WO2023027010A1 - Composition de résine photosensible, produit durci et dispositif d'affichage d'image - Google Patents

Composition de résine photosensible, produit durci et dispositif d'affichage d'image Download PDF

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Publication number
WO2023027010A1
WO2023027010A1 PCT/JP2022/031524 JP2022031524W WO2023027010A1 WO 2023027010 A1 WO2023027010 A1 WO 2023027010A1 JP 2022031524 W JP2022031524 W JP 2022031524W WO 2023027010 A1 WO2023027010 A1 WO 2023027010A1
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Prior art keywords
meth
crosslinkable
monomer
photosensitive resin
resin composition
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PCT/JP2022/031524
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English (en)
Japanese (ja)
Inventor
大 杉山
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大阪有機化学工業株式会社
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Application filed by 大阪有機化学工業株式会社 filed Critical 大阪有機化学工業株式会社
Priority to CN202280053681.0A priority Critical patent/CN117795420A/zh
Priority to KR1020247004556A priority patent/KR20240032114A/ko
Priority to JP2023543891A priority patent/JPWO2023027010A1/ja
Publication of WO2023027010A1 publication Critical patent/WO2023027010A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a photosensitive resin composition, a cured product obtained from the photosensitive resin composition, and an image display device containing the cured product.
  • a photospacer is used to maintain the thickness of the liquid crystal layer sandwiched between the substrate on the color filter side and the substrate on the thin film transistor (TFT) side.
  • the photospacer must have a high elastic recovery rate in order to suppress variations in the cell gap due to stress during use of the liquid crystal display device.
  • the object is to provide an active energy ray-curable resin composition that gives a cured product exhibiting an excellent elastic recovery rate against deformation due to external force.
  • a photosensitive resin composition has been proposed which comprises a polymerizable (meth)acrylic polymer (A), a polyfunctional (meth)acrylate monomer component (B), and a photopolymerization initiator (C).
  • the liquid crystal display element is easily deformed when pressure or impact is applied from the outside, the deformation may crack the photospacer, and the deformed photospacer may damage (scrape) the alignment film on the TFT side substrate. Therefore, there is a demand for a highly flexible photospacer that is less likely to be damaged and less likely to damage the alignment film.
  • Patent Document 2 when used as a spacer, it is a photospacer with a high restoration rate in which plastic deformation is suppressed, but a photosensitive resin that is extremely suppressed from scraping the liquid crystal alignment film provided on the opposing substrate.
  • a photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator and a polymerizable compound, wherein the urethane equivalent of the solid content of the resin composition is 1000 to 50000 g / mol, and an ethylenically unsaturated A photosensitive resin composition having a saturated group equivalent weight of 100 to 155 g/mol has been proposed.
  • Patent Document 3 with the object of providing a negative photosensitive resin composition capable of forming a photospacer having a high elastic recovery rate and excellent flexibility, (A) an alkali-soluble resin, (B) a photoradical polymerization initiator and (C) a photopolymerizable monomer, and the content of the (A) alkali-soluble resin is the same as the (A) alkali-soluble resin and the (C) ) 3 parts by weight or more and 45 parts by weight or less with respect to a total of 100 parts by weight with the photopolymerizable monomer, and the (C) photopolymerizable monomer contains a di(meth)acrylate having a poly(oxyalkylene) group , a negative photosensitive resin composition has been proposed.
  • Patent Documents 2 and 3 describe a photosensitive resin composition capable of forming a photospacer having a high elastic recovery rate and excellent flexibility. There has been a demand for development of a photosensitive resin composition capable of forming a photospacer having both excellent properties.
  • the present invention provides a photosensitive resin composition capable of forming a cured product (e.g., photospacer) having both a high elastic recovery rate and excellent flexibility, a cured product obtained from the photosensitive resin composition, and It aims at providing the image display apparatus containing the said hardened
  • a photosensitive resin composition capable of forming a cured product (e.g., photospacer) having both a high elastic recovery rate and excellent flexibility, a cured product obtained from the photosensitive resin composition, and It aims at providing the image display apparatus containing the said hardened
  • the present invention provides an alkali-soluble resin (A) having a double bond equivalent of 200 g/mol or less, A first crosslinkable (meth)acrylate monomer (B1) having six or more crosslinkable functional groups, at least one of which is a hydrogen-bonding crosslinkable functional group, and six or more crosslinkable It has a functional group, and the number of hydrogen-bonding crosslinkable functional groups in the crosslinkable functional group is greater than the number of the hydrogen-bonding crosslinkable functional groups in the first crosslinkable (meth)acrylate monomer (B1).
  • the present invention relates to a photosensitive resin composition containing a photopolymerization initiator (C).
  • the monomer group (B) preferably has a hydroxyl value of 15 to 70 mgKOH/g.
  • the second crosslinkable (meth)acrylate monomer (B2) preferably does not have a hydrogen-bonding crosslinkable functional group.
  • the photosensitive resin composition of the present invention preferably contains 80 to 200 parts by mass of the monomer group (B) with respect to 100 parts by mass of the alkali-soluble resin (A).
  • the mass ratio (B1:B2) between the first crosslinkable (meth)acrylate monomer (B1) and the second crosslinkable (meth)acrylate monomer (B2) is preferably 1:10 to 10:1. .
  • the cured product of the present invention is obtained from the photosensitive resin composition.
  • the cured product is preferably a photospacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a flattening film material.
  • the present invention also relates to an image display device containing the cured product.
  • the photosensitive resin composition of the present invention includes, together with an alkali-soluble resin (A) having a double bond equivalent of 200 g/mol or less, a first crosslinkable (meth)acrylate monomer (B1) and a second It is characterized by containing two types of cross-linkable monomers, a di-crosslinkable (meth)acrylate monomer (B2), and by using these three components, a cured product that achieves both a high elastic recovery rate and excellent flexibility. can be formed.
  • the cured product of the present invention is a photospacer
  • the photospacer of the present invention has a high elastic recovery rate, it is possible to effectively suppress fluctuations in the cell gap due to stress during use of the liquid crystal display device. can.
  • the photospacer of the present invention has excellent flexibility, so that it is hard to break and hard to damage the alignment film of the substrate on the TFT side (the alignment film is hard to scrape). Furthermore, when the cured product of the photosensitive resin composition of the present invention is used as a resist material, the solubility of the uncured portion in the developer (hereinafter simply referred to as the solubility in the developer) is excellent. In addition, it is possible to produce a cured product (for example, a photospacer) with small unevenness in height (scan unevenness, lens unevenness).
  • (meth)acrylic means acrylic and/or methacrylic.
  • (Meth)acrylate” and the like have the same meaning.
  • crosslinkable functional group means a functional group that forms a crosslinked structure by reacting with other functional groups or interacting with other atoms.
  • hydrophilicity crosslinkable functional group is a type of crosslinkable functional group, and other monomers (including not only heterogeneous monomers but also monomers of the same type) or alkali-soluble resins (A) in close proximity It means a structure that can be hydrogen-bonded and a functional group that forms a cross-linked structure by interacting with the hydrogen-bond.
  • the structure capable of hydrogen bonding is not particularly limited as long as it is capable of hydrogen bonding with other monomers or the structure of the alkali-soluble resin (A), and may be the crosslinkable functional group itself.
  • the group having a double bond is not particularly limited, it is typically an ethylenically unsaturated group, and examples of the ethylenically unsaturated group include an acryloyl group and a methacryloyl group.
  • the acid value in the present invention represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the object, and the molecular weight based on the structure of the object and the number of functional groups per molecule. It is a theoretical value calculated from (the number of acid groups). Specifically, the acid value of the object is a value obtained by [number of moles of acid groups of the object (mmol)] ⁇ [56.11/amount of object (g)].
  • the hydroxyl value in the present invention represents the mass (mg) of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group after acetylating 1 g of the object, and the molecular weight and It is a theoretical value calculated from the number of functional groups (number of hydroxyl groups) per molecule.
  • the hydroxyl value of the object is a value obtained by [number of moles of hydroxyl groups of the object (mmol)] ⁇ [56.11/amount of object (g)].
  • alkali-soluble resin (A) and monomer group (B) are mentioned as a target object in an acid value and a hydroxyl value.
  • Targets for the double bond equivalent, acid value, and hydroxyl value include the alkali-soluble resin (A) and the monomer group (B), and the structure of these targets and the content in the photosensitive resin composition
  • the amount and the like may be specified by analyzing the photosensitive resin composition by a known method, and specified from the structure and ratio of the raw material (object) used when producing the photosensitive resin composition. Also good.
  • the photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a monomer group (B), and a photopolymerization initiator (C).
  • the alkali-soluble resin (A) has a double bond equivalent of 200 g/mol or less.
  • the monomer group (B) contains a first crosslinkable (meth)acrylate monomer (B1) and a second crosslinkable (meth)acrylate monomer (B2), and has an acid value of 1 to 20 mgKOH/g.
  • the first crosslinkable (meth)acrylate monomer (B1) has six or more crosslinkable functional groups, and at least one of the crosslinkable functional groups is a hydrogen-bonding crosslinkable functional group.
  • the second crosslinkable (meth)acrylate monomer (B2) has 6 or more crosslinkable functional groups, and the number of hydrogen-bonding crosslinkable functional groups in the crosslinkable functional groups is the first crosslinkable (meth) It is less than the number of hydrogen-bonding crosslinkable functional groups possessed by the acrylate monomer (B1).
  • the reason why it is possible to form a cured product having both a high elastic recovery rate and excellent flexibility by using the photosensitive resin composition of the present invention is speculated as follows.
  • a monomer having a relatively large number of polymerizable functional groups is used in a photosensitive resin composition, it is not a structure in which the main chain is formed by serially bonding (polymerizing) the monomers, but one monomer unit has a plurality of A crosslinked structure is formed by combining with other monomers.
  • the present inventor uses two types of (meth)acrylate monomers, at least one (meth)acrylate monomer has a hydrogen-bonding crosslinkable functional group, and the other (meth)acrylate monomer has a hydrogen bond
  • the number of type crosslinkable functional groups smaller than the number of hydrogen bond type crosslinkable functional groups of one (meth) acrylate monomer, it is possible to prevent the crosslinkable functional groups from easily bonding to each other within the monomer unit, It was found that the formation of bonds between different monomer units (including not only the formation of bonds between different monomers but also the formation of bonds between monomers of the same type) and the bonding between the monomers and the alkali-soluble resin (A) can be promoted.
  • At least one (meth)acrylate monomer contains a hydrogen-bonding crosslinkable functional group
  • all the crosslinkable functional groups can be hydrogen-bonded crosslinkable instead of forming relatively strong covalent bonds.
  • At least part of the functional groups cross-link with hydrogen-bondable structures possessed by other adjacent monomers through relatively weak hydrogen bonds.
  • this structure and the hydrogen-bonding crosslinkable functional group of the monomer are compared by hydrogen bonding. Cross-linking with hydrogen bonds with weak physical bonding strength.
  • both hydrogen bonds with relatively weak bonding strength and covalent bonds with relatively strong bonding strength coexist in the cured product, so that the rigidity and elasticity of the cured product are precisely controlled. it is conceivable that. As a result, it is presumed that a network structure that achieves both a high elastic recovery rate and excellent flexibility is formed when the photosensitive resin composition is cured.
  • the alkali-soluble resin (A) is not particularly limited as long as it has a double bond equivalent of 200 g/mol or less.
  • the elastic recovery rate can be improved by using an alkali-soluble resin having a double bond equivalent of 200 g/mol or less, which has a relatively low double bond equivalent.
  • the double bond equivalent of the alkali-soluble resin (A) is preferably 160 g/mol or less.
  • Monomers forming the alkali-soluble resin (A) are not particularly limited, for example, (meth) acrylic acid, 2-(meth) acryloyloxyethyl succinic acid, maleic acid, and carboxy group-containing monomers such as itaconic acid; maleic anhydride Acids and carboxylic anhydride group-containing monomers such as itaconic anhydride; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) Alkyl (meth)acrylates such as acrylates, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethoxyethyl (meth)acrylate, and glycidyl (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)
  • styrene, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide, silicone-containing monomers, and the like may be used as copolymerizable monomers. These monomers may be used alone or in combination of two or more.
  • the alkali-soluble resin (A) may have an acid group in its side chain in order to impart alkali developability to the photosensitive resin composition.
  • the method for introducing an acid group into the side chain of the alkali-soluble resin (A) is not particularly limited, and known methods can be employed.
  • an ethylenically unsaturated group may be introduced into the side chain of the alkali-soluble resin (A).
  • a method for introducing an ethylenically unsaturated group into the side chain of the alkali-soluble resin (A) for example, a polymer obtained by copolymerizing an epoxy group-containing monomer such as glycidyl (meth)acrylate is added with (meth)acrylic acid or the like.
  • a method of adding a compound having an ethylenically unsaturated group and a carboxyl group, a polymer obtained by copolymerizing a carboxyl group-containing monomer such as (meth)acrylic acid, an ethylenically unsaturated group such as glycidyl (meth)acrylate, and an epoxy A method of adding a compound having a group, and an ethylenically unsaturated group such as (meth) acryloyloxyethyl isocyanate and an isocyanate group to a polymer obtained by copolymerizing a hydroxy group-containing monomer such as hydroxyethyl (meth) acrylate. and a method of adding a compound having the
  • At least one of the main chain and side chain of the alkali-soluble resin (A) may contain a structure capable of hydrogen bonding with the hydrogen-bonding crosslinkable functional group of the (meth)acrylate monomer (B1) or (B2). This is because, as described above, both hydrogen bonds with relatively weak bonding strength and covalent bonds with relatively strong bonding strength coexist in the cured product, so that the rigidity and elasticity of the cured product can be precisely controlled.
  • Structures capable of forming hydrogen bonds with hydrogen-bonding crosslinkable functional groups in the main chain and side chains of the alkali-soluble resin (A) include, for example, -COOH, -OH, and -NH-. -COOH and -OH are preferred from the viewpoint of easy maintenance.
  • the side chains of the alkali-soluble resin (A) contain structures capable of hydrogen bonding.
  • the weight average molecular weight (Mw) of the alkali-soluble resin (A) is not particularly limited, but when using the photosensitive resin composition as a resist material such as a photospacer, from the viewpoint of obtaining good exposure sensitivity and good developability (hereinafter , simply from the viewpoint of improving good exposure sensitivity and heat resistance), it is preferably 5,000 to 100,000, more preferably 10,000 to 30,000.
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC) in accordance with JIS K 7252-1:2016, and is a value converted from standard polystyrene.
  • the double bond equivalent of the alkali-soluble resin (A) is 200 g/mol or less, preferably 180 g/mol or less, more preferably 170 g, from the viewpoint of improving good exposure sensitivity and heat resistance of the photosensitive resin composition. /mol or less, more preferably 160 g/mol or less.
  • the acid value of the alkali-soluble resin (A) is not particularly limited, but from the viewpoint of imparting good developability to the photosensitive resin composition, it is preferably 10 to 200 mgKOH/g, more preferably 15 to 150 mgKOH/g. , more preferably 20 to 100 mgKOH/g, particularly preferably 25 to 75 mgKOH/g, most preferably 30 to 50 mgKOH/g.
  • the polymerizable (meth)acrylic polymer (A) described in International Publication No. 2018/169036 may be used as the alkali-soluble resin (A).
  • the monomer group (B) is a monomer group containing at least both the first crosslinkable (meth)acrylate monomer (B1) and the second crosslinkable (meth)acrylate monomer (B2).
  • the monomer group (B) contains three or more crosslinkable (meth)acrylate monomers, and all of them contain hydrogen-bonding crosslinkable functional groups, the one with the least number of hydrogen-bonding crosslinkable functional groups is selected. This is referred to as a second crosslinkable (meth)acrylate monomer (B2).
  • the monomer group (B) contains three or more crosslinkable (meth)acrylate monomers, at least one of which is a crosslinkable (meth)acrylate monomer having no hydrogen-bonding crosslinkable functional group.
  • a crosslinkable (meth)acrylate monomer having no hydrogen-bonding crosslinkable functional group is used as the second crosslinkable (meth)acrylate monomer (B2).
  • the photosensitive resin composition of the present invention may have, for example, the following aspects (1) to (5).
  • B1 first crosslinkable (meth)acrylate monomer
  • B2 second crosslinkable (meth)acrylate monomer
  • an embodiment further containing another monomer.
  • the plurality of types of monomers corresponding to the first crosslinkable (meth)acrylate monomer (B1) may have the same or different numbers of crosslinkable functional groups,
  • the number of hydrogen-bonding crosslinkable functional groups may be the same or different.
  • the number of hydrogen-bonding crosslinkable functional groups in the second crosslinkable (meth)acrylate monomer (B2) is the largest among the plurality of types of monomers corresponding to the first crosslinkable (meth)acrylate monomer (B1).
  • the number of hydrogen-bonding crosslinkable functional groups is less than the one with less.
  • the plurality of types of monomers corresponding to the second crosslinkable (meth)acrylate monomer (B2) may have the same or different numbers of crosslinkable functional groups, but hydrogen All the monomers corresponding to the second crosslinkable (meth)acrylate monomer (B2) have the same number of bonded crosslinkable functional groups. Also in the above aspect (3), the number of hydrogen-bonding crosslinkable functional groups is the same for all monomers corresponding to the second crosslinkable (meth)acrylate monomer (B2).
  • the monomer group (B) has an acid value of 1 to 20 mgKOH/g from the viewpoint of promoting the formation of a crosslinked structure between different monomer units and the formation of a crosslinked structure between the monomer and the alkali-soluble resin (A). Yes, preferably 3 to 15 mgKOH/g, more preferably 6 to 12 mgKOH/g.
  • the monomer group (B) contains at least a first crosslinkable (meth)acrylate monomer (B1) and a second crosslinkable (meth)acrylate monomer (B2), and optionally other monomers.
  • the acid value of the monomer group (B) is obtained by calculating the acid value of each monomer, multiplying the acid value of each monomer by the mass ratio of that monomer in the monomer group (B), and calculating these values.
  • the monomer group (B) has the viewpoint of promoting the formation of a crosslinked structure with the different monomers described above and the formation of a crosslinked structure between the monomer and the alkali-soluble resin (A). From the viewpoint of being able to maintain a high elastic recovery rate and excellent flexibility even when repeatedly pressed (hereinafter referred to as having high durability), adhesion to the application target when applying the photosensitive resin composition to a substrate etc. From the viewpoint of improving the property and the viewpoint of excellent solubility in a developer, the hydroxyl value is preferably 15 to 70 mgKOH/g, more preferably 20 to 60 mgKOH/g, and still more preferably 25 to 55 mgKOH. /g.
  • the first crosslinkable (meth)acrylate monomer (B1) has six or more crosslinkable functional groups, and at least one of the crosslinkable functional groups is a hydrogen-bonding crosslinkable functional group. Also, at least one crosslinkable functional group is an acryloyl group or a methacryloyl group.
  • the crosslinkable functional group is not particularly limited, and examples include acryloyl groups, methacryloyl groups, vinyl groups, carboxy groups, hydroxyl groups, thio groups, amino groups, epoxy groups, and isocyanate groups. Two or more of these crosslinkable functional groups may be contained. Acryloyl and methacryloyl groups contain a vinyl structure in their structure, but are recognized as different from acryloyl and methacryloyl groups and vinyl groups. Similarly, carboxy groups include --OH, but carboxy groups and hydroxyl groups are recognized as different.
  • the first crosslinkable (meth)acrylate monomer (B1) may have a functional group other than the crosslinkable functional group. These points are the same for the crosslinkable functional group of the second crosslinkable (meth)acrylate monomer (B2) described later.
  • the hydrogen-bonding crosslinkable functional group is not particularly limited as long as it is a functional group capable of hydrogen-bonding with other monomer units, and examples include a carboxy group, a hydroxyl group, an amino group, and the like.
  • One type of these hydrogen-bonding crosslinkable functional groups may be contained, or two or more types may be contained.
  • the hydrogen-bonding crosslinkable functional group preferably has at least one of a carboxy group and a hydroxyl group, and more preferably has one of a carboxy group and a hydroxyl group and does not have the other, from the viewpoint of easily maintaining a hydrogen bond. .
  • the first crosslinkable (meth)acrylate monomer (B1) has 6 or more crosslinkable functional groups from the viewpoint of obtaining a cured product having both a high elastic recovery rate and excellent flexibility.
  • the first crosslinkable (meth)acrylate monomer (B1) may have 7 or more, 8 or more, or 9 or more crosslinkable functional groups.
  • the upper limit of the number of crosslinkable functional groups is not particularly limited, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less from the viewpoint of suppressing a decrease in flexibility of the cured product.
  • the number of hydrogen-bonding crosslinkable functional groups possessed by the first crosslinkable (meth)acrylate monomer (B1) is not particularly limited as long as it is 1 or more. It is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.
  • Monomers that can be used as the first crosslinkable (meth)acrylate monomer (B1) include, for example, dipentaerythritol penta(meth)acrylate (number of crosslinkable functional groups: 6, of which the number of (meth)acrylic groups: 5, number of hydroxyl groups: 1), dipentaerythritol tetra(meth)acrylate (number of crosslinkable functional groups: 6, of which, number of (meth)acrylic groups: 4, number of hydroxyl groups: 2), tripentaerythritol hexa (Meth) acrylate (number of crosslinkable functional groups: 8, of which, number of (meth)acrylate groups: 6, number of hydroxyl groups: 2), tripentaerythritol penta (meth) acrylate (number of crosslinkable functional groups: 8 , among which, the number of (meth)acrylate groups: 5, the number of hydroxyl groups: 3), succinic anhydride addition-modified
  • the second crosslinkable (meth)acrylate monomer (B2) has 6 or more crosslinkable functional groups, and the number of hydrogen-bonding crosslinkable functional groups in the crosslinkable functional groups is the first crosslinkable (meth) It is less than the number of hydrogen-bonding crosslinkable functional groups possessed by the acrylate monomer (B1).
  • At least one crosslinkable functional group of the second crosslinkable (meth)acrylate monomer (B2) is an acryloyl group or a methacryloyl group.
  • the second crosslinkable (meth)acrylate monomer (B2) has 6 or more crosslinkable functional groups from the viewpoint of obtaining a cured product having both a high elastic recovery rate and excellent flexibility.
  • the second crosslinkable (meth)acrylate monomer (B2) may have 7 or more, 8 or more, or 9 or more crosslinkable functional groups.
  • the upper limit of the number of crosslinkable functional groups is not particularly limited, it is preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less from the viewpoint of solubility in a developer.
  • the number of hydrogen-bonding crosslinkable functional groups possessed by the second crosslinkable (meth)acrylate monomer (B2) is less than the number of hydrogen-bonded crosslinkable functional groups possessed by the first crosslinkable (meth)acrylate monomer (B1),
  • the difference from the number of hydrogen-bonding crosslinkable functional groups possessed by the first crosslinkable (meth)acrylate monomer (B1) is one, two, or three. can do.
  • the number of hydrogen-bonding crosslinkable functional groups possessed by the second crosslinkable (meth)acrylate monomer (B2) is preferably 1 or less. , 0.
  • Monomers that can be used as the second crosslinkable (meth)acrylate monomer (B2) include, for example, dipentaerythritol hexa(meth)acrylate (number of crosslinkable functional groups: 6, of which the number of (meth)acrylic groups: 6), sorbitol hexa(meth)acrylate (number of crosslinkable functional groups: 6, of which, number of (meth)acrylic groups: 6), tripentaerythritol octa(meth)acrylate (number of crosslinkable functional groups: 8, Among them, the number of (meth)acrylic groups: 8) and the like can be mentioned.
  • the monomers exemplified in the first crosslinkable (meth)acrylate monomer (B1) described above also have a relationship with the number of hydrogen-bonding crosslinkable functional groups possessed by the first crosslinkable (meth)acrylate monomer (B1). It can be used as the second crosslinkable (meth)acrylate monomer (B2) provided that it satisfies the above conditions. These monomers may be used alone or in combination of two or more.
  • the first crosslinkable (meth)acrylate monomer (B1) and the second crosslinkable (meth)acrylate monomer (B2) are often obtained as a mixture containing both monomers, and commercial products are also products containing both monomers. It may be for sale.
  • the mixing ratio of both monomers can be controlled, for example, by adjusting the conditions when alcohol and (meth)acrylic acid are esterified to produce a mixture containing both monomers.
  • Methods for adjusting the conditions during production include, for example, the mass ratio of alcohol and (meth)acrylic acid during esterification, the reaction time, the reaction temperature, and the purification method and purification time of the product obtained by esterification. and other known methods.
  • the mixture may be used alone, or the mixture may be further mixed and used. Also, if each monomer can be obtained and manufactured as a single item rather than a mixture, these may be used. These may be used alone or in combination.
  • the monomer group (B) contains known monomers other than the first crosslinkable (meth)acrylate monomer (B1) and the second crosslinkable (meth)acrylate monomer (B2) within a range that does not impair the effects of the present invention. You may
  • the photopolymerization initiator (C) is not particularly limited. - Acetophenones such as dichloroacetophenone; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2- thioxanthones such as chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxides and xanthones; These photopolymerization initiators may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention has the viewpoint of obtaining a cured product that has both a high elastic recovery rate and excellent flexibility, improves the solubility in a developer, and reduces the height variation of the cured product. From the viewpoint of suppression, etc., it is preferable to contain 80 to 200 parts by mass of the monomer group (B) with respect to 100 parts by mass of the alkali-soluble resin (A), and more preferably 100 to 170 parts by mass. , more preferably 120 to 150 parts by mass. At this time, the monomer group (B) preferably contains 80 parts by mass or more in total of the first crosslinkable (meth)acrylate monomer (B1) and the second crosslinkable (meth)acrylate monomer (B2).
  • the first crosslinkable (meth)acrylate monomer (B1) and the second crosslinkable (meth)acrylate monomer (B2) are added to 100 parts by mass of the alkali-soluble resin (A). is preferably contained in a total of 100 parts by mass or more, more preferably 120 parts by mass or more.
  • the acrylate monomer (B1) and the second crosslinkable (meth)acrylate monomer (B2) preferably contain a total of 200 parts by mass or less, more preferably 170 parts by mass or less, and 150 parts by mass or less. is more preferred.
  • the photosensitive resin composition of the present invention has the viewpoint of obtaining a cured product that has both a high elastic recovery rate and excellent flexibility, improves the solubility in a developer, and reduces the height variation of the cured product. From the viewpoint of suppressing the 1 is preferred, 1:5 to 5:1 is more preferred, 1:3 to 3:1 is even more preferred, and 1:2 to 2:1 is particularly preferred.
  • the content of the photopolymerization initiator (C) is not particularly limited, but from the viewpoint of solubility and curability of the photosensitive resin composition, 1 to 60 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). is preferably 3 to 40 parts by weight, more preferably 4 to 35 parts by weight, and particularly preferably 6 to 25 parts by weight.
  • the photosensitive resin composition of the present invention may contain a photopolymerization initiation aid.
  • photopolymerization initiation aids include 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-isocyanurate (Showa Denko manufactured by Karenz MT (registered trademark) NR1), trifunctional thiol compounds such as trimethylolpropane tris (3-mercaptopropionate); butyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) PEI) and other tetrafunctional thiol compounds; dipentaerythritol hexakis (3-propionate) and other hexafunctional thiol compounds.
  • These photopolymerization initiation aids may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention may contain a thermal polymerization initiator.
  • Thermal polymerization initiators include, for example, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy-2 -organic peroxides such as ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis(2-methylpropionate); These thermal polymerization initiators may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention may contain radically polymerizable oligomers such as unsaturated polyesters, epoxy acrylates, urethane acrylates and polyester acrylates; curable resins such as epoxy resins.
  • the photosensitive resin composition of the present invention may contain a solvent.
  • solvents include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy esters such as butyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; mentioned.
  • solvents may be used alone or in combination of two or more.
  • the content of the solvent may be appropriately set according to the optimum viscosity when using the composition.
  • the photosensitive resin composition of the present invention contains fillers such as aluminum hydroxide, talc, clay, barium sulfate, etc., dyes, pigments, antifoaming agents, coupling agents, leveling agents, Known additives such as sensitizers, release agents, lubricants, plasticizers, antioxidants, UV absorbers, flame retardants, polymerization inhibitors, thickeners and dispersants may be contained.
  • the cured product of the present invention is obtained by curing the photosensitive resin composition.
  • the photosensitive resin composition is injected into a molding mold (resin mold), and if necessary, heating (prebaking) is performed to the extent that the shape can be maintained.
  • prebaking heating
  • the cured product is suitably used as a photospacer, partition wall material, lens material, interlayer insulating film material, protective film material, optical waveguide material, or flattening film material, and is particularly suitably used as a photospacer.
  • the method for forming the photospacer is not particularly limited, and for example, the photosensitive resin composition may be applied to a substrate such as glass or a transparent plastic film, dried to form a coating film, and then formed by photolithography. can.
  • photolithography for example, a photomask is placed on the coating film, the coating film is photocured by irradiating with ultraviolet rays, and an alkaline aqueous solution is sprayed on the coating film after the ultraviolet irradiation to dissolve and remove the unexposed areas. The remaining exposed portions are washed with water and developed to form photospacers. A post-bake may then be performed.
  • the shape of the photospacer is not particularly limited, but examples include a cylindrical shape, a prismatic shape, a truncated cone shape, a truncated pyramid shape, and the like.
  • the photospacer of the present invention Since the photospacer of the present invention has a high elastic recovery rate, it can effectively suppress the fluctuation of the cell gap due to stress during use of the liquid crystal display device. It is difficult to damage the alignment film of the substrate on the TFT side (the alignment film is less likely to be scraped).
  • alkali-soluble resin (A-1) had an acid value of 37.4 mgKOH/g, a weight average molecular weight (Mw) of 24,000 by GPC, and a double bond equivalent of 154 g/mol.
  • reaction solution was analyzed at any time by high performance liquid chromatography (HPLC) under the following conditions, and about 30% by mass of the reaction solution was dipentaerythritol pentaacrylate (DPEPA), and about 70% by mass was dipentaerythritol hexaacrylate.
  • HPLC high performance liquid chromatography
  • the monomer mixture ⁇ contains succinic anhydride addition-modified dipentaerythritol penta(meth)acrylate (AM-DPEPA, number of crosslinkable functional groups: 6, of which, number of acrylic groups: 5, number of carboxyl groups: 1). about 30 parts by weight, containing about 70 parts by weight of DPEHA.
  • AM-DPEPA succinic anhydride addition-modified dipentaerythritol penta(meth)acrylate
  • Production example 4 [Synthesis of monomer mixture ⁇ ] A monomer mixture ⁇ was obtained in the same manner as in Production Example 3 above, except that the modification step was not performed.
  • Production example 5 [Synthesis of monomer mixture ⁇ ] A monomer mixture ⁇ was obtained in the same manner as in Production Example 3 above, except that the modification step was not performed.
  • Example 1 [Preparation of photosensitive resin composition] 250 parts by mass of 40% by mass solution of alkali-soluble resin (A-1) (content of alkali-soluble resin (A-1): 100 parts by mass), 40 parts by mass of monomer mixture ⁇ as monomer group (B), 80 parts by mass of monomer mixture ⁇ Parts by mass, 6 parts by mass of the product name IrgacureOXE01 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator (C), and 2.5 parts by mass of the product name Tinuvin 479 (manufactured by BASF Japan Ltd.) as an ultraviolet absorber. , a photosensitive resin composition having a solid content of 2.6% by mass was prepared.
  • the first crosslinkable (meth)acrylate monomer (B1) in the monomer group (B) corresponds to AM-DPEPA and DPEPA, and the total content thereof was 68 parts by mass.
  • DPEHA corresponds to the second crosslinkable (meth)acrylate monomer (B2), and its content was 52 parts by mass.
  • the acid value as the monomer group (B) was 8 mgKOH/g, and the hydroxyl value was 53 mgKOH/g.
  • Examples 2-4 and Comparative Examples 1-8 A photosensitive resin composition was prepared in the same manner as in Example 1, except that the composition was changed to that shown in Table 1.
  • the unit of the numerical values in Table 1 is parts by mass, and in the monomer group (B), the content ratio is indicated by a range due to the characteristics of the product, and the value calculated from this content is within this range. The values obtained from the maximum and minimum values of are described as ranges. Further, the product names and manufacturers of the monomer group (B) in Table 1 that are not described above, the photopolymerization initiator (C) and the ultraviolet absorber are as follows.
  • Monomer group (B) ⁇ Viscoat #295 (manufactured by Osaka Organic Chemical Industry Co., Ltd., trimethylolpropane triacrylate, number of crosslinkable functional groups: 3, number of acrylic groups: 3, number of hydroxyl groups: 0) - Viscoat #700 (manufactured by Osaka Organic Chemical Industry Co., Ltd., EO 3.8 mol adduct diacrylate of bisphenol A, number of crosslinkable functional groups: 2, number of acrylic groups: 2, number of hydroxyl groups: 0) ⁇ Viscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd., a mixture of 55 to 85 parts by mass of tripentaerythritol acrylate, 10 to 20 parts by mass of mono- and dipentaerythritol acrylate, and 5 to 15 parts by mass of polypentaerythritol acrylate) DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.,
  • TR-PBG-304 Trade name TR-PBG-304 (manufactured by Changzhou Strong Advanced Electronic Materials Co., Ltd.)
  • OXE-01 Product name Irgacure OXE01 (manufactured by BASF Japan Ltd.)
  • Irg-819 trade name Irgacure 819
  • EK SPEEDCURE EMK (manufactured by LAMBSON)
  • NCI-100 Product name Adeka Arcles NCI-100 (manufactured by Adeka Co., Ltd.)
  • Ultraviolet absorber SEESORB 106 trade name SEESORB 106 (manufactured by Shipro Kasei Co., Ltd.)
  • Tinuvin 479 Product name Tinuvin 479 (manufactured by BASF Japan Ltd.)
  • Upper base diameter of 90% part when film thickness is 100%
  • Lower base diameter of 10% part when film thickness is 100%
  • a hardness tester manufactured by Fischer Instruments, product name: FISCHERSCOPE HM-2000
  • a flat indenter with a diameter of 50 ⁇ m is used to apply a load of up to 40 mN at both a loading speed and an unloading speed of 2.0 mN / sec. After that, it was held for 5 seconds, then unloaded to 0 mN, held for 5 seconds, and a load-deformation curve at the time of loading and a load-deformation curve at the time of unloading were created.
  • the elastic recovery rate was calculated according to the following formula, with the amount of deformation at a load of 40 mN under load being L1 and the amount of deformation at a load of 0 mN under unloading being L2, and evaluated according to the following criteria.
  • Elastic recovery rate (%) ⁇ (L1-L2) ⁇ 100] / L1 ⁇ Evaluation Criteria>
  • C Elastic recovery rate of 70% or more and less than 80%
  • F Elastic recovery rate of less than 70%
  • the photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 and 8 were applied on a glass substrate by spin coating, dried under reduced pressure, and then allowed to stand for 2 minutes on a hot plate heated to 90°C. bottom. After dissipating heat from the glass substrate, put the glass substrate in a petri dish with a diameter of 12 cm ⁇ so that the coating surface faces upward, add 50 mg of a developer (manufactured by ADEKA, CD-379, 20 times pure water diluted solution), and add the petri dish for 2 minutes. was shaken horizontally, and then the lysate was collected.
  • a developer manufactured by ADEKA, CD-379, 20 times pure water diluted solution
  • the turbidity of the sampled solution was measured using a HACH turbidity meter 2100Q and evaluated according to the following criteria. Although no measurement was performed in Comparative Example 7, the monomer group (B) had an acid value of 0, and the first crosslinkable (meth)acrylate monomer (B1) and the second crosslinkable (meth)acrylate monomer (B1) ) and the acrylate monomer (B2), it is assumed to be F when evaluated.
  • C Cloudy (turbidity of 100 or more)
  • F Many deposits
  • the substrate with a protective film was washed with a UV/ozone device at a predetermined exposure amount, and the photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 8 were applied to the substrate with a protective film using a spin coater. painted on top. This was heat-dried (pre-baked) for 10 minutes in an inert oven at 105° C. to form a coating film having a thickness of 3.50 ⁇ m. Next, the substrate was cooled to room temperature and exposed through a negative photomask ( ⁇ (round) pattern design ⁇ of 10 ⁇ m) using a multi-lens scanning system.
  • ⁇ round
  • the photosensitive resin composition of the present invention is suitably used as a material for forming photospacers.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
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Abstract

La présente invention concerne : une composition de résine photosensible qui permet de former un produit durci (par exemple, un photo-espaceur) offrant à la fois une vitesse élevée de récupération élastique et une excellente flexibilité ; un produit durci obtenu à partir de la composition de résine photosensible ; et un dispositif d'affichage d'image comprenant le produit durci. La composition de résine photosensible de la présente invention contient : une résine (A) soluble dans les alcalis, ayant une double liaison équivalente à 200 g/mol ou moins ; un groupe monomère (B) qui comprend un premier monomère de (méth)acrylate réticulable (B1) ayant au moins six groupes fonctionnels réticulables, au moins l'un au moins des groupes fonctionnels réticulables étant un groupe fonctionnel réticulable de type liaison hydrogène, et un second monomère de (méth)acrylate réticulable (B2) qui comprend au moins six groupe fonctionnels réticulables, le nombre de groupes fonctionnels réticulables de type liaison hydrogène, parmi les groupes fonctionnels réticulables, étant inférieur au nombre de groupes fonctionnels réticulables de type liaison hydrogène que contient le premier monomère de (méth)acrylate réticulable (B1) , la valeur acide du groupe monomère (B) étant de 1 à 20 mgKOH/g ; et un initiateur de photopolymérisation (C).
PCT/JP2022/031524 2021-08-23 2022-08-22 Composition de résine photosensible, produit durci et dispositif d'affichage d'image WO2023027010A1 (fr)

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JP2007034119A (ja) * 2005-07-29 2007-02-08 Toray Ind Inc カラーフィルター用感光性着色組成物、およびカラーフィルター
JP2014041310A (ja) * 2012-07-27 2014-03-06 Fujifilm Corp 着色硬化性組成物、カラーフィルタ、及び表示装置
JP2016153835A (ja) * 2015-02-20 2016-08-25 富士フイルム株式会社 感光性組成物、硬化膜の製造方法、硬化膜、タッチパネル、タッチパネル表示装置、液晶表示装置、及び、有機ｅｌ表示装置
JP2018058976A (ja) * 2016-10-04 2018-04-12 三菱ケミカル株式会社 着色樹脂組成物、カラーフィルタ及び画像表示装置
WO2019059169A1 (fr) * 2017-09-22 2019-03-28 東レ株式会社 Composition de résine photosensible transparente, photo-espaceur, dispositif d'affichage à cristaux liquides, procédé de production de photo-espaceur, procédé de production de dispositif d'affichage à cristaux liquides, et utilisation d'une composition de résine photosensible transparente pour exposition par balayage de lentille

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CN102460772A (zh) 2009-05-26 2012-05-16 奥普图多特公司 利用直接涂覆在纳米孔隔板上的电极的电池
JP6461222B2 (ja) 2017-03-30 2019-01-30 本田技研工業株式会社 オイルストレーナ及び動力伝達装置
JP2020071483A (ja) 2018-10-29 2020-05-07 東レ株式会社 ネガ型感光性樹脂組成物、それを用いたフォトスペーサーおよび画像表示装置

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JP2007034119A (ja) * 2005-07-29 2007-02-08 Toray Ind Inc カラーフィルター用感光性着色組成物、およびカラーフィルター
JP2014041310A (ja) * 2012-07-27 2014-03-06 Fujifilm Corp 着色硬化性組成物、カラーフィルタ、及び表示装置
JP2016153835A (ja) * 2015-02-20 2016-08-25 富士フイルム株式会社 感光性組成物、硬化膜の製造方法、硬化膜、タッチパネル、タッチパネル表示装置、液晶表示装置、及び、有機ｅｌ表示装置
JP2018058976A (ja) * 2016-10-04 2018-04-12 三菱ケミカル株式会社 着色樹脂組成物、カラーフィルタ及び画像表示装置
WO2019059169A1 (fr) * 2017-09-22 2019-03-28 東レ株式会社 Composition de résine photosensible transparente, photo-espaceur, dispositif d'affichage à cristaux liquides, procédé de production de photo-espaceur, procédé de production de dispositif d'affichage à cristaux liquides, et utilisation d'une composition de résine photosensible transparente pour exposition par balayage de lentille

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