metal is 0.03-3 mol with respect to 1 mol of initiators as forms, such as a halide, Preferably it is used in the ratio of 0.1-2 mol. Furthermore, the ligand is used in a proportion of usually 1 to 5 mol, preferably 2 to 3 mol, per 1 mol of the transition metal (form of halide, etc.).
When the aromatic ring, heterocyclic ring, condensed aromatic ring and transition metal and ligand having the above-mentioned atom transfer radical polymerization initiating group are used in such proportions, the reactivity of living radical polymerization, the molecular weight of the produced polymer, etc. Is suitable.

  In addition, due to the characteristics of atom transfer radical polymerization, the resulting resin has an active carbon-halogen bond at the terminal end, which can be modified by a known method to introduce a functional group.

If the polymerization initiator has a functional group, it can have a functional group only at one end of the resin.
For example, after polymerization using an initiator having a tertiary butyl ester group, a method of introducing a carboxyl group into the resin piece end by ester hydrolysis, or polymerization using an initiator having a hydroxyl group, For example, a method in which a carboxyl group is introduced into one end of a resin by reaction with a polycarboxylic acid after a resin having a hydroxyl group alone is synthesized.

  Atom transfer radical polymerization can be allowed to proceed even without solvent, or may be allowed to proceed in the presence of a solvent such as butyl acetate, toluene, xylene, anisole, or MEK. In the case of using a solvent, in order to prevent a decrease in polymerization rate, the amount of the solvent used after the polymerization is preferably 50% by weight or less. Even if there is no solvent or a small amount of solvent, there is no particular safety problem with respect to the control of the heat of polymerization. Rather, the solvent reduction is preferable in terms of economic efficiency and environmental measures.

  As polymerization conditions, from the point of polymerization rate and catalyst deactivation, a polymerization temperature of 60 to 130 ° C. depends on the final molecular weight and polymerization temperature, but a polymerization time of about 1 to 100 hours may be used. . The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon in order to prevent the polymerization catalyst from being deactivated by oxygen.

The synthesis of the block copolymer can be carried out by a known method. After the monomers forming the block (A ′) are polymerized and the polymerization yield exceeds 90% to 100%, the block (B ′) is synthesized. It is preferable to carry out the polymerization by adding the monomer to be formed.

As a synthesis example, after completion of the polymerization reaction, the reaction is stopped by cooling the polymerization reaction system to 0 ° C. or less, preferably about −78 ° C., and the remaining monomer and / or solvent is removed according to a well-known method. Reprecipitation in the medium, filtration or centrifugation of the precipitated polymer, washing and drying of the polymer.
If necessary, the block metal of the present invention can be obtained by removing the transition metal contained in the polymerization system by a known method and then evaporating volatile components.
As the removal method, dilute the reaction mixture with an organic solvent such as THF, toluene, MEK, etc., wash with water / dilute hydrochloric acid or aqueous amine solution, etc., and contact the resin solution with a cation exchange resin or chelate resin, alumina / silica Alternatively, there are a method of passing through a clay column or pad, and a method of filtering and centrifuging after adding an adsorbent such as a reducing agent or hydrosartite.

  The block resin of the present invention may be further added with a pigment, a resin different from the block resin of the present invention, a solvent, and a pigment derivative having a basic group to form a pigment dispersion composition.

  The block resin of the present invention exhibits an excellent dispersion effect on generally commercially available pigments. For example, soluble and insoluble azo pigments, azo pigments such as condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene / perinone pigments, dioxazine pigments, anthraquinone pigments, diketopyrrolopyrrole pigments Organic pigments such as pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, thioindigo pigments, carbon black, acid value titanium, yellow lead, cadmium yellow, cadmium red, petal Inorganic pigments such as iron black, zinc white, bitumen, ultramarine blue and the like, and functional inorganic substances exemplified by metal oxides such as zirconium, antimony, aluminum, zinc, tin, and indium can be used for dispersion.

  The block resin of the present invention exhibits very good pigment dispersibility when used in combination with a pigment derivative having a basic group.

As the pigment derivative having a basic group used in the pigment dispersion of the present invention, a known one can be used, but it is preferable to use a pigment derivative represented by the following general formula (1).

P- [XYZN (R ¹ ) R ² ] n General formula (1)
(In the formula, P is an organic dye residue, and X is a divalent compound consisting of a chemically reasonable combination composed of 2 to 15 atoms selected from S, C, N, O, and H. Y is a direct bond, —NR— (wherein R is H or an alkyl group having 1 to 18 carbon atoms) or —O—, Z is an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² are each an independently substituted alkyl group having 1 to 18 carbon atoms or a heterocycle formed integrally with R ¹ and R ² , and n is 1 to 3 Represents an integer.)

  Specific examples of the organic dye residue P include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrone, indanthrone, and pyranthrone. Anthraquinone dyes such as violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complex systems It is a pigment such as a pigment.

X is, for example, —SO ₂ —, —CO—, —CH ₂ —, —CH ₂ S—, —CR, H ₂ O—, —COO—, —NH—, —CH ₂ NHCOCH—, or these Combinations are mentioned.
Of these, —SO ₂ —, —CO—, and —CH ₂ — are preferable. In addition, when a heterocyclic ring is formed with R ¹ and R ² , N, O, and S are listed as constituent elements other than carbon of the heterocyclic ring.

Note that the molecular skeleton of the organic pigment and the molecular skeleton of the organic dye residue P in the pigment derivative do not necessarily coincide with each other, but it is usually preferable to use the same molecular skeleton in terms of hue.
In particular, phthalocyanine residues for blue pigments, quinacridone residues, diketopyrrolopyrrole residues or benzimidazole residues for red pigments, and benzimidazole residues for yellow pigments. It is preferable.

The structure of the pigment derivative is preferably a to g in Table 1 below.

  The pigment derivative used in the pigment dispersion of the present invention is preferably used in a proportion of 0.5 to 30 parts by weight, more preferably 5 to 20 parts by weight, with respect to 100 parts by weight of the pigment in the pigment dispersion. .

  Further, the organic solvent used in the pigment dispersion of the present invention is not limited as long as the block resin of the present invention is soluble, but aliphatic hydrocarbons such as cyclohexane and n-heptane, toluene, xylene and the like Aromatic hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, diisobutyl ketone, cyclohexanone and other ketones, isopropyl alcohol, n-butyl alcohol and other alcohols, ethyl acetate, butyl acetate, isoamyl acetate, lactic acid Acetic acid esters such as ethyl, glycol ethers such as propylene glycol monomethyl ether, ethyl cellosolve and butyl cellosolve, glycols such as propylene glycol monomethyl ether acetate, cellosolve acetate and methoxybutyl acetate Such as glycol ester compounds and the like.

The amount of the block resin used in the present invention is preferably 5 to 300 parts by weight in terms of solid content with respect to 100 parts by weight of the pigment. In particular, when used as a concentrated dispersion, the block resin is preferably 10 to 150 parts by weight in terms of solid content with respect to 100 parts by weight of the pigment. Moreover, when using as a coating material or printing ink, 30-300 weight part of block resin is preferable in conversion of solid content with respect to 100 weight part of pigments. If the amount of the block resin is less than 5 parts by weight with respect to 100 parts by weight of the pigment, the pigment is difficult to disperse.
In addition, when using as a paint or printing ink, you may add hardening | curing agent resin, hardening catalysts, surfactant, etc., such as melanin resin and an epoxy resin.

  In the pigment dispersion of the present invention, the block resin may be used alone as the dispersion resin, but may be used in combination with a resin different from the block resin of the present invention. In this case, other resins used in combination may be those that are compatible with the block resin of the present invention, but those that are exposed and developed as a colored photosensitive composition are preferred, and acidic groups and unsaturated doubles are contained in the resin. Those having a bond are more preferred. Moreover, as a ratio of the other resin used, 5-200 weight part is preferable with respect to 100 weight part of pigments in a pigment dispersion.

  Examples of the resin used in the pigment dispersion in combination with the block resin of the present invention include, for example, polyvinyl chloride, poly (meth) acrylic ester, epoxy resin, polyurethane resin, cellulose derivative (for example, ethyl cellulose, cellulose acetate, Nitrocellulose), PVC-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, butadiene-acrylonitrile copolymer, acrylic resin, styrene-acrylic resin, styrene-maleic acid resin, rosin Resin, rosin ester resin, ethylene-vinyl acetate resin, petroleum resin, coumarone indene resin, terpene phenol resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, salt vinegar Bi-resin, xylene resin, aluminum Kid resins, aliphatic hydrocarbon resins, butyral resins, silicone resins, maleic acid resins and fumaric acid resins. It is preferable to use an acrylic resin having good compatibility with the block resin of the present invention, more specifically an acrylic resin having an acidic group and an unsaturated double bond.

  Further, a commercially available dispersant may be further added to the pigment dispersion of the present invention. In this case, the commercially available dispersant preferably has an acidic group.

Examples of the method of using the block resin of the present invention include the following 1. ~ 4. There is a method like this. The effects of the present invention are also achieved by these methods.
1. A pigment composition obtained by previously mixing a pigment and a block resin is dispersed by adding a non-aqueous or aqueous vehicle.
2. Add pigment and block resin to non-aqueous or aqueous vehicle and disperse.
3. Disperse the pigment and the block resin separately in a non-aqueous or aqueous vehicle in advance and mix the resulting dispersion. In this case, the block resin may be dispersed only with a solvent.
4. After dispersing the pigment in the non-aqueous or aqueous vehicle, the block resin is added to the obtained pigment dispersion.

1 above. ~ 4. As a method for adjusting the pigment composition containing, a sufficient dispersion effect can be obtained by simply mixing the pigment powder and the block resin of the present invention, but it is preferable to follow the following methods (a) to (c). .
(A) Mix mechanically with a kneader, dissolver, high-speed mixer, homomixer, 2-roll mill, 3-roll mill, other rolls, sand mill, super mill, attritor, other pulverizers, other dispersers, etc. Preparation method (a) Addition of a solution containing the block resin of the present invention to a suspension system of pigment with water or an organic solvent, and deposition of the block resin on the pigment surface (c) A solvent having strong dissolving power such as sulfuric acid Intelligent mixing method such as co-dissolving organic pigment and block resin and co-precipitation with poor solvent such as water

  Since the block resin of the present invention has a photocurable unsaturated double bond and an acid group, after making into a pigment dispersion, a photoinitiator / sensitizer is added according to a known method, masked, and active energy rays. Can be photocured by irradiation. A pattern can be formed by alkali developing the unexposed portion.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example shows a weight part and% shows weight%.

Production Example 1
In a four-necked flask equipped with a thermometer, stirrer, reflux condenser, and nitrogen gas inlet tube, 94 parts of MEK, 94 parts of normal butyl methacrylate, 0.6 part of hydroxyethyl methacrylate, 1.0 part of ethyl bromoisobutyrate, tetra 2.3 parts of methylethylenediamine was charged, the temperature was raised to 40 ° C., and nitrogen was introduced for 30 minutes. 1.0 part of cuprous chloride was added and the temperature was raised to 70 ° C. under a nitrogen stream to initiate polymerization. After polymerization for 5 hours, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 100% from the solid content of the polymerization. As a result of GPC measurement, Mn of the polymer was 19000 and Mw / Mn = 1.3. 0.5 parts of succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid SA) was added to the polymerization reaction product, and the temperature was raised to 85 ° C. 0.8 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and reacted for 4 hours. In the IR measurement of the product after the reaction, 1782 cm ⁻¹ derived from acid anhydride and The absorption at 1862 cm ⁻¹ disappeared. The acid value of the reaction product was 2.9 mgKOH / g. The number average molecular weight Mn of the polymer determined by GPC measurement was 20000, and the molecular weight distribution: Mw / Mn = 1.4.

Production Example 2
In the same manner as in the above production example, 94 parts of MEK, 94 parts of normal butyl methacrylate, 0.6 part of hydroxyethyl methacrylate, 1.0 part of ethyl bromoisobutyrate and 2.3 parts of tetramethylethylenediamine were used for polymerization. After 5 hours, 5.7 parts of hydroxyethyl methacrylate and 5.7 parts of MEK were added, and polymerization was further performed for 2 hours. The reaction mixture was sampled and the polymerization was stopped after confirming that the yield was 100% from the solid content of the polymerization. As a result of GPC measurement, Mn of the polymer was 21000, and Mw / Mn = 1.3 (resin X-0).

Production Example 3
0.5 part of succinic anhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid SA) was added to the reaction mixture obtained in Production Example 2, and the temperature was raised to 85 ° C. 0.8 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and reacted for 4 hours. Absorption of 1782cm ^-1 and 1862cm ^-1 derived from an acid anhydride in the IR measurement of the product after the reaction had disappeared. The acid value of the reaction product was 26.1 mgKOH / g. The number average molecular weight Mn of the polymer determined by GPC measurement was 20000, and the molecular weight distribution: Mw / Mn = 1.4. A resin having a block (A) having an acid group at random and an acid value of 2.9 mgKOH and a block (B) having an acid value of 243 mgKOH was obtained (resin X-1).

Production Example 4
To 200 parts of the resin having a hydroxyl group (resin X-0) obtained in Production Example 1, 0.8 part of isocyanate ethyl methacrylate, 4.4 parts of succinic anhydride, and 0.3 part of methoquinone are added, and dibutyltin laurate is added. 0.1 parts of (DBTDL) and 0.95 parts of 1,8-diazabicyclo [5.4.0] -7-undecene were added and reacted at 80 ° C. for 5 hours in a dry air stream. In the IR measurement of the product after the reaction, absorption at 2275 cm ⁻¹ by the isocyanate group and 1782 cm ⁻¹ derived from the acid anhydride and The absorption at 1862 cm ⁻¹ disappeared. The acid value of the reaction product was 23.5 mgKOH / g, and a block resin having an unsaturated double bond was obtained (resin X-2).

Comparative production example 1
In the same manner as in Production Example 1, 93.7 parts of MEK, 93.7 parts of normal butyl methacrylate, 1.0 part of ethyl bromoisobutyrate, and 2.3 parts of tetramethylethylenediamine were charged and polymerized for 5 hours. From the solid content of the reaction product, it was confirmed that the polymerization yield was 99%, and the flask was cooled to terminate the polymerization. This reactive organism was diluted with MEK, purified by precipitation with a large amount of methanol, and subjected to suction filtration and vacuum drying using a filter to obtain a macroinitiator (Mn is 18000, Mw / Mn = 1.3). 94.6 parts of the resulting macroinitiator, 100 parts of MEK, 2.3 parts of tetramethylethylenediamine, and 6.3 parts of 2-hydroxyethyl methacrylate were charged into a flask, and cuprous chloride 1 was prepared in the same manner as in the above production example. Polymerization was initiated by adding 0.0 part. After 2 hours, it was confirmed from the solid content of the solution that the polymerization yield was 100%, and the polymerization was stopped. Furthermore, a hydroxyl group in the resin was converted to an acid group by the same method as in Production Example 2 to obtain a block polymer having an acid group (Mn = 18800, Mw / Mn = 1.5, acid value 24.1 mgKOH / g Resin Y-1).

Comparative production example 2
In the same manner as in Production Example 1, 93.7 parts of MEK, 93.7 parts of normal butyl methacrylate, 1.0 part of ethyl bromoisobutyrate, and 2.3 parts of tetramethylethylenediamine were charged and polymerized for 5 hours. From the solid content of the reaction product, it was confirmed that the polymerization yield was 93%, and 6.3 parts of 2-hydroxyethyl methacrylate and 6.3 parts of MEK were added to the reaction mixture. Polymerization was further performed for 2 hours. The yield from the solid content after polymerization was 100%, and the polymer Mn = 19500 and Mw / Mn = 1.3. The hydroxyl group in the resin was converted to an acid group by the same method as in Production Example 2 (Mn = 19000, Mw / Mn = 1.4, acid value 26.1 mgKOH / g, resin Y-2).

Comparative production example 3
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet tube, 100 parts of MEK, 93.7 parts of normal butyl methacrylate, 6.3 parts of 2-hydroxyethyl methacrylate, ethyl bromoisobutyrate 1. 0 parts and 2.3 parts of tetramethylethylenediamine were charged, and nitrogen was introduced for 30 minutes. 1.0 part of cuprous chloride was added and the temperature was raised to 70 ° C. under a nitrogen stream to initiate polymerization. After polymerization for 5 hours, the polymerization solution was sampled, and after confirming that the polymerization yield was 100% from the solid content of the reaction mixture, the polymerization was stopped. As a result of GPC measurement, the polymer Mn was 23000, Mw / Mn = 1.3, and a random resin having a hydroxyl group was obtained. The hydroxyl group in the resin was converted into a carboxylic acid group by the same method as in Production Example 2. The acid value of the resin was 26.1 mgKOH / g (Resin Y-3).

  The obtained resin solutions of Resin X-1 and Resin Y-1 to Resin Y-1 to 3 were diluted with MEK, respectively, and filtered under pressure to remove polymerization catalyst residues in the resin solution. The solvent was removed by concentration to obtain an acidic acrylic resin.

CuPcは、銅フタロシアニン残基を表す。 (Examples 1-5, Comparative Examples 1-3)
As shown in Table 2, pigment (C.I. Pigment Blue 15: 6), resin X-1, X-2 or resin Y-1, Y-2, Y-3 acidic dispersion resin, general radical Acrylic resin (Z) having an acid group synthesized by polymerization (butyl methacrylate-acrylic acid copolymer Mw = 35000 acid value 130), a pigment derivative having a basic group represented by the following structural formula (2), and cyclohexanone And 100 parts of 0.8 mmφ zirconia beads were added and dispersed for 3 hours with a paint conditioner.
Formula (2)

CuPc represents a copper phthalocyanine residue.

  The obtained pigment dispersion composition was coated on a PET film with a bar coater and dried at 150 ° C. for 10 minutes. The gloss was measured by measuring 60 ° gloss with a digital variable gloss meter. The measurement results are shown in Table 2.

  About the obtained pigment dispersion composition, the viscosity was measured using the E-type viscometer, and the degree of thickening was investigated. The measurement results are shown in Table 2.

  The obtained pigment dispersion was applied onto a glass substrate with a spin coater so as to have a dry film thickness of 2 μm, and dried at 150 ° C. for 10 minutes. The obtained coating film was developed with a 1% aqueous solution of sodium carbonate, rinsed with water, and then dried at 180 ° C. for 60 minutes. The degree of the organic film or the remaining pigment in the coating film was visually judged as A (good) to D (bad). The measurement results are shown in Table 2.

Resin X-1, X-2 or resin Y-1, Y-2, Y-3 acrylic resin 15 parts Aronix M-240 (manufactured by Toa Gosei Chemical Co., Ltd. 15 parts of functional acrylate) and 70 parts of ethyl acetate were mixed and applied on a glass substrate by a spin coater so that the dry film thickness was 2 μm. Furthermore, the coating film was dried at 150 ° C. for 90 minutes. The turbidity of the obtained coating film was visually observed and rated from 5 (good) to 1 (bad). The measurement results are shown in Table 3.

From Table 2 and Table 3, the resin of the comparative example cannot achieve good pigment dispersibility or compatibility between alkali developability and photocurable resin, whereas the block resin of the present invention has good pigment dispersibility. Both alkali developability and compatibility with photo-curing resin were compatible, and all of them exhibited excellent effects. Since the resin of the present invention has both good dispersibility and compatibility with the photosensitive resin, it is also suitable for applications where alkali development is not required.

The block resin of the present invention can be used for pigment dispersion resins, resin-type dispersants and pigment compositions containing the same, and pigment dispersions for improving the proper use of printing inks and paints, as well as hydrophilic groups and non-hydrophilic groups. Since it has a functional group, it can be expected to be used as a surfactant, a phase transfer substance, a surface modifier, a dispersant for substances other than pigments, and the like.
The block resin of the present invention can be widely used for applications that require pigment dispersion such as ink, paint, resin molded product or hue material of flat screen panel, and black matrix.

Claims (13)

  A resin consisting of only a block having an acid group, comprising a block (A) having an acid value of 0.1 to 90 mgKOH / g and a block (B) having an acid value of 100 mgKOH / g or more, and obtained by living polymerization Block resin that can be used.   The block resin according to claim 1, wherein a hydroxyl group-containing resin obtained by living polymerization of a monomer having a hydroxyl group is modified with a compound (c) capable of causing an acid group to react with the hydroxyl group.   The block resin according to claim 1 or 2, wherein the living polymerization is atom transfer radical polymerization.   The block resin according to any one of claims 1 to 3, wherein the block resin has a number average molecular weight of 1,000 to 50,000.   The block according to any one of claims 1 to 4, wherein the mass ratio of the block (A) and the block (B) is (A) 60 to 99.9 wt% and (B) 0.1 to 40 wt%. resin.   The block resin according to any one of claims 2 to 5, wherein the compound (c) is a cyclic polycarboxylic acid anhydride.   Furthermore, the block of any one of Claims 2-6 using the compound (d) which can react with a hydroxyl group and has a curable unsaturated double bond with the said compound (c). resin.   Furthermore, it reacts with the acid group or hydroxyl group which block resin has, and is made to react with the compound (e) which has a curable unsaturated double bond, The block of any one of Claims 2-7 characterized by the above-mentioned. resin.   The pigment dispersion formed by disperse | distributing the block resin of any one of Claims 1-8, a pigment, and acidic resin other than a pigment derivative and / or a block resin as needed in an organic solvent or water.   The pigment dispersion according to claim 9, wherein the pigment derivative has a basic group.   By reacting with a hydroxyl group on a block resin having a block (A ′) of 70 wt% or less having a hydroxyl group and a block (B ′) of 80 wt% or more having a hydroxyl group, obtained by living polymerization, A method for producing a block resin, comprising reacting a compound (c) capable of causing an acid group to exist.   Furthermore, the compound (d) capable of reacting with a hydroxyl group and having a curable unsaturated double bond and / or the compound (e) capable of reacting with an acid group or a hydroxyl group and having a curable unsaturated double bond are reacted. The method for producing a block resin according to claim 11, wherein: The method for producing a block resin according to claim 11 or 12, wherein the living polymerization is atom transfer radical polymerization.