Dispersant composition, dispersion, photosensitive composition, and molding

Abstract

To provide a dispersion excellent in compatibility and dispersibility.SOLUTION: A dispersant composition contains a first dispersant and a second dispersant. The first dispersant contains a cyclic ester polymer moiety and an amine moiety. The second dispersant contains a vinyl polymer moiety and an amine moiety. The mass ratio of the first dispersant X to the second dispersant Y is preferably X / Y=0.3-3.0. The amine moieties of the first dispersant and the second dispersant preferably have a heterocyclic amino group having aromaticity.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a dispersant composition capable of dispersing various materials.

Background Art

[0002] Ink applications such as printing inks and inkjet inks use resin-based dispersants to finely disperse pigments in order to enhance color development. For example, as the resin-based dispersant, a basic dispersant containing a polycaprolactone chain as disclosed in Patent Document 1 is disclosed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the polycaprolactone chain of the conventional dispersant has high crystallinity. When such a dispersant is used in the production of inks or paints, the dispersant may crystallize in the ink and impair the appearance of the coating film. In addition, the types of polyamines that can be used in the dispersant are limited, and the pigment adsorption power for various pigments is weak, and an improvement in dispersibility has been demanded. In addition, the polycaprolactone chain has low heat resistance and is insufficient in heat resistance for applications that require heat resistance such as color filters.

[0005] An object of the present invention is to provide a dispersion excellent in compatibility, dispersibility, and heat resistance.

Means for Solving the Problems

[0006] The dispersant composition of the present invention includes a first dispersant and a second dispersant. The first dispersant includes a cyclic ester polymer part and an amine part. The second dispersant contains a vinyl polymer moiety and an amine moiety.

Advantages of the Invention

[0007] According to the present invention, a dispersion excellent in compatibility, dispersibility, and heat resistance can be provided.

Embodiments for Carrying Out the Invention

[0008] The terms in this specification are defined. When expressed as “(meth)acryloyl”, “(meth)acrylic”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide”, unless otherwise specified, they represent “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. Also, in this specification, “C.I.” means Color Index (C.I.). A vinyl monomer is a polymerizable unsaturated group-containing compound. The polymerizable unsaturated group is a vinyl group, a (meth)acryloyl group, or a (meth)allyl group. A monomer is a compound that forms a resin by polymerization. A monomer is in an unreacted state, and a monomer unit is a state in which the monomer forms a resin after polymerization.

[0009] The dispersant composition of the present invention contains a first dispersant and a second dispersant. The first dispersant contains a cyclic ester polymer moiety and an amine moiety. The second dispersant contains a vinyl polymer moiety and an amine moiety.

[0010] In the dispersant composition of the present invention, the first dispersant includes a cyclic ester polymer moiety and an amine moiety, and the steric repulsion moiety derived from the cyclic ester polymer has a relatively narrow molecular weight distribution compared to the vinyl polymer. Therefore, since the variation in the molecular weight of the steric repulsion moiety contributing to the dispersion stability can be suppressed, the first dispersant contributes to the dispersion stability of the object to be dispersed. Further, the second dispersant includes a vinyl polymer moiety capable of controlling the affinity for the resin type and the dispersion solvent by the selection of vinyl monomer units. Thereby, the second dispersant acts as a compatibilizer for the first dispersant, the object to be dispersed, etc., and the compatibility within the dispersant composition is improved. Therefore, the dispersion stability of the composition is improved and the viscosity can be suppressed. Further, since the first dispersant and the second dispersant have an amine moiety, they serve as strong adsorption groups for the object to be dispersed. As a result, regardless of whether they are organic particles or inorganic particles, they can adsorb to a wide range of materials and be stably dispersed.

[0011] The dispersant composition of the present invention can be used, for example, for the dispersion of colorants such as pigments and dyes in applications such as inks, paints, molded articles, color filters, etc., and for the dispersion of various objects to be dispersed such as inorganic particles such as carbon nanotubes and metal particles and organic particles such as cellulose nanofibers.

[0012] <First dispersant> The first dispersant includes a cyclic ester polymer moiety and an amine moiety. Note that the cyclic ester polymer moiety refers to a mode in which it constitutes a part of the dispersant. The cyclic ester polymer refers to a mode before the dispersant is synthesized. The same applies to the vinyl polymer moiety. Note that the first dispersant only needs to include a cyclic ester polymer moiety and an amine moiety, and its synthesis method is not limited.

[0013] <Cyclic ester polymer moiety> The cyclic ester polymer that forms the first dispersant has a hydroxyl group at its terminal. The cyclic ester polymer can be synthesized into a cyclic ester polymer having a hydroxyl group at one end by ring-opening polymerization of a cyclic ester using an active hydrogen compound as an initiator. When the active hydrogen compound is used, the polymerization reaction of the cyclic ester is controlled, so that a cyclic ester polymer with a narrow molecular weight distribution can be obtained.

[0014] The cyclic ester polymer is preferably a polymer containing a polymer of lactone which is a cyclic ester (polylactone). Lactones include, for example, cyclic esters having 2 to 15 carbon atoms such as α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, ζ-enanthrolactone, η-caprylolactone (=8-hydroxyoctanoic acid lactone), 12-hydroxydodecanoic acid lactone, 13-hydroxytridecanoic acid lactone, 14-hydroxytetradecanoic acid lactone, 15-hydroxypentadecanoic acid lactone, etc. Among these, from the viewpoint of reaction control, δ-valerolactone and ε-caprolactone are preferred, and ε-caprolactone is more preferred. For the synthesis of the cyclic ester polymer, cyclic compounds other than lactone may be used.

[0015] Examples of the cyclic compound include lactide, trimethylene carbonate, glycolide, lactam, etc. The content of polylactone is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass in 100% by mass of the cyclic ester polymer.

[0016] The cyclic esters can be used alone or in combination of two or more.

[0017] <Synthesis of the cyclic ester polymer moiety> <Active hydrogen compound> The active hydrogen compound used for the synthesis of the cyclic ester polymer part is not limited as long as it can provide active hydrogen contributing to the polymerization of the cyclic ester to the polymerization site. In the present specification, the active hydrogen compound is preferably a compound having at least one functional group selected from a hydroxyl group, a carboxyl group, a phosphoric acid group, an amino group, and a thiol group. Among these, a compound having a hydroxyl group is preferable in terms of excellent reactivity, and a monoalcohol is more preferable from the viewpoint of reaction control.

[0018] Monoalcohols include, for example, aliphatic monoalcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, oleyl alcohol; aromatic ring-containing monoalcohols such as benzyl alcohol, phenoxyethyl alcohol, p-cumylphenoxyethyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether,Examples of the monoalcohol include alkylene glycol monoalkyl ethers such as triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetraethylene glycol monomethyl ether; and reactive alcohols such as 3-ethyl-3-oxetanemethanol and 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane. The monoalcohol can be used alone or in combination of two or more.

[0019] For ring-opening polymerization, it is preferable to use a monoalcohol having a molecular weight of 100 to 300. By setting the molecular weight to 300 or less, a cyclic ester polymer moiety having a sharp molecular weight distribution can be obtained, and the dispersibility of the dispersant is improved. Further, by setting the molecular weight to 100 or more, the ring-opening polymerization of the cyclic ester becomes easy at high temperature, and the reaction yield is improved.

[0020] The amount of the initiator used is preferably 0.1 to 100 moles, more preferably 0.5 to 100 moles, and even more preferably 1 to 100 moles per 100 moles of the raw material compound of the cyclic ester polymer. By appropriately adjusting the molar ratio of the cyclic ester to the initiator, the molecular weight of the cyclic ester polymer moiety can be adjusted.

[0021] For ring-opening polymerization, a polymerization catalyst can be used. When using a polymerization catalyst, the reaction temperature can be lowered and the reaction time can be shortened. Examples of the polymerization catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide; quaternary phosphonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide; phosphorus compounds such as triphenylphosphine; organotin compounds such as monomethyltin oxide, monobutyltin oxide, monooctyltin oxide, dibutyltin oxide, dioctyltin dilaurate; organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, sodium benzoate; alkali metal alcoholates such as sodium alcoholate, potassium alcoholate, and other tertiary amines, organoaluminum compounds, organotitanate compounds, and zinc compounds such as zinc chloride, etc.

[0022] The usage amount of the polymerization catalyst is preferably 0.1 ppm to 3000 ppm, more preferably 1 ppm to 1000 ppm, based on the raw material compound of the cyclic ester polymer. When used within the above range, it is easy to obtain a cyclic ester polymer with no coloring at a polymerization rate suitable for production.

[0023] The polymerization temperature of the cyclic ester is preferably 100°C to 220°C, more preferably 110°C to 210°C. When carried out within the above range, it is easy to obtain a cyclic ester polymer with few by-products at a polymerization rate suitable for production.

[0024] The weight-average molecular weight of the cyclic ester polymer is preferably from 500 to 10,000, more preferably from 1,000 to 8,000, and even more preferably from 1,000 to 5,000. When the molecular weight is 500 or more, the pigment dispersibility can be further improved due to the steric repulsion effect. When the molecular weight is 10,000 or less, appropriate crystallinity and solvent solubility can be obtained, resulting in further improved dispersibility.

[0025] In this specification, it is preferable that the cyclic ester polymer reacts with a diisocyanate after synthesis to produce an intermediate having an isocyanato group at the terminal.

[0026] <Diisocyanate> Diisocyanate is a compound having two isocyanato groups. Examples of diisocyanates include diisocyanates having an aromatic group, diisocyanates having an aliphatic group, diisocyanates having an aromatic group and an aliphatic group, diisocyanates having an alicyclic group, and the like.

[0027] Examples of diisocyanates having an aromatic group include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, naphthylene diisocyanate, or 1,3-bis(isocyanatomethyl)benzene, and the like.

[0028] Examples of diisocyanates having an aliphatic group include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, or 2,4,4-trimethylhexamethylene diisocyanate, and the like.

[0029] Diisocyanates having an aromatic group and an aliphatic group include, for example, ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, or 1,3-tetramethylxylylene diisocyanate, etc.

[0030] Diisocyanates having an alicyclic group include, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, or methyl-2,6-cyclohexane diisocyanate, etc.

[0031] The diisocyanate can be used alone or in combination of two or more.

[0032] In order to selectively react the hydroxyl group of the cyclic ester polymer with only one isocyanato group of the diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) having different reactivities of two isocyanato groups (having a primary isocyanato group and a secondary isocyanato group) is preferred.

[0033] When the total amount of the hydroxyl groups of the cyclic ester polymer is 1 mol, the amount of the diisocyanate used is preferably 0.5 to 1.5 mol, more preferably 0.6 to 1.2 mol, and even more preferably 0.7 to 1.0 mol. By reacting with an appropriate amount, gelation can be suppressed, and a first dispersant in which the cyclic ester polymer and the amine moiety described later are appropriately bonded can be obtained.

[0034] <amine moiety> The amine moiety acts as an adsorption site for the object to be dispersed. From the viewpoints of dispersibility and stability over time, the amine moiety preferably contains a tertiary amine. The amine moiety can be formed by reacting a compound containing an amine moiety with the isocyanato group of a cyclic ester polymer having an isocyanato group at the end of the piece. The compound containing the amine moiety is not particularly limited as long as it has a functional group capable of reacting with the isocyanato group, and from the viewpoint of reaction control, an amino group or a hydroxyl group is preferable. The compound containing the amine moiety is preferably a compound containing one tertiary amino group and one functional group capable of reacting with the isocyanato group each, an amine having one tertiary amino group and one primary amino group or secondary amino group (hereinafter referred to as a diamine compound) or an alcohol having one tertiary amino group and one primary hydroxyl group or secondary hydroxyl group (hereinafter referred to as an amino alcohol) is more preferable, and a diamine compound is even more preferable. By using these, the urea group or urethane bond generated in this reaction has hydrogen bonding properties, so that it becomes a pigment adsorption site together with the tertiary amino group site, and the pigment dispersibility is improved. Furthermore, the reaction control becomes easy. From the viewpoints of reaction control of the dispersant and affinity with the object to be dispersed, a dispersant containing a urea bond is more preferable.

[0035] The diamine compounds include, for example, amines having a heterocyclic amino group with aromaticity such as 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 2-aminoethylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 2-aminomethyl-5-methylpyridine, bis(2-pyridylmethyl)amine, 2-aminomethylpyrazine; amines having a heterocyclic amino group without aromaticity such as N-(3-aminopropyl)piperidine, 1-(3-aminopropyl)-2-methylpiperidine, N-(2-aminoethyl)-4-pipecoline, N-(3-aminopropyl)-4-pipecoline, 4-(aminomethyl)piperidine, 4-aminomethyl-1-butylpiperidine, 1-(2-aminoethyl)pyrrolidine, 2-aminomethylpiperazine; amines having an aliphatic amino group such as 2-(dimethylamino)ethylamine, 3-(dimethylamino)propylamine, 2-diethylaminoethylamine, 3-diethylaminopropylamine, 2-diisopropylaminoethylamine, 3-(dibutylamino)propylamine, N,N-diisopropyl-1,3-propanediamine, 3-(diisobutylamino)propylamine, 3-(2-dimethylaminoethoxy)propylamine, etc. The amino alcohols include, for example, alcohols containing a heterocyclic amino group with aromaticity such as 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, 2-pyridineethanol, 3-pyridineethanol, 4-pyridineethanol, 5-ethyl-2-pyridineethanol, 6-methylpyridine-2-ethanol; alcohols containing a heterocyclic amino group without aromaticity such as 1-methyl-2-piperidinemethanol, 1-methyl-3-piperidinemethanol, N-methyl-2-piperidineethanol; alcohols having an aliphatic amino group such as 3-(dimethylamino)-1-propanol, 3-(diethylamino)-1-propanol, 2-[benzyl(methyl)amino]ethanol, N,N-dibenzyl-2-aminoethanol, etc. Among these, amines having a heterocyclic amino group with aromaticity or alcohols having a heterocyclic amino group with aromaticity are particularly preferred in terms of improving the adsorbability to the pigment.

[0036] When the total amount of isocyanato groups to be reacted is 1 mol, the amount of diamine compound or amino alcohol used is preferably 0.2 to 1.0 mol, more preferably 0.3 to 1.0 mol, and even more preferably 0.4 to 1.0 mol. By reacting an appropriate amount, a dispersant having an amine site at the terminal can be obtained.

[0037] <Synthesis of the first dispersant> As described above, the first dispersant of the present invention only needs to have a cyclic ester polymer site and an amine site, and its synthesis method is not limited. The synthesis of the first dispersant includes, for example, (1a) a step of synthesizing a cyclic ester polymer having a hydroxyl group at one end, Next, (2a) a step of reacting a diisocyanate with the hydroxyl group of the polymer to synthesize a cyclic ester polymer having an isocyanato group at one end (the intermediate is synthesized), Next, it preferably has (3a) a step of reacting a compound containing an amine site with the isocyanato group of the polymer to synthesize the first dispersant.

[0038] During the synthesis of the step (2a), a known catalyst can be used. Examples of the catalyst include tertiary amine compounds or organometallic compounds.

[0039] Examples of tertiary amine compounds include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, or diazabicycloundecene (DBU).

[0040] Examples of organometallic compounds include tin-based compounds or non-tin-based compounds.

[0041] Tin-based compounds include, for example, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, or tin 2-ethylhexanoate, etc.

[0042] Non-tin-based compounds include, for example, titanium-based such as dibutyltitanium dichloride, tetrabutyl titanate, or butoxytitanium trichloride; lead-based such as lead oleate, lead 2-ethylhexanoate, lead benzoate, or lead naphthenate; iron-based such as iron 2-ethylhexanoate, or iron acetylacetonate; cobalt-based such as cobalt benzoate, or cobalt 2-ethylhexanoate; zinc-based such as zinc naphthenate, or zinc 2-ethylhexanoate; or zirconium-based such as zirconium naphthenate, etc.

[0043] Among the above catalysts, dibutyltin dilaurate (DBTDL), or tin 2-ethylhexanoate, etc. are preferable in terms of reactivity and hygiene.

[0044] The catalyst can be used alone or in combination of two or more.

[0045] The reaction temperature of the step (2a) is preferably 120 °C or lower, more preferably 50 - 110 °C. When reacting at an appropriate temperature, it is easier to control the reaction rate. The reaction is preferably carried out at 50 - 110 °C for 1 - 20 hours in the presence of a catalyst.

[0046] The reaction temperature of the step (3a) is preferably 100 °C or lower, more preferably 50 - 90 °C. When reacting at an appropriate temperature, it is easier to control the reaction rate. The reaction between the compound containing an amine moiety and the isocyanato group of the polymer is preferably carried out at 50 - 90 °C for about 1 - 5 hours in the presence of a catalyst.

[0047] The end point of the reaction is determined by measuring the isocyanate % by titration or by the disappearance of the isocyanate peak by IR measurement.

[0048] <Second dispersant> The second dispersant of the present invention contains a vinyl polymer moiety and an amine moiety.

[0049] <Vinyl polymer moiety> The vinyl polymer moiety forming the second dispersant has a hydroxyl group at its terminal site that can react with a diisocyanate. A vinyl polymer having a hydroxyl group at one end can be synthesized by polymerizing a vinyl monomer in the presence of a thiol group-containing alcohol.

[0050] The vinyl polymer preferably contains a thermally crosslinkable group-containing monomer unit. Examples of the thermally crosslinkable group-containing monomer include monomers having a tert-butyl group, monomers having an oxetane group, monomers having a blocked isocyanato group, and the like.

[0051] Examples of the monomer having a tert-butyl group include tert-butyl methacrylate, tert-butyl acrylate, and the like. Examples of the monomer having an oxetane group include 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, and the like. Examples of the monomer having a blocked isocyanato group include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, and the like. The dispersant has improved heat resistance by having these thermally crosslinkable groups.

[0052] The content of the thermally crosslinkable group-containing monomer unit is preferably 5 to 90% by weight, more preferably 10 to 60% by weight, based on the total monomer units of the vinyl polymer. When used in an appropriate amount, a crosslinking effect can be obtained without impairing the polymerization stability.

[0053] Vinyl monomers other than monomers having a thermosetting group include, for example, linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, or isostearyl (meth)acrylate, methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, or methoxypolyethylene glycol polypropylene glycol (meth)acrylate; Cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, or isobornyl (meth)acrylate; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate; (Meth)acryloxy-modified polydimethylsiloxane (silicone macromer); (Meth)acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth)acrylate or glycidyl (meth)acrylate; (Meth)acrylates having an aromatic ring such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, or nonylphenoxypolyethylene glycol (meth)acrylate; (Meth)acrylates having a carboxyl group such as (meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate; (Meth)acrylates having a carboxyl group such as (meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate; Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; N-substituted (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate; Nitriles such as (meth)acrylonitrile;

[0054] (Meth)acrylates having a blocked isocyanate group such as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate or 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate; The thiol group-containing alcohol is preferably a compound having one or more hydroxyl groups and thiol groups in the molecule, and more preferably a compound having two hydroxyl groups and one thiol group in the molecule. Thereby, the vinyl polymer can form a second polymer moiety having an isocyanato group at the terminal by reaction with diisocyanate.

[0055] Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol. Examples of the compound having one hydroxyl group and one thiol group in the molecule include mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol, 2-mercapto-3-butanol. Among these, a compound having two hydroxyl groups and one thiol group in the molecule is preferable, and 3-mercapto-1,2-propanediol is more preferable from the viewpoints of polymerization control and odor.

[0056] The amount of the thiol group-containing alcohol used is preferably 1 to 10 parts by mass, more preferably 1.5 to 9 parts by mass, and still more preferably 2 to 8 parts by mass with respect to 100 parts by mass of all the monomers. When an appropriate amount is used, a vinyl polymer having an appropriate molecular weight that functions as a steric repulsion site of the dispersant is easily obtained, and the viscosity stability is improved.

[0057] The polymerization temperature is preferably 40 to 150°C, and more preferably 50 to 110°C. Polymerization at an appropriate temperature facilitates the control of the polymerization reaction and the adjustment of the molecular weight.

[0058] For the polymerization of vinyl monomers, a polymerization initiator is used. The amount of the polymerization initiator used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of all the monomers. Examples of the polymerization initiator include azo compounds and organic peroxides.

[0059] Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0060] Examples of the organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxy pivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide.

[0061] The polymerization initiator can be used alone or in combination of two or more.

[0062] The weight average molecular weight of the vinyl polymer is preferably 1,000 to 20,000. Being in this range reduces the heat-melting viscosity of the dispersant, improves productivity without impairing heat resistance, and also improves pigment dispersibility.

[0063] For the diisocyanate and amine compound used in the second dispersant, the compounds exemplified for the first dispersant can be used. Also, the amounts used and reaction conditions are preferably the same conditions.

[0064] <Synthesis of the Second Dispersant> As described above, the second dispersant of the present invention only needs to contain a vinyl polymer and an amine moiety, and its synthesis method is not limited. The synthesis of the second dispersant includes, for example, (1b) a step of synthesizing a vinyl polymer having a hydroxyl group at one end, and then (2b) reacting a diisocyanate with the hydroxyl group of the polymer to synthesize a cyclic ester polymer having an isocyanato group at one end. Subsequently, it preferably has (3b) a step of reacting an amine with the isocyanato group of the polymer to synthesize the second dispersant. The steps (2b) and (3b) above can be synthesized under the same conditions as the first dispersant.

[0065] In this specification, the first dispersant and the second dispersant can be manufactured in the same step (hereinafter referred to as the simultaneous synthesis method). The steps are as follows: After reacting a thiol group-containing alcohol with a vinyl monomer in the presence of a cyclic ester polymer synthesized as described above to synthesize a vinyl polymer having a hydroxyl group at one end, (2) reacting a diisocyanate with the hydroxyl group of the polymer to synthesize a cyclic ester polymer having an isocyanato group at one end and a vinyl polymer having an isocyanato group at one end, and (3) reacting a compound containing an amine moiety with the isocyanato group of the polymer to simultaneously synthesize the first dispersant and the second dispersant. In the simultaneous synthesis method, since the cyclic ester polymer functions as a reaction solvent during the polymerization of the vinyl monomer, polymerization can be carried out without using an organic solvent. Therefore, the first dispersant and the second dispersant obtained by the simultaneous synthesis method can be used in applications that do not use an organic solvent during production, such as resin molded articles. Note that the above description does not exclude the use of an organic solvent in the simultaneous synthesis method. The synthesis of the vinyl polymer is as described above.

[0066] In this specification, the weight average molecular weight (Mw) of the first and second dispersants is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and even more preferably 1,500 to 20,000. The storage stability of the dispersion is further improved with an appropriate weight average molecular weight.

[0067] In this specification, the total amine value of the first dispersant and the second dispersant is preferably 1 to 100 mgKOH / g, more preferably 2 to 50 mgKOH / g, and even more preferably 10 to 30 mgKOH / g. With an appropriate amine value, it is easy to obtain proper dispersibility without excess or deficiency.

[0068] The mass ratio of the first dispersant X to the second dispersant Y is preferably X / Y = 0.3 to 3.0, more preferably 0.4 to 2.5, and even more preferably 0.5 to 2.0. When used in an appropriate mass ratio, the viscosity of the dispersion can be reduced, and the compatibility with materials other than the colorant (for example, polymerizable compounds, binder resins) is improved. Further, when the first dispersant and the second dispersant are synthesized by a simultaneous synthesis method, the balance between thermal meltability and crystallinity is improved, and the reaction control during polymerization becomes easy. Furthermore, the handling property of the dispersant at room temperature is improved.

[0069] The dispersion of the present invention includes a dispersant composition and a material to be dispersed.

[0070] <Material to be dispersed> The material to be dispersed is particles that can be dispersed by the dispersant composition. The particles include materials with a large aspect ratio such as carbon nanotubes and cellulose nanofibers. Examples of the material to be dispersed include colorants, extender pigments, metal particles, carbon nanotubes, cellulose nanofibers, and the like.

[0071] <Colorant> The colorant of the present invention includes pigments and dyes. Examples of the pigments include organic pigments and inorganic pigments. Organic pigments with high color development and high thermal decomposition resistance are preferred. Specific examples of the organic pigments are shown by Color Index numbers below.

[0072] Red pigments include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, etc. Among these, C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296 are preferred, and C.I. Pigment Red 177, 254, 291, 295, 296 are more preferred.

[0073] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, etc.

[0074] Examples of the cyan pigment include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and C.I. Pigment Blue 15:6 is more preferred.

[0075] Examples of the purple pigment include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, C.I. Pigment Violet 19, or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.

[0076] Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. Among these, C.I. Pigment Green 36, 58, 59, 62, 63 are preferred.

[0077] Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, etc. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233 are preferred.

[0078] Inorganic pigments include, for example, barium sulfate, zinc white, lead sulfate, lead yellow, zinc yellow, red iron oxide (III), cadmium red, ultramarine, dark ultramarine, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, titanium oxide, iron tetraoxide, and other metal oxide powders, metal sulfide powders, or metal powders.

[0079] Known compounds can be used as dyes.

[0080] Extenders include, for example, calcium carbonate, barite powder, magnesium silicate, aluminum silicate, diatomaceous earth, silica, and mica.

[0081] Metal particles include, for example, gold, silver, copper, iron, nickel, platinum, palladium, molybdenum, aluminum, antimony, tin, chromium, lanthanum, indium, gallium, and germanium.

[0082] Carbon nanotubes include, for example, single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes. Cellulose nanofibers include, for example, fibers having a number average minor axis diameter of 1 nm or more and 1000 nm or less and composed of cellulose or cellulose derivatives.

[0083] The content of the dispersant composition in the dispersion is preferably 0.01 to 100 parts by mass, more preferably 0.01 to 60 parts by mass, and still more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the material to be dispersed. When the appropriate content is contained, a good dispersion effect can be obtained and the viscosity of the dispersion can be suppressed.

[0084] The content of the material to be dispersed in the dispersion is preferably 5 to 70% by mass, more preferably 5 to 60% by mass in the non-volatile content of the dispersion.

[0085] The uses of the dispersion of the present invention are preferably, for example, uses using pigment dispersions such as color filters, offset inks, inkjet inks, resin molded articles (hereinafter referred to as molded articles), etc. In these uses, the material to be dispersed is preferably a colorant. Hereinafter, the color filter application will be described as an example.

[0086] The dispersion can be produced, for example, by performing a dispersion treatment using a material to be dispersed, a first dispersant, a second dispersant, a solvent, etc. When the colorant is an organic pigment, a dispersion aid such as a dye derivative can be used in combination during the dispersion treatment to disperse the organic pigment more finely. Also, when the pigment has high solubility in the solvent, the dispersion treatment may not be required. When two or more kinds of pigments are used in combination, dispersions can be prepared separately for each pigment and then mixed. Note that the timing of blending each material is arbitrary. Also, the dispersion treatment can be performed multiple times.

[0087] For the dispersion treatment, for example, a dispersion device such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor can be used.

[0088] After preparing the dispersion, it is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means such as centrifugation, sintered filters, and membrane filters.

[0089] <Other dispersants> In this specification, in addition to the first dispersant and the second dispersant, other dispersants can be used in combination. Examples of other dispersants include other resin-type dispersants and surfactants other than the dispersants of the present invention.

[0090] Examples of other resin-type dispersants include anionic resin-type dispersants such as styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, poly(meth)acrylate, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-(meth)acrylic acid alkyl ester copolymer, (meth)acrylic acid-polyvinyl-based macromer copolymer, phosphoric acid ester group-containing acrylic resin, aromatic carboxyl group-containing acrylic resin, polystyrene sulfonate, acrylamide-(meth)acrylic acid copolymer, carboxymethyl cellulose, polyurethane having a carboxyl group, formalin condensate of naphthalene sulfonate, or sodium alginate; Nonionic resin-type dispersants such as polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, or polymer starch; Examples of cationic resin-type dispersants include polyethyleneimine, aminoalkyl (meth)acrylate copolymer, polyvinylimidazoline, polyurethane having an amino group, reaction product of poly(lower alkyleneimine) and polyester having a free carboxyl group, or satokinsan.

[0091] Commercially available resin-based dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. manufactured by BYK Japan Co., Ltd.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. manufactured by Lubrizol Japan Co., Ltd.; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF Japan Co., Ltd.; and AJISPER PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Inc.

[0092] Surfactants include anionic surfactants such as polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, or polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, or polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; or alkyl betaines such as alkyl dimethylaminoacetic acid betaine, or amphoteric surfactants such as alkyl imidazoline. Other dispersants can be used alone or in admixture of two or more.

[0093] The amount of other dispersants used is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the material to be dispersed. Appropriate use of other dispersants can further improve dispersibility.

[0094] <Dye Derivative> Dye derivatives are compounds having acidic groups, basic groups, or neutral groups, etc. in organic dye residues. Use of dye derivatives can disperse organic pigments more finely. Dye derivatives include, for example, compounds having acidic substituents such as sulfo groups, carboxy groups, phosphate groups, and amine salts thereof, compounds having basic substituents such as sulfonamide groups and tertiary amino groups at the ends, and compounds having neutral substituents such as phenyl groups and phthalimidalkyl groups. Since the resin-type dispersant used in combination has acidic groups, dye derivatives having basic groups are preferred. Organic pigments include, for example, diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, polyazo, etc.

[0095] The amount of the pigment derivative used is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by mass of the material to be dispersed. When used in an appropriate amount, it can be refined without impairing the coloring degree.

[0096] When the dispersion of this specification is used for the application of a molded article, it can be prepared by melt-kneading with a thermoplastic resin, a dispersant composition, and the material to be dispersed. Examples of the thermoplastic resin include polyacrylic, polyolefin, polyester, polycarbonate, polyamide, etc. Examples of the polyolefin include polyethylene, polypropylene, etc. Examples of the polyester include polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc.

[0097] Examples of the melt-kneading include a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, etc. The melt-kneading temperature varies depending on the type of the thermoplastic resin, but is usually about 150 to 350 °C.

[0098] In the above application of the molded article, wax, antioxidant, light stabilizer, dispersant, etc. can be further contained as required.

[0099] The dispersion for the application of the molded article can be prepared as a masterbatch containing the material to be dispersed at a high concentration. In this case, the content of the material to be dispersed is preferably 0.1 to 50% by mass, more preferably 3 to 40% by mass, in the masterbatch. When used within the above range, the dispersibility and compatibility are further improved.

[0100] In this specification, the molded article can be produced by molding a dispersion and a thermoplastic resin. Examples of the molding method include extrusion molding, injection molding, blow molding, etc. Examples of extrusion molding include compression molding, pipe extrusion molding, laminate molding, T-die molding, inflation molding, melt spinning, etc.

[0101] When producing a molded article using a masterbatch, a diluent resin is used. The diluent resin is the resin that becomes the main component of the molded article. The diluent resin is preferably, for example, the above-mentioned thermoplastic resin.

[0102] The molding temperature depends on the softening point of the diluent resin and is usually 160 to 320°C.

[0103] The content of the dispersed substance in the molded article is preferably 0.01 to 10% by mass, more preferably 0.3 to 5% by mass, in 100% by mass of the molded article.

[0104] The molded article can be widely used in applications such as food packaging materials, pharmaceutical packaging materials, cosmetic packaging materials, display applications, materials for optical sensors, optical control materials, etc. Also, it can be widely used in applications such as automotive parts, household electrical appliances, building materials for houses, etc., and toiletries. Note that the molded article includes a mode of putting resin into a mold to form an article and a mode of molding without using a mold such as a plastic film.

[0105] <Photosensitive composition> The photosensitive composition of the present invention preferably contains the above-mentioned dispersion, binder resin, polymerizable compound, and photoinitiator. The photosensitive composition preferably further contains a solvent. Hereinafter, it will be described for color filter applications.

[0106] <Solvent> The photosensitive composition can contain a solvent. Solvents include, for example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether,Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, or dibasic acid ester, etc. may be mentioned. The solvent can be used alone or in combination of two or more kinds.

[0107] In addition to a dispersant, a colorant, and a solvent, the photosensitive composition can contain a binder resin, a polymerizable compound, a photopolymerization initiator, etc.

[0108] <Binder resin> The binder resin is preferably a resin having a transmittance of 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region when a film having a thickness of 2 μm is formed. Examples of the binder resin include a thermoplastic resin, an alkali-soluble resin, a photosensitive resin, etc.

[0109] The thermoplastic resin is a resin having no alkali solubility. For example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, natural rubber resin, cyclized rubber resin, celluloses, polyethylene, polybutadiene, or polyimide resin, etc. may be mentioned.

[0110] Examples of the alkali-soluble resin include acrylic resins having acidic functional groups, α-olefin / (anhydrous) maleic acid copolymers, styrene / (anhydrous) maleic acid copolymers, styrene / styrenesulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydrous) maleic acid copolymers. Among these, acrylic resins having acidic functional groups, α-olefin / (anhydrous) maleic acid copolymers, styrene / (anhydrous) maleic acid copolymers, and styrene / styrenesulfonic acid copolymers are preferred.

[0111] The photosensitive resin is a resin having a polymerizable unsaturated group and reacts with light such as ultraviolet light. The photosensitive resin is preferably a resin obtained by adding a polymerizable unsaturated group to the above alkali-soluble resin.

[0112] The weight average molecular weight of the binder resin is preferably from 1,000 to 500,000, more preferably from 5,000 to 100,000.

[0113] The content of the binder resin is preferably from 20 to 400 parts by mass, more preferably from 50 to 250 parts by mass, based on 100 parts by mass of the colorant. When contained in an appropriate amount, a film can be easily formed and good color characteristics are easily obtained.

[0114] <Polymerizable compound> The polymerizable compound is a monomer or oligomer having a polymerizable unsaturated group. The number of polymerizable unsaturated groups in the polymerizable compound is 1 or more, preferably 2 or more and 20 or less.

[0115] The coincidence compound is, for example, a linear or branched alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth), tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, or isostearyl (meth)acrylate; a cyclic alkyl (meth)acrylate such as cyclohexyl (meth)acrylate, tertiary butyl cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, or isobornyl (meth)acrylate; a fluoroalkyl (meth)acrylate such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate; (meth)acryloxy-modified polydimethylsiloxane (silicone macromer); a (meth)acrylate having a heterocyclic ring such as tetrahydrofurfuryl (meth)acrylate, or 3-methyl-3-oxetanyl (meth)acrylate; a (meth)acrylate having an aromatic ring such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, parachlorophenylphenoxyethyl (meth)acrylate, parachlorophenylphenoxypolyethylene glycol (meth)acrylate, or nonylphenoxypolyethylene glycol (meth)acrylate; (Poly)alkylene glycol monoalkyl ether (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, tripropylene glycol mono(meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, or polyethylene glycol monostearyl ether (meth)acrylate; (Meth)acrylates having a carboxyl group such as (meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate; (Meth)acrylates having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth)phthalate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, or glycerol (meth)acrylate; (Poly)alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol-propylene glycol) di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene glycol-tetramethylene glycol) di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, or 2-ethyl,2-butyl-propanediol di(meth)acrylate; Di(meth)acrylate such as dimethylol dicyclopentane di(meth)acrylate, neopentyl glycol di(meth)acrylate hydroxypivalate, pentaerythritol di(meth)acrylate stearate modified, bisphenol A di(meth)acrylate ethylene oxide modified, bisphenol A di(meth)acrylate propylene oxide modified, bisphenol A di(meth)acrylate tetramethylene oxide modified, bisphenol F di(meth)acrylate ethylene oxide modified, bisphenol F di(meth)acrylate propylene oxide modified, bisphenol F di(meth)acrylate tetramethylene oxide modified, zinc diacrylate, triacrylate phosphate ethylene oxide modified, or glycerol di(meth)acrylate; (Meth)acrylate having a tertiary amino group such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, or diethylaminopropyl (meth)acrylate; Polyfunctional (meth)acrylate having trifunctional or more such as glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate; Glycerol triglycidyl ether-(meth)acrylic acid adduct, glycerol diglycidyl ether-(meth)acrylic acid adduct, polyglycerol polyglycidyl ether-(meth)acrylic acid adduct, 1,6-butanediol diglycidyl ether, alkyl glycidyl ether-(meth)acrylic acid adduct, allyl glycidyl ether-(meth)acrylic acid adduct, phenyl glycidyl ether-(meth)acrylic acid adduct, styrene oxide-(meth)acrylic acid adduct, bisphenol A diglycidyl ether-(meth)acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether-(meth)acrylic acid adduct, bisphenol F diglycidyl ether-(meth)acrylic acid adduct, epichlorohydrin modified phthalic acid-(meth)acrylic acid adduct, epichlorohydrin modified hexahydrophthalic acid-(meth)acrylic acid adduct, ethylene glycol diglycidyl ether-(meth)acrylic acid adduct, polyethylene glycol diglycidyl ether-(meth)acrylic acid adduct, propylene glycol diglycidyl ether-(meth)acrylic acid adduct, polypropylene glycol diglycidyl ether-(meth)acrylic acid adduct, phenol novolac type epoxy resin-(meth)acrylic acid adduct, cresol novolac type epoxy resin-(meth)acrylic acid adduct, or other epoxy resin-(meth)acrylic acid adducts such as epoxy (meth)acrylate; (Meth)acryloyl modified isocyanurate, (meth)acryloyl modified polyurethane, (meth)acryloyl modified polyester, (meth)acryloyl modified melamine, (meth)acryloyl modified silicone, (meth)acryloyl modified polybutadiene, or (meth)acryloyl modified rosin and other (meth)acryloyl modified resin oligomers; Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether; Amides such as (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, or N-vinylformamide; or acrylonitrile, etc. may be mentioned.

[0116] The polymerizable compound can be used alone or in admixture of two or more.

[0117] The content of the polymerizable compound is preferably 1 to 60% by mass, more preferably 2 to 50% by mass in the non-volatile content of the photosensitive composition. When blended in an appropriate amount, the photocurability and developability are further improved.

[0118] <Photopolymerization initiator> Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2 - Octanedione, 1 - [4 - (phenylthio)phenyl] -, 2 - (O - benzoyloxime), ethanol, 1 - [9 - ethyl - 6 - (2 - methylbenzoyl) - 9H - carbazol - 3 - yl] -, 1 - (O - acetyloxime) and other oxime ester compounds; Acylphosphine compounds such as bis(2,4,6 - trimethylbenzoyl)phenylphosphine oxide and diphenyl - 2,4,6 - trimethylbenzoylphosphine oxide; Quinone compounds such as 9,10 - phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds, etc. Among these, oxime ester compounds are preferred in terms of sensitivity.

[0119] In commercially available products, as acetophenone compounds, Omnirad907, 369E, 379EG, 127, 184, 1173, 2959 manufactured by IGM Resins; as acylphosphine compounds, Omnirad819, TPO manufactured by IGM Resins; as oxime compounds, IRGACURE OXE - 01, 02, 03, 04, 05 manufactured by BASF Japan, Adeka Arcles N - 1919, NCI - 730, 831E, 930 manufactured by ADEKA, TRONLY TR - PBG - 301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Qiangli New Materials, Omnirad1312, 1314, 1316 manufactured by IGM Resins, SPI - 02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI - 020, 306, EOX - 01 manufactured by Daito Chemicals, etc. can be mentioned.

[0120] The photoinitiator can be used alone or in a mixture of two or more.

[0121] The content of the photoinitiator is preferably 0.5 - 20% by mass, more preferably 1 - 15% by mass in the non - volatile matter of the photosensitive composition.

[0122] The photosensitive composition of the present invention can use a sensitizer in combination with a photoinitiator. Thereby, the photoreactivity is improved. Examples of the sensitizer include α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, or 4,4'-diethylaminobenzophenone.

[0123] The content of the sensitizer is preferably 0.1 to 60 parts by mass with respect to 100 parts by mass of the photoinitiator.

[0124] The photosensitive composition of the present invention can be prepared, for example, by stirring and mixing a dispersion, a binder resin, a polymerizable compound, a photoinitiator, and a solvent. In addition, a dispersion treatment can be performed as necessary. The photosensitive composition of the present invention can further appropriately select and use an antioxidant, an ultraviolet absorber, a storage stabilizer, a leveling agent, a polymerization inhibitor, etc. as additives.

[0125] <Color filter> Hereinafter, the case where the photosensitive composition is used for color filter applications will be described. The color filter preferably has a filter segment formed from the above photosensitive composition on a substrate (also referred to as a substrate). The color filter preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant to be used. In addition, the color filter can have a magenta filter segment, a cyan filter segment, and a yellow filter segment instead of or in addition to the color filter segment. Note that a transparent substrate or a reflective substrate can be used as the substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0126] It is preferable to first form a black matrix on a substrate and then form filter segments. Note that a thin-film transistor (TFT) can be formed in advance on the substrate and then the black matrix can be formed. Examples of the black matrix include inorganic films such as chromium, multilayer films of chromium / chromium oxide, titanium nitride, and resin films in which a light-shielding agent is dispersed.

[0127] The formation of the filter segments can be carried out, for example, by printing, electrodeposition, transfer, photolithography, inkjet, etc. In this specification, the most preferable photolithography method and inkjet method will be described.

[0128] Examples of the substrate include a glass plate with a high transmittance for visible light, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate.

[0129] In the photolithography method, for example, a coloring composition having a coloring agent of a certain color tone is applied onto a transparent substrate so that the dry film thickness becomes about 0.2 to 5 μm to form a film. The obtained film (hereinafter referred to as the first film) is exposed (light irradiated) through a mask having a predetermined pattern. Next, development is carried out by immersing it in a solvent or an alkaline developer or spraying the developer such as by spraying to remove the uncured portion to obtain a desired pattern. By performing this process in the same manner using a photosensitive coloring composition having a coloring agent of another color tone, a color filter having filter segments of each color can be manufactured. Further, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, since the first film is not in contact with oxygen, the exposure sensitivity is further improved. Also, the color filter can be heated (post-baked) to cure the uncured polymerizable compound in the filter segment.

[0130] Coating devices include, for example, spray coating, spin coating, slit coating, roll coating, etc. During coating, a drying process can be performed. Drying devices include, for example, hot air ovens, infrared heaters, etc.

[0131] As the developer, as an alkaline developer, for example, inorganic alkalis such as sodium carbonate and sodium hydroxide; organic alkalis such as dimethylbenzylamine and triethanolamine can be mentioned. Also, an antifoaming agent and a surfactant can be added to the developer.

[0132] The post-bake temperature is preferably about 80 to 230 °C. In recent years, in order to address environmental issues, low-temperature curing at 150 °C or lower is more preferable. The post-bake time for low-temperature curing is about 30 minutes to 1 hour.

[0133] In the inkjet method, a coloring composition having a coloring agent of a certain color tone is printed on a transparent substrate using an inkjet head to form a film. Since the formation of filter segments by the inkjet method can be patterned by printing, as a manufacturing method of color filters, it is low-cost and excellent in mass productivity. Note that the photosensitive composition used in an inkjet printing apparatus is also called inkjet ink. The printing methods by the inkjet method include a one-pass printing method and a multi-pass printing method. The one-pass printing method is a method in which a plurality of inkjet heads are fixedly arranged in a predetermined printing area and printed in one head scan. In contrast, the multi-pass printing method (also called a serial printing method) is a method in which a predetermined printing area is printed by a plurality of head scans.

[0134] As the inkjet head used in the inkjet method, either an on-demand type or a continuous type may be used. Also, as the ejection method, an electro-mechanical conversion method (for example, single cavity type, double cavity type, vendor type, piston type, (such as the shared mode type, shared wall type, etc.), electro-thermal conversion methods (for example, thermal inkjet type, bubble jet (registered trademark) type, etc.), electrostatic attraction methods (for example, electric field control type, slit jet type, etc.), discharge methods (for example, spark jet type, etc.), etc. can be cited as specific examples, but any ejection method may be used.

[0135] The volume of the ink droplets ejected from the inkjet head is preferably in the range of 0.5 to 100 pL. From the viewpoint of less coating unevenness and enabling high printing speed, it is more preferably in the range of 2 to 20 pL.

[0136] The photosensitive composition in this specification can be used for forming a color filter by a method of forming a pattern by a photolithography method. For the photosensitive composition for color filters by the photolithography method, it is preferable to use an alkali-soluble resin having an alkali-developable acid value. As the photoinitiator, it is preferable to use the following highly sensitive oxime ester compounds. Commercially available products include, for example, "NCI-831" manufactured by ADEKA of carbazole-based compounds, "OXE-04" manufactured by BASF of diphenyl sulfide-based compounds, "SPI-02" manufactured by Samyang of fluorene-based compounds, etc.

[0137] An image display device can be manufactured using the color filter obtained from the dispersion of the present invention. For the manufacture of an image display device, it is bonded to a counter substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing part, and then the injection port is sealed. If necessary, a polarizing film or a retardation film is bonded to the outside of the substrate, and a liquid crystal display device, which is a kind of image display device, can be obtained. This liquid crystal display device can be used in a liquid crystal display mode for colorization using color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optically compensated bend (OCB), etc.

[0138] In addition to the liquid crystal display device, the above image display device can be used for applications such as organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays. It can also be used for optical sensors (e.g., infrared sensors, etc.) and solid-state imaging devices, etc.

Examples

[0139] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the examples. In the examples, "parts" represents "parts by weight" and "%" represents "% by weight".

[0140] The weight-average molecular weight (Mw) of the dispersant was measured by GPC (HLC-8320GPC, manufactured by Tosoh Corporation) equipped with an RI detector using "TSK-GEL SUPER AW-4000", "AW-3000", and "AW-2500" (manufactured by Tosoh Corporation) for the column, and a polystyrene-equivalent mass-average molecular weight (Mw) measured using a solution of 30 mM triethylamine and 10 mM LiBr in N,N-dimethylformamide as the eluent. The mobile phase flow rate was 0.6 mL / min, the sample injection volume was 10 μL, the sample concentration was approximately 0.1% by mass, and the measurement temperature was 40°C.

[0141] The amine value (mgKOH / g) was determined by potentiometric titration using a 0.1N hydrochloric acid ethanol solution and then converted to the equivalent of potassium hydroxide.

[0142] (Example 1) [Synthesis of Dispersant 1] Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 9.8 parts of dodecanol, 90.2 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged and replaced with nitrogen gas. The reaction was carried out at 120 °C for 3 hours with stirring to synthesize a cyclic ester polymer. The internal temperature was cooled to 40 °C, and 2.8 parts of thioglycerol, 97.2 parts of butyl methacrylate, and 0.1 part of 2,2'-azobis(isobutyric acid) dimethyl (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., trade name: V-601) as a polymerization initiator were charged and reacted at 80 °C for 7 hours to synthesize a vinyl polymer. 23.4 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate as a catalyst were charged here and replaced with nitrogen gas. The reaction was carried out at 80 °C for 2 hours to obtain a polymer containing a poly(lactone) having an isocyanato group at one end and a vinyl polymer having an isocyanato group at one end. Next, 11.1 parts of 3-aminomethylpyridine was charged into the reaction vessel and reacted at 80 °C for 1 hour to obtain a mixture of a first dispersant with a non-volatile content of 100% and a second dispersant. The weight average molecular weight of these dispersants 1 was 8,600, and the amine value was 35.0 mgKOH / g.

[0143] (Examples 2 to 23) [Synthesis of Dispersants 2 to 23] Synthesis was carried out in the same manner as in Example 1 except that the raw materials in Example 1 were changed to the raw materials and amounts used described in Table 1 to obtain dispersants 2 to 23 with a non-volatile content of 100%.

[0144] (Synthesis Example 1) [Synthesis of Dispersant 24] Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 9.8 parts of dodecanol, 90.2 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged and replaced with nitrogen gas. The reaction was carried out at 120 °C for 3 hours with stirring to synthesize a cyclic ester polymer. The internal temperature was cooled to 40 °C, and 11.7 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate as a catalyst were charged here and replaced with nitrogen gas. The reaction was carried out at 80 °C for 2 hours to obtain a polymer containing a poly(lactone) having an isocyanato group at one end. Next, 5.6 parts of 3-aminomethylpyridine was charged into the reaction vessel and reacted at 80°C for 1 hour to obtain a dispersant 24 with a non-volatile content of 100%. The weight-average molecular weight of the dispersant 24 was 5,700, and the amine value was 25.0 mgKOH / g.

[0145] (Synthesis Example 2) [Synthesis of Dispersant 25] Into a reaction flask equipped with a thermometer, a stirrer, a nitrogen inlet, and a reflux tube, 100 parts of methyl ethyl ketone as a solvent, 2.8 parts of thioglycerol, 97.2 parts of butyl methacrylate, and 0.1 part of 2,2'-azobisisobutyronitrile dimethyl (manufactured by Fuji Film Wako Pure Chemical Industries, trade name: V-601) as a polymerization initiator were charged and reacted at 80°C for 7 hours to synthesize a vinyl polymer. Here, 11.7 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate as a catalyst were charged and replaced with nitrogen gas. The reaction was carried out at 80°C for 2 hours to obtain a vinyl polymer having an isocyanato group at one end. Next, 5.6 parts of 3-aminomethylpyridine was charged into the reaction vessel and reacted at 80°C for 1 hour. Then, methyl ethyl ketone was removed by heating under reduced pressure to obtain a dispersant 25 with a non-volatile content of 100%. The weight-average molecular weight of the dispersant 25 was 5,600, and the amine value was 24.9 mgKOH / g.

[0146] [Table 1]

[0147] [Table 2]

[0148] [Table 3]

[0149] The abbreviations in the table are as follows. DA: Dodecanol BzA: Benzyl alcohol DGME: Diethylene Glycol Monoethyl Ether Cp: ε-Caprolactone Va: δ-Valerolactone M-LA: meso-Lactide BMA: Butyl Methacrylate t-BA: tert-Butyl Acrylate MMA: Methyl Methacrylate 2-MTA: Methoxyethyl Acrylate OXMA: (3-Ethyl-3-oxetanyl)methyl methacrylate 1-TG: Thioglycerol IPDI: Isophorone Diisocyanate Amine 1: 3-Aminomethylpyridine Amine 2: 2-Aminomethylpyridine Amine 3: 4-Aminomethylpyridine Amine 4: Bis-2-picolylamine Amine 5: 2-(Dimethylamino)ethylamine Amine 6: 4-(Aminomethyl)piperidine Amine 7: 4-Pyridinemethanol Amine 8: 3-Pyridinemethanol Amine 9: 3-(Dimethylamino)-1-propanol Amine 10: 1-Methyl-3-piperidinemethanol

[0150] (Solvent-Free Synthesis) It indicates whether the obtained dispersant can be synthesized without a solvent. In the table, the dispersants that could be synthesized without a solvent are marked with 〇. Specifically, it was determined based on whether the synthesis could be controlled without the viscosity increasing during polymerization to the point where stirring became impossible or without being able to control the heat generation.

[0151] <Method for Producing Pigment Dispersion> (Example 24) Preparation of Pigment Dispersion P1-1 After uniformly stirring and mixing a mixture having the following composition with a high-speed mixer or the like, the obtained mill base was subjected to dispersion treatment with a horizontal sand mill for about 1 hour to prepare a pigment dispersion P1-1. 13.5 parts of C.I. Pigment Yellow 139 (PY139) 1.5 parts of pigment derivative (B1) 7.5 parts of dispersant 1 47.5 parts of dipropylene glycol diacrylate (DPGDA)

[0152] Pigment derivative (B1) [Chemical formula]

[0153] (Examples 25 to 50 and Comparative Examples 3 and 4) >[Preparation of Pigment Dispersions P2-1 to P27-1 and Comparative Pigment Dispersions Y1-1 and Y2-1] Pigment dispersions P2-1 to P27-1 and comparative pigment dispersions Y1-1 and Y2-1 were prepared in the same manner as pigment dispersion P1-1, except that the formulation of pigment dispersion P1-1 was changed to the formulation shown in Table 4.

[0154] [Table 4]

[0155] >[Method for Producing Photosensitive Composition] (Example 51) [Preparation of Photosensitive Composition P1-2] To the previously prepared pigment dispersion, a mixed solution of a polymerizable compound, a photoinitiator, and a stabilizer was slowly added so as to have the formulation described below, and the obtained mixed solution was stirred. Then, a leveling agent was added to the above mixed solution, and the mixture was shaken with a shaker for 6 hours to prepare a photosensitive composition (P1-2). The obtained photosensitive composition (P1-2) was filtered through a PTFE filter with a pore size of 0.5 μm to remove dust and coarse particles, and used as an evaluation ink. In addition, the addition and mixing of the raw materials for obtaining the above mixed solution may be in any order. Pigment Dispersion P1-1 15.0 parts VEEA 20.0 parts DPGDA 52.9 parts BHT 1.0 part PTA 1.0 part BYK-UV3510 0.1 part OMNIRAD TPO-L 2.5 parts Omnirad369 2.5 parts Omnirad819 2.5 parts KAYACURE BMS 2.5 parts

[0156] (Examples 52 to 77, Comparative Examples 5 to 6) Instead of the pigment dispersion P1-1 used in Example 51, the pigment dispersions shown in Table 5 were used, and the photosensitive composition was prepared in the same manner as in Example 51 except for this.

[0157]

Table 5

[0158] The abbreviations are as follows. <Polymerizable Compound> VEEA: 2-(2-Vinyloxyethoxy)ethyl acrylate DPGDA: Dipropylene glycol diacrylate <Stabilizer> BHT: 2,6-Di-t-butyl-4-methylphenol PTA: Phenothiazine <Leveling Agent> BYK-UV3510: Polyether-modified polydimethylsiloxane manufactured by BYK Chemie <Photoinitiator> OMNIRAD TPO-L: Ethyl(2,4,6-trimethylbenzoyl)-phenyl-phosphinate manufactured by IGM Resins Omnirad369: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 manufactured by IGM Resins Omnirad819: Manufactured by IGM Resins, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide KAYACURE BMS: 4-benzoyl-4'-methyl-diphenyl sulfide manufactured by Nippon Kayaku Co., Ltd.

[0159] <Evaluation method of photosensitive composition> A color filter was formed by inkjet printing the photosensitive composition of the present invention, and evaluation was carried out. Specifically, the evaluation inks prepared in each example and each comparative example were printed using a single-pass inkjet printer (One Pass Jet manufactured by Trytec Co., Ltd.) having an inkjet ejection mechanism equipped with a head (KJ4A) manufactured by Kyocera, a mechanism for transporting the substrate on which the ink landed at a desired speed, and a mechanism for subsequently irradiating with a UV lamp, under printing conditions of an ink droplet volume of 14 pl and 600×600 dpi, and various characteristics were evaluated. A UV lamp manufactured by GEW (240W) was used, and a sample of the cured film was prepared under the condition of an integrated light amount of 200 mJ / cm 2 The printing speed and the printed image were changed in each performance evaluation.

[0160] <Storage stability> The viscosities of the obtained pigment dispersion and the photosensitive composition were measured and used as the initial viscosities. Further, an accelerated aging test was carried out at 60°C for 2 weeks, and the accelerated aging viscosities of the pigment dispersion and the photosensitive composition were measured respectively. As the change rate due to accelerated aging, the accelerated aging viscosity / initial viscosity was calculated and evaluated according to the following criteria. ◎: Change rate less than 5% (excellent) ○: Change rate 5% or more and less than 10% (good) △: Change rate 10% or more and less than 20% (practically acceptable) ×: Change rate 20% or more (not practically acceptable)

[0161] <Particle size change rate> The obtained photosensitive composition was diluted 200 to 1000 times with methyl ethyl ketone, and the volume-based D50% average particle diameter (D1) was measured using a Microtrac UPA150 (manufactured by Nikkiso Co., Ltd., wet particle size distribution analyzer). Next, 100 ml of each photosensitive composition was placed in a sample bottle and sealed so that evaporation did not occur, and after being stored in a constant temperature bath at 60 °C for one week, in the same manner as the above method, the volume-based D50% average particle diameter (D2) after storage was measured, the change rate of the average particle diameter was determined according to the following formula, and the particle diameter change rate was evaluated according to the following evaluation criteria. Particle diameter change rate = {(D2 - D1) / D1} × 100%) ◎: The particle diameter change rate is less than 5% (excellent) ○: The particle diameter change rate is 5% or more and less than 10% (good) △: The particle diameter change rate is 10% or more and less than 30% (practically acceptable) ×: The particle diameter change rate is 30% or more (practically unacceptable)

[0162] <Spit stability> The obtained photosensitive composition was printed with a nozzle check pattern using the aforementioned inkjet printer (One Pass Jet manufactured by Trytec Co., Ltd.). After printing 100,000 shots, the nozzle check pattern was printed again, and the ejection performance was evaluated based on the number of nozzles with missing ejections. The evaluation criteria are as follows. The conveyor speed was set to 35 m / min. ○: No nozzles missing after printing 100,000 shots (good) △: 1 to 5 nozzles missing after printing 100,000 shots (practically acceptable) ×: 6 or more nozzles missing after printing 100,000 shots (practically unacceptable)

[0163] <Agglomeration foreign matter> The obtained photosensitive composition was printed on a 1.1-mm-thick glass substrate using the aforementioned inkjet printer, and irradiated in the same manner as above using a UV lamp manufactured by GEW to obtain a sample of the cured film. The conveyor speed was set at 35 m / min. Thereafter, the surface of the obtained sample was observed. For the evaluation, a metallurgical microscope "BX60" manufactured by Olympus Corporation was used. The magnification was 500 times, and the number of observable particles in any 5 fields of view under transmission conditions was counted as agglomerated foreign matter and evaluated. ⊙: The number of foreign matters is less than 10 (excellent). ○: The number of foreign matters is 10 or more and less than 20 (good). △: The number of foreign matters is 20 or more and less than 60 (practically acceptable). ×: The number of foreign matters is 60 or more (practically unacceptable).

[0164] <Heat resistance> The obtained photosensitive composition was printed on a 1.1-mm-thick glass substrate using the aforementioned inkjet printer, and irradiated in the same manner as above using a UV lamp manufactured by GEW to obtain a sample of the cured film. The conveyor speed was set at 35 m / min. Thereafter, the thickness of the obtained sample coating film with a thickness of 6 μm was measured using a contact-type film thickness measuring instrument. Next, the sample coating film was heated at 250 °C for 60 minutes, and then the film thickness was measured. The reduction rate of the film thickness before and after heating was calculated and evaluated. ⊙: The film thickness reduction rate is less than 3% (excellent). ○: The film thickness reduction rate is 3% or more and less than 5% (good). △: The film thickness reduction rate is 5% or more and less than 10% (practically acceptable). ×: The film thickness reduction rate is 10% or more (practically unacceptable).

[0165] <Manufacture of molded body> The materials used for the molded body are listed below. [Polyolefin resin] Novatec PP BC4ASW (manufactured by Nippon Polypropylene Corporation, MFR: 5 g / 10 min, polypropylene) [Inorganic pigment] Ultramarine (manufactured by Daiichi Kasei Kogyo Co., Ltd., average particle diameter 0.8 μm, Ultramarine No. 2000)

[0166] [Melt viscosity of polyolefin resin] MFR was measured in accordance with JIS (Japanese Industrial Standards) K-7210.

[0167] [Average particle diameter of inorganic pigment] The average particle diameter was measured as the volume average diameter using "UPA-EX150" manufactured by Nikkiso Co., Ltd.

[0168] [Example 78] (Molded body 1) 99.74 parts of polyolefin resin, 0.25 parts of inorganic pigment, and 0.01 part of dispersant were melt-mixed, melt-kneaded at 200 °C using a twin-screw extruder (manufactured by Nippon Steel Works, Ltd.), and then extruded. Subsequently, it was cut with a pelletizer to obtain a pelletized colored resin composition. Subsequently, 100 parts of the obtained colored resin composition was molded at 200 °C using an injection molding machine (manufactured by Toshiba Machine Co., Ltd.) to obtain a molded body with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm.

[0169] [Comparative Examples 7 and 8] Pelletized colored resin compositions were obtained in the same manner as in Molded body 1, except that the formulation was changed to the materials and formulation amounts (parts by mass) shown in Table 6. Subsequently, Molded bodies 2 to 3 were obtained from 100 parts of each of the obtained colored resin compositions in the same manner as in Molded body 1.

[0170] Using the obtained molded bodies, the Charpy impact strength and dispersibility were evaluated by the following method.

[0171] [Impact strength measurement] Using the obtained molded bodies, the notched Charpy impact strength was measured in accordance with JIS K7171:2016. Also, from each of the obtained measured values, the physical property retention rate for each measured value was calculated according to the following formula (1) and evaluated according to the following criteria. Note that the higher the value of the physical property retention rate, the better the strength. Formula (1) Physical property retention rate (%) = [Measured value of molded body / Physical property measured value of molded body of polyolefin resin alone] × 100 〇: Physical property retention rate of 70% or more (good) ×: Physical property retention rate less than 70% (not practical)

[0172] <Dispersibility> The obtained molded body was observed at a magnification of 1000 times in a field of view using an optical microscope "Digital Microscope VHX-100" (manufactured by Keyence Corporation), and the dispersibility was evaluated according to the following criteria. 〇: The number of pigment aggregates with a size of 20 μm or more observed in the field of view is 10 or less (good dispersibility) △: Similarly, 11 to 30 (practically acceptable) ×: Similarly, 31 or more (practically unacceptable)

[0173]

Table 6

[0174] From the results in Table 5, the dispersions and photosensitive compositions of the examples have good storage stability, little generation of aggregated foreign matter, and good compatibility. From the results in Table 6, the molded bodies of the examples have little generation of aggregates and excellent compatibility. Therefore, the dispersions and molded bodies of the present invention are excellent in versatility and can be used in a wide range of applications. On the other hand, the dispersions and molded bodies of the comparative examples have low dispersibility and compatibility, and the problems of the present application could not be solved.

Claims

1. A dispersant composition comprising a first dispersant and a second dispersant, wherein the first dispersant comprises a cyclic ester polymer moiety and an amine moiety, and the second dispersant comprises a vinyl polymer moiety and an amine moiety.

2. The dispersant composition according to Claim 1, wherein the mass ratio of the first dispersant X to the second dispersant Y is X / Y = 0.3 to 3.

0.

3. The dispersant composition according to Claim 1, wherein the amine moieties of the first dispersant and the second dispersant have a heterocyclic amino group having aromaticity.

4. The dispersant composition according to Claim 1, wherein the cyclic ester polymer moiety is a polymer containing polylactone.

5. A dispersion comprising the dispersant composition according to any one of Claims 1 to 4 and a material to be dispersed.

6. A photosensitive composition comprising the dispersion according to Claim 5, a binder resin, a polymerizable compound, and a photopolymerization initiator.

7. A molded article obtained by molding the dispersion according to Claim 5 and a thermoplastic resin.

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