WO2022138027A1 - 光硬化性赤色樹脂組成物、表示装置、及び有機発光素子と外光反射防止膜の積層体の製造方法 - Google Patents
光硬化性赤色樹脂組成物、表示装置、及び有機発光素子と外光反射防止膜の積層体の製造方法 Download PDFInfo
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to a photocurable red resin composition, a display device containing a cured product of the photocurable red resin composition, an organic light emitting element using the photocurable red resin composition, and prevention of external light reflection.
- the present invention relates to a method for producing a laminated body of a film.
- Such an organic light emitting element is provided with a circular polarizing plate as an antireflection film in order to prevent deterioration of visibility due to reflection of external light, especially in mobile devices that are expected to be used outdoors.
- this circularly polarizing plate cuts not only external light but also light emitted by the organic light emitting element, the efficiency of light utilization is greatly reduced.
- the circularly polarizing plate has a hard property, it is disadvantageous in making it flexible in that the flexibility is reduced. Therefore, it has been desired to develop a display device using an organic light emitting element having good visibility outdoors without using a circular polarizing plate.
- the red photosensitive resin composition for forming a pixel which comprises a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant contains a red pigment and a black pigment, and is red photosensitive.
- the red photosensitive resin composition is a resin composition having a spectral transmittance of 20% or less at a wavelength of 430 to 590 nm and a spectrum at a wavelength of 635 to 780 nm when formed into a cured film having a thickness of 3 ⁇ m.
- a red photosensitive resin composition having a transmittance of 70% or more and less than 90% is disclosed.
- the color filter that replaces the polarizing plate of Patent Document 1 is formed on a glass substrate. Therefore, there is a further problem in manufacturing a display device having improved thinness and flexibility.
- the present invention has been made in view of the above circumstances, and provides a photocurable red resin composition capable of suppressing external light reflection and producing an organic light emitting display device having a thin film and improved flexibility.
- the purpose Further, the present invention provides a display device containing a cured product of the photocurable red resin composition, which can suppress external light reflection and has improved flexibility with a thin film, and the photocurable red resin composition. It is an object of the present invention to provide a method for manufacturing a laminate of an organic light emitting element and an external light antireflection film used.
- the photocurable red resin composition according to the present invention is a photocurable red resin composition used for a cured film formed on an organic light emitting device.
- the photocurable red resin composition contains a coloring material, a photopolymerizable compound, and a photoinitiator.
- the coloring material includes a red material and a black material.
- the display device according to the present invention has a cured film of the photocurable red resin composition according to the present invention on the organic light emitting element.
- the method for manufacturing a laminate of an organic light emitting device and an external light antireflection film according to the present invention is as follows.
- the step of irradiating the coating film with light A post-baking step of heating the film after the light irradiation, and By including the step of developing the film after the light irradiation, It has a step of forming a cured film of the photocurable red resin composition according to the present invention on an organic light emitting element.
- the present invention it is possible to provide a photocurable red resin composition capable of suppressing external light reflection and producing an organic light emitting display device having a thin film and improved flexibility. Further, the present invention provides a display device containing a cured product of the photocurable red resin composition, which can suppress external light reflection and has improved flexibility with a thin film, and the photocurable red resin composition. It is possible to provide a method for manufacturing a laminate of the organic light emitting element and the external light antireflection film used.
- FIG. 1 is a schematic cross-sectional view showing an example of a display device provided with an organic light emitting element according to the present invention.
- the phrase “upper” or “lower” may be used for explanation, but the vertical direction may be reversed.
- a configuration such as a member or a region is "above (or below)” another configuration such as another member or another region, unless otherwise specified.
- This includes not only the case of being directly above (or directly below) the other configuration, but also the case of being above (or below) the other configuration, that is, another configuration in between above (or below) the other configuration.
- the light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams.
- (meth) acryloyl represents each of acryloyl and methacrylic
- (meth) acrylic represents each of acrylic and methacrylic
- (meth) acrylate represents each of acrylate and methacrylate.
- "-" indicating a numerical range is used in the sense that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
- the photocurable red resin composition according to the present invention is a photocurable red resin composition used for a cured film formed on an organic light emitting element.
- the photocurable red resin composition contains a coloring material, a photopolymerizable compound, and a photoinitiator.
- the coloring material includes a red material and a black material.
- the photocurable red resin composition according to the present invention since the coloring material contains a red material and a black material, the cured film of the photocurable red resin composition effectively reduces the transmittance of the film. It is possible to suppress external light reflection as an alternative to the polarizing plate. Further, the photocurable red resin composition according to the present invention is characterized in that it is used for a cured film formed on an organic light emitting device. That is, the photocurable red resin composition according to the present invention is used for a cured film directly formed on an element substrate provided with an organic light emitting element.
- the photocurable red resin composition according to the present invention is a photocurable red resin composition used for a cured film formed adjacent to or via at least one layer on an organic light emitting device, a substrate such as a glass substrate is used. It is possible to manufacture a display device that is thinner and more flexible than a display device in which the external color filter formed above is attached to an organic light emitting element.
- the photocurable red resin composition according to the present invention contains at least a coloring material, a photopolymerizable compound, and a photoinitiator, and further contains other components as long as the effects of the present invention are not impaired. It may be contained.
- each component of the photocurable red resin composition according to the present invention will be described in detail in order.
- the coloring material is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, and dyes are used. Two or more kinds of salt-forming compounds and the like can be mixed and used, but it is characterized by containing a red material and a black material.
- organic pigments are preferably used because they have high color-developing properties and high heat resistance.
- examples of the organic pigment include compounds classified as Pigments in the color index (CI; The Society of Dyers and Colorists), specifically, the following color index (CI). .) Examples include those with numbers.
- red material for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243,
- R 61 and R 62 are independently 4-chlorophenyl groups or 4-bromophenyl groups, respectively.
- At least one selected from Pigment Red 177, Pigment Red 254, and Pigment Red 291 is preferable because the rise of the transmission spectrum is steep and the effect of suppressing external light reflection is easily improved.
- Pigment Red 177, Pigment Red 254, and Pigment Red 291 are organic light emitting elements to be combined to perform external light reflection because the rising wavelengths of the transmission spectra are slightly different from the long wavelength side to the short wavelength side. Considering the spectrum of the red light emitting layer, it is preferable to appropriately select and use one type alone or two or more types in combination.
- black material examples include inorganic pigments such as carbon black and titanium black, organic pigments such as cyanine black, and C.I. I. It may be at least one selected from Pigment Black 1, 7, and the like.
- the black material preferably contains carbon black because it has good storage stability and easily improves the effect of suppressing external light reflection.
- the carbon black is not particularly limited as long as it is a pigment having a light-shielding property, and known carbon black can be used. Specific examples of the carbon black of the black pigment include channel black, furnace black, thermal black, and lamp black.
- coloring material other coloring materials may be further used from the viewpoint of adjusting the effect of suppressing external light reflection.
- examples of other coloring materials include green materials, blue materials, purple materials, yellow materials, orange materials, and the like.
- the color material contains at least one of a green material and a blue material as other color materials, it is easy to satisfactorily adjust the transmission spectral shape of the red material, and the effect of suppressing external light reflection is improved. It is preferable because it is easy to make it.
- Examples of the green material include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like.
- Examples of the blue material include C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and the like.
- the purple material for example, C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like.
- Examples of the yellow material include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and C.I. I.
- Examples thereof include derivative pigments of Pigment Yellow 150.
- Examples of the orange material include C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73 and the like.
- the content ratio of the red material, the black material, and other color materials that may be contained as needed in the present invention is such that a cured film is formed with a film thickness of 3.0 ⁇ m by the photocurable red resin composition. It is preferable to adjust the spectral transmittance so that the spectral transmittance at the wavelength of 430 nm to 580 nm is 15.0% or less and the spectral transmittance at the wavelength of 610 nm to 630 nm is 50.0% or more and 90.0% or less. ..
- the spectral transmittance at a wavelength of 430 nm to 580 nm is 15.0% or less, the decrease in red color purity is suppressed and the decrease in color purity from the light emitting element is suppressed. Is also easy to suppress.
- the spectral transmittance at a wavelength of 430 nm to 580 nm may be 10.0% or less, and may be 8.0% or less.
- the spectral transmittance at a wavelength of 610 nm to 630 nm is 50.0% or more, it is easy to suppress a decrease in brightness and poor visibility of the display device.
- the spectral transmittance at a wavelength of 610 nm to 630 nm may be 60.0% or more, and may be 70.0% or more.
- the spectral transmittance at a wavelength of 610 nm to 630 nm is 90.0% or less, the effect of suppressing external light reflection can be easily obtained.
- the spectral transmittance at a wavelength of 610 nm to 630 nm may be 80.0% or less, and may be 70.0% or less.
- the content of the red material may be usually 50% by mass or more and 99.9% by mass or less, preferably 70% by mass or more, based on the total amount of the coloring material. , More preferably 80% by mass or more, further preferably 90% by mass or more, preferably 99.6% by mass or less, and more preferably 99.0% by mass or less. good.
- the content of the black material may be usually 0.1% by mass or more and 20% by mass or less, preferably 0.4% by mass or more, based on the total amount of the coloring material. It may be more preferably 1.0% by mass or more, preferably 10% by mass or less, and more preferably 5% by mass or less.
- the total content of the red material and the black material may be usually 50% by mass or more, preferably 70% by mass or more, based on the total amount of the coloring material. It may be preferably 90% by mass or more, and may be 100% by mass, but when other coloring materials are contained, it may be 99% by mass or less, and may be 90% by mass or less.
- the total content of the other coloring materials may be 0% by mass, may be 1% by mass or more, and may be 10% by mass or more with respect to the total amount of the coloring materials. On the other hand, it may be usually 50% by mass or less, preferably 30% by mass or less.
- the total content may be usually 0.1% by mass or more and 30% by mass or less, preferably 1% by mass or more. It may be better, more preferably 10% by mass or more, preferably 30% by mass or less, and more preferably 20% by mass or less.
- the average primary particle size of the coloring material used in the present invention when a cured film is used, reflection of external light can be suppressed, and desired light from a light emitting element is transmitted to suppress a decrease in brightness of the display device. It may be as long as it is possible, and it is not particularly limited, and it varies depending on the type of the color material used, but it is preferably in the range of 10 nm to 100 nm, and more preferably 15 nm to 60 nm. When the average primary particle size of the coloring material is within the above range, the display device provided with the cured film produced by using the photocurable red resin composition according to the present invention can suppress the reflection of external light and is highly high. It can be contrasting and of high quality.
- the average dispersed particle size of the coloring material in the photocurable red resin composition varies depending on the type of the coloring material used, but is preferably in the range of 10 nm to 100 nm, and preferably in the range of 15 nm to 60 nm. Is more preferable.
- the average dispersed particle size of the coloring material in the photocurable red resin composition is at least the dispersed particle size of the coloring material particles dispersed in the dispersion medium containing a solvent, and is measured by a laser light scattering particle size distribution meter. Is to be done.
- the solvent used in the photocurable red resin composition is used, and the photocurable red resin composition is appropriately adjusted to a concentration that can be measured by the laser light scattering particle size distribution meter. It can be diluted (for example, 1000 times) and measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). ..
- the average distributed particle size here is the volume average particle size.
- the coloring material used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Further, a commercially available coloring material may be used after being miniaturized.
- the content of the coloring material is not particularly limited.
- the content of the coloring material is, for example, preferably 3% by mass to 65% by mass, more preferably 4% by mass or more, based on the total solid content of the photocurable red resin composition from the viewpoint of dispersibility and dispersion stability. It is in the range of 60% by mass.
- the cured film when the photocurable red resin composition is applied to a predetermined film thickness usually 1.0 ⁇ m to 5.0 ⁇ m, for example, 3.0 ⁇ m
- a predetermined film thickness usually 1.0 ⁇ m to 5.0 ⁇ m, for example, 3.0 ⁇ m
- the total content of the coloring material is preferably 15% by mass to 65% by mass, more preferably, with respect to the total solid content of the photocurable red resin composition. Is in the range of 25% by mass to 60% by mass.
- the solid content is all other than the solvent described later, and includes monomers and the like dissolved in the solvent.
- Examples of the photopolymerizable compound used in the photocurable red resin composition include compounds having a photopolymerizable group in the molecule.
- the photopolymerizable group may be any one that can be polymerized by a photoinitiator, and is not particularly limited, and examples thereof include an ethylenically unsaturated double bond, for example, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, or the like. Can be mentioned.
- an acryloyl group or a methacryloyl group is preferably used from the viewpoint of ultraviolet curability.
- the photopolymerizable compound preferably contains a compound having two or more photopolymerizable groups in one molecule from the viewpoint of curability, and contains a compound having three or more photopolymerizable groups in one molecule. It is more preferable to do so.
- a compound having two or more ethylenically unsaturated double bonds is preferably used, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.
- a polyfunctional (meth) acrylate a conventionally known one may be appropriately selected and used. Specific examples include those described in Japanese Patent Application Laid-Open No. 2013-029832.
- polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. Further, when the photocurable red resin composition of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional (meth) acrylate has three polymerizable double bonds (trifunctional). ) And above are preferable, and poly (meth) acrylates of trivalent or higher polyhydric alcohols and dicarboxylic acid-modified products thereof are preferable.
- a succinic acid-modified product of meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable.
- the content of the photopolymerizable compound used in the photocurable red resin composition is not particularly limited, but is preferably, for example, 5% by mass to 60% by mass with respect to the total solid content of the photocurable red resin composition. %, More preferably in the range of 10% by mass to 40% by mass.
- the content of the photopolymerizable compound is at least the above lower limit value, photocuring proceeds sufficiently, and it is easy to suppress elution of the exposed portion during development. Further, when the content of the photopolymerizable compound is not more than the above upper limit value, the alkali developability tends to be sufficient.
- photoinitiator used in the photocurable red resin composition of the present invention one or a combination of two or more of various conventionally known photoinitiators can be used.
- the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, ⁇ -aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, and thioxanthone. , Oxime esters and the like.
- a conventionally known photoinitiator can be used, and examples thereof include the photoinitiator described in International Publication No. 2018/062105.
- Examples of the oxime ester-based photoinitiator used in the present invention include 1,2-octadion-1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), etanone, 1-[. 9-Ethyl-6- (2-Methylbenzoyl) -9H-Carbazole-3-yl]-, 1- (o-Acetyloxime), JP-A-2000-80068, JP-A-2001-233842, Special Table Among the oxime ester-based photoinitiators described in JP-A-2010-527339, JP-A-2010-527338, JP-A-2013-041153, International Publication No. 2015/152153, JP-A-2010-256891, etc. It can be selected as appropriate.
- the heat resistance of the organic light emitting device is low, so that the heating in the manufacturing process is preferably a low temperature heat treatment of 130 ° C. or lower, further 100 ° C. or lower. It is said that.
- a heat treatment of about 230 ° C. is performed on a glass substrate to cure the cured film, whereas in a heat treatment of 130 ° C. or lower, the curing of the cured film by heat is difficult to proceed. That is, the cured film produced by low-temperature heat treatment tends to have insufficient substrate adhesion and solvent resistance.
- the photoinitiator is a compound represented by the following general formula (A) and the following general, from the viewpoint that the substrate adhesion and solvent resistance of the cured film are improved even by low-temperature heat treatment. It is preferable to contain at least one compound represented by the formula (B).
- R 1 and R 2 independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN, respectively.
- R 11 , R 12 and R 13 independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aryl alkyl group having 2 to 20 carbon atoms.
- R 11 , R 12 and R 13 Represents the heterocyclic group of
- the hydrogen atoms of the groups represented by R 11 , R 12 and R 13 are further R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR. 22 -OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , hydroxyl group, nitro group, CN, or may be substituted with a halogen atom.
- Each of R 21 , R 22 and R 23 independently has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aryl alkyl group having 2 to 20 carbon atoms.
- the hydrogen atom of the group represented by R 21 , R 22 and R 23 may be further substituted with a hydroxyl group, a nitro group, a CN, a halogen atom, or a carboxy group.
- the alkylene moieties of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 are -O-, -S-, -COO-, -OCO-, -NR 24- , -NR. It may contain 1 to 5 of 24 CO-, -NR 24 COO- , -OCONR 24- , -SCO-, -COS-, -OCS- or -CSO- under the condition that oxygen atoms are not adjacent to each other.
- R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
- the alkyl moieties of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 may have branched side chains or may be cyclic alkyl.
- R 3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl alkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
- the alkyl moiety of the represented group may have a branched side chain or a cyclic alkyl, and R 3 and R 7 and R 3 and R 8 together form a ring, respectively.
- R 3 May be The hydrogen atoms of the group represented by R 3 are further R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , NR. 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , hydroxyl group, nitro group, CN, or may be substituted with a halogen atom.
- R 4 , R 5 , R 6 and R 7 are independently R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 . , COSR 14 , CSOR 11 , hydroxylated, CN or halogen atom, R 4 and R 5 , R 5 and R 6 , and R 6 and R 7 may be combined to form a ring, respectively.
- R 14 , R 15 and R 16 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl moiety of the group represented by R 14 , R 15 and R 16 may have a branch side chain.
- R 8 is R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSO R 11 , hydroxyl group, CN or halogen atom.
- k represents 0 or 1.
- X 1 , X 3 and X 6 independently represent R 41 , OR 41 , COR 41 , SR 41 , CONR 42 R 43 or CN, respectively, and X 2 has 1 to 1 carbon atoms.
- R 41 , R 42 and R 43 independently has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or 2 to 20 carbon atoms.
- R 41 , R 42 and R 43 , and X 2 are further R 51 , OR 51 , COR 51 , SR 51 , NR 52 R 53 , CONR 52 R 53 , -NR 52 -OR. 53 , -NCOR 52 -OCOR 53 , NR 52 COR 51 , OCOR 51 , COOR 51 , SCOR 51 , OCSR 51 , COSR 51 , CSOR 51 , hydroxyl group, nitro group, CN, or halogen atom may be substituted.
- Each of R 51 , R 52 and R 53 independently has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or 2 to 20 carbon atoms. Represents the heterocyclic group of The hydrogen atom of the group represented by R 51 , R 52 and R 53 may be further substituted with a hydroxyl group, a nitro group, a CN, a halogen atom, or a carboxy group.
- the alkylene moiety of the group represented by R 41 , R 42 , R 43 , X 2 , R 51 , R 52 and R 53 is -O-, -S-, -COO-, -OCO-, -NR 54- . , -NR 54 CO-, -NR 54 COO-, -OCONR 54- , -SCO-, -COS-, -OCS- or -CSO- even if it contains 1 to 5 oxygen atoms.
- R 54 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
- the alkyl moiety of the group represented by R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 may have a branched side chain or may be cyclic alkyl.
- a and b are independently integers of 0 to 3.
- the oxime ester compound represented by the general formula (A) has geometric isomers due to double bonds of oxime, but these are not distinguished. That is, in the present specification, the compound represented by the general formula (A), the compound represented by the following general formula (A') which is a preferable form of the compound described later, and the exemplary compound thereof are a mixture of both or either. It represents one of them, and is not limited to the structure showing an isomer.
- the number of carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 , R 23 and R 24 in the above general formula (A) is 1 to 20.
- Examples of the alkyl group of the above include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-.
- Examples thereof include octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.
- Examples of the aryl group having 6 to 30 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in the above general formula (A) include phenyl. , Trill, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl and the like substituted with one or more of the above alkyl groups.
- Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in the above general formula (A) include, for example. Examples thereof include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and the like.
- Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , and R 24 in the above general formula (A) include: 5 ⁇ 7-membered heterocycles can be mentioned.
- the ring in the above general formula ( A) that can be formed by combining R4 and R5 , R5 and R6 and R6 and R7 , and R3 and R7 and R3 and R8 is as a ring.
- a 5- to 7-membered ring such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, or a lactam ring is preferable.
- R 13 , R 21 , R 22 and R 23 may be substituted with halogen atoms such as fluorine, chlorine, bromine and iodine.
- the alkylene moiety of the group represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 is -O-, -S-, -COO-, -OCO. -, -NR 24- , -NR 24 CO-, -NR 24 COO- , -OCONR 24- , -SCO-, -COS-, -OCS- or -CSO-under the condition that oxygen atoms are not adjacent to each other.
- Five or more divalent groups may be contained at this time, and one or more divalent groups may be contained, and two or more groups may be continuously contained in the case of a group that can be continuously contained. ..
- the alkyl (alkylene) portion of the group represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 has a branch side chain. It may be cyclic alkyl or cyclic alkyl.
- the compound represented by the aromatic ring in which R3 may be condensed or the compound represented by the following general formula (A') has high sensitivity and can be produced. Is preferable because it is easy to use.
- R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 and k are the same as the above general formula (A), and are R 31 , R 32 , R 33 , R 34 .
- R 35 are independently R 11 , OR 11 , SR 11 , COR 11 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , COR 11 , hydroxyl group, respectively.
- R 31 and R 32 , R 32 and R 33 , R 33 and R 34 , and R 34 and R 35 together are R 4 and R 5 , R 5 and R 6 and R 6 .
- R 7 and R 3 and R 7 and R 3 and R 8 can be formed together as an example of a ring similar to that mentioned above.
- R 1 is an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms
- R 11 is an aryl group having 6 to 12 carbon atoms and 1 carbon atom.
- Those having an alkyl group of to 8 are preferable because they have high solvent solubility, and those having a methyl group, an ethyl group or a phenyl group as R2 are preferable because they have high reactivity, and those having a hydrogen atom or cyano as R4 to R7 are preferable.
- R 31 to R 35 is a nitro group, CN or a halogen atom
- R 33 is a nitro group, CN or a halogen atom
- Preferred specific examples of the compound represented by the above general formula (A) include, for example, the following compounds. Further, the compound No. 1 described in International Publication No. 2015/152153. 1 to No. 212 is mentioned.
- the solvent, reaction temperature, reaction time, purification method and the like are appropriately selected according to the material to be used. Can be synthesized. Further, a commercially available product may be appropriately obtained and used.
- the oxime ester compound represented by the general formula (B) also has geometric isomers due to double bonds of oxime, but these are not distinguished. That is, in the present specification, the compound represented by the general formula (B) and the exemplary compound thereof represent a mixture of both or one of them, and are not limited to the structure showing an isomer.
- the alkyl group having 1 to 20 carbon atoms represented by X 2 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 in the general formula (B) is the above general formula. Examples thereof include the same as the alkyl group having 1 to 20 carbon atoms in (A).
- the aryl group having 6 to 30 carbon atoms represented by X2 , R41 , R42 , R43 , R51 , R52 , R53 and R54 in the general formula (B) is the general formula. The same as the aryl group having 6 to 30 carbon atoms in (A) can be mentioned.
- the arylalkyl group having 7 to 30 carbon atoms represented by X2 , R41 , R42 , R43 , R51 , R52 , R53 and R54 in the general formula (B) is generally described above. Examples thereof include arylalkyl groups having 7 to 30 carbon atoms in the formula (A).
- the heterocyclic group having 2 to 20 carbon atoms represented by X2, R41 , R42 , R43 , R51 , R52 , R53 and R54 in the above general formula (B) is the above-mentioned general.
- the same as the heterocyclic group having 2 to 20 carbon atoms in the formula (A) can be mentioned.
- the halogen atom in the general formula (B) the same thing as the halogen atom in the general formula (A) can be mentioned.
- the alkylene moiety of the group represented by R 41 , R 42 , R 43 , X 2 , R 51 , R 52 and R 53 is -O-, -S-, -COO-.
- -OCO-, -NR 54-, -NR 54 CO-, -NR 54 COO-, -OCONR 54- , -SCO-, -COS-, -OCS- or -CSO- 1 to 5 groups may be contained in the above, and the divalent group contained at this time may be one kind or two or more kinds of groups, and in the case of a group that can be continuously contained, two or more consecutively are contained. You may.
- X 1 is more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, from the viewpoint of sensitivity, solubility and compatibility.
- Alkyl groups having 1 to 10 carbon atoms such as t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and 2-ethylhexyl group, cyclopentyl group and cyclohexyl group having 5 carbon atoms.
- Cyclic alkyl groups may have up to 10 side chains, or methoxymethyl groups, ethoxymethyl groups, ethoxyethyl groups, 2- (1-methoxypropyl) groups, 2- (1-ethoxypropyl) groups, etc. It is an alkyl group having one ether bond in a methylene chain having 2 to 10 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a 2-ethylhexyl group.
- X 2 , X 3 and X 6 are independently, particularly preferably methyl group, ethyl group, n-propyl group and isopropyl from the viewpoint of sensitivity, solubility and compatibility.
- Alkyl group having 1 to 6 carbon atoms such as group, n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group and n-hexyl group, cyclopentyl group, cyclohexyl group and the like.
- An alkyl group having 2 to 6 and one ether bond in the methylene chain more preferably an alkyl group having 1 to 6 carbon atoms or one ether bond in a methylene chain having 2 to 6 carbon atoms. It is an alkyl group having.
- X 3 and X 6 are each independently an alkyl group having 1 to 6 carbon atoms, more preferably from the viewpoint of sensitivity, solubility and compatibility.
- X 2 is an alkyl group having one ether bond in a methylene chain having 2 to 6 carbon atoms, more preferably from the viewpoint of sensitivity, solubility and compatibility.
- X4 and X5 are independently, and particularly preferably hydrogen, or a methyl group, an ethyl group, or an n-propyl group, from the viewpoint of sensitivity, solubility, and compatibility. It is an alkyl group having 1 to 6 carbon atoms such as an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group and an n-hexyl group.
- Preferred specific examples of the compound represented by the above general formula (B) include, for example, the following compounds.
- the total content of the photoinitiator used in the photocurable red resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, but is based on the total solid content of the photocurable red resin composition. It is preferably in the range of 0.1% by mass to 15.0% by mass, and more preferably 1.0% by mass to 10.0% by mass. When this content is at least the above lower limit, photocuring is likely to proceed sufficiently, and solvent resistance and substrate adhesion are likely to be good. On the other hand, when it is at least the above upper limit, line width shift is suppressed and high definition is achieved. It is easy to form a simple pattern.
- the total content of at least one of the compound represented by the general formula (A) and the compound represented by the general formula (B) is a cured film having good substrate adhesion and solvent resistance even in low temperature heat treatment. Is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, still more preferably 70.0% by mass or more, and 100% by mass, based on the total amount of the photoinitiator. May be.
- the photocurable red resin composition according to the present invention contains a coloring material, a photopolymerizable compound, and a photoinitiator, and by using a liquid photopolymerizable compound, it does not contain a solvent. However, it is possible to form a coating film, and it is possible to form a patterned colored layer by using a means for applying the coating in a pattern, for example, an inkjet method.
- the photocurable red resin composition according to the present invention may be a photocurable red resin composition further containing an alkali-soluble resin and a solvent and having alkali developability.
- the alkali-soluble resin used in the present invention has an acidic group, acts as a binder resin, and is soluble in the alkaline developer used for pattern formation, and can be appropriately selected and used. can.
- the alkali-soluble resin can be referred to as having an acid value of 40 mgKOH / g or more as a guide.
- alkali-soluble resin a conventionally known alkali-soluble resin can be appropriately selected and used.
- the alkali-soluble resin described in International Publication No. 2016/1049493 can be appropriately selected and used.
- the preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, specifically, a (meth) acrylic copolymer having a carboxy group and a styrene- (meth) acrylic resin having a carboxy group.
- Examples thereof include (meth) acrylic resins such as copolymers and epoxy (meth) acrylate resins having a carboxy group, such as (meth) acrylic copolymers having a carboxy group and styrene- (meth) acrylics having a carboxy group.
- a (meth) acrylic resin such as a system copolymer is preferably used.
- those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved.
- the alkali-soluble resin used in the photocurable red resin composition may be used alone or in combination of two or more.
- the content of the alkali-soluble resin is not particularly limited, but is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the photocurable red resin composition. Is within the range of. When the content of the alkali-soluble resin is at least the above lower limit value, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at least the above upper limit value, film roughness and pattern chipping occur during development. Can be suppressed.
- the solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the photocurable red resin composition and can dissolve or disperse them.
- the solvent can be used alone or in combination of two or more.
- Specific examples of the solvent include, for example, alcohol-based solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol-based solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl but
- glycol ether acetate-based solvents examples include butyl carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents.
- the solvent used in the present invention propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, etc.
- BCA butyl carbitol acetate
- 3-methoxy-3-methyl-1-butyl acetate ethyl ethoxypropionate
- ethyl lactate etc.
- one or more selected from the group consisting of 3-methoxybutyl acetate is preferable from the viewpoint of solubility of other components and application suitability.
- the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy.
- the content of the solvent is usually preferably in the range of 55% by mass to 95% by mass, more preferably 65% by mass to 88% by mass, based on the total amount of the photocurable red resin composition containing the solvent. ..
- the content of the solvent is within the above range, the coating property can be made excellent.
- a dispersant may be further contained from the viewpoint of the color material dispersibility and the color material dispersion stability.
- the dispersant can be appropriately selected and used from conventionally known dispersants.
- a cationic, anionic, nonionic, amphoteric, silicone-based, or fluorine-based surfactant can be used.
- the surfactants the polymer dispersant is preferable because it can be dispersed uniformly and finely.
- polymer dispersant examples include (meth) acrylate copolymerization system dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (poly (lower alkyleneimine)). Amides obtained by reaction with free carboxy group-containing polyesters and their bases); Polyallylamine derivatives (polyallylamine and polyesters with free carboxy groups, polyamides or cocondensates of esters and amides (polyester amides)) Reaction products obtained by reacting with one or more compounds selected from the above compounds) and the like.
- acrylate copolymerization system dispersants examples include (meth) acrylate copolymerization system dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (poly (lower alkyleneimine)). Amides obtained by reaction with free
- a (meth) acrylate copolymer system dispersant as the dispersant because the solvent resistance tends to be good even in the low temperature heat treatment.
- the (meth) acrylate copolymer system dispersant comprises the photopolymerizable compound, the compound represented by the general formula (A), and at least one photoinitiator of the compound represented by the general formula (B). Since the compatibility is good, the initiator is likely to be uniformly present in the colored layer, and the colored layer is uniformly cured to reduce unreacted components and reduce the internal stress of the colored layer. It is presumed that the change in the colored layer when immersed is small.
- the (meth) acrylate copolymer system dispersant refers to a dispersant which is a copolymer and contains at least a structural unit derived from (meth) acrylate.
- the (meth) acrylate copolymer system dispersant is preferably a copolymer containing a structural unit that functions as a coloring material adsorption site and a structural unit that functions as a solvent-affinitive site, and functions as a solvent-friendly site. It is preferable that the structural unit to be subjected to contains at least a structural unit derived from (meth) acrylate.
- Examples of the structural unit that functions as the color material adsorption site include a structural unit derived from an ethylenically unsaturated monomer that can be copolymerized with a structural unit derived from (meth) acrylate.
- the coloring material adsorption site may be a structural unit derived from an acidic group-containing ethylenically unsaturated monomer or a basic unit derived from a basic group-containing ethylenically unsaturated monomer.
- the structural unit derived from the basic group-containing ethylenically unsaturated monomer the structural unit represented by the following general formula (I) is preferable because it is excellent in dispersibility.
- R 71 is a hydrogen atom or a methyl group
- a 1 is a divalent linking group
- R 72 and R 73 are hydrocarbons which may independently contain a hydrogen atom or a hetero atom. Representing a group, R 72 and R 73 may be bonded to each other to form a ring structure.
- a 1 is a divalent linking group.
- the divalent linking group include a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, an ⁇ CONH— group, a ⁇ COO— group and an ⁇ NHCOO—.
- examples thereof include a group, an ether group (—O— group), a thioether group (—S— group), and a combination thereof.
- the direction of bonding of the divalent linking group is arbitrary.
- a 1 in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and is preferably a -CONH- group or a -COO- group.
- a divalent linking group containing an alkylene group having 1 to 10 carbon atoms is more preferable.
- Examples of the hydrocarbon group in the hydrocarbon group which may contain a hetero atom in R 72 and R 73 include an alkyl group, an aralkyl group, an aryl group and the like.
- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group and the like, and the alkyl group has 1 carbon number.
- ⁇ 18 is preferable, and among them, a methyl group or an ethyl group is more preferable.
- Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like.
- the carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
- Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like.
- the aryl group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms. The preferable carbon number does not include the carbon number of the substituent.
- the hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is replaced with a hetero atom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced with a substituent containing a hetero atom.
- the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
- the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.
- R 72 and R 73 are bonded to each other to form a ring structure means that R 72 and R 73 form a ring structure via a nitrogen atom. Heteroatoms may be contained in the ring structure formed by R 72 and R 73 .
- the ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.
- R 72 and R 73 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 72 and R 73 are bonded to each other to form a pyrrolidine ring or piperidine. It is preferable to form a ring or a morpholine ring.
- Examples of the monomer for deriving the structural unit represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate and the like.
- Examples thereof include alkyl group-substituted amino group-containing (meth) acrylates, dimethylaminoethyl (meth) acrylamide, and alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminopropyl (meth) acrylamide.
- dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
- the structural unit represented by the general formula (I) may consist of one type or may contain two or more types of structural units.
- the structural unit that functions as the coloring material adsorption site is selected from the group consisting of at least a part of the nitrogen site of the structural unit represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon. At least one of them may form a salt (hereinafter, such a copolymer may be referred to as a salt-type copolymer).
- a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferable, and among the halogenated hydrocarbons, the following general formula (2) is preferable.
- Is preferred That is, as at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon, one or more compounds selected from the group consisting of the following general formulas (1) to (3) are preferably used. can.
- Ra has a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or —O—.
- Re represents Re , which is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or 1 to 4 carbon atoms.
- Re represents a (meth) acryloyl group via an alkylene group.
- R b , R b' , and R b " independently have a hydrogen atom, an acidic group or an ester group thereof, and a substituent. It may have a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or —O—. Representing R f , R f has a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, and a substituent.
- R c and R d are independently hydrogen atoms, hydroxyl groups, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, vinyl groups, phenyl groups or benzyl groups which may have substituents, respectively.
- Re is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a carbon number of carbon atoms.
- Re represents a (meth) acryloyl group via 1 to 4 alkylene groups, provided that at least one of R c and R d contains a carbon atom).
- the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
- the organic acid compound used for such a dispersant for example, the organic acid compound described in JP-A-2012-236882 can be mentioned as a suitable one.
- the halogenated hydrocarbon is preferably at least one of allyl halide such as allyl bromide and benzyl chloride and aralkyl halide, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
- allyl halide such as allyl bromide and benzyl chloride and aralkyl halide
- the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is salt-formed with the terminal nitrogen moiety of the structural unit represented by the general formula (I). Therefore, the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0 with respect to the terminal nitrogen moiety of the structural unit represented by the general formula (I). It is preferably 0.01 mol or more, more preferably 0.05 mol or more, further preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. When it is at least the above lower limit value, the effect of improving the dispersibility of the coloring material by salt formation can be easily obtained.
- it is preferably 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and particularly preferably 0.6 mol or less.
- it is not more than the above upper limit value, it can be made excellent in development adhesion and solvent resolubility.
- at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon may be used alone or in combination of two or more. When two or more kinds are combined, it is preferable that the total content is within the above range.
- the salt-type copolymer As a method for preparing the salt-type copolymer, at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is added to a solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred. Further, a method of heating if necessary can be mentioned.
- the nitrogen moiety at the terminal of the structural unit represented by the general formula (I) of the copolymer and at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon form a salt. It can be confirmed by a known method such as NMR.
- the copolymer having the structural unit represented by the general formula (I) has the structural unit represented by the general formula (I) from the viewpoint of dispersibility and dispersion stability, and has (1) in the graft polymer chain.
- the graft copolymer and the block copolymer will be described in order.
- the graft copolymer having the structural unit represented by the general formula (I) and having the structural unit derived from (meth) acrylate in the graft polymer chain includes the structural unit represented by the general formula (I).
- R 71' represents a hydrogen atom or a methyl group
- a 2 represents a direct bond or a divalent linking group
- Polymer represents a polymer chain
- the constituent unit of the polymer chain is (meth) acrylate. The structural unit of origin is included.
- a 2 is a direct bond or a divalent linking group.
- the divalent linking group in A 2 is not particularly limited as long as the carbon atom derived from the ethylenically unsaturated double bond and the polymer chain can be linked.
- Examples of the divalent linking group in A 2 include the same as the divalent linking group in A 1 .
- a 2 in the general formula (II) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and is preferably a -CONH- group or a -COO- group.
- a divalent linking group containing an alkylene group having 1 to 10 carbon atoms is more preferable.
- Polymer represents a polymer chain, and the structural unit of the polymer chain includes a structural unit derived from (meth) acrylate.
- the graft copolymer has a structural unit represented by the general formula (II) having a specific polymer chain, so that the solvent affinity is good, and the dispersibility and dispersion stability of the coloring material are good. In addition, the compatibility with the above-mentioned photoinitiator is also good.
- Examples of the structural unit of the polymer chain include the structural unit represented by the following general formula (III).
- R 74 " is a hydrogen atom or a methyl group
- a 4 is a divalent linking group
- R 80 is a hydrocarbon group which may contain a hydrogen atom or a hetero atom.
- Examples of the divalent linking group of A 4 include the same as the divalent linking group of A 1 .
- the structural unit derived from (meth) acrylate the structural unit represented by the general formula (III) in which A4 in the general formula (III) is a divalent linking group containing a —COO— group is used. , At least included. From the viewpoint of solubility in organic solvents used for color filter applications, A4 in the general formula (III) may contain a divalent linking group containing a —CONH— group.
- Examples of the hydrocarbon group in the hydrocarbon group which may contain a hetero atom in R80 include an alkyl group, an alkenyl group, an aryl group, and a combination thereof such as an aralkyl group and an alkyl substituted aryl group.
- Examples of the hydrocarbon group in the hydrocarbon group which may contain a hetero atom in R80 include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, and an aralkyl group or an alkyl substituted group. These combinations such as an aryl group can be mentioned.
- the alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or n-. Examples thereof include nonyl group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, boronyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group substituted adamantyl group and the like.
- the number of carbon atoms of the alkyl group is preferably 1 to 12, and more preferably 1 to 6.
- the alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group and the like.
- the position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond is at the end of the alkenyl group.
- the alkenyl group preferably has 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like.
- the aryl group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms.
- Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent.
- the carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
- a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded to the aromatic ring such as the aryl group or the aralkyl group as a substituent.
- the hydrocarbon group in R80 includes an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms in which the alkyl group may be substituted, and an alkyl group, among others, from the viewpoint of dispersion stability. It is preferably one or more selected from the group consisting of an aralkyl group having 7 to 14 carbon atoms which may be substituted, and is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or n.
- -It is preferably one or more selected from the group consisting of a nonyl group, an n-lauryl group, an n-stearyl group, a phenyl group and a benzyl group which may be substituted with an alkyl group.
- heteroatoms examples include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
- Hydrocarbon groups that may contain heteroatoms include, for example, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-,-in the carbon chain of the hydrocarbon group.
- S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O- , -O-NH- and the like are included in the structure.
- the hydrocarbon group may have a substituent as long as it does not interfere with the dispersion performance of the graft copolymer, and examples of the substituent include a halogen atom, a hydroxyl group, a carboxy group and an alkoxy group. Examples thereof include a nitro group, a cyano group, an epoxy group, an isocyanate group and a thiol group.
- the hydrocarbon group which may contain a heteroatom in R80 may have a structure in which a polymerizable group such as an alkenyl group is added to the terminal via a linking group containing a heteroatom in the hydrocarbon group.
- Examples of the monomer for deriving the structural unit represented by the general formula (III) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth).
- the R80 it is preferable to use one having excellent solubility in an organic solvent described later, and it may be appropriately selected according to the organic solvent used in the colorant dispersion.
- the organic solvent is an ether alcohol acetate-based, ether-based, ester-based, alcohol-based or other organic solvent generally used as an organic solvent for a coloring material dispersion, methyl is used.
- ethyl group isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group, cyclohexyl group, dicyclopentanyl group, hydroxyethyl group, phenoxyethyl group, adamantyl group, methoxypolyethylene glycol group, methoxypolypropylene glycol group , Polyethylene glycol group and the like are preferable.
- the graft copolymer is represented by the structural unit represented by the following general formula (IV) and the structural unit represented by the following general formula (IV') in the structural unit of the polymer chain in the structural unit represented by the general formula (II).
- the solvent resistance of the cured product of the photocurable red resin composition is further improved, and the photocurable red resin composition is further improved. It is preferable from the viewpoint of shortening the development time of the object.
- the structural unit represented by the following general formula (IV) and the structural unit represented by the following general formula (IV') are the structural units included in the structural unit represented by the general formula (III).
- R 74 is a hydrogen atom or a methyl group
- a 3 is a divalent linking group
- R 75 is an ethylene group or a propylene group
- R 76 is a hydrogen atom or a hydrocarbon group
- m Represents a number of 3 or more and 80 or less.
- R 74' is a hydrogen atom or a methyl group
- a 3' is a divalent linking group
- R 77 is an alkylene group having 1 to 10 carbon atoms
- R 78 has 3 to 7 carbon atoms.
- the alkylene group, R 79 is a hydrogen atom or a hydrocarbon group
- n represents a number of 1 or more and 40 or less.
- Examples of the divalent linking group of A 3 include the same as the divalent linking group of A 1 .
- A3 in the general formula (IV) is preferably a divalent linking group containing a -CONH- group or a -COO- group. , -CONH- group or -COO- group is more preferable, and -COO- group is even more preferable.
- the m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 3 or more. Among them, 19 or more is preferable, and 21 or more is preferable from the viewpoint of suppressing the generation of water stains and solvent resistance. It is more preferable to have.
- the graft copolymer contains a main chain portion having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II).
- the structural unit represented by the general formula (II) includes the structural unit represented by the general formula (IV) including a polyethylene oxide chain or a polypropylene oxide chain having a specific number of repetitions in the polymer chain.
- the structural unit of the polymer chain thus grafted includes a polyethylene oxide chain having a specific number of repetitions or a structural unit having a polypropylene oxide chain, and the graft is made.
- the polymer chain itself has a branched structure. Since the plurality of grafted polymer chains spread three-dimensionally in the film and the specific surface area becomes large, it is presumed that the invasion of the solvent into the coating film and the arrival of the color material can be further suppressed.
- the upper limit of m is 80 or less, but it is preferably 50 or less from the viewpoint of solubility in organic solvents used for color filters.
- the hydrocarbon group in R 76 may be the same as the hydrocarbon group in R 80 .
- the hydrocarbon group in R76 includes an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms in which the alkyl group may be substituted, and an aryl group having 6 to 12 carbon atoms, among others, from the viewpoint of dispersion stability and compatibility.
- the alkyl group is preferably at least one selected from the group consisting of aralkyl groups having 7 to 14 carbon atoms which may be substituted, and is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n-butyl.
- It is preferably one or more selected from the group consisting of a group, an n-nonyl group, an n-lauryl group, an n-stearyl group, a phenyl group in which an alkyl group may be substituted, and a benzyl group.
- A3'in the general formula (IV ' ) is a divalent linking group containing a -CONH- group or a -COO- group. Is preferable, and it is more preferably an —CONH-group or a —COO-group, and even more preferably a —COO-group.
- R 77 is an alkylene group having 1 to 10 carbon atoms, and among them, an alkylene group having 2 to 8 carbon atoms is preferable from the viewpoint of solvent resolubility.
- R 78 is an alkylene group having 3 to 7 carbon atoms, and among them, an alkylene group having 3 to 5 carbon atoms and an alkylene group having 5 carbon atoms are preferable from the viewpoint of substrate adhesion.
- R 79 is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group in the R 79 may be the same as the hydrocarbon group in the R 76 .
- n in the general formula (IV') represents the number of repeating units of the ester chain, and represents a number of 1 or more. Among them, 2 or more is used from the viewpoint of shortening the developing time and simultaneously satisfying excellent solvent resistance. It is preferably present, and more preferably 3 or more. On the other hand, the upper limit of n is 40 or less, but it is preferably 20 or less from the viewpoint of solubility in an organic solvent used for color filter applications.
- At least one structural unit selected from the group consisting of the structural unit represented by the general formula (IV) and the structural unit represented by the following general formula (IV') may be used alone. It is good, but two or more kinds may be mixed.
- the polymer chain contains the structural unit represented by the general formula (IV)
- the action of the solvent-affinitive portion by the oxygen atom becomes more remarkable, and the development time of the photocurable red resin composition is shortened. It is preferable from the viewpoint of improving the chemical resistance and solvent resistance.
- the polymer chain constituent unit in the constituent unit represented by the general formula (II) is m. From at least one selected from the group consisting of the structural units represented by the general formula (IV) of 19 or more and 80 or less, and from the structural units represented by the general formula (IV) having m of 3 or more and 10 or less. It is more preferable to contain at least one selected from the group consisting of at least one selected from the group consisting of the structural units represented by the general formula (IV) having m of 19 or more and 50 or less. , M is more preferably contained in combination with at least one selected from the group consisting of the structural units represented by the general formula (IV) having 3 or more and 8 or less.
- the total ratio of the structural units represented by the general formula (IV) in which m is 19 or more and 80 or less is the point of the water stain suppressing effect when all the structural units of the polymer chain are 100% by mass. Therefore, it is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 4% by mass or more, and on the other hand, in terms of solvent resolubility and water stain suppressing effect. Therefore, it is preferably 75% by mass or less, more preferably 65% by mass or less, and further preferably 50% by mass or less.
- the total ratio of the structural units represented by IV) is preferably 20% by mass or more when all the structural units of the polymer chain are 100% by mass.
- the total ratio of the structural units represented by the general formula (IV) in which m is 3 or more and 10 or less in the polymer chain is 100 mass by mass of all the structural units of the polymer chain. In terms of%, it is preferably 80% by mass or less, and more preferably 60% by mass or less. Further, in the polymer chain, a mixture of the structural unit represented by the general formula (IV) in which m is 19 or more and 80 or less and the structural unit represented by the general formula (IV) in which m is 3 or more and 10 or less.
- the ratio is represented by the structural unit represented by the general formula (IV) in which m is 19 or more and 80 or less and the general formula (IV) in which m is 3 or more and 10 or less from the viewpoint of improving the effect of suppressing the development residue.
- the total of the constituent units and the constituent units is 100 parts by mass
- the total of the constituent units represented by the general formula (IV) having m of 19 or more and 80 or less is preferably 3 parts by mass or more, and 6 parts by mass or more. It is more preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.
- the total ratio of at least one structural unit selected from the group consisting of the structural units and the structural units represented by the general formula (IV') is preferably 1% by mass or more, preferably 2% by mass or more. It is more preferable that there is, and it is even more preferable that it is 4% by mass or more.
- the total ratio of at least one structural unit selected from the group consisting of the structural unit represented by the general formula (IV) and the structural unit represented by the general formula (IV') is the point of solvent resolubility. Therefore, when the total structural unit of the polymer chain is 100% by mass, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.
- the structural unit represented by the general formula (III) including the structural unit represented by the general formula (IV) and the structural unit represented by the general formula (IV') is one kind. It may be used alone or in combination of two or more. From the viewpoint of dispersibility and dispersion stability of the coloring material, the total ratio of the structural units represented by the general formula (III) is 70% by mass or more when all the structural units of the polymer chain are 100% by mass. It is preferably present, and more preferably 90% by mass or more. On the other hand, from the viewpoint of simultaneously satisfying dispersion stability and excellent solvent resistance, the total ratio of the structural units represented by the general formula (III) in the polymer chain is 100 for all the structural units of the polymer chain.
- the total ratio of the constituent units derived from (meth) acrylate is 60% by mass when the total constituent units of the polymer chain are 100% by mass in terms of dispersion stability, solvent resistance, and compatibility with the initiator. The above is preferable, and 80% by mass or more is more preferable.
- the total ratio of the structural units derived from (meth) acrylate in the polymer chain was 100% by mass of all the structural units of the polymer chain. Sometimes it may be 100% by weight.
- the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer includes other structural units in addition to the structural unit represented by the general formula (III). You can go out.
- the other structural unit include a structural unit derived from a monomer having an unsaturated double bond copolymerizable with the monomer that induces the structural unit represented by the general formula (III).
- the monomer for inducing other constituent units include styrenes such as styrene and ⁇ -methylstyrene, vinyl ethers such as phenylvinyl ether, and the like.
- the total ratio of the other structural units is 100 for all the structural units of the polymer chain from the viewpoint of the effect of the present invention.
- mass% it is preferably 30% by mass or less, and more preferably 10% by mass or less.
- the mass average molecular weight Mw of the polymer chain in the polymer is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, from the viewpoint of the dispersibility and dispersion stability of the coloring material. , 15,000 or less, more preferably 12,000 or less. Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent-affinitive portion of the dispersant becomes large, so that the solvent penetrates into the coating film and reaches the coloring material. It becomes easy to suppress.
- the polymer chain in Polymer preferably has a solubility of 20 (g / 100 g solvent) or more at 23 ° C. with respect to the organic solvent used in combination.
- the solubility of the polymer chain can be determined by the fact that the raw material into which the polymer chain is introduced when preparing the graft copolymer has the solubility.
- the polymerizable oligomer is the above-mentioned. It suffices to have solubility.
- a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer is used.
- the polymer chain containing the reactive group has the solubility.
- the structural unit represented by the general formula (I) is preferably contained in a proportion of 3% by mass to 60% by mass, more preferably 6% by mass to 45% by mass. 9% by mass to 30% by mass is more preferable.
- the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the coloring material in the graft copolymer becomes appropriate, and the component is dissolved in an organic solvent. Since the deterioration of the property can be suppressed, the adsorptivity to the coloring material becomes good, and excellent dispersibility and dispersion stability can be easily obtained.
- the structural unit represented by the general formula (II) is preferably contained in a proportion of 40% by mass to 97% by mass, more preferably 55% by mass to 94% by mass. It is preferable, and it is more preferably 70% by mass to 91% by mass. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent-affinitive portion in the graft copolymer becomes appropriate, and a sufficient solid as a dispersant. Since the repulsive effect can be maintained and the specific surface area of the solvent-affinitive portion of the dispersant becomes large, it is easy to suppress the invasion of the solvent into the coating film and the arrival of the solvent to the coloring material.
- the graft copolymer used in the present invention is other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) within the range in which the effect of the present invention is not impaired.
- it may have other structural units.
- an ethylenically unsaturated double bond-containing monomer copolymerizable with the ethylenically unsaturated double bond-containing monomer or the like that induces the structural unit represented by the general formula (I) is appropriately selected. And can be copolymerized to introduce other building blocks.
- Examples of the other structural unit copolymerized with the structural unit represented by the general formula (I) include the structural unit represented by the general formula (III).
- the content ratio of the structural unit is the structural unit represented by the general formula (I), the structural unit represented by the general formula (II), and the structural unit represented by the general formula (II) when synthesizing the graft copolymer at the time of production. It is calculated from the amount of the monomer charged to induce the structural unit or the like represented by the general formula (III).
- the mass average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, still more preferably 8000 or more, from the viewpoint of dispersibility and dispersion stability. .. On the other hand, from the viewpoint of solvent resolubility, it is preferably 50,000 or less, and more preferably 30,000 or less.
- the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography).
- HLC-8120GPC manufactured by Tosoh was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh), and the measurement columns were TSK-GEL ALPHA-M x 2 (manufactured by Tosoh). Is.
- a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) is produced. Any method can be used, and the method is not particularly limited.
- a monomer represented by the following general formula (Ia) for example, a monomer represented by the following general formula (Ia).
- a method of producing a graft copolymer by copolymerizing the polymer chain and a polymerizable oligomer (macromonomer) composed of a group having an ethylenically unsaturated double bond at the end thereof as a copolymerization component can be mentioned. If necessary, other monomers are also used, and a graft copolymer can be produced by using a known polymerization means.
- R 71 , A 1 , R 72 and R 73 are the same as those in the general formula (I).
- the monomer represented by the general formula (Ia) is produced.
- the copolymer is formed by addition polymerization of and other monomers containing a group having an ethylenically unsaturated double bond, the copolymer contains a reactive group capable of reacting with the reactive group contained in the copolymer.
- the polymer chain may be introduced by using the polymer chain.
- a functional group that reacts with the substituent after synthesizing a copolymer having a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond forming group is used.
- the polymer chain may be introduced by reacting with the containing polymer chain.
- a polymer chain having a glycidyl group at the end may be reacted with a polymer chain having a carboxyl group at the end, or a polymer having an isocyanate group at the side chain may be reacted with a polymer chain having a hydroxy group at the end.
- an additive generally used for the polymerization for example, a polymerization initiator, a dispersion stabilizer, a chain transfer agent, or the like may be used.
- each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like can be used. Among them, AB block copolymers or ABA block copolymers are preferable because they are excellent in dispersibility.
- the A block is a block that functions as a color material adsorption site, and includes at least a structural unit represented by the general formula (I). At least a part of the nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon formed a salt. It may be a salt-type block copolymer.
- the A block may have a structural unit other than the structural unit represented by the general formula (I) as long as the object of the present invention is achieved, and the block A may have a structural unit represented by the general formula (I). It can be contained as long as it is a copolymerizable structural unit.
- the content ratio of the structural unit represented by the general formula (I) in the A block in the block copolymer before salt formation is 50% by mass to 100% by mass with respect to the total mass of all the structural units of the A block. It is preferably 80% by mass to 100% by mass, more preferably 100% by mass, and most preferably 100% by mass. This is because the higher the proportion of the structural unit represented by the general formula (I), the better the adsorptivity to the coloring material, and the better the dispersibility and dispersion stability of the block copolymer.
- the content ratio of the structural unit is calculated from the charged mass when synthesizing the A block having the structural unit represented by the general formula (I).
- the total content ratio of all the structural units of A block including the structural unit represented by the general formula (I) is a block from the viewpoint of good dispersibility and dispersion stability. It is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, based on the total mass of all the building blocks of the copolymer. Further, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is that the dispersibility and the dispersion stability are good, so that all the structural units of the block copolymer are good. It is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass, based on the total mass of the above.
- the content ratio of each structural unit in the block copolymer is calculated from the mass charged when the block copolymer before salt formation is synthesized.
- the structural unit represented by the general formula (I) may have an affinity with the coloring material and may be composed of one type or may include two or more types of structural units. good.
- the B block is a block that functions as a solvent-affinity site and contains at least a structural unit derived from (meth) acrylate.
- the structural unit derived from (meth) acrylate may be the same as described above.
- the B block is appropriately selected from among the monomers having an unsaturated double bond that can be copolymerized with the monomer that induces the structural unit represented by the general formula (I), depending on the solvent so as to have solvent affinity. It is preferable to select and use it. As a guide, it is preferable to introduce the B block so that the solubility of the copolymer at 23 ° C. is 20 (g / 100 g solvent) or more with respect to the solvent used in combination.
- the structural unit constituting the B block portion may be composed of one type, or may include two or more types of structural units. Examples of the structural unit included in the B block include the structural unit represented by the general formula (III).
- the number of units m of the structural unit represented by the general formula (I) and the number of units n of other structural units constituting the solvent-friendly block portion are
- the ratio m / n is preferably in the range of 0.01 or more and 1 or less, and in the range of 0.05 or more and 0.7 or less, from the viewpoint of dispersibility and dispersion stability of the coloring material. More preferred.
- the A block containing the structural unit represented by the general formula (I), the structural unit derived from the carboxy group-containing monomer, and the structural unit derived from (meth) acrylate are included.
- a block copolymer containing a B block containing B block, and at least a part of the nitrogen moiety of the block copolymer represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon From a block copolymer containing a B block containing B block, and at least a part of the nitrogen moiety of the block copolymer represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon. At least one selected from the group contains at least one salt-type block copolymer in which a salt is formed, and the acid value of at least one of the block copolymer and the salt-type block copolymer is 1 mgKOH /.
- the glass transition temperature is 30 ° C. or higher at g to 18 mgKOH / g improves the substrate adhesion and solvent resistance of the cured film even with low-temperature heat treatment, and suppresses the generation of development residues. preferable.
- the specific dispersant is combined with a photoinitiator containing at least one of the compound represented by the general formula (A) and the compound represented by the general formula (B), the solvent resistance is further improved. It is preferable from the viewpoint of The B block in this case contains a structural unit derived from (meth) acrylate as an essential component, but may be the same as the B block of International Publication No. 2016/1049493.
- a monomer having an unsaturated double bond and a carboxy group can be used, which can be copolymerized with a monomer having a structural unit represented by the general formula (I).
- monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer and the like.
- a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride
- a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ⁇ -carboxy-polycaprolactone.
- Mono (meth) acrylate and the like can also be used.
- an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used.
- (meth) acrylic acid is particularly preferable from the viewpoints of copo
- the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the range of the specific acid value, and in particular. Although not limited, it is preferably 0.05% by mass to 4.5% by mass, and 0.07% by mass to 3.7% by mass, based on the total mass of all the constituent units of the block copolymer. Is more preferable.
- the content ratio of the structural unit derived from the carboxy group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue is exhibited, and when it is at least the above upper limit value, the development adhesion is deteriorated and the solvent resolubility is deteriorated. It can prevent deterioration.
- the structural unit derived from the carboxy group-containing monomer may have the above-mentioned specific acid value, may be composed of one kind, or may contain two or more kinds of structural units.
- the B block of the block copolymer contains a structural unit derived from a hydroxyl group-containing monomer from the viewpoint of improving development adhesion.
- the B block contains a structural unit derived from a hydroxyl group-containing monomer, the development speed is further improved.
- the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.
- a monomer containing an unsaturated double bond and a hydroxyl group that can be copolymerized with the monomer that induces the structural unit represented by the general formula (I) can be used.
- examples of such a monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin mono (meth).
- Examples thereof include acrylate, polyethylene glycol mono (meth) acrylate, ⁇ -caprolactone 1 mol addition of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like. From the viewpoint of improving development adhesion, one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate is preferable.
- the content ratio of the constituent units derived from the hydroxyl group-containing monomer is preferably 1% by mass or more, preferably 2% by mass, based on the total mass of all the constituent units of the block copolymer. More preferably, it is more preferably 3% by mass or more, and particularly preferably 4% by mass or more. When it is at least the above lower limit value, the development adhesion can be preferable. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. When it is not more than the above upper limit value, it can be preferable from the viewpoint that the introduction ratio of other useful monomers can be increased.
- the content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.
- the acid value of at least one of the block copolymer and the salt-type block copolymer is preferably 1 mgKOH / g or more, preferably 2 mgKOH / g or more, as a lower limit from the viewpoint of the effect of suppressing the development residue. Is more preferable. Further, the acid value of at least one of the block copolymer and the salt-type block copolymer is 18 mgKOH / g or less as an upper limit from the viewpoint of preventing deterioration of development adhesion and solvent resolubility. It is preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less.
- the acid value of at least one of the block copolymer and the salt-type block copolymer can be determined by the method described in International Publication No. 2016/1049493.
- the glass transition temperature of at least one of the block copolymer and the salt-type block copolymer is preferably 30 ° C. or higher, particularly preferably 32 ° C. or higher, and more preferably 35 ° C. or higher from the viewpoint of development adhesion. .. On the other hand, the temperature is preferably 200 ° C. or lower from the viewpoint of operability during use, such as easy weighing.
- the glass transition temperature of at least one of the block copolymer and the salt-type block copolymer is determined by measuring by differential scanning calorimetry (DSC) in accordance with JIS K7121. When two or more peaks indicating the glass transition temperature are observed, the peak area, that is, the peak having the largest area protruding from the baseline of the obtained chart is used as the representative value of the glass transition temperature.
- the mass average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, preferably 2000 to 15000, from the viewpoint of improving the dispersibility and dispersion stability of the coloring material. More preferably, it is more preferably 3000 to 12000.
- the mass average molecular weight (Mw) can be measured in the same manner as described above.
- the total ratio of the structural units derived from (meth) acrylate is 100% by mass of all the structural units in the B block in the block copolymer from the viewpoint of dispersion stability, solvent resistance, and compatibility with the photoinitiator. In the above case, it is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. On the other hand, from the viewpoint of simultaneously satisfying dispersion stability and excellent solvent resistance, the total ratio of the constituent units derived from (meth) acrylate is 100 mass when all the constituent units in the B block are 100% by mass. May be%.
- the B block contains the structural unit derived from the carboxy group-containing monomer
- the total ratio of the structural units derived from the (meth) acrylate is different from the structural unit derived from the carboxy group-containing monomer in the B block.
- the unit is 100% by mass, it may be 100% by mass.
- the total content ratio of all the constituent units of the B block is based on the total mass of all the constituent units of the block copolymer from the viewpoint of good dispersibility and dispersion stability. It is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass. Further, in the block copolymer before salt formation, the content ratio of the structural unit represented by the above general formula (III) is the total mass of all the structural units of the block copolymer from the viewpoint of improving the dispersibility of the coloring material. On the other hand, it is preferably 40% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass. The content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.
- the (meth) acrylate-based copolymer containing the structural unit represented by the general formula (I) is a copolymer having an amine value of 40 mgKOH / g to 120 mgKOH / g, which has good dispersibility at the time of forming a coating film. It is preferable because it does not deposit foreign matter and improves brightness and contrast.
- the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and also in alkali developability and solvent resolubility.
- the amine value of the (meth) acrylate-based copolymer containing the structural unit represented by the general formula (I) is preferably 80 mgKOH / g or more, and 90 mgKOH / g or more. Is more preferable.
- the amine value of the (meth) acrylate-based copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH / g or less, preferably 105 mgKOH / g. The following is more preferable.
- the amine value refers to the number of mg of perchloric acid and equivalent potassium hydroxide required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group is salt-formed with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant itself. The amine value of can be measured.
- the content ratio (mol%) of each structural unit in the copolymer in the dispersant can be obtained from the amount of the raw material charged at the time of production, and can be measured using an analyzer such as NMR. Further, the structure of the dispersant can be measured by using NMR, various mass spectrometry and the like. Further, the dispersant is decomposed by thermal decomposition or the like as necessary, and the obtained decomposition product is subjected to high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS and the like. You can ask.
- the content of the dispersant may be selected so as to be excellent in the dispersibility and dispersion stability of the coloring material, and is not particularly limited, but the photocurable red resin composition. It is preferably in the range of, for example, 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, based on the total amount of solid content in the substance. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photocurable red resin composition is excellent. Further, when it is not more than the above upper limit value, the developability is good.
- the content of the dispersant is, for example, preferably 2% by mass to 25% by mass, more preferably, with respect to the total solid content of the photocurable red resin composition. Is in the range of 3% by mass to 20% by mass.
- the photocurable red resin composition of the present invention preferably further contains a thiol compound from the viewpoint of improving solvent resistance after low-temperature heat treatment and substrate adhesion.
- a thiol compound examples include a monofunctional thiol compound having one thiol group and a polyfunctional thiol group having two or more thiol groups. From the viewpoint of suppressing the line width shift and improving the adhesion to the substrate, it is more preferable to use a monofunctional thiol compound having one thiol group.
- Examples of the monofunctional thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzoimidazole, and 3-mercapto.
- Examples thereof include propionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate.
- polyfunctional thiol compound examples include 1,4-bis (3-mercaptobutylyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), di Examples thereof include pentaerythritol hexakis (3-mercaptopropionate) and tetraethylene glycol bis (3-mercaptopropionate).
- 2-mercaptobenzoxazole or 2-mercaptobenzothiazole may be used alone or in combination of two or more, and among them, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole improves solvent resistance after low-temperature heat treatment and substrate adhesion. It is preferable from the point of view.
- the content of the thiol compound is usually in the range of 0.5% by mass to 10% by mass, preferably 1% by mass to 5% by mass, based on the total solid content of the photocurable red resin composition. When it is at least the above lower limit value, the solvent resistance after low temperature heat treatment and the adhesion to the substrate are likely to be excellent. On the other hand, when it is not more than the above upper limit value, it is easy to assume that the photocurable red resin composition of the present invention has good developability and suppressed line width shift.
- the photocurable red resin composition of the present invention may further contain various additives, if necessary.
- the additive include antioxidants, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters and the like. .. Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.
- the photocurable red resin composition of the present invention further contains an antioxidant from the viewpoint of suppressing the line width shift amount of the cured film.
- the photocurable red resin composition of the present invention contains, for example, an antioxidant in combination with the compound represented by the general formula (A), whereby excessive curability is not impaired when forming a cured film. Since the radical chain reaction can be controlled, the linearity is further improved when the fine line pattern is formed, and the ability to form the fine line pattern according to the design of the mask line width is improved. In addition, the heat resistance can be improved, and the decrease in brightness after exposure and post-baking can be suppressed, so that the brightness can be improved.
- the antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones.
- the antioxidant examples include a hindered phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hydrazine-based antioxidant, and the like, and a line width mask. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to form a fine line pattern according to the design of the line width and the heat resistance. It may be a latent antioxidant as described in WO 2014/021023.
- hindered phenolic antioxidant examples include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF).
- 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3) , 5-Di-tert-butylbenzyl) Mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP-S, Sumitomo Chemical Co., Ltd.), 6,6'-thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxybenzylphosphone Examples thereof include diethyl acid (trade name: Irgamod 195, manufactured by BASF).
- pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. ..
- the content of the antioxidant is usually 0.1% by mass to 10.0% by mass, preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the photocurable red resin composition. Is within the range of. When it is at least the above lower limit value, the ability to form a fine line pattern according to the design of the mask line width is improved, and the heat resistance is excellent. On the other hand, when it is not more than the above upper limit value, the photocurable red resin composition of the present invention can be easily made into a highly sensitive photocurable red resin composition.
- silane coupling agent examples include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403. , KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like.
- KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 having a methacrylic group and an acrylic group are preferable from the viewpoint of adhesion of the SiN substrate.
- the content of the silane coupling agent is usually 0.05% by mass to 10.0% by mass, preferably 0.1% by mass to 5.0, based on the total solid content in the photocurable red resin composition. It is in the range of mass%. When it is at least the above lower limit value and at least the above upper limit value, the effect of improving the adhesion to the substrate tends to be good.
- a coloring material, a photopolymerizable compound, a photoinitiator, and various additive components used as desired are mixed by a known mixing means.
- Can be prepared by The photocurable red resin composition of the present invention contains a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additive components used as desired.
- a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion, and the dispersion is mixed with an alkali-soluble resin.
- the above methods (1) and (4) are preferable because they can effectively prevent the agglomeration of the coloring material and uniformly disperse the color material.
- the method for preparing the color material dispersion liquid can be appropriately selected and used from the conventionally known dispersion methods. For example, (1) a dispersant is mixed with a solvent and stirred in advance to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt of the amino group of the dispersant and the organic acid compound. Let me. A method of mixing this with a coloring material and other components as necessary and dispersing them using a known stirrer or disperser; (2) Mixing and stirring the dispersant with a solvent to prepare a dispersant solution, and then dispersing the dispersant.
- Coloring material and, if necessary, an organic acid compound, and if necessary, other components are mixed and dispersed using a known stirrer or disperser; (3) Dispersant is mixed with a solvent and stirred. , Dispersant solution is prepared, then the coloring material and other components are mixed if necessary to prepare a dispersion using a known stirrer or disperser, and then an organic acid compound is added as necessary.
- the method etc. can be mentioned.
- the disperser for performing the dispersion treatment examples include roll mills such as 2-roll and 3-roll, ball mills such as ball mills and vibration ball mills, paint conditioners, continuous disc type bead mills, and bead mills such as continuous annular type bead mills.
- the bead diameter used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.
- the photocurable red resin composition according to the present invention is suitably used for forming a colored cured film as a substitute for a circular polarizing plate because the cured film has an effect of suppressing external light reflection.
- the display device does not include the polarizing plate, and therefore the photocurable red resin composition according to the present invention can be used.
- the object is suitably used for display device applications that do not include a polarizing plate.
- the photocurable red resin composition according to the present invention is a photocurable red resin composition used for a cured film formed on an organic light emitting element, it is used for a display device that does not include an external color filter substrate. , It is suitably used for organic light emission display devices with a thin film and improved flexibility. Further, in the photocurable red resin composition according to the present invention, by appropriately selecting the components as described above, it is possible to form a cured film having good solvent resistance even in low temperature heat treatment and excellent substrate adhesion. Therefore, it can be suitably used for forming a cured film by low-temperature heat treatment at 130 ° C. or lower, further 100 ° C. or lower, or 90 ° C. or lower on a substrate on which an element having low heat resistance is formed.
- the display device according to the present invention is characterized by having a cured film of the photocurable red resin composition according to the present invention on an organic light emitting device.
- the cured film of the photocurable red resin composition used for the cured film formed on the organic light emitting device according to the present invention is formed on the organic light emitting element.
- An external circular polarizing plate or an external color filter substrate is not required, and it may be one that does not have these.
- the display device according to the present invention uses the photocurable red resin composition used for the cured film formed on the organic light emitting device according to the present invention, and the cured film is formed on the organic light emitting device. Since there is no substrate between the light emitting element and the cured film as used for an external color filter substrate, the film thickness and flexibility are improved.
- FIG. 1 is a schematic cross-sectional view showing an example of a display device provided with an organic light emitting element according to the present invention.
- the display device 100 according to the present invention has an element substrate 30 provided with an organic light emitting element and an external light reflection prevention including a colored cured film (9R, 9G, 9B) on the element substrate 30.
- a film 20 is provided, and a sealing film 11 is further provided on the film 20.
- a thin film transistor (TFT) 2 which is a driving element is arranged on the substrate 1 so as to correspond to each subpixel, and a sealing film 3 is provided on the thin film transistor (TFT) 2 and further.
- An electrode 4 anode corresponding to each subpixel and a partition wall 5 for partitioning each subpixel are provided on the 3, and an organic light emitting element (6R, 6G) constituting R, G, B3 color subpixels is provided in the partition.
- 6B is arranged, and an electrode 7 (cathode) is further provided on the organic light emitting element (6R, 6G, 6B).
- the element substrate 30 provided with the organic light emitting element further includes a sealing layer 8 for covering the organic light emitting element from above.
- a three-color colored cured film (corresponding to each organic EL element) formed on the sealing layer 8 on the organic EL element (6R, 6G, 6B) in the element substrate 30 by using the photocurable colored resin composition.
- the external light antireflection film 20 including the 9R, 9G, 9B) and the light-shielding portion 10 is provided, and the sealing film 11 is further provided on the external light antireflection film 20.
- the display device 100 has a known configuration such as, for example, a touch sensor layer composed of an insulating film and a transparent electrode layer on the sealing film 11, and a hard coat layer on the touch sensor layer. May be further provided as appropriate.
- the layers of the colored cured film (9R, 9G, 9B) and the light-shielding portion 10 provided on the element substrate 30 provided with the organic light-emitting element are used as the external light antireflection film 20.
- the external light antireflection film used in the present invention does not include a separate substrate unlike an external circular polarizing plate or an external color filter substrate, and can improve thinning and flexibility.
- the color of the subpixel (6R, 6G, 6B) of the organic light emitting element and the colored cured film (9R, 9G, 9R, 9G, directly above the color and at least one layer such as the sealing layer 8 are used. It is preferable to adjust the color of 9B) so that it is the same color.
- the colored cured film provided on the organic light emitting element shields the external light except for the color originally emitted by the organic light emitting element, and the light emitted by the organic light emitting element is not cut, so that the light utilization efficiency is improved. It is possible to suppress external light reflection without lowering it.
- the cured film of the photocurable red resin composition according to the present invention may be a red cured film (9R) among the three colored cured films (9R, 9G, 9B).
- TFT thin film transistor
- the electrode 7 (cathode) and the like can be appropriately selected and used with known configurations.
- the organic light emitting device may have known configurations such as a hole injection layer, a hole transport layer, and an electron injection layer.
- Examples of the sealing layer 8 on the organic EL element used in the display device according to the present invention include an inorganic film, an organic film, and a multilayer film in which they are laminated. It is preferable to use a multilayer film because it has a high effect of suppressing the infiltration of water and oxygen. Specific examples thereof include a metal film, a metal oxide film, a multilayer film in which an inorganic film such as SiOx and SiNx and an organic film are laminated.
- At least one of the colored cured films used in the display device according to the present invention is the cured film of the photocurable red resin composition according to the present invention.
- the colored cured film is usually formed at the opening of a light-shielding portion described later on the sealing layer 8 on the organic light emitting element, and is usually composed of a colored pattern of three or more colors. These may have the same coloring pattern as (6R, 6G, 6B) of the subpixel of the organic light emitting device.
- the arrangement of the colored cured films (9R, 9G, 9B) can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type.
- the width, area and the like of the colored layer can be appropriately set so as to match the subpixels (6R, 6G, 6B) of the organic light emitting element.
- the thickness of the colored cured film is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, etc. of the photocurable red resin composition, but is usually in the range of 1 ⁇ m to 5 ⁇ m.
- the light-shielding portion 10 used in the display device according to the present invention is usually formed in a pattern on the sealing layer 8 on the organic light emitting element, and is used as a light-shielding portion in a general color filter. Can be similar to.
- the pattern shape of the light-shielding portion may be appropriately selected according to the shape of the colored cured film, and examples thereof include a stripe shape and a matrix shape.
- the light-shielding portion may be a metal thin film such as chromium obtained by a sputtering method, a vacuum vapor deposition method, or the like.
- the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in the resin binder.
- a resin layer containing light-shielding particles a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, etc. be.
- the film thickness of the light-shielding portion is set to about 0.2 ⁇ m to 0.4 ⁇ m in the case of a metal thin film, and is set to about 0.5 ⁇ m to 2 ⁇ m in the case of a black pigment dispersed or dissolved in a binder resin. Will be done.
- the colored cured film (9R, 9G, 9B) and the sealing film 11 provided on the light-shielding portion 10 known materials can be appropriately selected and used.
- the display device according to the present invention is not limited to the configuration shown in FIG. 1, and may further include a configuration of a display device including a known organic light emitting element. ..
- the method for manufacturing a laminate of an organic light emitting element and an external light antireflection film according to the present invention is as follows.
- the step of irradiating the coating film with light A post-baking step of heating the film after the light irradiation, and By including the step of developing the film after the light irradiation, It has a step of forming a cured film of the photocurable red resin composition according to the present invention on an organic light emitting device.
- the photocurable red resin composition according to the present invention onto the organic light emitting device, it is not necessary to apply the photocurable red resin composition on the organic light emitting element adjacent to the organic light emitting element, and the photocurable red resin composition does not have to be applied adjacent to the organic light emitting element. May be applied.
- the electrode 7 and the infiltration of water and oxygen are usually further suppressed on the subpixels (6R, 6G, 6B) of the organic light emitting element. Since the sealing layer 8 for this purpose is provided, the coating may be applied onto the organic light emitting element via these electrodes, the sealing layer, and the like.
- a light-shielding portion 10 is provided in advance on the sealing layer 8 by a known method as exemplified above, and a colored cured film (9R, 9G, 9B) is formed at the opening of the light-shielding portion 10. It may be applied as follows.
- the above-mentioned photocurable red resin composition of the present invention can be obtained by using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, a die coating method, and an inkjet method. Apply on the organic light emitting element.
- a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, a die coating method, and an inkjet method. Apply on the organic light emitting element.
- a spin coating method or a die coating method can be preferably used.
- the wet coating film is dried using a hot plate, an oven, or the like to form a coating film.
- the obtained coating film is irradiated with light (exposure) through a mask having a predetermined pattern, and a photopolymerizable compound and, if necessary, an alkali-soluble resin and the like are subjected to a photopolymerization reaction.
- the patterned coating film is irradiated with light (exposure) to cause the photopolymerizable compound to undergo a photopolymerization reaction.
- the light source used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, electron beams, and the like. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
- a post-baking step of heating the film after the light irradiation may be performed.
- the heating conditions may be appropriately selected depending on the mixing ratio of each component in the photocurable red resin composition to be used, the thickness of the coating film, and the like.
- the post-baking step may be performed on the film after the light irradiation before the developing step described later, after the developing step, or before and after the developing step.
- the heating temperature in the post-baking step is preferably 130 ° C. or lower.
- the heating temperature is more preferably 100 ° C. or lower, and even more preferably 90 ° C. or lower.
- the heating temperature may be 30 ° C. or higher, 35 ° C. or higher, or 40 ° C. or higher.
- the film to be developed after irradiation with light may be a film after post-baking.
- a coating film is formed in a desired pattern by performing a developing process using a developing solution to dissolve and remove an unexposed portion.
- a developing solution a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used.
- An appropriate amount of a surfactant or the like may be added to this alkaline solution.
- a general method can be adopted as the developing method.
- the heating temperature in this post-baking step is preferably 130 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 90 ° C. or lower. ..
- the heating temperature may be 30 ° C. or higher, 35 ° C. or higher, or 40 ° C. or higher.
- additional light irradiation may be performed.
- the mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene-equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the above-mentioned specification of the present invention.
- EEMA 1-ethoxyethyl methacrylate
- TMSMA 2- (trimethylsilyloxy) ethyl methacrylate
- EHMA 2-ethylhexyl methacrylate
- BMA n-butyl methacrylate
- BzMA benzyl methacrylate
- MMA methyl methacrylate
- DMMA dimethylaminoethyl methacrylate
- MAA methacrylic acid
- the obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and the block copolymer 1 (amine value 95 mgKOH /) containing the structural unit represented by the general formula (I) is contained. g, acid value 8 mgKOH / g, Tg 38 ° C.) was obtained. The weight average molecular weight Mw was 7730.
- R 75 is an ethylene group
- R 76 is CH 3
- AIBN ⁇ , ⁇ '-azobisisobutyronitrile
- a mixed solution of 1.0 part by mass and 1.0 part by mass of AIBN was added dropwise over 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 part by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes. Further, the mixture was aged at the same temperature for 1 hour to obtain a 35.0% by mass solution of the graft copolymer 2.
- the obtained graft copolymer 2 had a weight average molecular weight (Mw) of 10000 as a result of GPC measurement.
- the amine value was 105 mgKOH / g.
- polystyrene was used as a standard substance and THF was used as an eluent to measure the weight average molecular weight by Shodex GPC System-21H (Shodex GPC System-21H).
- the acid value was measured based on JIS K 0070.
- Example 1 Production of photocurable red resin composition R-1)
- Production of Coloring Material Dispersion Solution R (1) In a 225 mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) of Preparation Example 1, Synthetic Example 1 9.2 parts by mass of the PGMEA solution (solid content 35% by mass) of the block copolymer 1 was added and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at room temperature for 30 minutes. There, as a red material, C.I. I.
- Pigment Red 254 (R254) was added in an amount of 12.0 parts by mass and 100 parts by mass of zirconia beads having a particle size of 2.0 mm, and the mixture was shaken with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as preliminary crushing, and then the particle size was 0. The mixture was changed to 200 parts of 1 mm zirconia beads and dispersed with a paint shaker for 4 hours as the main crushing to obtain a colorant dispersion liquid R (1).
- the block copolymer 1 is salt-formed by phenylphosphonic acid to become a salt-type block copolymer 1.
- Example 2 to 12 Production of photocurable red resin compositions R-2 to R-12
- the photocurable red resin composition R- except that the types and / or mass ratios of the red material and the black material and / or the type of the photoinitiator were changed as shown in Table 1.
- Photocurable red resin compositions R-2 to R-12 were obtained in the same manner as in 1.
- the color material dispersion liquid of Pigment Green 58 (G58) is used in the production of the color material dispersion liquid R (1).
- Pigment Red 177 (R177), C.I. I. Pigment Red 291 (R291), or C.I. I. It was obtained as the color material dispersion liquid R (2), R (3), or G in the same manner as in the production of the color material dispersion liquid R (1) except that the pigment green 58 (PG58) was changed.
- Example 13 Production of photocurable red resin composition R-13
- the color material dispersion R (2) instead of using the color material dispersion R (1), the color material dispersion R (2) is used, and instead of using the oxime ester-based photoinitiator represented by the above formula (A-2).
- 1- [4- (Phenylthio) phenyl] octane-1,2-dione 2- (O-benzoyloxime) (trade name: Irgacure OXE01, manufactured by BASF) in the same manner as in Example 1.
- a photocurable red resin composition R-13 was produced.
- Example 14 Production of photocurable red resin composition R-14
- Examples 15 to 20 Production of photocurable red resin compositions R-15 to R-20
- a monofunctional thiol compound (2-mercaptobenzoxazole, 2-MBO) was added.
- Example 21 Production of photocurable red resin composition R-21
- Example 21 Production of photocurable red resin composition R-21
- Example 21 Production of photocurable red resin composition R-21
- the color material dispersion liquid R (4) was obtained in the same manner as in the production of the color material dispersion liquid R (1) except that the graft copolymer 2 was changed to the PGMEA solution (solid content 35% by mass).
- the graft copolymer 2 is salt-formed by phenylphosphonic acid to become a salt-type graft copolymer 2.
- Example 3 Production of Photocurable Red Resin Composition R-21
- the color material dispersion liquid R (4) is used instead of the color material dispersion liquid R (1), and the color material dispersion liquid BK (1) is used.
- the photocurable red resin composition R-21 was produced in the same manner as in Example 1.
- Example 22 to 26 Production of photocurable red resin compositions R-22 to R-26
- the photocurable red color is the same as that of the photocurable red resin composition R-21, except that the types and / or mass ratios of the red material and the black material are changed.
- Resin compositions R-22 to R-26 were obtained.
- C.I. I. Pigment Red 177 (R177), or C.I. I. Pigment Red 291 The color material dispersion liquid of R291 is CI Pigment Red 254 (R254), CI Pigment Red 177 (R177), or C in the production of the color material dispersion liquid R (4). It was obtained as a color material dispersion liquid R (5) or R (6) in the same manner as in the production of the color material dispersion liquid R (4) except that it was changed to Pigment Red 291 (R291).
- Example 1 Production of Comparative Photocurable Red Resin Compositions CR-1 to CR-6)
- the black material was not used, only the red material was used, the type of the red material and / or the type of the initiator was changed, and the polyfunctionality with respect to the alkali-soluble resin A solution was changed. Hikari, except that the ratio of the monomer (trade name: Aronix M-305, manufactured by Toa Synthetic Co., Ltd.) and the initiator was not changed, and the amount of components other than the pigment was changed to the pigment concentration shown in Table 2.
- Comparative photocurable red resin compositions CR-1 to CR-6 were obtained in the same manner as the curable red resin composition R-1.
- a transmission spectrum of 380 nm to 780 nm was measured using a microspectroscopic optical measuring device OSP-SP200, and a maximum transmittance of 430 nm to 580 nm and a maximum transmittance and a minimum transmittance of 610 nm to 630 nm were measured.
- the photocurable red resin composition obtained in each Example and each Comparative Example was used as a glass substrate on which a SiNx film was formed (“NA35” manufactured by NH Technoglass Co., Ltd.) and PET on which a SiNx film was formed. After applying each to the SiNx film of the film (thickness 70 ⁇ m) using a spin coater so that the cured coating film has a thickness of 3.0 ⁇ m, it is dried at 80 ° C. for 3 minutes using a hot plate and applied onto the substrate. A film was formed.
- SiNx is exposed to this coating film with ultraviolet rays of 50 mJ / cm 2 using an ultra-high pressure mercury lamp via a photomask (chrome mask) having a pattern with an opening size of 2 ⁇ m to 100 ⁇ m for forming independent fine lines.
- a post-exposure coating film was formed on each of the films. Then, a 0.05 wt% potassium hydroxide aqueous solution was spin-developed as a developer, and the developer was indirectly liquid-developed for 60 seconds and then washed with pure water for development to obtain an independent fine line pattern-shaped coating film. Then, it was post-baked in a clean oven at 90 ° C. for 30 minutes to form a cured film having an independent fine line pattern. The obtained cured film was evaluated for adhesion and solvent resistance.
- the line width of the thinnest pattern is 5 ⁇ m to 10 ⁇ m or less
- Examples 1 to 26 of the photocurable red resin composition according to the present invention a cured film was formed by post-baking at a low temperature (90 ° C.) preferable for forming on the organic light emitting element.
- a cured film is formed with a film thickness of 3.0 ⁇ m, the spectral transmittance at a wavelength of 430 nm to 580 nm is 15.0% or less, and the spectral transmittance at a wavelength of 610 nm to 630 nm is 50.0% or more and 90.0%.
- the photocurable red resin composition according to the present invention is suitable for use as a cured film formed on an organic light emitting device, and the cured film is a thin film capable of suppressing external light reflection. It was shown that it is possible to manufacture an organic light emission display device with a thin film and improved flexibility.
- Substrate 2 Thin film transistor (TFT) 3 Sealing film 4 Electrode 5 Partition 6R, 6G, 6B Organic light emitting element 7 Electrode 8 Sealing layer 9R, 9G, 9B Colored cured film 10 Light-shielding part 11 Sealing film 20 External light antireflection film 30 Organic light emitting element Element board 100 display device
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Abstract
Description
前記光硬化性赤色樹脂組成物が、色材と、光重合性化合物と、光開始剤とを含有し、
前記色材が、赤色材と黒色材とを含む。
有機発光素子上に、前記本発明に係る光硬化性赤色樹脂組成物を塗布することにより塗膜を形成する工程、
前記塗膜に光照射する工程、
前記光照射後の膜を、加熱するポストベイク工程、及び、
前記光照射後の膜を、現像する工程を含有することにより、
有機発光素子上に前記本発明に係る光硬化性赤色樹脂組成物の硬化膜を形成する工程を有する。
本明細書において、ある部材又はある領域等のある構成が、他の部材又は他の領域等の他の構成の「上に(又は下に)」あるとする場合、特段の限定がない限り、これは他の構成の直上(又は直下)にある場合のみでなく、他の構成の上方(又は下方)にある場合を含み、すなわち、他の構成の上方(又は下方)において間に別の構成要素が含まれている場合も含む。
なお、本発明において光には、可視及び非可視領域の波長の電磁波、さらには放射線が含まれ、放射線には、例えばマイクロ波、電子線が含まれる。具体的には、波長5μm以下の電磁波、及び電子線のことをいう。
本発明において(メタ)アクリロイルとは、アクリロイル及びメタクリロイルの各々を表し、(メタ)アクリルとは、アクリル及びメタクリルの各々を表し、(メタ)アクリレートとは、アクリレート及びメタクリレートの各々を表す。
また、本明細書において数値範囲を示す「~」とは、その前後に記載された数値を下限値及び上限値として含む意味で使用される。
以下、本発明に係る光硬化性赤色樹脂組成物、表示装置、及び、有機発光素子と外光反射防止膜の積層体の製造方法について、順に詳細に説明する。
本発明に係る光硬化性赤色樹脂組成物は、有機発光素子上に形成する硬化膜に用いる光硬化性赤色樹脂組成物であって、
前記光硬化性赤色樹脂組成物が、色材と、光重合性化合物と、光開始剤とを含有し、
前記色材が、赤色材と黒色材とを含む。
また、本発明に係る光硬化性赤色樹脂組成物は、有機発光素子上に形成する硬化膜に用いることを特徴とする。すなわち、本発明に係る光硬化性赤色樹脂組成物は、有機発光素子を備えた素子基板上に直接形成する硬化膜に用いられるものである。本発明に係る光硬化性赤色樹脂組成物は、有機発光素子上に隣接して又は少なくとも1層介して形成する硬化膜に用いる光硬化性赤色樹脂組成物であることから、ガラス基板等の基板上に形成された外付けのカラーフィルタを有機発光素子に貼り合わせた表示装置に比べて、薄型化やフレキシブル化が向上した表示装置を製造可能である。
以下、このような本発明に係る光硬化性赤色樹脂組成物の各成分について、順に詳細に説明する。
本発明において、色材は、カラーフィルタの着色層を形成した際に所望の発色が可能なものであればよく、特に限定されず、種々の有機顔料、無機顔料、分散可能な染料、染料の造塩化合物等を、2種以上混合して用いることができるが、赤色材と黒色材とを含むことを特徴とする。
カーボンブラックとしては、遮光性がある顔料であれば特に限定はなく、公知のカーボンブラックを使用することができる。前記黒色顔料のカーボンブラックとしては、具体的には、チャンネルブラック、ファーネスブラック、サーマルブラック、ランプブラックなどが挙げられる。
中でも、前記色材が、その他の色材として、更に、緑色材及び青色材の少なくとも1種を含むことが、赤色材の透過スペクトル形状を良好に調整しやすく、外光反射の抑制効果を向上させやすい点から好ましい。
青色材としては、例えば、C.I.ピグメントブルー15、15:3、15:4、15:6、60等が挙げられる。
黄色材としては、例えば、C.I.ピグメントイエロー1、3、12、13、14、15、16、17、20、24、31、55、60、61、65、71、73、74、81、83、93、95、97、98、100、101、104、106、108、109、110、113、114、116、117、119、120、126、127、128、129、138、139、150、151、152、153、154、155、156、166、168、175、185、及びC.I.ピグメントイエロー150の誘導体顔料等が挙げられる。
オレンジ色材としては、例えば、C.I.ピグメントオレンジ1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73等が挙げられる。
膜厚3.0μmで硬化膜を形成した時に、430nm~580nmの波長におけるスペクトル透過率が15.0%以下であれば、赤色の色純度の低下が抑制され、発光素子からの色純度の低下も抑制しやすい。膜厚3.0μmで硬化膜を形成した時に、430nm~580nmの波長におけるスペクトル透過率は、10.0%以下であってよく、8.0%以下であってよい。
一方、膜厚3.0μmで硬化膜を形成した時に、610nm~630nmの波長におけるスペクトル透過率が50.0%以上であれば、表示装置の輝度低下や視認性の不良を抑制しやすい。膜厚3.0μmで硬化膜を形成した時に、610nm~630nmの波長におけるスペクトル透過率は、60.0%以上であってよく、70.0%以上であってよい。
また、膜厚3.0μmで硬化膜を形成した時に、610nm~630nmの波長におけるスペクトル透過率が90.0%以下であれば、外光反射の抑制効果を得やすい。膜厚3.0μmで硬化膜を形成した時に、610nm~630nmの波長におけるスペクトル透過率は、80.0%以下であってよく、70.0%以下であってよい。
本発明に用いられる色材において、黒色材の含有量は、色材全量に対して、通常、0.1質量%以上20質量%以下であってよく、好ましくは0.4質量%以上であってよく、より好ましくは1.0質量%以上であってよく、好ましくは10質量%以下であってよく、より好ましくは5質量%以下であってよい。
本発明に用いられる色材において、赤色材と黒色材の合計含有量は、色材全量に対して、通常、50質量%以上であってよく、好ましくは70質量%以上であってよく、より好ましくは90質量%以上であってよく、100質量%であってよいが、その他の色材を含有する場合には、99質量%以下であってよく、90質量%以下であってもよい。
その他の色材として緑色材及び青色材の少なくとも1種が用いられる場合の合計含有量は、通常、0.1質量%以上30質量%以下であってよく、好ましくは1質量%以上であってよく、より好ましくは10質量%以上であってよく、好ましくは30質量%以下であってよく、より好ましくは20質量%以下であってよい。
光硬化性赤色樹脂組成物中の色材の平均分散粒径は、少なくとも溶剤を含有する分散媒体中に分散している色材粒子の分散粒径であって、レーザー光散乱粒度分布計により測定されるものである。レーザー光散乱粒度分布計による粒径の測定としては、光硬化性赤色樹脂組成物に用いられている溶剤で、光硬化性赤色樹脂組成物をレーザー光散乱粒度分布計で測定可能な濃度に適宜希釈(例えば、1000倍など)し、レーザー光散乱粒度分布計(例えば、日機装社製ナノトラック粒度分布測定装置UPA-EX150)を用いて動的光散乱法により23℃にて測定することができる。ここでの平均分布粒径は、体積平均粒径である。
尚、本発明において固形分は、後述する溶剤以外のもの全てであり、溶剤中に溶解しているモノマー等も含まれる。
光硬化性赤色樹脂組成物において用いられる光重合性化合物としては、光重合性基を分子中に有する化合物が挙げられる。光重合性基としては、光開始剤によって重合可能なものであればよく、特に限定されないが、エチレン性不飽和二重結合が挙げられ、例えば、ビニル基、アリル基、アクリロイル基又はメタクリロイル基等が挙げられる。光重合性基としては、中でも紫外線硬化性の点から、アクリロイル基又はメタクリロイル基が好適に用いられる。
光重合性化合物としては、硬化性の点から、1分子中に光重合性基を2個以上有する化合物を含有することが好ましく、1分子中に光重合性基を3個以上有する化合物を含有することがより好ましい。
このような多官能(メタ)アクリレートとしては、従来公知のものの中から適宜選択して用いればよい。具体例としては、例えば、特開2013-029832号公報に記載のもの等が挙げられる。
本発明の光硬化性赤色樹脂組成物において用いられる光開始剤としては、従来知られている各種光開始剤の中から、1種又は2種以上を組み合わせて用いることができる。
光開始剤としては、例えば、芳香族ケトン類、ベンゾインエーテル類、ハロメチルオキサジアゾール化合物、α-アミノケトン類、ビイミダゾール類、N,N-ジメチルアミノベンゾフェノン、ハロメチル-S-トリアジン系化合物、チオキサントン、オキシムエステル類等を挙げることができる。このような光開始剤としては、従来公知の光開始剤を用いることができ、例えば、国際公開2018/062105号公報に記載されている光開始剤が挙げられる。
このような課題に対して、低温加熱処理でも硬化膜の基板密着性及び耐溶剤性が良好になる点から、中でも、光開始剤が、下記一般式(A)で表される化合物及び下記一般式(B)で表される化合物の少なくとも1種を含むことが好ましい。
R11、R12及びR13は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R11、R12及びR13で表される基の水素原子は、更にR21、OR21、COR21、SR21、NR22R23、CONR22R23、-NR22-OR23、-NCOR22-OCOR23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R21、R22及びR23は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R21、R22及びR23で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
R11、R12、R13、R21、R22及びR23で表される基のアルキレン部分は、-O-、-S-、-COO-、-OCO-、-NR24-、-NR24CO-、-NR24COO-、-OCONR24-、-SCO-、-COS-、-OCS-又は-CSO-を酸素原子が隣り合わない条件で1~5個含んでいてもよく、
R24は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R11、R12、R13、R21、R22、R23及びR24で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、
R3は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、R3で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、また、R3とR7、及びR3とR8はそれぞれ一緒になって環を形成していてもよく、
R3で表される基の水素原子は、更にR21、OR21、COR21、SR21、NR22R23、CONR22R23、-NR22-OR23、-NCOR22-OCOR23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R4、R5、R6及びR7は、それぞれ独立に、R11、OR11、SR11、COR14、CONR15R16、NR12COR11、OCOR11、COOR14、SCOR11、OCSR11、COSR14、CSOR11、水酸基、CN又はハロゲン原子を表し、R4とR5、R5とR6、及びR6とR7はそれぞれ一緒になって環を形成していてもよく、
R14、R15及びR16は、水素原子又は炭素数1~20のアルキル基を表し、R14、R15及びR16で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、
R8は、R11、OR11、SR11、COR11、CONR12R13、NR12COR11、OCOR11、COOR11、SCOR11、OCSR11、COSR11、CSOR11、水酸基、CN又はハロゲン原子を表し、
kは、0又は1を表す。)
R41、R42及びR43は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R41、R42及びR43、並びにX2で表される基の水素原子は、更にR51、OR51、COR51、SR51、NR52R53、CONR52R53、-NR52-OR53、-NCOR52-OCOR53、NR52COR51、OCOR51、COOR51、SCOR51、OCSR51、COSR51、CSOR51、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R51、R52及びR53は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R51、R52及びR53で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
R41、R42、R43、X2、R51、R52及びR53で表される基のアルキレン部分は、-O-、-S-、-COO-、-OCO-、-NR54-、-NR54CO-、-NR54COO-、-OCONR54-、-SCO-、-COS-、-OCS-又は-CSO-を酸素原子が隣り合わない条件で1~5個含んでいてもよく、
R54は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R41、R42、R43、R51、R52、R53及びR54で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよい。
a及びbは、それぞれ独立に、0~3の整数である。)
前記一般式(A)で表されるオキシムエステル化合物には、オキシムの二重結合による幾何異性体が存在するが、これらを区別するものではない。即ち、本明細書において、前記一般式(A)で表わされる化合物、並びに後述する該化合物の好ましい形態である下記一般式(A’)で表わされる化合物及びその例示化合物は、両方の混合物又はどちらか一方を表すものであり、異性体を示した構造に限定するものではない。
上記一般式(A)中の、R4とR5、R5とR6及びR6とR7並びにR3とR7及びR3とR8が一緒になって形成し得る環としては、例えば、シクロペンタン環、シクロヘキサン環、シクロペンテン環、ベンゼン環、ピペリジン環、モルフォリン環、ラクトン環、ラクタム環等の5~7員環が好ましく挙げられる。
上記一般式(A)で表される化合物の中でも、R3が縮合していてもよい芳香族環であるもの、あるいは下記一般式(A’)で表される化合物は、感度が高く、製造が容易であるため好ましい。
前記一般式(B)で表されるオキシムエステル化合物にも、オキシムの二重結合による幾何異性体が存在するが、これらを区別するものではない。即ち、本明細書において、前記一般式(B)で表わされる化合物及びその例示化合物は、両方の混合物又はどちらか一方を表すものであり、異性体を示した構造に限定するものではない。
上記一般式(B)中の、X2、R41、R42、R43、R51、R52、R53及びR54で表される炭素数6~30のアリール基としては、前記一般式(A)における炭素数6~30のアリール基と同様のものが挙げられる。
上記一般式(B)中の、X2、R41、R42、R43、R51、R52、R53及びR54で表される炭素数7~30のアリールアルキル基としては、前記一般式(A)における炭素数7~30のアリールアルキル基と同様のものが挙げられる。
上記一般式(B)中の、X2、R41、R42、R43、R51、R52、R53及びR54で表される炭素数2~20の複素環基としては、前記一般式(A)における炭素数2~20の複素環基と同様のものが挙げられる。
また、上記一般式(B)中のハロゲン原子としては、前記一般式(A)におけるハロゲン原子と同様のものが挙げられる。
X3、及びX6は、それぞれ独立に、感度、溶解性、相溶性の点から、さらに好ましくは炭素数が1~6のアルキル基である。
X2は感度、溶解性、相溶性の点から、さらに好ましくは炭素数が2~6のメチレン鎖中に1つのエーテル結合を有するアルキル基である。
本発明に係る光硬化性赤色樹脂組成物は、更にアルカリ可溶性樹脂、溶剤を含有し、アルカリ現像性を有する光硬化性赤色樹脂組成物であってもよい。
本発明に用いられるアルカリ可溶性樹脂は酸性基を有するものであり、バインダー樹脂として作用し、かつパターン形成する際に用いられるアルカリ現像液に可溶性であるものの中から、適宜選択して使用することができる。
本発明において、アルカリ可溶性樹脂とは、酸価が40mgKOH/g以上であることを目安にすることができる。
本発明における好ましいアルカリ可溶性樹脂は、酸性基、通常カルボキシ基を有する樹脂であり、具体的には、カルボキシ基を有する(メタ)アクリル系共重合体及びカルボキシ基を有するスチレン-(メタ)アクリル系共重合体等の(メタ)アクリル系樹脂、カルボキシ基を有するエポキシ(メタ)アクリレート樹脂等が挙げられ、カルボキシ基を有する(メタ)アクリル系共重合体及びカルボキシ基を有するスチレン-(メタ)アクリル系共重合体等の(メタ)アクリル系樹脂が好適に用いられる。これらの中で特に好ましいものは、側鎖にカルボキシ基を有するとともに、さらに側鎖にエチレン性不飽和基等の光重合性官能基を有するものである。光重合性官能基を含有することにより形成される硬化膜の膜強度が向上するからである。また、これら(メタ)アクリル系共重合体及びスチレン-(メタ)アクリル系共重合体等の(メタ)アクリル系樹脂、並びにエポキシ(メタ)アクリレート樹脂は、2種以上混合して使用してもよい。
本発明に用いられる溶剤としては、光硬化性赤色樹脂組成物中の各成分とは反応せず、これらを溶解もしくは分散可能な有機溶剤であればよく、特に限定されない。溶剤は単独もしくは2種以上組み合わせて使用することができる。
溶剤の具体例としては、例えば、メチルアルコール、エチルアルコール、N-プロピルアルコール、i-プロピルアルコール、メトキシアルコール、エトキシアルコールなどのアルコール系溶剤;メトキシエトキシエタノール、エトキシエトキシエタノールなどのカルビトール系溶剤;酢酸エチル、酢酸ブチル、メトキシプロピオン酸メチル、メトキシプロピオン酸エチル、エトキシプロピオン酸エチル、乳酸エチル、ヒドロキシプロピオン酸メチル、ヒドロキシプロピオン酸エチル、n-ブチルアセテート、イソブチルアセテート、酪酸イソブチル、酪酸n-ブチル、乳酸エチル、シクロヘキサノールアセテートなどのエステル系溶剤;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノンなどのケトン系溶剤;メトキシエチルアセテート、プロピレングリコールモノメチルエーテルアセテート、3-メトキシ-3-メチル-1-ブチルアセテート、3-メトキシブチルアセテート、エトキシエチルアセテートなどのグリコールエーテルアセテート系溶剤;メトキシエトキシエチルアセテート、エトキシエトキシエチルアセテート、ブチルカルビトールアセテート(BCA)などのカルビトールアセテート系溶剤;プロピレングリコールジアセテート、1,3-ブチレングリコールジアセテート等のジアセテート類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテルなどのグリコールエーテル系溶剤;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドンなどの非プロトン性アミド溶剤;γ-ブチロラクトンなどのラクトン系溶剤;テトラヒドロフランなどの環状エーテル系溶剤;ベンゼン、トルエン、キシレン、ナフタレンなどの不飽和炭化水素系溶剤;N-ヘプタン、N-ヘキサン、N-オクタンなどの飽和炭化水素系溶剤;トルエン、キシレン等の芳香族炭化水素類などの有機溶剤が挙げられる。これらの溶剤の中ではグリコールエーテルアセテート系溶剤、カルビトールアセテート系溶剤、グリコールエーテル系溶剤、エステル系溶剤が他の成分の溶解性の点で好適に用いられる。中でも、本発明に用いる溶剤としては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、ブチルカルビトールアセテート(BCA)、3-メトキシ-3-メチル-1-ブチルアセテート、エトキシプロピオン酸エチル、乳酸エチル、及び、3-メトキシブチルアセテートよりなる群から選択される1種以上であることが、他の成分の溶解性や塗布適性の点から好ましい。
本発明の光硬化性赤色樹脂組成物において、色材を分散させる場合には、色材分散性と色材分散安定性の点から、分散剤を更に含んでいても良い。
本発明において分散剤は、従来公知の分散剤の中から適宜選択して用いることができる。分散剤としては、例えば、カチオン系、アニオン系、ノニオン系、両性、シリコーン系、フッ素系等の界面活性剤を使用できる。界面活性剤の中でも、均一に、微細に分散し得る点から、高分子分散剤が好ましい。
(メタ)アクリレート共重合体系分散剤は、色材吸着部位として機能する構成単位と、溶剤親和性部位として機能する構成単位とを含有する共重合体であることが好ましく、溶剤親和性部位として機能する構成単位に少なくとも(メタ)アクリレート由来の構成単位を含むことが好ましい。
塩基性基含有エチレン性不飽和モノマー由来の構成単位としては、下記一般式(I)で表される構成単位が、分散性に優れている点から好ましい。
中でも、分散性の点から、一般式(I)におけるA1は、-CONH-基又は-COO-基を含む2価の連結基であることが好ましく、-CONH-基又は-COO-基と、炭素数1~10のアルキレン基とを含む2価の連結基であることがより好ましい。
アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、tert-ブチル基、2-エチルヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられ、アルキル基の炭素数は、1~18が好ましく、中でも、メチル基又はエチル基であることがより好ましい。
アラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられる。アラルキル基の炭素数は、7~20が好ましく、更に7~14が好ましい。
また、アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素数は、6~24が好ましく、更に6~12が好ましい。なお、上記好ましい炭素数には、置換基の炭素数は含まれない。
ヘテロ原子を含む炭化水素基とは、上記炭化水素基中の炭素原子がヘテロ原子で置き換えられた構造を有するか、上記炭化水素基中の水素原子がヘテロ原子を含む置換基で置き換えられた構造を有する。炭化水素基が含んでいてもよいヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、ケイ素原子等が挙げられる。
また、炭化水素基中の水素原子は、フッ素原子、塩素原子、臭素原子等のハロゲン原子により置換されていてもよい。
重合体において、一般式(I)で表される構成単位は、1種類からなるものであってもよく、2種以上の構成単位を含むものであってもよい。
前記有機酸化合物としては、中でも、下記一般式(1)で表される化合物及び下記一般式(3)で表される化合物が好ましく、前記ハロゲン化炭化水素としては、中でも、下記一般式(2)で表される化合物が好ましい。すなわち、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種としては、下記一般式(1)~(3)よりなる群から選択される1種以上の化合物を好ましく用いることができる。
前記有機酸化合物がフェニルホスホン酸やフェニルホスフィン酸等の酸性有機リン化合物であることが、色材の分散性及び分散安定性に優れる点から好ましい。このような分散剤に用いられる有機酸化合物の具体例としては、例えば、特開2012-236882号公報等に記載の有機酸化合物が好適なものとして挙げられる。
また、前記ハロゲン化炭化水素としては、臭化アリル、塩化ベンジル等のハロゲン化アリル及びハロゲン化アラルキルの少なくとも1種であることが、色材の分散性及び分散安定性に優れる点から好ましい。
なお、有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種は、1種単独で用いてもよく、2種以上を組み合わせてもよい。2種以上を組み合わせる場合は、その合計の含有量が上記範囲内であることが好ましい。
なお、共重合体の当該一般式(I)で表される構成単位が有する末端の窒素部位と、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種とが塩を形成していること、及びその割合は、例えばNMR等、公知の手法により確認することができる。
以下、前記グラフト共重合体、及び、前記ブロック共重合体について、順に説明する。
中でも、分散性の点から、一般式(II)におけるA2は、-CONH-基又は-COO-基を含む2価の連結基であることが好ましく、-CONH-基又は-COO-基と、炭素数1~10のアルキレン基とを含む2価の連結基であることがより好ましい。
当該ポリマー鎖の構成単位としては、下記一般式(III)で表される構成単位が挙げられる。
前記炭素数1~18のアルキル基は、直鎖状、分岐状、環状のいずれであってもよく、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、n-ノニル基、n-ラウリル基、n-ステアリル基、シクロペンチル基、シクロヘキシル基、ボルニル基、イソボルニル基、ジシクロペンタニル基、アダマンチル基、低級アルキル基置換アダマンチル基などを挙げることができる。アルキル基の炭素数は、1~12が好ましく、更に1~6が好ましい。
前記炭素数2~18のアルケニル基は、直鎖状、分岐状、環状のいずれであってもよい。このようなアルケニル基としては、例えばビニル基、アリル基、プロペニル基などを挙げることができる。アルケニル基の二重結合の位置には限定はないが、得られたポリマーの反応性の点からは、アルケニル基の末端に二重結合があることが好ましい。アルケニル基の炭素数は、2~12が好ましく、更に2~8が好ましい。
アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素数は、6~24が好ましく、更に6~12が好ましい。
また、アラルキル基としては、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられ、更に置換基を有していてもよい。アラルキル基の炭素数は、7~20が好ましく、更に7~14が好ましい。
また、前記アリール基やアラルキル基等の芳香環には、置換基として炭素数1~30の直鎖状、分岐状のアルキル基が結合していても良い。
また、当該炭化水素基は、前記グラフト共重合体の分散性能等を妨げない範囲で、置換基を有しても良く、置換基としては、例えば、ハロゲン原子、水酸基、カルボキシ基、アルコキシ基、ニトロ基、シアノ基、エポキシ基、イソシアネート基、チオール基等が挙げられる。
下記一般式(IV)で表される構成単位及び下記一般式(IV’)で表される構成単位は、前記一般式(III)で表される構成単位に包含される構成単位である。
一般式(IV’)中、R74’は水素原子又はメチル基、A3’は2価の連結基、R77は炭素数が1~10のアルキレン基、R78は炭素数が3~7のアルキレン基、R79は、水素原子、又は炭化水素基であり、nは1以上40以下の数を表す。)
前記mが19以上の場合には、前記グラフト共重合体は、一般式(I)で表される構成単位と一般式(II)で表される構成単位とを有する主鎖部分を含有し、前記一般式(II)で表される構成単位はポリマー鎖において、特定の繰り返し数を有するポリエチレンオキシド鎖又はポリプロピレンオキシド鎖を含む一般式(IV)で表される構成単位が含まれる。本発明に用いられる特定のグラフト共重合体においては、このようにグラフトしているポリマー鎖の構成単位に、特定の繰り返し数を有するポリエチレンオキシド鎖又はポリプロピレンオキシド鎖を有する構成単位が含まれ、グラフトしているポリマー鎖自体が枝分かれ構造を有する。グラフトしている複数のポリマー鎖が膜中で立体的に広がり、比表面積が大きくなることから、溶剤の塗膜への侵入や色材への到達をより抑制することができると推定される。
一方、mの上限値は80以下であるが、カラーフィルタ用途に使用される有機溶剤への溶解性の点から、50以下であることが好ましい。
R76における炭化水素基としては、中でも、分散安定性や相溶性の点から、炭素数1~18のアルキル基、アルキル基が置換されていても良い炭素数6~12のアリール基、及び、アルキル基が置換されていても良い炭素数7~14のアラルキル基からなる群から選択される1種以上であることが好ましく、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、n-ノニル基、n-ラウリル基、n-ステアリル基、アルキル基が置換されていても良いフェニル基及びベンジル基からなる群から選択される1種以上であることが好ましい。
前記一般式(IV’)において、R77は炭素数が1~10のアルキレン基であるが、中でも炭素数が2~8のアルキレン基であることが、溶剤再溶解性の点から好ましい。
R78は炭素数が3~7のアルキレン基であるが、中でも炭素数が3~5のアルキレン基、更に炭素数が5のアルキレン基であることが基材密着性の点から好ましい。
R79は、水素原子、又は炭化水素基であり、前記R79における炭化水素基としては、前記R76における炭化水素基と同様であって良い。
一方、nの上限値は40以下であるが、カラーフィルタ用途に使用される有機溶剤への溶解性の点から、20以下であることが好ましい。
前記ポリマー鎖において、前記一般式(IV)で表される構成単位が含まれることが、酸素原子による溶剤親和性部の作用がより顕著になり、光硬化性赤色樹脂組成物の現像時間の短縮化、及び耐溶剤性が向上する点から好ましい。
また、前記ポリマー鎖において、mが19以上80以下の前記一般式(IV)で表される構成単位と、mが3以上10以下の前記一般式(IV)で表される構成単位との混合割合は、現像残渣抑制効果向上の点から、mが19以上80以下の前記一般式(IV)で表される構成単位と、mが3以上10以下の前記一般式(IV)で表される構成単位との合計を100質量部とした時に、mが19以上80以下の前記一般式(IV)で表される構成単位の合計が3質量部以上であることが好ましく、6質量部以上であることがより好ましく、80質量部以下であることが好ましく、60質量部以下であることがより好ましい。
色材の分散性及び分散安定性の点から、前記一般式(III)で表される構成単位の合計割合は、当該ポリマー鎖の全構成単位を100質量%とした時に、70質量%以上であることが好ましく、90質量%以上であることがより好ましい。一方で、分散安定性、及び優れた耐溶剤性を同時に満たす点から、前記ポリマー鎖において、前記一般式(III)で表される構成単位の合計割合は、当該ポリマー鎖の全構成単位を100質量%とした時に、100質量%であってもよい。
中でも(メタ)アクリレート由来の構成単位の合計割合は、分散安定性及び耐溶剤性、開始剤との相溶性の点から、当該ポリマー鎖の全構成単位を100質量%とした時に、60質量%以上であることが好ましく、80質量%以上であることがより好ましい。一方で、分散安定性、及び優れた耐溶剤性を同時に満たす点から、前記ポリマー鎖において、(メタ)アクリレート由来の構成単位の合計割合は、当該ポリマー鎖の全構成単位を100質量%とした時に、100質量%であってもよい。
その他の構成単位としては、前記一般式(III)で表される構成単位を誘導するモノマーと共重合可能な不飽和二重結合を有する単量体由来の構成単位を挙げることができる。
その他の構成単位を誘導するモノマーとしては、例えば、スチレン、α-メチルスチレン等のスチレン類、フェニルビニルエーテル等のビニルエーテル類等が挙げられる。
前記範囲であることにより、分散剤としての十分な立体反発効果を保持できるとともに、分散剤の溶剤親和性部の比表面積が大きくなることにより、溶剤の塗膜への侵入や色材への到達を抑制しやすくなる。
当該ポリマー鎖の溶解性は、グラフト共重合体を調製する際のポリマー鎖を導入する原料が前記溶解度を有することを目安にすることができる。例えば、グラフト共重合体にポリマー鎖を導入するために、ポリマー鎖及びその末端にエチレン性不飽和二重結合を有する基を含む重合性オリゴマー(マクロモノマー)を用いる場合、当該重合性オリゴマーが前記溶解度を有すれば良い。また、エチレン性不飽和二重結合を有する基を含むモノマーにより共重合体が形成された後に、共重合体中に含まれる反応性基と反応可能な反応性基を含むポリマー鎖を用いて、ポリマー鎖を導入する場合、当該反応性基を含むポリマー鎖が前記溶解度を有すれば良い。
一方、前記グラフト共重合体において、前記一般式(II)で表される構成単位は、40質量%~97質量%の割合で含まれていることが好ましく、55質量%~94質量%がより好ましく、70質量%~91質量%がさらに好ましい。グラフト共重合体中の一般式(II)で表される構成単位が前記範囲内にあれば、グラフト共重合体中の溶剤親和性部の割合が適切になって、分散剤としての十分な立体反発効果を保持できるとともに、分散剤の溶剤親和性部の比表面積が大きくなることにより、溶剤の塗膜への侵入や色材への到達を抑制しやすい。
前記一般式(I)で表される構成単位と共重合されている他の構成単位としては、例えば、前記一般式(III)で表される構成単位等が挙げられる。
なお、前記構成単位の含有割合は、製造時には、グラフト共重合体を合成する際の、前記一般式(I)で表される構成単位、前記一般式(II)で表される構成単位、及び前記一般式(III)で表される構成単位等を誘導するモノマーの仕込み量から算出される。
なお、本発明において質量平均分子量Mwは、GPC(ゲルパーミエーションクロマトグラフィー)により測定された値である。測定は、東ソー製のHLC-8120GPCを用い、溶出溶剤を0.01モル/リットルの臭化リチウムを添加したN-メチルピロリドンとし、校正曲線用ポリスチレンスタンダードをMw377400、210500、96000、50400、20650、10850、5460、2930、1300、580(以上、Polymer Laboratories製 Easi PS-2シリーズ)及びMw1090000(東ソー製)とし、測定カラムをTSK-GEL ALPHA-M×2本(東ソー製)として行われたものである。
本発明において、前記グラフト共重合体の製造方法としては、前記一般式(I)で表される構成単位と、前記一般式(II)で表される構成単位とを有するグラフト共重合体を製造することができる方法であればよく、特に限定されない。前記一般式(I)で表される構成単位と前記一般式(II)で表される構成単位とを有するグラフト共重合体を製造する場合、例えば、下記一般式(Ia)で表されるモノマーと、前記ポリマー鎖及びその末端にエチレン性不飽和二重結合を有する基からなる重合性オリゴマー(マクロモノマー)とを共重合成分として含有して共重合し、グラフト共重合体を製造する方法が挙げられる。
必要に応じて更にその他のモノマーも用い、公知の重合手段を用いてグラフト共重合体を製造することができる。
例えば、側鎖にグリシジル基を有する共重合体に、末端にカルボキシル基を有するポリマー鎖を反応させたり、側鎖にイソシアネート基を有する共重合体に、末端にヒドロキシ基を有するポリマー鎖を反応させたりして、ポリマー鎖を導入することができる。
なお、前記重合においては、重合に一般的に用いられる添加剤、例えば重合開始剤、分散安定剤、連鎖移動剤などを用いてもよい。
本発明においてブロック共重合体の各ブロックの配置は特に限定されず、例えば、ABブロック共重合体、ABAブロック共重合体、BABブロック共重合体等とすることができる。中でも、分散性に優れる点で、ABブロック共重合体、又はABAブロック共重合体が好ましい。
Aブロックは、本発明の目的を達成する範囲で、一般式(I)で表される構成単位以外の構成単位を有するものであってもよく、一般式(I)で表される構成単位と共重合可能な構成単位であれば含有することができる。具体的には例えば、前記一般式(III)で表される構成単位等が挙げられる。
塩形成前のブロック共重合体におけるAブロック中、一般式(I)で表される構成単位の含有割合は、Aブロックの全構成単位の合計質量に対して、50質量%~100質量%であることが好ましく、80質量%~100質量%であることがより好ましく、100質量%であることが最も好ましい。一般式(I)で表される構成単位の割合が高いほど、色材への吸着力が向上し、ブロック共重合体の分散性、及び分散安定性が良好となるからである。なお、上記構成単位の含有割合は、一般式(I)で表される構成単位を有するAブロックを合成する際の仕込み質量から算出される。
また、塩形成前のブロック共重合体中、一般式(I)で表される構成単位の含有割合は、分散性、及び分散安定性が良好となる点から、ブロック共重合体の全構成単位の合計質量に対して、5質量%~60質量%であることが好ましく、10質量%~50質量%であることがより好ましい。なお、上記ブロック共重合体における各構成単位の含有割合は、塩形成前のブロック共重合体を合成する際の仕込み質量から算出される。
なお、一般式(I)で表される構成単位は、色材との親和性を有すればよく、1種からなるものであっても良いし、2種以上の構成単位を含んでいてもよい。
(メタ)アクリレート由来の構成単位としては、前記と同様であってよい。
Bブロックとしては、一般式(I)で表される構成単位を誘導するモノマーと共重合可能な、不飽和二重結合を有するモノマーの中から、溶剤親和性を有するように溶剤に応じて適宜選択して用いられることが好ましい。目安として、組み合わせて用いられる溶剤に対して、共重合体の23℃における溶解度が20(g/100g溶剤)以上となるように、Bブロックを導入することが好ましい。Bブロック部を構成する構成単位は1種からなるものであっても良いし、2種以上の構成単位を含んでいてもよい。
Bブロックに含まれる構成単位としては、例えば、前記一般式(III)で表される構成単位等が挙げられる。
この場合のBブロックは、(メタ)アクリレート由来の構成単位を必須成分として含むが、国際公開第2016/104493号のBブロックと同様であってよい。
カルボキシ基含有モノマー由来の構成単位の含有割合が、前記下限値以上であることより、現像残渣の抑制効果が発現され、前記上限値以下であることより現像密着性の悪化や溶剤再溶解性の悪化を防止できる。
なお、カルボキシ基含有モノマー由来の構成単位は、上記特定の酸価となればよく、1種からなるものであっても良いし、2種以上の構成単位を含んでいてもよい。
現像密着性が向上する点から、中でも、2-ヒドロキシエチルメタクリレート、及び2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレートよりなる群から選択される1種以上であることが好ましい。
前記ブロック共重合体並びに塩型ブロック共重合体の少なくとも1種の酸価は、国際公開第2016/104493号に記載の方法で求めることができる。
前記ブロック共重合体並びに塩型ブロック共重合体の少なくとも1種のガラス転移温度は、JIS K7121に準拠し、示差走査熱量測定(DSC)により測定することにより求める。ガラス転移温度を示すピークが2つ以上見られる場合には、ピーク面積、すなわち、得られたチャートのベースラインから突出した部分の面積が最も大きいピークをガラス転移温度の代表値とする。
ここで、質量平均分子量は(Mw)、前記と同様に測定することができる。
また、塩形成前のブロック共重合体中、上記一般式(III)で表される構成単位の含有割合は、色材分散性を向上する点から、ブロック共重合体の全構成単位の合計質量に対して、40質量%~95質量%であることが好ましく、50質量%~90質量%であることがより好ましい。なお、上記構成単位の含有割合は、塩形成前のブロック共重合体を合成する際の仕込み質量から算出される。
アミン価が上記範囲内であることにより、粘度の経時安定性や耐熱性に優れると共に、アルカリ現像性や、溶剤再溶解性にも優れている。本発明において、前記一般式(I)で表される構成単位を含む(メタ)アクリレート系共重合体のアミン価は、中でも、アミン価が80mgKOH/g以上であることが好ましく、90mgKOH/g以上であることがより好ましい。一方、溶剤再溶解性の点から、前記一般式(I)で表される構成単位を含む(メタ)アクリレート系共重合体のアミン価は、110mgKOH/g以下であることが好ましく、105mgKOH/g以下であることがより好ましい。
アミン価は、試料1g中に含まれるアミン成分を中和するのに要する過塩素酸と当量の水酸化カリウムのmg数をいい、JIS-K7237に定義された方法により測定することができる。当該方法により測定した場合には、分散剤中の有機酸化合物と塩形成しているアミノ基であっても、通常、当該有機酸化合物が解離するため、分散剤として用いられるブロック共重合体そのもののアミン価を測定することができる。
本発明の光硬化性赤色樹脂組成物は、低温加熱処理後の耐溶剤性、及び基板密着性を向上する点から、更に、チオール化合物を含有することが好ましい。
チオール化合物としては、チオール基が1つの単官能チオール化合物、チオール基が2つ以上の多官能チオール基が挙げられる。線幅シフトの抑制と基板密着性の向上の点からは、チオール基が1つの単官能チオール化合物を用いることがより好ましい。
単官能チオール化合物としては、例えば、2-メルカプトベンゾチアゾール、2-メルカプトベンゾオキサゾール、2-メルカプトベンゾイミダゾール、2-メルカプト-5-メトキシベンゾチアゾール、2-メルカプト-5-メトキシベンゾイミダゾール、3-メルカプトプロピオン酸、3-メルカプトプロピオン酸メチル、3-メルカプトプロピオン酸エチル、3-メルカプトプロピオン酸オクチル等が挙げられる。
多官能チオール化合物としては、例えば、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、1,3,5-トリス(3-メルカプトブチルオキシエチル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、トリメチロールプロパントリス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキス(3-メルカプトブチレート)、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)、およびテトラエチレングリコールビス(3-メルカプトプロピオネート)等が挙げられる。
チオール化合物としては、単独で又は2種以上組み合わせて用いても良く、中でも、2-メルカプトベンゾオキサゾール、又は2-メルカプトベンゾチアゾールが、低温加熱処理後の耐溶剤性、及び基板密着性を向上する点から好ましい。
チオール化合物の含有量としては、光硬化性赤色樹脂組成物の固形分全量に対して、通常0.5質量%~10質量%、好ましくは1質量%~5質量%の範囲内である。上記下限値以上であれば、低温加熱処理後の耐溶剤性、及び基板密着性に優れやすい。一方、上記上限値以下であれば、本発明の光硬化性赤色樹脂組成物を現像性が良好で線幅シフトが抑制されたものとしやすい。
本発明の光硬化性赤色樹脂組成物には、必要に応じて、更に各種添加剤を含むものであってもよい。添加剤としては、例えば、酸化防止剤、重合停止剤、連鎖移動剤、レベリング剤、可塑剤、界面活性剤、消泡剤、シランカップリング剤、紫外線吸収剤、密着促進剤等などが挙げられる。
界面活性剤及び可塑剤の具体例としては、例えば、特開2013-029832号公報に記載のものが挙げられる。
本発明に用いられる酸化防止剤としては、特に限定されず、従来公知のものの中から適宜選択すればよい。酸化防止剤の具体例としては、例えば、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、ヒドラジン系酸化防止剤等が挙げられ、線幅マスク線幅の設計通りに細線パターンを形成する能力が向上する点、及び耐熱性の点から、ヒンダードフェノール系酸化防止剤を用いることが好ましい。国際公開第2014/021023号に記載されているような潜在性酸化防止剤であっても良い。
本発明の光硬化性赤色樹脂組成物の製造方法は、色材と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分とを、公知の混合手段を用いて混合することにより、調製することができる。
本発明の光硬化性赤色樹脂組成物が、色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、溶剤と、所望により用いられる各種添加成分とを含有する場合、当該樹脂組成物の調製方法としては、例えば、(1)まず溶剤中に、色材と、分散剤とを添加して色材分散液を調製し、当該分散液に、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分を混合する方法;(2)溶剤中に、色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分とを同時に投入し混合する方法;(3)溶剤中に、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分とを添加し、混合したのち、色材を加えて分散する方法;(4)溶剤中に、色材と、分散剤と、アルカリ可溶性樹脂とを添加して色材分散液を調製し、当該分散液に、更にアルカリ可溶性樹脂と、溶剤と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分を添加し、混合する方法;などを挙げることができる。
これらの方法の中で、上記(1)及び(4)の方法が、色材の凝集を効果的に防ぎ、均一に分散させ得る点から好ましい。
本発明に係る光硬化性赤色樹脂組成物は、硬化膜が外光反射抑制効果を有することから、円偏光板代替の着色硬化膜の形成に好適に用いられる。本発明に係る光硬化性赤色樹脂組成物の硬化膜を円偏光板の代替に用いる場合には、偏光板を含まない表示装置とすることができるため、本発明に係る光硬化性赤色樹脂組成物は、偏光板を含まない表示装置用途に好適に用いられる。
また、本発明に係る光硬化性赤色樹脂組成物は、有機発光素子上に形成する硬化膜に用いる光硬化性赤色樹脂組成物であることから、外付けのカラーフィルタ基板を含まない表示装置用途、薄膜でフレキシブル性が向上した有機発光表示装置用途に好適に用いられる。
また、本発明に係る光硬化性赤色樹脂組成物は、前述のように成分を適宜選択することにより、低温加熱処理でも耐溶剤性が良好で、基板密着性に優れた硬化膜を形成可能であることから、耐熱性が低い素子が形成された基板上に、130℃以下、更に100℃以下や90℃以下の低温加熱処理で硬化膜を形成する用途に好適に用いることができる。
本発明に係る表示装置は、有機発光素子上に、前記本発明に係る光硬化性赤色樹脂組成物の硬化膜を有することを特徴とする。
本発明に係る表示装置は、前記本発明に係る有機発光素子上に形成する硬化膜に用いる光硬化性赤色樹脂組成物の硬化膜が、有機発光素子上に形成されているものであることから、外付けの円偏光板や、外付けのカラーフィルタ基板が不要であり、これらを有しないものであってよい。
本発明に係る表示装置は、前記本発明に係る有機発光素子上に形成する硬化膜に用いる光硬化性赤色樹脂組成物を用いて、有機発光素子上に硬化膜が形成されることから、有機発光素子と硬化膜の間に外付けのカラーフィルタ基板に用いられるような基板を有しないため、薄膜化とフレキシブル性が向上したものである。
前記有機発光素子を備えた素子基板30は、基板1上に駆動素子である薄膜トランジスタ(TFT)2が各サブピクセルに対応するよう配置され、その上に封止膜3を備え、さらに封止膜3上には各サブピクセルに対応する電極4(陽極)、各サブピクセルを区画する隔壁5を備え、その区画内にR、G,B3色のサブピクセルを構成する有機発光素子(6R、6G、6B)が配置され、当該有機発光素子(6R、6G、6B)上に、更に電極7(陰極)を備えている。前記有機発光素子を備えた素子基板30は、さらにその上から有機発光素子を覆う封止層8を備える。
素子基板30における有機EL素子(6R、6G、6B)上の封止層8上に、光硬化性着色樹脂組成物を用いて形成される各有機EL素子に対応した3色の着色硬化膜(9R、9G、9B)及び遮光部10を含む外光反射防止膜20を備え、更にその上に封止膜11を備える。
本発明に係る表示装置100は、図示しないが、例えば、さらに封止膜11上に絶縁膜および透明電極層からなるタッチセンサー層を備え、さらにタッチセンサー層上にハードコート層等、公知の構成をさらに適宜備えていてよいものである。
上記のように、前記有機発光素子を備えた素子基板30上に設けられた、着色硬化膜(9R、9G、9B)及び遮光部10の層が、外光反射防止膜20として用いられることから、本発明に用いられる外光反射防止膜は、外付けの円偏光板や外付けのカラーフィルタ基板のように別途基板が含まれず、薄膜化及びフレキシブル性を向上できる。
前記本発明に係る光硬化性赤色樹脂組成物の硬化膜は、前記3色の着色硬化膜(9R、9G、9B)のうち、赤色硬化膜(9R)であってよい。
有機発光素子には、発光層の他に、正孔注入層、正孔輸送層、電子注入層等、公知の構成を備えていてもよい。
具体的には例えば、金属膜、金属酸化物膜、SiOx、SiNx等の無機膜と有機膜を積層した多層膜等が挙げられる。
着色硬化膜は、通常、有機発光素子上の封止層8上の後述する遮光部の開口部に形成され、通常3色以上の着色パターンから構成される。これらは有機発光素子のサブピクセルの(6R、6G、6B)と同様の着色パターンであってよい。
着色硬化膜(9R、9G、9B)の配列としては、例えば、ストライプ型、モザイク型、トライアングル型、4画素配置型等の一般的な配列とすることができる。また、着色層の幅、面積等は有機発光素子のサブピクセルの(6R、6G、6B)に適合するように適宜設定することができる。
当該着色硬化膜の厚みは、塗布方法、光硬化性赤色樹脂組成物の固形分濃度や粘度等を調整することにより、適宜制御されるが、通常、1μm~5μmの範囲である。
当該遮光部のパターン形状としては、前記着色硬化膜の形状に合わせて適宜選択されればよく、例えば、ストライプ状、マトリクス状等の形状が挙げられる。遮光部は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法、感光性レジストを熱転写する方法等がある。
本発明に係る有機発光素子と外光反射防止膜の積層体の製造方法は、
有機発光素子上に、前記本発明に係る光硬化性赤色樹脂組成物を塗布することにより塗膜を形成する工程、
前記塗膜に光照射する工程、
前記光照射後の膜を、加熱するポストベイク工程、及び、
前記光照射後の膜を、現像する工程を含有することにより、
有機発光素子上に前記本発明に係る光硬化性赤色樹脂組成物の硬化膜を形成する工程を有する。
以下各工程について、説明する。
次いで、ホットプレートやオーブンなどを用いて、該ウェット塗膜を乾燥させ、塗膜を形成する。
ポストベイク工程は、前記光照射後の膜に対して、後述する現像工程前に行ってもよいし、現像工程後に行ってもよいし、現像工程前後に行ってもよい。
現像工程においては、現像液を用いて現像処理し、未露光部分を溶解、除去することにより、所望のパターンで塗膜が形成される。現像液としては、通常、水や水溶性溶剤にアルカリを溶解させた溶液が用いられる。このアルカリ溶液には、界面活性剤などを適量添加してもよい。また、現像方法は一般的な方法を採用することができる。
本発明では有機発光素子を備えた素子基板上に直接着色硬化膜を形成することから、このポストベイク工程における加熱温度も、130℃以下が好ましく、100℃以下がより好ましく、90℃以下が更に好ましい。また、加熱温度は、30℃以上であってよく、35℃以上であってよく、40℃以上であってよい。
塩形成前の共重合体の質量平均分子量(Mw)は、前述の本発明の明細書に記載した測定方法に従って、GPC(ゲルパーミエーションクロマトグラフィー)により標準ポリスチレン換算値として求めた。
冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた500mL丸底4口セパラブルフラスコにTHF250質量部、塩化リチウム0.6質量部を加え、充分に窒素置換を行った。反応フラスコを-60℃まで冷却した後、ブチルリチウム4.9質量部(15質量%ヘキサン溶液)、ジイソプロピルアミン1.1質量部、イソ酪酸メチル1.0質量部をシリンジを用いて注入した。Bブロック用モノマーのメタクリル酸1-エトキシエチル(EEMA)2.2質量部、メタクリル酸2-(トリメチルシリルオキシ)エチル(TMSMA) 29.1質量部、メタクリル酸2-エチルヘキシル(EHMA)12.8質量部、メタクリル酸n-ブチル(BMA)13.7質量部、メタクリル酸ベンジル(BzMA)9.5質量部、メタクリル酸メチル(MMA)17.5質量部を、添加用ロートを用いて60分かけて滴下した。30分後、Aブロック用モノマーであるメタクリル酸ジメチルアミノエチル(DMMA)26.7質量部を20分かけて滴下した。30分間反応させた後、メタノール1.5質量部を加えて反応を停止させた。得られた前駆体ブロック共重合体THF溶液はヘキサン中で再沈殿させ、濾過、真空乾燥により精製を行い、PGMEAで希釈し固形分30質量%溶液とした。水を32.5質量部加え、100℃に昇温し7時間反応させ、EEMA由来の構成単位を脱保護しメタクリル酸(MAA)由来の構成単位とし、TMSMA由来の構成単位を脱保護してメタクリル酸2-ヒドロキシエチル(HEMA)由来の構成単位とした。得られたブロック共重合体PGMEA溶液はヘキサン中で再沈殿させ、濾過、真空乾燥により精製を行い、前記一般式(I)で表される構成単位を含むブロック共重合体1(アミン価 95mgKOH/g、酸価 8mgKOH/g、Tg38℃)を得た。重量平均分子量Mwは7730であった。
(1)マクロモノマーAの製造
冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、プロピレングリコールメチルエーテルアセテート(PGMEA)70.0質量部を仕込み、窒素気流下攪拌しながら、温度90℃に加温した。一般式(III)で表される構成単位を誘導する、PEG鎖を有するモノマー(Evonik製、商品名:VISIOMER MPEG 1005 MA W、一般式(IV)中のR74はCH3、A3はCOO、R75はエチレン基、R76はCH3、m=22)6.0質量部、トリエチレングリコールモノエチルエーテルメタクリレート(東京化成工業製、m=3)69.0質量部、メタクリル酸メチル(MMA)25.0質量部、メルカプトエタノール4.0質量部、PGMEA30質量部、α,α’-アゾビスイソブチロニトリル(AIBN)1.0質量部の混合溶液を1.5時間かけて滴下し、さらに3時間反応した。次に、窒素気流を止めて、この反応溶液を80℃に冷却し、カレンズMOI(昭和電工(株)社製)8.74質量部、ジラウリン酸ジオクチルすず0.125g、p-メトキシフェノール0.125質量部、及びPGMEA30質量部、を加えて3時間攪拌することで、マクロモノマーAの50%溶液を得た。得られたマクロモノマーBを、GPC(ゲルパーミエーションクロマトグラフィー)にて、N-メチルピロリドン、0.01モル/L臭化リチウム添加/ポリスチレン標準の条件で確認したところ、重量平均分子量(Mw)5800、分子量分布(Mw/Mn)1.6であった。
冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、PGMEA63.1質量部を仕込み、窒素気流下攪拌しながら、温度85℃に加温した。前記マクロモノマーA溶液141質量部(有効固形分70.5質量部)、メタクリル酸2-(ジメチルアミノ)エチル(DMMA)29.5質量部、n-ドデシルメルカプタン1.24質量部、PGMEA49.4質量部、AIBN1.0質量部の混合溶液を1.5時間かけて滴下し、3時間加熱攪拌したのち、AIBN0.10質量部 、PGMEA6.0質量部の混合液を10分かけて滴下し、さらに同温で1時間熟成することで、グラフト共重合体2の35.0質量%溶液を得た。得られたグラフト共重合体2は、GPC測定の結果、重量平均分子量(Mw)10000であった。なおアミン価は105mgKOH/gであった。
国際公開2015/152153号公報の段落0114~0117の化合物No.73の製造と同様にして、前記式(A-2)で表されるオキシムエステル系光開始剤を合成した。
特開2010-256891号公報の段落0080の光重合開始剤W(式(3)で表される光重合開始剤)の製造と同様にして、前記式(B-1)で表されるオキシムエステル系光開始剤を合成した。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA54質量部、メタクリル酸(MAA)36質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)2質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂A溶液(重量平均分子量(Mw)8500、酸価75mgKOH/g、固形分40質量%)を得た。
なお、上記重量平均分子量の測定方法は、ポリスチレンを標準物質とし、THFを溶離液としてショウデックスGPCシステム-21H(Shodex GPC System-21H)により重量平均分子量を測定した。また酸価の測定方法は、JIS K 0070に基づいて測定した。
(1)色材分散液R(1)の製造
225mLマヨネーズ瓶中に、PGMEA64.9質量部、調製例1のアルカリ可溶性樹脂A溶液(固形分40質量%)13.5質量部、合成例1のブロック共重合体1のPGMEA溶液(固形分35質量%)9.2質量部を入れ攪拌した。そこへフェニルホスホン酸(商品名:PPA、日産化学社製)0.39質量部を加え、室温で30分攪拌した。
そこへ、赤色材としてC.I.ピグメントレッド254(R254)を12.0質量部、粒径2.0mmジルコニアビーズ100質量部を入れ、予備解砕としてペイントシェーカー(浅田鉄工社製)で1時間振とうし、次いで粒径0.1mmのジルコニアビーズ200部に変更し本解砕としてペイントシェーカーで4時間分散を行い、色材分散液R(1)を得た。なお、ブロック共重合体1は、フェニルホスホン酸によって塩形成され、塩型ブロック共重合体1となっている。
色材分散液R(1)の製造において、C.I.ピグメントレッド254(R254)を、カーボンブラック(BK)(三菱ケミカル製、MA77)に変更した以外は色材分散液R(1)の製造と同様にして、色材分散液BK(1)を得た。
製造例1で得られた色材分散液R(1)を44.16質量部、色材分散液BK(1)を0.18質量部、調製例1で得られたアルカリ可溶性樹脂A溶液を2.61質量部、多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)を4.18質量部、前記式(A-2)で表されるオキシムエステル系光開始剤を0.46質量部、フッ素系界面活性剤(商品名メガファックR-08MH、DIC(株)製)を0.03質量部、PGMEAを48.38質量部加え、光硬化性赤色樹脂組成物R-1を得た。
実施例1において、表1に示したように、赤色材と黒色材の種類及び/又は質量比、及び/又は、光開始剤の種類を変更した以外は、光硬化性赤色樹脂組成物R-1と同様にして、光硬化性赤色樹脂組成物R-2~R-12を得た。
なお、C.I.ピグメントレッド177(R177)、C.I.ピグメントレッド291(R291)、又はC.I.ピグメントグリーン58(G58)の色材分散液は、色材分散液R(1)の製造において、C.I.ピグメントレッド254(R254)を、C.I.ピグメントレッド177(R177)、C.I.ピグメントレッド291(R291)、又は、C.I.ピグメントグリーン58(PG58)に変更した以外は色材分散液R(1)の製造と同様にして、色材分散液R(2)、R(3)、又はGとして得た。
実施例1において、色材分散液R(1)を用いる代わりに、色材分散液R(2)を用い、前記式(A-2)で表されるオキシムエステル系光開始剤を用いる代わりに、1-[4-(フェニルチオ)フェニル]オクタン-1,2-ジオン=2-(O-ベンゾイルオキシム)(商品名イルガキュアOXE01、BASF社製)に変更した以外は、実施例1と同様にして光硬化性赤色樹脂組成物R-13を製造した。
色材分散液R(1)を40.07質量部、色材分散液BK(1)を0.88質量部、色材分散液Gを0.71質量部、調製例1で得られたアルカリ可溶性樹脂A溶液を2.61質量部、多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)を4.18質量部、前記式(A-2)で表されるオキシムエステル系光開始剤を0.39質量部、前記式(B-1)で表されるオキシムエステル系光開始剤を0.07質量部、フッ素系界面活性剤(商品名メガファックR-08MH、DIC(株)製)を0.03質量部、PGMEAを48.24質量部加え、光硬化性赤色樹脂組成物R-14を得た。
実施例1、3、5、7、9、又は11の光硬化性赤色樹脂組成物において、それぞれ、単官能チオール化合物(2-メルカプトベンゾオキサゾール、2-MBO)を0.22質量部追加した以外は、実施例1、3、5、7、9、又は11と同様にして、光硬化性赤色樹脂組成物R-15~R-20を製造した。
(1)色材分散液R(4)の製造
色材分散液R(1)の製造において、合成例1のブロック共重合体1のPGMEA溶液(固形分35質量%)を、合成例2のグラフト共重合体2のPGMEA溶液(固形分35質量%)に変更した以外は色材分散液R(1)の製造と同様にして、色材分散液R(4)を得た。なお、グラフト共重合体2は、フェニルホスホン酸によって塩形成され、塩型グラフト共重合体2となっている。
色材分散液R(4)の製造において、C.I.ピグメントレッド254(R254)を、カーボンブラック(BK)(三菱ケミカル製、MA77)に変更した以外は色材分散液R(4)の製造と同様にして、色材分散液BK(2)を得た。
実施例1において、色材分散液R(1)を用いる代わりに色材分散液R(4)を用い、色材分散液BK(1)を用いる代わりに色材分散液BK(2)を用いた以外は、実施例1と同様にして光硬化性赤色樹脂組成物R-21を製造した。
実施例21において、表1に示したように、赤色材と黒色材の種類及び/又は質量比を変更した以外は、光硬化性赤色樹脂組成物R-21と同様にして、光硬化性赤色樹脂組成物R-22~R-26を得た。
なお、C.I.ピグメントレッド177(R177)、又はC.I.ピグメントレッド291(R291の色材分散液は、色材分散液R(4)の製造において、C.I.ピグメントレッド254(R254)を、C.I.ピグメントレッド177(R177)、又は、C.I.ピグメントレッド291(R291)に変更した以外は色材分散液R(4)の製造と同様にして、色材分散液R(5)、又はR(6)として得た。
実施例1において、表1に示したように、黒色材を用いず、赤色材のみを用い、赤色材の種類、及び/又は、開始剤の種類を変更し、アルカリ可溶性樹脂A溶液に対する多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)と開始剤の比率は変更せずに、顔料以外の成分量を表2に示した顔料濃度になるよう変更した以外は、光硬化性赤色樹脂組成物R-1と同様にして、比較光硬化性赤色樹脂組成物CR-1~CR-6を得た。
<透過率>
各実施例及び各比較例で得られた光硬化性赤色樹脂組成物を、SiNx膜を形成したガラス基板(NHテクノグラス(株)社製、「NA35」)上にそれぞれ、スピンコーターを用いて硬化塗膜が厚さ3.0μmとなるように塗布した後、ホットプレートを用いて80℃で3分間乾燥し基板上に塗膜を形成した。この塗膜に、超高圧水銀灯を用いて50mJ/cm2の紫外線で露光することにより、SiNx膜上にそれぞれ、露光後塗膜を形成した。その後、90℃のクリーンオーブンで30分間ポストベイクすることにより、硬化膜を形成した。
顕微分光測定装置OSP-SP200を用いて380nm~780nmの透過スペクトルを測定し、430nm~580nmの最大透過率、610nm~630nmの最大透過率と最小透過率を測定した。
得られた硬化膜を光学顕微鏡で観察して、マスク開口が何μmのパターンまで残存しているか、最も細いパターンの線幅の確認を行った。
(密着性評価の評価基準)
AA:マスク開口4μm以下までパターンが残存(最も細いパターンの線幅が4μm以下)
A:最も細いパターンの線幅が5μmから10μm以下
B:最も細いパターンの線幅が11μmから20μm以下
C:最も細いパターンの線幅が21μmから30μm以下
D:最も細いパターンの線幅が31μm以上
評価結果がBであれば基板密着性は良好であり、評価結果がA、更にAAであれば基板密着性に優れている。
得られた硬化膜の膜厚を測定した後、プロピレングリコールモノメチルエーテル(PGME)に10分間浸漬した後、風乾し、再び膜厚を測定した。なお、膜厚測定には、触針式段差膜厚計「P-15Tencor」(Instruments製)を用いた。溶剤浸漬後膜厚/溶剤浸漬前膜厚を×100を、残膜率として算出した。
(耐溶剤性の評価基準)
AA:溶剤浸漬後の残膜率が98.5%以上
A:溶剤浸漬後の残膜率が96%以上98.5%未満
B:溶剤浸漬後の残膜率が94%以上96%未満
C:溶剤浸漬後の残膜率が92%以上94%未満
D:溶剤浸漬後の残膜率が92%未満
評価結果がBであれば耐溶剤性は良好であり、評価結果がA、更にAAであれば耐溶剤性に優れている。
・R254(C.I.ピグメントレッド254)
・R177(C.I.ピグメントレッド177)
・R291(C.I.ピグメントレッド291)
・BK(カーボンブラック、三菱ケミカル製 MA77)
・G58(C.I.ピグメントグリーン58)
・A-2:前記化学式(A-2)で表される化合物
・B-1:前記化学式(B-1)で表される化合物
・OXE01:1-[4-(フェニルチオ)フェニル]オクタン-1,2-ジオン=2-(O-ベンゾイルオキシム)(商品名イルガキュアOXE01、BASF社製)
・2-MBO(2-メルカプトベンゾオキサゾール)
反射防止性能を上げるためには、膜の透過率を下げる必要があるが、赤色材のみを含む比較例1~6の比較光硬化性赤色樹脂組成物では、膜厚を3.0μmで610nm~630nmの最大透過率を90%以下にするには、顔料濃度を高くする必要があり、実施例と同じバインダー成分を用いても、耐溶剤性や基板密着性を持たせることが困難であった。
それに対して、本発明に係る光硬化性赤色樹脂組成物である実施例1~26では、有機発光素子上に形成する際に好ましい低温(90℃)でポストベイクを行って硬化膜が形成されたが、膜厚3.0μmで硬化膜を形成した時に、430nm~580nmの波長におけるスペクトル透過率が15.0%以下、610nm~630nmの波長におけるスペクトル透過率が50.0%以上90.0%以下となり、外光反射抑制効果が良好になることが明らかにされ、且つ、低温加熱処理でも耐溶剤性が良好で、基板密着性に優れた硬化膜を形成可能であることが示された。従って、本発明に係る光硬化性赤色樹脂組成物は、有機発光素子上に形成する硬化膜に用いるのに適しており、且つ、硬化膜は、薄膜で外光反射を抑制可能であって、薄膜でフレキシブル性が向上した有機発光表示装置を製造可能であることが示された。
2 薄膜トランジスタ(TFT)
3 封止膜
4 電極
5 隔壁
6R、6G、6B 有機発光素子
7 電極
8 封止層
9R、9G、9B 着色硬化膜
10 遮光部
11 封止膜
20 外光反射防止膜
30 有機発光素子を備えた素子基板
100 表示装置
Claims (10)
- 有機発光素子上に形成する硬化膜に用いる光硬化性赤色樹脂組成物であって、
前記光硬化性赤色樹脂組成物が、色材と、光重合性化合物と、光開始剤とを含有し、
前記色材が、赤色材と黒色材とを含む、光硬化性赤色樹脂組成物。 - 膜厚3.0μmで硬化膜を形成した時に、430nm~580nmの波長におけるスペクトル透過率が15.0%以下、610nm~630nmの波長におけるスペクトル透過率が50.0%以上90.0%以下となる、請求項1に記載の光硬化性赤色樹脂組成物。
- 前記光開始剤が、下記一般式(A)で表される化合物及び下記一般式(B)で表される化合物の少なくとも1種を含む、請求項1又は2に記載の光硬化性赤色樹脂組成物。
R11、R12及びR13は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R11、R12及びR13で表される基の水素原子は、更にR21、OR21、COR21、SR21、NR22R23、CONR22R23、-NR22-OR23、-NCOR22-OCOR23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R21、R22及びR23は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R21、R22及びR23で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
R11、R12、R13、R21、R22及びR23で表される基のアルキレン部分は、-O-、-S-、-COO-、-OCO-、-NR24-、-NR24CO-、-NR24COO-、-OCONR24-、-SCO-、-COS-、-OCS-又は-CSO-を酸素原子が隣り合わない条件で1~5個含んでいてもよく、
R24は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R11、R12、R13、R21、R22、R23及びR24で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、
R3は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、R3で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、また、R3とR7、及びR3とR8はそれぞれ一緒になって環を形成していてもよく、
R3で表される基の水素原子は、更にR21、OR21、COR21、SR21、NR22R23、CONR22R23、-NR22-OR23、-NCOR22-OCOR23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R4、R5、R6及びR7は、それぞれ独立に、R11、OR11、SR11、COR14、CONR15R16、NR12COR11、OCOR11、COOR14、SCOR11、OCSR11、COSR14、CSOR11、水酸基、CN又はハロゲン原子を表し、R4とR5、R5とR6、及びR6とR7はそれぞれ一緒になって環を形成していてもよく、
R14、R15及びR16は、水素原子又は炭素数1~20のアルキル基を表し、R14、R15及びR16で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、
R8は、R11、OR11、SR11、COR11、CONR12R13、NR12COR11、OCOR11、COOR11、SCOR11、OCSR11、COSR11、CSOR11、水酸基、CN又はハロゲン原子を表し、
kは、0又は1を表す。)
R41、R42及びR43は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R41、R42及びR43、並びにX2で表される基の水素原子は、更にR51、OR51、COR51、SR51、NR52R53、CONR52R53、-NR52-OR53、-NCOR52-OCOR53、NR52COR51、OCOR51、COOR51、SCOR51、OCSR51、COSR51、CSOR51、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R51、R52及びR53は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R51、R52及びR53で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
R41、R42、R43、X2、R51、R52及びR53で表される基のアルキレン部分は、-O-、-S-、-COO-、-OCO-、-NR54-、-NR54CO-、-NR54COO-、-OCONR54-、-SCO-、-COS-、-OCS-又は-CSO-を酸素原子が隣り合わない条件で1~5個含んでいてもよく、
R54は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R41、R42、R43、R51、R52、R53及びR54で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよい。
a及びbは、それぞれ独立に、0~3の整数である。) - 前記色材が、更に、緑色材及び青色材の少なくとも1種を含む、請求項1~3のいずれか1項に記載の光硬化性赤色樹脂組成物。
- 前記黒色材が、カーボンブラックを含む、請求項1~4のいずれか1項に記載の光硬化性赤色樹脂組成物。
- 前記赤色材が、ピグメントレッド177、ピグメントレッド254、及びピグメントレッド291から選ばれる少なくとも1種を含む、請求項1~5のいずれか1項に記載の光硬化性赤色樹脂組成物。
- 更に、チオール化合物を含有する、請求項1~6のいずれか1項に記載の光硬化性赤色樹脂組成物。
- 有機発光素子上に、請求項1~7のいずれか1項に記載の光硬化性赤色樹脂組成物の硬化膜を有する、表示装置。
- 有機発光素子上に、請求項1~7のいずれか1項に記載の光硬化性赤色樹脂組成物を塗布することにより塗膜を形成する工程、
前記塗膜に光照射する工程、
前記光照射後の膜を、加熱するポストベイク工程、及び、
前記光照射後の膜を、現像する工程を含有することにより、
有機発光素子上に請求項1~7のいずれか1項に記載の光硬化性赤色樹脂組成物の硬化膜を形成する工程を有する、有機発光素子と外光反射防止膜の積層体の製造方法。 - 前記ポストベイク工程における加熱温度が、130℃以下である、請求項9に記載の有機発光素子と外光反射防止膜の積層体の製造方法。
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