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KR-20260066082-A - Polyimide, resin composition, molded article and film

KR20260066082AKR 20260066082 AKR20260066082 AKR 20260066082AKR-20260066082-A

Abstract

The present invention relates to a polyimide and a resin composition comprising a polyimide and an acrylic resin. The polyimide comprises, as a diamine component, a diamine having one or more structures selected from CF3 - O-, -( CF2 -O) n- and -O-( CF2 - CF2 -O) n- (where n is an integer from 1 to 20), and as a tetracarboxylic acid dianhydride component, one or more tetracarboxylic acid dianhydrides selected from the group consisting of a tetracarboxylic acid dianhydride having an ether bond, a tetracarboxylic acid dianhydride having a fluorene structure, a tetracarboxylic acid dianhydride having a xanthen structure, and a bis(trimellitic anhydride) ester.

Inventors

  • 이시구로, 후미야스
  • 가타야마, 게이스케
  • 가와시마, 유키

Assignees

  • 가부시키가이샤 가네카

Dates

Publication Date
20260512
Application Date
20240919
Priority Date
20230919

Claims (14)

  1. It is a polyimide having a tetracarboxylic acid dianhydride component and a diamine component, and As a diamine component, it comprises a fluorine atom-containing diamine having one or more structures selected from CF3 -O-, -( CF2 -O) n- , and -O-( CF2 - CF2 -O) n- (where n is an integer from 1 to 20), and As a tetracarboxylic acid dianhydride component, comprising one or more tetracarboxylic acid dianhydrides selected from the group consisting of tetracarboxylic acid dianhydrides having ether bonds, tetracarboxylic acid dianhydrides having a fluorene structure, tetracarboxylic acid dianhydrides having a xanthen structure, and bis(trimellitic anhydride) esters, Polyimide.
  2. A polyimide according to claim 1, wherein the fluorine atom-containing diamine is 2,2'-bis(trifluoromethoxy)benzidine, 3,3'-bis(trifluoromethoxy)benzidine, or 2,3'-bis(trifluoromethoxy)benzidine.
  3. In claim 1, one or more tetracarboxylic acid dianhydrides selected from the group consisting of tetracarboxylic acid dianhydrides having ether bonds, tetracarboxylic acid dianhydrides having a fluorene structure, tetracarboxylic acid dianhydrides having a xanthene structure, and bis(trimellitic anhydride) esters are 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 3,4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, A polyimide selected from the group consisting of 5,5'-(9H-fluorene-9-ylidenebis(2-methyl-4,1-phenylene)bis[1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylate], p-phenylenebis(trimellitic acid monoester anhydride), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)-biphenyl-4,4'-diyl and bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)-2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diyl.
  4. In claim 1, as a tetracarboxylic acid dianhydride component, additionally 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, spiro[fluorene-9,9'xanthene]-2',3',6',7'-tetracarboxylic acid dianhydride and A polyimide comprising one or more tetracarboxylic acid dianhydrides selected from the group consisting of 5,5'-spiro[9H-fluorene-9,9'-[9H]xanthen]-3',6'-diylbis(1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylate).
  5. In claim 1, as a tetracarboxylic acid dianhydride component, it comprises an alicyclic tetracarboxylic acid dianhydride, and Polyimide having an amount of alicyclic tetracarboxylic acid dianhydride of 1 to 80 mol% relative to the total amount of tetracarboxylic acid dianhydride components.
  6. In paragraph 5, the above-mentioned alicyclic tetracarboxylic acid dianhydride is 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, bicyclo[2.2.2]oct-7-en-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid dianhydride and 1,1'-bicyclohexane-3,3',4,4'tetracarboxylic acid-3,4: Polyimide, one or more selected from the group consisting of 3',4'-dianhydrides.
  7. In claim 1, the amount of a diamine having a structure in which CF₃- or -C( CF₃ ) ₂- is directly bonded to a carbon atom of an aromatic ring is less than 0.5 mol% relative to the total amount of the diamine component, and The amount of tetracarboxylic acid dianhydride having a structure in which CF3- or -C( CF3 ) 2- is directly bonded to a carbon atom of an aromatic ring, relative to the total amount of tetracarboxylic acid dianhydride components, is less than 0.5 mol% Polyimide.
  8. In claim 1, a polyimide that is soluble in dimethylformamide at 23°C.
  9. A molded body comprising a polyimide described in any one of claims 1 to 8.
  10. A film comprising a polyimide as described in any one of claims 1 to 8.
  11. A resin composition comprising a polyimide described in any one of claims 1 to 8 and an acrylic resin.
  12. A resin composition according to claim 11, comprising the polyimide and the acrylic resin in a weight ratio ranging from 98:2 to 2:98.
  13. A molded body comprising the resin composition described in paragraph 11.
  14. A film comprising the resin composition described in paragraph 11.

Description

Polyimide, resin composition, molded article and film The present invention relates to a polyimide, a resin composition comprising said polyimide, and a molded body such as a film. In display devices such as liquid crystals, organic ELs, and electronic paper, as well as in electronic devices such as solar cells and touch panels, there is a demand for thinning, lightweighting, and further flexibility. By replacing the glass materials used in these devices with film materials, flexibility, thinning, and lightweighting can be achieved. As a glass substitute material, transparent polyimide films have been developed and are being used as display substrates and cover films. As a method for manufacturing a polyimide film having high transparency, a method has been proposed using a polyimide resin that is soluble in organic solvents and does not require imidization at high temperatures after film formation. In order to balance transparency and mechanical properties, fluorine-containing compounds are used as monomers for diamines and/or tetracarboxylic acid dianhydrides, and many soluble polyimides have been proposed using fluoroalkyl-substituted benzidines such as 2,2'-bis(trifluoromethyl)benzidine (TFMB) as diamines (e.g., Patent Document 1). Patent Document 2 describes that the transparency of a transparent polyimide film can be improved by mixing a soluble polyimide with an acrylic resin. [Polyimide] Polyimide is obtained by dehydrating a polyamic acid obtained by the addition polymerization of a tetracarboxylic acid dianhydride (hereinafter referred to as "acid dianhydride") and a diamine. That is, the polyimide is a polycondensate of a tetracarboxylic acid dianhydride and a diamine, and has a structure derived from the acid dianhydride (acid dianhydride component) and a structure derived from the diamine (diamine component). Diamine (Specific diamine) The polyimide of the present invention comprises, as a diamine component, one or more diamines having a structure selected from CF3 -O-, -( CF2 -O) n- , and -O-( CF2 - CF2 -O) n- . n is an integer from 1 to 20. Hereinafter, such diamines are described as "specific diamines." In certain diamines, the carbon atom of a trifluoromethyl group ( -CF3 ) or the carbon atom of a difluoromethylene group ( -CF2- ) is bonded to an oxygen atom, and compared to a structure in which a trifluoromethyl group is bonded to a carbon atom (-C- CF3 ) or a structure in which carbon atoms are bonded to both ends of a difluoromethylene group (-C- CF2 -C-), there is a tendency for higher degradability and lower environmental persistence. Therefore, polyimides containing certain diamines as diamine components have superior environmental safety compared to conventional soluble polyimides containing organic fluorine compounds such as fluoroalkyl-substituted benzidines as diamine components. Among specific diamines, it is preferable to have CF3 - O- or -( CF2 -O) n- in that it does not correspond to the "specific fluorine structure" described below, and from the perspective of the polymerization and mechanical strength of the polyimide, a diamine having a trifluoromethoxy group (CF3 - O-) is preferred, and among them, a diamine in which the oxygen atom of the trifluoromethoxy group is bonded to the carbon atom of the aromatic ring is preferred. From the perspective of reactivity, a diamine in which the trifluoromethoxy group is bonded to the carbon atom of the aromatic ring is preferable not to have a fluorine atom that is directly bonded to the aromatic ring to which the trifluoromethoxy group is bonded, and it is particularly preferable not to contain a fluorine atom other than the trifluoromethoxy group. Examples of specific diamines in which the trifluoromethoxy group is bonded to the carbon atom of the aromatic ring include trifluoromethoxy-substituted benzidine and trifluoromethoxy-substituted phenylenediamine. Examples of trifluoromethoxy-substituted benzidines include 2-(trifluoromethoxy)benzidine, 3-(trifluoromethoxy)benzidine, 2,3-bis(trifluoromethoxy)benzidine, 2,5-bis(trifluoromethoxy)benzidine, 2,6-bis(trifluoromethoxy)benzidine, 2,3,5-tris(trifluoromethoxy)benzidine, 2,3,6-tris(trifluoromethoxy)benzidine, 2,3,5,6-tetrakis(trifluoromethoxy)benzidine, 2,2'-bis(trifluoromethoxy)benzidine (TFMOB), 3,3'-bis(trifluoromethoxy)benzidine, 2,3'-bis(trifluoromethoxy)benzidine, 2,2',3-tris(trifluoromethoxy)benzidine, Examples include 2,3,3'-tris(trifluoromethoxyl)benzidine, 2,2',5-tris(trifluoromethoxy)benzidine, 2,2',6-tris(trifluoromethoxy)benzidine, 2,3',5-tris(trifluoromethoxy)benzidine, 2,3',6-tris(trifluoromethoxy)benzidine, 2,2',3,3'-tetrakis(trifluoromethoxy)benzidine, 2,2',5,5'-tetrakis(trifluoromethoxy)benzidine, and 2,2',6,6'-tetrakis(trifluoromethoxy)benzidine. Examples of trifluoromethoxy-substituted phenylenediamines include 1,2-diamino-4-(trifluoromethoxy)benzene, 1,3-diamino-4-(trifluoromethoxy)benzene, 1,4-diamino-2-(trifluoromethoxy)benzene, 1,4-diamino-2,3-bis(trifluorome