TWI680011B - Dispersant - Google Patents

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TWI680011B
TWI680011B TW104144068A TW104144068A TWI680011B TW I680011 B TWI680011 B TW I680011B TW 104144068 A TW104144068 A TW 104144068A TW 104144068 A TW104144068 A TW 104144068A TW I680011 B TWI680011 B TW I680011B
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dispersant
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structural unit
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TW201628703A (en
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高沢史博
Fumihiro TAKAZAWA
井樋昭人
Akito Itoi
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日商花王股份有限公司
Kao Corporation
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00Pigment pastes, e.g. for mixing in paints
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Optical Filters (AREA)

Abstract

本發明提供一種用以獲得平均粒徑較小、低黏度、保存穩定性優異、且耐熱性優異之顏料分散體及著色組合物的分散劑、使用該分散劑之顏料分散體及著色組合物、及使用該著色組合物所製造之彩色濾光片。 The present invention provides a dispersant for obtaining a pigment dispersion and a coloring composition having a small average particle size, low viscosity, excellent storage stability, and excellent heat resistance, a pigment dispersion and a coloring composition using the dispersant, And a color filter manufactured using the coloring composition.

[1]一種分散劑,其於分子結構中具有式(A)所表示之結構單元A,一分子結構中所含之結構單元A之平均數量為1.0以上且22.0以下;[2]一種彩色濾光片用顏料分散體,其含有上述[1]中記載之分散劑、有機顏料及有機溶劑;[3]一種彩色濾光片,其係使用上述[2]中記載之彩色濾光片用著色組合物而製造;[4]一種分散劑之製造方法,其具有步驟1:使於分子結構中具有式(B)所表示之結構單元B且一分子結構中所含之結構單元B之平均數量為1.0以上且22.0以下之聚胺化合物與式(3)所表示之化合物進行反應之步驟;[5]一種四級銨鹽化合物,其以式(1)表示。 [1] A dispersant having a structural unit A represented by formula (A) in a molecular structure, and an average number of the structural unit A contained in a molecular structure is 1.0 or more and 22.0 or less; [2] a color filter A pigment dispersion for an optical sheet, which contains the dispersant, an organic pigment, and an organic solvent described in the above [1]; [3] a color filter that is colored using the color filter described in the above [2] [4] A method for producing a dispersant, which has step 1: having the molecular structure having the structural unit B represented by formula (B) and the average number of structural units B contained in one molecular structure A step of reacting a polyamine compound of 1.0 or more and 22.0 or less with a compound represented by formula (3); [5] a quaternary ammonium salt compound represented by formula (1).

Description

分散劑 Dispersant

本發明係關於一種分散劑、彩色濾光片用顏料分散體、彩色濾光片用著色組合物、使用其之彩色濾光片及四級銨鹽化合物。 The present invention relates to a dispersant, a pigment dispersion for a color filter, a coloring composition for a color filter, a color filter using the same, and a quaternary ammonium salt compound.

近年來,隨著電子零件、電池、印刷、液晶顯示等產業領域之發展,使功能性粒子分散至溶劑中而成之分散體之需求不斷提高。進而,業界正積極地進行可使顏料等表面具有極性之粒子分散至有機溶劑等非水系溶劑中之分散劑之開發。 In recent years, with the development of industrial fields such as electronic parts, batteries, printing, and liquid crystal displays, the demand for dispersions in which functional particles are dispersed in a solvent has been increasing. Furthermore, the industry is actively developing a dispersant that can disperse polar particles on the surface of pigments and the like into non-aqueous solvents such as organic solvents.

藉由使用此種分散劑使例如顏料分散至有機溶劑中,可獲得非水系顏料分散體。液晶顯示裝置中所使用之彩色濾光片係藉由將於上述非水系顏料分散體中調配有樹脂等之著色組合物塗敷於玻璃等透明基板後,使其曝光/硬化、顯影、熱硬化之光微影法等而製造。作為非水系顏料分散體之製造中所使用之油中分散劑,已知有接枝聚合物等高分子分散劑,為了滿足各種要求性能而進行分散劑之改良研究。 By dispersing a pigment in an organic solvent using such a dispersant, a non-aqueous pigment dispersion can be obtained. A color filter used in a liquid crystal display device is coated on a transparent substrate such as glass by applying a coloring composition such as a resin to the non-aqueous pigment dispersion, and then exposing / hardening, developing, and thermosetting Light lithography method. As a dispersant in oil used in the manufacture of a non-aqueous pigment dispersion, a macromolecular dispersant such as a graft polymer is known, and improvement studies of the dispersant are performed in order to satisfy various required properties.

例如,於專利文獻1中,以提供平均粒徑較小、低黏度、保存穩定性優異、具有良好之再分散性之彩色濾光片用顏料分散體為目的,記載有一種彩色濾光片用顏料分散體,其含有具有烷氧基聚伸烷基二醇基及四級銨基且具有特定結構之顏料分散劑、有機顏料及醚系有機溶劑。 For example, Patent Document 1 describes a color filter for the purpose of providing a pigment dispersion for a color filter having a small average particle size, low viscosity, excellent storage stability, and good redispersibility. A pigment dispersion containing a pigment dispersant having an alkoxy polyalkylene glycol group and a quaternary ammonium group and a specific structure, an organic pigment, and an ether-based organic solvent.

於專利文獻2中,以提供即便為低曝光量亦可形成順錐形狀且耐溶劑性亦優異之像素之著色感放射線性組合物為目的,記載有一種著 色放射線性組合物,其含有著色劑、鹼可溶性樹脂、具有己內酯結構之多官能性單體及含有2-(4-甲基苄基)-2-(二甲胺基)-1-(4-嗎啉基苯基)丁烷-1-酮之光聚合起始劑。 Patent Document 2 describes a novel color-sensitive radiation composition for the purpose of providing a pixel having a forward cone shape even at a low exposure and excellent solvent resistance. A color radioactive composition containing a colorant, an alkali-soluble resin, a polyfunctional monomer having a caprolactone structure, and containing 2- (4-methylbenzyl) -2- (dimethylamino) -1- Photopolymerization initiator of (4-morpholinylphenyl) butane-1-one.

於專利文獻3中,以即便僅使用少量之分散劑亦使大量之顏料微細且均勻地分散,及形成製版特性優異、即便較薄而著色濃度亦較高、表面平滑性良好、且雜質不會溶出之高電氣可靠性之著色層為目的,記載有一種著色抗蝕劑用顏料分散液及感光性著色組合物,其含有顏料、包含含有特定分子結構且含有酸性官能基及聚酯鏈之共聚物之顏料分散劑、具有使具備酸性官能基之結構單元、具備光硬化性官能基之結構單元及SP(Solubility Parameter,溶解度參數)值為10以上且不含酸性官能基之結構單元連結而成之分子結構之共聚物及有機溶劑。又,以電氣可靠性較高且實現較廣之顏色再現區域為目的,記載有一種彩色濾光片,其特徵在於:其係使該感光性著色組合物硬化而形成者。 In Patent Document 3, even if only a small amount of a dispersant is used, a large amount of pigment is finely and uniformly dispersed, and plate-forming properties are excellent, the coloring density is high even if it is thin, the surface smoothness is good, and impurities are not affected. For the purpose of eluted coloring layer with high electrical reliability, a pigment dispersion for coloring resist and a photosensitive coloring composition are described, which contain a pigment, a copolymer containing a specific molecular structure, an acidic functional group, and a polyester chain. The pigment dispersant of the substance is formed by connecting a structural unit having an acidic functional group, a structural unit having a photocurable functional group, and a structural unit having an SP (Solubility Parameter) value of 10 or more and containing no acidic functional group. Molecular structure of copolymers and organic solvents. In addition, for the purpose of realizing a wide color reproduction area with high electrical reliability, there is described a color filter characterized by being formed by curing the photosensitive coloring composition.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]國際公開第2014/104289號 [Patent Document 1] International Publication No. 2014/104289

[專利文獻2]日本專利特開2010-217872號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2010-217872

[專利文獻3]日本專利特開2004-287299號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2004-287299

於彩色濾光片中,例如為了提高對比度而將顏料進一步微細化。然而,顏料等粒子由於藉由進行微細化而使粒子彼此之凝聚力提高,故而於分散體中引起粒子彼此之凝聚而使粒徑增大。因此,包含經微細化之粒子之分散體之保存穩定性降低之傾向。 In the color filter, for example, the pigment is further refined to increase the contrast. However, since particles such as pigments are made finer to increase the cohesion of the particles, the particles are agglomerated in the dispersion to increase the particle size. Therefore, the dispersion stability of the dispersion containing the refined particles tends to decrease.

因此,進行使用導入有對顏料等粒子表面之吸附優異之吸附基 及與溶劑之親和性優異之分散基之分散劑而提高分散特性之研究。然而,於現狀下所獲得之分散劑於分散體之微粒化及凝聚抑制方面尚有改善之餘地,或者雖然於該分散體之微粒化及凝聚抑制方面優異,但另一方面,就將包含該顏料分散體之著色組合物用於彩色濾光片之製造步驟之觀點而言仍有課題。具體而言,就於將所形成之圖案細線化時無法獲得細線部之密接性等顯影性之觀點而言、或者就於對塗膜進行熱處理時產生膜厚之變化等耐熱性之觀點而言,尚有改善之餘地。 Therefore, the use of an adsorption group that is excellent in the adsorption of the surface of particles such as pigments is introduced. And a dispersant with a dispersing group which has excellent affinity with a solvent, and studies to improve dispersion characteristics. However, the dispersant obtained under the current situation still has room for improvement in dispersion micronization and aggregation inhibition, or although it is excellent in the dispersion micronization and aggregation inhibition, on the other hand, it will include the There is still a problem from the viewpoint that the coloring composition of the pigment dispersion is used in the manufacturing process of a color filter. Specifically, from the viewpoint that the developability such as the adhesion of the fine-line portion cannot be obtained when the formed pattern is thinned, or from the viewpoint of heat resistance such as a change in film thickness that occurs when the coating film is heat-treated. There is still room for improvement.

因此,本發明之課題在於提供一種用以獲得平均粒徑較小、低黏度、保存穩定性優異、且顯影性及耐熱性優異之顏料分散體及著色組合物的分散劑、彩色濾光片用顏料分散體、彩色濾光片用著色組合物、使用其之彩色濾光片及四級銨鹽化合物。 Therefore, an object of the present invention is to provide a dispersant and a color filter for obtaining a pigment dispersion and a coloring composition having a small average particle diameter, low viscosity, excellent storage stability, and excellent developability and heat resistance. Pigment dispersion, coloring composition for color filter, color filter using the same, and quaternary ammonium salt compound.

本發明者等人發現,於顏料等粒子之分散體中,藉由使用具有式(A)所表示之結構單元A且具有特定結構之分散劑,可解決上述課題。 The present inventors have found that the above-mentioned problems can be solved by using a dispersant having a structural unit A represented by formula (A) and having a specific structure in a dispersion of particles such as pigments.

即,本發明係關於下述[1]~[5]。 That is, the present invention relates to the following [1] to [5].

[1]一種分散劑,其於分子結構中具有式(A)所表示之結構單元A,一分子結構中所含之結構單元A之平均數量為1.0以上且22.0以下,

Figure TWI680011B_D0001
[1] A dispersant having a structural unit A represented by formula (A) in a molecular structure, and an average number of the structural units A contained in one molecular structure is 1.0 or more and 22.0 or less,
Figure TWI680011B_D0001

[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基,R6表示碳數1以上且4以下之烷二基,(M1)-表示陰離子;複數個[(C=O)Rx1O]可相同亦可不同]。 [Wherein, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, and is 2 or more and 100 or less, R 4 A part of hydrogen atoms may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, R 5 represents an alkanediyl group having 1 to 18 carbon atoms, R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (M 1) - represents an anion; a plurality of [(C = O) R x1 O] may be the same or different].

[2]一種彩色濾光片用顏料分散體,其含有如上述[1]之分散劑、有機顏料及有機溶劑。 [2] A pigment dispersion for a color filter, which contains the dispersant, the organic pigment, and the organic solvent as described in the above [1].

[3]一種彩色濾光片,其係使用如上述[2]之彩色濾光片用著色組合物而製造。 [3] A color filter manufactured by using the coloring composition for a color filter as described in [2] above.

[4]一種分散劑之製造方法,其具有步驟1:使於分子結構中具有式(B)所表示之結構單元B且一分子結構中所含之結構單元B之平均數量為1以上且22以下之聚胺化合物與式(3)所表示之化合物進行反應之步驟,

Figure TWI680011B_D0002
[4] A method for producing a dispersant, which includes step 1: having a structural unit B represented by formula (B) in a molecular structure and an average number of structural units B contained in a molecular structure of 1 or more and 22 The step of reacting the following polyamine compound with a compound represented by formula (3),
Figure TWI680011B_D0002

[式中,R4可相同或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基] [In the formula, R 4 may be the same or different, and a part of hydrogen atoms may be substituted with a hydrocarbon group having 1 or more and 10 or less carbon atoms, and R 5 represents an alkyldiyl group having 1 or more and 18 carbon atoms]

Figure TWI680011B_D0003
Figure TWI680011B_D0003

[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以 上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R6表示碳數1以上且4以下之烷二基,Y1表示藉由脫離而成為陰離子(M1)-之基;複數個[(C=O)Rx1O]可相同亦可不同]。 [In the formula, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, and is 2 or more and 100 or less, R 6 a carbon number of 1 or more and 4 or less alkanediyl group, Y 1 represents an anion become disengaged by (M 1) - of the group; a plurality of [(C = O) R x1 O] may be the same or different].

[5]一種四級銨鹽化合物,其以式(1)表示,

Figure TWI680011B_D0004
[5] A quaternary ammonium salt compound represented by formula (1),
Figure TWI680011B_D0004

[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,Ry1表示碳數2以上且4以下之烷二基,Ry2表示碳數1以上且18以下之烴基,d表示平均加成莫耳數,為1以上且100以下,R1、R2及R4可相同或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,R5表示碳數1以上且18以下之烷二基(其中,與R1鄰接之R5表示單鍵),R6表示碳數1以上且4以下之烷二基,(M1)-及(M2)-分別獨立地表示陰離子,n、p、m及k表示平均結構單元數,(n+p+m+k)為1.0以上且22.0以下,(n+p)為1.0以上且22.0以下,n為0.3以上且22.0以下,p為0以上且11.0以下,m為0以上且21.0以下,k為0以上且21.0以下;複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以n、p、m、k表示其平均結構單元數之各結構單元可為任意排列順序]。 [In the formula, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, is 2 or more and 100 or less, and R y1 It represents an alkyldiyl group having 2 or more and 4 carbon atoms, R y2 represents a hydrocarbon group having 1 or more and 18 carbon atoms, d represents an average addition mole number, and is 1 or more and 100 or less. R 1 , R 2, and R 4 It may be the same or different, and represents a hydrocarbon group having a carbon number of 1 or more and 10 or less in which a part of hydrogen atoms may be substituted with a hydroxyl group, and R 3 represents a carbon number of 1 or more and 10 or less in which a hydrogen atom and a part of hydrogen atoms may be substituted with a hydroxyl group. At least one of the hydrocarbon groups, R 5 represents an alkanediyl group having 1 to 18 carbon atoms (wherein R 5 adjacent to R 1 represents a single bond), R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (m 1) - and (m 2) - each independently represent an anion, n, p, m and k represents the average number of structural units, (n + p + m + k) is 1.0 or more and 22.0 or less, (n + p ) Is 1.0 or more and 22.0 or less, n is 0.3 or more and 22.0 or less, p is 0 or more and 11.0 or less, m is 0 or more and 21.0 or less, and k is 0 or more and 21.0 or less; a plurality of [(C = O) R x1 O] can be the same as It can be different, the plural [R y1 O] can be the same or different, and each structural unit whose average structural unit number is represented by n, p, m, and k can be in any order].

根據本發明,可提供一種用以獲得平均粒徑較小、低黏度、保存穩定性優異、且耐熱性優異之顏料分散體及著色組合物的分散劑、彩色濾光片用顏料分散體、彩色濾光片用著色組合物、使用其之彩色濾光片及四級銨鹽化合物。 According to the present invention, it is possible to provide a dispersant for obtaining a pigment dispersion and a coloring composition having a small average particle diameter, low viscosity, excellent storage stability, and excellent heat resistance, a pigment dispersion for a color filter, and a color A coloring composition for a filter, a color filter using the same, and a quaternary ammonium salt compound.

本發明之分散劑於分子結構中具有式(A)所表示之結構單元A(以下亦簡稱為「結構單元A」),一分子結構中所含之結構單元A之平均數量為1.0以上且22.0以下。 The dispersant of the present invention has a structural unit A represented by formula (A) in the molecular structure (hereinafter also referred to as "structural unit A"), and the average number of structural units A contained in a molecular structure is 1.0 or more and 22.0 the following.

本發明之分散劑作為用以獲得平均粒徑較小、低黏度、保存穩定性優異、且彩色濾光片製造過程中之耐熱性優異之顏料分散體及著色組合物的分散劑較佳。其原因尚不明確,但認為如下。 The dispersant of the present invention is preferably used as a dispersant for obtaining a pigment dispersion and a coloring composition having a small average particle diameter, low viscosity, excellent storage stability, and excellent heat resistance during the manufacture of a color filter. The reason is not clear, but it is considered as follows.

本發明之分散劑具有與有機溶劑之親和性較高之聚酯鏈及可長期維持對顏料表面之較強之吸附性之四級銨基。於彩色濾光片用顏料分散體中使用本發明之分散劑作為分散劑之情形時,本發明之化合物中之聚酯鏈於有機溶劑中擴展,因此於顏料分散體中之有機顏料粒子間產生較強之斥力。因此,認為能夠有效地抑制顏料彼此之凝聚,且能夠將顏料分散體之黏度維持為較低。另一方面,四級銨基較強地吸附於有機顏料表面且長期維持其較強之吸附性。因此,認為本發明之分散劑雖然具有與溶劑之較高之親和性,但不易自顏料表面脫離。因此,認為本發明之分散劑係分散時之顏料之微粒化優異,於將所獲得之顏料分散體於高溫下長期保存時、或者將顏料分散體或著色組合物濃縮之塗敷時,亦維持優異之分散性者。 The dispersant of the present invention has a polyester chain with high affinity with organic solvents and a quaternary ammonium group that can maintain strong adsorption on the pigment surface for a long time. When the dispersant of the present invention is used as a dispersant in a pigment dispersion for a color filter, the polyester chain in the compound of the present invention expands in an organic solvent, and thus occurs between the organic pigment particles in the pigment dispersion. Strong repulsion. Therefore, it is considered that aggregation of the pigments can be effectively suppressed, and the viscosity of the pigment dispersion can be maintained low. On the other hand, the quaternary ammonium group is strongly adsorbed on the surface of the organic pigment and maintains its strong adsorption property for a long time. Therefore, although the dispersant of the present invention has a high affinity with a solvent, it is considered that it is not easy to detach from the pigment surface. Therefore, it is considered that the dispersant of the present invention is excellent in micronization of the pigment when dispersed, and is maintained when the obtained pigment dispersion is stored at a high temperature for a long period of time, or when the pigment dispersion or the coloring composition is concentrated and applied Excellent dispersion.

本發明之分散劑為高分子化合物,並且可減少每分子之四級銨 基之數量(即結構單元A之數量)且控制為緻密。因此,認為對顏料分散體中之顏料微粒子之吸附損失變少,進而極不易引起成為凝聚之原因之微粒子間之交聯吸附。因此,認為本發明之彩色濾光片用顏料分散體係平均粒徑較小、低黏度、保存穩定性優異者。 The dispersant of the present invention is a polymer compound and can reduce the quaternary ammonium per molecule The number of bases (ie, the number of structural units A) is controlled to be dense. Therefore, it is considered that the adsorption loss on the pigment fine particles in the pigment dispersion is reduced, and it is extremely difficult to cause cross-linking and adsorption between the fine particles that are the cause of aggregation. Therefore, it is considered that the pigment dispersion system for color filters of the present invention has a small average particle diameter, low viscosity, and excellent storage stability.

進而,本發明之分散劑之聚酯鏈藉由去除有機溶劑而相互作用增強,因此例如若於彩色濾光片用著色組合物中使用本發明之分散劑,則於塗膜形成時之溶劑去除、曝光等顯影處理之過程中,於塗膜中形成擬交聯結構。因此,認為可抑制因顯影液之滲透或擴散所致之塗膜之剝離等,細線密接性提高而顯影性優異,並且亦可抑制熱處理中之膜厚之減少,具有優異之耐熱性。 Furthermore, since the polyester chain of the dispersant of the present invention is enhanced by removing an organic solvent, for example, if the dispersant of the present invention is used in a coloring composition for a color filter, the solvent is removed during the formation of a coating film. During the development process such as exposure and exposure, a pseudo-crosslinked structure is formed in the coating film. Therefore, it is thought that peeling of the coating film due to penetration or diffusion of the developer can be suppressed, the fine wire adhesion is improved and the developability is excellent, and the reduction in film thickness during heat treatment is also suppressed, and it has excellent heat resistance.

以下,對本發明中所使用之各成分、步驟等進行說明。 Hereinafter, each component, a process, etc. used in this invention are demonstrated.

[分散劑] [Dispersant]

本發明之分散劑於分子結構中具有式(A)所表示之結構單元A,一分子結構中所含之結構單元A之平均數量為1.0以上且22.0以下。 The dispersant of the present invention has a structural unit A represented by formula (A) in a molecular structure, and the average number of structural units A contained in one molecular structure is 1.0 or more and 22.0 or less.

Figure TWI680011B_D0005
Figure TWI680011B_D0005

[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基,R6表示碳數1以上且4以下之烷二 基,(M1)-表示陰離子。複數個[(C=O)Rx1O]可相同亦可不同] [Wherein, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, and is 2 or more and 100 or less, R 4 A part of hydrogen atoms may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, R 5 represents an alkanediyl group having 1 to 18 carbon atoms, R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (M 1) - represents an anion. [(C = O) R x1 O] may be the same or different]

就提高分散體之分散性及分散體之保存穩定性之觀點而言,分散劑一分子結構中所含之結構單元A之平均數量為1.0以上,較佳為1.5以上,更佳為1.8以上,就相同之觀點而言,為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下。 From the viewpoint of improving the dispersibility of the dispersion and the storage stability of the dispersion, the average number of structural units A contained in the molecular structure of the dispersant is 1.0 or more, preferably 1.5 or more, and more preferably 1.8 or more. From the same viewpoint, it is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, still more preferably 4.0 or less, and even more preferably 3.0 or less.

就提高分散體之分散性及保存穩定性之觀點、提高著色組合物之顯影性及耐熱性之觀點而言,Rx1之碳數為2以上,較佳為3以上,更佳為4以上,進而較佳為5以上,就相同之觀點而言,為12以下,較佳為10以下,更佳為7以下,進而較佳為6以下,進而較佳為5以下。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, and from the viewpoint of improving the developability and heat resistance of the coloring composition, the carbon number of R x1 is 2 or more, preferably 3 or more, and more preferably 4 or more. It is more preferably 5 or more, and from the same viewpoint, it is 12 or less, preferably 10 or less, more preferably 7 or less, still more preferably 6 or less, and even more preferably 5 or less.

作為Rx1,例如可列舉選自伸乙基、各種丙烷二基、各種丁烷二基、各種戊烷二基、各種己烷二基及各種庚烷二基中之至少一種,就提高分散體之分散性及保存穩定性之觀點、提高著色組合物之顯影性及耐熱性之觀點而言,較佳為選自丁烷-1,4-二基、戊烷-1,5-二基及己烷-1,6-二基中之至少一種,更佳為戊烷-1,5-二基。 As R x1 , for example, at least one selected from the group consisting of ethylene, various propanediyl groups, various butanediyl groups, various pentanediyl groups, various hexanediyl groups, and various heptanediyl groups can be used to enhance the dispersion. From the viewpoint of dispersibility and storage stability, and from the viewpoint of improving the developability and heat resistance of the coloring composition, it is preferably selected from butane-1,4-diyl, pentane-1,5-diyl, and At least one of hexane-1,6-diyl, more preferably pentane-1,5-diyl.

就提高分散體之分散性及保存穩定性之觀點、提高著色組合物之顯影性及耐熱性之觀點而言,a為2以上,較佳為10以上,更佳為15以上,就相同之觀點而言,為100以下,較佳為70以下,更佳為50以下,進而較佳為30以下。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, and from the viewpoint of improving the developability and heat resistance of the coloring composition, a is 2 or more, preferably 10 or more, and more preferably 15 or more. From the same viewpoint It is 100 or less, Preferably it is 70 or less, More preferably, it is 50 or less, More preferably, it is 30 or less.

複數個[(C=O)Rx1O]可相同亦可不同,於具有兩種以上之[(C=O)Rx1O]之情形時,其排列可為無規或嵌段之任一種。 A plurality of [(C = O) R x1 O] may be the same or different. When there are two or more kinds of [(C = O) R x1 O], the arrangement may be random or block. .

就分散劑與有機溶劑之親和性之觀點、以及著色組合物之顯影性及耐熱性之觀點而言,[(C=O)Rx1O]較佳為包含選自源自ε-己內酯之結構單元及源自δ-戊內酯之結構單元中之至少一種,更佳為包含源自ε-己內酯之結構單元。 From the viewpoint of the affinity of the dispersant and the organic solvent, and the viewpoint of the developability and heat resistance of the coloring composition, [(C = O) R x1 O] preferably contains a material selected from ε-caprolactone. At least one of a structural unit and a structural unit derived from δ-valerolactone, more preferably a structural unit derived from ε-caprolactone.

就提高分散體之分散性及保存穩定性之觀點而言,Rx2之碳數為1 以上,較佳為6以上,更佳為10以上,就相同之觀點而言,為18以下,較佳為16以下,更佳為14以下。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, the carbon number of R x2 is 1 or more, preferably 6 or more, more preferably 10 or more, and from the same viewpoint, 18 or less, preferably It is 16 or less, and more preferably 14 or less.

就提高分散體之分散性及保存穩定性之觀點而言,Rx2較佳為選自脂肪族烴基及具有芳香環之烴基中之至少一種,更佳為脂肪族烴基,進而較佳為選自烷基及烯基中之至少一種,進而較佳為烷基。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, R x2 is preferably at least one selected from the group consisting of an aliphatic hydrocarbon group and a hydrocarbon group having an aromatic ring, more preferably an aliphatic hydrocarbon group, and further preferably selected from At least one of an alkyl group and an alkenyl group, and an alkyl group is more preferable.

作為Rx2,例如可列舉選自甲基、乙基、辛基、癸基、月桂基、肉豆蔻基、鯨蠟基、油烯基、硬脂基、苯基、對辛基苯基及對壬基苯基中之至少一種,就提高分散體之分散性及保存穩定性之觀點而言,較佳為選自甲基、辛基、癸基、月桂基、油烯基及硬脂基中之至少一種,更佳為選自甲基、辛基、癸基及月桂基中之至少一種,進而較佳為選自辛基及月桂基中之至少一種,進而較佳為月桂基。 Examples of R x2 include methyl, ethyl, octyl, decyl, lauryl, myristyl, cetyl, oleyl, stearyl, phenyl, p-octylphenyl and p-octyl. At least one of nonylphenyl is preferably selected from the group consisting of methyl, octyl, decyl, lauryl, oleyl, and stearyl from the viewpoint of improving the dispersibility and storage stability of the dispersion. At least one of them is more preferably at least one selected from methyl, octyl, decyl, and lauryl, further preferably at least one selected from octyl and lauryl, and further preferably lauryl.

就提高分散體之分散性及保存穩定性之觀點而言,R4之碳數為10以下,較佳為4以下,更佳為2以下,並且,較佳為1以上,進而較佳為1。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, the carbon number of R 4 is 10 or less, preferably 4 or less, more preferably 2 or less, and more preferably 1 or more, and further preferably 1 .

R4較佳為未經羥基取代之烴基。 R 4 is preferably an unsubstituted hydroxy group.

具體而言,R4例如可列舉選自甲基、乙基、各種丙基及各種丁基中之至少一種,較佳為選自甲基及乙基中之至少一種,更佳為甲基。 Specifically, for example, R 4 includes at least one selected from the group consisting of methyl, ethyl, various propyl, and various butyl, preferably at least one selected from methyl and ethyl, and more preferably methyl.

就提高分散體之分散性及保存穩定性之觀點而言,R5之烷二基之碳數為1以上,較佳為2以上,更佳為3以上,就提高分散體之分散性之觀點而言,為18以下,較佳為14以下,更佳為10以下,進而較佳為6以下。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, the carbon number of the alkanediyl group of R 5 is 1 or more, preferably 2 or more, and more preferably 3 or more. From the viewpoint of improving the dispersibility of the dispersion In other words, it is 18 or less, preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.

作為R5之烷二基,例如可列舉選自伸乙基、各種丙烷二基、各種己烷二基及各種壬烷二基中之至少一種,就提高分散體之分散性及保存穩定性之觀點而言,較佳為選自丙烷-1,3-二基、己烷-1,6-二基及壬烷-1,9-二基中之至少一種,更佳為選自丙烷-1,3-二基及己烷-1,6-二基中之至少一種。 Examples of the alkanediyl group of R 5 include at least one selected from the group consisting of ethylene, various propanediyl groups, various hexanediyl groups, and various nonanediyl groups. In order to improve the dispersibility and storage stability of the dispersion, From the viewpoint, at least one selected from the group consisting of propane-1,3-diyl, hexane-1,6-diyl, and nonane-1,9-diyl is preferred, and more preferably selected from propane-1 At least one of 1,3-diyl and hexane-1,6-diyl.

就本發明之分散劑之製造容易性之觀點而言,R6之碳數為4以下,較佳為3以下,更佳為2以下,並且,較佳為1以上,進而較佳為1。作為R6,較佳為亞甲基。 From the viewpoint of the ease of production of the dispersant of the present invention, the carbon number of R 6 is 4 or less, preferably 3 or less, more preferably 2 or less, and more preferably 1 or more, and even more preferably 1. R 6 is preferably a methylene group.

(M1)-為陰離子,就本發明之分散劑之製造容易性、以及提高分散體之分散性及保存穩定性之觀點而言,較佳為選自鹵化物離子、烷基硫酸根離子、烷基苯磺酸根離子及烷基碳酸根離子中之至少一種,更佳為鹵化物離子,進而較佳為選自氯化物離子、溴化物離子及碘化物離子中之至少一種,進而較佳為氯化物離子。 (M 1 ) -is an anion, and is preferably selected from the group consisting of a halide ion, an alkyl sulfate ion, and the like from the viewpoints of ease of production of the dispersant of the present invention and improvement of dispersibility and storage stability of the dispersion. At least one of an alkylbenzenesulfonate ion and an alkyl carbonate ion, more preferably a halide ion, more preferably at least one selected from the group consisting of chloride ion, bromide ion, and iodide ion, and more preferably Chloride ion.

本發明之分散劑亦可於一分子結構中進而具有選自式(B)所表示之結構單元B(以下亦簡稱為「結構單元B」)及式(C)所表示之結構單元C(以下亦簡稱為「結構單元C」)中之至少一種。 The dispersant of the present invention may further have, in a molecular structure, a structural unit B (hereinafter also simply referred to as "structural unit B") represented by formula (B) and a structural unit C (hereinafter Also referred to simply as "structural unit C").

Figure TWI680011B_D0006
Figure TWI680011B_D0006

[式中,R4、R5與式(A)中所說明者相同] [Wherein R 4 and R 5 are the same as those described in formula (A)]

Figure TWI680011B_D0007
Figure TWI680011B_D0007

[式中,R4、R5與式(A)中所說明者相同,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一 種,(M2)-表示陰離子] [In the formula, R 4 and R 5 are the same as those described in the formula (A), and R 3 represents at least one selected from the group consisting of a hydrogen atom and a part of hydrogen atoms which may be substituted with a hydroxyl group having a carbon number of 1 or more and 10 or less. , (M 2) - represents an anion]

就提高分散體之分散性及保存穩定性之觀點而言,R3較佳為選自氫原子及碳數1以上且10以下之烴基中之至少一種。就提高分散體之分散性及保存穩定性之觀點而言,R3之烴基之碳數為10以下,較佳為7以下,更佳為4以下,進而較佳為2以下,並且,為1以上。作為R3,可列舉選自氫原子、甲基、乙基、丙基及苄基中之至少一種,就提高分散體之分散性及保存穩定性之觀點而言,較佳為選自氫原子及甲基中之至少一種。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, R 3 is preferably at least one selected from a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. From the viewpoint of improving the dispersibility and storage stability of the dispersion, the carbon number of the hydrocarbon group of R 3 is 10 or less, preferably 7 or less, more preferably 4 or less, even more preferably 2 or less, and 1 the above. Examples of R 3 include at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a benzyl group. From the viewpoint of improving the dispersibility and storage stability of the dispersion, it is preferably selected from a hydrogen atom. And at least one of methyl.

(M2)-為陰離子,例如可列舉:羧酸根離子、磺酸根離子、鹵化物離子、硫酸根離子、硝酸根離子、亞硝酸根離子、磷酸根離子、亞磷酸根離子、碳酸根離子。上述離子亦可具有烴基等取代基。 (M 2 ) -is an anion, and examples thereof include a carboxylate ion, a sulfonate ion, a halide ion, a sulfate ion, a nitrate ion, a nitrite ion, a phosphate ion, a phosphite ion, and a carbonate ion. The ion may have a substituent such as a hydrocarbon group.

作為(M2)-,就本發明之分散劑之製造容易性、以及提高分散體之分散性及保存穩定性之觀點而言,較佳為選自羧酸根離子、鹵化物離子、烷基硫酸根離子及烷基苯磺酸根離子中之至少一種。 As (M 2) -, to manufacture the dispersant of this invention ease, and the viewpoint of improving dispersibility and storage stability of the dispersion, it is preferably selected from a carboxylate ion, a halide ion, alkylsulfate At least one of a root ion and an alkylbenzenesulfonate ion.

作為羧酸根離子,較佳為乙酸根離子。 The carboxylate ion is preferably an acetate ion.

作為鹵化物離子,較佳為選自氯化物離子、溴化物離子及碘化物離子中之至少一種,更佳為氯化物離子。 The halide ion is preferably at least one selected from chloride ion, bromide ion, and iodide ion, and more preferably a chloride ion.

作為烷基硫酸根離子,較佳為選自甲基硫酸根離子及乙基硫酸根離子中之至少一種,更佳為甲基硫酸根離子。 The alkyl sulfate ion is preferably at least one selected from the group consisting of methyl sulfate ion and ethyl sulfate ion, and more preferably methyl sulfate ion.

作為烷基苯磺酸根離子,較佳為對甲苯磺酸根離子。 The alkylbenzenesulfonate ion is preferably p-toluenesulfonate ion.

作為(M2)-,就上述觀點而言,進而較佳為選自乙酸根離子、氯化物離子、甲基硫酸根離子及對甲苯磺酸根離子中之至少一種。 (M 2 ) is more preferably at least one selected from the group consisting of an acetate ion, a chloride ion, a methyl sulfate ion, and a p-toluenesulfonate ion from the viewpoint described above.

式(B)、式(C)之R4及R5之烷二基之較佳例與上述式(A)中者相同。 Preferable examples of the alkanediyl groups of R 4 and R 5 in the formula (B) and the formula (C) are the same as those in the formula (A).

就獲得優異之分散性之觀點而言,本發明之分散劑較佳為於分子結構中進而具有式(D)所表示之結構單元D(以下亦簡稱為「結構單 元D」)。 From the viewpoint of obtaining excellent dispersibility, the dispersant of the present invention preferably has a structural unit D represented by the formula (D) in the molecular structure (hereinafter also simply referred to as "the structural unit" Yuan D ").

Figure TWI680011B_D0008
Figure TWI680011B_D0008

[式中,Ry1表示碳數2以上且4以下之烷二基,Ry2表示碳數1以上且18以下之烴基,d表示平均加成莫耳數,為1以上且100以下,R4、R5、R6、(M1)-與式(A)中所說明者相同。再者,[Ry1O]於存在複數個之情形時,可相同亦可不同] [In the formula, R y1 represents an alkanediyl group having 2 or more and 4 carbon atoms, R y2 represents a hydrocarbon group having 1 or more and 18 carbon atoms, d represents an average addition mole number, and is 1 or more and 100 or less, R 4 , R 5, R 6, ( M 1) - the same as in the formula (A) are described. In addition, [R y1 O] may be the same or different when there are multiple cases]

就提高分散體之分散性及分散體之保存穩定性之觀點而言,分散劑一分子結構中所含之結構單元D之平均數量較佳為0.3以上,更佳為0.5以上,進而較佳為0.6以上,進而較佳為0.8以上,就相同之觀點而言,較佳為11.0以下,較佳為5.5以下,更佳為3.5以下,進而較佳為2.5以下,進而較佳為2.0以下,進而較佳為1.5以下,進而較佳為1.0以下,進而較佳為0.8以下。 From the viewpoint of improving the dispersibility of the dispersion and the storage stability of the dispersion, the average number of the structural units D contained in the molecular structure of the dispersant is preferably 0.3 or more, more preferably 0.5 or more, and even more preferably 0.6 or more, and more preferably 0.8 or more, and from the same viewpoint, 11.0 or less, preferably 5.5 or less, more preferably 3.5 or less, still more preferably 2.5 or less, still more preferably 2.0 or less, It is preferably 1.5 or less, more preferably 1.0 or less, and still more preferably 0.8 or less.

就分散性及保存穩定性之觀點而言,Ry1之碳數較佳為4以下,更佳為3以下,較佳為2以上。作為Ry1,可較佳地列舉選自伸乙基及伸丙基中之至少一種。 From the viewpoint of dispersibility and storage stability, the carbon number of R y1 is preferably 4 or less, more preferably 3 or less, and more preferably 2 or more. As R y1 , at least one selected from the group consisting of ethylene and propyl is preferred.

就分散性及保存穩定性之觀點而言,d較佳為1以上,更佳為15以上,進而較佳為21以上,進而較佳為30以上,進而較佳為40以上,且較佳為100以下,更佳為95以下,進而較佳為70以下,進而較佳為50以下。 From the viewpoint of dispersibility and storage stability, d is preferably 1 or more, more preferably 15 or more, still more preferably 21 or more, still more preferably 30 or more, still more preferably 40 or more, and more preferably 100 or less, more preferably 95 or less, still more preferably 70 or less, even more preferably 50 or less.

於上述式(D)中,就分散性及保存穩定性之觀點而言,(Ry1O)d較 佳為下述式(D-a)所表示之結構單元。 In the formula (D), (R y1 O) d is preferably a structural unit represented by the following formula (Da) from the viewpoint of dispersibility and storage stability.

Figure TWI680011B_D0009
Figure TWI680011B_D0009

[式(D-a)中,PO表示源自環氧丙烷之結構單元,EO表示源自環氧乙烷之結構單元,d1、d2表示平均加成莫耳數,d1為0以上且100以下,d2為0以上且100以下,d1+d2為1以上且100以下,*表示鍵結部位。再者,上述式(D-a)較佳為該結構單元為嵌段聚合物,更佳為二嵌段聚合物,較佳為上述式(D-a)之(PO)末端側與Ry2O鍵結,(EO)末端側與羰基鍵結] [In the formula (Da), PO represents a structural unit derived from propylene oxide, EO represents a structural unit derived from ethylene oxide, d1 and d2 represent average addition mole numbers, d1 is 0 or more and 100 or less, and d2 It is 0 or more and 100 or less, d1 + d2 is 1 or more and 100 or less, and * indicates a bonding site. Furthermore, the above formula (Da) is preferably a block polymer, more preferably a diblock polymer, and more preferably the (PO) terminal side of the above formula (Da) is bonded to R y2 O, (EO) The terminal side is bonded to a carbonyl group]

就分散性及保存穩定性之觀點而言,d1較佳為11以上,更佳為15以上,進而較佳為21以上,進而更佳為25以上,就分散性及製造容易性之觀點而言,較佳為60以下,更佳為50以下,進而較佳為35以下。 From the viewpoint of dispersibility and storage stability, d1 is preferably 11 or more, more preferably 15 or more, still more preferably 21 or more, and even more preferably 25 or more. From the viewpoint of dispersibility and ease of production Is preferably 60 or less, more preferably 50 or less, and even more preferably 35 or less.

就分散性及保存穩定性之觀點而言,d2較佳為1以上,更佳為5以上,進而較佳為11以上,進而更佳為13以上,就再分散性及於醚系有機溶劑中之溶解性之觀點而言,較佳為95以下,更佳為70以下,進而較佳為50以下,進而較佳為30以下,進而較佳為20以下。 From the viewpoint of dispersibility and storage stability, d2 is preferably 1 or more, more preferably 5 or more, even more preferably 11 or more, and even more preferably 13 or more. In terms of redispersibility and in an ether-based organic solvent, From the viewpoint of solubility, it is preferably 95 or less, more preferably 70 or less, still more preferably 50 or less, still more preferably 30 or less, and still more preferably 20 or less.

就分散性及保存穩定性之觀點而言,d1與d2之合計(d1+d2)較佳為15以上,更佳為21以上,更佳為30以上,進而較佳為40以上,且較佳為95以下,更佳為70以下,進而較佳為50以下。 From the viewpoint of dispersibility and storage stability, the total of d1 and d2 (d1 + d2) is preferably 15 or more, more preferably 21 or more, even more preferably 30 or more, even more preferably 40 or more, and more preferably It is 95 or less, more preferably 70 or less, and even more preferably 50 or less.

就分散性及保存穩定性之觀點而言,d1相對於d1與d2之合計之比率(d1/(d1+d2))較佳為0.20以上,更佳為0.40以上,進而較佳為0.50以上,就分散性及製造容易性之觀點而言,較佳為0.97以下,更佳為0.86以下,進而較佳為0.80以下。 From the viewpoint of dispersibility and storage stability, the ratio of d1 to the total of d1 and d2 (d1 / (d1 + d2)) is preferably 0.20 or more, more preferably 0.40 or more, and even more preferably 0.50 or more. From the viewpoint of dispersibility and ease of production, it is preferably 0.97 or less, more preferably 0.86 or less, and still more preferably 0.80 or less.

就分散性及再分散性之觀點而言,Ry2之碳數較佳為1以上,更佳為6以上,進而較佳為10以上,就分散性及保存穩定性之觀點而言,較佳為18以下,更佳為16以下,進而較佳為14以下,進而較佳為12以下。就分散性及保存穩定性之觀點而言,Ry2較佳為選自脂肪族烴基及可具有脂肪族烴基之芳香族烴基中之至少一種,更佳為脂肪族烴基,進而較佳為選自烷基及烯基中之至少一種。 From the viewpoint of dispersibility and redispersibility, the carbon number of R y2 is preferably 1 or more, more preferably 6 or more, and even more preferably 10 or more. From the viewpoint of dispersibility and storage stability, it is more preferable. It is 18 or less, more preferably 16 or less, still more preferably 14 or less, and still more preferably 12 or less. From the viewpoint of dispersibility and storage stability, R y2 is preferably at least one selected from the group consisting of an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may have an aliphatic hydrocarbon group, more preferably an aliphatic hydrocarbon group, and still more preferably selected from At least one of an alkyl group and an alkenyl group.

作為Ry2,可列舉選自甲基、乙基、癸基、月桂基、肉豆蔻基、鯨蠟基、油烯基、硬脂基、苯基、對辛基苯基及對壬基苯基中之至少一種,較佳為選自甲基、乙基、癸基、月桂基、肉豆蔻基、鯨蠟基、油烯基、硬脂基及苯基中之至少一種,更佳為選自甲基、癸基、月桂基及苯基中之至少一種,就再分散性之觀點而言,較佳為選自苯基、癸基及月桂基中之至少一種,就分散性及保存穩定性之觀點而言,較佳為選自甲基、癸基、月桂基中之至少一種,就優異之分散性、保存穩定性及再分散性之觀點而言,更佳為癸基或月桂基,進而較佳為月桂基。 Examples of R y2 include methyl, ethyl, decyl, lauryl, myristyl, cetyl, oleyl, stearyl, phenyl, p-octylphenyl, and p-nonylphenyl. At least one selected from the group consisting of methyl, ethyl, decyl, lauryl, myristyl, cetyl, oleyl, stearyl and phenyl, more preferably selected from From the viewpoint of redispersibility, at least one of methyl, decyl, lauryl, and phenyl is preferably at least one selected from phenyl, decyl, and lauryl in terms of dispersibility and storage stability. From the viewpoint, it is preferably at least one selected from the group consisting of methyl, decyl, and lauryl. From the viewpoint of excellent dispersibility, storage stability, and redispersibility, decyl or lauryl is more preferable. Further preferred is lauryl.

本發明之分散劑較佳為具有包含1個以上結構單元A之排列結構,更佳為於一分子結構中具有包含結構單元A、任意地選自結構單元B、結構單元C及結構單元D中之至少一種之排列結構,進而較佳為於一分子結構中具有包含結構單元A、任意地選自結構單元B及結構單元C中之至少一種之排列結構,進而較佳為於一分子結構中具有包含結構單元A及結構單元D、任意地選自結構單元B及結構單元C中之至少一種之排列結構。 The dispersant of the present invention preferably has an arrangement structure including more than one structural unit A, and more preferably has a molecular structure including structural unit A, arbitrarily selected from structural unit B, structural unit C, and structural unit D. At least one of the arrangement structures, and further preferably has an arrangement structure including at least one of structural unit A, arbitrarily selected from structural unit B and structural unit C in a molecular structure, and further preferably in a molecular structure It has an array structure including structural unit A and structural unit D, and at least one selected from structural unit B and structural unit C arbitrarily.

就提高分散體之分散性及保存穩定性之觀點而言,本發明之分散劑中之一分子結構中之結構單元A、結構單元B、結構單元C及結構單元D之合計平均數量較佳為22.0以下,更佳為11.0以下,進而較佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為 3.0以下,就相同之觀點而言,為1.0以上,較佳為1.5以上,更佳為1.8以上。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the total average number of the structural unit A, the structural unit B, the structural unit C, and the structural unit D in one of the molecular structures of the dispersant of the present invention is preferably 22.0 or less, more preferably 11.0 or less, still more preferably 7.0 or less, still more preferably 5.0 or less, still more preferably 4.0 or less, and even more preferably From the same viewpoint, 3.0 or less is 1.0 or more, preferably 1.5 or more, and more preferably 1.8 or more.

上述排列結構之末端較佳為一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,更佳為選自碳數1以上且10以下之烴基及碳數2以上且6以下之羥基烷基中之至少一種,進而較佳為選自碳數1以上且5以下之烴基及碳數3以上且6以下之羥基烷基中之至少一種,進而較佳為選自碳數1以上且3以下之烴基及碳數4以上且6以下之羥基烷基中之至少一種。 The terminal of the above-mentioned arrangement is preferably a hydrocarbon group having a carbon number of 1 or more and 10 or less, in which a part of hydrogen atoms can be substituted with a hydroxyl group, more preferably a hydrocarbon group having a carbon number of 1 or more and 10 or less and a carbon number of 2 or more and 6 or less. At least one kind of hydroxyalkyl group, more preferably at least one kind selected from a hydrocarbon group having 1 to 5 carbon atoms, and at least one kind of hydroxyalkyl group having 3 to 6 carbon atoms, further preferably selected from a carbon number 1 or more. At least one of a hydrocarbon group having 3 or less and a hydroxyalkyl group having 4 or more and 6 or less carbon atoms.

上述末端係指包含1個以上結構單元A之排列結構之兩端之N原子上所分別鍵結之末端基。於具有結構單元B、結構單元C或結構單元D之情形時,上述末端係指結構單元A、結構單元B、結構單元C或結構單元D所表示之結構單元之N原子上所鍵結之末端基。上述之較佳之末端基之例係於R5側末端為TR5-(T為末端原子或取代基)。 The term “terminal” refers to a terminal group bonded to N atoms at both ends of an array structure including one or more structural units A, respectively. When there is a structural unit B, a structural unit C, or a structural unit D, the above-mentioned terminal means the terminal bonded to the N atom of the structural unit represented by the structural unit A, the structural unit B, the structural unit C, or the structural unit D base. Examples of the preferred terminal group described above are those in which the terminal at the R 5 side is TR 5- (T is a terminal atom or a substituent).

就提高分散體之分散性及保存穩定性之觀點而言,分散劑之重量平均分子量Mw較佳為2,000以上,更佳為3,000以上,進而較佳為3,500以上,並且,較佳為50,000以下,更佳為25,000以下,進而較佳為20,000以下,進而較佳為15,000以下。重量平均分子量之測定方法係依據實施例中所記載之方法。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, the weight average molecular weight Mw of the dispersant is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 3,500 or more, and more preferably 50,000 or less, It is more preferably 25,000 or less, even more preferably 20,000 or less, and still more preferably 15,000 or less. The measurement method of weight average molecular weight is based on the method described in an Example.

本發明之分散劑較佳為包含式(1)所表示之化合物之分散劑。 The dispersant of the present invention is preferably a dispersant containing a compound represented by formula (1).

Figure TWI680011B_D0010
Figure TWI680011B_D0010

[式中,Rx1、Rx2、a、R4、R6及(M1)-與式(A)中者相同,Ry1、Ry2及d與式(D)中者相同,R3及(M2)-與式(C)中者相同,R1及R2可相同或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基(其中,與R1鄰接之R5表示單鍵),n、p、m及k表示平均結構單元數,(n+p+m+k)為1.0以上且22.0以下,(n+p)為1.0以上且22.0以下,n為0.3以上且22.0以下,p為0以上且11.0以下,m為0以上且21.0以下,k為0以上且21.0以下。複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以n、p、m、k表示其平均結構單元數之各結構單元可為任意排列順序] [Wherein, R x1, R x2, a , R 4, R 6 and (M 1) - the same as the formula (A), who, R y1, Ry 2, and the same as those d and Formula (D), R 3 And (M 2 ) -same as those in formula (C), R 1 and R 2 may be the same or different, and a part of hydrogen atoms may be substituted with a hydrocarbon group having a carbon number of 1 to 10, and R 5 represents a carbon number Alkyl groups of 1 or more and 18 or less (where R 5 adjacent to R 1 represents a single bond), n, p, m, and k represent the average number of structural units, and (n + p + m + k) is 1.0 or more and 22.0 or less, (n + p) is 1.0 or more and 22.0 or less, n is 0.3 or more and 22.0 or less, p is 0 or more and 11.0 or less, m is 0 or more and 21.0 or less, and k is 0 or more and 21.0 or less. A plurality of [(C = O) R x1 O] may be the same or different, a plurality of [R y1 O] may be the same or different, and each structural unit whose average structural unit number is represented by n, p, m, and k may be For any sort order]

就提高分散體之分散性及保存穩定性之觀點而言,(n+p+m+k)為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,就相同之觀點而言,為1.0以上,較佳為1.5以上,更佳為1.8以上。 From the viewpoint of improving the dispersion and storage stability of the dispersion, (n + p + m + k) is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, and more preferably It is preferably 4.0 or less, and more preferably 3.0 or less. From the same viewpoint, it is 1.0 or more, preferably 1.5 or more, and more preferably 1.8 or more.

就提高分散體之分散性及保存穩定性之觀點而言,(n+p)為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,就相同之觀點而言,為1.0以上,較佳為1.5以上,更佳為1.8以上。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, (n + p) is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, and even more preferably 4.0 or less It is more preferably 3.0 or less, and from the same viewpoint, it is 1.0 or more, preferably 1.5 or more, and more preferably 1.8 or more.

就提高分散體之分散性及保存穩定性之觀點而言,n為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,就相同之觀點而言,為0.3以上,較佳為0.5以上,更佳為0.6以上,進而較佳為0.8以上,進而較佳為1.0以上,進而較佳為1.5以上,進而較佳為1.8以上。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, n is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, still more preferably 4.0 or less, and even more preferably 3.0 or less, and from the same viewpoint, 0.3 or more, preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.8 or more, still more preferably 1.0 or more, still more preferably 1.5 or more, and more It is preferably 1.8 or more.

p為0以上,就提高分散體之分散性及保存穩定性之觀點而言,較佳為0.3以上,更佳為0.5以上,進而較佳為0.6以上,進而較佳為0.8以上,就相同之觀點而言,較佳為11.0以下,較佳為5.5以下,更 佳為3.5以下,進而較佳為2.5以下,進而較佳為2.0以下,進而較佳為1.5以下,進而較佳為1.0以下,進而較佳為0.8以下。 p is 0 or more, from the viewpoint of improving the dispersibility and storage stability of the dispersion, it is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.6 or more, and still more preferably 0.8 or more. From a viewpoint, 11.0 or less is preferable, 5.5 or less is more preferable, and It is preferably 3.5 or less, more preferably 2.5 or less, still more preferably 2.0 or less, still more preferably 1.5 or less, still more preferably 1.0 or less, and still more preferably 0.8 or less.

就提高分散體之分散性及保存穩定性之觀點而言,m為21.0以下,較佳為4.0以下,更佳為2.0以下,進而較佳為1.0以下,進而較佳為0.5以下,就相同之觀點而言,為0以上。 From the viewpoint of improving the dispersion and storage stability of the dispersion, m is 21.0 or less, preferably 4.0 or less, more preferably 2.0 or less, still more preferably 1.0 or less, and still more preferably 0.5 or less, the same From a viewpoint, it is 0 or more.

就提高分散體之分散性及保存穩定性之觀點而言,k為21.0以下,較佳為4.0以下,更佳為2.0以下,進而較佳為1.2以下,就相同之觀點而言,為0以上。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, k is 21.0 or less, preferably 4.0 or less, more preferably 2.0 or less, and even more preferably 1.2 or less, and 0 or more from the same viewpoint. .

就提高分散體之分散性及保存穩定性之觀點而言,(n+p)與(n+p+m+k)之比((n+p)/(n+p+m+k))較佳為0.3以上,更佳為0.6以上,就本發明之分散劑之製造容易性之觀點而言,為1.0以下,較佳為0.9以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the ratio of (n + p) to (n + p + m + k) ((n + p) / (n + p + m + k)) It is preferably 0.3 or more, more preferably 0.6 or more, and from the viewpoint of ease of production of the dispersant of the present invention, it is 1.0 or less, and more preferably 0.9 or less.

上述平均結構單元數、n、p、m、k、(n+p+m+k)例如可藉由實施例中所記載之方法而測定。 The average number of structural units, n, p, m, k, and (n + p + m + k) can be measured, for example, by a method described in Examples.

以n、p、m、k表示其平均結構單元數之各結構單元可為任意排列順序。於n、p、m、k之任一者以上為複數之情形時,各結構單元可為無規、嵌段等任意排列順序。 Each structural unit whose average structural unit number is represented by n, p, m, and k can be in any order. In the case where any one or more of n, p, m, and k is plural, each structural unit may be in any order such as random, block, and the like.

就提高分散體之分散性及保存穩定性之觀點而言,R1、R2之碳數為10以下,較佳為8以下,更佳為6以下,進而較佳為1。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, the carbon number of R 1 and R 2 is 10 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 1.

R1及R2較佳為未經羥基取代之烴基。 R 1 and R 2 are preferably unsubstituted hydroxy-substituted hydrocarbon groups.

R1及R2較佳為選自碳數1以上且10以下之烴基及碳數2以上且6以下之羥基烷基中之至少一種,更佳為選自碳數1以上且5以下之烴基及碳數3以上且6以下之羥基烷基中之至少一種,進而較佳為選自碳數1以上且3以下之烴基及碳數4以上且6以下之羥基烷基中之至少一種。 R 1 and R 2 are preferably at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxyalkyl group having 2 to 6 carbon atoms, and more preferably a hydrocarbon group selected from 1 to 5 carbon atoms And at least one of a hydroxyalkyl group having 3 or more and 6 or less carbons, and more preferably at least one selected from a hydrocarbon group having 1 or more and 3 or less carbon atoms and a hydroxyalkyl group having 4 or more and 6 or less carbon atoms.

具體而言,R1及R2例如可列舉選自甲基、乙基、丁基、己基、羥基甲基、羥基丁基及羥基己基中之至少一種,較佳為選自甲基、乙 基、羥基丁基及羥基己基中之至少一種,更佳為選自甲基及羥基己基中之至少一種。 Specifically, R 1 and R 2 include, for example, at least one selected from methyl, ethyl, butyl, hexyl, hydroxymethyl, hydroxybutyl, and hydroxyhexyl, and is preferably selected from methyl and ethyl. At least one of hydroxybutyl and hydroxyhexyl, more preferably at least one selected from methyl and hydroxyhexyl.

Rx1、Rx2、a、Ry1、Ry2、d、R3、R4、R5、R6、(M1)-、(M2)-及包含式(1)所表示之化合物之分散劑之重量平均分子量之較佳範圍與上述範圍相同。 Compounds of which comprise the formula (1) represented by the - R x1, R x2, a , R y1, R y2, d, R 3, R 4, R 5, R 6, (M 1) -, (M 2) The preferable range of the weight average molecular weight of the dispersant is the same as the above range.

上述式(1)所表示之化合物中,較佳為包含式(1)中之k為0之化合物之分散劑,更具體而言,較佳為包含式(1a)所表示之化合物之分散劑。 Among the compounds represented by the above formula (1), a dispersant containing a compound whose k is 0 in the formula (1) is preferred, and more specifically, a dispersant containing a compound represented by the formula (1a) is preferred .

Figure TWI680011B_D0011
Figure TWI680011B_D0011

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R4、R5、R6、(M1)-、n、m及p與式(1)中所說明者相同,(n+p+m)為1.0以上且22.0以下。複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以n、p、m表示其平均結構單元數之各結構單元可為任意排列順序] [In the formula, R x1 , R x2 , a, R y1 , R y2 , d, R 1 , R 2 , R 4 , R 5 , R 6 , (M 1 ) - , n, m, and p are the same as those in formula (1 ) Are the same as described above, and (n + p + m) is 1.0 or more and 22.0 or less. A plurality of [(C = O) R x1 O] may be the same or different, a plurality of [R y1 O] may be the same or different, and each structural unit whose average structural unit number is represented by n, p, and m may be arbitrary Order]

就提高分散體之分散性及保存穩定性之觀點而言,(n+p)與(n+p+m)之比((n+p)/(n+p+m))較佳為0.3以上,更佳為0.6以上,就本發明之分散劑之製造容易性之觀點而言,為1.0以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the ratio of (n + p) to (n + p + m) ((n + p) / (n + p + m)) is preferably 0.3. The above is more preferably 0.6 or more, and from the viewpoint of ease of production of the dispersant of the present invention, it is 1.0 or less.

本發明之分散劑亦可為包含式(1')所表示之化合物之混合物。 The dispersant of the present invention may be a mixture containing a compound represented by formula (1 ').

[化12]

Figure TWI680011B_D0012
[Chemical 12]
Figure TWI680011B_D0012

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R3、R4、R5、R6、(M1)-及(M2)-與式(1)中所說明者相同,ni、pi、mi及ki表示結構單元數,(ni+pi+mi+ki)為1以上且22以下之整數,ni為1以上且22以下之整數,pi為0以上且11以下之整數,mi為0以上且21以下之整數,ki為0以上且21以下之整數。複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以ni、pi、mi、ki表示其結構單元數之各結構單元可為任意排列順序] [Wherein, R x1, R x2, a , R y1, R y2, d, R 1, R 2, R 3, R 4, R 5, R 6, (M 1) - and (M 2) - and The descriptions in formula (1) are the same, ni, pi, mi, and ki represent the number of structural units, (ni + pi + mi + ki) is an integer of 1 or more and 22 or less, and ni is an integer of 1 or more and 22 or less, pi is an integer of 0 or more and 11 or less, mi is an integer of 0 or more and 21 or less, and ki is an integer of 0 or more and 21 or less. The plural [(C = O) R x1 O] may be the same or different, and the plural [R y1 O] may be the same or different. Each structural unit whose number of structural units is represented by ni, pi, mi, and ki may be Arbitrary order]

就提高分散體之分散性及保存穩定性之觀點而言,(ni+pi+mi+ki)為22以下,較佳為11以下,更佳為7以下,進而較佳為5以下,進而較佳為4以下,進而更佳為3以下,就相同之觀點而言,為1以上,較佳為2以上。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, (ni + pi + mi + ki) is 22 or less, preferably 11 or less, more preferably 7 or less, still more preferably 5 or less, and more preferably It is preferably 4 or less, and even more preferably 3 or less. From the same viewpoint, it is 1 or more, and more preferably 2 or more.

就提高分散體之分散性及保存穩定性之觀點而言,ni為22以下,較佳為11以下,更佳為7以下,進而較佳為5以下,進而較佳為4以下,進而更佳為3以下,就相同之觀點而言,為1以上,較佳為2以上。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, ni is 22 or less, preferably 11 or less, more preferably 7 or less, still more preferably 5 or less, still more preferably 4 or less, and even more preferably From 3 or less, from the same viewpoint, it is 1 or more, and preferably 2 or more.

pi為0以上,就提高分散體之分散性及保存穩定性之觀點而言,較佳為1以上,就相同之觀點而言,為11以下,較佳為5以下,更佳為3以下,進而較佳為2以下,進而較佳為1。 pi is 0 or more, from the viewpoint of improving the dispersibility and storage stability of the dispersion, it is preferably 1 or more, and from the same viewpoint, it is 11 or less, preferably 5 or less, more preferably 3 or less, It is more preferably 2 or less, and still more preferably 1.

就提高分散體之分散性及保存穩定性之觀點而言,mi為21以 下,較佳為4以下,進而較佳為2以下,進而較佳為1以下,就相同之觀點而言,為0以上,進而更佳為0。 From the viewpoint of improving the dispersion and storage stability of the dispersion, mi is 21 to Below, it is preferably 4 or less, more preferably 2 or less, still more preferably 1 or less, and from the same viewpoint, it is 0 or more, and even more preferably 0.

就提高分散體之分散性及保存穩定性之觀點而言,ki為21以下,較佳為4以下,更佳為2以下,進而較佳為1以下,就相同之觀點而言,為0以上。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, ki is 21 or less, preferably 4 or less, more preferably 2 or less, and even more preferably 1 or less. From the same viewpoint, it is 0 or more. .

就含有本發明之化合物之分散體之分散性及保存穩定性之觀點而言,(ni+pi)與(ni+pi+mi+ki)之比((ni+pi)/(ni+pi+mi+ki))較佳為0.3以上,更佳為0.6以上,就本發明之化合物之製造容易性之觀點而言,為1.0以下,較佳為0.9以下。 From the viewpoint of the dispersibility and storage stability of the dispersion containing the compound of the present invention, the ratio of (ni + pi) to (ni + pi + mi + ki) ((ni + pi) / (ni + pi + mi + ki)) is preferably 0.3 or more, more preferably 0.6 or more, and from the viewpoint of ease of production of the compound of the present invention, it is 1.0 or less, and preferably 0.9 or less.

以ni、pi、mi、ki表示其結構單元數之各結構單元可為任意排列順序。於ni、pi、mi、ki之任一者以上為複數之情形時,各結構單元可為無規、嵌段等任意排列順序。 Each structural unit whose number of structural units is represented by ni, pi, mi, ki may be in any order. In the case where any one or more of ni, pi, mi, and ki is plural, each structural unit may be in any order such as random, block, and the like.

上述式(1')所表示之化合物中,分散劑較佳為式(1a')所表示之化合物。 Among the compounds represented by the formula (1 '), the dispersant is preferably a compound represented by the formula (1a').

Figure TWI680011B_D0013
Figure TWI680011B_D0013

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R4、R5、R6及(M1)-與式(1)中所說明者相同,ni、pi及mi與式(1')中所說明者相同,(ni+pi+mi)為1以上且22以下之整數。複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以ni、pi、mi表示其結構單元數 之各結構單元可為任意排列順序] [Wherein, R x1, R x2, a , R y1, R y2, d, R 1, R 2, R 4, R 5, R 6 , and (M 1) - formula (1) described in the same by , Ni, pi, and mi are the same as those described in formula (1 ′), and (ni + pi + mi) is an integer of 1 or more and 22 or less. A plurality of [(C = O) R x1 O] may be the same or different, a plurality of [R y1 O] may be the same or different, and each structural unit whose number of structural units is represented by ni, pi, mi may be arbitrarily arranged. order]

式(1a')中之ni及mi之較佳範圍與上述範圍相同。 The preferable ranges of ni and mi in the formula (1a ′) are the same as those described above.

就提高分散體之分散性及保存穩定性之觀點而言,(ni+pi)與(ni+pi+mi)之比((ni+pi)/(ni+pi+mi))較佳為0.3以上,更佳為0.6以上,就本發明之化合物之製造容易性之觀點而言,為1.0以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the ratio of (ni + pi) to (ni + pi + mi) ((ni + pi) / (ni + pi + mi)) is preferably 0.3. The above is more preferably 0.6 or more, and from the viewpoint of ease of production of the compound of the present invention, it is 1.0 or less.

(第1形態) (First Form)

本發明之第1形態之分散劑為包含式(1)中之p為0之化合物之分散劑,更具體而言,為包含式(1-1)所表示之化合物之分散劑。 The dispersant according to the first aspect of the present invention is a dispersant containing a compound in which p is 0 in Formula (1), and more specifically, a dispersant containing a compound represented by Formula (1-1).

Figure TWI680011B_D0014
Figure TWI680011B_D0014

[式中,Rx1、Rx2、a、R1、R2、R3、R4、R5、R6、(M1)-、(M2)-、m及k與式(1)中所說明者相同,(n+m+k)為1.0以上且22.0以下,n為1.0以上且22.0以下。複數個[(C=O)Rx1O]可相同亦可不同,以n、m、k表示其平均結構單元數之各結構單元可為任意排列順序] [In the formula, R x1 , R x2 , a, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , (M 1 ) - , (M 2 ) - , m and k are the same as those in formula (1) The descriptions are the same, (n + m + k) is 1.0 or more and 22.0 or less, and n is 1.0 or more and 22.0 or less. The plural [(C = O) R x1 O] may be the same or different, and each structural unit whose average structural unit number is represented by n, m, and k may be in any order.]

就提高分散體之分散性及保存穩定性之觀點而言,(n+m+k)為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,就相同之觀點而言,為1.0以上,較佳為1.5以上,更佳為1.8以上。 From the viewpoint of improving dispersion and storage stability of the dispersion, (n + m + k) is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, and even more preferably 4.0 or less, further preferably 3.0 or less, and from the same viewpoint, it is 1.0 or more, preferably 1.5 or more, and more preferably 1.8 or more.

於式(1-1)中,就提高分散體之分散性及保存穩定性之觀點而言,n為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0 以下,進而較佳為4.0以下,進而較佳為3.0以下,就相同之觀點而言,為1.0以上,較佳為1.5以上,更佳為1.8以上。 In the formula (1-1), from the viewpoint of improving the dispersibility and storage stability of the dispersion, n is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, and even more preferably 5.0. Hereinafter, it is more preferably 4.0 or less, and still more preferably 3.0 or less. From the same viewpoint, it is 1.0 or more, preferably 1.5 or more, and more preferably 1.8 or more.

就提高分散體之分散性及保存穩定性之觀點而言,n與(n+m+k)之比(n/(n+m+k))較佳為0.3以上,更佳為0.6以上,就本發明之分散劑之製造容易性之觀點而言,為1.0以下,較佳為0.9以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the ratio of n to (n + m + k) (n / (n + m + k)) is preferably 0.3 or more, more preferably 0.6 or more, From the viewpoint of ease of production of the dispersant of the present invention, it is 1.0 or less, and preferably 0.9 or less.

上述平均結構單元數、n、m、k、(n+m+k)例如可藉由實施例中所記載之方法而測定。 The average number of structural units, n, m, k, and (n + m + k) can be measured, for example, by a method described in Examples.

以n、m、k表示其平均結構單元數之各結構單元可為任意排列順序。於n、m、k之任一者以上為複數之情形時,各結構單元可為無規、嵌段等任意排列順序。 Each structural unit whose average structural unit number is represented by n, m, and k may be in any order. In the case where any one of n, m, and k is plural, each structural unit may be in any order such as random, block, and the like.

上述式(1-1)所表示之化合物中,較佳為包含式(1-1)中之k為0之化合物之分散劑,更具體而言,較佳為包含式(1-1a)所表示之化合物之分散劑。 Among the compounds represented by the above formula (1-1), a dispersant containing a compound in which k is 0 in the formula (1-1) is preferred, and more specifically, a dispersant containing the compound represented by the formula (1-1a) is preferred. Dispersant of the indicated compound.

Figure TWI680011B_D0015
Figure TWI680011B_D0015

[式中,Rx1、Rx2、a、R1、R2、R4、R5、R6、(M1)-、n及m與式(1-1)中所說明者相同,(n+m)為1.0以上且22.0以下。複數個[(C=O)Rx1O]可相同亦可不同,以n、m表示其平均結構單元數之各結構單元可為任意排列順序] [ Wherein R x1 , R x2 , a, R 1 , R 2 , R 4 , R 5 , R 6 , (M 1 ) , n and m are the same as those described in formula (1-1), ( n + m) is 1.0 or more and 22.0 or less. A plurality of [(C = O) R x1 O] may be the same or different, and each structural unit whose average structural unit number is represented by n and m may be in any order.]

就提高分散體之分散性及保存穩定性之觀點而言,n與(n+m)之 比(n/(n+m))較佳為0.3以上,更佳為0.6以上,就本發明之分散劑之製造容易性之觀點而言,為1.0以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, between n and (n + m), The ratio (n / (n + m)) is preferably 0.3 or more, more preferably 0.6 or more, and from the viewpoint of ease of production of the dispersant of the present invention, it is 1.0 or less.

上述式(1-1)所表示之化合物中,就獲得平均粒徑較小、低黏度、保存穩定性優異之分散體之觀點而言,較佳為包含式(1-1)中之m為0、更具體而言式(1-1b)所表示之化合物之分散劑。 Among the compounds represented by the above formula (1-1), from the viewpoint of obtaining a dispersion having a small average particle size, low viscosity, and excellent storage stability, it is preferable that m in the formula (1-1) is 0. More specifically, a dispersant for a compound represented by formula (1-1b).

Figure TWI680011B_D0016
Figure TWI680011B_D0016

[式中,Rx1、Rx2、a、R1、R2、R3、R4、R5、R6、(M1)-、n及k與式(1-1)中所說明者相同,(n+k)為1.0以上且22.0以下。複數個[(C=O)Rx1O]可相同亦可不同,以n、k表示其平均結構單元數之各結構單元可為任意排列順序] [ Wherein R x1 , R x2 , a, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , (M 1 ) - , n, and k are as described in formula (1-1) Similarly, (n + k) is 1.0 or more and 22.0 or less. A plurality of [(C = O) R x1 O] may be the same or different, and each structural unit whose average structural unit number is represented by n and k may be in any order.]

就提高分散體之分散性及保存穩定性之觀點而言,n與(n+k)之比(n/(n+k))較佳為0.3以上,更佳為0.6以上,就本發明之分散劑之製造容易性之觀點而言,為1.0以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the ratio of n to (n + k) (n / (n + k)) is preferably 0.3 or more, and more preferably 0.6 or more. From the viewpoint of ease of production of the dispersant, it is 1.0 or less.

R3較佳為乙基或甲基,更佳為甲基。 R 3 is preferably ethyl or methyl, and more preferably methyl.

本發明之分散劑亦可為包含式(1'-1)所表示之化合物之混合物。 The dispersant of the present invention may be a mixture containing a compound represented by the formula (1'-1).

[化17]

Figure TWI680011B_D0017
[Chemical 17]
Figure TWI680011B_D0017

[式中,Rx1、Rx2、a、R1、R2、R3、R4、R5、R6、(M1)-及(M2)-與式(1)中所說明者相同,ni、mi及ki與式(1')中所說明者相同,(ni+mi+ki)為1以上且22以下之整數。複數個[(C=O)Rx1O]可相同亦可不同,以ni、mi、ki表示其結構單元數之各結構單元可為任意排列順序] [Wherein, R x1, R x2, a , R 1, R 2, R 3, R 4, R 5, R 6, (M 1) - and (M 2) - formula (1) as described by Similarly, ni, mi, and ki are the same as those described in formula (1 ′), and (ni + mi + ki) is an integer of 1 or more and 22 or less. A plurality of [(C = O) R x1 O] may be the same or different, and each structural unit whose number of structural units is represented by ni, mi, ki may be in any order]

就提高分散體之分散性及保存穩定性之觀點而言,(ni+mi+ki)為22以下,較佳為11以下,更佳為7以下,進而較佳為5以下,進而較佳為4以下,進而更佳為3以下,就相同之觀點而言,為1以上,較佳為2以上。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, (ni + mi + ki) is 22 or less, preferably 11 or less, more preferably 7 or less, still more preferably 5 or less, and even more preferably 4 or less, more preferably 3 or less, and from the same viewpoint, it is 1 or more, and more preferably 2 or more.

就含有本發明之化合物之分散體之分散性及保存穩定性之觀點而言,ni與(ni+mi+ki)之比(ni/(ni+mi+ki))較佳為0.3以上,更佳為0.6以上,就本發明之化合物之製造容易性之觀點而言,為1.0以下,較佳為0.9以下。 From the viewpoint of the dispersibility and storage stability of the dispersion containing the compound of the present invention, the ratio of ni to (ni + mi + ki) (ni / (ni + mi + ki)) is preferably 0.3 or more, and more It is preferably 0.6 or more, and from the viewpoint of ease of production of the compound of the present invention, it is 1.0 or less, and more preferably 0.9 or less.

以ni、mi、ki表示其結構單元數之各結構單元可為任意排列順序。於ni、mi、ki之任一者以上為複數之情形時,各結構單元可為無規、嵌段等任意排列順序。 Each structural unit whose number of structural units is represented by ni, mi, ki may be in any order. When any one or more of ni, mi, and ki is plural, each structural unit may be arranged in any order such as random, block, and the like.

上述式(1'-1)所表示之化合物中,較佳為式(1'-1)中之ki為0之化合物,更具體而言,較佳為式(1'-1a)所表示之化合物。 Among the compounds represented by the above formula (1'-1), those in which ki in formula (1'-1) is 0, and more specifically, those represented by formula (1'-1a) are preferred. Compound.

[化18]

Figure TWI680011B_D0018
[Chemical 18]
Figure TWI680011B_D0018

[式中,Rx1、Rx2、a、R1、R2、R4、R5、R6及(M1)-與式(1)中所說明者相同,ni及mi與式(1')中所說明者相同,(ni+mi)為1以上且22以下之整數。複數個[(C=O)Rx1O]可相同亦可不同,以ni、mi表示其結構單元數之各結構單元可為任意排列順序] [Wherein, R x1, R x2, a , R 1, R 2, R 4, R 5, R 6 , and (M 1) - formula (1) described in the same persons, ni and mi of formula (1 The descriptions in ') are the same, and (ni + mi) is an integer of 1 or more and 22 or less. A plurality of [(C = O) R x1 O] may be the same or different, and each structural unit whose number of structural units is represented by ni and mi may be in any order.]

就提高分散體之分散性及保存穩定性之觀點而言,ni與(ni+mi)之比(ni/(ni+mi))較佳為0.3以上,更佳為0.6以上,就本發明之化合物之製造容易性之觀點而言,為1.0以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the ratio of ni to (ni + mi) (ni / (ni + mi)) is preferably 0.3 or more, and more preferably 0.6 or more. From the viewpoint of ease of production of the compound, it is 1.0 or less.

上述式(1'-1)所表示之化合物中,就獲得平均粒徑較小、低黏度、保存穩定性優異之分散體之觀點而言,較佳為式(1'-1)中之mi為0之化合物,更具體而言,較佳為式(1'-1b)所表示之化合物。 Among the compounds represented by the above formula (1'-1), from the viewpoint of obtaining a dispersion having a small average particle size, low viscosity, and excellent storage stability, it is preferably mi in formula (1'-1). A compound which is 0, more specifically, a compound represented by the formula (1′-1b) is preferable.

Figure TWI680011B_D0019
Figure TWI680011B_D0019

[式中,Rx1、Rx2、a、R1、R2、R3、R4、R5、R6、(M1)-及(M2)-與式(1)中所說明者相同,ni及ki與式(1')中所說明者相同,(ni+ki)為1.0以上且22.0以下。複數個[(C=O)Rx1O]可相同亦可不同,以ni、ki表示 其結構單元數之各結構單元可為任意排列順序] [Wherein, R x1, R x2, a , R 1, R 2, R 3, R 4, R 5, R 6, (M 1) - and (M 2) - formula (1) as described by Similarly, ni and ki are the same as those described in the formula (1 ′), and (ni + ki) is 1.0 or more and 22.0 or less. A plurality of [(C = O) R x1 O] may be the same or different, and each structural unit whose number of structural units is represented by ni and ki may be in any order.]

就提高分散體之分散性及保存穩定性之觀點而言,ni與(ni+ki)之比(ni/(ni+ki))較佳為0.3以上,更佳為0.6以上,就本發明之化合物之製造容易性之觀點而言,為1.0以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the ratio of ni to (ni + ki) (ni / (ni + ki)) is preferably 0.3 or more, and more preferably 0.6 or more. From the viewpoint of ease of production of the compound, it is 1.0 or less.

(第2形態) (Second form)

本發明之第2形態之分散劑為包含式(1)中p為0.3以上且11.0以下之化合物之分散劑,更具體而言,較佳為包含式(1-2)所表示之化合物之分散劑。 The dispersant in the second aspect of the present invention is a dispersant containing a compound having p of 0.3 or more and 11.0 or less in formula (1), and more specifically, a dispersant containing a compound represented by formula (1-2) Agent.

Figure TWI680011B_D0020
Figure TWI680011B_D0020

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R3、R4、R5、R6、(M1)-及(M2)-、n、m、k、(n+p+m+k)及(n+p)與式(1)中所說明者相同,p為0.3以上且11.0以下。複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以n、p、m、k表示其平均結構單元數之各結構單元可為任意排列順序] [Wherein, R x1, R x2, a , R y1, R y2, d, R 1, R 2, R 3, R 4, R 5, R 6, (M 1) - and (M 2) -, n, m, k, (n + p + m + k), and (n + p) are the same as those described in the formula (1), and p is 0.3 or more and 11.0 or less. A plurality of [(C = O) R x1 O] may be the same or different, a plurality of [R y1 O] may be the same or different, and each structural unit whose average structural unit number is represented by n, p, m, and k may be For any sort order]

就提高分散體之分散性及保存穩定性之觀點而言,p為0.3以上,較佳為0.5以上,更佳為0.6以上,進而較佳為0.8以上,就相同之觀點而言,較佳為11.0以下,較佳為5.5以下,更佳為3.5以下,進而較佳為2.5以下,進而較佳為2.0以下,進而較佳為1.5以下,進而較佳為1.0以下,進而較佳為0.8以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, p is 0.3 or more, preferably 0.5 or more, more preferably 0.6 or more, and still more preferably 0.8 or more. From the same viewpoint, it is preferably 11.0 or less, preferably 5.5 or less, more preferably 3.5 or less, still more preferably 2.5 or less, still more preferably 2.0 or less, still more preferably 1.5 or less, still more preferably 1.0 or less, and even more preferably 0.8 or less.

就提高分散體之分散性及保存穩定性之觀點而言,n/p較佳為0.1以上,更佳為0.2以上,進而較佳為0.3以上,就獲得優異之顯影性之觀點而言,進而較佳為0.5以上,進而較佳為0.8以上,進而更佳為1.5以上,就提高分散體之分散性及保存穩定性之觀點而言,較佳為5.0以下,更佳為3.5以下,進而較佳為2.5以下,進而較佳為2.0以下。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, n / p is preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.3 or more. From the viewpoint of obtaining excellent developability, further It is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 1.5 or more. From the viewpoint of improving the dispersibility and storage stability of the dispersion, it is preferably 5.0 or less, more preferably 3.5 or less, and more preferably It is preferably 2.5 or less, and further preferably 2.0 or less.

上述式(1-2)所表示之化合物中,較佳為包含式(1)中p為0.3以上且11.0以下且k為0之化合物之分散劑,更具體而言,較佳為包含式(1-2a)所表示之化合物之分散劑。 Among the compounds represented by the above formula (1-2), a dispersant containing a compound in which p is 0.3 or more and 11.0 or less and k is 0 in the formula (1), and more specifically, preferably contains a formula ( Dispersant for the compound represented by 1-2a).

Figure TWI680011B_D0021
Figure TWI680011B_D0021

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R4、R5、R6、(M1)-、n、p及m與式(1-2)中所說明者相同,(n+p+m)為1.0以上且22.0以下。複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以n、p、m表示其平均結構單元數之各結構單元可為任意排列順序] [ Wherein R x1 , R x2 , a, R y1 , R y2 , d, R 1 , R 2 , R 4 , R 5 , R 6 , (M 1 ) - , n, p, and m are the same as those in formula (1 The descriptions in -2) are the same, and (n + p + m) is 1.0 or more and 22.0 or less. A plurality of [(C = O) R x1 O] may be the same or different, a plurality of [R y1 O] may be the same or different, and each structural unit whose average structural unit number is represented by n, p, and m may be arbitrary Order]

就提高分散體之分散性及保存穩定性之觀點而言,(n+p+m)為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,就相同之觀點而言,為1.0以上,較佳為1.5以上,更佳為1.8以上。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, (n + p + m) is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, and even more preferably 4.0 or less, further preferably 3.0 or less, and from the same viewpoint, it is 1.0 or more, preferably 1.5 or more, and more preferably 1.8 or more.

就提高分散體之分散性及保存穩定性之觀點而言,(n+p)與(n+ p+m)之比[(n+p)/(n+p+m)]較佳為0.3以上,更佳為0.6以上,就本發明之分散劑之製造容易性之觀點而言,為1.0以下,較佳為0.9以下。 From the viewpoint of improving dispersion and storage stability of the dispersion, (n + p) and (n + The ratio [(n + p) / (n + p + m)] is preferably 0.3 or more, more preferably 0.6 or more, and from the viewpoint of ease of production of the dispersant of the present invention, it is 1.0. Hereinafter, it is preferably 0.9 or less.

上述平均結構單元數、n、p、m、(n+p+m)例如可藉由實施例中所記載之方法而測定。 The average number of structural units, n, p, m, and (n + p + m) can be measured, for example, by a method described in Examples.

以n、p、m表示其平均結構單元數之各結構單元可為任意排列順序。於n、p、m之任一者以上為複數之情形時,各結構單元可為無規、嵌段等任意排列順序。 Each structural unit whose average structural unit number is represented by n, p, and m may be in any order. In the case where any one of n, p, and m is plural, each structural unit may be in any order such as random, block, and the like.

本發明之分散劑較佳為包含式(1')中pi為1以上且11以下之化合物之分散劑,更具體而言,亦可為包含式(1'-2)所表示之化合物之混合物。 The dispersant of the present invention is preferably a dispersant containing a compound having a pi of 1 or more and 11 or less in formula (1 '), and more specifically, a dispersant containing a compound represented by formula (1'-2) .

Figure TWI680011B_D0022
Figure TWI680011B_D0022

[式中,Rx1、Rx2、Ry1、Ry2、a、d、R1、R2、R3、R4、R5、R6、(M1)-及(M2)-與式(1)中所說明者相同,ni、mi及ki與式(1')中所說明者相同,(ni+pi+mi+ki)為2以上且22以下之整數,pi為1以上且11以下之整數。複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以ni、pi、mi、ki表示其結構單元數之各結構單元可為任意排列順序] [Wherein, R x1, R x2, R y1, R y2, a, d, R 1, R 2, R 3, R 4, R 5, R 6, (M 1) - and (M 2) - and The formula (1) is the same, ni, mi, and ki are the same as those described in the formula (1 '), (ni + pi + mi + ki) is an integer of 2 or more and 22 or less, and pi is 1 or more and An integer of 11 or less. The plural [(C = O) R x1 O] may be the same or different, and the plural [R y1 O] may be the same or different. Each structural unit whose number of structural units is represented by ni, pi, mi, and ki may be Arbitrary order]

就提高分散體之分散性及保存穩定性之觀點而言,(ni+pi+mi +ki)為22以下,較佳為11以下,更佳為7以下,進而較佳為5以下,進而較佳為4以下,進而更佳為3以下,就相同之觀點而言,為2以上。 From the viewpoint of improving the dispersion and storage stability of the dispersion, (ni + pi + mi + ki) is 22 or less, preferably 11 or less, more preferably 7 or less, still more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, and from the same viewpoint, 2 or more .

就提高分散體之分散性及保存穩定性之觀點而言,pi為1以上,就相同之觀點而言,為11以下,較佳為5以下,更佳為3以下,進而較佳為2以下,進而較佳為1。 From the viewpoint of improving the dispersibility and storage stability of the dispersion, pi is 1 or more, and from the same viewpoint, it is 11 or less, preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. , And more preferably 1.

(ni+pi)與(ni+pi+mi+ki)之比((ni+pi)/(ni+pi+mi+ki))亦較佳為與式(1')之較佳範圍相同之範圍。 The ratio of (ni + pi) to (ni + pi + mi + ki) ((ni + pi) / (ni + pi + mi + ki)) is also preferably the same as the preferred range of formula (1 ') range.

上述式(1'-2)所表示之化合物中,較佳為包含式(1'-2)中ki為0之化合物之分散劑,更具體而言,較佳為式(1'-2a)所表示之化合物。 Among the compounds represented by the above formula (1'-2), a dispersant containing a compound whose ki is 0 in the formula (1'-2) is preferred, and more specifically, the formula (1'-2a) is preferred. The indicated compound.

Figure TWI680011B_D0023
Figure TWI680011B_D0023

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R4、R5、R6及(M1)-與式(1)中所說明者相同,ni、pi及mi與式(1'-2)中所說明者相同,(ni+pi+mi)為2以上且22以下之整數。複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以ni、pi、mi表示其結構單元數之各結構單元可為任意排列順序] [Wherein, R x1, R x2, a , R y1, R y2, d, R 1, R 2, R 4, R 5, R 6 , and (M 1) - formula (1) described in the same by , Ni, pi, and mi are the same as those described in the formula (1'-2), and (ni + pi + mi) is an integer of 2 or more and 22 or less. A plurality of [(C = O) R x1 O] may be the same or different, a plurality of [R y1 O] may be the same or different, and each structural unit whose number of structural units is represented by ni, pi, mi may be arbitrarily arranged. order]

式(1'-2a)中之ni、pi及mi之較佳範圍與上述範圍相同。 The preferable ranges of ni, pi, and mi in the formula (1'-2a) are the same as those described above.

就提高分散體之分散性及保存穩定性之觀點而言,(ni+pi)與(ni+pi+mi)之比((ni+pi)/(ni+pi+mi))較佳為0.3以上,更佳為0.6以 上,就本發明之化合物之製造容易性之觀點而言,為1.0以下。 From the viewpoint of improving the dispersion and storage stability of the dispersion, the ratio of (ni + pi) to (ni + pi + mi) ((ni + pi) / (ni + pi + mi)) is preferably 0.3. Above, more preferably 0.6 or more From the viewpoint of ease of production of the compound of the present invention, it is 1.0 or less.

(第3形態) (Third form)

就獲得優異之分散性之觀點而言,本發明之第3形態之分散劑為包含式(1-1)所表示之化合物之分散劑與包含下述式(1-3)所表示之化合物之分散劑之混合物。 From the viewpoint of obtaining excellent dispersibility, the dispersant of the third aspect of the present invention is a dispersant containing a compound represented by the formula (1-1) and a dispersant containing a compound represented by the following formula (1-3) Mixture of dispersants.

Figure TWI680011B_D0024
Figure TWI680011B_D0024

[式中,Ry1、Ry2、d、R1、R2、R3、R4、R5、R6、(M1)-及(M2)-與式(1)中所說明者相同,p、m及k表示平均結構單元數,(p+m+k)為1.0以上且22.0以下,m為0以上且21.0以下,p為1.0以上且22.0以下,k為0以上且21.0以下。複數個[Ry1O]可相同亦可不同,以p、m、k表示其平均結構單元數之各結構單元可為任意排列順序] [Wherein, R y1, R y2, d , R 1, R 2, R 3, R 4, R 5, R 6, (M 1) - and (M 2) - formula (1) as described by Similarly, p, m, and k represent the average number of structural units, (p + m + k) is 1.0 or more and 22.0 or less, m is 0 or more and 21.0 or less, p is 1.0 or more and 22.0 or less, and k is 0 or more and 21.0 or less. . The plural [R y1 O] may be the same or different, and each structural unit whose average structural unit number is represented by p, m, and k may be in any order.]

上述混合物中之包含式(1-1)所表示之化合物之分散劑較佳為包含式(1-1a)所表示之化合物之分散劑。 The dispersant containing the compound represented by the formula (1-1) in the above mixture is preferably a dispersant containing the compound represented by the formula (1-1a).

就優異之分散性、優異之保存穩定性及優異之耐熱性之觀點而言,上述混合物中之包含式(1-1)所表示之化合物之分散劑與包含式(1-3)所表示之化合物之分散劑之質量比[(1-1)/(1-3)]較佳為10/90以上,更佳為20/80以上,進而較佳為30/70以上,進而較佳為40/60以上,進而較佳為45/55以上,並且,較佳為90/10以下,更佳為80/20以下,進而較佳為70/30以下。 From the viewpoints of excellent dispersibility, excellent storage stability, and excellent heat resistance, the dispersant containing the compound represented by the formula (1-1) in the above mixture and the dispersant containing the compound represented by the formula (1-3) The mass ratio of the compound dispersant [(1-1) / (1-3)] is preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more, and still more preferably 40 / 60 or more, more preferably 45/55 or more, and more preferably 90/10 or less, more preferably 80/20 or less, and still more preferably 70/30 or less.

<分散劑之製造方法> <Manufacturing method of dispersant>

本發明之分散劑例如藉由具有如下步驟之分散劑之製造方法而獲得。 The dispersant of the present invention is obtained, for example, by a method for producing a dispersant having the following steps.

步驟1:使於分子結構中具有式(B)所表示之結構單元B且一分子結構中所含之結構單元B之平均數量為1.0以上且22.0以下之聚胺化合物、式(3-1)所表示之化合物、及任意之式(3-2)所表示之化合物進行反應之步驟。 Step 1: A polyamine compound having the structural unit B represented by the formula (B) in the molecular structure and the average number of the structural unit B contained in one molecular structure is 1.0 or more and 22.0 or less, and the formula (3-1) A step of reacting the compound represented by the formula and any compound represented by the formula (3-2).

Figure TWI680011B_D0025
Figure TWI680011B_D0025

[式中,R4、R5與式(A)中所說明者相同] [Wherein R 4 and R 5 are the same as those described in formula (A)]

Figure TWI680011B_D0026
Figure TWI680011B_D0026

[式中,Rx1、Rx2、a、R6與式(A)中所說明者相同。Y1表示藉由脫離而成為陰離子(M1)-之基] [In the formula, R x1 , R x2 , a, and R 6 are the same as those described in formula (A). Y 1 represents an anion become disengaged by (M 1) - of-yl]

Figure TWI680011B_D0027
Figure TWI680011B_D0027

[式中,Ry1、Ry2、d、R6與式(D)中所說明者相同。Y1表示藉由脫離而成為陰離子(M1)-之基] [In the formula, R y1 , R y2 , d, and R 6 are the same as those described in formula (D). Y 1 represents an anion become disengaged by (M 1) - of-yl]

Y1較佳為藉由脫離而成為上述較佳之(M1)-之基。就分散劑之製造容易性、以及提高分散體之分散性及保存穩定性之觀點而言,Y1較佳為鹵素原子,更佳為選自氯原子、溴原子及碘原子中之至少一種,進而較佳為氯原子。 Y 1 is preferably becomes disengaged by the above-described preferred (M 1) - the groups. From the standpoint of ease of production of the dispersant and improvement of the dispersibility and storage stability of the dispersion, Y 1 is preferably a halogen atom, more preferably at least one selected from a chlorine atom, a bromine atom, and an iodine atom, Furthermore, a chlorine atom is preferable.

R4、R5、Rx1、Rx2、a、Ry1、Ry2、d、R6之較佳範圍與上述範圍相同。 The preferred ranges of R 4 , R 5 , R x1 , R x2 , a, R y1 , R y2 , d, and R 6 are the same as those described above.

例如藉由使上述原料於無溶劑下或溶劑中反應而獲得本發明之分散劑。反應中所使用之溶劑例如較佳為下述本發明中所使用之醚系有機溶劑。作為醚系有機溶劑,較佳為(聚)伸烷基二醇單烷基醚乙酸酯,更佳為丙二醇單甲醚乙酸酯(以下亦稱為「PGMEA」)、二乙二醇單丁醚乙酸酯(以下亦稱為「BCA」),就光微影法中之顏料分散體之操作容易性及作業性之觀點而言,進而較佳為PGMEA。 The dispersant of the present invention is obtained, for example, by reacting the above raw materials in a solvent-free or solvent. The solvent used in the reaction is preferably, for example, an ether-based organic solvent used in the present invention described below. The ether-based organic solvent is preferably (poly) alkylene glycol monoalkyl ether acetate, more preferably propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA"), diethylene glycol mono Butyl ether acetate (hereinafter also referred to as "BCA") is more preferably PGMEA from the viewpoint of ease of handling and workability of the pigment dispersion in the photolithography method.

聚胺化合物例如為式(2)所表示之聚胺化合物。 The polyamine compound is, for example, a polyamine compound represented by formula (2).

Figure TWI680011B_D0028
Figure TWI680011B_D0028

[式中,R1、R2、R4、R5與式(A)中所說明之取代基相同。(n+p+m+k)表示平均結構單元數,為1.0以上且22.0以下] [In the formula, R 1 , R 2 , R 4 , and R 5 are the same as the substituents described in formula (A). (n + p + m + k) represents the average number of structural units, which is 1.0 or more and 22.0 or less]

上述聚胺化合物例如藉由於Cu-Ni觸媒之存在下使伸烷基二醇與一級胺或二級胺反應之方法、或利用醛使伸烷基二胺進行還原烷基化之方法而獲得。 The polyamine compound is obtained, for example, by a method of reacting an alkylene glycol with a primary amine or a secondary amine in the presence of a Cu-Ni catalyst, or a method of reductively alkylating an alkylene diamine by using an aldehyde. .

此外,作為市售品,可使用N,N,N',N'-四甲基己二胺(花王股份有限公司製造之「Kaolizer No.1」)、N,N,N',N'-四甲基丙二胺(花王股份有限公司製造之「Kaolizer No.2」)、聚胺二醇(花王股份有限公司製造之「Kaolizer P200」)等。 In addition, as a commercially available product, N, N, N ', N'-tetramethylhexanediamine ("Kaolizer No. 1" manufactured by Kao Corporation), N, N, N', N'- Tetramethylpropanediamine ("Kaolizer No. 2" manufactured by Kao Corporation), polyamine glycol ("Kaolizer P200" manufactured by Kao Corporation) and the like.

式(3-1)所表示之化合物例如藉由如下方式而獲得:於鈦化合物等金屬觸媒之存在下,使具有Rx2之烴基之醇與形成[(C=O)Rx1O]之內酯進行加成聚合而獲得烷氧基聚酯,進而使其與具有鹵化烷基之羧酸進行脫水縮合。於本說明書中,烷氧基表示Rx2O-(Rx2表示上述烴基)。 The compound represented by the formula (3-1) is obtained, for example, by the following: in the presence of a metal catalyst such as a titanium compound, an alcohol having a hydrocarbon group of R x2 and a compound of [(C = O) R x1 O] The lactone is subjected to addition polymerization to obtain an alkoxy polyester, which is further subjected to dehydration condensation with a carboxylic acid having a halogenated alkyl group. In the present specification, an alkoxy group represents R x2 O- (R x2 represents the above-mentioned hydrocarbon group).

式(3-2)所表示之鹵化烷基酯例如藉由如下方式而獲得:使具有Ry2之烴基之醇與形成Ry1O之環氧烷化合物於鹼性物質之存在下反應,藉此獲得烷氧基聚伸烷基二醇,進而使其與具有鹵化烷基之羧酸進行脫水縮合。再者,於本說明書中,烷氧基表示Ry2O-(Ry2表示上述烴基)。 The halogenated alkyl ester represented by the formula (3-2) is obtained, for example, by reacting an alcohol having a hydrocarbon group of R y2 with an alkylene oxide compound forming R y1 O in the presence of a basic substance, whereby An alkoxy polyalkylene glycol is obtained, which is further subjected to dehydration condensation with a carboxylic acid having a halogenated alkyl group. In the present specification, an alkoxy group represents R y2 O- (R y2 represents the above-mentioned hydrocarbon group).

步驟1中之式(3-1)所表示之化合物(莫耳量)相對於聚胺化合物之胺官能基數(例如式(2)中之(n+p+m+k))×莫耳量之比能夠根據目標化合物而適當設定,例如為0.3~1.2。藉由適當設定上述比率,可調整分散劑中所含之結構單元A之數量。 The compound (mole amount) represented by formula (3-1) in step 1 with respect to the number of amine functional groups of the polyamine compound (e.g. (n + p + m + k) in formula (2)) × mole amount The ratio can be appropriately set depending on the target compound, and is, for example, 0.3 to 1.2. By appropriately setting the above ratio, the number of the structural units A contained in the dispersant can be adjusted.

步驟1中之式(3-2)所表示之化合物(莫耳量)相對於聚胺化合物之胺官能基數(例如式(2)中之(n+p+m+k))×莫耳量之比能夠根據目標化合物而適當設定,例如為0.3~1.2。藉由適當設定上述比率,可調整分散劑中所含之結構單元D之數量。 The compound (mole amount) represented by formula (3-2) in step 1 with respect to the number of amine functional groups of the polyamine compound (e.g. (n + p + m + k) in formula (2)) × mole amount The ratio can be appropriately set depending on the target compound, and is, for example, 0.3 to 1.2. By appropriately setting the above ratio, the number of structural units D contained in the dispersant can be adjusted.

就更準確地控制n、m之數之觀點而言,上述聚胺化合物與上述鹵化烷基酯化合物之反應量比較佳為以由聚胺化合物之胺官能基數與鹵化烷基酯化合物之鹵素量所算出之莫耳當量作為基準進行調整。 From the viewpoint of more accurately controlling the numbers of n and m, the reaction amount between the polyamine compound and the halogenated alkyl ester compound is preferably based on the number of halogenated alkyl ester compounds and the number of amine functional groups of the polyamine compound. The calculated molar equivalent is adjusted as a reference.

該步驟中之反應環境較佳為氮氣環境、氬等惰性氣體環境。該 步驟中之反應之溫度例如較佳為50℃以上,更佳為80℃以上,且較佳為100℃以下。 The reaction environment in this step is preferably an inert gas environment such as a nitrogen environment and argon. The The reaction temperature in the step is preferably 50 ° C or higher, more preferably 80 ° C or higher, and more preferably 100 ° C or lower.

於獲得k之值超過0之式(1)所表示之化合物之情形時,本發明之製造方法進而具有如下步驟。 When a compound represented by formula (1) whose value of k exceeds 0 is obtained, the production method of the present invention further has the following steps.

步驟2:使步驟1中所獲得之化合物與式(4)所表示之化合物進行反應之步驟。 Step 2: A step of reacting the compound obtained in Step 1 with a compound represented by formula (4).

R3-Y2 (4) R 3 -Y 2 (4)

[式中,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,Y2表示藉由脫離而成為陰離子(M2)-之基]。 [In the formula, R 3 represents at least one selected from a hydrogen atom and a hydrocarbon group having a carbon number of 1 or more and 10 or less which may be substituted with a hydroxyl group, and Y 2 represents an anion (M 2 ) - base].

作為式(4)所表示之化合物,使用與三級胺基反應而將該胺基中和或四級銨化之物質。 As the compound represented by formula (4), a substance which reacts with a tertiary amine group to neutralize or quaternize the amine group is used.

R3較佳為與上述之R3相同者。Y2之較佳例為藉由脫離而成為上述較佳之(M2)-之基。 R 3 is preferably the same as R 3 described above. The preferred embodiments of Y 2 become disengaged by the above-described preferred (M 2) - the groups.

作為式(4)所表示之化合物,可列舉酸及除式(3)所表示之化合物以外之四級化劑。作為上述酸,例如可列舉鹽酸、乙酸、對甲苯磺酸、甲基硫酸。作為上述四級化劑,例如可列舉硫酸二烷基酯、鹵代烷、對甲苯磺酸烷基酯。作為硫酸二烷基酯,可列舉硫酸二甲酯、硫酸二乙酯等,作為鹵代烷,可列舉氯化甲烷、碘化甲烷、氯化苄烷等,作為對甲苯磺酸烷基酯,可列舉對甲苯磺酸甲酯、對甲苯磺酸乙酯等。作為式(4)所表示之化合物,較佳為選自鹽酸、乙酸、氯化甲烷、硫酸二甲酯及硫酸二乙酯中之至少一種,更佳為選自乙酸及硫酸二甲酯中之至少一種。 Examples of the compound represented by the formula (4) include acids and quaternizing agents other than the compound represented by the formula (3). Examples of the acid include hydrochloric acid, acetic acid, p-toluenesulfonic acid, and methylsulfuric acid. Examples of the quaternizing agent include dialkyl sulfate, alkyl halide, and alkyl p-toluenesulfonate. Examples of the dialkyl sulfate include dimethyl sulfate and diethyl sulfate. Examples of the halogenated alkyl group include methane chloride, methyl iodide, and benzyl chloride. Examples of the alkyl p-toluenesulfonate include: Methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and the like. The compound represented by formula (4) is preferably at least one selected from the group consisting of hydrochloric acid, acetic acid, methane chloride, dimethyl sulfate, and diethyl sulfate, and more preferably one selected from acetic acid and dimethyl sulfate. At least one.

步驟2可使用與上述反應中所使用之溶劑相同者。該步驟中之反應環境較佳為氮氣環境、氬等惰性氣體環境。該步驟中之反應之溫度亦取決於式(4)所表示之化合物之種類,就反應性之觀點而言,較佳 為20℃以上,就抑制反應產物之著色等之觀點而言,較佳為100℃以下。 In step 2, the same solvent as that used in the above reaction can be used. The reaction environment in this step is preferably an inert gas environment such as a nitrogen environment and argon. The temperature of the reaction in this step also depends on the kind of the compound represented by formula (4), and it is preferable from the viewpoint of reactivity. It is 20 ° C or higher, and from the viewpoint of suppressing the coloring of the reaction product, etc., it is preferably 100 ° C or lower.

[彩色濾光片用顏料分散體] [Pigment dispersion for color filters]

本發明之彩色濾光片用顏料分散體含有本發明之分散劑、有機顏料及有機溶劑。 The pigment dispersion for a color filter of the present invention contains the dispersant of the present invention, an organic pigment, and an organic solvent.

<有機顏料> <Organic pigment>

作為本發明中所使用之有機顏料(以下亦簡稱為「顏料」),較佳為較佳地用於彩色濾光片者,例如可列舉偶氮顏料、酞菁顏料、縮合多環顏料、色澱顏料等。 As the organic pigment (hereinafter also simply referred to as "pigment") used in the present invention, it is preferably used in a color filter, and examples thereof include an azo pigment, a phthalocyanine pigment, a condensed polycyclic pigment, and a color Lake pigment and so on.

作為偶氮顏料,可列舉C.I.顏料紅3等不溶性偶氮顏料、C.I.顏料紅48:1等溶性偶氮顏料、C.I.顏料紅144等縮合偶氮顏料。作為酞菁顏料,可列舉C.I.顏料藍15:6等酞菁銅顏料、C.I.顏料綠58等酞菁鋅顏料等。 Examples of the azo pigment include insoluble azo pigments such as C.I. Pigment Red 3, soluble azo pigments such as C.I. Pigment Red 48: 1, and condensed azo pigments such as C.I. Pigment Red 144. Examples of the phthalocyanine pigment include copper phthalocyanine pigments such as C.I. Pigment Blue 15: 6, and zinc phthalocyanine pigments such as C.I. Pigment Green 58.

作為縮合多環顏料,可列舉:C.I.顏料紅177等蒽醌系顏料、C.I.顏料紅123等苝系顏料、C.I.顏料橙43等紫環酮(perinone)系顏料、C.I.顏料紅122等喹吖啶酮系顏料、C.I.顏料紫23等二

Figure TWI680011B_D0029
系顏料、C.I.顏料黃109等異吲哚啉酮系顏料、C.I.顏料橙66等異吲哚啉系顏料、C.I.顏料黃138等喹酞酮系顏料、C.I.顏料黃150等鎳偶氮錯合物系顏料、C.I.顏料紅88等靛藍系顏料、C.I.顏料綠8等金屬錯合物顏料、C.I.顏料紅254、C.I.顏料紅255、C.I.顏料橙71等吡咯并吡咯二酮系顏料等。 Examples of the condensed polycyclic pigment include anthraquinone pigments such as CI Pigment Red 177, fluorene pigments such as CI Pigment Red 123, perinone pigments such as CI Pigment Orange 43, and quinacridines such as CI Pigment Red 122. Ketone pigment, CI Pigment Violet 23, etc.
Figure TWI680011B_D0029
Series pigments, isoindolone pigments such as CI Pigment Yellow 109, isoindoline pigments such as CI Pigment Orange 66, quinophthalone pigments such as CI Pigment Yellow 138, and nickel azo complexes such as CI Pigment Yellow 150 Pigments, indigo pigments such as CI Pigment Red 88, metal complex pigments such as CI Pigment Green 8, pyrrolopyrrole dione pigments such as CI Pigment Red 254, CI Pigment Red 255, and CI Pigment Orange 71.

該等之中,就更有效地表現本發明之效果之觀點而言,式(P1)所表示之吡咯并吡咯二酮系顏料(以下亦稱為「DPP顏料」)。 Among these, from the viewpoint of more effectively expressing the effect of the present invention, a pyrrolopyrrole dione pigment represented by formula (P1) (hereinafter also referred to as a "DPP pigment").

[化29]

Figure TWI680011B_D0030
[Chemical 29]
Figure TWI680011B_D0030

式(P1)中,X11及X12分別獨立地表示氫原子、鹵素原子、或氫原子可被取代之芳香族烴基,Y11及Y12分別獨立地表示氫原子、-SO3H、或-SO3 -Z+,Z+表示陽離子。 In the formula (P1), X 11 and X 12 each independently represent a hydrogen atom, a halogen atom, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted, and Y 11 and Y 12 each independently represent a hydrogen atom, -SO 3 H, or -SO 3 - Z + , Z + represents a cation.

X11及X12較佳為鹵素原子,更佳為選自氯原子及溴原子中之至少一種。Y11及Y12較佳為氫原子。 X 11 and X 12 are preferably a halogen atom, more preferably at least one selected from a chlorine atom and a bromine atom. Y 11 and Y 12 are preferably a hydrogen atom.

作為DPP顏料,就更有效地表現本發明之效果之觀點而言,進而較佳為於式(P1)中,Y11及Y12為氫原子,X11及X12為氯原子(C.I.顏料紅254:以下亦稱為「PR254」)或溴原子。 As a DPP pigment, from the viewpoint of more effectively expressing the effects of the present invention, it is further preferred that in the formula (P1), Y 11 and Y 12 are hydrogen atoms, and X 11 and X 12 are chlorine atoms (CI Pigment Red 254: hereinafter also referred to as "PR254") or a bromine atom.

作為DPP顏料之市售品,可列舉:BASF日本股份有限公司製造之商品名「Irgaphor Red」系列之「S 3610 CF」(舊「B-CF」)、「S 3612 CF」(舊「BK-CF」)、「S 3611 CF」(舊「BT-CF」)、「S 3621 CF」;「Irgazin DPP Red」系列之「L 3660 HD」(舊「BO」)、「BL」;「Cromophtal DPP Red」系列之「BP」、「BOC」;Clariant股份有限公司製造之「HOSTAPERM RED D2B」系列之「COF01」、「COFLV3781」;大日精化工業股份有限公司製造之「CHROMOFINE RED 6156EC」等。 Examples of commercially available DPP pigments include "S 3610 CF" (formerly "B-CF") and "S 3612 CF" (formerly "BK-" CF ")," S 3611 CF "(formerly" BT-CF ")," S 3621 CF ";" L 3660 HD "(formerly" BO ")," BL "of the" Irgazin DPP Red "series;" Cromophtal DPP "BP" and "BOC" of the "Red" series; "COF01" and "COFLV3781" of the "HOSTAPERM RED D2B" series manufactured by Clariant Co., Ltd .; "CHROMOFINE RED 6156EC" manufactured by Dainichi Fine Chemical Industry Co., Ltd.

就光學特性之提高之觀點而言,有機顏料較理想的是使用使其平均一次粒徑成為較佳為100nm以下、進而較佳為20~60nm之微粒化處理品。有機顏料之平均一次粒徑可藉由自電子顯微鏡照片直接測量一次粒子之大小之方法而求出。具體而言,將各個一次粒子之與長 軸徑正交之徑設為短軸徑,測量短軸徑與長軸徑而將其平均值設為該粒子之粒徑,針對100個以上之粒子,將各個粒子之體積與以粒徑為一邊之立方體近似而求出體積平均粒徑,將其設為平均一次粒徑。 From the viewpoint of improvement of optical characteristics, it is preferable to use a micronized product in which the average primary particle diameter is preferably 100 nm or less, and more preferably 20 to 60 nm, as the organic pigment. The average primary particle diameter of the organic pigment can be obtained by a method of directly measuring the size of the primary particles from an electron microscope photograph. Specifically, the sum of the lengths of each primary particle The diameter of the orthogonal axis is set to the short axis diameter. The short axis diameter and the long axis diameter are measured and the average value is set to the particle diameter of the particle. For more than 100 particles, the volume of each particle and the particle diameter are taken as The cube on one side is approximated to obtain the volume average particle diameter, and this is set as the average primary particle diameter.

上述有機顏料可單獨使用或組合兩種以上使用。 These organic pigments can be used alone or in combination of two or more.

就提高有機顏料與有機溶劑之親和性,提高分散性及保存穩定性之觀點而言,亦可使用對有機顏料之表面藉由樹脂或高分子、顏料衍生物等預先實施了表面處理之顏料。 From the viewpoint of improving the affinity between organic pigments and organic solvents, improving dispersibility, and storage stability, it is also possible to use pigments that have been surface-treated with a resin, polymer, or pigment derivative in advance on the surface of the organic pigment.

關於本發明之有機顏料中之DPP顏料之含量,就使顏色特性最佳化之觀點而言,相對於顏料之總量,較佳為20質量%以上,更佳為30質量%以上,進而較佳為50質量%以上,進而更佳為60質量%以上,且較佳為100質量%以下,更佳為90質量%以下。 Regarding the content of the DPP pigment in the organic pigment of the present invention, from the viewpoint of optimizing color characteristics, it is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably It is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 100% by mass or less, and even more preferably 90% by mass or less.

<有機溶劑> <Organic solvent>

本發明之顏料分散體含有有機溶劑。就提高顏料之分散性,並且提高與彩色濾光片中所使用之黏合劑成分等之相溶性,兼顧所獲得之硬化膜之基板密接性與顯影性之觀點而言,有機溶劑較佳為醚系有機溶劑。 The pigment dispersion of the present invention contains an organic solvent. The organic solvent is preferably an ether from the viewpoints of improving the dispersibility of the pigment, improving the compatibility with the binder components used in the color filter, and taking into consideration the substrate adhesion and developability of the obtained cured film. Department of organic solvents.

就顏料分散體及著色組合物之操作容易性之觀點而言,有機溶劑於25℃下之黏度(單位:mPa‧s)較佳為0.8以上,更佳為0.9以上,進而較佳為1.0以上,就提高使用顏料分散體之硬化膜之對比度之觀點及使著色組合物易於塗敷之觀點而言,較佳為5.0以下,更佳為3.5以下,進而較佳為2.0以下。 From the viewpoint of ease of handling of the pigment dispersion and the coloring composition, the viscosity (unit: mPa · s) of the organic solvent at 25 ° C is preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 1.0 or more. From the viewpoint of improving the contrast of the cured film using the pigment dispersion and the viewpoint of making the coloring composition easy to apply, it is preferably 5.0 or less, more preferably 3.5 or less, and even more preferably 2.0 or less.

就與顏料表面之適度之親和性,低表面張力,提高與彩色濾光片中所使用之黏合劑成分等之相溶性,提高所獲得之硬化膜之對比度之觀點而言,有機溶劑之SP值(單位:(cal/cm3)1/2)較佳為7.5以上,更佳為8.0以上,進而較佳為8.5以上,且較佳為10.5以下,更佳為9.5以下,進而較佳為9.0以下。SP值係藉由Fedors之方法[Robert F.Fedors, Polymer Engineering and Science,14,147-154(1974)]而求出。 From the viewpoints of moderate affinity with the pigment surface, low surface tension, improving compatibility with the binder components used in color filters, and improving the contrast of the obtained cured film, the SP value of the organic solvent (Unit: (cal / cm 3 ) 1/2 ) is preferably 7.5 or more, more preferably 8.0 or more, still more preferably 8.5 or more, and preferably 10.5 or less, more preferably 9.5 or less, and even more preferably 9.0 the following. The SP value is obtained by the method of Fedors [Robert F. Fedors, Polymer Engineering and Science, 14,147-154 (1974)].

就作業安全性之觀點而言,有機溶劑之沸點較佳為50℃以上,更佳為100℃以上,進而較佳為120℃以上,就塗膜形成時之溶劑去除之容易性之觀點而言,較佳為300℃以下,更佳為260℃以下,進而較佳為200℃以下。 From the viewpoint of work safety, the boiling point of the organic solvent is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 120 ° C. or higher. From the viewpoint of ease of solvent removal during coating film formation It is preferably 300 ° C or lower, more preferably 260 ° C or lower, and even more preferably 200 ° C or lower.

作為有機溶劑,就提高分散特性之觀點而言,較佳為(聚)伸烷基二醇單烷基醚乙酸酯、(聚)伸烷基二醇單烷基醚丙酸酯及(聚)伸烷基二醇二烷基醚,更佳為(聚)伸烷基二醇單烷基醚乙酸酯。於本說明書中,所謂「(聚)伸烷基二醇」係指選自伸烷基二醇及聚伸烷基二醇中之至少一種。 As the organic solvent, (poly) alkylene glycol monoalkyl ether acetate, (poly) alkylene glycol monoalkyl ether propionate, and (poly) The alkylene glycol dialkyl ether is more preferably a (poly) alkylene glycol monoalkyl ether acetate. In the present specification, the "(poly) alkylene glycol" means at least one selected from the group consisting of an alkylene glycol and a polyalkylene glycol.

作為(聚)伸烷基二醇單烷基醚乙酸酯之例,可列舉:乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、PGMEA、丙二醇單***乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、BCA等。其中,就顏料之分散特性之觀點而言,較佳為選自PGMEA(沸點:146℃,25℃下之黏度:1.1mPa‧s,SP值:8.73)及BCA(沸點:247℃,25℃下之黏度:3.1mPa‧s,SP值:8.94)中之至少一種,更佳為PGMEA。 Examples of the (poly) alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate. , PGMEA, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, BCA, and the like. Among them, from the viewpoint of the dispersion characteristics of the pigment, it is preferably selected from PGMEA (boiling point: 146 ° C, viscosity at 25 ° C: 1.1 mPa · s, SP value: 8.73) and BCA (boiling point: 247 ° C, 25 ° C) Lower viscosity: 3.1 mPa · s, SP value: 8.94), more preferably PGMEA.

<鹼可溶性樹脂> <Alkali soluble resin>

本發明之彩色濾光片用顏料分散體較佳為進而含有鹼可溶性樹脂。鹼可溶性樹脂通常係用以於藉由光微影法製造彩色濾光片時使非曝光部溶解於顯影液中。 The pigment dispersion for a color filter of the present invention preferably further contains an alkali-soluble resin. The alkali-soluble resin is generally used to dissolve a non-exposed portion in a developing solution when a color filter is manufactured by a photolithography method.

作為鹼可溶性樹脂,可列舉負型抗蝕劑中通常使用者,只要為於鹼性水溶液中具有可溶性者、即於0.05質量%氫氧化四甲基銨水溶液中於20℃下溶解1質量%以上者即可。 Examples of the alkali-soluble resin include ordinary users in negative resists, as long as they are soluble in an alkaline aqueous solution, that is, 1% by mass or more is dissolved in a 0.05% by mass tetramethylammonium hydroxide aqueous solution at 20 ° C. That's all.

鹼可溶性樹脂較佳為包含源自(甲基)丙烯酸酯之結構單元(as1)與源自具有酸基之單體之結構單元(as2)之共聚物。鹼可溶性樹脂亦可進 而包含源自其他可進行共聚合之單體之結構單元(as3)。 The alkali-soluble resin is preferably a copolymer containing a structural unit (as1) derived from a (meth) acrylate and a structural unit (as2) derived from a monomer having an acid group. Alkali soluble resin is also available It contains structural units (as3) derived from other copolymerizable monomers.

作為(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異

Figure TWI680011B_D0031
基酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸1-金剛烷基酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-二甲胺基乙酯、(甲基)丙烯酸縮水甘油酯,較佳為(甲基)丙烯酸苄酯及(甲基)丙烯酸甲酯。 Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) N-butyl acrylate, second butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (methyl) ) Phenoxyethyl acrylate, cyclohexyl (meth) acrylate, iso (meth) acrylate
Figure TWI680011B_D0031
Ester, dicyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2-dimethylaminoethyl ester and glycidyl (meth) acrylate are preferably benzyl (meth) acrylate and methyl (meth) acrylate.

作為具有酸基之單體,例如可列舉選自(甲基)丙烯酸、丙烯酸之二聚物、伊康酸、丁烯酸、順丁烯二酸、反丁烯二酸及該等之酸酐中之至少一種。 Examples of the monomer having an acid group include those selected from (meth) acrylic acid, dimers of acrylic acid, itaconic acid, butenoic acid, maleic acid, fumaric acid, and anhydrides thereof At least one of them.

作為其他可進行共聚合之單體,例如可列舉選自α-羥基甲基丙烯酸之醚二聚物、乙烯基乙酸、2,2'-氧基雙(亞甲基)雙-2-丙烯酸酯、苯乙烯、γ-甲基苯乙烯、二官能丙烯酸酯、N-乙烯基-2-吡咯啶酮、N-甲基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺及N-苯基順丁烯二醯亞胺中之至少一種。 Examples of other copolymerizable monomers include ether dimers selected from α-hydroxymethacrylic acid, vinylacetic acid, and 2,2′-oxybis (methylene) bis-2-acrylate. , Styrene, γ-methylstyrene, difunctional acrylate, N-vinyl-2-pyrrolidone, N-methylcis-butenedifluorene imine, N-cyclohexylcis-butenedifluorene imine At least one of N-benzyl maleimide diimide and N-phenyl maleimide diimide.

於本說明書中,所謂「(甲基)丙烯酸酯」係指選自丙烯酸酯及甲基丙烯酸酯中之至少一種,所謂「(甲基)丙烯酸」係指選自丙烯酸及甲基丙烯酸中之至少一種。 In the present specification, the "(meth) acrylate" refers to at least one selected from acrylate and methacrylate, and the "(meth) acrylic" refers to at least one selected from acrylic and methacrylic acid. One.

作為本發明中所使用之鹼可溶性樹脂,就維持顏料於硬化膜中之分散,提高對比度之觀點而言,較佳為包含源自(甲基)丙烯酸酯之結構單元與源自(甲基)丙烯酸之結構單元之共聚物。 As the alkali-soluble resin used in the present invention, from the viewpoint of maintaining the dispersion of the pigment in the cured film and improving the contrast, it is preferable to include a structural unit derived from (meth) acrylate and a source derived from (meth) Copolymer of acrylic acid structural units.

作為上述共聚物,較佳為選自包含源自(甲基)丙烯酸苄酯之結構 單元與源自(甲基)丙烯酸之結構單元之共聚物及包含源自(甲基)丙烯酸甲酯之結構單元與源自(甲基)丙烯酸之結構單元之共聚物中之至少一種,更佳為包含源自(甲基)丙烯酸苄酯之結構單元與源自(甲基)丙烯酸之結構單元之共聚物。 The above copolymer is preferably selected from a structure containing benzyl (meth) acrylate A copolymer of a unit and a structural unit derived from (meth) acrylic acid and a copolymer including a structural unit derived from methyl (meth) acrylate and a structural unit derived from (meth) acrylic acid, more preferably A copolymer comprising a structural unit derived from benzyl (meth) acrylate and a structural unit derived from (meth) acrylic acid.

作為鹼可溶性樹脂,就於曝光時與下述多官能單體反應而使顯影性提高之觀點而言,亦可較佳地列舉於上述共聚物中進而導入有反應性基之樹脂。作為反應性基,就製造容易性之觀點而言,更佳為選自縮水甘油基及乙烯性不飽和基中之至少一種。作為此種鹼可溶性樹脂之市售品,例如可列舉:日本觸媒股份有限公司製造之「Acrycure AXD」系列之「RD-KA-501」、「RD-KA-502」、「BX-KA-01」、「BX-KA-02」;東亞合成股份有限公司製造之「ARONIX」系列之「M6100」、「M7100」、「M8030」。 As the alkali-soluble resin, from the viewpoint of improving the developability by reacting with a polyfunctional monomer described below during exposure, a resin in which a reactive group is further introduced into the copolymer may also be mentioned. The reactive group is more preferably at least one selected from a glycidyl group and an ethylenically unsaturated group in terms of ease of production. Examples of commercially available products of such alkali-soluble resins include "RD-KA-501", "RD-KA-502", and "BX-KA-" of the "Acrycure AXD" series manufactured by Japan Catalyst Corporation. 01 "," BX-KA-02 ";" M6100 "," M7100 "," M8030 "of the" ARONIX "series manufactured by Toa Synthesis Corporation.

鹼可溶性樹脂中,源自丙烯酸酯之結構單元(as1)之量較佳為30質量%以上,更佳為50質量%以上,進而較佳為60質量%以上,且較佳為90質量%以下,更佳為80質量%以下,進而較佳為70質量%以下。 In the alkali-soluble resin, the amount of the structural unit (as1) derived from the acrylate is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and preferably 90% by mass or less , More preferably 80% by mass or less, still more preferably 70% by mass or less.

鹼可溶性樹脂中,源自具有酸基之單體之結構單元(as2)之量較佳為5質量%以上,更佳為10質量%以上,進而較佳為20質量%以上,且較佳為50質量%以下,更佳為40質量%以下,進而較佳為30質量%以下。 In the alkali-soluble resin, the amount of the structural unit (as2) derived from a monomer having an acid group is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 20 mass% or more, and more preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

鹼可溶性樹脂中,源自其他可進行共聚合之單體之結構單元(as3)之量較佳為5質量%以上,更佳為10質量%以上,進而較佳為20質量%以上,且較佳為50質量%以下,更佳為40質量%以下,進而較佳為30質量%以下。 In the alkali-soluble resin, the amount of the structural unit (as3) derived from other copolymerizable monomers is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. It is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

結構單元(as1)與結構單元(as2)之莫耳比[(as1)/(as2)]較佳為90/10~50/50,更佳為80/20~60/40。 The molar ratio [(as1) / (as2)] of the structural unit (as1) and the structural unit (as2) is preferably 90/10 to 50/50, and more preferably 80/20 to 60/40.

就塗膜之硬化性之觀點而言,鹼可溶性樹脂之重量平均分子量較佳為5,000以上,更佳為10,000以上,就顯影性之觀點而言,較佳為50,000以下,更佳為40,000以下,進而較佳為20,000以下。 From the viewpoint of the hardenability of the coating film, the weight-average molecular weight of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, and from the viewpoint of developability, 50,000 or less, more preferably 40,000 or less, It is more preferably 20,000 or less.

就分散性及顯影性之觀點而言,鹼可溶性樹脂之酸值(單位:mgKOH/g)較佳為50以上,更佳為80以上,就塗膜之硬化性之觀點而言,較佳為260以下,更佳為240以下,進而較佳為220以下。 From the viewpoint of dispersibility and developability, the acid value (unit: mgKOH / g) of the alkali-soluble resin is preferably 50 or more, and more preferably 80 or more. From the viewpoint of the hardening property of the coating film, it is more preferable 260 or less, more preferably 240 or less, and still more preferably 220 or less.

<順丁烯二醯亞胺化合物> <Cibutenediamidoimine compound>

就耐熱性之觀點而言,本發明之分散體較佳為含有具有2個以上順丁烯二醯亞胺基之芳香族化合物(以下亦稱為「順丁烯二醯亞胺化合物」)。 From the viewpoint of heat resistance, the dispersion of the present invention preferably contains an aromatic compound having two or more maleimide groups (hereinafter also referred to as a "maleimide compound").

順丁烯二醯亞胺化合物係用以於使著色組合物硬化後曝露於高溫條件時防止顏料之昇華,提高硬化膜之耐熱性。 The maleimide compound is used to prevent the sublimation of the pigment and improve the heat resistance of the cured film when the coloring composition is cured and exposed to high temperature conditions.

本發明中所使用之順丁烯二醯亞胺化合物具有至少一個芳香環。 The maleimide compound used in the present invention has at least one aromatic ring.

作為順丁烯二醯亞胺化合物,可列舉選自1,3-苯二順丁烯二醯亞胺、1,4-苯二順丁烯二醯亞胺、4-甲基-1,3-苯二順丁烯二醯亞胺、4,4'-二苯基碸雙順丁烯二醯亞胺、雙-(3-乙基-5-甲基-4-順丁烯二醯亞胺苯基)甲烷及2,2-雙-[4-(4-順丁烯二醯亞胺苯氧基)苯基]丙烷中之至少一種。 Examples of the maleimide compound include 1,3-benzenedimaleimide diimine, 1,4-benzenedimaleimide diimide, and 4-methyl-1,3. -Phenylenedibutylene difluorene imine, 4,4'-diphenylfluorene biscisene difluorene imine, bis- (3-ethyl-5-methyl-4-cis butene difluorene At least one of aminophenyl) methane and 2,2-bis- [4- (4-cis-butenediamidophenoxy) phenyl] propane.

作為順丁烯二醯亞胺化合物,就於溶劑中之溶解性之觀點及提高耐熱性亦提高基板密接性之觀點而言,較佳為苯二順丁烯二醯亞胺,更佳為N,N'-1,3-苯二順丁烯二醯亞胺(以下亦稱為「PDM」)。 As the maleimide compound, from the viewpoint of solubility in a solvent and the viewpoint of improving heat resistance and improving substrate adhesion, phenylenediimide is preferred, and N is more preferred. N'-1,3-phenylenedibutene difluorene imine (hereinafter also referred to as "PDM").

<顏料分散體之製造方法> <Method for Manufacturing Pigment Dispersion>

就製造平均粒徑較小、低黏度、保存穩定性亦優異之彩色濾光片用顏料分散體之觀點而言,本發明之顏料分散體之製造方法較佳為具有下述步驟。 From the viewpoint of producing a pigment dispersion for a color filter having a small average particle size, low viscosity, and excellent storage stability, the method for producing a pigment dispersion of the present invention preferably has the following steps.

使本發明之分散劑、有機顏料及有機溶劑、視需要之鹼可溶性樹脂、順丁烯二醯亞胺化合物分散之步驟。 A step of dispersing the dispersant, the organic pigment and the organic solvent, the alkali-soluble resin, and the maleimide compound as needed in the present invention.

分散中所使用之混合分散機可使用公知之各種分散機。例如可列舉:均質攪拌機等高速攪拌混合裝置、輥磨機、捏合機、擠壓機等混練機、高壓均質機等高壓式分散機、塗料振盪機、珠磨機等介質式分散機等。該等裝置亦可組合複數種使用。 As the mixing and dispersing machine used for the dispersing, various known dispersing machines can be used. Examples include a high-speed stirring and mixing device such as a homomixer, a kneader such as a roll mill, a kneader, an extruder, a high-pressure disperser such as a high-pressure homogenizer, a medium-type disperser such as a paint shaker, and a bead mill. These devices can also be used in combination.

該等之中,就使有機顏料均勻地混合於醚系有機溶劑中之觀點而言,較佳為均質攪拌機等高速攪拌混合裝置、塗料振盪機或珠磨機等介質式分散機。作為市售之介質式分散機,可列舉壽工業股份有限公司製造之「Ultra Apex Mill」、淺田鐵工股份有限公司製造之「Pico Mill」等。 Among these, from the viewpoint of uniformly mixing the organic pigment in the ether-based organic solvent, a high-speed stirring mixing device such as a homomixer, a media-type disperser such as a paint shaker, or a bead mill is preferred. Examples of commercially available media-type dispersers include "Ultra Apex Mill" manufactured by Shou Industry Co., Ltd. and "Pico Mill" manufactured by Asada Iron Works Co., Ltd.

於使用介質式分散機之情形時,作為分散步驟中所使用之介質之材質,較佳為氧化鋯、氧化鈦等陶瓷、聚乙烯、尼龍等高分子材料、金屬等,就磨耗性之觀點而言,較佳為氧化鋯。作為介質之直徑,就將有機顏料中之凝聚粒子壓碎之觀點而言,較佳為0.003mm以上,更佳為0.01mm以上,且較佳為0.5mm以下,更佳為0.4mm以下。 When a media-type disperser is used, as the material of the media used in the dispersing step, ceramics such as zirconia, titanium oxide, polymer materials such as polyethylene, nylon, and metals are preferred. In other words, zirconia is preferred. The diameter of the medium is preferably 0.003 mm or more, more preferably 0.01 mm or more, and more preferably 0.5 mm or less, and more preferably 0.4 mm or less from the viewpoint of crushing aggregated particles in the organic pigment.

就將有機顏料充分微細化之觀點而言,分散時間較佳為0.3小時以上,更佳為1小時以上,就顏料分散體之製造效率之觀點而言,較佳為200小時以下,更佳為50小時以下。 From the viewpoint of sufficiently miniaturizing the organic pigment, the dispersion time is preferably 0.3 hours or more, more preferably 1 hour or more, and from the viewpoint of production efficiency of the pigment dispersion, preferably 200 hours or less, more preferably Less than 50 hours.

本製造法之上述分散步驟中之分散方法可將上述混合物利用一次分散而獲得目標顏料分散體,但就獲得更微細且均勻之顏料分散體之觀點而言,較佳為使用介質將上述混合物預分散後,進而使用較上述預分散步驟小之介質進行正式分散。 The dispersing method in the dispersing step of the present manufacturing method can obtain the target pigment dispersion by dispersing the above-mentioned mixture in one time, but from the viewpoint of obtaining a finer and more uniform pigment dispersion, it is preferable to use a medium to preliminarily disperse the above-mentioned mixture. After dispersing, a medium smaller than the pre-dispersing step is used for formal dispersion.

(預分散) (Pre-dispersed)

預分散中所使用之混合分散機可使用上述各種分散機,但就使 有機顏料均勻地混合於醚系有機溶劑中之觀點而言,較佳為塗料振盪機或珠磨機等介質式分散機。 As the mixing and dispersing machine used in the pre-dispersion, the above-mentioned various dispersing machines can be used. From the viewpoint of uniformly mixing the organic pigment in the ether-based organic solvent, a media-type disperser such as a paint shaker or a bead mill is preferred.

作為預分散步驟中所使用之介質之直徑,就將有機顏料中之凝聚粒子壓碎之觀點而言,較佳為0.1mm以上,較佳為0.5mm以下,更佳為0.4mm以下。 As the diameter of the medium used in the pre-dispersing step, from the viewpoint of crushing the agglomerated particles in the organic pigment, it is preferably 0.1 mm or more, preferably 0.5 mm or less, and more preferably 0.4 mm or less.

就將有機顏料中之凝聚粒子壓碎之觀點而言,預分散步驟中之分散時間較佳為0.1小時以上,更佳為0.5小時以上,進而較佳為1小時以上,就顏料分散體之製造效率之觀點而言,較佳為10小時以下,更佳為5小時以下,進而較佳為4小時以下。 From the viewpoint of crushing the agglomerated particles in the organic pigment, the dispersion time in the pre-dispersion step is preferably 0.1 hours or more, more preferably 0.5 hours or more, and further preferably 1 hour or more. From the viewpoint of efficiency, it is preferably 10 hours or less, more preferably 5 hours or less, and still more preferably 4 hours or less.

(正式分散) (Formally dispersed)

正式分散係將預分散中所獲得之預分散液進行分散處理之步驟,為了將上述預分散步驟中所獲得之混合物進一步微細化而進行,就將有機顏料微細化之觀點而言,較佳為使用介質式分散機,亦可併用上述高壓式分散機。 Formal dispersion is a step of dispersing the pre-dispersion liquid obtained in the pre-dispersion. In order to further refine the mixture obtained in the pre-dispersion step, it is preferable from the viewpoint of miniaturizing the organic pigment. A media-type disperser may be used, or the above-mentioned high-pressure disperser may be used in combination.

作為正式分散步驟中所使用之介質之直徑,就將有機顏料微細化之觀點而言,較佳為未達0.1mm,更佳為0.08mm以下,進而較佳為0.07mm以下,就將介質與顏料分離之觀點而言,較佳為0.003mm以上,進而較佳為0.01mm以上。 As the diameter of the medium used in the formal dispersion step, from the viewpoint of miniaturizing the organic pigment, it is preferably less than 0.1 mm, more preferably 0.08 mm or less, and still more preferably 0.07 mm or less. From a viewpoint of pigment separation, 0.003 mm or more is preferable, and 0.01 mm or more is more preferable.

就將有機顏料充分微細化之觀點而言,正式分散之分散時間較佳為2小時以上,更佳為3小時以上,就顏料分散體之製造效率之觀點而言,較佳為200小時以下,更佳為50小時以下。 From the viewpoint of sufficiently miniaturizing the organic pigment, the dispersion time for formal dispersion is preferably 2 hours or more, more preferably 3 hours or more, and from the viewpoint of production efficiency of the pigment dispersion, preferably 200 hours or less, More preferably, it is 50 hours or less.

<顏料分散體之組成及物性> <Composition and physical properties of pigment dispersion>

就獲得良好之著色性之觀點而言,本發明之顏料分散體中之有機顏料之含量較佳為3質量%以上,更佳為5質量%以上,進而較佳為10質量%以上,就縮小顏料分散體中之平均粒徑之觀點及獲得較低黏度之顏料分散體之觀點而言,較佳為30質量%以下,更佳為20質量% 以下,進而較佳為16質量%以下。 From the standpoint of obtaining good coloring properties, the content of the organic pigment in the pigment dispersion of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. From the viewpoint of the average particle diameter in the pigment dispersion and the viewpoint of obtaining a pigment dispersion with a lower viscosity, the content is preferably 30% by mass or less, and more preferably 20% by mass. Hereinafter, it is more preferably 16% by mass or less.

就提高顏料分散體之保存穩定性之觀點及提高對比度之觀點而言,本發明之顏料分散體中之分散劑相對於顏料之質量比[分散劑/顏料]較佳為0.1以上,更佳為0.2以上,進而較佳為0.3以上,就增加黏合劑成分之調配量之觀點及提高塗膜之物性之觀點而言,較佳為1.5以下,更佳為1.2以下,進而較佳為0.9以下,進而更佳為0.5以下。 From the viewpoint of improving the storage stability of the pigment dispersion and the viewpoint of improving the contrast, the mass ratio of the dispersant to the pigment in the pigment dispersion of the present invention [dispersant / pigment] is preferably 0.1 or more, more preferably 0.2 or more, and more preferably 0.3 or more. From the viewpoint of increasing the blending amount of the binder component and the viewpoint of improving the physical properties of the coating film, it is preferably 1.5 or less, more preferably 1.2 or less, and still more preferably 0.9 or less. Furthermore, it is more preferably 0.5 or less.

就分散體之低黏度化之觀點而言,本發明之顏料分散體中之有機溶劑之含量較佳為30質量%以上,更佳為50質量%以上,進而較佳為60質量%以上,就獲得良好之著色性之觀點而言,較佳為95質量%以下,更佳為90質量%以下。 From the viewpoint of reducing the viscosity of the dispersion, the content of the organic solvent in the pigment dispersion of the present invention is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. From the viewpoint of obtaining good coloring properties, it is preferably 95% by mass or less, and more preferably 90% by mass or less.

本發明之顏料分散體中之鹼可溶性樹脂之含量較佳為1質量%以上,更佳為2質量%以上,進而較佳為3質量%以上,且較佳為15質量%以下,更佳為12質量%以下,進而較佳為9質量%以下。 The content of the alkali-soluble resin in the pigment dispersion of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and more preferably 15% by mass or less, more preferably 12% by mass or less, more preferably 9% by mass or less.

本發明之顏料分散體中之順丁烯二醯亞胺化合物之含量相對於顏料100質量份,較佳為0.2質量份以上,更佳為1質量份以上,進而較佳為3質量份以上,且較佳為20質量%以下,更佳為15質量%以下,進而較佳為10質量%以下。 The content of the maleimide compound in the pigment dispersion of the present invention is preferably 0.2 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more relative to 100 parts by mass of the pigment. The content is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

為了獲得作為彩色濾光片用有色材料良好之對比度,本發明之顏料分散體中之平均粒徑較佳為200nm以下,更佳為100nm以下,進而較佳為90nm以下,進而較佳為70nm以下,且較佳為20nm以上。將顏料分散體於一定條件、例如於室溫下保存一週時之平均粒徑(以下亦稱為「保存後平均粒徑」)之較佳範圍與上述範圍相同。平均粒徑及保存後平均粒徑之測定係依據實施例中所記載之方法。 In order to obtain good contrast as a colored material for a color filter, the average particle diameter in the pigment dispersion of the present invention is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 90 nm or less, and even more preferably 70 nm or less. And preferably 20 nm or more. A preferable range of the average particle diameter (hereinafter also referred to as "average particle diameter after storage") when the pigment dispersion is stored under certain conditions, for example, at room temperature for one week, is the same as the above range. The average particle diameter and the average particle diameter after storage were measured according to the methods described in the examples.

就塗膜之製造容易性之觀點而言,本發明之顏料分散體於顏料濃度10質量%時於20℃下之黏度(單位:mPa‧s)較佳為2以上,更佳為3以上,進而較佳為5以上,就塗膜之平滑性及光學特性之觀點而 言,較佳為200以下,更佳為50以下,進而較佳為20以下,進而較佳為15以下。將顏料分散體於一定條件、例如於室溫下保存一週時之20℃之黏度(以下亦稱為「保存後黏度」)之較佳範圍與上述範圍相同。黏度及保存後黏度之測定係依據實施例中所記載之方法。 From the viewpoint of the ease of production of the coating film, the viscosity (unit: mPa‧s) of the pigment dispersion of the present invention at 20 ° C at a pigment concentration of 10% by mass is preferably 2 or more, more preferably 3 or more, It is more preferably 5 or more, from the viewpoint of smoothness and optical characteristics of the coating film. In other words, it is preferably 200 or less, more preferably 50 or less, still more preferably 20 or less, and still more preferably 15 or less. The preferable range of the viscosity of the pigment dispersion (for example, "viscosity after storage") at 20 ° C when stored at room temperature for one week at the same conditions is the same as the above range. The viscosity and the viscosity after storage are measured according to the methods described in the examples.

[彩色濾光片用著色組合物] [Coloring composition for color filter]

本發明之彩色濾光片用著色組合物(以下亦稱為「著色組合物」)含有顏料分散體、多官能單體及光聚合起始劑。著色組合物較佳為進而含有鹼可溶性樹脂。 The coloring composition for color filters of the present invention (hereinafter also referred to as "coloring composition") contains a pigment dispersion, a polyfunctional monomer, and a photopolymerization initiator. The coloring composition preferably further contains an alkali-soluble resin.

較佳之鹼可溶性樹脂與上述者相同。 Preferred alkali-soluble resins are the same as those described above.

著色組合物中之鹼可溶性樹脂之含量於彩色濾光片用著色組合物之除溶劑以外之有效成分中較佳為10質量%以上且40質量%以下。 The content of the alkali-soluble resin in the coloring composition is preferably 10% by mass or more and 40% by mass or less in an active ingredient other than the solvent of the coloring composition for a color filter.

(多官能單體) (Multifunctional monomer)

多官能單體較佳為具有複數個聚合性基,更佳為具有2個以上乙烯性不飽和雙鍵。作為多官能單體,可列舉具有2個以上乙烯性不飽和鍵之(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯醯胺、烯丙基化合物、乙烯酯等。作為多官能單體,較佳為具有2個以上乙烯性不飽和雙鍵之丙烯酸酯,更佳為二季戊四醇六丙烯酸酯(以下亦稱為「DPHA」)。 The polyfunctional monomer preferably has a plurality of polymerizable groups, and more preferably has two or more ethylenically unsaturated double bonds. Examples of the polyfunctional monomer include (meth) acrylate, (meth) acrylic acid urethane, (meth) acrylamidonium, allyl compound, and ethylene having two or more ethylenically unsaturated bonds. Esters, etc. The polyfunctional monomer is preferably an acrylate having two or more ethylenically unsaturated double bonds, and more preferably dipentaerythritol hexaacrylate (hereinafter also referred to as "DPHA").

多官能單體之含量於彩色濾光片用著色組合物之除溶劑以外之有效成分中較佳為5質量%以上且30質量%以下。 The content of the polyfunctional monomer is preferably 5% by mass or more and 30% by mass or less in an active ingredient other than the solvent of the coloring composition for a color filter.

(光聚合起始劑) (Photopolymerization initiator)

作為光聚合起始劑,可列舉:芳香族酮類、咯吩二聚物、安息香、安息香醚類、多鹵化物類等。作為光聚合起始劑,較佳為選自4,4'-雙(二乙基胺基)二苯甲酮與2-(鄰氯苯基)-4,5-二苯基咪唑二聚物之組合、4-[對-N,N-二(乙氧基羰基甲基)-2,6-二(三氯甲基)-均三

Figure TWI680011B_D0032
]、2-甲基-4'-(甲硫基)-2-嗎啉基苯丙酮、2-(4-甲基苄基)-2-(二甲胺基)-1-(4- 嗎啉基苯基)丁烷-1-酮(以下亦稱為「MBz-MPB」)及2-[4-(甲硫基)苯甲醯基]-2-(4-嗎啉基)丙烷(以下亦稱為「MTB-MP」)中之至少一種,更佳為選自MBz-MPB及MTB-MP中之至少一種。 Examples of the photopolymerization initiator include aromatic ketones, rophene dimers, benzoin, benzoin ethers, polyhalides, and the like. As the photopolymerization initiator, a dimer selected from 4,4'-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole is preferred. Combination, 4- [p-N, N-bis (ethoxycarbonylmethyl) -2,6-bis (trichloromethyl) -mesanthine
Figure TWI680011B_D0032
], 2-methyl-4 '-(methylthio) -2-morpholinyl phenylacetone, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-? (Phenylphenyl) butane-1-one (hereinafter also referred to as "MBz-MPB") and 2- [4- (methylthio) benzylfluorenyl] -2- (4-morpholinyl) propane ( It is also hereinafter referred to as "MTB-MP"), more preferably at least one selected from MBz-MPB and MTB-MP.

光聚合起始劑之含量於彩色濾光片用著色組合物之除溶劑以外之有效成分中較佳為0.2質量%以上且20質量%以下。 The content of the photopolymerization initiator is preferably 0.2% by mass or more and 20% by mass or less in the active ingredient other than the solvent of the coloring composition for a color filter.

作為著色組合物之其他成分,可列舉多官能低聚物、單官能之單體及增感劑等。上述鹼可溶性樹脂、多官能單體、光聚合起始劑、進而多官能低聚物、單官能之單體及增感劑等黏合劑成分可單獨使用或組合兩種以上使用。黏合劑成分之含量於彩色濾光片用著色組合物之除溶劑以外之有效成分中較佳為20質量%以上且80質量%以下。 Examples of other components of the coloring composition include polyfunctional oligomers, monofunctional monomers, and sensitizers. The binder components such as the alkali-soluble resin, polyfunctional monomer, photopolymerization initiator, and further polyfunctional oligomer, monofunctional monomer, and sensitizer can be used alone or in combination of two or more. The content of the binder component is preferably 20% by mass or more and 80% by mass or less of the active ingredients other than the solvent of the coloring composition for color filters.

[彩色濾光片] [Color filter]

本發明之著色組合物係用以製造彩色濾光片。 The coloring composition of the present invention is used for manufacturing a color filter.

於彩色濾光片之製造方法中,較佳為具有將本案發明之著色組合物塗佈於基板上並進行光硬化、顯影而獲得塗膜之步驟(F-1)、將上述步驟(F-1)中所獲得之塗膜加熱至200~300℃而獲得硬化膜之步驟(F-2)。 In the method for manufacturing a color filter, it is preferable to have a step (F-1) of applying the coloring composition of the present invention on a substrate, photocuring and developing to obtain a coating film, and the step (F- Step (F-2) of obtaining the cured film by heating the coating film obtained in 1) to 200 to 300 ° C.

步驟(F-1)中之塗佈較佳為於玻璃基板上利用輥式塗佈機、狹縫式塗佈機、噴霧、棒式塗佈機、敷料器、旋轉塗佈機、浸漬塗佈機、噴墨、或網版印刷進行塗佈。於塗佈後,就將溶劑去除而獲得均勻之膜厚之塗膜之觀點而言,較佳為水平靜置。就溶劑之去除效率之觀點而言,靜置溫度較佳為10℃以上,更佳為15℃以上,就塗膜之平滑性、作業性及抑制多官能單體之聚合等之觀點而言,較佳為115℃以下,更佳為95℃以下,進而較佳為35℃以下,進而較佳為30℃以下。靜置時間亦取決於靜置溫度,較佳為10分鐘以上,更佳為30分鐘以上,且較佳為100分鐘以下,更佳為60分鐘以下。 The coating in step (F-1) is preferably performed on a glass substrate using a roll coater, a slit coater, a spray, a bar coater, an applicator, a spin coater, or dip coating. Machine, inkjet, or screen printing. From the viewpoint of removing a solvent after coating to obtain a coating film having a uniform film thickness, it is preferably left standing horizontally. From the viewpoint of the removal efficiency of the solvent, the standing temperature is preferably 10 ° C or higher, and more preferably 15 ° C or higher. From the viewpoints of the smoothness of the coating film, workability, and inhibition of polymerization of the polyfunctional monomer, The temperature is preferably 115 ° C or lower, more preferably 95 ° C or lower, even more preferably 35 ° C or lower, and even more preferably 30 ° C or lower. The standing time also depends on the standing temperature, preferably 10 minutes or more, more preferably 30 minutes or more, and preferably 100 minutes or less, and more preferably 60 minutes or less.

光硬化較佳為對塗膜照射紫外線而進行。藉此,可使著色組合 物中之多官能單體進行交聯反應而使塗膜硬化。光硬化較佳為為了於接下來之顯影中於玻璃基板上殘留圖案而進行。因此,光硬化較佳為預先載置組入有圖案之光罩而進行,從而不會使要於顯影中去除之塗膜之部分硬化。光硬化較佳為於紫外線照射量為10~100mJ/cm2下進行。 The photocuring is preferably performed by irradiating the coating film with ultraviolet rays. This allows the polyfunctional monomer in the coloring composition to undergo a crosslinking reaction to harden the coating film. The photocuring is preferably performed in order to leave a pattern on the glass substrate in the subsequent development. Therefore, it is preferable to perform photocuring by placing a patterned photomask in advance, so that a portion of the coating film to be removed during development is not hardened. The photocuring is preferably performed at a UV irradiation amount of 10 to 100 mJ / cm 2 .

顯影係藉由如下方式而進行:將光硬化後之硬化塗膜較佳地浸漬於鹼性水溶液中,較佳為進而利用水進行沖洗而將未硬化部分去除。作為所使用之鹼性水溶液,鹼劑之濃度較佳為0.001~10質量%,較佳為0.01~1質量%。作為顯影中所使用之鹼劑,較佳為氨、氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙基胺、三乙醇胺、氫氧化四甲基銨等之水溶液,更佳為氫氧化四甲基銨水溶液。 The development is performed by immersing the cured coating film after photo-curing in an alkaline aqueous solution, and preferably by rinsing with water to remove the uncured portion. As the alkaline aqueous solution used, the concentration of the alkaline agent is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. As the alkali agent used in the development, aqueous solutions such as ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, triethanolamine, tetramethylammonium hydroxide, etc. are preferred, and hydrogen is more preferred. Tetramethylammonium oxide in water.

作為鹼性水溶液之pH值,較佳為10.0~13.0。 The pH value of the alkaline aqueous solution is preferably 10.0 to 13.0.

步驟(F-2)係將上述步驟(F-1)中所獲得之塗膜加熱至200~300℃而獲得硬化膜之步驟。步驟(F-2)係後烘烤步驟,藉由進行本步驟,可形成硬度更優異之硬化膜。 Step (F-2) is a step of heating the coating film obtained in the above step (F-1) to 200 to 300 ° C to obtain a cured film. Step (F-2) is a post-baking step. By carrying out this step, a hardened film with better hardness can be formed.

就獲得硬度及光學特性優異之硬化膜之觀點而言,加熱之溫度較佳為210~280℃,更佳為220~270℃。就相同之觀點而言,加熱之時間較佳為5~120分鐘,更佳為10~40分鐘。 From the viewpoint of obtaining a cured film excellent in hardness and optical characteristics, the heating temperature is preferably 210 to 280 ° C, and more preferably 220 to 270 ° C. From the same viewpoint, the heating time is preferably 5 to 120 minutes, and more preferably 10 to 40 minutes.

關於上述實施形態,本發明進而揭示以下之分散劑、分散劑之製造方法、彩色濾光片用著色組合物、彩色濾光片及彩色濾光片之製造方法。 Regarding the above embodiment, the present invention further discloses the following dispersant, a method for producing the dispersant, a coloring composition for a color filter, a color filter, and a method for producing a color filter.

<1>一種分散劑,其於分子結構中具有式(A)所表示之結構單元A,一分子結構中所含之結構單元A之平均數量為1.0以上且22.0以下,[化30]

Figure TWI680011B_D0033
<1> A dispersant having a structural unit A represented by the formula (A) in a molecular structure, and an average number of the structural unit A contained in a molecular structure is 1.0 or more and 22.0 or less, [Chem. 30]
Figure TWI680011B_D0033

[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基,R6表示碳數1以上且4以下之烷二基,(M1)-表示陰離子;複數個[(C=O)Rx1O]可相同亦可不同]。 [Wherein, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, and is 2 or more and 100 or less, R 4 A part of hydrogen atoms may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, R 5 represents an alkanediyl group having 1 to 18 carbon atoms, R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (M 1) - represents an anion; a plurality of [(C = O) R x1 O] may be the same or different].

<2>如<1>之分散劑,其中分散劑一分子結構中所含之結構單元A之平均數量為1.0以上,較佳為1.5以上,更佳為1.8以上,且為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下。 <2> The dispersant according to <1>, wherein the average number of structural units A contained in the molecular structure of the dispersant is 1.0 or more, preferably 1.5 or more, more preferably 1.8 or more, and 22.0 or less, preferably It is 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, still more preferably 4.0 or less, and still more preferably 3.0 or less.

<3>如<1>或<2>之分散劑,其中Rx1之碳數為2以上,較佳為3以上,更佳為4以上,進而較佳為5以上,且為12以下,較佳為10以下,更佳為7以下,進而較佳為6以下,進而較佳為5以下。 <3> A dispersant such as <1> or <2>, in which the carbon number of R x1 is 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and 12 or less. It is preferably 10 or less, more preferably 7 or less, even more preferably 6 or less, and still more preferably 5 or less.

<4>如<1>至<3>中任一項之分散劑,其中Rx1較佳為選自伸乙基、各種丙烷二基、各種丁烷二基、各種戊烷二基、各種己烷二基及各種庚烷二基中之至少一種,更佳為選自丁烷-1,4-二基、戊烷-1,5-二基及己烷-1,6-二基中之至少一種,進而較佳為戊烷-1,5-二基。 <4> The dispersant according to any one of <1> to <3>, wherein R x1 is preferably selected from the group consisting of ethylene, various propanediyl groups, various butanediyl groups, various pentanediyl groups, and various hexanes. At least one of alkanediyl and various heptanediyl, more preferably selected from butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl At least one, and more preferably pentane-1,5-diyl.

<5>如<1>至<4>中任一項之分散劑,其中a為2以上,較佳為10以上,更佳為15以上,且為100以下,較佳為70以下,更佳為50以下。 <5> The dispersant according to any one of <1> to <4>, wherein a is 2 or more, preferably 10 or more, more preferably 15 or more, and 100 or less, preferably 70 or less, more preferably It is 50 or less.

<6>如<1>至<5>中任一項之分散劑,其中Rx2之碳數為1以 上,較佳為6以上,更佳為10以上,且為18以下,較佳為16以下,更佳為14以下。 <6> The dispersant according to any one of <1> to <5>, wherein the carbon number of R x2 is 1 or more, preferably 6 or more, more preferably 10 or more, and 18 or less, and preferably 16 Hereinafter, it is more preferably 14 or less.

<7>如<1>至<6>中任一項之分散劑,其中Rx2較佳為選自脂肪族烴基及具有芳香環之烴基中之至少一種,更佳為脂肪族烴基,進而較佳為選自烷基及烯基中之至少一種,進而較佳為烷基。 <7> The dispersant according to any one of <1> to <6>, wherein R x2 is preferably at least one selected from an aliphatic hydrocarbon group and a hydrocarbon group having an aromatic ring, more preferably an aliphatic hydrocarbon group, and more preferably It is preferably at least one selected from the group consisting of an alkyl group and an alkenyl group, and more preferably an alkyl group.

<8>如<1>至<7>中任一項之分散劑,其中Rx2較佳為選自甲基、乙基、辛基、癸基、月桂基、肉豆蔻基、鯨蠟基、油烯基、硬脂基、苯基、對辛基苯基及對壬基苯基中之至少一種,更佳為選自甲基、辛基、癸基、月桂基、油烯基及硬脂基中之至少一種,進而較佳為選自甲基、辛基、癸基及月桂基中之至少一種,進而較佳為選自辛基及月桂基中之至少一種,進而較佳為月桂基。 <8> The dispersant according to any one of <1> to <7>, wherein R x2 is preferably selected from methyl, ethyl, octyl, decyl, lauryl, myristyl, cetyl, At least one of oleyl, stearyl, phenyl, p-octylphenyl, and p-nonylphenyl, more preferably selected from methyl, octyl, decyl, lauryl, oleyl, and stearyl At least one kind of a base, further preferably at least one kind selected from methyl, octyl, decyl, and lauryl, further preferably at least one kind selected from octyl and lauryl, further preferably lauryl .

<9>如<1>至<8>中任一項之分散劑,其中R4之碳數為10以下,較佳為4以下,更佳為2以下,並且,較佳為1以上,進而較佳為1。 <9> The dispersant according to any one of <1> to <8>, wherein the carbon number of R 4 is 10 or less, preferably 4 or less, more preferably 2 or less, and preferably 1 or more, further It is preferably 1.

<10>如<1>至<9>中任一項之分散劑,其中R4較佳為未經羥基取代之烴基。 <10> The dispersant according to any one of <1> to <9>, wherein R 4 is preferably a hydrocarbon group which is not substituted with a hydroxyl group.

<11>如<1>至<10>中任一項之分散劑,其中R4較佳為選自甲基、乙基、各種丙基及各種丁基中之至少一種,更佳為選自甲基及乙基中之至少一種,進而較佳為甲基。 <11> The dispersant according to any one of <1> to <10>, wherein R 4 is preferably at least one selected from the group consisting of methyl, ethyl, various propyl, and various butyl, and more preferably selected from At least one of methyl and ethyl, and more preferably methyl.

<12>如<1>至<11>中任一項之分散劑,其中R5之烷二基之碳數為1以上,較佳為2以上,更佳為3以上,且為18以下,較佳為14以下,更佳為10以下,進而較佳為6以下。 <12> The dispersant according to any one of <1> to <11>, wherein the carbon number of the alkanediyl group of R 5 is 1 or more, preferably 2 or more, more preferably 3 or more, and 18 or less, It is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.

<13>如<1>至<12>中任一項之分散劑,其中R5較佳為選自伸乙基、各種丙烷二基、各種己烷二基及各種壬烷二基中之至少一種,更佳為選自丙烷-1,3-二基、己烷-1,6-二基及壬烷-1,9-二基中之至少一種,進而較佳為選自丙烷-1,3-二基及己烷-1,6-二基中之至少一 種。 <13> The dispersant according to any one of <1> to <12>, wherein R 5 is preferably at least one selected from the group consisting of ethylene, various propanediyl groups, various hexanediyl groups, and various nonanediyl groups. One type, more preferably at least one selected from the group consisting of propane-1,3-diyl, hexane-1,6-diyl, and nonane-1,9-diyl, and further preferably selected from propane-1, At least one of 3-diyl and hexane-1,6-diyl.

<14>如<1>至<13>中任一項之分散劑,其中R6之碳數為4以下,較佳為3以下,更佳為2以下,並且,較佳為1以上,進而較佳為1。 <14> The dispersant according to any one of <1> to <13>, wherein the carbon number of R 6 is 4 or less, preferably 3 or less, more preferably 2 or less, and preferably 1 or more, furthermore It is preferably 1.

<15>如<1>至<14>中任一項之分散劑,其中R6較佳為亞甲基。 <15> The dispersant according to any one of <1> to <14>, wherein R 6 is preferably a methylene group.

<16>如<1>至<15>中任一項之分散劑,其中(M1)-較佳為選自鹵化物離子、烷基硫酸根離子、烷基苯磺酸根離子及烷基碳酸根離子中之至少一種,更佳為鹵化物離子,進而較佳為選自氯化物離子、溴化物離子及碘化物離子中之至少一種,進而較佳為氯化物離子。 <16> The <1> to <15> any of a dispersing agent, wherein (M 1) - is preferably selected from halide ion, alkyl sulfate ion, alkylbenzene sulfonate ion, and an alkyl carbonate At least one of the root ions is more preferably a halide ion, more preferably at least one selected from chloride ions, bromide ions, and iodide ions, and still more preferably chloride ions.

<17>如<1>至<16>中任一項之分散劑,其中分散劑較佳為於一分子結構中進而具有選自式(B)所表示之結構單元B及式(C)所表示之結構單元C中之至少一種,

Figure TWI680011B_D0034
<17> The dispersant according to any one of <1> to <16>, wherein the dispersant is preferably in a molecular structure and further has a structure selected from the structural unit B represented by formula (B) and the formula (C). At least one of the structural units C represented,
Figure TWI680011B_D0034

[式中,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基] [In the formula, R 4 represents a part of hydrogen atoms which can be substituted with a hydrocarbon group having 1 or more and 10 carbon atoms, and R 5 represents an alkyldiyl group having 1 or more and 18 carbon atoms]

Figure TWI680011B_D0035
Figure TWI680011B_D0035

[式中,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基,(M2)-表示陰離子]。 [In the formula, R 3 represents at least one selected from a hydrogen atom and a hydrocarbon group having a carbon number of 1 or more and 10 or less which may be substituted with a hydroxyl group, and R 4 represents a carbon number of 1 may be substituted with a part of hydrogen atoms or more and 10 or less of the hydrocarbon group, R 5 represents a carbon number of 1 or more and 18 or less -alkanediyl, (M 2) - represents an anion].

<18>如<17>之分散劑,其中R3較佳為選自氫原子及碳數1以上且10以下之烴基中之至少一種。 <18> The dispersant according to <17>, wherein R 3 is preferably at least one selected from a hydrogen atom and a hydrocarbon group having a carbon number of 1 to 10.

<19>如<17>或<18>之分散劑,其中R3之烴基之碳數為10以下,較佳為7以下,更佳為4以下,進而較佳為2以下,並且,為1以上。 <19> The dispersant according to <17> or <18>, wherein the carbon number of the hydrocarbon group of R 3 is 10 or less, preferably 7 or less, more preferably 4 or less, further preferably 2 or less, and 1 the above.

<20>如<17>至<19>中任一項之分散劑,其中R3較佳為選自氫原子、甲基、乙基、丙基及苄基中之至少一種,更佳為選自氫原子及甲基中之至少一種。 <20> The dispersant according to any one of <17> to <19>, wherein R 3 is preferably at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a benzyl group, and is more preferably selected. From at least one of a hydrogen atom and a methyl group.

<21>如<17>至<20>中任一項之分散劑,其中(M2)-較佳為選自羧酸根離子、磺酸根離子、鹵化物離子、硫酸根離子、硝酸根離子、亞硝酸根離子、磷酸根離子、亞磷酸根離子及碳酸根離子中之至少一種。 <21><17> to <20> any of a dispersing agent, wherein (M 2) - is preferably selected from a carboxylate ion, a sulfonate ion, a halide ion, sulfate ion, nitrate ion, At least one of a nitrite ion, a phosphate ion, a phosphite ion, and a carbonate ion.

<22>如<17>至<21>中任一項之分散劑,其中(M2)-較佳為選自羧酸根離子、鹵化物離子、烷基硫酸根離子及烷基苯磺酸根離子中之至少一種。 <22><17> to <21> to any one of the dispersing agent, wherein (M 2) - is preferably selected from a carboxylate ion, a halide ion, sulfate ion and alkyl benzene sulfonate ion At least one of them.

<23>如<17>至<22>中任一項之分散劑,其中分散劑於分子結構中進而具有式(D)所表示之結構單元D, [化33]

Figure TWI680011B_D0036
<23> The dispersant according to any one of <17> to <22>, wherein the dispersant has a structural unit D represented by formula (D) in the molecular structure, [Chem. 33]
Figure TWI680011B_D0036

[式中,Ry1表示碳數2以上且4以下之烷二基,Ry2表示碳數1以上且18以下之烴基,d表示平均加成莫耳數,為1以上且100以下,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基,R6表示碳數1以上且4以下之烷二基,(M1)-表示陰離子;再者,[Ry1O]於存在複數個之情形時,可相同亦可不同]。 [In the formula, R y1 represents an alkanediyl group having 2 or more and 4 carbon atoms, R y2 represents a hydrocarbon group having 1 or more and 18 carbon atoms, d represents an average addition mole number, and is 1 or more and 100 or less, R 4 A part of hydrogen atoms may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, R 5 represents an alkanediyl group having 1 to 18 carbon atoms, R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (M 1) - represents an anion; Furthermore, [R y1 O] in the presence of a plurality of situation may be the same or different].

<24>如<23>之分散劑,其中分散劑於一分子結構中所含之結構單元D之平均數量較佳為0.3以上,更佳為0.5以上,進而較佳為0.6以上,進而較佳為0.8以上,且較佳為11.0以下,較佳為5.5以下,更佳為3.5以下,進而較佳為2.5以下,進而較佳為2.0以下,進而較佳為1.5以下,進而較佳為1.0以下,進而較佳為0.8以下。 <24> The dispersant according to <23>, wherein the average number of the structural unit D contained in the molecular structure of the dispersant is preferably 0.3 or more, more preferably 0.5 or more, further preferably 0.6 or more, and even more preferably 0.8 or more, and preferably 11.0 or less, preferably 5.5 or less, more preferably 3.5 or less, still more preferably 2.5 or less, still more preferably 2.0 or less, still more preferably 1.5 or less, and even more preferably 1.0 or less , More preferably 0.8 or less.

<25>如<1>至<24>中任一項之分散劑,其中分散劑較佳為具有包含1個以上結構單元A之排列結構,更佳為於一分子結構中具有包含結構單元A、任意地選自結構單元B、結構單元C及結構單元D中之至少一種之排列結構,進而較佳為於一分子結構中具有包含結構單元A、任意地選自結構單元B及結構單元C中之至少一種之排列結構,進而較佳為於一分子結構中具有包含結構單元A及結構單元D、任意地選自結構單元B及結構單元C中之至少一種之排列結構。 <25> The dispersant according to any one of <1> to <24>, wherein the dispersant preferably has an arrangement structure including more than one structural unit A, and more preferably has a structural unit A in a molecular structure. An arrangement structure arbitrarily selected from at least one of structural unit B, structural unit C, and structural unit D, and further preferably has a molecular structure including structural unit A, arbitrarily selected from structural unit B and structural unit C The arrangement structure of at least one of them is preferably an arrangement structure including at least one of structural unit A and structural unit D, and at least one selected from structural unit B and structural unit C in a molecular structure.

<26>如<1>至<25>中任一項之分散劑,其中分散劑中之一分子結構中之結構單元A、結構單元B、結構單元C及結構單元D之合計平均數量較佳為22.0以下,更佳為11.0以下,進而較佳為7.0以下, 進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,且為1.0以上,較佳為1.5以上,更佳為1.8以上。 <26> The dispersant according to any one of <1> to <25>, wherein the total average number of structural unit A, structural unit B, structural unit C, and structural unit D in one of the molecular structures of the dispersant is better. 22.0 or less, more preferably 11.0 or less, even more preferably 7.0 or less, It is more preferably 5.0 or less, still more preferably 4.0 or less, still more preferably 3.0 or less, and 1.0 or more, more preferably 1.5 or more, and even more preferably 1.8 or more.

<27>如<1>至<26>中任一項之分散劑,其具有包含1個以上之上述結構單元A之排列結構,且該排列結構之末端較佳為一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,更佳為選自碳數1以上且10以下之烴基及碳數2以上且6以下之羥基烷基中之至少一種,進而較佳為選自碳數1以上且5以下之烴基及碳數3以上且6以下之羥基烷基中之至少一種,進而較佳為選自碳數1以上且3以下之烴基及碳數4以上且6以下之羥基烷基中之至少一種。 <27> The dispersant according to any one of <1> to <26>, which has an arrangement structure including one or more of the above-mentioned structural unit A, and the end of the arrangement structure is preferably a part of hydrogen atoms which may be substituted as The hydrocarbon group having 1 to 10 carbon atoms in the hydroxyl group is more preferably at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxyalkyl group having 2 to 6 carbon atoms, and more preferably selected from carbon At least one of a hydrocarbon group of 1 or more and 5 or less and a hydroxyalkyl group of 3 or more and 6 or less carbon, and more preferably a hydrocarbon group of 1 or more and 3 or less and a hydroxyl group of 4 or more and 6 or less carbon At least one of alkyl groups.

<28>如<1>至<27>中任一項之分散劑,其中分散劑之重量平均分子量Mw較佳為2,000以上,更佳為3,000以上,進而較佳為3,500以上,並且,較佳為50,000以下,更佳為25,000以下,進而較佳為20,000以下,進而較佳為15,000以下。 <28> The dispersant according to any one of <1> to <27>, wherein the weight average molecular weight Mw of the dispersant is preferably 2,000 or more, more preferably 3,000 or more, and further preferably 3,500 or more, and more preferably It is 50,000 or less, more preferably 25,000 or less, still more preferably 20,000 or less, and still more preferably 15,000 or less.

<29>一種化合物,其以式(1)表示,

Figure TWI680011B_D0037
<29> a compound represented by formula (1),
Figure TWI680011B_D0037

[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,Ry1表示碳數2以上且4以下之烷二基,Ry2表示碳數1以上且18以下之烴基,d表示平均加成莫耳數,為1以上且100以下,R1、R2及R4可相同 或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,R5表示碳數1以上且18以下之烷二基(其中,與R1鄰接之R5表示單鍵),R6表示碳數1以上且4以下之烷二基,(M1)-及(M2)-分別獨立地表示陰離子,n、p、m及k表示平均結構單元數,(n+p+m+k)為1.0以上且22.0以下,(n+p)為1.0以上且22.0以下,n為0.3以上且22.0以下,p為0以上且11.0以下,m為0以上且21.0以下,k為0以上且21.0以下;複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以n、p、m、k表示其平均結構單元數之各結構單元可為任意排列順序]。 [In the formula, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, is 2 or more and 100 or less, and R y1 It represents an alkyldiyl group having 2 or more and 4 carbon atoms, R y2 represents a hydrocarbon group having 1 or more and 18 carbon atoms, d represents an average addition mole number, and is 1 or more and 100 or less. R 1 , R 2, and R 4 It may be the same or different, and represents a hydrocarbon group having a carbon number of 1 or more and 10 or less in which a part of hydrogen atoms may be substituted with a hydroxyl group, and R 3 represents a carbon number of 1 or more and 10 or less in which a hydrogen atom and a part of hydrogen atoms may be substituted with a hydroxyl group. At least one of the hydrocarbon groups, R 5 represents an alkanediyl group having 1 to 18 carbon atoms (wherein R 5 adjacent to R 1 represents a single bond), R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (m 1) - and (m 2) - each independently represent an anion, n, p, m and k represents the average number of structural units, (n + p + m + k) is 1.0 or more and 22.0 or less, (n + p ) Is 1.0 or more and 22.0 or less, n is 0.3 or more and 22.0 or less, p is 0 or more and 11.0 or less, m is 0 or more and 21.0 or less, and k is 0 or more and 21.0 or less; a plurality of [(C = O) R x1 O] can be the same as It can be different, the plural [R y1 O] can be the same or different, and each structural unit whose average structural unit number is represented by n, p, m, and k can be in any order].

<30>如<29>之化合物,其中(n+p+m+k)為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,且為1.0以上,較佳為1.5以上,更佳為1.8以上。 <30> The compound according to <29>, wherein (n + p + m + k) is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, and even more preferably 4.0 or less, It is more preferably 3.0 or less, and 1.0 or more, more preferably 1.5 or more, and even more preferably 1.8 or more.

<31>如<29>或<30>之化合物,其中(n+p)為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,且為1.0以上,較佳為1.5以上,更佳為1.8以上。 <31> Compounds such as <29> or <30>, in which (n + p) is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, and even more preferably 4.0 or less, It is more preferably 3.0 or less, and 1.0 or more, more preferably 1.5 or more, and even more preferably 1.8 or more.

<32>如<29>至<31>中任一項之化合物,其中n為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,且為0.3以上,較佳為0.5以上,更佳為0.6以上,進而較佳為0.8以上,進而較佳為1.0以上,較佳為1.5以上,更佳為1.8以上。 <32> The compound according to any one of <29> to <31>, wherein n is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, and even more preferably 4.0 or less, It is further preferably 3.0 or less, and 0.3 or more, more preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.8 or more, still more preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 1.8 or more.

<33>如<29>至<32>中任一項之化合物,其中p為0以上,較佳為0.3以上,更佳為0.5以上,進而較佳為0.6以上,進而較佳為0.8以上,且較佳為11.0以下,較佳為5.5以下,更佳為3.5以下,進而 較佳為2.5以下,進而較佳為2.0以下,進而較佳為1.5以下,進而較佳為1.0以下,進而較佳為0.8以下。 <33> The compound according to any one of <29> to <32>, wherein p is 0 or more, preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.6 or more, and even more preferably 0.8 or more, It is preferably 11.0 or less, more preferably 5.5 or less, and even more preferably 3.5 or less. It is preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.5 or less, still more preferably 1.0 or less, and still more preferably 0.8 or less.

<34>如<29>至<33>中任一項之化合物,其中m為21.0以下,較佳為4.0以下,更佳為2.0以下,進而較佳為1.0以下,進而較佳為0.5以下,且為0以上。 <34> The compound according to any one of <29> to <33>, wherein m is 21.0 or less, preferably 4.0 or less, more preferably 2.0 or less, still more preferably 1.0 or less, and still more preferably 0.5 or less, And it is 0 or more.

<35>如<29>至<34>中任一項之化合物,其中k為21.0以下,較佳為4.0以下,更佳為2.0以下,進而較佳為1.2以下,且為0以上。 <35> The compound according to any one of <29> to <34>, wherein k is 21.0 or less, preferably 4.0 or less, more preferably 2.0 or less, still more preferably 1.2 or less, and 0 or more.

<36>如<29>至<35>中任一項之化合物,其中(n+p)與(n+p+m+k)之比((n+p)/(n+p+m+k))較佳為0.3以上,更佳為0.6以上,且為1.0以下,較佳為0.9以下。 <36> The compound according to any one of <29> to <35>, wherein the ratio of (n + p) to (n + p + m + k) is ((n + p) / (n + p + m + k)) is preferably 0.3 or more, more preferably 0.6 or more, and 1.0 or less, and more preferably 0.9 or less.

<37>如<29>至<36>中任一項之化合物,其具有如<2>至<16>、<18>至<22>中記載之限定事項。 <37> The compound according to any one of <29> to <36>, which has the restrictions described in <2> to <16> and <18> to <22>.

<38>如<29>至<37>中任一項之化合物,其中R1、R2之碳數為10以下,較佳為8以下,更佳為6以下,進而較佳為1。 <38> The compound according to any one of <29> to <37>, wherein the carbon number of R 1 and R 2 is 10 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 1.

<39>如<29>至<38>中任一項之化合物,其中R1及R2較佳為未經羥基取代之烴基。 <39> The compound according to any one of <29> to <38>, wherein R 1 and R 2 are preferably unsubstituted hydroxy-substituted hydrocarbon groups.

<40>如<29>至<39>中任一項之化合物,其中R1及R2較佳為選自碳數1以上且10以下之烴基及碳數2以上且6以下之羥基烷基中之至少一種,更佳為選自碳數1以上且5以下之烴基及碳數3以上且6以下之羥基烷基中之至少一種,進而較佳為選自碳數1以上且3以下之烴基及碳數4以上且6以下之羥基烷基中之至少一種。 <40> The compound according to any one of <29> to <39>, wherein R 1 and R 2 are preferably selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxyalkyl group having 2 to 6 carbon atoms At least one of them is more preferably at least one selected from a hydrocarbon group having 1 to 5 carbons and a hydroxyalkyl group having 3 to 6 carbons, and further preferably selected from one to 3 carbons. At least one of a hydrocarbon group and a hydroxyalkyl group having 4 or more and 6 or less carbon atoms.

<41>如<29>至<40>中任一項之化合物,其中R1及R2較佳為選自甲基、乙基、丁基、己基、羥基甲基、羥基丁基及羥基己基中之至少一種,更佳為選自甲基、乙基、羥基丁基及羥基己基中之至少一種,進而較佳為選自甲基及羥基己基中之至少一種。 <41> The compound according to any one of <29> to <40>, wherein R 1 and R 2 are preferably selected from methyl, ethyl, butyl, hexyl, hydroxymethyl, hydroxybutyl, and hydroxyhexyl At least one of these is more preferably at least one selected from methyl, ethyl, hydroxybutyl, and hydroxyhexyl, and even more preferably at least one selected from methyl and hydroxyhexyl.

<42>如<29>至<41>中任一項之化合物,其較佳為以式(1a)表示,

Figure TWI680011B_D0038
<42> The compound according to any one of <29> to <41>, which is preferably represented by formula (1a),
Figure TWI680011B_D0038

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R4、R5、R6、(M1)-、n、m及p與式(1)中所說明者相同,(n+p+m)為1.0以上且22.0以下;複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以n、p、m表示其平均結構單元數之各結構單元可為任意排列順序]。 [In the formula, R x1 , R x2 , a, R y1 , R y2 , d, R 1 , R 2 , R 4 , R 5 , R 6 , (M 1 ) - , n, m, and p are the same as those in formula (1 ) Are the same, (n + p + m) is 1.0 or more and 22.0 or less; multiple [(C = O) R x1 O] may be the same or different, multiple [R y1 O] may be the same or different Different, each structural unit whose average structural unit number is represented by n, p, and m can be in any order.]

<43>如<42>之化合物,其中式(1a)中之n為22.0以下,較佳為11.0以下,更佳為7.0以下,進而較佳為5.0以下,進而較佳為4.0以下,進而較佳為3.0以下,且為1.0以上,較佳為1.5以上,更佳為1.8以上。 <43> The compound according to <42>, wherein n in the formula (1a) is 22.0 or less, preferably 11.0 or less, more preferably 7.0 or less, still more preferably 5.0 or less, still more preferably 4.0 or less, and more preferably It is preferably 3.0 or less, and 1.0 or more, preferably 1.5 or more, and more preferably 1.8 or more.

<44>如<42>或<43>之化合物,其中式(1a)中之m為21.0以下,較佳為4.0以下,更佳為2.0以下,進而較佳為1.0以下,進而較佳為0.5以下,且為0以上。 <44> A compound such as <42> or <43>, wherein m in the formula (1a) is 21.0 or less, preferably 4.0 or less, more preferably 2.0 or less, still more preferably 1.0 or less, and still more preferably 0.5 Below, it is 0 or more.

<45>如<42>至<44>中任一項之化合物,其中(n+p)與(n+p+m)之比((n+p)/(n+p+m))較佳為0.3以上,更佳為0.6以上,且為1.0以下。 <45> The compound according to any one of <42> to <44>, wherein the ratio of (n + p) to (n + p + m) ((n + p) / (n + p + m)) is It is preferably 0.3 or more, more preferably 0.6 or more, and 1.0 or less.

<46>一種化合物,其以式(1')表示,

Figure TWI680011B_D0039
<46> a compound represented by the formula (1 '),
Figure TWI680011B_D0039

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R3、R4、R5、R6、(M1)-及(M2)-與式(1)中所說明者相同,ni、pi、mi及ki表示結構單元數,(ni+pi+mi+ki)為1以上且22以下之整數,ni為1以上且22以下之整數,pi為0以上且11以下之整數,mi為0以上且21以下之整數,ki為0以上且21以下之整數;複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以ni、pi、mi、ki表示其結構單元數之各結構單元可為任意排列順序]。 [Wherein, R x1, R x2, a , R y1, R y2, d, R 1, R 2, R 3, R 4, R 5, R 6, (M 1) - and (M 2) - and The descriptions in formula (1) are the same, ni, pi, mi, and ki represent the number of structural units, (ni + pi + mi + ki) is an integer from 1 to 22, and ni is an integer from 1 to 22, pi is an integer from 0 to 11; mi is an integer from 0 to 21; ki is an integer from 0 to 21; plural [(C = O) R x1 O] may be the same or different, plural [R y1 O] may be the same or different, and each structural unit whose number of structural units is represented by ni, pi, mi, ki may be in any order].

<47>如<46>之化合物,其中(ni+pi+mi+ki)為22以下,較佳為11以下,更佳為7以下,進而較佳為5以下,進而較佳為4以下,進而更佳為3以下,且為1以上,較佳為2以上。 <47> The compound according to <46>, wherein (ni + pi + mi + ki) is 22 or less, preferably 11 or less, more preferably 7 or less, still more preferably 5 or less, and even more preferably 4 or less, Furthermore, it is more preferably 3 or less, and is 1 or more, and more preferably 2 or more.

<48>如<46>或<47>之化合物,其中ni為22以下,較佳為11以下,更佳為7以下,進而較佳為5以下,進而較佳為4以下,進而更佳為3以下,且為1以上,較佳為2以上。 <48> Compounds such as <46> or <47>, in which ni is 22 or less, preferably 11 or less, more preferably 7 or less, still more preferably 5 or less, still more preferably 4 or less, and even more preferably 3 or less, and 1 or more, preferably 2 or more.

<49>如<46>至<48>中任一項之化合物,其中pi為0以上,較佳為1以上,且為11以下,較佳為5以下,更佳為3以下,進而較佳為2以下,進而較佳為1。 <49> The compound according to any one of <46> to <48>, wherein pi is 0 or more, preferably 1 or more, and 11 or less, preferably 5 or less, more preferably 3 or less, and further preferably It is 2 or less, and more preferably 1.

<50>如<46>至<49>中任一項之化合物,其中mi為21以下,較佳為4以下,進而較佳為2以下,進而較佳為1以下,且為0以 上,進而更佳為0。 <50> The compound according to any one of <46> to <49>, wherein mi is 21 or less, preferably 4 or less, further preferably 2 or less, further preferably 1 or less, and 0 or more. It is more preferably 0.

<51>如<46>至<50>中任一項之化合物,其中ki為21以下,較佳為4以下,更佳為2以下,進而較佳為1以下,且為0以上。 <51> The compound according to any one of <46> to <50>, wherein ki is 21 or less, preferably 4 or less, more preferably 2 or less, still more preferably 1 or less, and 0 or more.

<52>如<46>至<51>中任一項之化合物,其中(ni+pi)與(ni+pi+mi+ki)之比((ni+pi)/(ni+pi+mi+ki))較佳為0.3以上,更佳為0.6以上,且為1.0以下,較佳為0.9以下。 <52> The compound according to any one of <46> to <51>, wherein the ratio of (ni + pi) to (ni + pi + mi + ki) ((ni + pi) / (ni + pi + mi + ki)) is preferably 0.3 or more, more preferably 0.6 or more, and 1.0 or less, and more preferably 0.9 or less.

<53>如<46>至<52>中任一項之化合物,其較佳為以式(1a')表示,

Figure TWI680011B_D0040
<53> The compound according to any one of <46> to <52>, which is preferably represented by formula (1a '),
Figure TWI680011B_D0040

[式中,Rx1、Rx2、a、Ry1、Ry2、d、R1、R2、R4、R5、R6及(M1)-與式(1)中所說明者相同,ni、pi及mi與式(1')中所說明者相同,(ni+pi+mi)為1以上且22以下之整數;複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以ni、pi、mi表示其結構單元數之各結構單元可為任意排列順序]。 [Wherein, R x1, R x2, a , R y1, R y2, d, R 1, R 2, R 4, R 5, R 6 , and (M 1) - formula (1) described in the same by , Ni, pi, and mi are the same as those described in formula (1 '), (ni + pi + mi) is an integer from 1 to 22; the plural [(C = O) R x1 O] may be the same or Different, a plurality of [R y1 O] may be the same or different, and each structural unit whose number of structural units is represented by ni, pi, mi may be in any order.]

<54>如<53>之化合物,其中(ni+pi)與(ni+pi+mi)之比((ni+pi)/(ni+pi+mi))較佳為0.3以上,更佳為0.6以上,且為1.0以下。 <54> The compound according to <53>, in which the ratio of (ni + pi) to (ni + pi + mi) ((ni + pi) / (ni + pi + mi)) is preferably 0.3 or more, more preferably 0.6 or more and 1.0 or less.

<55>一種分散劑之製造方法,其具有步驟1:使於分子結構中具有式(B)所表示之結構單元B且一分子結構中所含之結構單元B之平均數量為1.0以上且22.0以下之聚胺化合物、式(3-1)所表示之化合物、及任意之式(3-2)所表示之化合物進行反應之步驟,

Figure TWI680011B_D0041
<55> A method for producing a dispersant, which has step 1: having a structural unit B represented by formula (B) in a molecular structure and an average number of structural units B contained in a molecular structure of 1.0 or more and 22.0 A step of reacting the following polyamine compound, a compound represented by formula (3-1), and any compound represented by formula (3-2),
Figure TWI680011B_D0041

[式中,R4、R5與式(A)中所說明者相同] [Wherein R 4 and R 5 are the same as those described in formula (A)]

Figure TWI680011B_D0042
Figure TWI680011B_D0042

[式中,Rx1、Rx2、a、R6與式(A)中所說明者相同;Y1表示藉由脫離而成為陰離子(M1)-之基] [In the formula, the R x1, R x2, a, R 6 in the formula (A) are the same as those described; Y 1 represents an anion become disengaged by (M 1) - of-yl]

Figure TWI680011B_D0043
Figure TWI680011B_D0043

[式中,Ry1、Ry2、d、R6與式(D)中所說明者相同;Y1表示藉由脫離而成為陰離子(M1)-之基]。 [Wherein, R y1, R y2, d , R 6 in the formula (D) as described by the same; Y 1 represents an anion become disengaged by (M 1) - the groups].

<56>如<55>之分散劑之製造方法,其中聚胺化合物較佳為式(2)所表示之聚胺化合物,[化41]

Figure TWI680011B_D0044
<56> The method for producing a dispersant according to <55>, wherein the polyamine compound is preferably a polyamine compound represented by formula (2), [Chem. 41]
Figure TWI680011B_D0044

[式中,R1、R2、R4、R5與式(A)中所說明之取代基相同;(n+p+m+k)表示平均結構單元數,為1.0以上且22.0以下]。 [In the formula, R 1 , R 2 , R 4 , and R 5 are the same as the substituents described in formula (A); (n + p + m + k) represents the average number of structural units, which is 1.0 or more and 22.0 or less] .

<57>如<55>或<56>之分散劑之製造方法,其較佳為進而具有如下步驟,步驟2:使步驟1中所獲得之化合物與式(4)所表示之化合物進行反應之步驟,R3-Y2 (4) <57> The method for producing a dispersant such as <55> or <56>, which preferably further has the following steps, step 2: reacting the compound obtained in step 1 with a compound represented by formula (4) Steps, R 3 -Y 2 (4)

[式中,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,Y2表示藉由脫離而成為陰離子(M2)-之基]。 [In the formula, R 3 represents at least one selected from a hydrogen atom and a hydrocarbon group having a carbon number of 1 or more and 10 or less which may be substituted with a hydroxyl group, and Y 2 represents an anion (M 2 ) - base].

<58>一種彩色濾光片用顏料分散體,其含有如<1>至<28>中任一項之分散劑、有機顏料及有機溶劑。 <58> A pigment dispersion for a color filter, comprising the dispersant according to any one of <1> to <28>, an organic pigment, and an organic solvent.

<59>一種彩色濾光片用顏料分散體,其含有包含如<29>至<45>中任一項之化合物之分散劑、有機顏料及有機溶劑。 <59> A pigment dispersion for a color filter, which contains a dispersant containing a compound according to any one of <29> to <45>, an organic pigment, and an organic solvent.

<60>一種彩色濾光片用顏料分散體,其含有包含如<46>至<54>中任一項之化合物之分散劑、有機顏料及有機溶劑。 <60> A pigment dispersion for a color filter, which contains a dispersant containing a compound according to any one of <46> to <54>, an organic pigment, and an organic solvent.

<61>如<58>至<60>中任一項之彩色濾光片用顏料分散體,其中有機顏料較佳為包含式(P1)所表示之吡咯并吡咯二酮系顏料,[化42]

Figure TWI680011B_D0045
<61> The pigment dispersion for a color filter according to any one of <58> to <60>, wherein the organic pigment preferably contains a pyrrolopyrrole diketone pigment represented by the formula (P1), [Chem 42 ]
Figure TWI680011B_D0045

[式(P1)中,X11及X12分別獨立地表示氫原子、鹵素原子、或氫原子可被取代之芳香族烴基,Y11及Y12分別獨立地表示氫原子、-SO3H、或-SO3 -Z+,Z+表示陽離子;X11及X12較佳為鹵素原子,更佳為選自氯原子及溴原子中之至少一種;Y11及Y12較佳為氫原子]。 [In the formula (P1), X 11 and X 12 each independently represent a hydrogen atom, a halogen atom, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted, and Y 11 and Y 12 each independently represent a hydrogen atom, -SO 3 H, Or -SO 3 - Z + , Z + represents a cation; X 11 and X 12 are preferably a halogen atom, more preferably at least one selected from a chlorine atom and a bromine atom; Y 11 and Y 12 are preferably a hydrogen atom] .

<62>如<61>之彩色濾光片用顏料分散體,其中有機顏料中之吡咯并吡咯二酮系顏料之含量相對於顏料之總量較佳為20質量%以上,更佳為30質量%以上,進而較佳為50質量%以上,進而更佳為60質量%以上,且較佳為100質量%以下,更佳為90質量%以下。 <62> The pigment dispersion for a color filter according to <61>, wherein the content of the pyrrolopyrrole dione pigment in the organic pigment is preferably 20% by mass or more, more preferably 30% by mass relative to the total amount of the pigment. % Or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 100% by mass or less, and even more preferably 90% by mass or less.

<63>如<61>或<62>之彩色濾光片用顏料分散體,其中有機溶劑較佳為醚系有機溶劑。 <63> The pigment dispersion for a color filter according to <61> or <62>, wherein the organic solvent is preferably an ether-based organic solvent.

<64>如<61>至<63>中任一項之彩色濾光片用顏料分散體,其中有機溶劑較佳為選自丙二醇單甲醚乙酸酯及二乙二醇單丁醚乙酸酯中之至少一種,更佳為丙二醇單甲醚乙酸酯。 <64> The pigment dispersion for a color filter according to any one of <61> to <63>, wherein the organic solvent is preferably selected from propylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate At least one of the esters is more preferably propylene glycol monomethyl ether acetate.

<65>如<61>至<64>中任一項之彩色濾光片用顏料分散體,其較佳為進而含有鹼可溶性樹脂。 <65> The pigment dispersion for a color filter according to any one of <61> to <64>, which preferably further contains an alkali-soluble resin.

<66>如<61>至<65>中任一項之彩色濾光片用顏料分散體,其中鹼可溶性樹脂較佳為包含源自(甲基)丙烯酸酯之結構單元(as1)與源自具有酸基之單體之結構單元(as2)之共聚物。 <66> The pigment dispersion for a color filter according to any one of <61> to <65>, wherein the alkali-soluble resin preferably contains a structural unit (as1) derived from a (meth) acrylate and is derived from Copolymer of structural unit (as2) of monomer having acid group.

<67>如<61>至<66>中任一項之彩色濾光片用顏料分散體,其中鹼可溶性樹脂之結構單元(as1)與結構單元(as2)之莫耳比[(as1)/(as2)]較佳為90/10~50/50,更佳為80/20~60/40。 <67> The pigment dispersion for a color filter according to any one of <61> to <66>, wherein the molar ratio of the structural unit (as1) of the alkali-soluble resin to the structural unit (as2) [(as1) / (as2)] It is preferably 90/10 to 50/50, and more preferably 80/20 to 60/40.

<68>如<61>至<67>中任一項之彩色濾光片用顏料分散體,其較佳為進而含有具有2個以上順丁烯二醯亞胺基之芳香族化合物。 <68> The pigment dispersion for a color filter according to any one of <61> to <67>, which preferably further contains an aromatic compound having two or more cis butylene diimide groups.

<69>如<61>至<68>中任一項之彩色濾光片用顏料分散體,其中顏料分散體中之有機顏料之含量較佳為3質量%以上,更佳為5質量%以上,進而較佳為10質量%以上,且較佳為30質量%以下,更佳為20質量%以下,進而較佳為16質量%以下。 <69> The pigment dispersion for a color filter according to any one of <61> to <68>, wherein the content of the organic pigment in the pigment dispersion is preferably 3% by mass or more, and more preferably 5% by mass or more It is still more preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 16% by mass or less.

<70>如<61>至<69>中任一項之彩色濾光片用顏料分散體,其中顏料分散體中之分散劑相對於顏料之質量比[分散劑/顏料]較佳為0.1以上,更佳為0.2以上,進而較佳為0.3以上,且較佳為1.5以下,更佳為1.2以下,進而較佳為0.9以下,進而更佳為0.5以下。 <70> The pigment dispersion for a color filter according to any one of <61> to <69>, wherein the mass ratio of the dispersant to the pigment in the pigment dispersion [dispersant / pigment] is preferably 0.1 or more It is more preferably 0.2 or more, even more preferably 0.3 or more, and more preferably 1.5 or less, more preferably 1.2 or less, still more preferably 0.9 or less, and still more preferably 0.5 or less.

<71>如<61>至<69>中任一項之彩色濾光片用顏料分散體,其中顏料分散體中之有機溶劑之含量較佳為30質量%以上,更佳為50質量%以上,進而較佳為60質量%以上,且較佳為95質量%以下,更佳為90質量%以下。 <71> The pigment dispersion for a color filter according to any one of <61> to <69>, wherein the content of the organic solvent in the pigment dispersion is preferably 30% by mass or more, and more preferably 50% by mass or more It is more preferably 60% by mass or more, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

<72>如<65>至<67>中任一項之彩色濾光片用顏料分散體,其中顏料分散體中之鹼可溶性樹脂之含量較佳為1質量%以上,更佳為2質量%以上,進而較佳為3質量%以上,且較佳為15質量%以下,更佳為12質量%以下,進而較佳為9質量%以下。 <72> The pigment dispersion for a color filter according to any one of <65> to <67>, wherein the content of the alkali-soluble resin in the pigment dispersion is preferably 1% by mass or more, and more preferably 2% by mass The above is more preferably 3% by mass or more, more preferably 15% by mass or less, even more preferably 12% by mass or less, and still more preferably 9% by mass or less.

<73>如<68>之彩色濾光片用顏料分散體,其中顏料分散體中之順丁烯二醯亞胺化合物之含量相對於顏料100質量份較佳為0.2質量份以上,更佳為1質量份以上,進而較佳為3質量份以上,且較佳為20質量%以下,更佳為15質量%以下,進而較佳為10質量%以下。 <73> The pigment dispersion for a color filter according to <68>, wherein the content of the maleimide compound in the pigment dispersion is preferably 0.2 parts by mass or more relative to 100 parts by mass of the pigment, and more preferably 1 mass part or more, more preferably 3 mass parts or more, and more preferably 20 mass% or less, more preferably 15 mass% or less, and still more preferably 10 mass% or less.

<74>如<58>至<73>中任一項之彩色濾光片用顏料分散體,其中顏料分散體之平均粒徑較佳為200nm以下,更佳為100nm以下,進而較佳為90nm以下,進而較佳為70nm以下,且較佳為20nm以上。 <74> The pigment dispersion for a color filter according to any one of <58> to <73>, wherein the average particle diameter of the pigment dispersion is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 90 nm Hereinafter, it is more preferably 70 nm or less, and more preferably 20 nm or more.

<75>如<58>至<74>中任一項之彩色濾光片用顏料分散體,其中顏料分散體於顏料濃度10質量%時於20℃下之黏度(單位:mPa‧s)較佳為2以上,更佳為3以上,進而較佳為5以上,且較佳為200以下,更佳為50以下,進而較佳為20以下,進而較佳為15以下。 <75> The pigment dispersion for a color filter according to any one of <58> to <74>, wherein the viscosity of the pigment dispersion at a pigment concentration of 10% by mass at 20 ° C (unit: mPa‧s) is It is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 200 or less, more preferably 50 or less, still more preferably 20 or less, and still more preferably 15 or less.

<76>一種彩色濾光片用著色組合物,其含有如<58>至<75>中任一項之分散體、多官能單體及光聚合起始劑。 <76> A coloring composition for a color filter, comprising the dispersion according to any one of <58> to <75>, a polyfunctional monomer, and a photopolymerization initiator.

<77>如<76>之彩色濾光片用著色組合物,其中鹼可溶性樹脂之含量於彩色濾光片用著色組合物之除溶劑以外之有效成分中較佳為10質量%以上且40質量%以下。 <77> The coloring composition for a color filter according to <76>, wherein the content of the alkali-soluble resin is preferably 10% by mass or more and 40% by mass of the active ingredient other than the solvent of the coloring composition for the color filter. %the following.

<78>如<76>或<77>之彩色濾光片用著色組合物,其中多官能單體較佳為具有2個以上乙烯性不飽和雙鍵之丙烯酸酯,更佳為二季戊四醇六丙烯酸酯。 <78> The coloring composition for a color filter such as <76> or <77>, in which the polyfunctional monomer is preferably an acrylate having two or more ethylenically unsaturated double bonds, and more preferably dipentaerythritol hexaacrylic acid. ester.

<79>如<76>至<78>中任一項之彩色濾光片用著色組合物,其中多官能單體之含量於彩色濾光片用著色組合物之除溶劑以外之有效成分中較佳為5質量%以上且30質量%以下。 <79> The coloring composition for a color filter according to any one of <76> to <78>, wherein the content of the polyfunctional monomer is greater than the effective ingredients other than the solvent of the coloring composition for a color filter. It is preferably 5 mass% or more and 30 mass% or less.

<80>如<76>至<79>中任一項之彩色濾光片用著色組合物,其中光聚合起始劑之含量於彩色濾光片用著色組合物之除溶劑以外之有效成分中較佳為0.2質量%以上且20質量%以下。 <80> The coloring composition for a color filter according to any one of <76> to <79>, wherein the content of the photopolymerization initiator is in an active ingredient other than a solvent of the coloring composition for a color filter It is preferably 0.2% by mass or more and 20% by mass or less.

<81>一種彩色濾光片,其係使用如<76>至<80>中任一項之彩色濾光片用著色組合物而製造。 <81> A color filter manufactured by using the coloring composition for color filters according to any one of <76> to <80>.

<82>一種彩色濾光片之製造方法,其具有將如<76>至<80>中任一項之著色組合物塗佈於基板上並進行光硬化、顯影而獲得塗膜 之步驟(F-1)、將上述步驟(F-1)中所獲得之塗膜加熱至200~300℃而獲得硬化膜之步驟(F-2)。 <82> A method for manufacturing a color filter, which comprises applying a coloring composition according to any one of <76> to <80> on a substrate, photocuring, and developing to obtain a coating film. Step (F-1), step (F-2) of heating the coating film obtained in the above step (F-1) to 200 to 300 ° C to obtain a cured film.

<83>一種彩色濾光片用著色組合物之用途,其係將如<76>至<80>中任一項之彩色濾光片用著色組合物用於製造彩色濾光片。 <83> The use of a coloring composition for a color filter, which uses the coloring composition for a color filter according to any one of <76> to <80> to manufacture a color filter.

[實施例] [Example]

於本實施例中,「聚酯(X)」之表述中之X係指構成該聚酯之結構單元之平均聚合度(以下亦稱為「聚酯之平均聚合度」),「聚伸烷基二醇(Y)」之表述中之Y係指該聚伸烷基二醇之環氧烷平均加成莫耳數。 In the present embodiment, X in the expression of "polyester (X)" refers to the average degree of polymerization of the structural units constituting the polyester (hereinafter also referred to as "average degree of polymerization of polyester"), and "polyextend "Y" in the expression "" refers to the average addition mole number of alkylene oxide of the polyalkylene glycol.

於本實施例中,藉由下述方法進行測定及評價。 In this example, measurement and evaluation were performed by the following methods.

[測定方法] [test methods]

(1)烷氧基聚酯中之聚酯之平均聚合度之測定 (1) Determination of average polymerization degree of polyester in alkoxy polyester

將烷基聚酯單醇之末端羥基利用三氟乙酸進行酯化而成之樣品之0.01g溶解於氘氯仿0.99g中,將所得者作為測定試樣,進行1H-NMR測定(裝置:安捷倫科技股份有限公司製造之「400-MR DD2」,非解耦法,緩和時間:10秒,累計次數:32次)。根據所獲得之光譜,藉由以下之式算出烷基聚酯中之聚酯之平均聚合度。 0.01 g of a sample obtained by esterifying a terminal hydroxyl group of an alkyl polyester monool with trifluoroacetic acid was dissolved in 0.99 g of deuterium chloroform, and the obtained was used as a measurement sample for 1 H-NMR measurement (device: Agilent "400-MR DD2" manufactured by Technology Co., Ltd., non-decoupling method, relaxation time: 10 seconds, cumulative times: 32 times). Based on the obtained spectrum, the average degree of polymerization of the polyester in the alkyl polyester was calculated by the following formula.

平均聚合度=(源自與構成烷氧基聚酯之酯基之氧原子鄰接之亞甲基的訊號之積分值)/(源自與源自三氟乙酸之酯基之氧原子鄰接之亞甲基的訊號之積分值)+1 Average degree of polymerization = (Integral value of signal derived from methylene group adjacent to oxygen atom constituting ester group of alkoxy polyester) / (from sub-group adjacent to oxygen atom of ester group derived from trifluoroacetic acid) (Integral value of methyl signal) +1

(2)重量平均分子量之測定 (2) Determination of weight average molecular weight

重量平均分子量係於下述<條件1>、<條件2>之任一條件下測定。 The weight average molecular weight is measured under any one of the following <Condition 1> and <Condition 2>.

測定試樣之製備係藉由以下之方法進行。 The measurement sample was prepared by the following method.

採取包含下述製造例中所獲得之化合物之溶液之固形物成分成為0.01g之量置於玻璃瓶(Maruemu股份有限公司製造之「螺旋管 No.5」)中,添加下述溶離液使總量成為10mL並將其栓緊。繼而,將上述玻璃瓶使用試驗管混合機(IKA公司製造之「Minishaker MS1」)以2,500r/min攪拌1分鐘,使用所獲得之溶液之100μL作為測定試樣。 The solid content of the solution containing the compound obtained in the following production example was taken in an amount of 0.01 g and placed in a glass bottle ("spiral tube manufactured by Maruemu Co., Ltd." No. 5 "), the following eluent was added to make the total amount 10 mL, and this was plugged. Then, the above glass bottle was stirred at 2,500 r / min for 1 minute using a test tube mixer ("Minishaker MS1" manufactured by IKA Corporation), and 100 μL of the obtained solution was used as a measurement sample.

<條件1> <Condition 1>

以將二甲基+二烷基胺(花王股份有限公司製造之「Farmin DM20」)以成為1mmol/L之方式溶解於氯仿而成之溶液作為溶離液,藉由凝膠層析法(GPC法,裝置:東曹股份有限公司製造之「HLC-8320GPC」,檢測器:裝置所附帶之示差折射計,管柱:昭和電工股份有限公司製造之「K-804L」×2,流速:1.0mL/min,管柱溫度:40℃)進行測定。作為標準物質,使用下述之單分散聚苯乙烯。 A solution obtained by dissolving dimethyl + dialkylamine ("Farmin DM20" manufactured by Kao Corporation) in chloroform so as to have a concentration of 1 mmol / L was used as an eluent, and gel chromatography (GPC method) was used. Device: "HLC-8320GPC" manufactured by Tosoh Corporation, Detector: Differential refractometer attached to the device, column: "K-804L" manufactured by Showa Denko Corporation × 2, flow rate: 1.0mL / min, column temperature: 40 ° C). As a standard substance, the following monodisperse polystyrene was used.

[標準物質:聚苯乙烯] [Standard substance: polystyrene]

東曹股份有限公司製造之「A-500(Mw:500)」、「A-5000(Mw:5,060)」、「F-2(Mw:18,100)」、「F-10(Mw:96,400)」、「F-40(Mw:427,000)」;Pressure Chemical公司製造之「PS30908(Mw:50,000)」 "A-500 (Mw: 500)", "A-5000 (Mw: 5,060)", "F-2 (Mw: 18,100)", "F-10 (Mw: 96,400)" manufactured by Tosoh Corporation "F-40 (Mw: 427,000)"; "PS30908 (Mw: 50,000)" manufactured by Pressure Chemical

<條件2> <Condition 2>

以將溴化鋰與乙酸以分別成為50mmol/L與1質量%之濃度之方式溶解於乙醇/水混合溶劑(質量比8/2)而成之溶液作為溶離液,藉由凝膠層析法(GPC法,裝置:東曹股份有限公司製造之「HLC-8320GPC」,檢測器:裝置所附帶之示差折射計,管柱:東曹股份有限公司製造之「TSK-GEL α-M」×2,流速:0.6mL/min,管柱溫度:40℃)進行測定。作為標準物質,使用下述之單分散聚乙二醇。 A solution prepared by dissolving lithium bromide and acetic acid in a mixed solvent of ethanol / water (mass ratio 8/2) so as to have a concentration of 50 mmol / L and 1% by mass, respectively, was used as an eluent, and gel chromatography (GPC) was used. Method, Device: "HLC-8320GPC" manufactured by Tosoh Corporation, Detector: Differential refractometer attached to the device, Tube: "TSK-GEL α-M" manufactured by Tosoh Corporation × 2, Flow rate : 0.6 mL / min, column temperature: 40 ° C). As a standard substance, the following monodisperse polyethylene glycol was used.

[標準物質:聚乙二醇] [Standard substance: polyethylene glycol]

GL Science股份有限公司製造之「高分子材料標準物質聚乙二醇(分子量:100、400、1,500、6,500)」;東曹股份有限公司製造之「標準聚環氧乙烷(分子量:5萬、25萬、90萬)」 "Polyethylene glycol reference material (molecular weight: 100, 400, 1,500, 6,500)" manufactured by GL Science Co., Ltd .; "Standard polyethylene oxide (molecular weight: 50,000, 250,000, 900,000)

(3)固形物成分之測定 (3) Determination of solid content

向培養皿中放入乾燥無水硫酸鈉10g及玻璃棒,稱量試樣2g,利用玻璃棒進行混合,利用105℃之減壓乾燥機(壓力8kPa)乾燥2小時。稱量乾燥後之質量,根據下式算出固形物成分。 10 g of dry anhydrous sodium sulfate and a glass rod were placed in a petri dish, and 2 g of a sample was weighed, mixed with the glass rod, and dried using a reduced-pressure dryer (pressure 8 kPa) at 105 ° C. for 2 hours. The weight after drying was measured and the solid content was calculated according to the following formula.

固形物成分(質量%)=[(乾燥後之質量g)-(培養皿+玻璃棒+乾燥無水硫酸鈉之質量g)]/(試樣之質量g)×100 Solid content (% by mass) = [(mass g after drying)-(mass dish + glass rod + mass g of dried anhydrous sodium sulfate)] / (mass g of sample) × 100

(4)反應率之測定 (4) Measurement of reaction rate

(反應率Cl:氯離子量之比率基準) (Reaction rate Cl : Ratio standard of chloride ion amount)

由於藉由反應而烷氧基聚酯單氯乙酸酯之氯成為氯離子,故而氯離子量之比率基準之反應率Cl根據下式而算出。 Since the chlorine of the alkoxy polyester monochloroacetate becomes chloride ion by the reaction, the reaction rate Cl based on the ratio of the chloride ion amount is calculated according to the following formula.

反應率Cl(%)=[氯離子量(質量%)]/[總氯含量(質量%)]×100 Reaction rate Cl (%) = [Amount of chloride ion (mass%)] / [Total content of chlorine (mass%)] × 100

氯離子量係設為藉由Volhard法所定量之值,總氯含量係設為利用丁酸鈉進行分解後藉由Volhard法所定量之值。 The amount of chloride ions is a value quantified by the Volhard method, and the total chlorine content is a value quantified by the Volhard method after decomposition using sodium butyrate.

(反應率Am:胺值減少率基準) (Reaction rate Am : Standard for reduction of amine value)

由於藉由反應而聚胺成為四級鹽,胺值減少,故而胺值減少率基準之反應率Am根據下式而算出。 Since the polyamine becomes a quaternary salt by the reaction and the amine value decreases, the reaction rate Am based on the amine value reduction rate is calculated according to the following formula.

反應率Am(%)=[(反應前之胺值mgKOH/g)-(反應後之胺值mgKOH/g)]/(反應前之胺值mgKOH/g)×100 Reaction rate Am (%) = [(amine value before reaction mgKOH / g)-(amine value after reaction mgKOH / g)] / (amine value before reaction mgKOH / g) × 100

上述胺值係藉由ASTM D2073-66之「三級胺值」而測定。 The amine value is measured by the "tertiary amine value" of ASTM D2073-66.

(5)酸值之測定 (5) Determination of acid value

依據JIS K 0070之記載,利用電位差滴定法進行測定。 The measurement was performed by a potentiometric titration method according to JIS K 0070.

(6)四級化反應之確認 (6) Confirmation of quaternary reaction

針對聚胺化合物、鹵化烷基酯化合物及四級化物之各者,將其0.01g溶解於氘氯仿0.99g中,將所得者作為測定試樣。進行1H-NMR測定(裝置:安捷倫科技股份有限公司製造之「400-MR DD2」,非解耦法,緩和時間:10秒,累計次數:32次),藉由所獲得之光譜進行 四級化反應之確認。 For each of a polyamine compound, a halogenated alkyl ester compound, and a quaternary compound, 0.01 g thereof was dissolved in 0.99 g of deuterochloroform, and the obtained sample was used as a measurement sample. 1 H-NMR measurement was performed (apparatus: "400-MR DD2" manufactured by Agilent Technologies Co., Ltd., non-decoupling method, relaxation time: 10 seconds, total number of times: 32 times), and four levels were performed from the obtained spectrum Confirmation of chemical reaction.

(7)分散劑中之式(1)中之平均結構單元數(n+p+m+k)、n、p、m及k之測定 (7) Measurement of the average number of structural units (n + p + m + k), n, p, m and k in the formula (1) in the dispersant

式(1)中之(n+p+m+k)係根據反應前之聚胺化合物之平均胺官能基數(式(1)中之(n+p+m+k))而求出。 (N + p + m + k) in the formula (1) is determined based on the average number of amine functional groups of the polyamine compound before the reaction ((n + p + m + k) in the formula (1)).

該平均胺官能基數係藉由聚胺化合物之1H-NMR測定之積分比而求出。更具體而言,於如合成例c2及c3等於末端具有OH基之情形時,與上述「四級化反應之確認」中所記載之方法同樣地進行所獲得之聚胺化合物之1H-NMR測定,根據源自與R1及R2之OH基鄰接之亞甲基之氫的波峰面積(q)及源自與N鍵結之甲基之氫的波峰面積(r),藉由下述之式而算出。 The average number of amine functional groups is determined by an integral ratio measured by 1 H-NMR of a polyamine compound. More specifically, when Synthesis Examples c2 and c3 are equivalent to having an OH group at the end, the 1 H-NMR of the obtained polyamine compound is performed in the same manner as described in "Confirmation of the Quaternary Reaction" above. The measurement was based on the peak area (q) of hydrogen derived from a methylene group adjacent to the OH group of R 1 and R 2 and the peak area (r) of hydrogen derived from a methyl group bonded to N. To calculate.

(n+p+m+k)=(4×r)/(3×q) (n + p + m + k) = (4 × r) / (3 × q)

關於聚胺化合物之一分子內之胺數,於使用單一化合物之情形時,使用其胺數作為(n+p+m+k)。 Regarding the number of amines in one molecule of the polyamine compound, when a single compound is used, the number of amines is used as (n + p + m + k).

(n+p)、m及k係根據上述反應後之胺值及下述(M1)-、(M2)-量而求出。 (n + p), m and k, and the following line in accordance with an amine value (M 1) After the above reaction - the amount determined -, (M 2).

將下述(nKOH+pKOH)、mKOH及kKOH之比設為(n+p)、m及k之比,以(n+p)+m+k與製造例中用於分散劑之合成之聚胺化合物之平均胺官能基數(n+p+m+k)相等之方式分別算出(n+p)、m及k。(nKOH+pKOH)及kKOH係將(n+p)、k所表示之結構單元中所含之四級銨基數換算成胺值之數值。 The ratio of (n KOH + p KOH ), m KOH, and k KOH below is (n + p), the ratio of m and k, and (n + p) + m + k is used as the dispersant in the production example. The average polyamine compound number (n + p + m + k) of the synthesized polyamine compound was calculated such that (n + p), m, and k were equal. (n KOH + p KOH ) and k KOH are numerical values obtained by converting the quaternary ammonium group number contained in the structural unit represented by (n + p) and k into an amine value.

根據下式算出(nKOH+pKOH)。 (N KOH + p KOH ) was calculated according to the following formula.

(nKOH+pKOH)=[(M1)-量(質量%)]/(100×[(M1)-之分子量])×56×1,000 (n KOH + p KOH) = [(M 1) - (mass%)] / (100 × [ (M 1) - molecular weight]) × 56 × 1,000

mKOH係定義為反應後之胺值(mgKOH/g)。 m KOH is defined as the amine value (mgKOH / g) after the reaction.

根據下式算出kKOHK KOH is calculated by the following formula.

kKOH={[(M2)-量(質量%)]/(100×[(M2)-之分子量])}×56×1,000 k KOH = {[(M 2 ) - (mass%)] / (100 × [ (M 2) - with a molecular weight])} × 56 × 1,000

關於(M1)-及(M2)-量,於為Cl-之情形時,使用藉由上述Volhard法定量相對於試樣中之固形物成分之氯濃度所得之值。 About (M 1) - and (M 2) - the amount, as in Cl - when the situation, using the value obtained by the above-described chlorine concentration quantified with respect to Volhard of the solid content of the sample.

於其他情形時,(M1)-及(M2)-量係藉由以下方法進行測定。將包含下述製造例中所獲得之分散劑之溶液0.1g利用超純水稀釋1,000~5,000倍,獲得分散劑之濃度已知之溶液,將其25μL設為測定試樣。藉由離子層析法(裝置:Thermo Scientific製造之「Dionex ICS-2100」,抑制器(suppressor):「ASRS-300」,檢測器:裝置所附帶之導電率檢測器,檢測器溫度:35℃,管柱:日本Dionex股份有限公司製造之「Ion Pac AS11-HC」+「Ion Pac AG11-HC」,流速:1.5mL/min,管柱溫度:35℃,溶離液:氫氧化鉀溶液)對測定試樣進行測定。溶離液濃度係設為10mmol/L至40mmol/L(25min)之線性梯度溶出。作為標準物質,使用(M1)-或(M2)-之鈉鹽。於本實施例中,根據分散劑使用甲基硫酸鈉(東京化成工業股份有限公司製造,試劑)或乙基硫酸鈉(東京化成工業股份有限公司製造,試劑)。根據測定結果獲得化合物中之(M1)-或(M2)-量(質量%)。 When in other cases, (M 1) - and (M 2) - was measured by the following amounts based methods. 0.1 g of the solution containing the dispersant obtained in the following production examples was diluted 1,000-5,000 times with ultrapure water to obtain a solution with a known concentration of the dispersant, and 25 μL of the solution was used as a measurement sample. By ion chromatography (device: "Dionex ICS-2100" manufactured by Thermo Scientific, suppressor: "ASRS-300", detector: conductivity detector attached to the device, detector temperature: 35 ° C , Column: "Ion Pac AS11-HC" + "Ion Pac AG11-HC" manufactured by Japan Dionex Co., Ltd., flow rate: 1.5mL / min, column temperature: 35 ° C, eluent: potassium hydroxide solution) The measurement sample is measured. The eluent concentration is a linear gradient of 10 to 40 mmol / L (25 min). As the standard substance used (M 1) - or (M 2) - the sodium salt. In this embodiment, sodium methyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) or sodium ethyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) is used according to the dispersant. Or (M 2) - - (% by mass) based on the measurement results of the compound (M 1) is obtained.

p及n係藉由分散劑之1H-NMR測定之積分比而求出。於(Ry1O)d為上述式(D-a)所表示之結構單元之情形時,與上述「四級化反應之確認」中所記載之方法同樣地進行所獲得之聚胺化合物之1H-NMR測定,根據源自與Rx1之C=O(羰基)基鄰接之亞甲基之氫的波峰面積(s)、及源自Ry1中之源自環氧丙烷之結構單元PO之甲基之氫的波峰面積(t1)、源自源自環氧乙烷之結構單元EO之亞甲基之氫的波峰面積(t2)、式中之平均加成莫耳數a、d1及d2,以如下方式求出。 p and n are calculated | required from the integral ratio of 1 H-NMR measurement of a dispersing agent. When (R y1 O) d is a structural unit represented by the above formula (Da), 1 H- of the obtained polyamine compound is performed in the same manner as described in "Confirmation of Quaternary Reaction" above. NMR measurement based on the peak area (s) of the hydrogen derived from the methylene group adjacent to the C = O (carbonyl) group of R x1 and the methyl group derived from the structural unit PO derived from propylene oxide in R y1 The peak area (t 1 ) of hydrogen, the peak area (t 2 ) of hydrogen derived from the methylene group derived from the structural unit EO of ethylene oxide, and the average addition mole numbers a, d1, and d2 in the formula Calculate it as follows.

(d1≠0,d2≠0之情形) (d1 ≠ 0, d2 ≠ 0)

nKOH=[nKOH+pKOH]×(s/a)/[(s/a)+{(t1×2/3)/d1+(t2/2)/d2}/2] n KOH = [n KOH + p KOH] × (s / a) / [(s / a) + {(t 1 × 2/3) / d1 + (t 2/2) / d2} / 2]

pKOH=[nKOH+pKOH]×[{(t1×2/3)/d1+(t2/2)/d2}/2]/[(s/a)+ {(t1×2/3)/d1+(t2/2)/d2}/2] p KOH = [n KOH + p KOH] × [{(t 1 × 2/3) / d1 + (t 2/2) / d2} / 2] / [(s / a) + {(t 1 × 2 / 3) / d1 + (t 2 /2) / d2} / 2]

(d1≠0,d2=0之情形) (d1 ≠ 0, d2 = 0)

nKOH=[nKOH+pKOH]×(s/a)/[(s/a)+(t1×2/3)/d1] n KOH = [n KOH + p KOH ] × (s / a) / [(s / a) + (t 1 × 2/3) / d1]

pKOH=[nKOH+pKOH]×{(t1×2/3)/d1}/[(s/a)+(t1×2/3)/d1] p KOH = [n KOH + p KOH ] × {(t 1 × 2/3) / d1} / [(s / a) + (t 1 × 2/3) / d1]

(d1=0,d2≠0之情形) (d1 = 0, d2 ≠ 0)

nKOH=[nKOH+pKOH]×(s/a)/[(s/a)+{(t2/2)/d2}] n KOH = [n KOH + p KOH] × (s / a) / [(s / a) + {(t 2/2) / d2}]

pKOH=[nKOH+pKOH]×[{(t2/2)/d2}]/[(s/a)+{(t2/2)/d2}] p KOH = [n KOH + p KOH] × [{(t 2/2) / d2}] / [(s / a) + {(t 2/2) / d2}]

將nKOH與pKOH之比設為n與p之比,根據上述之n+p之值算出n與p。 Let the ratio of n KOH and p KOH be the ratio of n and p, and calculate n and p from the above-mentioned value of n + p.

於未觀察到源自(Ry1O)d之波峰之情形時,將p設為0,將上述之n+p之值設為n。 When a peak derived from (R y1 O) d is not observed, p is set to 0, and the above-mentioned value of n + p is set to n.

(8)分散劑中之結構單元A之平均數量 (8) Average number of structural units A in the dispersant

分散劑中之結構單元A之平均數量係根據反應前之聚胺化合物之平均胺官能基數藉由以下之式而算出。 The average number of structural units A in the dispersant is calculated by the following formula based on the average number of amine functional groups of the polyamine compound before the reaction.

[於分散劑之結構中不含結構單元D之情形:未觀察到源自上述(7)中之(Ry1O)d之波峰之情形] [A case where the structural unit D is not included in the structure of the dispersant: a case where a peak derived from (R y1 O) d in (7) above is not observed]

結構單元A之平均數量=(AKOH/反應前之胺值)×原料之平均胺官能基數 The average number of structural units A = (A KOH / amine value before the reaction) × the average number of amine functional groups of the raw material

AKOH係將分子中所含之四級銨基數換算為胺值之數值,藉由以下之式而算出。 A KOH is a numerical value obtained by converting the number of quaternary ammonium groups contained in the molecule into an amine value, and is calculated by the following formula.

AKOH=[(M1)-量(質量%)]/(100×[(M1)-之分子量])×56×1,000 A KOH = [(M 1) - (mass%)] / (100 × [ (M 1) - molecular weight]) × 56 × 1,000

(M1)-量係利用與上述(7)相同之方法獲得。 (M 1) - obtained using an amount in the same procedure (7) above.

[於分散劑之結構中含有結構單元D之情形:觀察到源自上述(7)中之(Ry1O)d之波峰之情形] [Case where Structural Unit D is included in the structure of the dispersant: Case where a peak derived from (R y1 O) d in (7) above is observed]

(d1≠0,d2≠0之情形) (d1 ≠ 0, d2 ≠ 0)

結構單元A之平均數量=AKOH×(s/a)/[(s/a)+{(t1×2/3)/d1+ (t2/2)/d2}/2]×[原料之平均胺官能基數/反應前之胺值] The average number of structural unit A of = A KOH × (s / a ) / [(s / a) + {(t 1 × 2/3) / d1 + (t 2/2) / d2} / 2] × [ raw materials Average number of amine functional groups / amine value before reaction]

(d1≠0,d2=0之情形) (d1 ≠ 0, d2 = 0)

結構單元A之平均數量=AKOH×(s/a)/[(s/a)+(t1×2/3)/d1]×[原料之平均胺官能基數/反應前之胺值] The average number of structural units A = A KOH × (s / a) / [(s / a) + (t 1 × 2/3) / d1] × [average number of amine functional groups of raw materials / amine value before reaction]

(d1=0,d2≠0之情形) (d1 = 0, d2 ≠ 0)

結構單元A之平均數量=AKOH×(s/a)/[(s/a)+{(t2/2)/d2}]×[原料之平均胺官能基數/反應前之胺值] The average number of structural unit A = A KOH × (s / a ) / [(s / a) + {(t 2/2) / d2}] × [ average amine functionality of base material / amine value before the reaction]

上述式中,AKOH與上述者相同,s、t1、t2、a、d1、d2與上述(7)相同。 In the above formula, A KOH is the same as the above, and s, t 1 , t 2 , a, d1, and d2 are the same as the above (7).

(9)顏料分散體之黏度之測定 (9) Determination of viscosity of pigment dispersion

將顏料分散體1mL設為試樣,使用E型黏度計(東機產業股份有限公司製造之「TV-25 typeL」,轉子:1°34'×R24),於轉子之轉數50r/min、溫度25℃、測定時間5min之條件下測定黏度。其中,於轉數50r/min下之測定值超過60mPa‧s之情形時,將轉子之轉數變更為20r/min而進行測定,於轉數20r/min下之測定值超過150mPa‧s之情形時,將轉子之轉數變更為10r/min而進行測定。 Set 1 mL of pigment dispersion as a sample, use an E-type viscometer ("TV-25 typeL" manufactured by Toki Sangyo Co., Ltd., rotor: 1 ° 34 '× R24), the number of revolutions of the rotor is 50 r / min, The viscosity was measured at a temperature of 25 ° C and a measurement time of 5 minutes. Among them, when the measured value at a revolution of 50r / min exceeds 60mPa · s, the rotor is changed to 20r / min for measurement, and when the measured value at a revolution of 20r / min exceeds 150mPa · s At this time, the number of revolutions of the rotor was changed to 10 r / min for measurement.

(10)顏料分散體之保存後黏度之測定 (10) Determination of the viscosity of pigment dispersions after storage

含有DPP-1及DPP-2之顏料分散體係填充至玻璃製密閉容器,於25℃下靜置7天。 The pigment dispersion system containing DPP-1 and DPP-2 was filled into a glass closed container and left to stand at 25 ° C for 7 days.

含有DPP-1及DPP-3之顏料分散體係填充至玻璃製密閉容器,於45℃下靜置7天。 The pigment dispersion system containing DPP-1 and DPP-3 was filled into a glass closed container and left at 45 ° C for 7 days.

將靜置後之顏料分散體1mL設為試樣,利用與上述「顏料分散體之黏度之測定」相同之方法測定。 1 mL of the pigment dispersion after standing was used as a sample, and it measured by the same method as the said "measurement of the viscosity of a pigment dispersion."

(11)顏料分散體之平均粒徑之測定 (11) Determination of average particle size of pigment dispersion

向加入有PGMEA 15g之玻璃瓶(Maruemu股份有限公司製造之「螺旋管No.5」)中添加顏料分散體0.01g,使用試驗管混合機(IKA 公司製造之「Minishaker MS1」)以2,500r/min攪拌1分鐘,將所得者作為試樣,使用粒徑測定裝置(堀場製作所股份有限公司製造之「SZ-100」,試樣折射率:1.51,分散介質折射率:1.400,分散介質黏度:1.136mPa‧s,測定溫度:25℃)進行測定。將基於JIS Z 8826中所記載之粒徑解析-光子相關法進行累積解析而求出之累積平均粒徑設為顏料分散體之平均粒徑。 0.01 g of pigment dispersion was added to a glass bottle ("spiral tube No. 5" manufactured by Maruemu Co., Ltd.) containing 15 g of PGMEA, and a test tube mixer (IKA "Minishaker MS1" manufactured by the company) was stirred at 2,500 r / min for 1 minute, and the obtained sample was used as a sample, and a particle size measuring device ("SZ-100" manufactured by Horiba, Ltd. was used. Sample refractive index: 1.51, The refractive index of the dispersion medium: 1.400, the viscosity of the dispersion medium: 1.136 mPa · s, and the measurement temperature: 25 ° C.) were measured. The cumulative average particle diameter obtained by cumulative analysis based on the particle size analysis-photon correlation method described in JIS Z 8826 was defined as the average particle diameter of the pigment dispersion.

(12)顏料分散體之保存後平均粒徑之測定 (12) Measurement of average particle size of pigment dispersion after storage

將顏料分散體填充至玻璃製密閉容器,於25℃下靜置7天。利用與上述「顏料分散體之平均粒徑之測定」相同之方法對該靜置後之顏料分散體進行測定,設為保存後平均粒徑。 The pigment dispersion was filled in a glass closed container and left to stand at 25 ° C for 7 days. This pigment dispersion after standing was measured by the same method as the above "measurement of the average particle diameter of a pigment dispersion", and it was set as the average particle diameter after storage.

[評價方法] [Evaluation method]

(13)顯影性之評價 (13) Evaluation of developability

於10cm×10cm之玻璃基板上利用旋轉塗佈機(ACTIVE股份有限公司製造之「ACT-300AII」)塗佈著色組合物後,於水平台上靜置5分鐘,進而於80℃之加熱板上靜置3分鐘,獲得於基板上具有厚度2μm之塗膜之基板。於基板之塗佈有著色組合物之面之側,距離基板0.3mm而設置光罩。上述光罩具有寬度(單位μm)1、2、3、4、5、6、7、8、9、10、20、30、40、50、60、70、80、90及100之狹縫。使用紫外線纖維點照射裝置(High Tech股份有限公司製造之「HTE-505-HA-X」,燈:Ushio Lighting股份有限公司製造之「USH-500MB」),經由上述光罩對基板以40mJ/cm2照射紫外線。 After applying the coloring composition on a 10 cm × 10 cm glass substrate using a spin coater (“ACT-300AII” manufactured by ACTIVE Co., Ltd.), it was left to stand on a water platform for 5 minutes, and then heated on a heating plate at 80 ° C. After standing for 3 minutes, a substrate having a coating film having a thickness of 2 μm on the substrate was obtained. A photomask is set on the side of the substrate on the side on which the coloring composition is applied, 0.3 mm from the substrate. The photomask has slits having a width (unit: μm) of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100. A UV fiber spot irradiation device ("HTE-505-HA-X" manufactured by High Tech Co., Ltd., lamp: "USH-500MB" manufactured by Ushio Lighting Co., Ltd.) was used to pass the substrate to the substrate at 40 mJ / cm 2 Irradiate ultraviolet rays.

將紫外線照射後之基板浸漬於含有碳酸鈉0.35質量%及聚氧乙烯二苯乙烯化苯醚(花王股份有限公司製造之「Emulgen A-60」)0.2質量%之水溶液中。自開始顯現曝光.圖案起,進而浸漬20秒後,利用離子交換水對基板進行沖洗,將殘存於基板上之水去除。 The substrate after the ultraviolet irradiation was immersed in an aqueous solution containing 0.35 mass% of sodium carbonate and 0.2 mass% of polyoxyethylene styrenated phenyl ether ("Emulgen A-60" manufactured by Kao Corporation). After the exposure and pattern started to appear, and after immersion for 20 seconds, the substrate was rinsed with ion-exchanged water to remove the water remaining on the substrate.

使用光學顯微鏡,觀察藉由上述光罩而顯影之基板上之細線, 將殘存於基板上之最細之細線之線寬設為細線密接性之指標。上述線寬越小,細線密接性良好,顯影性越優異。 Using an optical microscope, observe the thin lines on the substrate developed by the above mask, The line width of the thinnest thin line remaining on the substrate is set as an index of the fine line adhesion. The smaller the line width, the better the fine-line adhesiveness, and the better the developability.

(14)耐熱性之評價 (14) Evaluation of heat resistance

利用與上述「顯影性之評價」相同之方法獲得於基板上具有厚度2μm之塗膜之基板。於基板之塗佈有著色組合物之面之側,使用紫外線纖維點照射裝置(High Tech股份有限公司製造之「HTE-505-HA-X」,燈:Ushio Lighting股份有限公司製造之「USH-500MB」),對基板以40mJ/cm2照射紫外線。 A substrate having a coating film having a thickness of 2 μm on the substrate was obtained by the same method as the above “Evaluation of developability”. On the side of the substrate on which the coloring composition is applied, an ultraviolet fiber spot irradiation device ("HTE-505-HA-X" manufactured by High Tech Co., Ltd.) is used. Lamp: "USH-" manufactured by Ushio Lighting Co., Ltd. 500 MB "), and the substrate was irradiated with ultraviolet rays at 40 mJ / cm 2 .

將紫外線照射後之基板於230℃之潔淨烘箱中進行20分鐘熱處理,測定塗膜之膜厚(T20)。其後,進而將基板於230℃之潔淨烘箱中進行80分鐘熱處理,測定塗膜之膜厚(T100)。 The substrate after the ultraviolet irradiation was heat-treated in a clean oven at 230 ° C. for 20 minutes, and the film thickness (T 20 ) of the coating film was measured. Thereafter, the substrate was further heat-treated in a clean oven at 230 ° C. for 80 minutes, and the film thickness (T 100 ) of the coating film was measured.

塗膜之膜厚係使用東京精密股份有限公司製造之「SURFCOM 1500DX」進行測定,根據下式算出膜厚維持率(%)。膜厚維持率越接近100%,耐熱性越優異。 The film thickness of the coating film was measured using "SURFCOM 1500DX" manufactured by Tokyo Precision Co., Ltd., and the film thickness maintenance ratio (%) was calculated according to the following formula. The closer the film thickness maintenance rate is to 100%, the better the heat resistance.

膜厚維持率(%)=T100(μm)/T20(μm)×100 Film thickness retention rate (%) = T 100 (μm) / T 20 (μm) × 100

合成例a1[聚酯a1:月桂氧基聚(ε-己內酯)(21)之合成] Synthesis example a1 [Polyester a1: Synthesis of lauryloxy poly (ε-caprolactone) (21)]

於安裝有攪拌裝置、溫度計、氮氣吹入管之10L之燒瓶中,添加月桂醇(花王股份有限公司製造之「Kalcol 2098」)350g(1.89莫耳)、ε-己內酯(東京化成工業股份有限公司製造)4,500g(39.4莫耳)、正鈦酸四丁酯0.0606g,並開始攪拌。對燒瓶內進行氮氣置換,於150℃下反應2小時,進而於170℃下反應5小時。其後,冷卻至室溫,獲得月桂氧基聚(ε-己內酯)(21)(聚酯a1)。 To a 10 L flask equipped with a stirring device, a thermometer, and a nitrogen blowing tube, add 350 g (1.89 mol) of lauryl alcohol ("Kalcol 2098" manufactured by Kao Corporation) and ε-caprolactone (Tokyo Chemical Industry Co., Ltd. 4,500 g (39.4 mol), 0.0606 g of tetrabutyl orthotitanate, and stirring was started. The flask was purged with nitrogen, and reacted at 150 ° C for 2 hours and further at 170 ° C for 5 hours. Thereafter, it was cooled to room temperature to obtain lauryloxy poly (ε-caprolactone) (21) (polyester a1).

合成例a2[聚酯a2:辛氧基聚(ε-己內酯)(20)之合成] Synthesis Example a2 [Polyester a2: Synthesis of Octyloxy Poly (ε-caprolactone) (20)]

將反應容器設為1L之燒瓶,並設為下述表1記載之醇及內酯,將正鈦酸四丁酯設為0.0085g,除此以外,與合成例a1同樣地獲得辛氧基聚(ε-己內酯)(20)(聚酯a2)。 A reaction vessel was set to a 1 L flask, the alcohols and lactones described in Table 1 below were used, and tetrabutyl orthotitanate was set to 0.0085 g. Except that octyloxy polymer was obtained in the same manner as in Synthesis Example a1 (ε-caprolactone) (20) (polyester a2).

合成例a3~a10[聚酯a3~a10:烷氧基聚內酯之合成] Synthesis Examples a3 ~ a10 [Polyester a3 ~ a10: Synthesis of Alkoxy Polylactone]

設為下述表1記載之醇及內酯,除此以外,與合成例a2同樣地獲得烷氧基聚內酯(聚酯a3~a10)。 An alkoxy polylactone (polyesters a3 to a10) was obtained in the same manner as in Synthesis Example a2, except that the alcohols and lactones described in Table 1 were used.

合成例b1[氯乙酸酯b1:月桂氧基聚(ε-己內酯)(21)單氯乙酸酯之合成] Synthesis Example b1 [Chloroacetate b1: Synthesis of lauryloxy poly (ε-caprolactone) (21) monochloroacetate]

於安裝有攪拌裝置、溫度計、氮氣吹入管、冷卻管之10L之燒瓶中,添加合成例1中所獲得之聚酯a1 4,790g、單氯乙酸(和光純藥工業股份有限公司製造,特級試劑)199g、對甲苯磺酸‧一水合物(岸田化學股份有限公司製造,特級試劑)17.5g,並開始攪拌。對燒瓶內進行氮氣置換,於140℃、大氣壓下反應2小時,進而一面吹入氮氣一面於140℃、-0.1MPaG(表壓)之減壓條件下反應21小時。其後,利用氮氣恢復至大氣壓,冷卻至80℃,添加鋁碳酸鎂(協和化學工業股份有限公司製造之「Kyoword 500SH」)131.8g,於80℃下攪拌3小時。將所獲得之溶液保持為80℃,利用濾紙(Advantec東洋股份有限公司製造之「No.5A」)進行過濾,獲得月桂氧基聚(ε-己內酯)(21)單氯乙酸 酯(氯乙酸酯b1)。 In a 10 L flask equipped with a stirring device, a thermometer, a nitrogen blowing tube, and a cooling tube, 4,790 g of polyester a1 obtained in Synthesis Example 1, and monochloroacetic acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) were added. 199 g, 17.5 g of p-toluenesulfonic acid ‧ monohydrate (manufactured by Kishida Chemical Co., Ltd.), and start stirring. The flask was purged with nitrogen, and reacted at 140 ° C and atmospheric pressure for 2 hours, and further reacted for 21 hours at 140 ° C under a reduced pressure of -0.1 MPaG (gauge pressure) while blowing nitrogen gas. Thereafter, the atmosphere was returned to atmospheric pressure with nitrogen, cooled to 80 ° C, and 131.8 g of magnesium aluminum carbonate ("Kyoword 500SH" manufactured by Kyowa Chemical Industry Co., Ltd.) was added, followed by stirring at 80 ° C for 3 hours. The obtained solution was maintained at 80 ° C and filtered through a filter paper ("No. 5A" manufactured by Advantec Toyo Co., Ltd.) to obtain lauryloxy poly (ε-caprolactone) (21) monochloroacetic acid. Ester (chloroacetate b1).

合成例b2[氯乙酸酯b2:辛氧基聚(ε-己內酯)(20)單氯乙酸酯之合成] Synthesis Example b2 [Chloroacetate b2: Synthesis of octyloxy poly (ε-caprolactone) (20) monochloroacetate]

將反應容器設為1L之燒瓶,使用下述表2記載之聚酯及單氯乙酸,將對甲苯磺酸‧一水合物設為1.48g,將「Kyoword 500SH」設為16.8g,除此以外,與合成例b1同樣地獲得辛氧基聚(ε-己內酯)(20)單氯乙酸酯(氯乙酸酯b2)。 The reaction vessel was a 1-liter flask, the polyester and monochloroacetic acid described in Table 2 below were used, p-toluenesulfonic acid monohydrate was 1.48 g, and "Kyoword 500SH" was 16.8 g. In the same manner as in Synthesis Example b1, octyloxy poly (ε-caprolactone) (20) monochloroacetate (chloroacetate b2) was obtained.

合成例b3~b10[氯乙酸酯b3~b10:烷氧基聚內酯單氯乙酸酯之合成] Synthesis Examples b3 ~ b10 [Chloroacetate b3 ~ b10: Synthesis of alkoxy polylactone monochloroacetate]

使用下述表2記載之聚酯及單氯乙酸,除此以外,與合成例b2同樣地獲得烷氧基聚內酯單氯乙酸酯b3~b10。 An alkoxy polylactone monochloroacetate b3 to b10 was obtained in the same manner as in Synthesis Example b2, except that the polyester and monochloroacetic acid described in Table 2 below were used.

合成例a51[聚醚a51:月桂氧基聚丙二醇(29)聚乙二醇(15)之合成] Synthesis example a51 [Polyether a51: Synthesis of lauryloxy polypropylene glycol (29) and polyethylene glycol (15)]

於具備攪拌裝置、溫度控制裝置之6L之高壓釜中,添加月桂醇(花王股份有限公司製造之「Kalcol 2098」)375g(2.0莫耳)、48質量%氫氧化鉀水溶液12.4g。對高壓釜內進行氮氣置換後,升溫至40℃,並開始攪拌。其後,於100℃、4.7kPa(絕對壓力)之減壓下,歷時1.0小時去除水分。於氮氣下恢復至大氣壓並升溫至110℃後,一面以壓 力成為0.1~0.45MPaG之方式導入環氧丙烷3,694g(63.6莫耳),一面歷時36小時進行加成反應。進而,升溫至140℃後,一面以壓力成為0.1~0.4MPaG之方式導入環氧乙烷1,405g(31.9莫耳),一面歷時12小時進行加成反應。其後,冷卻至60℃,添加冰乙酸(岸田化學股份有限公司製造,特級試劑)5.3g,於60℃下攪拌1小時,獲得月桂氧基聚丙二醇(29)聚乙二醇(15)(聚醚a51)。 To a 6-liter autoclave equipped with a stirring device and a temperature control device, 375 g (2.0 mol) of lauryl alcohol ("Kalcol 2098" manufactured by Kao Corporation) and 12.4 g of a 48% by mass potassium hydroxide aqueous solution were added. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 40 ° C, and stirring was started. Thereafter, the water was removed for 1.0 hour at a reduced pressure of 100 ° C and 4.7 kPa (absolute pressure). After returning to atmospheric pressure under nitrogen and raising the temperature to 110 ° C, 3,694 g (63.6 mol) of propylene oxide was introduced so that the force became 0.1 to 0.45 MPaG, and an addition reaction was performed over 36 hours. After the temperature was raised to 140 ° C, 1,405 g (31.9 mol) of ethylene oxide was introduced so that the pressure became 0.1 to 0.4 MPaG, and an addition reaction was performed over 12 hours. Thereafter, it was cooled to 60 ° C, 5.3 g of glacial acetic acid (manufactured by Kishida Chemical Co., Ltd.) was added, and stirred at 60 ° C for 1 hour to obtain lauryloxy polypropylene glycol (29) polyethylene glycol (15) ( Polyether a51).

合成例b51[氯乙酸酯b51:月桂氧基聚丙二醇(29)聚乙二醇(15)單氯乙酸酯之合成] Synthesis Example b51 [Chloroacetate b51: Synthesis of lauryloxy polypropylene glycol (29) polyethylene glycol (15) monochloroacetate]

於安裝有攪拌裝置、溫度計、氮氣吹入管、冷卻管之1L之燒瓶中,添加合成例a51中所獲得之聚醚a51 653g、單氯乙酸(和光純藥工業股份有限公司製造,特級試劑)35.1g、對甲苯磺酸‧一水合物(岸田化學股份有限公司製造,特級試劑)3.5g,並開始攪拌。一面對燒瓶內進行氮氣置換而吹入氮氣一面於140℃、-0.1MPaG之減壓下反應16小時。於氮氣下恢復至大氣壓,冷卻至80℃,添加無水碳酸鈉(岸田化學股份有限公司製造,特級試劑)26.8g,於80℃下攪拌2小時。利用濾紙(Advantec東洋股份有限公司製造之「No.5A」)對所獲得之溶液進行過濾,獲得月桂氧基聚丙二醇(29)聚乙二醇(15)單氯乙酸酯(氯乙酸酯b51)。 In a 1 L flask equipped with a stirring device, a thermometer, a nitrogen blowing tube, and a cooling tube, 653 g of polyether a51 obtained in Synthesis Example a51 and monochloroacetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added 35.1 g, 3.5 g of p-toluenesulfonic acid ‧ monohydrate (manufactured by Kishida Chemical Co., Ltd.), and start stirring. The reaction was carried out at 140 ° C under a reduced pressure of -0.1 MPaG for 16 hours while nitrogen was blown into the flask. After returning to atmospheric pressure under nitrogen, cooling to 80 ° C, 26.8 g of anhydrous sodium carbonate (manufactured by Kishida Chemical Co., Ltd.) was added, and the mixture was stirred at 80 ° C for 2 hours. The obtained solution was filtered with a filter paper ("No. 5A" manufactured by Advantec Toyo Co., Ltd.) to obtain lauryloxy polypropylene glycol (29) polyethylene glycol (15) monochloroacetate (chloroacetate b51).

合成例c2[聚胺c2:聚三級胺二醇(平均胺官能基數:3.7)之合成] Synthesis example c2 [Polyamine c2: Synthesis of polytriamine diol (average number of amine functional groups: 3.7)]

於安裝有用以將反應水分離之冷凝器及分離器之1L燒瓶中,添加1,6-己二醇600g及Cu-Ni觸媒(花王股份有限公司製造之「MX-2141」)12g。一面攪拌一面利用氮氣對體系內進行置換,並開始升溫。於開始升溫之同時,將氫氣以30L/hr之流速吹入至反應體系內,歷時約40分鐘升溫至185℃。達到185℃後,將單甲基胺以22L/hr之流速吹入至反應體系內,歷時約10分鐘升溫至195℃。於195℃下進行6.0小時反應。反應後,停止單甲基胺之供給,僅以氫使反應持續進 行1小時。對反應物進行冷卻、過濾,藉此獲得聚胺c2:聚三級胺二醇(平均胺官能基數:3.7且於式(2)中R1、R2=C6H12OH、R4=CH3、R5=C6H12(其中,與R1鄰接之R5為直接鍵)、(n+p+m+k)=3.7之化合物)。 In a 1 L flask equipped with a condenser and a separator for separating reaction water, 600 g of 1,6-hexanediol and 12 g of Cu-Ni catalyst ("MX-2141" manufactured by Kao Corporation) were added. The inside of the system was replaced with nitrogen while stirring, and the temperature started to rise. At the same time when the temperature was started, hydrogen was blown into the reaction system at a flow rate of 30 L / hr, and the temperature was raised to 185 ° C over about 40 minutes. After reaching 185 ° C, monomethylamine was blown into the reaction system at a flow rate of 22 L / hr, and the temperature was raised to 195 ° C over about 10 minutes. The reaction was carried out at 195 ° C for 6.0 hours. After the reaction, the supply of monomethylamine was stopped, and the reaction was continued with only hydrogen for 1 hour. The reactant was cooled and filtered to obtain polyamine c2: polytriamine amine (average number of amine functional groups: 3.7 and R 1 , R 2 = C 6 H 12 OH, R 4 = CH 3 , R 5 = C 6 H 12 (wherein R 5 adjacent to R 1 is a direct bond), (n + p + m + k) = 3.7 compound).

合成例c3[聚胺c3:聚三級胺二醇(平均胺官能基數:9.3)之合成] Synthesis example c3 [Polyamine c3: Synthesis of polytriamine diol (average number of amine functional groups: 9.3)]

將反應時間由6.0小時變換為7.5小時,除此以外,藉由與合成例c2相同之方法,獲得聚胺c3:聚三級胺二醇(平均胺官能基數:9.3且於式(2)中R1、R2=C6H12OH、R4=CH3、R5=C6H12(其中,與R1鄰接之R5為直接鍵)、(n+p+m+k)=9.3之化合物)。 Except that the reaction time was changed from 6.0 hours to 7.5 hours, polyamine c3: polytriamine diol (average number of amine functional groups: 9.3 and in formula (2)) was obtained by the same method as in Synthesis Example c2. R 1 , R 2 = C 6 H 12 OH, R 4 = CH 3 , R 5 = C 6 H 12 (where R 5 adjacent to R 1 is a direct bond), (n + p + m + k) = Compound of 9.3).

製造例1[分散劑1:N,N,N',N'-四甲基-N,N'-雙[月桂氧基聚(ε-己內酯)(21)羰基亞甲基]-丙烷二氯化胺之合成] Production Example 1 [Dispersant 1: N, N, N ', N'-tetramethyl-N, N'-bis [lauryloxypoly (ε-caprolactone) (21) carbonylmethylene] -propane Synthesis of amine dichloride]

於安裝有回流冷卻器、溫度計、氮氣導入管、攪拌裝置之500mL之可分離式燒瓶中,添加合成例b1中所獲得之氯乙酸酯b1 200g、N,N,N',N'-四甲基丙二胺(花王股份有限公司製造之「Kaolizer No.2」,以下亦稱為「聚胺c1」)5.0g,並開始攪拌。對燒瓶內進行氮氣置換,於80℃下反應20小時。添加丙二醇單甲醚乙酸酯(PGMEA)300g,於80℃下攪拌1小時後,冷卻至室溫,獲得分散劑1之PGMEA溶液。該溶液之固形物成分為39.8質量%,重量平均分子量為9,800(基於<條件1>之測定值)。 In a 500 mL separable flask equipped with a reflux cooler, a thermometer, a nitrogen introduction tube, and a stirring device, 200 g of chloroacetate b1 obtained in Synthesis Example b1, N, N, N ', N'-quad 5.0 g of methyl propylene diamine ("Kaolizer No. 2" manufactured by Kao Corporation, hereinafter also referred to as "polyamine c1"), and stirring was started. The flask was purged with nitrogen and reacted at 80 ° C for 20 hours. 300 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and after stirring at 80 ° C. for 1 hour, it was cooled to room temperature to obtain a PGMEA solution of Dispersant 1. The solid content of this solution was 39.8% by mass, and the weight average molecular weight was 9,800 (based on the measured value of <Condition 1>).

反應率Cl為90莫耳%,n為1.8,p為0.0,m為0.2,k為0.0。即,獲得以下述之化合物1-1作為主成分之分散劑1。 The reaction rate Cl was 90 mol%, n was 1.8, p was 0.0, m was 0.2, and k was 0.0. That is, a dispersant 1 containing the following compound 1-1 as a main component was obtained.

於NMR測定結果中,藉由反應,使源自聚胺c1之N上所鍵結之甲基及亞甲基的訊號分別自2.2、2.3ppm分別移動至3.3、3.2ppm,源自與N進而相隔1個之亞甲基的訊號自1.6ppm移動至2.2ppm。將本製造例中所獲得之分散劑之結構對照本說明書之式(1)而示於表4。 In the NMR measurement results, the signals derived from the methyl group and methylene group bonded to N of the polyamine c1 were shifted from 2.2 and 2.3 ppm to 3.3 and 3.2 ppm, respectively. The methylene signal separated by one moved from 1.6 ppm to 2.2 ppm. The structure of the dispersant obtained in this manufacturing example is shown in Table 4 with reference to Formula (1) of this specification.

[化43]

Figure TWI680011B_D0048
[Chemical 43]
Figure TWI680011B_D0048

(上述式中,甲基(s)相當於式(1)中之R1,單鍵(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, the methyl group (s) corresponds to R 1 in formula (1), and the single bond (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

製造例2~14、17、19~21[分散劑2~14、17、19~21之合成] Production Examples 2-14, 17, 19-21 [Synthesis of Dispersants 2-14, 17, 19-21]

使用下述表3記載之氯乙酸酯、聚胺及PGMEA,除此以外,與製造例1同樣地獲得分散劑2~14、17、19~21。將本製造例中所獲得之分散劑之結構對照本說明書之式(1)而示於表4。 Dispersants 2 to 14, 17, 19 to 21 were obtained in the same manner as in Production Example 1 except that chloroacetate, polyamine, and PGMEA described in Table 3 below were used. The structure of the dispersant obtained in this manufacturing example is shown in Table 4 with reference to Formula (1) of this specification.

表中所使用之原料如下所述。 The raw materials used in the table are as follows.

聚胺c4:N,N-二甲胺基己醇、花王股份有限公司製造之「Kaolizer No.25」 Polyamine c4: N, N-dimethylaminohexanol, "Kaolizer No. 25" manufactured by Kao Corporation

聚胺c5:N,N,N',N",N"-五甲基二伸丙基三胺、Air Products日本股份有限公司製造之「Polycat 77」 Polyamine c5: N, N, N ', N ", N" -Pentamethyldipropanetriamine, "Polycat 77" manufactured by Air Products Japan Co., Ltd.

製造例15[分散劑15(由月桂氧基聚(ε-己內酯)(21)單氯乙酸酯及硫酸二甲酯獲得之N,N,N',N'-四甲基丙二胺四級化物)之合成] Production Example 15 [Dispersant 15 (N, N, N ', N'-tetramethylpropanediamine obtained from lauryloxy poly (ε-caprolactone) (21) monochloroacetate and dimethyl sulfate Synthesis of amine quaternary)

使用下述表3記載之氯乙酸酯、聚胺及PGMEA,除此以外,與製造例1同樣地獲得氯乙酸酯b1與聚胺c1之反應物之37.3質量%PGMEA溶液。反應率Cl為96莫耳%。 A 37.3% by mass PGMEA solution of a reaction product of chloroacetate b1 and polyamine c1 was obtained in the same manner as in Production Example 1 except that chloroacetate, polyamine, and PGMEA described in Table 3 below were used. The reaction rate Cl was 96 mol%.

將作為四級化劑之硫酸二甲酯(和光純藥工業股份有限公司製造)2.6g與PGMEA 5.0g之混合液於常溫下一面攪拌一面滴加至上述溶 液中。進而攪拌5分鐘後,於氮氣環境下、85℃下攪拌3小時。將其冷卻而獲得分散劑15之PGMEA溶液。反應率Am為99莫耳%,n為1.0,p為0.0,m為0.0,k為1.0。該溶液之固形物成分為35.5質量%,重量平均分子量為9,000(基於<條件1>之測定值)。將本製造例中所獲得之分散劑之結構對照本說明書之式(1)而示於表4。 A mixed solution of 2.6 g of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) and 5.0 g of PGMEA as a quaternizing agent was added dropwise to the above solution while stirring at room temperature. After further stirring for 5 minutes, it was stirred at 85 ° C for 3 hours under a nitrogen atmosphere. This was cooled to obtain a PGMEA solution of Dispersant 15. The reaction rate Am was 99 mole%, n was 1.0, p was 0.0, m was 0.0, and k was 1.0. The solid content of this solution was 35.5% by mass, and the weight average molecular weight was 9,000 (based on the measured value of <Condition 1>). The structure of the dispersant obtained in this manufacturing example is shown in Table 4 with reference to Formula (1) of this specification.

製造例16、18[分散劑16、18之合成] Production Examples 16, 18 [Synthesis of Dispersants 16, 18]

使用下述表3記載之氯乙酸酯、聚胺、PGMEA及四級化劑,除此以外,與製造例15同樣地獲得分散劑16、18。 Dispersants 16 and 18 were obtained in the same manner as in Production Example 15 except that chloroacetate, polyamine, PGMEA, and a quaternizing agent described in Table 3 below were used.

分散劑2係以下述之化合物1-2作為主成分。 The dispersant 2 contains the following compound 1-2 as a main component.

Figure TWI680011B_D0050
Figure TWI680011B_D0050

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

於NMR測定結果中,藉由反應,使源自聚胺c1之N上所鍵結之甲基及亞甲基的訊號分別自2.2、2.3ppm分別移動至3.3、3.2ppm,源自與N進而相隔1個之亞甲基的訊號自1.6ppm移動至2.2ppm。 In the NMR measurement results, the signals derived from the methyl group and methylene group bonded to N of the polyamine c1 were shifted from 2.2 and 2.3 ppm to 3.3 and 3.2 ppm, respectively. The methylene signal separated by one moved from 1.6 ppm to 2.2 ppm.

分散劑3係以下述之化合物1-3作為主成分。 The dispersant 3 contains the following compounds 1-3 as a main component.

Figure TWI680011B_D0051
Figure TWI680011B_D0051

(上述式中,羥基己基(u)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵。再者,例示了聚胺之末端之胺部位未經四級化 之例,但各結構單元之排列可為任一種) (In the above formula, hydroxyhexyl (u) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond. Furthermore, polyamines are exemplified The amine site at the end is not quaternized, but the arrangement of each structural unit can be any type)

於NMR測定結果中,藉由反應而確認到以下之波峰之移動。源自聚胺c2之N上所鍵結之甲基及亞甲基的訊號分別自2.2、2.3ppm分別移動至3.4、3.2ppm。源自氯乙酸酯b1之氯上所鍵結之亞甲基的訊號自4.1ppm移動至4.4ppm。 From the NMR measurement results, the following peak shifts were confirmed by the reaction. The signals derived from the methyl and methylene groups bonded to N of the polyamine c2 moved from 2.2 and 2.3 ppm to 3.4 and 3.2 ppm, respectively. The signal derived from the methylene group bonded to the chlorine of chloroacetate b1 moved from 4.1 ppm to 4.4 ppm.

分散劑4係以下述之化合物1-4作為主成分。 The dispersant 4 contains the following compounds 1-4 as a main component.

Figure TWI680011B_D0052
Figure TWI680011B_D0052

(上述式中,羥基己基(u)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵。再者,例示了聚胺之末端之胺部位未經四級化之例,但各結構單元之排列可為任一種) (In the above formula, hydroxyhexyl (u) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond. Furthermore, polyamines are exemplified The amine site at the end is not quaternized, but the arrangement of each structural unit can be any type)

於NMR測定結果中,藉由反應而確認到以下之波峰之移動。源自聚胺c3之N上所鍵結之甲基及亞甲基的訊號分別自2.2、2.3ppm分別移動至3.4、3.2ppm。源自氯乙酸酯b1之氯上所鍵結之亞甲基的訊號自4.1ppm移動至4.4ppm。 From the NMR measurement results, the following peak shifts were confirmed by the reaction. The signals derived from the methyl and methylene groups bonded to N of the polyamine c3 moved from 2.2 and 2.3 ppm to 3.4 and 3.2 ppm, respectively. The signal derived from the methylene group bonded to the chlorine of chloroacetate b1 moved from 4.1 ppm to 4.4 ppm.

分散劑5係以下述之化合物1-5作為主成分。 The dispersant 5 contains the following compounds 1-5 as a main component.

[化47]

Figure TWI680011B_D0053
[Chemical 47]
Figure TWI680011B_D0053

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

分散劑6係以下述之化合物1-6作為主成分。 The dispersant 6 contains the following compounds 1-6 as a main component.

Figure TWI680011B_D0054
Figure TWI680011B_D0054

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

分散劑7係以下述之化合物1-7作為主成分。 The dispersant 7 contains the following compounds 1-7 as a main component.

[化49]

Figure TWI680011B_D0055
[Chemical 49]
Figure TWI680011B_D0055

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

分散劑8係以下述之化合物1-8作為主成分。 The dispersant 8 contains the following compounds 1-8 as a main component.

Figure TWI680011B_D0056
Figure TWI680011B_D0056

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

分散劑9係以下述之化合物1-9作為主成分。 The dispersant 9 contains the following compounds 1-9 as a main component.

[化51]

Figure TWI680011B_D0057
[Chemical 51]
Figure TWI680011B_D0057

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

分散劑10係以下述之化合物1-10作為主成分。 The dispersant 10 is based on the following compounds 1-10 as a main component.

Figure TWI680011B_D0058
Figure TWI680011B_D0058

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵。再者,ε-己內酯單元及δ-戊內酯單元係無規排列) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond. Furthermore, ε-caproline (Ester units and δ-valerolactone units are randomly arranged.)

分散劑11係以下述之化合物1-11作為主成分。 The dispersant 11 contains the following compounds 1-11 as a main component.

[化53]

Figure TWI680011B_D0059
[Chem 53]
Figure TWI680011B_D0059

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵。再者,ε-己內酯單元及δ-戊內酯單元係無規排列) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond. Furthermore, ε-caproline (Ester units and δ-valerolactone units are randomly arranged.)

分散劑12係以下述之化合物1-12作為主成分。 The dispersant 12 contains the following compounds 1-12 as a main component.

Figure TWI680011B_D0060
Figure TWI680011B_D0060

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵。再者,ε-己內酯單元及δ-戊內酯單元係無規排列) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond. Furthermore, ε-caproline (Ester units and δ-valerolactone units are randomly arranged.)

分散劑13係以下述之化合物1-13作為主成分。 The dispersant 13 contains the following compounds 1-13 as a main component.

[化55]

Figure TWI680011B_D0061
[Chem 55]
Figure TWI680011B_D0061

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

分散劑14係以下述之化合物1-14作為主成分。 The dispersant 14 contains the following compounds 1-14 as a main component.

Figure TWI680011B_D0062
Figure TWI680011B_D0062

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

分散劑15係以下述之化合物1-15作為主成分。 The dispersant 15 contains the following compounds 1-15 as a main component.

[化57]

Figure TWI680011B_D0063
[Chemical 57]
Figure TWI680011B_D0063

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

分散劑16係以下述之化合物1-16作為主成分。 The dispersant 16 contains the following compounds 1-16 as a main component.

Figure TWI680011B_D0064
Figure TWI680011B_D0064

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵。再者,例示了上述例,但各結構單元之排列可為任一種) (In the above formula, methyl (s) corresponds to R 1 in formula (1), and (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond. Furthermore, the above examples are exemplified. , But the arrangement of each structural unit can be any kind)

分散劑17係以下述之化合物1-17作為主成分。 The dispersant 17 contains the following compounds 1-17 as a main component.

[化59]

Figure TWI680011B_D0065
[Chemical 59]
Figure TWI680011B_D0065

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵。再者,例示了上述例,但各結構單元之排列可為任一種) (In the above formula, methyl (s) corresponds to R 1 in formula (1), and (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond. Furthermore, the above examples are exemplified. , But the arrangement of each structural unit can be any kind)

分散劑18係以下述之化合物1-18作為主成分。 The dispersant 18 contains the following compounds 1-18 as a main component.

Figure TWI680011B_D0066
Figure TWI680011B_D0066

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵。再者,例示了上述例,但各結構單元之排列可為任一種) (In the above formula, methyl (s) corresponds to R 1 in formula (1), and (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond. Furthermore, the above examples are exemplified. , But the arrangement of each structural unit can be any kind)

分散劑19~21含有下述之化合物1-19。 The dispersants 19 to 21 contain the following compounds 1-19.

[化61]

Figure TWI680011B_D0067
[Chem 61]
Figure TWI680011B_D0067

(上述式中,甲基(s)相當於式(1)中之R1,(t)相當於式(1)中與R1鄰接之R5、即單鍵) (In the above formula, methyl (s) corresponds to R 1 in formula (1), (t) corresponds to R 5 adjacent to R 1 in formula (1), that is, a single bond)

製造例51[分散劑51:N,N,N',N'-四甲基-N,N'-雙[月桂氧基聚丙二醇(29)聚乙二醇(15)羰基亞甲基]-丙烷二氯化胺之合成] Production Example 51 [Dispersant 51: N, N, N ', N'-tetramethyl-N, N'-bis [lauryloxy polypropylene glycol (29) polyethylene glycol (15) carbonylmethylene]- Synthesis of propane dichloride]

於安裝有回流冷卻器、溫度計、氮氣導入管、攪拌裝置之500mL之可分離式燒瓶中,添加合成例51中所獲得之氯乙酸酯b51 100g、聚胺c1 2.4g,並開始攪拌。對燒瓶內進行氮氣置換,於80℃下反應20小時。添加PGMEA 130g,於80℃下攪拌1小時後,冷卻至室溫,獲得分散劑51之PGMEA溶液。該溶液之固形物成分為41.5質量%,重量平均分子量為4,200(基於<條件2>之測定值)。反應率Cl為94莫耳%,n為2.0,m為0.0,k為0.0。 In a 500 mL separable flask equipped with a reflux cooler, a thermometer, a nitrogen introduction tube, and a stirring device, 100 g of chloroacetate b51 obtained in Synthesis Example 51 and 2.4 g of polyamine c1 were added, and stirring was started. The flask was purged with nitrogen and reacted at 80 ° C for 20 hours. 130 g of PGMEA was added, and after stirring at 80 ° C. for 1 hour, it was cooled to room temperature to obtain a PGMEA solution of Dispersant 51. The solid content of this solution was 41.5% by mass, and the weight average molecular weight was 4,200 (based on the measured value of <Condition 2>). The reaction rate Cl was 94 mole%, n was 2.0, m was 0.0, and k was 0.0.

製造例52[分散劑52:N,N,N',N'-四甲基-N,N'-雙[甲基羰基亞甲基]-己烷二氯化胺之合成] Production Example 52 [Dispersant 52: Synthesis of N, N, N ', N'-tetramethyl-N, N'-bis [methylcarbonylmethylene] -hexane dichloride]

於安裝有回流冷卻器、溫度計、氮氣導入管、攪拌裝置之500mL之可分離式燒瓶中,添加聚胺c1 40.2g、甲醇200g,進行氮氣置換。開始攪拌並升溫至75℃後,歷時30分鐘滴加氯乙酸甲酯(關東化學股份有限公司製造)50g,進而於75℃下反應20小時後,冷卻至室溫而獲得反應液。使用蒸發器,於60℃、減壓下,自所獲得之反應液中去除甲醇,獲得分散劑52。該化合物之固形物成分為100質量%。 反應率Cl為98%,n為2.0,m為0.0,k為0.0。 In a 500 mL separable flask equipped with a reflux cooler, a thermometer, a nitrogen introduction tube, and a stirring device, 40.2 g of polyamine c1 and 200 g of methanol were added, and nitrogen substitution was performed. After stirring was started and the temperature was raised to 75 ° C, 50 g of methyl chloroacetate (manufactured by Kanto Chemical Co., Ltd.) was added dropwise over 30 minutes, and the mixture was further reacted at 75 ° C for 20 hours, and then cooled to room temperature to obtain a reaction solution. Using an evaporator, methanol was removed from the obtained reaction solution at 60 ° C. under reduced pressure to obtain a dispersant 52. The solid content of this compound was 100% by mass. The reaction rate Cl was 98%, n was 2.0, m was 0.0, and k was 0.0.

將所獲得之分散劑之詳情示於表4。 The details of the obtained dispersant are shown in Table 4.

合成例AS1[ASR1:甲基丙烯酸苄酯/甲基丙烯酸共聚物(鹼可溶性樹脂)之合成] Synthesis example AS1 [ASR1: Synthesis of benzyl methacrylate / methacrylic acid copolymer (alkali soluble resin)]

於安裝有攪拌機、回流冷卻器、氮氣導入管及溫度計之反應容器中,添加甲基丙烯酸(以下亦稱為「MAA」)12.0g、甲基丙烯酸苄酯(以下亦稱為「BzMA」)28.0g、3-巰基丙酸0.56g、PGMEA 40g,一面對反應容器內進行攪拌一面進行氮氣置換。一面對反應容器內進行攪拌一面升溫至78℃後,歷時3小時滴加另外製備之單體溶液[MAA In a reaction vessel equipped with a stirrer, a reflux cooler, a nitrogen introduction tube, and a thermometer, 12.0 g of methacrylic acid (hereinafter also referred to as "MAA") and 28.0 benzyl methacrylate (hereinafter also referred to as "BzMA") were added. g, 0.56 g of 3-mercaptopropionic acid, and 40 g of PGMEA. Nitrogen was replaced while stirring in the reaction vessel. The temperature was raised to 78 ° C while stirring in the reaction vessel, and a separately prepared monomer solution [MAA] was added dropwise over 3 hours.

48.0g、BzMA 112.0g、3-巰基丙酸2.2g、PGMEA 160g、2,2-偶氮雙-(2,4-二甲基戊腈)(和光純藥工業股份有限公司製造之「V-65」;以下亦稱為「V-65」)2.0g]。滴加結束後,添加將V-65 2.0g溶解於PGMEA 10.0g而成之溶液,持續攪拌1小時。其後,進而添加將V-65 1.0g溶解於PGMEA 10.0g而成之溶液,持續攪拌1小時。將其冷卻而獲得莫耳比70/30之BzMA/MAA共聚物(ASR1)之PGMEA溶液。該溶液之固形物成分為50質量%,ASR1之酸值為190mgKOH/g,重量平均分子量為14,000(基於<條件2>之測定值)。 48.0g, BzMA 112.0g, 3-mercaptopropionic acid 2.2g, PGMEA 160g, 2,2-azobis- (2,4-dimethylvaleronitrile) ("V- 65 "; hereinafter also referred to as" V-65 ") 2.0g]. After completion of the dropwise addition, a solution prepared by dissolving 2.0 g of V-65 in 10.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution prepared by dissolving 1.0 g of V-65 in 10.0 g of PGMEA was further added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of BzMA / MAA copolymer (ASR1) with a molar ratio of 70/30. The solid content of this solution was 50% by mass, the acid value of ASR1 was 190 mgKOH / g, and the weight-average molecular weight was 14,000 (based on the measured value of <Condition 2>).

表示下述實施例中所使用之原料之詳情。 Details of the raw materials used in the following examples are shown.

(DPP顏料) (DPP pigment)

DPP-1:BASF公司製造之「Irgaphor Red S 3621 CF」 DPP-1: "Irgaphor Red S 3621 CF" manufactured by BASF

DPP-2:Clariant公司製造之「Hostaperm Red D2B-COF01 LV3916」 DPP-2: "Hostaperm Red D2B-COF01 LV3916" manufactured by Clariant

DPP-3:山陽色素股份有限公司製造之「PIGMENT RED 5414」 DPP-3: "PIGMENT RED 5414" manufactured by Sanyo Pigment Co., Ltd.

(多官能單體) (Multifunctional monomer)

DPHA:日本化藥股份有限公司製造之「DPHA」 DPHA: "DPHA" manufactured by Nippon Kayaku Co., Ltd.

(光聚合起始劑) (Photopolymerization initiator)

MBz-MPB:BASF公司製造之「Irgacure 369」 MBz-MPB: "Irgacure 369" manufactured by BASF

MTB-MP:BASF公司製造之「Irgacure 907」 MTB-MP: "Irgacure 907" manufactured by BASF

(分散劑) (Dispersant)

分散劑53:Ajinomoto Fine-Techno股份有限公司製造之「Ajisper PB821」(固形物成分:100質量%) Dispersant 53: "Ajisper PB821" (solid content: 100% by mass) manufactured by Ajinomoto Fine-Techno Co., Ltd.

實施例1[顏料分散體1之製備] Example 1 [Preparation of Pigment Dispersion 1]

將DPP-1 16.6g、DPP-2 2.93g、1,3-苯二順丁烯二醯亞胺(以下亦稱為「PDM」)0.98g、製造例1中所獲得之分散劑1之溶液19.6g(固形物成分7.8g)、合成例AS1中所獲得之ASR1之50質量%之PGMEA溶液 11.7g、PGMEA 98.2g、粒徑0.2mm之氧化鋯珠300g加入至500mL塑膠容器中,進行3小時利用分散機(淺田鐵工股份有限公司製造之「塗料振盪機」)之分散(預分散)後,藉由過濾將氧化鋯珠去除。將所獲得之溶液100g及粒徑0.05mm之氧化鋯珠200g添加至250mL塑膠容器中,進行12小時利用分散機(淺田鐵工股份有限公司製造之「塗料振盪機」)之分散(正式分散)後,藉由過濾將氧化鋯珠去除,獲得下述表5中記載之顏料分散體1。 A solution of 16.6 g of DPP-1, 2.93 g of DPP-2, 1,3-phenylenedibutene diamidine (hereinafter also referred to as "PDM"), and a dispersant 1 solution obtained in Production Example 1 19.6 g (7.8 g of solid content), 50% by mass of PGMEA solution of ASR1 obtained in Synthesis Example AS1 11.7 g, PGMEA 98.2 g, and 300 g of zirconia beads with a particle diameter of 0.2 mm were added to a 500 mL plastic container, and dispersed (pre-dispersed) using a disperser ("paint shaker" manufactured by Asada Iron Works Co., Ltd.) for 3 hours Then, the zirconia beads were removed by filtration. 100 g of the obtained solution and 200 g of zirconia beads having a diameter of 0.05 mm were added to a 250 mL plastic container, and dispersed for 12 hours using a disperser ("paint shaker" manufactured by Asada Iron Works Co., Ltd.) for dispersion (formal dispersion) Then, the zirconia beads were removed by filtration to obtain Pigment Dispersion 1 described in Table 5 below.

[著色組合物1之製備] [Preparation of coloring composition 1]

將顏料分散體1 4.62g、合成例AS1中所獲得之ASR1之50質量%PGMEA溶液0.34g、DPHA 0.21g、MBz-MPB 0.042g、MTB-MP 0.028g、PGMEA 4.76g混合直至變得均勻,獲得下述表6中所記載之著色組合物1。 Mix 4.62 g of Pigment Dispersion 1, 0.34 g of 50% by mass PGMEA solution of ASR1 obtained in Synthesis Example AS1, 0.21 g of DPHA, MBz-MPB 0.042 g, MTB-MP 0.028 g, and PGMEA 4.76 g until uniform, The colored composition 1 described in Table 6 below was obtained.

實施例2~4、20~25、比較例1~3[顏料分散體2~4、20~25、51~53、著色組合物2~4、20~25、51~53之製備] Examples 2 to 4, 20 to 25, and Comparative Examples 1 to 3 [Preparation of pigment dispersions 2 to 4, 20 to 25, 51 to 53, and coloring compositions 2 to 4, 20 to 25, and 51 to 53]

將分散劑1分別變換為表5所示之分散劑,並設為各分散劑溶液之固形物成分成為7.8g之量,此外,進行與實施例1相同之操作,獲得下述表5中所記載之顏料分散體2~4、20~25、51~53、下述表6中所記載之著色組合物2~4、20~25、51~53。 The dispersant 1 was converted into the dispersant shown in Table 5, and the solid content of each dispersant solution was set to an amount of 7.8 g. In addition, the same operation as in Example 1 was performed to obtain as shown in Table 5 below. The pigment dispersions 2 to 4, 20 to 25, 51 to 53, and the coloring compositions 2 to 4, 20 to 25, and 51 to 53 described in Table 6 below.

實施例5~19、比較例4[顏料分散體5~19、54、著色組合物5~19、54之製備] Examples 5 to 19, Comparative Example 4 [Preparation of Pigment Dispersions 5 to 19, 54 and Coloring Compositions 5 to 19, 54]

將分散劑1分別變換為表5所示之分散劑,將DPP-1 16.6g、DPP-2 2.93g變更為DPP-1 5.85g、DPP-3 13.7g,並設為各分散劑溶液之固形物成分成為7.8g之量,此外,進行與實施例1相同之操作,獲得下述表6中所記載之顏料分散體5~19、54、著色組合物5~19、54。 The dispersant 1 was converted into the dispersant shown in Table 5, and DPP-1 16.6g and DPP-2 2.93g were changed to DPP-1 5.85g and DPP-3 13.7g, and the solid form of each dispersant solution was set. The amount of the component was 7.8 g, and the same operation as in Example 1 was performed to obtain pigment dispersions 5 to 19 and 54 and coloring compositions 5 to 19 and 54 described in Table 6 below.

將所獲得之顏料分散體1~25、51~54及著色組合物1~25、51~54之評價結果示於下述表5、表6。 The evaluation results of the obtained pigment dispersions 1 to 25, 51 to 54 and the coloring compositions 1 to 25, 51 to 54 are shown in Tables 5 and 6 below.

根據表4~表6,使用製造例1~21之四級銨鹽化合物作為分散劑之實施例1~25之顏料分散體及著色組合物與不使用本發明之分散劑而使用分散劑51~53之比較例1~4之顏料分散體及著色組合物相比,保存後平均粒徑較小且具有良好之顯影性及耐熱性。因此,可知本發明之四級銨鹽化合物作為顏料分散體中之分散劑有用,使用該化合物之顏料分散體及著色組合物之平均粒徑較小,為低黏度,保存穩定性優異,且顯影性及耐熱性優異。 According to Tables 4 to 6, the pigment dispersions and coloring compositions of Examples 1 to 25 using the quaternary ammonium salt compounds of Production Examples 1 to 21 as dispersants, and dispersants 51 to 51 without using the dispersant of the present invention Compared with the pigment dispersions and coloring compositions of Comparative Examples 1 to 4, 53, the average particle diameter after storage is smaller and has good developability and heat resistance. Therefore, it is known that the quaternary ammonium salt compound of the present invention is useful as a dispersant in a pigment dispersion. The average particle diameter of the pigment dispersion and the coloring composition using the compound is small, has a low viscosity, is excellent in storage stability, and is developed Excellent resistance and heat resistance.

Claims (23)

一種分散劑,其於分子結構中具有式(A)所表示之結構單元A,一分子結構中所含之結構單元A之平均數量為1.0以上且22.0以下,[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基,R6表示碳數1以上且4以下之烷二基,(M1)-表示陰離子;複數個[(C=O)Rx1O]可相同亦可不同]。A dispersant having a structural unit A represented by formula (A) in a molecular structure, and an average number of the structural unit A contained in a molecular structure is 1.0 or more and 22.0 or less, [Wherein, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, and is 2 or more and 100 or less, R 4 A part of hydrogen atoms may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, R 5 represents an alkanediyl group having 1 to 18 carbon atoms, R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (M 1) - represents an anion; a plurality of [(C = O) R x1 O] may be the same or different]. 如請求項1之分散劑,其中一分子結構中所含之結構單元A之平均數量為1.5以上且3.0以下。As in the dispersant of claim 1, the average number of structural units A contained in one molecular structure is 1.5 or more and 3.0 or less. 如請求項1之分散劑,其中a為15以上且100以下。The dispersant of claim 1, wherein a is 15 or more and 100 or less. 如請求項1至3中任一項之分散劑,其中Rx1為碳數3以上且7以下之烷二基。The dispersant according to any one of claims 1 to 3, wherein R x1 is an alkyldiyl group having 3 or more and 7 or less carbon atoms. 如請求項1至3中任一項之分散劑,其中R4為選自甲基及乙基中之至少一種。The dispersant according to any one of claims 1 to 3, wherein R 4 is at least one selected from methyl and ethyl. 如請求項1至3中任一項之分散劑,其於分子結構中進而具有式(D)所表示之結構單元D,一分子結構中所含之結構單元D之平均數量為0.3以上且11.0以下,[式中,Ry1表示碳數2以上且4以下之烷二基,Ry2表示碳數1以上且18以下之烴基,d表示平均加成莫耳數,為1以上且100以下,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基,R6表示碳數1以上且4以下之烷二基,(M1)-表示陰離子;再者,[Ry1O]於存在複數個之情形時,可相同亦可不同]。If the dispersant of any one of claims 1 to 3 further has a structural unit D represented by formula (D) in the molecular structure, the average number of structural units D contained in one molecular structure is 0.3 or more and 11.0 the following, [In the formula, R y1 represents an alkanediyl group having 2 or more and 4 carbon atoms, R y2 represents a hydrocarbon group having 1 or more and 18 carbon atoms, d represents an average addition mole number, and is 1 or more and 100 or less, R 4 A part of hydrogen atoms may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, R 5 represents an alkanediyl group having 1 to 18 carbon atoms, R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (M 1) - represents an anion; Furthermore, [R y1 O] in the presence of a plurality of situation may be the same or different]. 如請求項1至3中任一項之分散劑,其具有包含1個以上結構單元A之排列結構,該排列結構之末端為一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基。For example, the dispersant according to any one of claims 1 to 3 has an arrangement structure including one or more structural units A, and the end of the arrangement structure is a part of hydrogen atoms which can be substituted with a hydroxyl number of 1 or more and 10 or less. Alkyl. 如請求項1至3中任一項之分散劑,其重量平均分子量Mw為2,000以上且50,000以下。The dispersant according to any one of claims 1 to 3, whose weight average molecular weight Mw is 2,000 or more and 50,000 or less. 如請求項1至3中任一項之分散劑,其中分散劑為包含式(1-1)所表示之化合物之分散劑與包含下述式(1-3)所表示之化合物之分散劑之混合物,[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R1、R2及R4可相同或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,R5表示碳數1以上且18以下之烷二基(其中,與R1鄰接之R5表示單鍵),R6表示碳數1以上且4以下之烷二基,(M1)-及(M2)-分別獨立地表示陰離子,n、m及k表示平均結構單元數,(n+m+k)為1.0以上且22.0以下,n為1.0以上且22.0以下,m為0以上且21.0以下,k為0以上且21.0以下;複數個[(C=O)Rx1O]可相同亦可不同,以n、m、k表示其平均結構單元數之各結構單元可為任意排列順序][式中,Ry1表示碳數2以上且4以下之烷二基,Ry2表示碳數1以上且18以下之烴基,d表示平均加成莫耳數,為1以上且100以下,R1、R2及R4可相同或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,R5表示碳數1以上且18以下之烷二基(其中,與R1鄰接之R5表示單鍵),R6表示碳數1以上且4以下之烷二基,(M1)-及(M2)-分別獨立地表示陰離子,p、m及k表示平均結構單元數,(p+m+k)為1.0以上且22.0以下,m為0以上且21.0以下,p為1.0以上且22.0以下,k為0以上且21.0以下;複數個[Ry1O]可相同亦可不同,以p、m、k表示其平均結構單元數之各結構單元可為任意排列順序]。The dispersant according to any one of claims 1 to 3, wherein the dispersant is a dispersant comprising a compound represented by the formula (1-1) and a dispersant comprising a compound represented by the following formula (1-3) mixture, [Wherein, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, and is 2 or more and 100 or less, R 1 , R 2 and R 4 may be the same or different and represent a hydrocarbon group having a carbon number of 1 or more and 10 or less in which a part of hydrogen atoms can be substituted with a hydroxyl group, and R 3 represents a carbon number selected from a hydrogen atom and a part of hydrogen atoms that can be substituted with a hydroxyl group At least one of hydrocarbon groups of 1 or more and 10 or less, R 5 represents an alkanediyl group having 1 or more and 18 or less carbons (where R 5 adjacent to R 1 represents a single bond), and R 6 represents 1 or more and 4 carbons the following of -alkanediyl, (m 1) - and (m 2) - each independently represent an anion, n, m and k represents the average number of structural units, (n + m + k) is 1.0 or more and 22.0 or less, n is 1.0 or more and 22.0 or less, m is 0 or more and 21.0 or less, k is 0 or more and 21.0 or less; plural [(C = O) R x1 O] may be the same or different, and the average structure is represented by n, m, and k The number of units of each structural unit can be in any order.] [In the formula, R y1 represents an alkanediyl group having 2 or more and 4 carbon atoms, R y2 represents a hydrocarbon group having 1 or more and 18 carbon atoms, d represents an average addition mole number, and is 1 or more and 100 or less, R 1 , R 2 and R 4 may be the same or different and represent a hydrocarbon group having a carbon number of 1 or more and 10 or less in which a part of hydrogen atoms can be substituted with a hydroxyl group, and R 3 represents a carbon number selected from a hydrogen atom and a part of hydrogen atoms that can be substituted with a hydroxyl group At least one of hydrocarbon groups of 1 or more and 10 or less, R 5 represents an alkanediyl group having 1 or more and 18 or less carbons (where R 5 adjacent to R 1 represents a single bond), and R 6 represents 1 or more and 4 carbons the following of -alkanediyl, (m 1) - and (m 2) - each independently represent an anion, p, m and k represents the average number of structural units, (p + m + k) is 1.0 or more and 22.0 or less, m is 0 or more and 21.0 or less, p is 1.0 or more and 22.0 or less, k is 0 or more and 21.0 or less; plural [R y1 O] may be the same or different, and each structure of the average structural unit number is represented by p, m, and k Units can be in any order.] 如請求項9之分散劑,其中上述混合物中之包含式(1-1)所表示之化合物之分散劑與包含式(1-3)所表示之化合物之分散劑之質量比[(1-1)/(1-3)]為10/90以上且90/10以下。The dispersant according to claim 9, wherein the mass ratio of the dispersant containing the compound represented by the formula (1-1) to the dispersant containing the compound represented by the formula (1-3) in the above mixture [(1-1 ) / (1-3)] is 10/90 or more and 90/10 or less. 一種彩色濾光片用顏料分散體,其含有如請求項1至10中任一項之分散劑、有機顏料及有機溶劑。A pigment dispersion for a color filter, comprising the dispersant according to any one of claims 1 to 10, an organic pigment, and an organic solvent. 如請求項11之彩色濾光片用顏料分散體,其中有機顏料包含吡咯并吡咯二酮系顏料。The pigment dispersion for a color filter according to claim 11, wherein the organic pigment comprises a pyrrolopyrrole dione pigment. 如請求項11之彩色濾光片用顏料分散體,其中上述有機溶劑為醚系溶劑。The pigment dispersion for a color filter according to claim 11, wherein the organic solvent is an ether-based solvent. 如請求項11至13中任一項之彩色濾光片用顏料分散體,其進而含有鹼可溶性樹脂。The pigment dispersion for a color filter according to any one of claims 11 to 13, further comprising an alkali-soluble resin. 一種彩色濾光片用著色組合物,其含有如請求項11至14中任一項之顏料分散體、多官能單體及光聚合起始劑。A coloring composition for a color filter, comprising the pigment dispersion according to any one of claims 11 to 14, a polyfunctional monomer, and a photopolymerization initiator. 一種彩色濾光片,其係使用如請求項15之彩色濾光片用著色組合物而製造。A color filter manufactured by using the coloring composition for a color filter according to claim 15. 一種分散劑之製造方法,其具有步驟1:使於分子結構中具有式(B)所表示之結構單元B且一分子結構中所含之結構單元B之平均數量為1.0以上且22.0以下之聚胺化合物與式(3-1)所表示之化合物進行反應之步驟,[式中,R4表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基][式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R6表示碳數1以上且4以下之烷二基,Y1表示藉由脫離而成為陰離子(M1)-之基;複數個[(C=O)Rx1O]可相同亦可不同]。A method for producing a dispersant, comprising the steps of: having a molecular structure having a structural unit B represented by formula (B) and having an average number of structural units B contained in a molecular structure of 1.0 or more and 22.0 or less A step of reacting an amine compound with a compound represented by formula (3-1), [In the formula, R 4 represents a part of hydrogen atoms which can be substituted with a hydrocarbon group having 1 or more and 10 carbon atoms, and R 5 represents an alkyldiyl group having 1 or more and 18 carbon atoms] [In the formula, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, and is 2 or more and 100 or less, R 6 a carbon number of 1 or more and 4 or less alkanediyl group, Y 1 represents an anion become disengaged by (M 1) - of the group; a plurality of [(C = O) R x1 O] may be the same or different]. 一種四級銨鹽化合物,其以式(1)表示,[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,Ry1表示碳數2以上且4以下之烷二基,Ry2表示碳數1以上且18以下之烴基,d表示平均加成莫耳數,為1以上且100以下,R1、R2及R4可相同或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,R5表示碳數1以上且18以下之烷二基(其中,與R1鄰接之R5表示單鍵),R6表示碳數1以上且4以下之烷二基,(M1)-及(M2)-分別獨立地表示陰離子,n、p、m及k表示平均結構單元數,(n+p+m+k)為1.0以上且22.0以下,(n+p)為1.0以上且22.0以下,n為0.3以上且22.0以下,p為0以上且11.0以下,m為0以上且21.0以下,k為0以上且21.0以下;複數個[(C=O)Rx1O]可相同亦可不同,複數個[Ry1O]可相同亦可不同,以n、p、m、k表示其平均結構單元數之各結構單元可為任意排列順序]。A quaternary ammonium salt compound represented by formula (1), [In the formula, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, is 2 or more and 100 or less, and R y1 It represents an alkyldiyl group having 2 or more and 4 carbon atoms, R y2 represents a hydrocarbon group having 1 or more and 18 carbon atoms, d represents an average addition mole number, and is 1 or more and 100 or less. R 1 , R 2, and R 4 It may be the same or different, and represents a hydrocarbon group having a carbon number of 1 or more and 10 or less in which a part of hydrogen atoms may be substituted with a hydroxyl group, and R 3 represents a carbon number of 1 or more and 10 or less in which a hydrogen atom and a part of hydrogen atoms may be substituted with a hydroxyl group. At least one of the hydrocarbon groups, R 5 represents an alkanediyl group having 1 to 18 carbon atoms (wherein R 5 adjacent to R 1 represents a single bond), R 6 represents an alkanediyl group having 1 to 4 carbon atoms, (m 1) - and (m 2) - each independently represent an anion, n, p, m and k represents the average number of structural units, (n + p + m + k) is 1.0 or more and 22.0 or less, (n + p ) Is 1.0 or more and 22.0 or less, n is 0.3 or more and 22.0 or less, p is 0 or more and 11.0 or less, m is 0 or more and 21.0 or less, and k is 0 or more and 21.0 or less; a plurality of [(C = O) R x1 O] can be the same as It can be different, the plural [R y1 O] can be the same or different, and each structural unit whose average structural unit number is represented by n, p, m, and k can be in any order]. 如請求項18之四級銨鹽化合物,其以式(1-1)表示,[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R1、R2及R4可相同或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R3表示選自氫原子及一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基中之至少一種,R5表示碳數1以上且18以下之烷二基(其中,與R1鄰接之R5表示單鍵),R6表示碳數1以上且4以下之烷二基,(M1)-及(M2)-分別獨立地表示陰離子,n、m、k表示平均結構單元數,(n+m+k)為1.0以上且22.0以下,n為1.0以上且22.0以下,m為0以上且21.0以下,k為0以上且21.0以下;複數個[(C=O)Rx1O]可相同亦可不同,以n、m、k表示其平均結構單元數之各結構單元可為任意排列順序]。If the quaternary ammonium salt compound of claim 18 is represented by formula (1-1), [In the formula, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, is 2 or more and 100 or less, and R 1 , R 2 and R 4 may be the same or different and represent a hydrocarbon group having a carbon number of 1 or more and 10 or less in which a part of hydrogen atoms can be substituted with a hydroxyl group, and R 3 represents a carbon number selected from a hydrogen atom and a part of hydrogen atoms that can be substituted with a hydroxyl group At least one of hydrocarbon groups of 1 or more and 10 or less, R 5 represents an alkanediyl group having 1 or more and 18 or less carbons (where R 5 adjacent to R 1 represents a single bond), and R 6 represents 1 or more and 4 carbons the following of -alkanediyl, (m 1) - and (m 2) - each independently represent an anion, n, m, k represents the average number of structural units, (n + m + k) is 1.0 or more and 22.0 or less, n is 1.0 or more and 22.0 or less, m is 0 or more and 21.0 or less, k is 0 or more and 21.0 or less; plural [(C = O) R x1 O] may be the same or different, and the average structure is represented by n, m, and k The number of units of each structural unit can be in any order.] 如請求項18之四級銨鹽化合物,其以式(1-1a)表示,[式中,Rx1表示碳數2以上且12以下之烷二基,Rx2表示碳數1以上且18以下之烴基,a表示平均加成莫耳數,為2以上且100以下,R1、R2及R4可相同或不同,表示一部分氫原子可被取代為羥基之碳數1以上且10以下之烴基,R5表示碳數1以上且18以下之烷二基(其中,與R1鄰接之R5表示單鍵),R6表示碳數1以上且4以下之烷二基,(M1)-表示陰離子,n、m表示平均結構單元數,(n+m)為1.0以上且22.0以下,n為1.0以上且22.0以下,m為0以上且21.0以下;複數個[(C=O)Rx1O]可相同亦可不同,以n、m表示其平均結構單元數之各結構單元可為任意排列順序]。If the quaternary ammonium salt compound of claim 18 is represented by formula (1-1a), [Wherein, R x1 represents an alkanediyl group having 2 or more and 12 or less carbon, R x2 represents a hydrocarbon group having 1 or more and 18 or less carbon, a represents an average addition mole number, and is 2 or more and 100 or less, R 1 , R 2 and R 4 may be the same or different, and a part of hydrogen atoms may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, and R 5 represents an alkyldiyl group having 1 to 18 carbon atoms (wherein, and R 1 adjacent to the R 5 represents a single bond), R 6 represents the carbon number of 1 or more and 4 or less -alkanediyl, (m 1) - represents an anion, n, m represents the average number of structural units, (n + m) is 1.0 or more And 22.0 or less, n is 1.0 or more and 22.0 or less, m is 0 or more and 21.0 or less; a plurality of [(C = O) R x1 O] may be the same or different, and each of the average structural unit numbers is represented by n and m Structural units can be in any order.] 如請求項19之四級銨鹽化合物,其中於式(1-1)中,m為0。For example, the quaternary ammonium salt compound of claim 19, wherein m is 0 in formula (1-1). 如請求項18之四級銨鹽化合物,其中於式(1)中,p為0.3以上且11.0以下。For example, the quaternary ammonium salt compound of claim 18, wherein in formula (1), p is 0.3 or more and 11.0 or less. 如請求項22之四級銨鹽化合物,其中於式(1)中,k為0。For example, the quaternary ammonium salt compound of claim 22, wherein k is 0 in formula (1).
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