CN108026402A

CN108026402A - The manufacture method of pigment dispersion, the manufacture method of solidification compound, the manufacture method of cured film, possess cured film solid-state imager manufacture method, possess cured film colour filter manufacture method and possess cured film image display device manufacture method

Info

Publication number: CN108026402A
Application number: CN201680051980.5A
Authority: CN
Inventors: 久保田诚
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2015-09-30
Filing date: 2016-09-26
Publication date: 2018-05-11
Also published as: JP6644803B2; JPWO2017057222A1; WO2017057222A1

Abstract

The present invention provide a kind of manufacture method of the pigment dispersion for the pigment dispersion that can manufacture processing time is short and excellent storage stability, the manufacture method of solidification compound, the manufacture method of cured film, possess cured film solid-state imager manufacture method, possess cured film colour filter manufacture method, possess cured film image display device manufacture method.The manufacture method of the pigment dispersion of the present invention has：Process 1, the precursor composition that the viscosity comprising pigment, dispersant and organic solvent and at 25 DEG C is 3~20mPas is preheated；And process 2, the fluid temperature for the precursor composition being preheated is remained 40 DEG C less than 60 DEG C, and the decentralized processing based on ball mill is implemented to precursor composition.

Description

The manufacture method of pigment dispersion, the manufacture method of solidification compound, cured film Manufacture method, possess cured film solid-state imager manufacture method, possess curing The manufacture method of the colour filter of film and possess cured film image display device manufacture Method

Technical field

The present invention relates to a kind of manufacture method of pigment dispersion, the manufacture method of solidification compound, the system of cured film Make method, possess cured film solid-state imager manufacture method, possess cured film colour filter manufacture method and possess The manufacture method of the image display device of cured film.

Background technology

From the viewpoint of the fastnesses such as light resistance are excellent, pigment can function properly as colouring agent.Using pigment In the case of, in general, pigment exists as condensation product, therefore carries out defined decentralized processing to decompose the condensation product, system It is standby go out the pigment dispersion that imperceptibly disperses of pigment and use.

For example, Patent Document 1 discloses following methods, i.e. to the combination comprising pigment and polymer (dispersant) Thing is implemented to have used the decentralized processing of pearl, so as to obtain pigment dispersion.

Conventional art document

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2006-182885 publications

The content of the invention

The invention technical task to be solved

In recent years, it is desirable to the pigment dispersion of pigment concentration higher, however, in order to obtain this pigment dispersion, it is necessary to Improve and implement to load pigment concentration included in the precursor composition of decentralized processing.On the other hand, if attempting to improve precursor Pigment concentration in composition, then can cause the viscosity of precursor composition to increase.

The inventors of the present invention have found, are preparing the high precursor composition of viscosity, and precursor composition is implemented such as patent text In the case of offering in 1 the described decentralized processing (so-called ball mill) for having used pearl, the sufficient of pigment is unable to reach Micro disperse, if alternatively, attempting to reach the sufficiently scattered of pigment, processing time extends, and productivity is deteriorated.

And if, it was also found that obtained pigment dispersion is taken care of the stipulated time, the viscosity of generation pigment dispersion Increase and/or pigment precipitation etc., required further improvement on this point of so-called storage stability.

In view of above-mentioned actual conditions, it is an object of the invention to provide a kind of manufacture method of pigment dispersion, it can Manufacture the pigment dispersion of processing time is short and excellent storage stability.

Also, another object of the present invention is to also provide a kind of manufacture method of solidification compound, the system of cured film Make method, possess cured film solid-state imager manufacture method, possess cured film colour filter manufacture method and possess The manufacture method of the image display device of cured film.

For solving the means of technical task

It is that the present inventor is furtherd investigate in order to solve the above problems as a result, finding to include by setting defined Process that the precursor composition of component is preheated and the above subject can be solved, and complete the present invention.

That is, the inventors of the present invention are had found by that can solve the above subject with lower structure.

(1) a kind of manufacture method of pigment dispersion, it has：

Process 1, will include the precursor group that the viscosity at pigment, dispersant and organic solvent and 25 DEG C is 3~20mPas Compound is preheated；And

Process 2,40 DEG C are remained less than 60 DEG C by the fluid temperature for the precursor composition being preheated, and to precursor Composition implements the decentralized processing based on ball mill.

(2) manufacture method of the pigment dispersion according to (1), wherein, the primary particle size of pigment is less than 55nm.

(3) according to the manufacture method of the pigment dispersion described in (1) or (2), wherein, the acid number of dispersant for 30~ 100mgKOH/g。

(4) manufacture method of the pigment dispersion according to any one of (1) to (3), wherein, used in ball mill The pearl of a diameter of below 0.05mm.

(5) manufacture method of the pigment dispersion according to any one of (1) to (4), wherein, in process 1, precursor The fluid temperature of composition is preheated as 40~60 DEG C.

(6) manufacture method of the pigment dispersion according to any one of (1) to (5), wherein, the precursor in process 2 The fluid temperature of composition is remained more than 40 DEG C and less than 57 DEG C.

(7) a kind of manufacture method of solidification compound, it has：

The process that pigment dispersion is obtained by the manufacture method any one of (1) to (6)；And

Pigment dispersion, polymerization initiator, polymerizable compound and alkali soluble resins it will be carried out as obtained from process It is obtained by mixing the process of solidification compound.

(8) a kind of manufacture method of cured film, it has：

The process that pigment dispersion is obtained by the manufacture method any one of (1) to (6)；

Pigment dispersion, polymerization initiator, polymerizable compound and alkali soluble resins it will be carried out as obtained from process It is obtained by mixing the process of solidification compound；And

Make to cure to obtain the process of cured film by solidification compound obtained from process.

(9) a kind of manufacture method for the solid-state imager for possessing cured film, it has：

(10) a kind of manufacture method for the colour filter for possessing cured film, it has：

(11) a kind of manufacture method for the image display device for possessing cured film, it has：

Invention effect

In accordance with the invention it is possible to provide a kind of pigment dispersion that can manufacture processing time is short and excellent storage stability Pigment dispersion manufacture method.

Also, in accordance with the present invention it is further possible to provide a kind of manufacture method of solidification compound, the manufacturer of cured film Method, possess cured film solid-state imager manufacture method, possess cured film colour filter manufacture method and possess curing The manufacture method of the image display device of film.

Brief description of the drawings

Fig. 1 is the skeleton diagram for showing schematically the embodiment for implementing the manufacturing method of the present invention.

Fig. 2 is the stereogram for the solid-state imaging device for representing the 1st embodiment.

Fig. 3 is the exploded perspective view of the solid-state imaging device of the 1st embodiment.

Fig. 4 is the sectional view for the solid-state imaging device for representing the 1st embodiment.

Fig. 5 is the sectional view for the solid-state imaging device for representing the 2nd embodiment.

Fig. 6 is the sectional view for the solid-state imaging device for representing the 3rd embodiment.

Fig. 7 is the sectional view for the solid-state imaging device for representing the 4th embodiment.

Embodiment

Hereinafter, illustrated on the mode for implementing the present invention.

In addition, in the statement of group (atomic group) in the present specification, substitution is not recorded and unsubstituted statement is also wrapped Group containing the group without substituent and with substituent.For example, " alkyl " not only includes the alkyl without substituent (unsubstituted alkyl), and including the alkyl (substitution alkyl) with substituent.

In the present specification, " (methyl) acrylate " represents acrylate and methacrylate, " (methyl) propylene Acid " represents acrylic acid and methacrylic acid, and " (methyl) acryloyl group " represents acryloyl group and methylacryloyl.

Pigment in the present invention refers to the indissolubility dye compound being for example not dissolved in solvent.Here, on molten Agent, can enumerate the solvent illustrated in the chapters and sections of aftermentioned solvent.So as to the dye compound phase being not dissolved in these solvents When the pigment in the present invention.

"~" is using the implication included by the numerical value as lower limit and upper limit value that will be recorded in before and after it in the present specification And use.

In addition, in the present specification, " construction unit " is identical with the implication of " repetitive unit ".

One of characteristic point as the present invention, can enumerate following characteristics point：First, before to comprising defined component Before body composition implements the decentralized processing based on ball mill, implement the processing for being preheated precursor composition.Initial precursor It is also difficult to the dispersion force of precursor composition even if implementing the decentralized processing based on ball mill in the case of the viscosity height of composition To be passed, it is not easy to carry out the micro disperse of pigment.In patent document 1, while precursor composition is heated to be set point of temperature, one Side implement decentralized processing, however, through the present inventor studied as a result, even if by it is this processing can not also obtain sufficiently Effect.Then, it was found that situations below：After heating (preheating) precursor composition in advance is so that its viscosity fully reduces, guarantor Hold set point of temperature and implement the decentralized processing based on ball mill, thus can obtain desirable effect.

Also, as the preferred embodiment of the present invention, it has been found that following characteristics points：On used component, preferably make With the pigment less than prescribed level and the dispersant of defined acid number.Especially, if using this component, by precursor composition tune Whole dispersant is improved the adsorptivity of pigment when being set point of temperature, as a result, can speculate that to can obtain storage stability more excellent Different pigment dispersion.

The manufacture method of the pigment dispersion of the present invention at least has following two processes.

Process 1：The precursor group that the viscosity at pigment, dispersant and organic solvent and 25 DEG C is 3~20mPas will be included The process that compound is preheated

Process 2：The fluid temperature for the precursor composition being preheated is remained 40 DEG C less than 60 DEG C, and to precursor The process that composition implements the decentralized processing based on ball mill

Hereinafter, it is described in detail on each operation.In addition, the detailed content on the material used in this manufacture method, It will be described in detail in the lump below.

＜ processes 1 (preheating procedure) ＞

The precursor group that process 1, which is, to be 3~20mPas comprising the viscosity at pigment, dispersant and organic solvent and 25 DEG C The process that compound is preheated.Before aftermentioned decentralized processing is implemented, by fully preheating precursor composition, in decentralized processing Dispersion force be fully passed, processing time shortens, also, the storage stability of obtained pigment dispersion is also carried It is high.

Pigment, dispersant and organic solvent are included at least in precursor composition used in this process.On being contained in Each component in precursor composition, followed by detailed description.

Viscosity of the precursor composition at 25 DEG C used in this process is 3~20mPas, from meeting decentralized processing The viewpoint that further shortens of processing time and pigment dispersion the more excellent viewpoint of storage stability in a little less (following, also referred to as " the more excellent viewpoint of effect of the invention ") considers that the viscosity is preferably 3~17mPas, more excellent Elect 3~15mPas as.

Precursor composition is adjusted to 25 DEG C, and is come using viscosimeter RE-85L (TOKI SANGYO CO., LTD. manufacture) Measure above-mentioned viscosity.

Precursor composition is preheated (heating) in this process.By preheating precursor composition, except organic solvent pair Beyond the wetability of surface of pigments is improved, the dissolving of dispersant and the homogenization of dispersant are promoted.Also, due to dividing The effective real estate life of absorption of the powder to pigment, therefore processing time shortening, the excellent storage stability of pigment dispersion.

Moreover, absorption of the dispersant to pigment is effectively performed since decentralized processing initial stage, thus it is unadsorbed scattered The amount of agent is reduced, it can thus be appreciated that can inhibit with time going by and produce foreign matter (pigment particles, unadsorbed dispersant etc. are solidifying Polymers).Especially, when using black pigment, its significant effect.

And, it is contemplated that reduce the viscosity of precursor composition by being preheated, it is believed that shearing force by followed by The pearl of detailed description and become easily to transmit, scattered be accelerated.

It it is 40 DEG C preferably by the fluid temperature preheating of precursor composition from the viewpoint of it can obtain significant the effect above More than.Wherein, it is 40~60 DEG C preferably by aforesaid liquid preheating temperature, more from the viewpoint of the effect of the present invention is more excellent It is preferred that preheating is more than 40 DEG C and less than 57 DEG C, further preferably preheating is 42~50 DEG C.

Also, when preheating time is preferably 5 minutes~3 small, more preferably 10 minutes~2 it is small when, more preferably 15 When minute~1.5 are small.If above range, then absorption of the dispersant to pigment since the initial stage of decentralized processing effectively into OK, therefore significant the effect above can be obtained, also, in addition to preventing overheat, also there is no problem on the activity duration.

The method of preheating precursor composition is not particularly limited, and can use known method.

In addition, the process of preheating precursor composition is the process different from aftermentioned process 2 (decentralized processing process).As after Face describes in detail, the ball mill dispersion machine for being used for implementing ball mill is used in process 2, but process 1 is in precursor composition quilt The processing implemented before being supplied in the pulverizing chamber of ball mill dispersion machine.As disperse precursor composition is supplied to ball mill The processing preheated before in the pulverizing chamber of machine to it.

In addition, pulverizing chamber refers to configure rotor (rotor) and filling pearl, and by the rotation of rotor and agitation beads Son, assigns the pigment in precursor composition by the pearl being stirred the chamber of shearing force.

＜ processes 2 (decentralized processing process) ＞

Process 2 is following process, i.e. by the fluid temperature for the precursor composition being preheated remain 40 DEG C less than 60 DEG C, and implement the process of the decentralized processing based on ball mill to precursor composition.By implementing the process, pigment is decomposed, So as to obtain the high pigment dispersion of the dispersion stabilization of pigment.

In process 2, the fluid temperature for the precursor composition being preheated in process 1 is remained 40 DEG C less than 60 DEG C, and implement aftermentioned decentralized processing.That is, 40 DEG C are adjusted to fluid temperature less than 60 DEG C of precursor composition reality Apply decentralized processing.Wherein, from the viewpoint of the effect of the present invention is more excellent, the fluid temperature of precursor composition is preferably maintained at More than 40 DEG C and less than 57 DEG C, 42~50 DEG C are more preferably remained.

By being handled under above-mentioned temperature conditionss, the effective real estate life of absorption of the dispersant to pigment, therefore during processing Between shorten, the excellent storage stability of pigment dispersion.

Also, the temperature from the pre-heat treatment (process 1) is maintained, or is set to the temperature higher than its, thus dispersant pair The absorption of pigment is effectively performed since the initial stage of decentralized processing, therefore the amount of unadsorbed dispersant is reduced, it follows that It can inhibit with time going by and produce foreign matter (condensation product such as pigment particles, unadsorbed dispersant).Especially, when using When black pigment and Chinese white, compared with color pigment, the activity of surface of pigments is high, therefore pigment easily agglomerates each other, its Significant effect.

It will be explained later, the decentralized processing of process 2 is implemented using known ball mill dispersion machine.By in process 1 The indoor method of crushing that the precursor composition being preheated is supplied to ball mill dispersion machine is not particularly limited, for example, such as Fig. 1 It is shown, the precursor composition W being preheated as set point of temperature is put into tank 200, using pump (not shown), can be passed through from tank 200 The pulverizing chamber of ball mill dispersion machine 500 is continuously fed into by pipe arrangement 300.In addition, pipe arrangement 300 itself can also be heated to be regulation temperature Degree, in case the temperature of precursor composition W changes.

In addition, the precursor composition W for showing to be preheated in Fig. 1 as set point of temperature is continuously fed into the powder of ball mill pulverizer Mode in broken room, but which is not limited to, for example, can be while circulating precursor composition, while implementing scattered place Reason, to be supplied to after ball mill pulverizer implements processing the precursor composition for set point of temperature will be preheated, and then, The precursor composition for being carried out processing is supplied again to ball mill pulverizer once again.

In addition, when the precursor composition being preheated is supplied to ball mill dispersion machine (pulverizing chamber in ball mill dispersion machine) Quantity delivered (the treatment fluid scale of construction) be not particularly limited, from the viewpoint of productivity, the quantity delivered is preferably 3~ 500kg/ minutes, more preferably 10~100kg/ minutes.

In process 2, the decentralized processing based on ball mill is implemented by using known ball mill dispersion machine.

As ball mill dispersion machine, Ultra-micro-grinding machine (Ultra Visco Mill), agitator mill (Agitator can be enumerated Mill), super love pass grinding machine (Ultra Apex Mill), enlightening promise grinding machine (Dyno Mill), fine grinding machine (Fine Mill), annular gap-type grinding machine (Annular gap type mill) and MSC grinding machines etc., can be suitably used.

Also, there are centrifugation mode, method for sieving and slit mode in pearl separate mode, as use below 0.1mm Pearl when, preferably centrifuge mode.

Also, such as followed by detailed description, in the case of using more small pearl, from the viewpoint of pearl separation, more It is preferred for the rotor of pearl movement and separator (centrifuge mechanism) is individually driven.As this device, The NPM-Pilot of Shinmaru Enterprises Corporation. manufactures, ASADA IRON WORKS.CO., LTD. systems Twin shaft grinding machine (Dual Apex Mill) of ECOMILL and KOTOBUKI KOGYOU.CO., LTD. manufactures made etc. is filled without sieve Putting further can avoid liquid from blocking, therefore preferably.

Pulverizing chamber is provided with ball mill dispersion machine.As described above, in general, rotor is provided with pulverizing chamber.This turn Son is connected to the rotation axis being driven in rotation by driving device such as in the form of annular discs, bar-shaped or foliaceous.Therefore, turn The rotation that son is configured to accompanying rotation axis can be to rotating in a circumferential direction.Furthermore, it is also possible to it has been formed about in the end of rotor prominent Rise, pearl can be effectively stirred will pass through the rotation of rotor.

Pearl is filled with pulverizing chamber.

The species of pearl is not particularly limited, and can enumerate bead, alumina bead, Zirconia silicates pearl and oxidation Zirconium pearl etc..

The diameter of pearl is not particularly limited, in general, be below 3mm in most cases, it is more excellent from the effect of the present invention It is preferably below 1mm from the viewpoint of different, more preferably below 0.3mm, more preferably below 0.05mm.Lower limit has no Special limitation, in general, being more than 0.01mm in most cases.

A diameter of average value of above-mentioned pearl, specifically, the diameter of a diameter of any 100 pearls of measure, and Carried out the value of arithmetic average.In addition, in the case where pearl is not round type, it is measured major diameter as diameter.

The filling rate of pearl in pulverizing chamber is not particularly limited, and is preferably more than 40 volume %, more preferably 50 bodies Product more than %, more preferably more than 60 volume %.It is preferably below 98 volume % as the upper limit, more preferably 95 bodies Product below %, more preferably below 90 volume %.By the way that filling rate is set to more than above-mentioned lower limit, can have pigment Effect ground disperses.Also, by being set to below upper limit value, it can be ensured that the space that pearl moves around in pulverizing chamber.It is here, logical Cross the weight of pearl divided by the bulk density of pearl and calculate the packing volume of pearl, the appearance of the packing volume divided by pulverizing chamber Product, thus obtains the filling rate of pearl.

In pulverizing chamber, the decentralized processing of pigment is carried out by rotor and pearl.That is, by the rotation of rotor and agitation beads Son.By the pearl being stirred, shearing force is assigned to pigment.By the shearing force, the offspring of pigment is decomposed and becomes Primary particle.Also, these pigment are stirred by pearl, therefore it is homogeneously dispersed in organic solvent equal solvent.

The peripheral speed of rotor is not particularly limited when rotor rotates, generally, it is preferred to more than 0.1m/ seconds, more preferably 1m/ Second more than, it is 5m/ seconds further preferred more than.The upper limit is not particularly limited, following for 15m/ seconds in most cases.Here, turn The peripheral speed of son refers to the speed in rotor periphery portion.

In addition, as described above, having following device according to the species of ball mill dispersion machine, i.e. it makes above-mentioned rotor and will be by The pigment and pearl of decomposition carry out separated separator (separation unit.Especially centrifugation portion) moved by respective drive system It is dynamic.In the case of this device, separator is also rotated in the same manner as above-mentioned rotor, thus carries out point of pigment and pearl From.In this case, the peripheral speed of separator is not particularly limited, generally, it is preferred to more than 0.1m/ seconds, more preferably 1m/ seconds with On, it is 5m/ seconds further preferred more than.The upper limit is not particularly limited, following for 15m/ seconds in most cases.Here, separator Peripheral speed refer to the speed of separator outer edge.

The processing time of decentralized processing is not particularly limited, and from the viewpoint of the effect of the present invention is more excellent, works as place The charge weight of reason liquid is when being set to 15kg, when the processing time is preferably 1~10 small, more preferably 5~9.0 it is small when.Although place It is not stringent to manage the length of time, it is preferred that its length and amount of liquid are generally proportionate.

Moreover, if rotor is rotated, heat can be produced because of the friction of pearl.Therefore, configured around pulverizing chamber Pipe arrangement, by making refrigerant to adjust the fluid temperature for crushing indoor precursor composition with Bottomhole pressure.

The pigment being decomposed in pulverizing chamber is separated into pearl by filter etc. and is recovered.In addition, as described above, In the case of separator progress is rotating, pigment and pearl are separated into by centrifugation.

It is carried out average grain diameter (that is, the face in pigment dispersion of the pigment (micronized pigment) of above-mentioned decentralized processing The average grain diameter of material) be not particularly limited, it is different according to the primary particle size of used pigment, but from the present invention effect It is preferably the scope of (primary particle size × 10 times of pigment) below more than (primary particle size of pigment) from the viewpoint of more excellent, The scope of (primary particle size × 6 times of pigment) below more preferably more than (primary particle size of pigment).

Assay method as the average grain diameter of the pigment in pigment dispersion, it is known to dynamic light scattering method (FFT (Fast Fourier Transform：Fast Fourier Transform (FFT)) power spectrum method).More specifically, Micro Trac will be passed through EX-150 (manufacture of Nikkiso Co., Ltd.s) and the D90 that obtains are set to the average grain diameter of above-mentioned pigment.

Hereinafter, it is described in detail on a variety of materials used in this manufacture method.

＜ pigment ＞

Pigment can use conventionally known various inorganic pigments or organic pigment.

Also, the primary particle size of the pigment used in the present invention is preferably smaller than 55nm.The initial stage of decentralized processing, with disperseing The surface area increase of the related pigment particles of the absorption-desorption of agent, effect of the invention are more excellent.Moreover, more preferably 50nm with Under, further preferred below 40nm.Lower limit is not particularly limited, and is in most cases more than 5nm.

The primary particle size of pigment is average value, it is the once grain that any 400 pigment is measured by electron microscope Footpath, and by these primary particle sizes carry out arithmetic average value.In addition, in the case where pigment is not round type, justified using equivalent Diameter.In addition, diameter of equivalent circle refers to area (projected area) equal area equivalent to the two dimensional image with observed pigment Diameter of a circle.

As inorganic pigment, the metallic compounds such as metal oxide and metal complex salt can be enumerated.Specifically, may be used To enumerate the composite oxides of the metal oxides such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony and above-mentioned metal.

As organic pigment, for example, following pigment.

C.I.Pigment YELLOW (pigment yellow) 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20, 24,31,32,34,35,35：1,36,36：1,37,37：Isosorbide-5-Nitrae 0,42,43,53,55,60,61,62,63,65,73,74,77, 81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118, 119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155, 156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181, 182,185,187,188,193,194,199,213,214 etc.,

C.I.Pigment Orange (pigment orange) 2,5,13,16,17：1,31,34,36,38,43,46,48,49,51, 52,55,59,60,61,62,64,71,73 etc.,

C.I.Pigment Red (paratonere) 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48：1, 48：2,48：3,48：4,49,49：Isosorbide-5-Nitrae 9：2,52：1,52：2,53：1,57：1,60：1,63：1,66,67,81：1,81：2,81： 3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172, 175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220, 224,226,242,246,254,255,264,270,272,279

C.I.Pigment Green (naphthol green) 7,10,36,37,58,59

C.I.Pigment Violet (pigment violet) 1,19,23,27,32,37,42

C.I.Pigment Blue (alizarol saphirol) 1,2,15,15：1,15：2,15：3,15：4,15：6,16,22,60,64, 66,79,80

C.I.Pigment Rlack (pigment black) 1

These organic pigments can be used alone, or can combine various organic pigments in order to improve excitation purity and make With.

Wherein, as pigment, black pigment can preferably be enumerated.

Black pigment can use various known black pigments.Especially, it just can realize that high optics is dense from on a small quantity The oxidation tungsten compounds such as from the viewpoint of degree, preferably carbon black, titanium be black, titanium oxide, tungsten oxide and caesium tungsten oxide, metal boride, Iron oxide, manganese oxide, graphite, titanium carbide, zirconium carbide, zirconium boride, boron carbide and silicon boride, more preferably carbon black or titanium are black, into one It is black to walk preferred titanium.

Black titanium is the black particles containing titanium atom.Preferably titanium suboxide or titanium oxynitrides.Titanium is black scattered to improve Property and for the purpose of suppressing coherency etc., as needed, surface can be modified.Specifically, the black surface of titanium can Coated with silica, titanium oxide, germanium oxide, aluminium oxide, magnesia or zirconium oxide.Also, the black surface of titanium also can Handled with the water repellency material as represented by Japanese Unexamined Patent Publication 2007-302836 publications.

Titanium black typically particle shape, the primary particle size of preferably each particle is small.

The black specific surface area of titanium is not particularly limited, in general, being 5m by the value that BET method measures²/ more than g and 150m²/ Below g left and right, is preferably 20m²/ more than g and 120m²/ below g.

The example of the commercially available product black as titanium, can enumerate the black 10S, 12S of titanium, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names：More than, Mitsubishi Materials Corporation manufactures) and Tilack D (trade names： Ako Kasei Co., Ltd.s manufacture) etc..

Moreover, it is also preferred that as comprising titanium is black and Si atoms to contain titanium by dispersion black.

It is black as titanium is contained by dispersion in the composition in which, by the Si atoms in dispersion and Ti atoms Content ratio (Si/Ti) with mass conversion be preferably more than 0.05.

Here, the above-mentioned state two that the black state and agglomerate (offspring) for primary particle of titanium is included by dispersion Person.

If in addition, being less than 0.5 by the content ratio (Si/Ti) of the Si atoms in dispersion and Ti atoms, use Become easier to by the manufacture of the pigment dispersion of dispersion, therefore its upper limit is preferably 0.5.

Also, when to having used the photomask by dispersion to form pattern, it is not easy by photoetching in removal portion residual Residue is stayed, from the viewpoint of light shielding ability is excellent, more than 0.05 and less than 0.5 are more preferably by the Si/Ti of dispersion, into one Step is preferably more than 0.07 and less than 0.4.

In order to change (for example, being set to more than 0.05) by the Si/Ti of dispersion, can profit with the following method.

First, titanium oxide is made by using dispersion machine and silicon dioxide granule carries out scattered and obtains mixture, this is mixed Compound carried out under high temperature (for example, 850~1000 DEG C) also member processing, thus, it is possible to obtain using titanium black track producing particle as mainly into Divide and containing Si and Ti by dispersion.

Here, on being illustrated for changing by the specific mode of the Si/Ti of dispersion.

Si/Ti be adjusted to it is such as 0.05 black with first-class titanium, can be for example, by public in Japanese Unexamined Patent Publication 2008-266045 Described method in (0005) section and (0016)~(0021) section of report and make.

Hereinafter, when Si atoms are imported into by dispersion, as long as using the materials containing Si such as silica.

As workable silica, can enumerate precipitated silica, aerosil, cataloid and Synthetic silica etc., as long as properly selecting these materials carries out use.

Titanium is black can be used only a kind, can also use two or more.

The content of pigment in precursor composition is not particularly limited, and the viewpoint more excellent from the effect of the present invention is examined Consider, be preferably 5~50 mass % relative to precursor composition gross mass, more preferably 10~40 mass %, more preferably 15~35 mass %.

＜ dispersants ＞

Dispersant helps to improve the dispersiveness of above-mentioned pigment.

The acid number of dispersant is preferably 30~100mgKOH/g, more excellent from the viewpoint of the effect of the present invention is more excellent Elect 30~90mgKOH/g as.If above range, then the amount of unadsorbed dispersant can be further reduced, except advantageously obtaining Beyond effect of the invention, with the pre-heat treatment (process 1) and it is scattered when the effect of heating (process 2) be combined, with The process of time, foreign matter (condensation product such as pigment particles, unadsorbed dispersant) is not likely to produce.

As the computational methods of the acid number of dispersant, potential difference titration can be enumerated.That is, dispersant is made to be dissolved in titration Solvent (for example, propylene glycol monomethyl ether and mixed solvent that water is 9 to 1), is dripped with the potassium hydroxide aqueous solution of 0.1 mole/L It is fixed, by until the titer of the flex point on titration curve can calculate acid number.

The acid number of dispersant can also be calculated by the average content of the acidic group in such as dispersant.

The weight average molecular weight of dispersant is not particularly limited, as the polyphenyl second based on GPC (gel permeation chromatography) method Alkene scaled value, is preferably 4, more than 000 and 300, less than 000, and more preferably 5, more than 000 and 200, less than 000, it is further excellent Elect 6, more than 000 and 100, less than 000 as, especially preferably 10, more than 000 and 50, less than 000.

GPC method is based on following methods：Using HLC-8020GPC (TOSOH CORPORATION manufactures), used as column TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (TOSOH CORPORATION systems Make, 4.6mmID × 15cm), THF (tetrahydrofuran) is used as eluent.

As dispersant, known pigment dispersing agent can be properly selected and used.Wherein, preferred macromolecule chemical combination Thing.

As dispersant, macromolecule dispersing agent can be enumerated (for example, polyamide-amide or its salt, polycarboxylic acids or its salt, height Molecular weight unsaturated acid ester, modified polyurethane, modified poly ester, modified poly- (methyl) acrylate, (methyl) acrylic copolymer Thing, naphthalenesulfonic acid formalin fusion thing) and polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine etc..

High-molecular compound can be categorized further, as straight-chain macromolecule, terminal-modified type macromolecule by its structure, connect Branch type macromolecule and block type polymer.

High-molecular compound is adsorbed in pigment etc. by the surface of dispersion, plays the role of preventing them from re-uniting.Therefore, As high-molecular compound, preferably there is terminal-modified type macromolecule, the graft type macromolecule to the anchor site of surface of pigments Or block type polymer.

On the other hand, by being modified to the surface of pigment, high-molecular compound can also be promoted to the pigment table The adsorptivity in face.

High-molecular compound is preferably provided with the construction unit with grafted chain.

Possesses the high-molecular compound of the construction unit with this grafted chain by grafted chain and the compatibility with solvent Be improved, thus the dispersiveness of pigment and through when after dispersion stabilization it is excellent.

If grafted chain is elongated, steric repulsion effect is improved, and the dispersiveness of pigment is improved, if however, grafting Chain is long, then high-molecular compound reduces the adsorption capacity of pigment, and the dispersiveness of pigment is in the tendency reduced.Therefore, grafted chain It is preferred that the scope that the atomicity in addition to hydrogen atom is 40~10,000, the atomicity more preferably in addition to hydrogen atom is 50 ~2,000, the atomicity further preferably in addition to hydrogen atom is 60~500.

Here, grafted chain represents (in the group from main chain branch, to be bonded with main chain from the root of the main chain of copolymer Atom) to from the end of the group of main chain branch.

Grafted chain preferably has polymer architecture, and as this polymer architecture, for example, poly- (methyl) propylene Acrylate structure (for example, poly- (methyl) acrylic acid structure), polyester construction, polyurethane structural, polyurea structure, polyamide structure and poly- Ether structure etc..

In order to improve the dispersiveness of pigment by improving the interaction of grafted chain and solvent, grafted chain is preferably to have There is at least one kind of grafted chain in the group for including polyester construction, polyether structure and poly- (methyl) acrylate structural, it is more excellent Elect the grafted chain with least one of polyester construction and polyether structure as.

It is not particularly limited as the macromonomer that this polymer architecture is set to grafted chain and is had, is preferably Macromonomer with reactive double bond group.

As corresponding with the construction unit with grafted chain possessed by high-molecular compound, and it is suitably used in high score Commercially available macromonomer in the synthesis of sub- compound, preferably AA-6 (trade name, TOAGOSEI CO., LTD.), AA-10 (trade name, TOAGOSEI CO., LTD. manufacture), AB-6 (trade name, TOAGOSEI CO., LTD. manufacture), AS-6 (business The name of an article claims, TOAGOSEI CO., LTD.), AN-6 (trade name, TOAGOSEI CO., LTD. manufacture), AW-6 (trade name, TOAGOSEI CO., LTD. manufacture), AA-714 (trade name, TOAGOSEI CO., LTD. manufacture), AY-707 (trade names Claim, TOAGOSEI CO., LTD. manufactures), AY-714 (trade name, TOAGOSEI CO., LTD. manufacture), AK-5 (trade names Claim, TOAGOSEI CO., LTD. manufactures), AK-30 (trade name, TOAGOSEI CO., LTD. manufacture), AK-32 (trade names Claim, TOAGOSEI CO., LTD. manufactures), BLEMMER PP-100 (trade name, NOF CORPORATION manufactures), BLEMMER PP-500 (trade name, NOF CORPORATION manufactures), BLEMMER PP-800 (trade name, NOF CORPORATION is manufactured), BLEMMER PP-1000 (trade name, NOF CORPORATION manufacture), BLEMMER 55- PET-800 (trade name, NOF CORPORATION manufactures), BLEMMER PME-4000 (trade name, NOF CORPORATION is manufactured), BLEMMER PSE-400 (trade name, NOF CORPORATION manufacture), BLEMMER PSE- 1300 (trade name, NOF CORPORATION manufactures) and BLEMMER 43PAPE-600B (trade name, NOF CORPORATION is manufactured) etc..Wherein, preferably AA-6 (trade name, TOAGOSEI CO., LTD. manufacture), AA-10 (trade names Claim, TOAGOSEI CO., LTD.), AB-6 (trade name, TOAGOSEI CO., LTD. manufacture), AS-6 (trade name, TOAGOSEI CO., LTD.), AN-6 (trade name, TOAGOSEI CO., LTD. manufacture) or BLEMMER PME-4000 (business The name of an article claims, NOF CORPORATION manufactures) etc..

(preferred embodiment 1)

High-molecular compound (dispersant) preferably comprises the structure list represented by any one in following formula (1)~formula (4) Member is as the construction unit with grafted chain, more preferably comprising by following formula (1A), following formula (2A), following formula (3A), following Any one construction unit represented in formula (3B) and following (4).

[chemical formula 1]

In formula (1)~formula (4), W¹、W²、W³And W⁴Separately represent oxygen atom or NH.W¹、W²、W³And W⁴Preferably Oxygen atom.

In formula (1)~formula (4), X¹、X²、X³、X⁴And X⁵Separately represent the organic group of hydrogen atom or 1 valency.Make For X¹、X²、X³、X⁴And X⁵, from the viewpoint of being limited from synthesis, be preferably separately hydrogen atom or carbon number be 1~ 12 alkyl, is more preferably separately hydrogen atom or methyl, more preferably methyl.

In formula (1)~formula (4), Y¹、Y²、Y³And Y⁴Separately represent divalent linking group, linking group is in structure On be not particularly limited.As by Y¹、Y²、Y³And Y⁴The divalent linking group of expression, specifically, can enumerate following (Y- 1) linking group of~(Y-21) etc..In following shown structures, A and B are referred respectively to and the left-end point in formula (1)~formula (4) The bonding position of base and right terminal groups.In following shown structures, consider from the simplicity of synthesis, preferably (Y-2) or (Y-13) Linking group.

[chemical formula 2]

In formula (1)~formula (4), Z¹、Z²、Z³And Z⁴Separately represent the organic group of 1 valency.The kind of organic group Class is not particularly limited, and specifically, can enumerate alkyl, hydroxyl, alkoxy, aryloxy group, heteroaryloxy, alkyl thioether Base, aryl thioethers base, heteroaryl thioether group and amino etc..Wherein, as with Z¹、Z²、Z³And Z⁴Come the organic group represented, from It is improved particularly from the viewpoint of the dispersiveness of pigment, it is however preferred to have the organic group of steric repulsion effect, it is separately excellent The alkyl or alkoxy that carbon number is 5 to 24 are selected, more preferably carbon number is 5 to 24 branch-like alkyl, more preferably carbon Atomicity is 5 to 24 cyclic alkyl, or the alkoxy that carbon number is 5 to 24.In addition, alkyl included in alkoxy Can be any of straight-chain, branch-like and ring-type.

In formula (1)~formula (4), n, m, p and q are separately 1~500 integer.

Also, in formula (1) and formula (2), j and k separately represent 2~8 integer.From the dispersion stabilization of pigment From the viewpoint of, formula (1) and j in formula (2) and k are preferably 4~6 integer, and more preferably 5.

In formula (3), R³Represent the alkylidene of branch or straight chain, preferably carbon number is 1~10 alkylidene, more preferably Carbon number is 2 or 3 alkylidene.When p is 2~500, there are multiple R³It may be the same or different each other.

In formula (4), R⁴Represent the organic group of hydrogen atom or 1 valency, the species of the organic group of 1 valency has no particularly Limitation.As R⁴, preferably hydrogen atom, alkyl, aryl or heteroaryl, more preferably hydrogen atom or alkyl.R⁴In the case of for alkyl, As alkyl, branch-like alkyl that straight-chain alkyl that preferably carbon number is 1~20, carbon number are 3~20, or carbon are former Subnumber is 5~20 cyclic alkyl, and more preferably carbon number is 1~20 straight-chain alkyl, and further preferred carbon number is 1 ~6 straight-chain alkyl.In formula (4), when q is 2~500, there are multiple X in graft copolymer⁵And R⁴Each other can be with It is identical, can not also be same.

Also, high-molecular compound can with structure of more than two kinds construction unit different, with grafted chain.That is, In the molecule of high-molecular compound, the structure construction unit different from each other represented by formula (1)~formula (4) can be included, and And in formula (1)~formula (4), in the case that n, m, p and q represent more than 2 integer respectively, in formula (1) and formula (2), side chain In can include j and k structures different from each other, in formula (3) and formula (4), there are multiple R for intramolecular³、R⁴And X⁵Each other may be used , can not also be same with identical.

As the construction unit represented by formula (1), from the viewpoint of the dispersion stabilization of pigment, preferably by following formula The construction unit that (1A) is represented.

Also, as the construction unit represented by formula (2), from the viewpoint of the dispersion stabilization of pigment, preferably under State the construction unit of formula (2A) expression.

[chemical formula 3]

In formula (1A), X¹、Y¹、Z¹And the n and X in formula (1)¹、Y¹、Z¹And n implications are identical, preferred scope is also identical. In formula (2A), X²、Y²、Z²And the m and X in formula (2)²、Y²、Z²And m implications are identical, preferred scope is also identical.

Also, as the construction unit represented by formula (3), from the viewpoint of the dispersion stabilization of pigment, preferably under State the construction unit that formula (3A) or formula (3B) represent.

[chemical formula 4]

In formula (3A) or (3B), X³、Y³、Z³And the p and X in formula (3)³、Y³、Z³And p implications are identical, preferred scope also phase Together.

High-molecular compound is more preferably with the construction unit represented by formula (1A) as the construction unit with grafted chain.

In high-molecular compound, there is the construction unit of grafted chain (for example, the knot represented by above-mentioned formula (1)~formula (4) Structure unit) in mass conversion, relative to the gross mass of high-molecular compound, preferably with 2~90% scope comprising more excellent Choosing with 5~30% scope and comprising.If include the construction unit with grafted chain, pigment within the range (especially titanium is black) Dispersiveness it is high.

Also, high-molecular compound preferably with it is different from the construction unit with grafted chain (that is, not equivalent to The construction unit of grafted chain) hydrophobic structure unit.However, in the present invention, hydrophobic structure unit is without acidic group (example Such as, carboxylic acid group, sulfonic group, phosphate or phenolic hydroxyl group etc.) construction unit.

Hydrophobic structure unit is preferably derived from (corresponding) knot for the compound (monomer) that ClogP values are more than 1.2 Structure unit, the more preferably construction unit from the compound that ClogP values are 1.2~8.Thereby, it is possible to more reliably show this The effect of invention.

ClogP values are the journey by that can be obtained from Daylight Chemical Information System, Inc. Sequence " CLOGP " is come the value that calculates.The program is provided by Hansch, and what the fragment method (referring to following documents) of Leo calculated " calculates The value of logP ".Chemical constitution of the fragment method based on compound, and chemical constitution is divided into part-structure (fragment), to the piece The logP contribution amounts that Duan Xiangjia is allocated, thus extrapolate the logP values of compound.Its detailed content is recorded in documents below. In the present invention, using by program CLOGP v4.82 and the ClogP values that calculate.

A.J.Leo, Comprehensive Medicinal Chemistry, Vol.4, C.Hansch, P.G.Sammnens, J.B.Taylor and C.A.Ramsden, Eds., p.295, Pergamon Press, 1990 C.Hansch&A.J.Leo.SUbstituent Constants For Correlation Analysis in Chemistry and Biology.John Wiley&Sons.A.J.Leo.CalculatinglogPoct from Structure.Chem.Rev., 93,1281-1306,1993.

LogP refers to distribution coefficient P (Partition Coefficient：Distribution coefficient) common logarithm, be as fixed The numerical value of amount represents the physical property how a certain organic compound distributes in oil (being usually 1- octanols) and the balance of 2 phase system of water Value, is expressed from the next.

LogP=log (Coil/Cwater)

In formula, Coil represents the molar concentration of the compound in oil phase, and Cwater represents mole of the compound in water phase Concentration.

If logP values, on the occasion of increase, to refer to oil-soluble increase, if increasing with negative, refer to water across 0 Dissolubility increase, water-soluble negatively correlated with organic compound, the parameter as the hydrophilic/hydrophobic of assessment organic compound It is widely used.

High-molecular compound preferably has be selected from the construction unit from the monomer by the following general formula (i)~(iii) a kind Construction unit above is as hydrophobic structure unit.

[chemical formula 5]

In above-mentioned general formula (i)~(iii), R¹、R²And R³Separately represent hydrogen atom, halogen atom (for example, fluorine Atom, chlorine atom and bromine atoms etc.) or carbon number be 1~6 alkyl (for example, methyl, ethyl, propyl group etc.).

R¹、R²And R³Preferably hydrogen atom or carbon number are 1~3 alkyl, more preferably hydrogen atom or methyl.R²And R³ More preferably hydrogen atom.

X represents oxygen atom (- O-) or imino group (- NH-), is preferably oxygen atom.

L is singly-bound or divalent linking group.As divalent linking group, can enumerate divalent fatty group (for example, alkylidene, Substituted alkylene, alkenylene, substitution alkenylene, alkynylene and substitution alkynylene), divalent aromatic series base is (for example, arlydene and take For arlydene), divalent heterocyclic radical, oxygen atom (- O-), sulphur atom (- S-), imino group (- NH-), substituted imido (- NR³¹-, This, R³¹For fatty group, aromatic series base or heterocyclic radical), carbonyl (- CO-) or combinations thereof etc..

Divalent fatty group can be branch-like.The carbon number of fatty group is preferably 1~20, and more preferably 1~15, More preferably 1~10.Fatty group can be unsaturated aliphatic base or representative examples of saturated aliphatic base, but be preferably Representative examples of saturated aliphatic base.Also, fatty group can have substituent.As substituent, halogen atom, aromatic series base can be enumerated And heterocyclic radical etc..

The carbon number of divalent aromatic series base is preferably 6~20, more preferably 6~15, more preferably 6~10.And And aromatic series base can have substituent.As substituent, halogen atom, fatty group, aromatic series base and heterocycle can be enumerated Base etc..

Divalent heterocyclic radical preferably has 5 Yuans rings or 6 Yuans rings as heterocycle.Other heterocycles, aliphatic can have been condensed on heterocycle Ring or aromatic ring.Also, heterocyclic radical can have substituent.As substituent, halogen atom, hydroxyl, oxo can be enumerated Base (=0), thio group (=S), imino group (=NH), substituted imido (=N-R³², here, R³²For fatty group, aromatic series Base or heterocyclic radical), fatty group, aromatic series base and heterocyclic radical.

L is preferably the divalent linking group for including singly-bound, alkylidene or alkylene oxide structure.Alkylene oxide structure is ethylene oxide knot Structure or oxypropylene structure.Also, L can include the polyoxyalkylene structure for repeating to include the alkylene oxide structure of more than 2.As poly- Alkylene oxide structure, is preferably polyoxyethylene structure or polyoxypropylene structure.Polyoxyethylene structure is by-(OCH₂CH₂) n- represents, n The integer of preferably more than 2 integer, more preferably 2~10.

As Z, fatty group can be enumerated (for example, alkyl, substitution alkyl, unsaturated alkyl and the unsaturated alkane of substitution Base), aromatic series base (for example, aryl and substituted aryl) or the group that these groups will be combined.In addition, in above-mentioned each group Heterocyclic radical, oxygen atom (- O-), sulphur atom (- S-), imino group (- NH-), substituted imido (- NR can be included³¹-, here, R³¹ Represent fatty group, aromatic series base or heterocyclic radical.) or carbonyl (- CO-).

Fatty group can be branch-like or ring-type.The carbon number of fatty group is preferably 1~20, more excellent Elect 1~15 as, more preferably 1~10.Comprising ring set alkyl and crosslinking ring type alkyl in fatty group, as ring collection Alkyl is closed, dicyclohexyl, perhydro naphthyl, xenyl and 4- cyclohexyl phenyls etc. can be enumerated., can be with as crosslinking ring type hydrocarbon ring Enumerate pinane, camphane, norpinane, norcamphane, double-octane ring (two rings [2.2.2] octane ring and two rings [3.2.1] octane ring Deng) etc. 2 ring type hydrocarbon rings, equal mine-laying alkane (homobledane), adamantane, tricyclic [5.2.1.0^2,6] decane and tricyclic [4.3.1.1^2,5] 3 ring type hydrocarbon rings and the Fourth Ring [4.4.0.1 such as hendecane ring^2,5.1^7,10] dodecane and perhydro-Isosorbide-5-Nitrae-methylene- 4 ring type hydrocarbon ring such as 5,8- methylene naphthalene nucleus etc..Also, condensed ring formula hydrocarbon ring, such as perhydro can also be included in crosslinking ring type hydrocarbon ring 5~8 Yuans cycloalkanes hydrocarbon rings fusions such as naphthalene (decahydronaphthalene), perhydro anthracene, perhydro phenanthrene, perhydro acenaphthene, perhydro fluorenes, perhydro indenes and perhydro flower ring are more A condensed ring.

On fatty group, representative examples of saturated aliphatic base is more preferably compared to unsaturated aliphatic base.Also, fatty group can be with With substituent.As substituent, halogen atom, aromatic series base and heterocyclic radical can be enumerated.However, fatty group is without acid Base is as substituent.

The carbon number of aromatic series base is preferably 6~20, more preferably 6~15, more preferably 6~10.Also, virtue Fragrant race's base can have substituent.As substituent, halogen atom, fatty group, aromatic series base and heterocyclic radical can be enumerated.So And aromatic series base does not have acidic group as substituent.

Heterocyclic radical preferably has 5 Yuans rings or 6 Yuans rings as heterocycle.Other heterocycles, aliphatic can also have been condensed on heterocycle Ring or aromatic ring.Also, heterocyclic radical can have substituent.As substituent, halogen atom, hydroxyl, oxo can be enumerated Base (=O), thio group (=S), imino group (=NH), substituted imido (=N-R³², here, R³²For fatty group, aromatic series Base or heterocyclic radical), fatty group, aromatic series base and heterocyclic radical.However, heterocyclic radical does not have acidic group as substituent.

In above-mentioned formula (iii), R⁴、R⁵And R⁶Separately represent hydrogen atom, halogen atom (for example, fluorine atom, chlorine are former Son, bromine atoms etc.), carbon number be 1~6 alkyl (for example, methyl, ethyl, propyl group etc.), Z or-L-Z.Here, L and Z with L and Z implications in above-mentioned are identical.As R⁴、R⁵And R⁶, preferably hydrogen atom or carbon number is 1~3 alkyl, is more preferably Hydrogen atom.

In the present invention, as the monomer represented by above-mentioned general formula (i), preferably R¹、R²And R³It is for hydrogen atom or methyl, L Singly-bound or alkylidene or divalent linking group comprising alkylene oxide structure, X be oxygen atom or imino group, Z be fatty group, it is miscellaneous The compound of ring group or aromatic series base.

Also, as the monomer represented by above-mentioned general formula (ii), preferably R¹Be alkylidene for hydrogen atom or methyl, L, Z be The compound of fatty group, heterocyclic radical or aromatic series base.

Also, as the monomer represented by above-mentioned general formula (iii), preferably R⁴、R⁵And R⁶For hydrogen atom or methyl, Z is fat The compound of race's base, heterocyclic radical or aromatic series base.

As the representative compound represented by general formula (i)~(iii), can enumerate selected from esters of acrylic acid, methyl-prop The free-radical polymerised compound of olefin(e) acid esters and phenylethylene etc..

In addition, as the representative compound represented by general formula (i)~(iii), can refer in Japanese Unexamined Patent Publication 2013- Compound described in 0089~0093 section of No. 249417 publications, these contents are incorporated in this specification.

In high-molecular compound, hydrophobic structure unit is in mass conversion, relative to total matter of high-molecular compound Amount, preferably with 10~90% scope comprising, more preferably with 20~80% scope comprising.Content within the above range may be used Form sufficient pattern.

High-molecular compound can have the functional group that interaction can be formed with pigment (especially titanium is black).It is here, high Molecular compound preferably also possesses the construction unit for the functional group that interaction can be formed with pigment.

As the functional group that interaction can be formed with the pigment, for example, acidic group, basic group, coordinating base And functional group with reactivity etc..

High-molecular compound possess acidic group, basic group, coordinating base or with reactivity functional group in the case of, preferably Have respectively：Construction unit with acidic group, the construction unit with basic group, the construction unit with coordinating base or with The construction unit of reactivity.

Also, since high-molecular compound possesses the construction unit with acidic group, high-molecular compound easily with it is molten Agent is merged, and coating is also in the tendency improved.

It can speculate that its reason is, there is the acidic group in the construction unit of acidic group easily to interact with pigment, producing high-molecular Compound disperses with making pigment stabilizer, and reduces the viscosity for the high-molecular compound that pigment disperses, and high-molecular compound is in itself Also readily and stably disperse.

However, the construction unit with the alkali solubility base as acidic group can be and the above-mentioned construction unit with grafted chain Identical construction unit or different construction units, but the construction unit with the alkali solubility base as acidic group is The construction unit (that is, not equivalent to above-mentioned hydrophobic structure unit) different from above-mentioned hydrophobic structure unit.

As the acidic group for the functional group that interaction can be formed with pigment, have for example carboxylic acid group, sulfonic group, phosphate or It is at least one kind of in phenolic hydroxyl group etc., preferably carboxylic acid group, sulfonic group and phosphate, it is good from the adsorption capacity to pigment and pigment From the viewpoint of dispersed high, more preferably carboxylic acid group.

That is, high-molecular compound preferably also possesses at least one kind of structure list in carboxylic acid group, sulfonic group and phosphate Member.

High-molecular compound can be with the one kind or two or more construction unit with acidic group.

High-molecular compound, which can contain, can not also contain the construction unit with acidic group, contain the construction unit In the case of, there is the content of construction unit of acidic group in mass conversion, the gross mass relative to high-molecular compound is preferably 5 ~80%, consider from the image intensity damage viewpoint for suppressing to produce by alkaline development, more preferably 10~60%.

As the functional group i.e. basic group that interaction can be formed with pigment, there are such as primary amino radical, secondary amino group, tertiary ammonia Base, the heterocycle comprising N atoms and amide groups etc., from the viewpoint of good from the adsorption capacity to pigment and pigment dispersiveness is high, It is preferred that tertiary amino.High-molecular compound can have these one kind or two or more basic groups.

High-molecular compound, which can contain, can not also contain the construction unit with basic group, contain the construction unit In the case of, there is the content of construction unit of basic group in mass conversion, it is excellent relative to the gross mass of high-molecular compound Elect 0.01~50% as, from the viewpoint of developability obstruction is suppressed, more preferably 0.01~30%.

, can be with as the i.e. coordinating base of functional group that interaction can be formed with pigment and the functional group with reactivity Enumerate such as acetoacetoxy groups, trialkoxysilyl, isocyanate group, acid anhydrides and acyl chlorides.Wherein, to pigment Suction is good and the dispersiveness of pigment it is high from the viewpoint of, preferred acetoacetoxy groups.High-molecular compound can have a kind or Two or more these base.

High-molecular compound, which can contain, can not also contain the construction unit with coordinating base or possess with reaction The construction unit of the functional group of property, in the case of containing the component unit, the content of these construction units is in mass conversion In, the gross mass relative to high-molecular compound is preferably less than 10~80%, from the viewpoint of developability obstruction is suppressed, more Preferably 20~60%.

In high-molecular compound in addition to grafted chain, also there is the functional group that interaction can be formed with pigment In the case of, preferably there is be selected from the construction unit for being derived from the monomer by the following general formula (iv)~(vi) expressions more than a kind Construction unit.

[chemical formula 6]

In general formula (iv)~general formula (vi), R¹¹、R¹²And R¹³Separately represent hydrogen atom, halogen atom (for example, Fluorine atom, chlorine atom and bromine atoms etc.) or carbon number be 1~6 alkyl (for example, methyl, ethyl and propyl group etc.).

In general formula (iv)~general formula (vi), R¹¹、R¹²And R¹³Separately represent that hydrogen atom or carbon number are 1~3 Alkyl, be more preferably separately hydrogen atom or methyl.In general formula (iv), R¹²And R¹³Further preferably it is respectively hydrogen Atom.

X in general formula (iv)₁Represent oxygen atom (- O-) or imino group (- NH-), be preferably oxygen atom.

Also, the Y in general formula (v) represents methine or nitrogen-atoms.

Also, the L in general formula (iv)~general formula (v)₁Represent singly-bound or divalent linking group., can as divalent linking group To enumerate divalent fatty group (for example, alkylidene, substituted alkylene, alkenylene, substitution alkenylene, alkynylene and the sub- alkynes of substitution Base), it is divalent aromatic series base (for example, arlydene and substitution arlydene), divalent heterocyclic radical, oxygen atom (- O-), sulphur atom (- S-), sub- Amino (- NH-), substituted imido key (- NR³¹'-, is here, R³¹' be fatty group, aromatic series base or heterocyclic radical), carbonyl bond (- ) or combinations thereof etc. CO-.

Divalent fatty group can be branch-like or ring-type.The carbon number of fatty group is preferably 1~20, more Preferably 1~15, more preferably 1~10.On fatty group, saturated fat is more preferably compared to unsaturated aliphatic base Race's base.Also, fatty group can have substituent.As substituent, can enumerate halogen atom, hydroxyl, aromatic series base and Heterocyclic radical.

The carbon number of divalent aromatic series base is preferably 6~20, more preferably 6~15, more preferably 6~10.And And aromatic series base can have substituent.As substituent, halogen atom, hydroxyl, fatty group, aromatic series base can be enumerated And heterocyclic radical.

Divalent heterocyclic radical preferably has 5 Yuans rings or 6 Yuans rings as heterocycle.Other heterocycles, aliphatic ring can be condensed on heterocycle Or more than 1 in aromatic ring.Also, heterocyclic radical can have substituent.As substituent, can enumerate halogen atom, Hydroxyl, oxo base (=O), thio group (=S), imino group (=NH), substituted imido (=N-R³², here, R³²For aliphatic Base, aromatic series base or heterocyclic radical), fatty group, aromatic series base and heterocyclic radical.

L₁Preferably singly-bound, alkylidene or the divalent linking group comprising alkylene oxide structure.Alkylene oxide structure is preferably oxygen second Alkene structure or oxypropylene structure.Also, L₁The polyoxyalkylene structure for repeating to include the alkylene oxide structure of more than 2 can be included. As polyoxyalkylene structure, preferably polyoxyethylene structure or polyoxypropylene structure.Polyoxyethylene structure is by-(OCH₂CH₂) n- carrys out table Show, n is preferably more than 2 integer, more preferably 2~10 integer.

In general formula (iv)~general formula (vi), Z₁In addition to representing grafted chain, it is also represented by be formed mutually with pigment The functional group of effect, is preferably carboxylic acid group or tertiary amino, more preferably carboxylic acid group.

In general formula (vi), R¹⁴、R¹⁵And R¹⁶Separately represent hydrogen atom, halogen atom (for example, fluorine atom, chlorine are former Son and bromine atoms etc.), the alkyl (for example, methyl, ethyl and propyl group etc.) that carbon number is 1~6 ,-Z₁Or-L₁-Z₁.Here, L₁ And Z₁With it is above-mentioned in L₁And Z₁Implication is identical, and preference is also identical.As R¹⁴、R¹⁵And R¹⁶, it is preferably separately former for hydrogen Son or the alkyl that carbon number is 1~3, more preferably hydrogen atom.

It is preferably R as the monomer represented by general formula (iv)¹¹、R¹²And R¹³It is separately hydrogen atom or methyl, L₁ The compound that divalent linking group for alkylidene or comprising alkylene oxide structure, X are oxygen atom or imino group, Z are carboxylic acid group.

Also, it is preferably R as the monomer represented by general formula (v)¹¹For hydrogen atom or methyl, L₁For alkylidene, Z₁For carboxylic Acidic group, the compound that Y is methine.

It is preferably R moreover, as the monomer represented by general formula (vi)¹⁴、R¹⁵And R¹⁶It is separately hydrogen atom or first The compound that base, L are singly-bound or alkylidene, Z are carboxylic acid group.

Hereinafter, the representative example of monomer (compound) represented by general formula (iv)~general formula (vi) is shown.

As the example of monomer, can enumerate methacrylic acid, crotonic acid, iso-crotonic acid, intramolecular has addition polymerization Property double bond and the reactant of compound (for example, methacrylic acid 2- ethoxys) and succinic anhydride of hydroxyl, intramolecular have plus Reactant, intramolecular into the compound and phthalic anhydride of polymeric double bond and hydroxyl have addition polymerization double bond and hydroxyl The compound of base has addition polymerization double bond and the compound of hydroxyl with the reactant of tetrahydroxy phthalic anhydride, intramolecular Reactant, intramolecular with trimellitic acid have addition polymerization double bond and the compound of hydroxyl and the reaction of pyromellitic dianhydride Thing, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4- vinyl benzoic acids, ethene Base phenol and 4- hydroxyphenylmethyl acrylic acid amides etc..

From the viewpoint of the dispersion stabilization of pigment, there is the structure for the functional group that interaction can be formed with pigment The content of unit is preferably 0.05~90 mass %, is more preferably 1.0~80 matter relative to the gross mass of high-molecular compound Measure %, more preferably 10~70 mass %.

Moreover, high-molecular compound to improve multiple performance as a purpose, as long as not damaging the effect of the present invention, then may be used also To possess with the construction unit with grafted chain, hydrophobic structure unit and with the function that interaction can be formed with pigment Group construction unit is different, other structures units with various functions are (for example, the construction unit with functional group etc., institute Stating functional group has and the compatibility for the dispersant being used in dispersion).

As this other structures unit, for example, from selected from vinyl cyanide and metering system nitrile etc. from By the construction unit of base polymerizable compound.

High-molecular compound can include these one kind or two or more other structures units, its content is in mass conversion In, the gross mass relative to high-molecular compound is preferably 0~80%, and more preferably 10~60%.

(preferred embodiment 2)

As other preferred embodiments of dispersant, the high-molecular compound X represented by leading to formula (X) can be enumerated.

Hereinafter, it is described in detail on leading to each group in formula (X).

In addition, substituent A possessed by high-molecular compound X¹It can interact with pigment, therefore high-molecular compound X has n (1~9) substituent As¹, thus, it is possible to consumingly interact with pigment.Also, high-molecular compound X has m A polymer chain P¹Played function as steric repulsion base, by playing good steric repulsion power with m, so that It can be uniformly dispersed pigment.

[chemical formula 7]

In above-mentioned logical formula (X), A¹Represent acidic group, the base with basic nitrogen atom, urea groups, carbamate groups, with Base, phenolic group, alkyl, aryl, base, imide, alkoxy carbonyl, the alkanamine with alkylidene epoxide chain of coordinating oxygen atom Base carbonyl, carboxylate group, sulfoamido, alkoxysilyl, epoxy group, isocyanate group, hydroxyl, or such as heterocyclic radical one Sample has pigment the functional group of adsorption capacity.

In addition, it is following, the position (above-mentioned functional group) for having adsorption capacity to the pigment is suitably referred to as " adsorption section Position " simultaneously illustrates.

Adsorption site is in 1 A¹In include at least 1, can also include more than 2.

As in 1 A¹In the mode comprising the adsorption site of more than 2, for example, via chain saturated hydrocarbyl (can be straight-chain or branch-like, preferably carbon number is 1~10), (preferably carbon number be cyclic saturated hydrocarbon base 3~10), aromatic series base (preferably carbon number is 5~10, for example, phenylene) etc. is bonded the adsorption site of more than 2, and shape Into the substituent A of 1 valency¹Mode etc., be bonded the adsorption site of more than 2 preferably via chain saturated hydrocarbyl, and 1 valency of formation Substituent A¹Mode.

In addition, in the case where adsorption site forms the substituent of 1 valency in itself, adsorption site can be by A in itself¹Represent 1 valency substituent.

First, on forming A¹Adsorption site, it is described below.

As " acidic group ", preferably carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, monophosphate ester group, phosphonate group, secondary phosphine Acidic group or boronate, more preferably carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, monophosphate ester group, phosphonate group or phosphinic acids Base, further preferred carboxylic acid group.

As " urea groups ", such as preferably-NR¹⁵CONR¹⁶R¹⁷(here, R¹⁵、R¹⁶And R¹⁷Separately represent hydrogen atom, The aralkyl that the aryl or carbon number that alkyl that carbon number is 1~20, carbon number are more than 6 are more than 7.), it is more excellent Choosing-NR¹⁵CONHR¹⁷(here, R¹⁵And R¹⁷Separately represent hydrogen atom, the alkyl that carbon number is 1~10, carbon number The aralkyl that aryl or carbon number for more than 6 are more than 7.), further preferred-NHCONHR¹⁷(here, R¹⁷Represent that hydrogen is former Son, carbon number be 1~10 alkyl, carbon number be more than 6 aryl or carbon number be more than 7 aralkyl.).

As " carbamate groups ", such as preferably-NHCOOR¹⁸、-NR¹⁹COOR²⁰、-OCONHR²¹Or-OCONR²²R²³ (here, R¹⁸、R¹⁹、R²⁰、R²¹、R²²And R²³Separately represent that alkyl, carbon number that carbon number is 1~20 are more than 6 Aryl or carbon number be more than 7 aralkyl.), more preferably-NHCOOR¹⁸Or-OCONHR²¹(here, R¹⁸、R²¹It is only respectively On the spot represent the aryl that alkyl, carbon number that carbon number is 1~20 are more than 6 or the aralkyl that carbon number is more than 7 Base.), further preferred-NHCOOR¹⁸Or-OCONHR²¹(here, R¹⁸、R²¹It is 1~10 separately to represent carbon number The aralkyl that the aryl or carbon number that alkyl, carbon number are more than 6 are more than 7.).

As the group of coordinating oxygen atom " have ", come of age ether for example, levulinic ketone group.

As " group with basic nitrogen atom ", such as preferably amino (- NH₂), substituted imido (- NHR⁸、-NR⁹R¹⁰、 Here, R⁸、R⁹And R¹⁰Separately represent the aryl or carbon original that alkyl, carbon number that carbon number is 1~20 are more than 6 Subnumber is more than 7 aralkyl.), the guanidine radicals represented by following formula (a1) or the amidino groups etc. represented by following formula (a2).

[chemical formula 8]

In formula (a1), R¹¹And R¹²Separately represent that alkyl, carbon number that carbon number is 1~20 are more than 6 Aryl or the aralkyl that carbon number is more than 7.

In formula (a2), R¹³And R¹⁴Separately represent that alkyl, carbon number that carbon number is 1~20 are more than 6 Aryl or the aralkyl that carbon number is more than 7.

Wherein, more preferably amino (- NH₂), substituted imido (- NHR⁸、-NR⁹R¹⁰, here, R⁸、R⁹And R¹⁰Separately Represent alkyl, phenyl or the benzyl that carbon number is 1~10.), by formula (a1) represent guanidine radicals (in formula (a1), R¹¹And R¹²Point Alkyl, phenyl or the benzyl that carbon number is 1~10 are not represented independently.) or by formula (a2) represent amidino groups (in formula (a2), R¹³And R¹⁴Separately represent alkyl, phenyl or the benzyl that carbon number is 1~10.〕.

Especially, further preferred amino (- NH₂), substituted imido (- NHR⁸、-NR⁹R¹⁰, here, R⁸、R⁹And R¹⁰It is only respectively On the spot represent alkyl, phenyl or the benzyl that carbon number is 1~5.), by formula (a1) represent guanidine radicals (in formula (a1), R¹¹And R¹² Separately represent alkyl, phenyl or the benzyl that carbon number is 1~5.) or by formula (a2) represent amidino groups (in formula (a2), R¹³And R¹⁴Separately represent alkyl, phenyl or the benzyl that carbon number is 1~5.) etc..

It can be straight-chain or branch-like as " alkyl ", be preferably the alkyl that carbon number is 1~40, more Preferably carbon number is 4~30 alkyl, and more preferably carbon number is 10~18 alkyl.

It is preferably the aryl that carbon number is 6~10 as " aryl ".

As " group with alkylidene epoxide chain ", preferably end is formed with alkoxy or hydroxyl, more preferably carbon atom Number is 1~20 alkoxy.Also, as alkylidene epoxide chain, as long as there is at least one alkylidene epoxide just without special limit System, but preferably include the alkylidene epoxide that carbon number is 1~6.As alkylidene epoxide, for example,-CH₂CH₂O- And-CH₂CH₂CH₂O- etc..

As the moieties in " alkoxy carbonyl ", preferably carbon number is 1~20 alkyl.

As the moieties in " alkylaminocarbonyl ", preferably carbon number is 1~20 alkyl.

As " carboxylate group ", the group being made of the ammonium salt of carboxylic acid can be enumerated.

As " sulfoamido ", the hydrogen atom with nitrogen atom bonding is by alkyl (methyl etc.) or acyl group (acetyl group, trifluoro second Acyl group etc.) etc. substitution.

As " heterocyclic radical ", for example, thienyl, furyl, Xanthones base, pyrrole radicals, pyrrolinyl, pyrrolidines pah Base, dioxolanyl, pyrazolyl, pyrazolinyl, pyrazoles piperidinyl, imidazole radicals, oxazolyls, thiazolyl, oxadiazolyls, triazolyl, Thiadiazolyl group, pyranose, pyridine radicals, piperidyl, alkyl dioxins, morpholinyl, pyridazinyl, pyrimidine radicals, piperazinyl, triazine radical, three Thiophene base, isoindoline base, isoindoline ketone group, benzimidazole ketone group, benzothiazolyl, hydantoins base, indyl, quinoline Base, carbazyl, acridinyl, acridine ketone group and anthraquinonyl.

As " imide ", succinimido, phthalimide-based and naphthalimide base can be enumerated Deng imide.

In addition, " heterocyclic radical " and " imide " can also have substituent, it is former for example, carbon as substituent Aryl that alkyl that subnumber is 1~20, carbon number are 6~16, hydroxyl, amino, carboxylic acid group, sulfoamido, N- sulfoamidos, Alkoxy that acyloxy that the carbon numbers such as acetoxyl group are 1~6, carbon number are 1~20, halogen atom, methoxycarbonyl, The carbon number such as ethoxy carbonyl and cyclohexyloxy carbonyl is the carbonic acid such as 2~7 alkoxy carbonyl, cyano group and tert-butyl carbonate Ester group.

Can be monoalkoxy silicyl, dialkoxy silicyl and three alcoxyls as " alkoxysilyl " Any one in base silicyl, but preferred trialkoxysilyl, for example, trimethoxysilyl and three Triethoxysilyl etc..

As " epoxy group ", substituted or unsubstituted epoxy ethyl (Oxyranyle) can be enumerated.

Especially, A¹The preferably substituent of 1 valency of the functional group with least one kind of more than pKa5, more preferably has extremely The substituent of 1 valency of the functional group of few a kind of pKa5~14.

Here, so-called " pKa " be Chemical manual (II) (revision 4 editions, 1993, Japanization association write, Maruzen Inc. the definition described in).

As the functional group of above-mentioned more than pKa5, the group with coordinating oxygen atom can be enumerated, with basic nitrogen original The group of son, phenolic group, urea groups, carbamate groups, alkyl, aryl, alkoxy carbonyl, alkylaminocarbonyl, have alkylene oxide Group, imide, carboxylate group, sulfoamido, hydroxyl and the heterocyclic radical of base chain.

As the functional group of more than pKa5, specifically, for example, phenolic group (pKa 8~10 or so), alkyl (pKa 46~53 or so), aryl (pKa 40~43 or so), urea groups (pKa 12~14 or so), carbamate groups (pKa 11~13 degree) ,-COCH as coordinating oxygen atom₂(pKa 9~11 is left for CO- (pKa 8~10 or so), sulfoamido It is right), hydroxyl (pKa 15~17 or so) and heterocyclic radical (pKa 12~30 or so).

In above-mentioned, as A¹, it is however preferred to have it is at least one kind of selected from acidic group, phenolic group, alkyl, aryl, there is alkylidene epoxide The group of chain, hydroxyl, urea groups, carbamate groups, sulfoamido, the group of imide and the group with coordinating oxygen atom In group 1 valency substituent.

In logical formula (X), R²Represent singly-bound or divalent linking group.N R²It may be the same or different.

As by R²The divalent linking group of expression, comprising by 1~100 carbon atom, 0~10 nitrogen-atoms, 0~50 The group of oxygen atom, 1~200 hydrogen atom and 0~20 sulphur atom composition, can be unsubstituted, can also have substituent.

As R², preferably singly-bound, or by 1~10 carbon atom, 0~5 nitrogen-atoms, 0~10 oxygen atom, 1~30 The divalent linking group of a hydrogen atom and 0~5 sulphur atom composition.

As R², it (can be straight-chain or branch-like, preferably carbon that being more preferably selected from, which includes chain saturated hydrocarbyl, Atomicity is 1~20), cyclic saturated hydrocarbon base (preferably carbon number is 3~20), aromatic series base (preferably carbon number be 5~ 20, for example, phenylene), thioether bond, ester bond, amido link, the base in ehter bond and the group that is made of nitrogen-atoms and carbonyl, or group The group of 2 the above groups is closed, being further preferably selected from includes chain saturated hydrocarbyl, cyclic saturated hydrocarbon base, fragrance Race's base, thioether bond, ester bond, ehter bond and amido link group in base, or the group of 2 the above groups of combination, especially Be preferably selected from including the group in the group of chain saturated hydrocarbyl, thioether bond, ester bond, ehter bond and amido link, or be combined with 2 with The group of these upper groups.

In above-mentioned, by R²In the case that the divalent linking group of expression has substituent, as substituent, example can be enumerated As alkyl that carbon number is 1~20, carbon number be 6~16 aryl, hydroxyl, amino, carboxylic acid group, sulfoamido, N- sulphurs Alkoxy, chlorine atom and the bromine atoms that acyloxy that the carbon numbers such as amide groups, acetoxyl group are 1~6, carbon number are 1~6 Deng alkoxy carbonyl of the carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl and cyclohexyloxy carbonyl for 2~7, cyanogen Carbonate group such as base and tert-butyl carbonate etc..

In logical formula (X), R¹The linking group of (m+n) valency of expression.M+n meets 3~10.

As by R¹The linking group of (m+n) valency represented, comprising by 1~100 carbon atom, 0~10 nitrogen-atoms, 0 The group of~50 oxygen atoms, 1~200 hydrogen atom and 0~20 sulphur atom composition, can be unsubstituted, can also have and take Dai Ji.

By R¹The linking group of (m+n) valency represented is preferably the group represented by any one in the following general formula.

[chemical formula 9]

In above-mentioned general formula,

L₃Represent the group of trivalent.T₃Represent singly-bound or divalent linking group, there are the T of 3₃Each other can be identical, can also It is different.

L₄Represent the group of 4 valencys.T₄Represent singly-bound or divalent linking group, there are the T of 4₄Each other can be identical, can also It is different.

L₅Represent the group of 5 valencys.T₅Represent singly-bound or divalent linking group, there are the T of 5₅Each other can be identical, can also It is different.

L₆Represent the group of 6 valencys.T₆Represent singly-bound or divalent linking group, there are the T of 6₆Each other can be identical, can also It is different.

It is described below by R¹The specific example (concrete example (1)~(17)) of the linking group of (m+n) valency represented.But simultaneously It is not limited to these.

[chemical formula 10]

[chemical formula 11]

In above-mentioned concrete example, Yi Huoxing from raw material, synthesis easness and the deliquescent viewpoint of various solvents is examined Consider, as the linking group of (m+n) valency, the group of preferably following (1), (2), (10), (11), (16) or (17).

[chemical formula 12]

In logical formula (X), m represents less than 8 positive number.It is preferably 0.5~5 as m, more preferably 1~4, further preferably For 1~3.

Also, in logical formula (X), n represents 1~9.It is preferably 2~8 as n, more preferably 2~7, more preferably 3 ~6.

In logical formula (X), P¹Represent polymer chain, can be made choice from known polymer etc. according to purpose etc..M P¹ It may be the same or different.

In the polymer, the polymer of preferred vinyl monomer or copolymer, esters polymer, ether polymer, amino Formate ester polymer, acylamide polymer, epoxide polymer, silicone polymer and their modifier or they be total to Polymers is (for example, the copolymer etc. comprising polyethers/polyurethane copolymer, the polymer of polyethers/vinyl monomer (can be random Any one in copolymer, block copolymer and graft copolymer.).), it is more preferably selected from the polymer for including vinyl monomer Or copolymer, esters polymer, ether polymer, carbamates polymer and their modifier or copolymer are formed At least one of group, the polymer or copolymer of further preferred vinyl monomer.

Polymer chain P¹Polymer or copolymer, the esters polymer and ether polymer for the vinyl monomer that can have It is preferred that there is the structure represented by the following general formula (L), (M) or (N) respectively.

[chemical formula 13]

In above-mentioned general formula,

X¹Represent the organic group of hydrogen atom or 1 valency.From the viewpoint of the limitation in synthesis, X¹Preferably hydrogen atom or Carbon number is 1~12 alkyl, more preferably hydrogen atom or methyl, more preferably methyl.

R¹⁰Represent the organic group of hydrogen atom or 1 valency.R¹⁰Preferably hydrogen atom, alkyl, aryl or heteroaryl, more preferably For hydrogen atom or alkyl.R¹⁰In the case of for alkyl, as alkyl, preferably straight-chain alkyl, carbon original of the carbon number for 1~20 The cyclic alkyl that the branch-like alkyl or carbon number that subnumber is 3~20 are 5~20, more preferably carbon number be 1~20 it is straight Chain-like alkyl, further preferred carbon number are 1~6 straight-chain alkyl.Polymer chain can have the R in general formula (L)¹⁰No Same repetitive unit of more than two kinds.

R¹¹And R¹²(carbon number is preferably 1~10 to the alkylidene of expression straight or branched, is more preferably 2~8, further Preferably 3~6.).Polymer chain can have the R in each general formula¹¹Or R¹²Different repetitive units of more than two kinds.

K1, k2 and k3 separately represent 5~140 number.

Polymer chain P¹Preferably comprise at least one kind of repetitive unit.

From playing steric repulsion power and from the viewpoint of improving dispersion stabilization, polymer chain P¹In at least one kind of repetition The number of repeat unit k of unit is preferably more than 5, and more preferably more than 7.

Also, increase from the volume for realizing suppression high-molecular compound X, and the viewpoint for making pigment closely be present in film Consider, the number of repeat unit k of at least one kind of repetitive unit is preferably less than 140, more preferably less than 130, more preferably 60 Below.

In addition, polymer is preferably able to be dissolved in organic solvent.If high with the compatibility of organic solvent, with dispersant Compatibility enhancing.

Be not particularly limited as above-mentioned vinyl monomer, preferably for example (methyl) esters of acrylic acid, crotonic acid esters, Vinyl ester, vinyl monomer, maleic acid diester class, dimethyl ester class, two esters of itaconic acid, (methyl) with acidic group Acrylic amide, phenylethylene, vinyl ethers, vinyl ketones, olefines, maleimide or (methyl) acrylonitrile, More preferably (methyl) esters of acrylic acid, crotonic acid esters, vinyl ester or the vinyl monomer with acidic group, further preferably (methyl) esters of acrylic acid or crotonic acid esters.

As the preference of vinyl monomer, can enumerate Japanese Unexamined Patent Publication 2007-277514 publications 0089~ 0094th, 0096 and 0097 (in corresponding No. 2010/233595 specification of U.S. Patent Application Publication No. for 0105~0117 and 0119~0120 section) vinyl monomer described in section, these contents are incorporated herein in specification.

In addition to above-claimed cpd, additionally it is possible to which using has such as carbamate groups, urea groups, sulfoamido, phenolic group And the vinyl monomer of the functional group such as imide.As the monomer with this carbamate groups or urea groups, can utilize Such as the synthesis that isocyanate group is appropriate with the addition reaction of hydroxyl or amino.Specifically, can be by containing isocyanate group Monomer and the compound with 1 hydroxyl or the compound containing 1 primary amino radical or secondary amino group addition reaction and synthesize.

In the high-molecular compound represented by leading to formula (X), preferably by the high-molecular compound of the following general formula (Y) expression.

[chemical formula 14]

In general formula (Y), A²With the A in logical formula (X)¹Implication is identical, and preferred embodiment is also identical.

In general formula (Y), R⁴、R⁵Separately represent singly-bound or divalent linking group.N R⁴Can be identical, can not also Together.Also, m R⁵It may be the same or different.

As by R⁴、R⁵The divalent linking group of expression, can use with as by lead to formula (X) R²The divalent connection of expression The identical group that group enumerates, preferred embodiment are also identical.

Wherein, as by R⁴、R⁵The divalent linking group of expression, is preferably that chain saturated hydrocarbyl (can be straight-chain, also may be used To be branch-like, preferably carbon number is 1~20), cyclic saturated hydrocarbon base (preferably carbon number is 3~20), aromatic series base it is (excellent Select carbon number be 5~20, for example, phenylene), ester bond, amido link, ehter bond, nitrogen-atoms, carbonyl or be combined with more than 2 this The group of a little groups, more preferably chain saturated hydrocarbyl, cyclic saturated hydrocarbon base, aromatic series base, ester bond, ehter bond, amido link or combination The group of 2 the above groups, further preferred chain saturated hydrocarbyl, ester bond, ehter bond, amido link or be combined with 2 with The group of these upper groups.

In general formula (Y), R³The linking group of (m+n) valency of expression.M+n meets 3~10.

As by R³Represent (m+n) valency linking group, can also have substituent, can use with as by general formula (X) R¹The identical group that the linking group of (m+n) valency represented enumerates, preferred embodiment are also identical.

In general formula (Y), m, n are identical with m, n implication in logical formula (X) respectively, and preferred embodiment is also identical.

Also, the P in general formula (Y)²With the P in logical formula (X)¹Implication is identical, and preferred embodiment is also identical.M P²Can phase Together, can not also be same.

In the high-molecular compound represented by general formula (Y), most preferably all meet R as shown below³、R⁴、R⁵、P², m and n Compound.

R³：Above-mentioned concrete example (1), (2), (10), (11), (16) or (17)

R⁴：Singly-bound, chain saturated hydrocarbyl, cyclic saturated hydrocarbon base, aromatic series base, ester bond, amido link, ehter bond, nitrogen-atoms, carbonyl Base or the group for being combined with 2 the above groups

R⁵：Singly-bound, vinyl, acrylic, following bases (a) or following bases (b)

In addition, in following bases, R¹²Represent hydrogen atom or methyl, 1 represents 1 or 2.

[chemical formula 15]

P²：Polymer or copolymer, esters polymer, ether polymer, the carbamate Type of Collective of vinyl monomer Thing or their modifier

m：1~3

n：3~6

It is excellent from the viewpoint of the dispersion stabilization of pigment in the high-molecular compound represented by logical formula (X) or (Y) The high-molecular compound that choosing is represented by the following general formula (Z).

[chemical formula 16]

In above-mentioned general formula (Z),

R⁶The linking group of (m+n1+n2) valency of expression, R⁷~R⁹Separately represent singly-bound or divalent linking group.

A³Represent the substituent of 1 valency with least one kind of acidic group.A⁴Expression is different from A³1 valency substituent.N1 A³ And R⁷It may be the same or different respectively.N2 A⁴And R⁸It may be the same or different respectively.

M is identical with the m implications in logical formula (X), and preferred embodiment is also identical.

N1 represents that 1~8, n2 represents that 1~8, m+n1+n2 meets 3~10.

P³With the P in general formula (Y)²Implication is identical, and preferred embodiment is also identical.M P³And R⁹Difference can be identical, can also It is different.

As on R⁶(m+n1+n2) valency linking group, can use as by lead to formula (X) R¹Or general formula (Y) R³The identical group that the linking group of (m+n) valency represented enumerates, preferred embodiment are also identical.

As on R⁷~R⁹Divalent linking group, can use as the R by general formula (Y)⁴And R⁵The divalent connection of expression The identical group that group enumerates, preferred embodiment are also identical.

As above-mentioned substituent A³The concrete example and preference for the acidic group that can have, can enumerate and on leading to formula (X) In the acidic group concrete example and preference that have described.

Above-mentioned substituent A³Preferably there is the substituent of 1 valency of acidic groups of at least one kind of pKa less than 5, more preferably have The substitution of 1 valency of at least one kind of group in the group including sulfonic group, carboxylic acid group, phosphate, phosphonate group and phosphinic acids base Base, more preferably carboxylic acid group.

As different from A³1 valency substituent A⁴Concrete example and preference, can enumerate with logical formula (X) A¹The identical substituent of the group in addition to acidic group in the concrete example and preference that have described.Wherein, above-mentioned substituent A⁴More The preferably substituent of 1 valency of the functional group with least one kind of more than pKa5, it is however preferred to have at least one kind of be selected from includes having The group of coordinating oxygen atom, group, phenolic group, urea groups, carbamate groups, alkyl, aryl, the alcoxyl with basic nitrogen atom Base carbonyl, alkylaminocarbonyl, have the group of alkylidene epoxide chain, imide, carboxylate group, sulfoamido, hydroxyl and miscellaneous The substituent of 1 valency of the group in the group of ring group, more preferably alkyl, aryl, the group with coordinating oxygen atom, with alkali Group, urea groups or the carbamate groups of property nitrogen-atoms.

As substituent A³And substituent A⁴Combination, preferred substituents A³To be less than 5 functional group with least one kind of pKa 1 valency substituent, and substituent A⁴For the substituent of 1 valency of the functional group with least one kind of more than pKa5.

More preferably substituent A³To include carboxylic acid group, sulfonic group, phosphate, phosphonate group and secondary phosphine with least one kind of be selected from The substituent of 1 valency of the group in the group of acidic group, and substituent A⁴To include with least one kind of be selected from coordinating oxygen atom Group, have basic nitrogen atom group, phenolic group, urea groups, carbamate groups, alkyl, aryl, alkoxy carbonyl, alkanamine Base carbonyl, have in the group of the group of alkylidene epoxide chain, imide, carboxylate group, sulfoamido, hydroxyl and heterocyclic radical The substituent of 1 valency of group.

Further preferred substituent A³For the substituent of 1 valency with carboxylic acid group, and substituent A⁴For alkyl, aryl, have The group of coordinating oxygen atom, group, urea groups or the carbamate groups with basic nitrogen atom.

From pigment and substituent A³Alkyl absorption it is good from the viewpoint of, particularly preferred substituent A³For carboxylic acid group, and Substituent A⁴For alkyl.

As the concrete example of dispersant, for example, BYK Chemie GmbH manufactures " Disperbyk-161,162, 163rd, 164,165,166,170,190 (trade name, high-molecular copolymer) " and EFKA companies manufacture " EFKA4047, 4050th, 4010,4165 (trade name, polyurethanes), EFKA4330,4340 (trade name, block copolymers) " etc..

Also, as the concrete example of dispersant, can refer to Japanese Unexamined Patent Publication 2013-249417 publications 0127~ High-molecular compound described in 0129 section, these contents are incorporated in this specification.

Also, as dispersant, the 0037~0115 (corresponding of Japanese Unexamined Patent Publication 2010-106268 publications can be used 0075~0133 section of US2011/0124824) section graft copolymer, these contents can quote and be incorporated to this specification.

Also, in addition to above-mentioned copolymer, additionally it is possible to use the macromolecule for including the constituent with side-chain structure Compound, 0028~0084 (the corresponding US2011/ that the side-chain structure passes through Japanese Unexamined Patent Publication 2011-153283 publications 0075~0133 section of 0279759) acidic groups of section forms via linking group bonding, and these contents can be quoted and be incorporated to this In specification.

Dispersant can be used alone, and can also combine two or more and use.

The content of dispersant in precursor composition is not particularly limited, and the more excellent viewpoint of effect of the invention is examined Consider, the total solid content relative to composition is preferably 1~30 mass %, more preferably 1~20 mass %, more preferably 1~15 mass %.

Also, from dispersion liquid through when viscosity and solid constituent stability is more excellent and the thick surface of coated film in uniformly Property it is good from the viewpoint of, the quality of the dispersant (D) in precursor composition and the mass ratio (D/P ratios) of pigment (P) are preferred For 0.1~0.45, more preferably 0.12~0.4, more preferably 0.14~0.35.

＜ organic solvents ＞

Precursor composition contains organic solvent.

As the example of organic solvent, for example, acetone, methyl ethyl ketone, hexamethylene, ethyl acetate, dichloroethanes, Tetrahydrofuran, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propane diols list second Ether, acetylacetone,2,4-pentanedione, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethylene glycol list isopropyl Ether, ethylene glycol monomethyl ether acetate, 3- methoxypropanols, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol list Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3- first Epoxide propyl-acetic acid ester, n,N-Dimethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, ethyl acetate, butyl acetate, lactic acid first Ester and ethyl lactate etc., but it is not limited to these.

Organic solvent can be used alone, and can also combine two or more and use.

By organic solvent combination two or more and in the case of use, preferably by selected from 3- ethoxypropanoates, 3- ethoxies Base ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- methoxypropionic acid first Ester, 2-HEPTANONE, cyclohexanone, ethylcarbitol acetate, acetate of butyl carbitol, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetic acid The mixed solution that two or more of ester is formed.

The content of organic solvent in precursor composition is not particularly limited, the viewpoint more excellent from the effect of the present invention Consider, be preferably 10~95 mass % relative to composition gross mass, more preferably 50~95 mass %, more preferably 55 ~90 mass %.

(other additives)

Precursor composition can contain other additives in the range of the effect of the present invention is not damaged as needed.As Other additives, for example, drying retarder (wetting agent), anti-fading agent, emulsion stabilizer, impregnation-accelerator, ultraviolet Absorbent, preservative, mould inhibitor, pH regulators, surface tension regulator, defoamer, viscosity modifier, antirust agent, chelating agent, Additive known to antioxidant, closely sealed auxiliary agent, surfactant, resinous coat agent and pigment derivative etc..

＜ pigment dispersions ＞

Pigment, dispersant and organic solvent are included in the pigment dispersion manufactured according to said sequence.In pigment dispersion Pigment average grain diameter preferred scope it is as described above.

In obtained pigment dispersion, it is each that polymerization initiator, polymerizable compound, alkali soluble resins etc. can be added Main component and form solidification compound.

As solidification compound, various uses is can be applied to, for example, having used the feelings of black pigment as pigment Under condition, it can be applied to photomask and formed in purposes.

Also, it can be applied to by the cured film that above-mentioned solidification compound is formed in various uses, for example, Colour filter etc..

Also, above-mentioned cured film can be applied to various devices, for example, solid-state imager, image display to fill Put.

Hereinafter, (below, " combination is also expressed as to form solidification compound to the pigment dispersion using the present invention Thing ".) the detailed content of situation illustrate.

(polymerization initiator)

The composition of the present invention can contain polymerization initiator.

It is not particularly limited, can be suitably made choice from known polymerization initiator as polymerization initiator, It is preferred that for example with photosensitive polymerization initiator (so-called Photoepolymerizationinitiater initiater).

As Photoepolymerizationinitiater initiater, as long as there is triggering the ability of polymerization compound with regard to without particular limitation, energy It is enough suitably to be made choice from known Photoepolymerizationinitiater initiater.For example, it is preferable to have to ultraviolet range to visible region Photosensitive polymerization initiator.And or the sensitizer with being optically excited produces some effects, and generate active free The activating agent of base.And or trigger the initiator of cationic polymerization according to the species of monomer.

Also, Photoepolymerizationinitiater initiater is in about 300nm~800nm (more preferably 330nm~500nm.) in the range of, preferably Contain at least one kind of compound with least about 50 molar absorption coefficient.

As Photoepolymerizationinitiater initiater, for example, halogenated hydrocarbon derivatives (for example, the halogenated hydrocarbons with triazine skeleton spreads out Halogenated hydrocarbon derivatives etc. of biology, Ju You oxadiazole skeletons), the acylphosphine compounds such as acylphosphine oxide, six aryl bisglyoxalines, The oxime compounds such as 9 oxime derivate, organic peroxide, sulphur compound, ketone compound, aromatic series salt, ketoxime ether, aminobenzene second Ketone compound and hydroxy acetophenone etc..As the halogenated hydrocarbon compound with above-mentioned triazine skeleton, if for example, woods etc. People writes, Bull.Chem.Soc.Japan, No. 1388492 explanation secretaries of compound, British patent of 42,2924 (1969) record No. 3337024 compound of load, the compound of Japanese Unexamined Patent Application 53-133428 publications record, Deutsche Bundespatent specifications are recorded Compound, the J.Org.Chem. according to F.C.Schaefer etc.；29th, compound, the Japanese Unexamined Patent Application of 1527 (1964) record The compound of 62-58241 publications record, the compound of Japanese Unexamined Patent Publication 5-281728 publications record, Japanese Unexamined Patent Publication 5- Described compound etc. in No. 4212976 specifications of compound and U.S. Patent No. that No. 34920 publications are recorded.

Also, from the viewpoint of exposure sensitivity, it is preferably selected from including trihalomethyl triaizine compounds, benzyl dimethyl Ketal compound, alpha-hydroxyacetone compounds, α-aminoketone compound, acylphosphine compounds, phosphine oxide compound, metallocene chemical combination Thing, oxime compound, triarylimidazoles dimer, compound, benzothiazole compound, benzophenone cpd, acetophenone Compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halogen Jia oxadiazoles compound, the tonka-bean of 3- aryl substitution Compound in the group of plain compound.

Wherein, more preferably trihalomethyl triaizine compounds, α-aminoketone compound, acylphosphine compounds, phosphine oxide chemical combination Thing, oxime compound, triarylimidazoles dimer, compound, benzophenone cpd or acetophenone compound, further preferably Trihalomethyl triaizine compounds, α-aminoketone compound, oxime compound, triarylimidazoles dimer or benzophenone cpd.

Especially, in the making of the photomask of solid-state imager use solidification compound in the case of, it is necessary to point Thin shape forms fine pattern, it is therefore important that curability and being shown in unexposed portion in a manner of no residue Shadow.Consider from this viewpoint, as Photoepolymerizationinitiater initiater, preferably oxime compound.Especially, formed in solid-state imager fine Pattern in the case of, curing with being exposed using stepping in exposing, the exposure machine can be damaged because of halogen sometimes, also need The additive amount of Photoepolymerizationinitiater initiater is suppressed relatively low, if therefore consider this some, forming such as solid-state imager one During the fine pattern of sample, as Photoepolymerizationinitiater initiater, particularly preferably using oxime compound.Also, by using oxime compound Migrating property can further be optimized.

As the concrete example of Photoepolymerizationinitiater initiater, can see, for example Japanese Unexamined Patent Publication 2013-29760 publications 0265~ 0268 section, which is incorporated herein in specification.

As Photoepolymerizationinitiater initiater, it is also preferred that hydroxy acetophenone compound, aminoacetophenone compounds and acylphosphanes chemical combination Thing.More specifically, aminoacetophenone class described in such as Japanese Unexamined Patent Publication 10-291969 publications can also be enumerated to draw Send out acyl group phosphine initiator described in No. 4225898 agent, Japanese Patent No. publications.

As hydroxy acetophenone class initiator, IRGACURE-184, DAROCUR-1173, IRGACURE- can be enumerated 500th, IRGACURE-2959, IRGACURE-127 (trade name：Manufactured by BASF AG).

As aminoacetophenone class initiator, can enumerate IRGACURE-907, IRGACURE-369 as commercially available product, IRGACURE-379 and IRGACURE-379EG (trade names：Manufactured by BASF AG).Trigger as aminoacetophenone class Agent, can also enumerate the Japanese Unexamined Patent Publication 2009-191179 that absorbing wavelength is matched with the long wavelength optical light sources such as 365nm or 405nm Described compound in publication.

As acyl group phosphine initiator, IRGACURE-819 and the DAROCUR-TPO (commodity as commercially available product can be enumerated Title：Manufactured by BASF AG).

As Photoepolymerizationinitiater initiater, preferably oxime compound (oximes initiator).Oxime compound is high sensitivity and polymerization effect Rate is high, unrelated with color material concentration and can cure, and the concentration of color material easily is set to higher, therefore preferably.

As the concrete example of oxime compound, compound, day that Japanese Unexamined Patent Publication 2001-233842 publications are recorded can be enumerated The compound that the compound and Japanese Unexamined Patent Publication 2006-342166 publications that this special open 2000-80068 publications are recorded are recorded.

As the preferred embodiment of oxime compound, for example, 3- Benzoyloxyimino butane -2- ketone, 3- acetyl Epoxide iminobutanes -2- ketone, 3- propionyloxy iminobutanes -2- ketone, 2- Acetyloxyimino pentane -3- ketone, 2- second Acyloxy imino group -1- phenyl-propane -1- ketone, 2- Benzoyloxyimino -1- phenyl-propane -1- ketone, 3- (4- tosyls Epoxide) iminobutanes -2- ketone and 2- ethyoxyl carbonyloxy group imino group -1- phenyl-propane -1- ketone etc..

Also, J.C.S.Perkin II (1979) pp.1653-1660, J.C.S.Perkin II can also be enumerated (1979) pp.156-162, Journal of Photopolymer Science and Technology (nineteen ninety-five) Pp.202-232, Japanese Unexamined Patent Publication 2000-66385 publications, Japanese Unexamined Patent Publication 2000-80068 publications, Japanese Unexamined Patent Application Publication 2004- No. 534797 publications, Japanese Unexamined Patent Publication 2006-342166 publications each publication in described compound etc..

As commercially available product, it is also preferred that using IRGACURE-OXE01 (BASF AG's manufacture), IRGACURE-OXE02 (BASF Company manufactures).Also, it can also use TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd manufacture), ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (ADEKA CORPORATION manufactures).

Also, as the oxime compound in addition to above-mentioned record, the Japan that oxime is connected with carbazole N positions can be used Described compound in special table 2009-519904 publications, at benzophenone position be imported with the United States Patent (USP) of miscellaneous substituent Described compound in No. 7626957 publication, the Japanese Unexamined Patent Publication 2010-15025 public affairs for being imported with pigment position nitro Remembered in report and U.S. Patent Publication No. 2009-292039 compound recorded, published International patent 2009-131189 publications The ketoxime compounds of load, same intramolecular contain described in No. 7556910 publications of United States Patent (USP) of triazine skeleton and oxime skeleton Compound and there is maximum absorption in 405nm, and to g ray sources have good sensitivity Japanese Unexamined Patent Publication Described compound etc. in 2009-221114 publications.

Also, as oxime compound, can see, for example 0274~0275 section of Japanese Unexamined Patent Publication 2013-29760 publications, The content is incorporated herein in specification.

Specifically, as oxime compound, the compound preferably represented by following formula (OX-1).In addition, the N-O keys of oxime can Can be the oxime compound or the mixture of (E) body and (Z) body of (Z) body to be the oxime compound of (E) body.

[chemical formula 17]

In general formula (OX-1), R and B separately represent monovalent substituent, and A represents divalent organic group, and Ar represents virtue Base.

It is preferably monovalence nonmetallic atom group as the monovalent substituent represented by R in general formula (OX-1).

As monovalence nonmetallic atom group, alkyl, aryl, acyl group, alkoxy carbonyl, aryloxy carbonyl, heterocycle can be enumerated Base, alkane thiocarbonyl group and fragrant thiocarbonyl group.Also, these groups can have the substituent of more than 1.Also, the substituent is also It can be substituted by other substituents.

As substituent, halogen atom, aryloxy group, alkoxy carbonyl, aryloxy carbonyl, acyloxy, acyl group, alkane can be enumerated Base and aryl.

In general formula (OX-1), as the monovalent substituent represented by B, preferred aryl groups, heterocyclic radical, aromatic carbonyl or heterocycle carbonyl Base.These groups can have the substituent of more than 1.As substituent, the substituent can be exemplified.

In general formula (OX-1), as the divalent organic group represented by A, alkylidene, the Asia that preferably carbon number is 1~12 Cycloalkyl or alkynylene.These groups can have the substituent of more than 1.As substituent, the substitution can be exemplified Base.

As Photoepolymerizationinitiater initiater, the oxime compound with fluorine atom can be also used.As the oximate with fluorine atom The concrete example of compound, can enumerate described compound in Japanese Unexamined Patent Publication 2010-262028 publications, Japanese Unexamined Patent Application Publication It is described in described compound 24,36~40, Japanese Unexamined Patent Publication 2013-164471 publications in 2014-500852 publications Compound (C-3) etc..The content is incorporated in this specification.

As Photoepolymerizationinitiater initiater, the compound by the following general formula (1) or (2) expression can be also used.

[chemical formula 18]

In formula (1), R¹And R²Separately represent the fat that alkyl, carbon number that carbon number is 1~20 are 4~20 The aralkyl that the aryl or carbon number that ring type alkyl, carbon number are 6~30 are 7~30, in R¹And R²For the situation of phenyl Under, phenyl bonds together and can form fluorenyl, R³And R⁴Separately represent hydrogen atom, carbon number is 1~20 alkane The heterocyclic radical that the aralkyl or carbon number that aryl that base, carbon number are 6~30, carbon number are 7~30 are 4~20, X tables Show direct key or carbonyl.

In formula (2), R¹、R²、R³And R⁴With the R in formula (1)¹、R²、R³And R⁴Implication is identical, R⁵Expression-R⁶、-OR⁶、-SR⁶、- COR⁶、-CONR⁶R⁶、-NR⁶COR⁶、-OCOR⁶、-COOR⁶、-SCOR⁶、-OCSR⁶、-COSR⁶、-CSOR⁶,-CN, halogen atom or hydroxyl Base, R⁶Represent the aralkyl that aryl, carbon number that alkyl, carbon number that carbon number is 1~20 are 6~30 are 7~30 Or the heterocyclic radical that carbon number is 4~20, X represent direct key or carbonyl, a represents 0~4 integer.

In above-mentioned formula (1) and formula (2), R¹And R²It is preferred that it is separately methyl, ethyl, n-propyl, isopropyl, hexamethylene Base or phenyl.R³Preferably methyl, ethyl, phenyl, tolyl or xylyl.R⁴It is preferred that carbon number be 1~6 alkyl or Phenyl.R⁵It is preferred that methyl, ethyl, phenyl, tolyl or naphthyl.X is preferably direct key.

As the concrete example by formula (1) and the compound of formula (2) expression, for example, in Japanese Unexamined Patent Publication 2014- Compound described in 0076~0079 section of No. 137466 publications.The content is incorporated in this specification.

In the present invention described below preferably using oxime compound concrete example, but be not limited to these concrete examples.

[chemical formula 19]

Oxime compound is preferably compound of the wavelength region with maximum absorption wavelength in 350nm~500nm, more preferably To have the compound of maximum absorption wavelength in the wavelength region of 360nm~480nm, more preferably in 365nm and 405nm The high compound of absorbance.

From the viewpoint of sensitivity, molar absorption coefficient of the oxime compound in 365nm or 405nm is preferably 1,000 ~300,000, more preferably 2,000~300,000, more preferably 5,000~200,000.

The molar absorption coefficient of compound can be measured by known method, be divided preferably for example by UV, visible light Photometer (the Cary-5 spectrophotometer (spectrophotometer) of Varian companies manufacture), and it is molten using ethyl acetate Agent, is measured with the concentration of 0.01g/L.

Polymerization initiator combines two or more as needed and uses.

The content of polymerization initiator is preferably 0.1~50 mass % relative to the total solid content of solidification compound, more Preferably 0.5~30 mass %, more preferably 1~20 mass %.Within the range, better sensitivity can be obtained And patternability.The solidification compound of the present invention can only include a kind of polymerization initiator, can also include of more than two kinds Polymerization initiator.Comprising in the case of of more than two kinds, preferably its total amount becomes above range.

(b) polymerizable compound

Polymerizable compound is preferably the olefinic unsaturated group for being capable of addition polymerization with least one, and boiling point is in normal pressure It is more than 100 DEG C of compound down.Especially, 2~10 olefinic unsaturated groups are preferably comprised in polymerizable compound, are preferably So-called multifunctional polymerizable compound.

As the olefinic unsaturated group for being capable of addition polymerization with least one, and boiling point is more than 100 DEG C under normal pressure Compound, for example, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, benzene oxygen ethyl The acrylate or methyl acrylate of the simple functions such as (methyl) acrylate；Polyethylene glycol two (methyl) acrylate, three hydroxyl first Base ethane three (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, season penta Tetrol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, hexylene glycol two (methyl) acrylate, three hydrocarbon first Base propane three (acryloxypropyl) ether, three (acryloyl-oxyethyl) isocyanuric acid esters, in glycerine or trihydroxy methyl second The compound, Ji Wusi of (methyl) acroleic acid esterification are carried out in the polyfunctional alcohols such as alkane after addition ethylene oxide or propylene oxide Compound, the Japanese Patent Publication No. 48-41708 number of poly- (methyl) acroleic acid esterification of alcohol or dipentaerythritol, Japanese Patent Publication 50- No. 6034, urethane acrylate class described in each publication of Japanese Unexamined Patent Application 51-37193, Japanese Unexamined Patent Application No. 48-64183, Japanese Patent Publication 49-43191, Japanese Patent Publication 52-30490 each publication in described polyester third Olefin(e) acid esters, epoxy resin and (methyl) acrylic acid the polyfunctional acrylate such as reaction product, that is, Epoxy Acrylates or Methyl acrylate.It can also use in Japanese then association's will (Journal of the Adhesion Society of Japan) Vol.20, No.7, the compound introduced as photo-curable monomer and oligomer in page 300~308.

Also, can also use in Japanese Unexamined Patent Publication 10-62986 publications as general formula (1) and general formula (2) and and its In the polyfunctional alcohol that concrete example is together recorded (methyl) acroleic acid esterification has been carried out after addition of ethylene oxide or propylene oxide Compound.

Wherein, preferably dipentaerythritol five (methyl) acrylate, (methyl) acrylate of dipentaerythritol six and these Acryloyl group is connected to the structure of dipentaerythritol via ethylene glycol and diol residues.Also these oligomeric species can be used Type.

Also, it is also preferred that such as Japanese Patent Publication 48-41708, Japanese Unexamined Patent Application 51-37193, Japanese Patent Publication 2- Described urethane acrylate class or Japan are special public in each publication of No. 32293 and Japanese Patent Publication 2-16765 Clear No. 58-49860, Japanese Patent Publication 56-17654, Japanese Patent Publication 62-39417 and Japanese Patent Publication 62-39418 Each publication described in the carbamate compounds class with ethylene oxide skeleton.Moreover, it is also preferred that in Japanese Unexamined Patent Publication Clear No. 63-277653, described in each publication of Japanese Unexamined Patent Application 63-260909 and Japanese Unexamined Patent Publication 1-105238, point Addition polymerization compounds with amino structure or sulfide based structural in sub.

As commercially available product, oligourethane UAS-10, UAB-140 (trade name, NIPPON can be enumerated PAPER Chemicals CO., LTD. manufacture), UA-7200 (manufacture of Shin-Nakamura Chemical Co., Ltd.s), DPHA-40H (trade name, Nippon Kayaku Co., Ltd.s manufacture), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (trade name, KYOEISHA CHEMICAL Co., LTD. manufacture) etc..

Also, it is also preferred that the alefinically unsaturated compounds class with acidic group, as commercially available product, for example, 3 functional acrylates containing carboxylic acid group, that is, TO-756 of TOAGOSEI CO., LTD. manufactures and 5 functions third containing carboxylic acid group Olefin(e) acid ester, that is, TO-1382 etc..As the polymerizable compound being used in the present invention, more preferably acrylate more than 4 functions Compound.As acrylate compounds more than 4 functions, for example, KAYARD DPHA (trade name, Nippon Kayaku Co., Ltd.s manufacture) etc..

Polymerizable compound can be used alone, and can also combine two or more and use.

Polymerizable compound of more than two kinds is combined in the case of use, its combination can be according to composition institute It is required that physical property etc. suitably set.One of preferred compositions mode as polymerizable compound, for example, selected from upper The polymerizable compound of more than two kinds of polyfunctional acrylate compounds is stated, as its an example, dipentaerythritol can be enumerated The combination of six acrylate and pentaerythritol triacrylate.

The content of polymerizable compound is preferably 3~55 mass % relative to the total solid content in solidification compound, More preferably 10~50 mass %.

(silane coupling agent)

The composition of the present invention can contain silane coupling agent.

Silane coupling agent refers to the compound in molecule with functional group with hydrolization group and in addition.In addition, The hydrolization groups such as alkoxy and silicon atom bonding.

Hydrolization group refers to directly and silicon atom bonding, and can generate silicon by hydrolysis and/or fusion reaction The substituent of oxygen alkane key.As hydrolization group, for example, halogen atom, alkoxy, acyloxy and alkenyloxy group.Hydrolysis Property group have carbon atom in the case of, which is preferably less than 6, more preferably less than 4.Particularly preferred carbon number For less than 4 alkoxy, or the alkenyloxy group that carbon number is less than 4.

Also, in order to improve the adaptation between substrate and cured film, silane coupling agent does not preferably include fluorine atom and silicon Atom (but the silicon atom for being bonded with hydrolization group forecloses), it is generally desirable to (but be bonded with not comprising fluorine atom, silicon atom The silicon atom of hydrolization group forecloses), the alkylidene that is substituted by silicon atom, the straight-chain alkyl that carbon number is more than 8 And carbon number is more than 3 to divide alkyl group.

Silane coupling agent preferably has the group represented by following formula (Z).* bonding position is represented.

Formula (Z) *-Si- (R_Z1)₃

In formula (Z), R_Z1Represent hydrolization group, its is as defined above.

Silane coupling agent, which preferably has, to be selected from the group including (methyl) acryloxy, epoxy group and oxetanylmethoxy More than a kind of curability functional group.Curability functional group can directly and silicon atom bonding, can also be via linking group and silicon Atomistic binding.

In addition, the preferred embodiment as curability functional group included in above-mentioned silane coupling agent, can also enumerate certainly By base polymerism base.

The molecular weight of silane coupling agent is not particularly limited, from the viewpoint of operability, in most cases for 100~ 1,000, it is preferably more than 270 from the viewpoint of the effect of the present invention is more excellent, more preferably 270~1,000.

One of preferred embodiment as silane coupling agent, can enumerate the silane coupling agent X represented by formula (W).

Formula (W) R_Z2-Lz-Si-(R_Z1)₃

R_z1Represent hydrolization group, it is as defined above.

R_z2Represent curability functional group, as defined above, preferred scope is also as described above.

Lz represents singly-bound or divalent linking group., can as divalent linking group in the case that Lz represents divalent linking group With the arlydene ,-NR that enumerates the alkylidene that can be substituted with halogen atoms, can be substituted with halogen atoms¹²-、-CONR¹²-、- CO-、-CO₂-、SO₂NR¹²-、-O-、-S-、-SO₂- or combinations thereof.Wherein, be preferably selected from carbon number be 2~10 can be with The alkylidene and carbon number being substituted with halogen atoms be 6~12 the arlydene that can be substituted with halogen atoms group in extremely Few a kind, or these groups and by selected from including-NR¹²-、-CONR¹²-、-CO-、-CO₂-、SO₂NR¹²- ,-O- ,-S- and SO₂- Group at least one kind of group the group that forms of combination, more preferably carbon number is that 2~10 can be substituted with halogen atoms Alkylidene ,-CO₂-、-O-、-CO-、-CONR¹²-, or the group being made of the combination of these groups.Here, above-mentioned R¹²Table Show hydrogen atom or methyl.

As silane coupling agent X, N- β-aminoethyl-γ-aminopropyl-methyl dimethoxysilane (Shin- can be enumerated Etsu Chemical Co., Ltd.s manufacture trade name KBM-602), N- β-aminoethyl-γ-aminopropyl-trimethoxy silane (Shin-Etsu Chemical Co., Ltd.s manufacture trade name KBM-603), the N- β-aminoethyl-γ-ethoxy of aminopropyl-three Base silane (Shin-Etsu Chemical Co., Ltd.s manufacture trade name KBE-602), γ-aminopropyl-trimethoxy silane (Shin-Etsu Chemical Co., Ltd.s manufacture trade name KBM-903), γ-aminopropyl-triethoxysilane (Shin- Etsu C hemicalCo., Ltd. manufacture trade name KBE-903), 3- methacryl propyl trimethoxy silicanes (Shin- Etsu Chemical Co., Ltd.s manufacture trade name KBM-503) and glycidoxy octyl group trimethoxy silane (Shin- Etsu Chemical Co., Ltd.s manufacture trade name KBM-4803) etc..

As other preferred embodiments of silane coupling agent, can enumerate intramolecular at least has silicon atom, nitrogen-atoms and consolidates Hua Xing functional groups, and with the silane coupling agent Y with the hydrolization group of silicon atom bonding.

Silane coupling agent Y has at least one silicon atom in the molecule, and silicon atom can be with following atom or substitution Base is bonded.The atom or substituent that can be bonded can enumerate hydrogen atom, halogen atom, hydroxyl, the alkane that carbon number is 1~20 Base, alkenyl, alkynyl, aryl, the amino that can be substituted by alkyl and/or aryl, silylation, the alcoxyl that carbon number is 1~20 Base, aryloxy group etc..These substituents can also by silylation, alkenyl, alkynyl, aryl, alkoxy, aryloxy group, thio alkoxy, The amino that can be substituted by alkyl and/or aryl, halogen atom, sulfoamido, alkoxy carbonyl, amide groups, urea groups, ammonium, Alkyl ammonium group, carboxylic acid group or its salt and the substitution such as sulfo group or its salt.

In addition, at least one in silicon atom be bonded with hydrolization group.Hydrolization group is as defined above.

The group represented by formula (Z) can be included in silane coupling agent Y.

Silane coupling agent Y has nitrogen-atoms more than at least one in the molecule, and nitrogen-atoms is preferably with secondary amino group or tertiary amino Form exist, i.e., nitrogen-atoms preferably with least one organic group as substituent., can be with addition, the structure as amino It is present in intramolecular in the form of nitrogenous heterocyclic part-structure, can also exists as substituted-aminos such as aniline.

Here, as organic group, alkyl, alkenyl, alkynyl, aryl or combinations thereof etc. can be enumerated.These bases are also There can be substituent, as the substituent that can be imported, silylation, alkenyl, alkynyl, aryl, alkoxy, fragrant oxygen can be enumerated Base, thio alkoxy, amino, halogen atom, sulfoamido, alkoxy carbonyl, carbonyloxy group, amide groups, urea groups, alkylidene epoxide Ammonium, alkyl ammonium group, carboxylic acid group or its salt and sulfo group etc..

Also, nitrogen-atoms is bonded preferably via arbitrary organo linking group with curability functional group.As preferably having Machine linking group, can enumerate the substituent that can be directed in above-mentioned nitrogen-atoms and organic group bonded thereto.

Curability functional group is as defined above included in silane coupling agent Y, and preferred scope is also as described above.

In silane coupling agent Y, in the molecule with curability functional group more than at least one, it can also use Mode with the curability functional group of more than 2, from the viewpoint of sensitivity and stability, preferably has with 2~20 Curability functional group, more preferably with 4~15, further preferably with 6~10.

The molecular weight of silane coupling agent X and silane coupling agent Y are not particularly limited, and can enumerate above range (preferably More than 270).

The content of silane coupling agent in the composition of the present invention is preferably 0.1 relative to the total solid content in composition ~10 mass %, more preferably 0.5~8 mass %, more preferably 1.0~6 mass %.

The composition of the present invention can individually include a kind of silane coupling agent, can also include two or more.In composition bag In the case of silane coupling agent of more than two kinds, its total content is within the above range.

(alkali soluble resins)

The composition of the present invention can contain alkali soluble resins.

As alkali soluble resins, preferably using threadlike organic polymers., can be any as this threadlike organic polymers Use known threadlike organic polymers.In order to carry out water development or alkalescent water development, can preferably enumerate to water or Alkalescent water is resolvability or the threadlike organic polymers of swellability.

As alkali soluble resins, it is preferably threadlike organic polymers and (is preferably by acrylic copolymer, benzene in molecule Molecule of the ethene copolymer as main chain) in there is the alkali soluble resins that at least one promotes alkali-soluble group.

From the viewpoint of heat resistance, preferably polycarboxylated styrene resinoid, polysiloxanes resinoid, acrylic compounds tree Fat, acrylamide resinoid or acrylic acid/acrylamide copolymer resin, from the viewpoint of control developability, acrylic compounds Resin, acrylamide resinoid or acrylic acid/acrylamide copolymer resin.

As alkali-soluble group (following, to be also referred to as acidic group) is promoted, for example, carboxylic acid group, phosphate, sulfonic acid Base and phenolic hydroxyl group etc., but organic solvent and the group that can develop by weak alkaline aqueous solution are preferably soluble in, more preferably Carboxylic acid group.These acidic groups can be only a kind, or two or more.

As alkali soluble resins, for example, the free radical polyalcohol on side chain with carboxylic acid group, such as in day This tekiaki 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54- No. 25957, Japanese Unexamined Patent Application 54-92723, Japanese Unexamined Patent Application 59-53836, described in Japanese Unexamined Patent Application 59-71048 Resin, i.e. make resin that the monomer with carboxylic acid group is polymerized alone or is copolymerized, make the monomer with acid anhydrides be polymerized alone or be copolymerized And anhydride unit is hydrolyzed, half-esterification or semi-amidation resin, epoxy resin is passed through unsaturated monocarboxylic and acid anhydrides And modified epoxy acrylate etc..As the example with carboxylic acid group's monomer, acrylic acid, methacrylic acid, clothing can be enumerated Health acid, crotonic acid, maleic acid, fumaric acid and 4- carboxyl styrenes etc., can be with it is predicted that maleic acid as the monomer with acid anhydrides Acid anhydride.Also, can also enumerate has the acid cellulose derivative of carboxylic acid group equally on side chain.In addition, with hydroxyl Addition monomer of cyclic acid anhydride etc. is effectively in polymer.

Also, European Patent the 993966th, European Patent the 1204000th, Japanese Unexamined Patent Publication 2001-318463 etc. are each The film-strength of the ethylidene ether modification polyvinyl alcohol series adhesive polymer with acidic group described in publication and the balance of developability are excellent It is different, therefore preferably.

Moreover, in addition, as water-soluble threadlike organic polymers, polyvinylpyrrolidone or polyethylene oxide etc. are useful.

Especially, wherein, (benzyl (methyl) acrylate/(methyl) acrylic acid/as needed other addition polymerization sex ethylenes Base monomer) copolymer and (pi-allyl (methyl) acrylate/(methyl) acrylic acid/as needed other addition polymerization sex ethylenes Base monomer) film-strength of copolymer, sensitivity and developability balancing good, therefore preferably.

As commercially available product, for example, ACRYLIC BASE FF-187, FF-426 (FUJIKURA KASEI CO., LTD. manufacture), ACRYCURE-RD-F8 (NIPPON SHOKUBAI CO., LTD.) and DAICEL-ALLNEX LTD. manufacture CYCLOMER P (ACA) 230AA etc..

In the manufacture of alkali soluble resins, the method for example based on known radical polymerization can be applied.For this For field technology personnel, can easily be set by radical polymerization manufacture alkali soluble resins when temperature, pressure, freedom The polymerizing condition such as the species and its amount of base initiator, the species of solvent, also can experimentally determine condition.

Also, as alkali soluble resins, it is also preferred that using possess the construction unit with grafted chain, with acidic group (alkali soluble Property base) construction unit polymer.

The definition of construction unit with grafted chain contains with the construction unit with grafted chain possessed by above-mentioned dispersant Justice is identical, and preferred scope is also identical.

As acidic group, for example, carboxylic acid group, sulfonic group, phosphate and phenolic hydroxyl group etc., preferably carboxylic acid group, sulfonic acid It is at least one kind of in base and phosphate, more preferably carboxylic acid group.

As the construction unit with acidic group, it is preferably selected from being derived from the list represented by the following general formula (vii)~general formula (ix) More than a kind of construction unit of the construction unit of body.

[chemical formula 20]

In general formula (vii)~general formula (ix), R²¹、R²²And R²³Separately represent hydrogen atom, halogen atom (for example, fluorine Atom, chlorine atom, bromine atoms etc.) or carbon number be 1~6 alkyl (for example, methyl, ethyl, propyl group etc.).

In general formula (vii)~general formula (ix), R²¹、R²²And R²³More preferably it is separately hydrogen atom or carbon number is 1~3 alkyl, is further preferably separately hydrogen atom or methyl.In general formula (vii), R²¹And R²³Particularly preferably respectively For hydrogen atom.

X in general formula (vii)₂Represent oxygen atom (- O-) or imino group (- NH-), be preferably oxygen atom.

Also, the Y in general formula (viii) represents methine or nitrogen-atoms.

Also, the L in general formula (vii)~general formula (ix)₂Represent singly-bound or divalent linking group.As divalent linking group, Divalent fatty group (such as alkylidene, substituted alkylene, alkenylene, substitution alkenylene, alkynylene and the sub- alkynes of substitution can be enumerated Base), it is divalent aromatic series base (for example, arlydene and substitution arlydene), divalent heterocyclic radical, oxygen atom (- O-), sulphur atom (- S-), sub- Amino (- NH-), substituted imido key (- NR⁴¹'-, is in this R⁴¹' be fatty group, aromatic series base or heterocyclic radical), carbonyl bond (- ) or combinations thereof etc. CO-.

Divalent heterocyclic radical preferably has 5 Yuans rings or 6 Yuans rings as heterocycle.Other heterocycles, fat can have been condensed on heterocycle More than 1 in race's ring or aromatic ring.Also, heterocyclic radical can have substituent.As substituent, halogen original can be enumerated Son, hydroxyl, oxo base (=O), thio group (=S), imino group (=NH), substituted imido (=N-R⁴², here, R⁴²For fat Race's base, aromatic series base or heterocyclic radical), fatty group, aromatic series base and heterocyclic radical.

L₂Preferably singly-bound, alkylidene or the divalent linking group comprising alkylene oxide structure.Alkylene oxide structure is more preferably oxygen Ethylene unit or oxypropylene structure.Also, L₂The polyoxyalkylene knot for repeating to include the alkylene oxide structure of more than 2 can be included Structure.As polyoxyalkylene structure, preferably polyoxyethylene structure or polyoxypropylene structure.Polyoxyethylene structure is by-(OCH₂CH₂)n- Represent, n is preferably more than 2 integer, more preferably 2~10 integer.

In general formula (vii)~general formula (ix), Z₂For acidic group, more preferably carboxylic acid group.

In general formula (ix), R²⁴、R²⁵And R²⁶Separately represent hydrogen atom, halogen atom (for example, fluorine atom, chlorine atom And bromine atoms etc.), carbon number be 1~6 alkyl (for example, methyl, ethyl and propyl group etc.) ,-Z₂Or-L₂-Z₂.Here, L₂ And Z₂With it is above-mentioned in L₂And Z₂Implication is identical, and preference is also identical.As R²⁴、R²⁵And R²⁶, separately preferably hydrogen is former Son or the alkyl that carbon number is 1~3, more preferably hydrogen atom.

As the monomer represented by general formula (vii), preferably R²¹、R²²And R²³It is each independently hydrogen atom or methyl, L₂For Asia Alkyl or divalent linking group comprising alkylene oxide structure, X₂For oxygen atom or imino group, Z₂For the compound of carboxylic acid group.

Also, as the monomer represented by general formula (vii), preferably R²¹For hydrogen atom or methyl, L₂For alkylidene, Z₂For carboxylic Acidic group, the compound that Y is methine.

Moreover, as the monomer represented by general formula (ix), preferably R²⁴、R²⁵And R²⁶Be separately hydrogen atom or methyl, Z₂For the compound of carboxylic acid group.

Above-mentioned alkali soluble resins can be synthesized by known method.

Above-mentioned alkali soluble resins can be with the one kind or two or more construction unit with acidic group.

Gross mass of the content of construction unit with acidic group relative to above-mentioned alkali soluble resins in mass conversion is preferred For 5~95%, from the viewpoint of the image intensity damage for suppressing to produce by alkaline development, more preferably 10~90%.

The content of alkali soluble resins in the composition of the present invention relative to the total solid content of composition be preferably 0.1~ 30 mass %, more preferably 0.3~25 mass %.

(solvent)

The composition of the present invention can contain solvent.

As solvent, water or organic solvent can be enumerated.

As organic solvent, for example, acetone, methyl ethyl ketone, hexamethylene, ethyl acetate, dichloroethanes, tetrahydrochysene furan Mutter, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, acetyl Acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethylene glycol list isopropyl Ether, ethylene glycol monomethyl ether acetate, 3- methoxypropanols, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol list Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3- first Epoxide propyl-acetic acid ester, n,N-Dimethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, ethyl acetate, butyl acetate, lactic acid first Ester and ethyl lactate etc..

Solvent can be used alone, and can also combine two or more and use.

By solvent combination two or more and in the case of use, preferably by selected from including 3- ethoxypropanoates, 3- ethoxies Base ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- methoxypropionic acid first Ester, 2-HEPTANONE, cyclohexanone, cyclopentanone, ethylcarbitol acetate, acetate of butyl carbitol, propylene glycol monomethyl ether and propane diols Two or more composition in the group of methyl ether acetate.

As the amount of solvent included in the composition of the present invention, the gross mass relative to composition is preferably 10~90 Quality %, more preferably 20~85 mass %.

(other)

Ultra-violet absorber can be included in the composition of the present invention.Thereby, it is possible to make the more excellent (essence of the shape of pattern Carefully).

As ultra-violet absorber, salicylic acid esters, benzophenone, benzotriazole, substituted acrylonitrile can be enumerated Class and triazine-based ultraviolet absorbent.As their concrete example, can use in Japanese Unexamined Patent Publication 2012-068418 publications The compound of 0137~0142 section (0251~0254 section of corresponding US2012/0068292), these contents can quote and It is incorporated in this specification.

In addition it is also possible to enumerate lignocaine-phenylSulphon base class ultra-violet absorber (DAITO CHEMICAL CO., LTD. manufacture, trade name：UV-503) etc..

As ultra-violet absorber, can also enumerate in 0134~0148 section of Japanese Unexamined Patent Publication 2012-32556 publications The compound of illustration.

The composition of the present invention, which can include, can not also include ultra-violet absorber, but the feelings comprising ultra-violet absorber Under condition, the content of ultra-violet absorber is preferably 0.001~15 mass % relative to the total solid content of composition, more preferably 0.01~10 mass %, more preferably 0.1~5 mass %.

From the viewpoint of coating is further improved, various surfactants can be included in composition of the invention. As surfactant, can use fluorine class surfactant, nonionic class surfactant, cationic based surfactants, The various surfactants such as anionic based surfactants and silicone surfactant.Especially, composition of the invention passes through Liquid characteristic (especially mobility) can be further improved containing fluorine class surfactant, it is thick thus, it is possible to further improve coating The uniformity of degree is saved fluid.

As fluorine class surfactant, for example, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173、MEGAFACE F176、MEGAFACE F177、MEGAFACE F141、MEGAFACE F142、MEGAFACE F143、 MEGAFACE F144、MEGAFACE R30、MEGAFACE F437、MEGAFACE F475、MEGAFACE F479、MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, MEGAFACE F781F (more than, DIC Corporation. manufacture), Fluorad FC430, Fluorad FC431, Fluorad FC171 (more than, Sumitomo 3M Limited manufacture), Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、 Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (more than, ASAHI GLASS CO., LTD. manufacture) etc..

As the concrete example of other surfaces activating agent, for example, in Japanese Unexamined Patent Publication 2013-249417 publications Surfactant described in 0174~0177, these contents are incorporated in this specification.

Surfactant can be used only a kind, two or more also can be combined.

The additive amount of surfactant is preferably 0.001~2.0 mass % relative to the gross mass of composition, more preferably 0.005~1.0 mass %.

In addition to mentioned component, composition of the invention can also include following component.For example, sensitizer, Sensitizer, crosslinking agent, curing accelerator, filler, thermosetting accelerator, polymerization inhibitor, plasticizer, diluent, sense grease agent, close altogether Close accelerating agent and other auxiliary agent classes and (such as conductive particle, filler, defoamer, fire retardant, levelling agent, peel off accelerating agent, antioxygen Agent, spices, surface tension regulator, chain-transferring agent etc.) etc. known to additive.

These components can be (corresponding see, for example 0183~0228 section of Japanese Unexamined Patent Publication 2012-003225 publications [0237]~[0309] of No. 2013/0034812 specification of U.S. Patent Application Publication No.), Japanese Unexamined Patent Publication 2008-250074 0101~0102 section of publication, 0103~0104 section, 0107~0109 section, the 0159 of Japanese Unexamined Patent Publication 2013-195480 publications The record of~0184 section of grade, these contents are incorporated herein in specification.

The solid component concentration of the composition of the present invention is preferably 5~50 mass %, from the thickness of the dyed layer formed From the viewpoint of the balance of light-proofness, more preferably 15~40 mass %.

The preparation method ＞ of ＜ compositions

The present invention composition can by known mixed method (for example, mixer, homogenizer, high-pressure emulsification device, Wet crushing mill, wet type dispersion machine) prepared to mix above-mentioned various composition.

The composition of the present invention is preferably filtered for the purpose of removing foreign matter or reducing defect etc. with filter.As Filter, as long as the filter of filtration applications etc. is used in the past, it is just without particular limitation.For example, based on PTFE The vistanexes such as the polyamide-based resins such as fluororesin such as (polytetrafluoroethylene (PTFE)), nylon, polyethylene and polypropylene (PP) (include height Density, super high molecular weight) etc. filter.In these raw material, preferably polypropylene (including high density poly propylene) or nylon.

The aperture of filter is suitably 0.1~7.0 μm or so, is preferably 0.2~2.5 μm, more preferably 0.2~1.5 μm, More preferably 0.3~0.7 μm.If above range, then the filtering that can suppress pigment blocks, and can reliably go Except fine foreign matters such as the impurity or condensation product included in pigment.

When using filter, different filters can be combined.At this time, the filtering in the 1st filter can only carry out 1 It is secondary, it can also carry out more than 2 times.In the case where the different filter of combination carries out the filtering of more than 2 times, with the 1st filtering Aperture compare, preferably the 2nd later aperture be identical or bigger.Also, different pore size within the above range, can be combined 1st filter.Here, aperture can refer to the nominal value of filter manufacturer., can be from for example as commercially available filter Pall Corporation, Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (former Nippon Squirrel co., Ltd.) or the various filters that are provided such as KITZ MICRO FILTER Corporation in selected Select.

2nd filter can use the filter formed by material identical with above-mentioned 1st filter etc..

The aperture of 2nd filter is suitably 0.2~10.0 μm or so, is preferably 0.2~7.0 μm, more preferably 0.3~ 6.0μm。

＜ cured films and its manufacture method ＞

Cured film can be formed by using above-mentioned composition.

The thickness of cured film is not particularly limited, from the viewpoint of the effect of the present invention is more excellent, preferably 0.2~ 25 μm, more preferably 1.0~10 μm.

Above-mentioned thickness is average thickness, is to measure any more than 5 points of thickness of cured film and carried out arithmetic to put down Equal value.

The manufacture method of cured film is not particularly limited, can enumerate above-mentioned solidification compound is coated with substrate and Form film, and the method that curing process is implemented to film and manufactures cured film.

The method of curing process is not particularly limited, and photocuring processing or heat cure processing can be enumerated, from easy shape Into from the viewpoint of pattern, preferably photocuring is handled (at the curing for especially, activating light or radioactive ray by irradiation to carry out Reason).

In addition, the species of used substrate is not particularly limited.Wherein, cured film is configured in solid-state imaging device In the case of, as substrate, the various parts preferably in solid-state imaging device are (for example, infrared cut of light optical filter, solid-state image pickup Peripheral part, wafer-level lens peripheral part and solid-state imager back side of element etc.) etc..

Preferred embodiment during as the cured film for manufacturing pattern form, can enumerate in the following manner, it includes：Pass through spin coating Method is coated with the composition of the present invention on substrate, so that the process for forming composition layer (below, is suitably referred to as " composition Layer formation process ".)；By activation light or radioactive ray are irradiated to composition layer and be exposed process (it is following, suitably Referred to as " exposure process ".)；And to after exposure composition layer carry out alkaline development so that formed cured film process (with Under, suitably referred to as " developing procedure ".).

Specifically, the composition of the present invention directly or via other layers is coated with substrate by spin-coating method, so that shape Into composition layer (composition layer formation process), carried out by irradiating activation light or radioactive ray via defined mask pattern Exposure, only makes the coated film of illuminated light partially cured (exposure process), is developed (developing procedure) using alkaline-based developer, Cured film thus, it is possible to manufacture pattern form.

Hereinafter, illustrated on each operation in aforesaid way.

(composition layer formation process)

In composition layer formation process, the composition of the present invention is coated with substrate and forms composition layer.

The species of substrate is not particularly limited, and in the case of configuring cured film in solid-state imaging device, can be enumerated Such as the various parts in solid-state imaging device are (for example, the peripheral part of infrared cut of light optical filter, solid-state imager, chip Level lens peripheral part and the solid-state imager back side etc.) etc..

As the coating method to the composition of the invention on substrate, spin-coating method (Spin coat), slit can be applied The various coating methods such as rubbing method, ink-jet method, spraying process, method of spin coating, cast coating method, rolling method and silk screen print method, Preferably spun on method.

In general, the composition being coated on substrate is dried under conditions of 70~110 DEG C and 2~4 minutes or so, So as to form composition layer.

(exposure process)

In exposure process, via mask to the composition layer irradiation activation light formed in composition layer formation process Or radioactive ray are exposed, only make the coated film of illuminated light partially cured.

Exposure is preferably carried out by the irradiation of radioactive ray, as the radioactive ray that can be used when exposing, preferably g rays, h The ultraviolet such as ray and i rays, as light source, preferably high-pressure sodium lamp.Exposure intensity is preferably 5~1,500mJ/cm², more preferably For 10~1,000mJ/cm²。

(developing procedure)

And then, exposure process carries out development treatment (developing procedure), elutes the light irradiated portion in exposure process To developer solution.Thus, photo-cured portion is only remained.

As developer solution, it is generally desirable to use organic basic developer solution.In general, development temperature is 20~30 DEG C, in general, aobvious The shadow time is 20~90 seconds.

As alkaline aqueous solution, for example, include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, silicic acid The inorganic developer solution of the alkali compounds such as sodium and sodium metasilicate and comprising ammonium hydroxide, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyl trimethyl hydroxide The organic basic of the alkali compounds such as ammonium, choline, pyrroles, piperidines and 1,8- diazabicyclo-[5,4,0] -7- endecatylenes is shown Shadow liquid.

The concentration of above-mentioned alkali compounds is preferably 0.001~10 mass %, more preferably 0.005~0.5 mass %.

Water-miscible organic solvent or surfactant such as methanol and ethanol can be added in right amount in alkaline aqueous solution Deng.In addition, in the case where having used the developer solution being made of this alkaline aqueous solution, in general, after developing, with pure water into Row cleaning (flushing).

In addition, after composition layer formation process, exposure process and developing procedure has been carried out, can implement as needed Cured curing process is carried out by the photomask for heating and/or exposing the pattern form that will be formed.

Infrared cut of light optical filters of the ＜ with photomask, solid-state imaging device ＞

In the case of having used black pigment as colouring agent, above-mentioned cured film can be excellent as so-called photomask Choosing application.Also, this photomask can be preferably applied in solid-state imaging device.

Hereinafter, first, the 1st embodiment on the solid-state imaging device of the photomask with the present invention is described in detail.

As shown in Figures 2 and 3, solid-state imaging device 2 possesses the CMOS (complementary metal oxide as solid-state imager Semiconductor) sensor 3, the circuit substrate 4 for assembling the cmos sensor 3, the ceramic system ceramic substrate 5 of holding circuit substrate 4.And And solid-state imaging device 2 possesses the IR cut-offs for being held in ceramic substrate 5 and blocking the infrared light (IR) towards cmos sensor 3 Optical filter 6, photographic lens 7, the lens carrier 8 for keeping the photographic lens 7, the holding for movably keeping the lens carrier 8 Cylinder 9.And it is possible to CCD (charge coupling device) sensors or organic C mos sensor is set to replace cmos sensor 3.

Formed with the opening 5a being inserted into for cmos sensor 3 on ceramic substrate 5, its is in the shape of a frame and surrounds cmos sensor 3 Side.Under the state, the circuit substrate 4 for being equipped with cmos sensor 3 passes through bonding agent (such as epoxies bonding agent, similarly hereinafter) And it is fixed on ceramic substrate 5.Formed with various circuit patterns on circuit substrate 4.

Reflectance coating of the IR edge filters 6 formed with reflection infrared light on plate glass or blue tinted glass, formed with this The face of reflectance coating becomes plane of incidence 6a.IR edge filters 6 are formed with the size of bigger than opening 5a one circle, and to cover opening The mode of 5a is fixed on ceramic substrate 5 by bonding agent.

The rear portion (lower section in Fig. 3 and Fig. 4) of photographic lens 7 is configured with cmos sensor 3, in photographic lens 7 and CMOS IR edge filters 6 are configured between sensor 3.Object light after photographic lens 7, IR edge filters 6 by being incident in The smooth surface of cmos sensor 3.At this time, if infrared light IR edge filters 6 and be blocked.

Circuit substrate 4 and the control unit company for being provided with the electronic equipment (for example, digital camera) for carrying solid-state imaging device 2 Connect, solid-state imaging device 2 is powered from electronic equipment.Cmos sensor 3 is arranged with more in two dimensions on smooth surface Incident light is carried out opto-electronic conversion, and signal charge caused by accumulation by a colour element, each colour element.

As shown in Figures 3 and 4, IR edge filters 6 plane of incidence 6a end, be configured with above-mentioned shading throughout complete cycle Film (light shield layer) 11, formed with the infrared cut of light optical filter with photomask.It is emitted from photographic lens 7 and in ceramic substrate 5 The reflected light R1 of front surface (upper surface in Fig. 3 and Fig. 4) reflection is incident in CMOS after reflecting or reflect repeatedly in the device The reflected light R2 that the internal face in lens carrier 8 being emitted in the case of sensor 3 and from photographic lens 7 reflects is incident in In the case of cmos sensor 3, the reason for producing hot spot is formed on photographs.Photomask 11 is blocked towards cmos sensor Harmful light such as 3 reflected light R1 and R2.Photomask 11 is applied for example, by spin-coating method and spraying process.In addition, in Fig. 3 and In Fig. 4, amplification depicts the thickness of photomask 11.

The solid-state imaging device 20 of 2nd embodiment is shown in Fig. 5.In addition, for the composition identical with the 1st embodiment Component marks identical symbol, and omits detail explanation.

Solid-state imaging device 20 possesses cmos sensor 3, circuit substrate 4, ceramic substrate 5, IR edge filters 6, photography Lens 7, lens carrier 8 and holding cylinder 9.In the side end face of IR edge filters 6, (hidden formed with above-mentioned photomask throughout complete cycle Photosphere) 21.Be emitted from photographic lens 7 and ceramic substrate 5 front surface reflection reflected light R3 in the device repeatedly reflection or In the case of being incident in cmos sensor 3 after refraction, the reason for producing hot spot is formed on photographs.Photomask 21 stops Harmful light such as the reflected light R3 towards cmos sensor 3.

The solid-state imaging device 30 of 3rd embodiment is shown in Fig. 6.In addition, for the composition identical with the 1st embodiment Component marks identical symbol, and omits detail explanation.

Solid-state imaging device 30 possesses cmos sensor 3, circuit substrate 4, ceramic substrate 5, IR edge filters 6, photography Lens 7, lens carrier 8 and holding cylinder 9.Formed in the end of the plane of incidence 6a of IR edge filters 6 and side end face throughout complete cycle There is above-mentioned photomask (light shield layer) 31.That is, the mode for being combined the 1st embodiment and the 2nd embodiment is become.The reality Apply in mode, since shading performance is higher than the 1st embodiment and the 2nd embodiment, be reliably suppressed the generation of hot spot.

The solid-state imaging device 40 of 4th embodiment is shown in Fig. 7.In addition, for the composition identical with the 1st embodiment Component marks identical symbol, and omits detail explanation.

Solid-state imaging device 40 possesses cmos sensor 3, circuit substrate 4, ceramic substrate 5, IR edge filters 6, photography Lens 7, lens carrier 8 and holding cylinder 9.Formed in the end of the plane of incidence 6a of IR edge filters 6 and side end face throughout complete cycle There is above-mentioned photomask (light shield layer) 31.

Also, ceramic substrate 5 internal face formed with photomask (light shield layer) 41.It is emitted and passes through from photographic lens 7 After IR edge filters 6 in the case where the reflected light that the internal face of ceramic substrate 5 reflects is incident in cmos sensor 3, structure Into the hot spot Producing reason of photographs.The shading performance of photomask 41 is higher than the internal face of ceramic substrate 5, therefore reliably Suppress the generation of hot spot.

＜ colour filters ＞

Also, the cured film of the present invention can also apply in colour filter.That is, can act as the present invention possesses cured film Colour filter.

Colour filter can be particularly suitable for more than 1,000,000 pixels preferably using in the solid-state imagers such as CCD or CMOS High-resolution CCD or CMOS etc..Colour filter can be configured at the light accepting part and use of each pixel for forming such as CCD or CM0S Used between the lenticule of optically focused.

Also, colour filter can be used as organic electroluminescent (organic EL) element purposes.As organic EL element, Preferred white organic EL element.Organic EL element is preferably cascaded structure.On the cascaded structure of organic EL element, day is recorded in This special open 2003-45676 publications, Ming Yi chief editors, " forefront-high brightness/high accuracy/length of organic EL technological development on three Service life/proprietary technology collection-", technical information association, in 326-328 pages, 2008 etc..Tandem junction as organic EL element Structure, for example, the one side in substrate, the lower electrode for possessing light reflective and possess translucency upper electrode it Between be provided with structure of organic EL layer etc..Lower electrode is preferably by having the material of sufficient reflectivity in visible wavelength region Form.Organic EL layer includes multiple luminescent layers, preferably has the stepped construction (cascaded structure) for being laminated with these multiple luminescent layers. It can include red light emitting layer, green light emitting layer and blue light-emitting layer in for example multiple luminescent layers of organic EL layer.Moreover, with it is multiple Luminescent layer together, preferably has and is used to make multiple luminous auxiliary layers that luminescent layer shines in the lump.Organic EL layer can be set to for example Luminescent layer and the alternately stacked stepped construction of luminous auxiliary layer.The organic EL element of organic EL layer with this structure can be sent out Go out white light.In this case, the spectrum for the white light that organic EL element is sent is preferably in blue region (430nm-485nm), green area Domain (530nm-580nm) and yellow area (580nm-620nm) have powerful very big luminescence peak.More preferably except these are sent out Beyond photopeak value, also there is very big luminescence peak in red area (650nm-700nm).By the way that organic EL members of white light will be sent Part (white organic EL unit) and the colour filter of the present invention are combined, and can obtain spectrum excellent on colorrendering quality, and It can show distincter image or image.

The thickness of colored pattern (colored pixels) on colour filter is preferably less than 2.0 μm, more preferably less than 1.0 μm, More preferably less than 0.7 μm.Lower limit can be set to such as more than 0.1 μm, can also be set to more than 0.2 μm.

Also, the size (pattern width) of colored pattern (colored pixels), is preferably less than 2.5 μm, more preferably 2.0 μm Hereinafter, it is more preferably less than 1.7 μm.Lower limit can be set to such as more than 0.1 μm, can also be set to more than 0.2 μm.

＜ image display devices ＞

The cured film (colour filter, photomask etc.) of the present invention can be used in liquid crystal display device or organic electroluminescent is shown The image display devices such as showing device.

On the definition of display device or the detailed content of each display device, for example, " electronic display unit (and assistant assistant wood it is clear Husband writes, and Kogyo Chosakai Publishing Co., Ltd.'s nineteen nineties issue) ", " display device (she blows writes along chapter, Sangyo Tosho Publishing Co., Ltd.s 1989 issue) " etc. in.Also, on liquid crystal display device, it is recorded in Such as " (Uchida Tatsuo edits LCD Technology of future generation, Kogyo Chosakai Publishing Co., Ltd.s 1994 Year distribution) " in.It is not particularly limited, is can be applied to for example above-mentioned in the liquid crystal display device that the present invention can apply The liquid crystal display device of various modes described in " LCD Technology of future generation ".

Colour filter in the present invention can be used in colored TFT (Thin Film Transistor：Thin film transistor (TFT)) side In the liquid crystal display device of formula.On the liquid crystal display device of colored TFT modes, such as " color TFT-LCD display is recorded in (KYORITSU SHUPPAN CO., LTD.1996 distribution) ".And then the present invention can also be applied to IPS (In Plane Switching：Plane conversion) etc. transverse electric field type of drive, MVA (Multi-domain Vertical Alignment：It is more Farmland is vertical orientated) etc. the widened liquid crystal display device in visual angle, STN (the Super-Twist Nematic such as pixel partitioning scheme：It is super Twisted nematic), TN (Twisted Nematic：Twisted nematic), VA (Vertical Alignment：It is vertical orientated), OCS(on-chip spacer：On piece sept), FFS (fringe field switching：Wide viewing angle technology) and R-OCB (Reflective Optically Compensated Bend：Reflect optical compensation curved) etc..

Also, the colour filter in the present invention is also capable of providing COA (the Color-filter On in order and fine Array：Color filter array) mode.In the liquid crystal display device of COA modes, on the requirement characteristic to colour filter, as above institute State, except it is common require characteristic in addition to, it is also necessary to the requirement characteristic to interlayer dielectric, i.e. low-k and stripper are resistance to Property.The light resistance of colour filter of the present invention etc. is excellent, therefore is capable of providing the COA modes of high resolution and long durability of backside protective sheet excellent Liquid crystal display device.In addition, in order to meet the requirement characteristic of low-k, resin coating can also be set on colour filter Film.

On these image display patterns, be recorded in for example " new advancement of EL, PDP, LCD display technology and market- Page 43 etc. of (Toray Research Center, Inc. tune Check research departments issue for 2001) ".

In addition to the colour filter in the present invention, liquid crystal display device is also thin by electrode base board, polarizing coating, phase difference Film, backlight, sept and visual angle ensure that the various parts such as film are formed.The colour filter of the present invention can be applied to as known in these Component form liquid crystal display device in.On these components, such as " ' 94 liquid crystal display periphery material/chemistry is recorded in The market (island Itou Kentaro CMC corporation.1994 distribution) of product ", " present situation of 2003 liquid crystal relevant markets and following exhibition Hope (last volume) (the good Ji Fuji Chimera Research Institute, Inc. of table, issue for 2003) " in.

SID meeting Digest 1380 (2005) (A.Konno et.al) are recorded on backlight or monthly magazine is shown In page 18~24 (island health is abundant) in device in December, 2005 number, page 25~30 (Yagi spark gap is grand bright) in December, 2005 number etc..

Embodiment

Hereinafter, embodiment is enumerated the present invention is further concretely demonstrated.Material, use shown in following embodiments Amount, ratio, process content and processing sequence etc. just being capable of suitably make a changes without departing from the purport of the present invention.So as to, The scope of the present invention is not limited to concrete example as shown below.If in addition, without special explanation, " part ", " % " are quality Benchmark.

The preparation ＞ of ＜ precursor compositions

Pigment, dispersant and solvent described in aftermentioned table 1 is mixed into ormal weight respectively, so as to prepare combination of precursors Thing.

In addition, in table 1, " D/P " represents the quality of quality/pigment of dispersant.

Also, in table 1, " viscosity (25 DEG C) (mPas) " on " precursor composition " column refers to the combination of precursors at 25 DEG C The viscosity of thing.

Also, in table 1, " 1 fluid temperature of process " on " treatment conditions " column refers to the liquid of the precursor composition in process 1 Temperature (fluid temperature for the precursor composition being preheated).

Also, in table 1, " 2 fluid temperature of process " on " treatment conditions " column refers to the liquid of the precursor composition in process 2 Temperature (fluid temperature for being carried out the precursor composition of decentralized processing).

Hereinafter, each component shown in table 1 is described in detail.

(making of pigment 1)

It is 110m by BET specific surface area²Titanium oxide TTO-51N (the trade names of/g：ISHIHARA SANGYO KAISHA, LTD. are manufactured) 120g, BET surface area 300m²The silicon dioxide granule AEROSIL300 (registration mark) 300/ of/g 30 (manufacture of EVONIK companies) 25g and dispersant Disperbyk190 (trade names：BYK Japan K.K. manufacture) 100g into Weighing is gone.Ion exchange water 71g is with the addition of in mixture to mixing these materials.Then, using KURABO manufactures MAZERSTAR KK-400W, the processing of 30 minutes is carried out with the rotating speed 1360rpm that revolves round the sun, rotation rotating speed 1047rpm, is thus obtained Uniform mixture aqueous solution.The aqueous solution is filled in quartz container, using small rotary kiln (Motoyama Co., Ltd. manufacture), it is heated to be in oxygen atmosphere gas after 920 DEG C, substitutes environmental gas with nitrogen, in identical temperature Under, make ammonia with 100mL/min flow through 5 it is small when, thus implement reduction-nitridation processing.After end, crushed and recycled with mortar Powder, obtained comprising Si atoms and be 85m in powdered specific surface area²The titanium black (pigment 1) of/g (includes titanium black track producing particle And Si atoms by dispersion).

Pigment 2：The TTO-51 (C) (titanium oxide) of ISHIHARA SANGYO KAISHA, LTD. manufactures

Pigment 3：The 13M-T of Mitsubishi Materials Corporation manufactures (titanium is black)

Pigment 4：The 12S of Mitsubishi Materials Corporation manufactures (titanium is black)

(synthesis of dispersant 1~2 and 4~7)

The dispersant 1~2 and 4~7 recorded below is synthesized with reference to the record of Japanese Unexamined Patent Publication 2013-249417 publications.

In addition, dispersant 1 is the compound (acid number that the x/y/z (mole %) in formula (D1) is 43/8/49：75mgKOH/ G), dispersant 4 is the compound (acid number that the x/y/z (mole %) in formula (D1) is 63/8/29：110mgKOH/g), dispersant 5 It is the compound (acid number that the x/y/z (mole %) in formula (D1) is 69/8/23：120mgKOH/g), dispersant 6 is in formula (D1) X/y/z (mole %) be 14/8/78 compound (acid number：25mgKOH/g), dispersant 7 is that the x/y/z in formula (D1) (rubs Your %) be 11/8/81 compound (acid number：20mgKOH/g).

[chemical formula 21]

(synthesis of dispersant 3)

The dispersant 3 recorded below is synthesized with reference to the record of Japanese Unexamined Patent Publication 2014-62221 publications.In addition, following knot Mole % of each repetitive unit of digital representation in structure formula.

[chemical formula 22]

PGMEA：Propylene glycol methyl ether acetate

PGME：Propylene glycol monomethyl ether

2 ＞ of ＜ processes 1 and process

By each embodiment and the precursor composition of comparative example, with as fluid temperature (the 1 liquid temperature of process described in table 1 Degree) mode carry out the pre-heat treatment, the precursor composition for being preheated to set point of temperature is supplied to ball mill dispersion machine (NPM- Pilot (Shinmaru Enterprises Corporation. manufactures)), and decentralized processing is implemented by ball mill, manufacture Go out pigment dispersion.In addition, the condition of ball mill is as follows.

The species of pearl：Zirconium oxide bead, diameter 0.05mm (YSZ, NIKKATO CORPORATION manufactures)

Main body peripheral speed：12m/s

Separator peripheral speed：13m/s

Pearl filling rate：65 volume %

Quantity delivered：90kg/ minutes

The treatment fluid scale of construction：15kg

Refrigerant category：NYBRINE Z-1 types (TOKYO RIKAKIKAI CO., LTD.)

In addition, in comparative example 1~3, implement the cold of precursor composition in a manner of as the fluid temperature described in table 1 But handle, the pre-heat treatment of precursor composition is not carried out in comparative example 7.

Also, during being handled by ball mill, become with the fluid temperature of precursor composition described in table 1 The mode of (2 fluid temperature of process) institute's temperature displaying function is adjusted, while implements decentralized processing.

In addition, the end on decentralized processing, carries out according to following benchmark.Processing time in each embodiment and comparative example It is shown in the lump in table 1.

In addition, the finish time of each embodiment and the decentralized processing of comparative example is identified below.

The midway of decentralized processing is being carried out, every the treatment fluid of 10 minutes sampling 0.063mL, is processing the sample mixed of sampling In 10g propylene glycol methyl ether acetate and formation determination sample, and by Micro Trac EX-150 (Nikkiso Co., Ltd. manufacture) and measure the average grain diameter (D90) of pigment.By every the change of the average grain diameter (D90) of the sample of sampling in 10 minutes It is melted into the terminal that decentralized processing is set at the time of continuing for continuous 4 times of the state of below 10nm.

The primary particle size evaluation ＞ of ＜ pigment

Each pigment dispersion is diluted to 500 times using propylene glycol methyl ether acetate, the pigment dispersion that will be diluted It is added dropwise on C film and making its drying, and passes through TEM (transmission electron microscope) (Hitachi High- Technologies Corporation. are manufactured) shape to the pigment particles (by dispersion) being contained in each pigment dispersion State observation photo is photographed.By obtained photo, the projected area of outer surface is obtained on 400 particles of pigment, and The diameter of a circle equivalent to the area is calculated, as its average value, has obtained the primary particle size of pigment.

The viscosimetric analysis ＞ of ＜ precursor compositions

Using viscosimeter RE-85 (TOKI SANGYO CO., LTD. manufacture), before having carried out each embodiment and comparative example The measure of the viscosity (25 DEG C) of body composition.

The measure ＞ of the average grain diameter of pigment in ＜ pigment dispersions

Using propylene glycol methyl ether acetate, pigment dispersion is diluted to 500 times, and pass through Micro Trac EX- 150 (manufactures of Nikkiso Co., Ltd.s) determine average grain diameter (D90).

The viscosimetric analysis ＞ of ＜ pigment dispersions

Will in each embodiment and comparative example obtained pigment dispersion at the specified temperature take care of the stipulated time after, Determine the thickening efficiency of viscosity.

Specifically, measure respectively through when before (keeping before) pigment dispersion viscosity and through when after (stipulated time protects After pipe) pigment dispersion viscosity, and obtained thickening efficiency according to the following formula.

In addition, as maintaining requirement, on taking care of the mode of 1 month at 23 DEG C and the mode of 1 month being taken care of at 7 DEG C Both modes are studied.

Thickening efficiency=(through when after pigment dispersion viscosity-through when before pigment dispersion viscosity)/(through when before The viscosity of pigment dispersion) × 100

＜ evaluates (precipitability experiment) ＞

Precipitability experiment in, obtain relative to the stipulated time through when before pigment dispersion it is solid component concentration, rule Fix time through when after pigment dispersion solid component concentration, the precipitability of particle is have rated as index.

Specifically, the measure on solid component concentration, the pigment dispersion of weighing 1g, adds in 165 DEG C of baking oven Hot 60 points of kinds, and the scattered object amount after heating is measured, calculate scattered object amount/heating after solid content [quality %]=heating Preceding scattered object amount × 100.At this time, in order to measure through when after solid component concentration, be using dispersion liquid is put into internal diameter 5cm, capacity be 1L glass container in the environment of 23 DEG C the quiet dispersion liquid for putting 9 months, from ullage gather 5g upper clear liquids untill 1cm depth have carried out the measure of solid content [quality %].

Then, rate of deposition is calculated according to the following formula.

Rate of deposition=(through when after solid content [quality %]-through when before solid content [quality %])/(through when Preceding solid content [quality %]) × 100

As shown in table 1, following situation is confirmed：Manufacturing method according to the invention, during the processing for the dispersion that makes paints Between shorten, moreover, the storage stability of obtained pigment dispersion is more excellent.Especially, precursor composition in process 2 It is more excellent to confirm effect more than 40 DEG C and less than in the case of 50 DEG C for fluid temperature.

Also, confirmed by the comparison of embodiment 2 and embodiment 10~13, dispersant acid number for 30~ Effect is more excellent in the case of 100mgKOH/g.

Also, confirmed by the comparison of embodiment 2 and embodiment 14~15, be less than the feelings of 55nm in the primary particle size of pigment Effect is more excellent under condition.

On the other hand, process 1 temperature be not be prescribed limit comparative example 1~7 in, desirable effect can not be obtained Fruit.

(embodiment 16)

In embodiment 5, pigment is changed to carbon black (manufacture of Degussa companies, trade name Color Black S170 Average primary particle diameter is 17nm), in addition, pigment dispersion has been obtained in an identical manner.It is same as Example 5 through carrying out It is evaluation as a result, having obtained result same as Example 5.Confirm also obtain on other above-mentioned pigment by the result Obtain the effect of the application.

(embodiment 17)

In embodiment 5, by pigment be changed to paratonere 254 (Ciba Specialty Chemicals Inc. manufacture, Trade name BK-CF average primary particle diameter 30nm), in addition, pigment dispersion has been obtained in an identical manner.Through carry out with The identical evaluation as a result, having obtained result same as Example 5 of embodiment 5.By the result confirm on it is above-mentioned other Pigment can also obtain the effect of the application.

(embodiment 18)

In embodiment 5, dispersant is changed into Disperbyk110 (trade name, BYK Japan KK. manufactures, acid Value 53mgKOH/g), in addition, pigment dispersion has been obtained in an identical manner.Through carrying out evaluation same as Example 5 As a result, having obtained result same as Example 5.Confirmed also obtain the application on other dispersants by the result Effect.

(embodiment 19)

In embodiment 1, improve solid component concentration and be adjusted, so that the viscosity (25 DEG C) of precursor composition becomes 17mPas, and carried out decentralized processing.Compared with Example 1, scattered processing time is longer, but can obtain roughly the same Evaluation result.

(embodiment 20)

In decentralized processing, the zirconium oxide bead of a diameter of 0.1mm is used, in addition, with side same as Example 1 Formula has carried out decentralized processing.In addition to the scattered time is longer than embodiment 1, the yield of pigment dispersion reduces.Through carrying out Various evaluations as a result, compared with Example 1, in addition to the solid component precipitates amount after 9 months becomes 3.0%, obtain Evaluation result same as Example 1 is arrived.

(comparative example 8)

In embodiment 1, improve solid component concentration and be adjusted, so that the viscosity (25 DEG C) of precursor composition becomes 23mPas, and carried out decentralized processing.Understand that the solid component precipitates amount after 9 months becomes 11.2%, preserve and stablize Property is poor.

(comparative example 9)

In embodiment 1, reduce solid component concentration and be adjusted, so that the viscosity (25 DEG C) of precursor composition becomes 2mPas, and carried out decentralized processing.When processing time is small more than 20, jitter time length.

(preparation of binder solution 1)

1- methoxy-2-propanol 159g are put into the three-neck flask of 1,000mL, are heated to 85 DEG C under nitrogen flowing.It is right This through 2 it is small when be added dropwise benzyl methacrylate 63.4g, methacrylic acid 72.3g, V-601 (Wako Pure Chemical Industries, Ltd. are manufactured) the 4.15g solution that is added to 1- methoxy-2-propanols 159g and prepares.After completion of dropwise addition, And then heat 5 it is small when make its reaction.

Then, stop heating, obtained comprising benzyl methacrylate/methacrylic acid (30/70mol ratios) copolymer Solution.

Then, in obtained copolymer solution, 120.0g is transferred in the three-neck flask of 300mL, adds methyl Glycidyl acrylate 16.6g, p methoxy phenol 0.16g is stirred makes its dissolving.After dissolving, triphenylphosphine is added 3.0g, is heated to be 100 DEG C and has carried out addition reaction.Confirm that glycidyl methacrylate has disappeared by gas chromatography Lose, and stopped heating.1- methoxy-2-propanol 184g are added in reaction solution, weight average molecular weight 12,000 is prepared and (passes through The polystyrene scaled value that GPC method is obtained), acid number 35mgKOH/g, the binder solution 1 that solid constituent is 30 mass %.

(preparation of solidification compound A)

The component of following compositions is mixed with mixer, and is filtered by filter, so as to prepare curability group Compound A.In addition, following " part " refers to mass parts.

(composition)

Just the solidification compound A after liquid is adjusted to be put into the solution cup of spray equipment, under following coating and heating condition It is coated on glass substrate, and then, implement curing process and form cured film 1.

Spray equipment：GSI Creos Corporation manufacture PS-268

Spray atmospheric pressure conditions：3,000cc/ minutes

Coating weight：0.2cc/ minutes

Nozzle diameter：0.4mm

The discharge opening of spraying is set with glass substrate coated face with vertical direction.

The discharge opening of spraying and the distance of glass substrate：3cm

The spray angle * of spraying：90 degree

(angles of the * from the discharge opening of spraying to the normal of glass substrate both direction to the left and right)

Implement spraying untill the average film thickness of coated portion becomes 2.5 μm, after coating, by hot plate 120 It heated at DEG C 2 minutes.

(evaluation that spraying blocks)

On solidification compound A, sprayed under the following conditions, blocking is evaluated.

Spray equipment：The PS-268 of GSI Creos Corporation manufactures

The solidification compound A evaluated is put into the solution cup of spray equipment, at 25 DEG C place 96 it is small when it Afterwards, it is coated by above-mentioned spray equipment, when being evaluated as not blocking, can without blocking be carried out under the following conditions Coating.

Spray atmospheric pressure conditions：3,000cc/ minutes

Coating weight：0.2cc/ minutes

Nozzle diameter：0.4mm

(measure of surface reflectivity)

The spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation., in ripple Surface reflectivity (5 degree of incident angle) is measured to above-mentioned obtained cured film 1 under long 450hm, reflectivity is determined with %.

Especially, in the case of solid-state imager purposes, if as less than 4% surface reflectivity, it is judged as having There is practicality.It is obtained result below.

Surface reflectivity：0.38%

(light-proofness)

The spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation., to upper The transmissivity under the obtained measure wavelength of cured film 1 550nm is stated, and is set to the index of shading rate.Especially, in solid-state image pickup member In the case of part purposes, if as less than 1% transmissivity, it is judged as with practicality.It is obtained result below.

Transmissivity：0.004%

As can be known from these results, the spraying adaptive of cured film of the invention is good and light-proofness and antireflection property are excellent.

Also, according to this as a result, the light-proofness of the cured film manufactured due to the use of the pigment dispersion of the application, counnter attack Penetrate excellent performance, thus can preferably using in the solid-state imager, colour filter and black matrix for possessing light shield layer, and then, Preferably using in the manufacture for the image display device for possessing the part.

Symbol description

2nd, 20,30,40- solid-state imaging devices, 3-CMOS sensors, 4- circuit substrates, 5- ceramic substrates, 5a- openings, 5b- internal faces, 6-IR edge filters, 7- photographic lens, 8- lens carriers, 9- holding cylinder, 10,11,21,31,41- photomasks (light shield layer), 12- black layers, 14- clads, 100- substrates, 200- tanks, 300- pipe arrangements, 500- ball mill dispersion machines.

Claims

1. a kind of manufacture method of pigment dispersion, it has：

Process 1, will include the precursor composition that the viscosity at pigment, dispersant and organic solvent and 25 DEG C is 3~20mPas Preheated；And

Process 2,40 DEG C are remained less than 60 DEG C by the fluid temperature for the precursor composition being preheated, and utilize pearl Grinding machine implements decentralized processing to the precursor composition.

2. the manufacture method of pigment dispersion according to claim 1, wherein,

The primary particle size of the pigment is less than 55nm.

3. the manufacture method of pigment dispersion according to claim 1 or 2, wherein,

The acid number of the dispersant is 30~100mgKOH/g.

4. the manufacture method of pigment dispersion according to any one of claim 1 to 3, wherein,

The pearl of a diameter of below 0.05mm is used in the ball mill.

5. the manufacture method of pigment dispersion according to any one of claim 1 to 4, wherein,

In the process 1, the fluid temperature of the precursor composition is preheated as 40~60 DEG C.

6. the manufacture method of pigment dispersion according to any one of claim 1 to 5, wherein,

The fluid temperature of the precursor composition in the process 2 is remained more than 40 DEG C and less than 57 DEG C.

7. a kind of manufacture method of solidification compound, it has：

The process that pigment dispersion is obtained by the manufacture method any one of claim 1 to 6；And

Pigment dispersion, polymerization initiator, polymerizable compound and alkali soluble resins it will be carried out as obtained from the process It is obtained by mixing the process of solidification compound.

8. a kind of manufacture method of cured film, it has：

The process that pigment dispersion is obtained by the manufacture method any one of claim 1 to 6；

Pigment dispersion, polymerization initiator, polymerizable compound and alkali soluble resins it will be carried out as obtained from the process It is obtained by mixing the process of solidification compound；And

Make to cure to obtain the process of cured film by solidification compound obtained from the process.

9. a kind of manufacture method for the solid-state imager for possessing cured film, it has：

10. a kind of manufacture method for the colour filter for possessing cured film, it has：

11. a kind of manufacture method for the image display device for possessing cured film, it has：