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CN-116194501-B - Polymer, polymer solution, and photosensitive resin composition

CN116194501BCN 116194501 BCN116194501 BCN 116194501BCN-116194501-B

Abstract

The polymer of the present invention is represented by the following general formula (P). In the general formula (P), Y is an organic group having 1 to 6 carbon atoms and 1 to 30 or less derived from a thiol group-containing compound having 2 functions or more, chain contains a structural unit represented by the following general formula (AE-1) and a structural unit represented by the following general formula (AE-2), and n is an integer of 1 to 6.

Inventors

  • Tian Yingyi

Assignees

  • 住友电木株式会社

Dates

Publication Date
20260505
Application Date
20210917
Priority Date
20200923

Claims (20)

  1. 1.A polymer, wherein, The polymer is represented by the following general formula (P), In the general formula (P), Y is an organic group having 1 to 6 carbon atoms of 1 to 30 inclusive derived from a compound represented by the following chemical formulas (s-1) to (s-21), The Chain contains a structural unit represented by the following general formula (AE-1) and a structural unit represented by the following general formula (AE-2), In the general formula (AE-1), Z is a group containing 1 or more (meth) acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X is an oxygen atom, a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, the alkyl group of Q is bonded to any carbon atom of the alkylene group of X to form a ring or is not bonded, in the general formula (AE-2), R A is a group containing 1 or more (meth) acryloyl groups, the substituent of the substituted alkyl group having 1 to 6 carbon atoms and the substituent of the substituted alkylene group having 1 to 4 carbon atoms are halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups or mercapto groups, N is an integer of 1 to 6, and other structures except Chain are bonded or not bonded on Y.
  2. 2. The polymer according to claim 1, wherein, Y is an organic group having 1 to 6 carbon atoms of 1 to 30 inclusive derived from a thiol group-containing compound having 3 or more functions selected from the compounds represented by the chemical formulas (s-1) to (s-21).
  3. 3. The polymer according to claim 1 or 2, wherein, Y is an organic group having 1 to 6 carbon atoms of 1 to 30 inclusive derived from an ester structure-containing compound selected from the compounds represented by the chemical formulas (s-1) to (s-21).
  4. 4. The polymer according to claim 1 or 2, wherein, The Chain further comprises a structural unit represented by the following general formula (NB), In the general formula (NB), R 1 、R 2 、R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a1 is 0,1 or 2, The organic group having 1 to 30 carbon atoms is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an allyl group, a pentenyl group, an vinyl group, an ethynyl group, a methylene group, an ethylene group, a tolyl group, a xylyl group, a phenyl group, a naphthyl group, an anthryl group, a benzyl group, a phenethyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxy group, an epoxy group or an oxetanyl group, which are substituted or unsubstituted with a fluorine atom, a hydroxyl group, a carboxyl group.
  5. 5. The polymer according to claim 1 or 2, wherein, Wherein Z comprises a group represented by the following general formula (1 a), In the general formula (1 a), R is a hydrogen atom, a methyl group or an ethyl group.
  6. 6. The polymer according to claim 1 or 2, wherein, The Chain contains a structural unit represented by the following general formula (D), In the general formula (D), R D is a group containing a polyfunctional (meth) acryl group.
  7. 7. The polymer according to claim 1 or 2, wherein, The R A contains at least one group containing 2-6 (meth) acryloyl groups.
  8. 8. The polymer according to claim 1 or 2, wherein, R A contains at least one group represented by the following general formula (1 b), (1 c) or (1 d), In the general formula (1 b), K is 2 or 3 and is not less than 3, R is a hydrogen atom or a methyl group, a plurality of R are the same or different, X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by-Z-X-wherein Z is-O-or-OCO-, X is an alkylene group having 1 to 6 carbon atoms, and X 1 are the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by-X ' -Z ' -wherein X ' is an alkylene group having 1 to 6 carbon atoms and Z ' is-O-or-COO-, X 2 is a k+1-valent organic group having 1 to 12 carbon atoms, In the general formula (1 c), K. R, X 1 and X 2 have the same meanings as R, k, X 1 and X 2 in the above general formula (1 b), respectively, a plurality of R are the same or different from each other, a plurality of X 1 are the same or different from each other, X 3 is a 2-valent organic group having 1 to 6 carbon atoms, X 4 and X 5 are each independently a single bond or a 2-valent organic group having 1 to 6 carbon atoms, X 6 is a 2-valent organic group having 1 to 6 carbon atoms, In the general formula (1 d), n is an integer of 2 to 5.
  9. 9. The polymer according to claim 1 or 2, wherein, The Chain contains a structural unit represented by the following general formula (S), In the general formula (S), R S is a group containing only 1 (meth) acryloyl group.
  10. 10. The polymer according to claim 1 or 2, wherein, The Chain further comprises a structural unit represented by the following general formula (MA), 。
  11. 11. The polymer according to claim 1 or 2, wherein, The Chain further comprises at least one selected from the group consisting of a structural unit represented by the following general formula (E) and a structural unit represented by the following general formula (EE), In the general formulae (E) and (EE), Z is a group containing 1 or more (meth) acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X is an oxygen atom, a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, the alkyl group of Q is bonded to any carbon atom of the alkylene group of X to form a ring or is not bonded, the substituent of the substituted alkyl group having 1 to 6 carbon atoms and the substituent of the substituted alkylene group having 1 to 4 carbon atoms are a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group or a mercapto group, In the general formula (EE), a plurality of Z, Q and X are the same or different.
  12. 12. The polymer according to claim 1 or 2, wherein, The Chain further comprises a structural unit represented by the following general formula (M), 。
  13. 13. The polymer according to claim 1, wherein, The polymer is represented by the following general formula (P1), In the general formula (P1), P, q and r represent the molar contents of A, B and C in the polymer, respectively, p+q+r=1, P is greater than 0, q is greater than 0, r is 0 or more, P, q or r are the same or different in each of the structural units within n [ ], N is an integer of 1 to 6, X is hydrogen or an organic group having 1 to 30 carbon atoms, The organic group having 1 to 30 carbon atoms is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an allyl group, a pentenyl group, an vinyl group, an ethynyl group, a methylene group, an ethylene group, a tolyl group, a xylyl group, a phenyl group, a naphthyl group, an anthryl group, a benzyl group, a phenethyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxy group, an epoxy group or an oxetanyl group, which are substituted or unsubstituted by a fluorine atom, Y is an organic group having 1 to 6 carbon atoms of 1 to 30 inclusive derived from a compound represented by the following chemical formulas (s-1) to (s-21), A comprises a structural unit represented by the following general formula (NB), B comprises a structural unit represented by the following general formula (AE), C contains a 2-valent structural unit derived from a copolymerizable compound having a double bond, The copolymerizable compound having a double bond is indene, maleimide, styrene, acenaphthene, norbornadiene, dihydrofuran, pinene, limonene, pentene, cyclohexene, cyclododecatriene, tricycloundecene, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, coumarin, methyl methacrylate, methyl acrylate, vinyl acetate or 2-hydroxyethyl vinyl ether, which groups are substituted or unsubstituted with alkyl groups, aryl groups, There are a plurality of A, B or C which are identical to or different from each other, Y is bonded or not bonded with other structures than the polymer chain represented by [ ] n, In the general formula (NB), R 1 、R 2 、R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a1 is 0,1 or 2, The organic group having 1 to 30 carbon atoms is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an allyl group, a pentenyl group, an vinyl group, an ethynyl group, a methylene group, an ethylene group, a tolyl group, a xylyl group, a phenyl group, a naphthyl group, an anthryl group, a benzyl group, a phenethyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxy group, an epoxy group or an oxetanyl group, which are substituted or unsubstituted by a fluorine atom, In the general formula (AE), Z, Q, X has the same meaning as in the general formula (AE-1), and R A is a group containing 1 or more (meth) acryloyl groups.
  14. 14. The polymer according to claim 13, wherein, The 2-valent structural units constituting the C are 2-valent structural units represented by the following general formulas (1) - (4), R 1 and R 2 in the general formula (1) independently represent a hydrogen atom, an alkyl group or an aryl group, R 3 in the general formula (2) independently represent a hydrogen atom, an alkyl group or an aryl group, R 4 ～R 6 in the general formula (3) independently represent a hydrogen atom, an alkyl group or an aryl group, and R 7 ～R 10 in the general formula (4) independently represent a hydrogen atom, a hydroxyl group or an organic group having 1 to 30 carbon atoms.
  15. 15. The polymer according to claim 13 or 14, wherein, Wherein B comprises at least one structural unit selected from the structural units represented by the following general formula (DE) and general formula (SE) and, if necessary, at least one structural unit selected from the structural units represented by the following general formula (D), general formula (S), general formula (MA), general formula (E), general formula (EE) and general formula (M), In the general formula (DE), Q, X, Z has the same meaning as the general formula (AE-1), R D is a group containing more than 2 (meth) acryloyl groups, In the general formula (SE), Q, X, Z has the same meaning as in the general formula (AE-1), R S is a group containing only 1 (meth) acryloyl group, In the general formula (D), R D is a group containing a polyfunctional (meth) acryloyl group, In the general formula (S), R S is a group containing only 1 (meth) acryloyl group, In the general formula (E), Z, Q, X has the same meaning as in the general formula (AE-1), In the general formula (EE), Z, Q, X has the same meaning as the general formula (AE-1), a plurality of Z, Q and X are the same or different, 。
  16. 16. The polymer according to claim 1 or 13, wherein, The organic group constituting Y contains an organic group having 1 to 6 carbon atoms of 1 to 30 inclusive derived from at least one compound selected from the group consisting of compounds represented by the following chemical formulas (s-1) to (s-3), (s-5) and (s-8) to (s-10), 。
  17. 17. A polymer, wherein, The polymer is obtained by the following steps: polymerizing a monomer composition containing a monomer represented by the following general formula (NBm) and maleic anhydride in the presence of a difunctional or higher thiol group-containing compound to prepare a base polymer; Reacting the resulting base polymer with a polyfunctional (meth) acrylic monomer and/or a monofunctional (meth) acrylic monomer in the presence of a basic catalyst to produce a polymer precursor, and Then, the polymer precursor thus obtained is reacted with an epoxy group-containing (meth) acrylic compound in the presence of a catalyst to obtain a polymer, In the general formula (NBm), R 1 、R 2 、R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a1 is 0,1 or 2, The organic group having 1 to 30 carbon atoms is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an allyl group, a pentenyl group, an vinyl group, an ethynyl group, a methylene group, an ethylene group, a tolyl group, a xylyl group, a phenyl group, a naphthyl group, an anthryl group, a benzyl group, a phenethyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxy group, an epoxy group or an oxetanyl group, which are substituted or unsubstituted with a fluorine atom, a hydroxyl group, a carboxyl group.
  18. 18. The polymer of claim 17, wherein, In the base polymer, a polymer chain having a structural unit represented by the following general formula (NB) and a structural unit represented by the following general formula (MA) is bonded via a thioether group derived from at least 1 thiol group of the thiol group-containing compound having a functionality of 2 or more, In the general formula (NB), R 1 、R 2 、R 3 , R 4 and a1 have the same meanings as those of the general formula (NBm), 。
  19. 19. The polymer of claim 18, wherein, In the polymer precursor, a polymer chain having a structural unit represented by the general formula (NB), a structural unit represented by the general formula (D) and/or a structural unit represented by the general formula (S) is bonded via a thioether group derived from at least 1 thiol group of the thiol group-containing compound having a functionality of 2 or more, In the general formula (D), R D is a group containing 2 or more (meth) acryloyl groups, and in the general formula (S), R S is a group containing only 1 (meth) acryloyl group.
  20. 20. The polymer of claim 19, wherein, In the polymer, a polymer chain having the structural unit represented by the general formula (NB), the structural unit represented by the general formula (D) and/or the structural unit represented by the general formula (S), the structural unit represented by the general formula (DE) and/or the structural unit represented by the general formula (SE) is bonded via a thioether group derived from at least 1 thiol group of the thiol-group-containing compound having a functionality of 2 or more, In the general formula (DE), Z is a group containing 1 or more (meth) acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X is an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, the alkyl group of Q is bonded to any carbon atom of the alkylene group of X to form a ring or is not bonded, R D is a group containing 2 or more (meth) acryloyl groups, The substituent of the substituted alkyl group with 1-6 carbon atoms and the substituent of the substituted alkylene group with 1-4 carbon atoms are halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups or mercapto groups, In the general formula (SE), Z, Q, X has the same meaning as in the general formula (DE), and R S is a group containing only 1 (meth) acryloyl group.

Description

Polymer, polymer solution, and photosensitive resin composition Technical Field The present invention relates to a polymer, a polymer solution, and a photosensitive resin composition. Background A liquid crystal display device or a solid-state imaging element is generally provided with a color filter or a black matrix. Photosensitive resin compositions are often used in the formation of color filters or black matrices. For example, patent document 1 discloses a photosensitive resin composition comprising an alkali-soluble resin having a group containing an acidic group at least in a side chain and two or more kinds of polymerizable unsaturated groups different from each other, a polymerizable compound, and a photopolymerization initiator, as described in claim 1. In the example of patent document 1, it is described that an allyl methacrylate/glycidyl methacrylate adduct is synthesized as an alkali-soluble resin, and a photosensitive resin composition is prepared using the alkali-soluble resin. Patent document 2 describes a resin composition containing a resin, a polybasic acid monoester of a polyfunctional (meth) acrylate containing a hydroxyl group, and a solvent, the resin containing an epoxy group and an acid group, the resin composition being characterized in that the epoxy group is 0.5 to 3.0 mol relative to 1 mol of the acid group in the resin containing the epoxy group and the acid group. Patent document 3 discloses a method for producing a polymer, which includes a step of reacting a compound having an epoxy group with a precursor polymer having a maleic anhydride site open. Glycidyl methacrylate (GLYCIDYL METHACRYLATE) is described as a compound having an epoxy group. Prior art literature Patent literature Patent document 1, international publication No. 2012/147706. Patent document 2 International publication No. 2016/103844. Patent document 3 International publication No. 2017/154439. Disclosure of Invention Technical problem to be solved by the invention A polymer having a property of polymerization reaction by light and curing is used in the photosensitive resin composition for forming a color filter or a black matrix. The color filter or black matrix is produced by patterning a photosensitive resin composition by exposure and development, and then curing the composition. In the photosensitive resin composition, "high sensitivity" is considered as a general problem, and a higher level of high sensitivity is required with the complexity and popularization of the display device and the image pickup device. The higher the sensitivity (the better the sensitivity) of the photosensitive resin composition, the shorter the time required for exposure, and the productivity can be improved. Further, the cured product of the photosensitive resin composition is required to have excellent transparency and thermochromatic properties while suppressing yellowing. In addition, when a pattern is formed by applying a photosensitive resin composition to a substrate or the like and exposing the obtained coating film to light and developing, excellent adhesion to the substrate or the like is required from the viewpoint of yield of a product or reliability of the product. In patent documents 1 to 3, there is room for improvement in these characteristics. Means for solving the technical problems The inventors of the present invention have found that a resin cured product having excellent heat discoloration resistance, which is suppressed in yellowing, and excellent adhesion to a substrate can be obtained by improving a polymer used in a photosensitive resin composition, and have achieved the present invention. That is, the present invention can be shown as follows. According to the present invention, there can be provided a polymer, wherein the polymer is represented by the following general formula (P). In the general formula (P), Y is an organic group having 1 to 6 carbon atoms and 1 to 30 carbon atoms derived from a thiol group-containing compound having 2 or more functions. The Chain contains a structural unit represented by the following general formula (AE-1) and a structural unit represented by the following general formula (AE-2). In the general formula (AE-1), Z is a group containing 1 or more (methyl) acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group with 1-6 carbon atoms, X is an oxygen atom or a substituted or unsubstituted alkylene group with 1-4 carbon atoms, the alkyl group of Q is bonded with any carbon atom of the alkylene group of X to form a ring or is not bonded, in the general formula (AE-2), R A is a group containing 1 or more (methyl) acryloyl groups, N is an integer of 1 to 6, and other structures except Chain are bonded or not bonded on Y. According to the present invention, a polymer can be provided, wherein the polymer is obtained by the following process. A method for producing a polymer, which comprises polymerizing a monomer composition comprising a monome