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WO2021028960A1 - Composition de résine colorée, produit durci et stratifié - Google Patents

Composition de résine colorée, produit durci et stratifié Download PDF

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Publication number
WO2021028960A1
WO2021028960A1 PCT/JP2019/031565 JP2019031565W WO2021028960A1 WO 2021028960 A1 WO2021028960 A1 WO 2021028960A1 JP 2019031565 W JP2019031565 W JP 2019031565W WO 2021028960 A1 WO2021028960 A1 WO 2021028960A1
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WIPO (PCT)
Prior art keywords
resin composition
colored resin
organic solvent
group
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/031565
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English (en)
Japanese (ja)
Inventor
中村　仁美
譲 本松
寛哉 秋田
斉二郎 福田
敏之 五島
浩二 遠藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wingo Technology Co Ltd
Taiyo Holdings Co Ltd
Original Assignee
Wingo Technology Co Ltd
Taiyo Holdings Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wingo Technology Co Ltd, Taiyo Holdings Co Ltd filed Critical Wingo Technology Co Ltd
Priority to PCT/JP2019/031565 priority Critical patent/WO2021028960A1/fr
Priority to PCT/JP2020/029613 priority patent/WO2021029243A1/fr
Priority to TW109126668A priority patent/TW202120593A/zh
Publication of WO2021028960A1 publication Critical patent/WO2021028960A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a colored resin composition, and a cured product and a laminate formed by using the colored resin composition.
  • Polyimide compounds are widely used in various fields because they have excellent properties such as high heat resistance and dimensional stability.
  • glass substrates such as cover glasses provided in organic EL display devices have been used.
  • a polyimide film a resin film (hereinafter referred to as a polyimide film) base material containing a polyimide compound and to impart flexibility to these.
  • the organic EL display device or the like is provided with a metal wiring in the ITO film pattern formed in the image display area and the peripheral portion thereof, and further, a cover is provided so that the metal wiring is not visually recognized by the user.
  • a shielding portion is provided on the inner peripheral portion of the glass.
  • This shielding portion is composed of a cured product formed by applying a colored resin composition containing a resin material and a coloring agent to the inner peripheral portion of the cover glass and drying it.
  • the glass base material has been changed to a polyimide film base material, and a resin material contained in a colored resin composition used for forming a shielding portion.
  • the use of polyimide compounds is being considered.
  • a polyimide compound has low solubility in an organic solvent, and when a cured product is to be formed, the polyimide compound is dissolved in an organic solvent as a precursor (polyamic acid), coated, and then heated at a high temperature to form a ring. It was necessary to carry out a chemical dehydration reaction (polyimide).
  • Patent Document 1 proposes the use of an organic solvent-soluble polyimide compound in order to solve the problem caused by high-temperature heating during the formation of a cured product.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2007-12990
  • the present inventors have adhered to a polyimide film substrate in a cured product formed by using a colored resin composition containing a conventionally known organic solvent-soluble polyimide compound as disclosed in Patent Document 1.
  • a new issue that was not enough and there was room for improvement.
  • the present invention has been made to solve such a problem, and its main purpose is to form a cured product containing a polyimide compound having high solubility in an organic solvent and having excellent adhesion to a polyimide film substrate. It is to provide a colored resin composition which can be made.
  • Another object of the present invention is to provide a cured product and a laminate formed by using the colored resin composition.
  • the colored resin composition of the present invention (A) Organic solvent-soluble polyimide compound and (B) Colorant and (C) A colored resin composition containing an organic solvent.
  • the organic solvent-soluble polyimide compound (A) is (A-1) The diamine compound represented by the following general formula (1) and (A-2) A diamine compound having at least one of a carboxyl group and a hydroxyl group, and at least one of a diamine compound having a siloxane bond. (A-3) It is characterized in that it is an imidized polyimide precursor composed of a reaction component containing an acid anhydride.
  • R 1 to R 4 is selected from an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 6 to 10 carbon atoms, and a benzyloxy group having 6 to 10 carbon atoms.
  • Other R 1 to R 4 are hydrogen atoms.
  • the (A) organic solvent-soluble polyimide compound contains a diamine compound having at least one of a carboxyl group and a hydroxyl group as a reaction component (A-2).
  • the diamine compound having at least one of a carboxyl group and a hydroxyl group is represented by the following general formula (2) or (3).
  • R 5 is selected from a divalent organic group or a single bond, and n is an integer of 1 to 10, preferably 1 to 5.
  • R 6 is independently selected from COOH or OH, o is an integer of 0 to 4, and the diamine compound represented by the general formula (2) has at least one R 6.
  • p is an integer of 1 to 4.
  • the (A) organic solvent-soluble polyimide compound contains a diamine compound having a siloxane bond as a reaction component (A-2).
  • the diamine compound having a siloxane bond is represented by the following general formula (4).
  • R 7 to R 12 are alkyl groups or phenyl groups. q and r are independently integers of 1 to 10, and s is an integer of 0 to 10. )
  • the organic solvent is an aromatic carboxylic acid ester.
  • the (A) organic solvent-soluble polyimide compound contains both a diamine compound having at least one of a carboxyl group and a hydroxyl group and a diamine compound having a siloxane bond as a reaction component (A-2).
  • the cured product of the present invention is characterized by being formed by using the above-mentioned colored resin composition.
  • the laminate of the present invention is characterized by including a polyimide film base material and a layer made of a cured product formed by using the colored resin composition.
  • a colored resin composition capable of forming a cured product without requiring excessive heating and forming a cured product having good adhesion to a polyimide film substrate can be obtained. Can be provided. Further, according to the present invention, it is possible to provide a cured product and a laminate formed by using the colored resin composition.
  • the colored resin composition of the present invention is characterized by containing (A) an organic solvent-soluble polyimide compound, (B) a colorant, and (C) an organic solvent.
  • the colored resin composition of the present invention may contain an antifoaming agent.
  • the organic solvent-soluble polyimide compound is composed of (A-1) a diamine compound represented by the following general formula (1), (A-2) a diamine compound having at least one of a carboxyl group and a hydroxyl group, and a diamine compound having a siloxane bond.
  • a polyimide precursor (polyamic acid) composed of a reaction component containing at least one of them and (A-3) acid anhydride is dehydrated and ring-closed to be polyimideized.
  • Such an organic solvent-soluble polyimide compound is highly soluble in an organic solvent and does not need to be contained in the colored resin composition in the state of a polyimide precursor (polyamic acid).
  • the cured product in the formation of the cured product, it is not necessary to excessively heat for the dehydration ring closure reaction, and the cured product can be formed by volatilizing the organic solvent in the colored resin composition by drying, and the polyimide film can be formed. It is possible to effectively prevent discoloration of the resin. Further, the cured product formed by using the colored resin composition containing such an organic solvent-soluble polyimide compound exhibits excellent adhesion to the polyimide film base material.
  • the content of the organic solvent-soluble polyimide compound in the colored resin composition is preferably 15% by mass or more and 35% by mass or less, and more preferably 20% by mass or more and 30% by mass or less.
  • the constituent ratio of the constituent unit derived from the diamine compound represented by the general formula (1) and the constituent unit derived from the diamine compound having at least one of a carboxyl group and a hydroxyl group is based on mol%. It is preferably 1: 1 to 1: 4, and more preferably 1: 1 to 1: 3.
  • the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved.
  • the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be effectively improved. Further, the coefficient of thermal expansion of this cured product can be effectively improved.
  • the structural unit derived from the diamine compound represented by the general formula (1) and the structural unit derived from the diamine compound having a siloxane bond are 1: 1 to 1 on a mol% basis. : 4 is preferable, and 1: 1 to 1: 3 is more preferable.
  • the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved.
  • the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be effectively improved.
  • the coefficient of thermal expansion of this cured product can be effectively improved.
  • the organic solvent-soluble polyimide compound contains both a diamine compound having at least one of a carboxyl group and a hydroxyl group and a diamine compound having a siloxane bond as a reaction component (A-2).
  • A-2 a reaction component
  • the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be more effectively improved.
  • this organic solvent-soluble polyimide compound a structural unit derived from a diamine compound represented by the general formula (1), a diamine compound having at least one of a carboxyl group and a hydroxyl group, and a structural unit derived from a diamine compound having a siloxane bond.
  • the composition ratio of and is preferably 1: 1 to 1: 6 on a molar% basis, and more preferably 1: 1 to 1: 5.
  • the organic solvent-soluble polyimide compound contains both a diamine compound having at least one of a carboxyl group and a hydroxyl group and a diamine compound having a siloxane bond as the reaction component (A-2), the organic solvent-soluble polyimide compound is used.
  • the constituent ratio of the constituent unit derived from the diamine compound having at least one of a carboxyl group and the hydroxyl group and the constituent unit derived from the diamine compound having a siloxane bond is preferably 4: 1 to 1: 4. More preferably, it is 3: 2 to 2: 3.
  • the weight average molecular weight (Mw) of the organic solvent-soluble polyimide compound is preferably 30,000 or more and 100,000 or less, more preferably 33,000 or more and 80,000 or less, and 33,000 or more. It is particularly preferably 50,000 or less.
  • Mw means a value measured by gel permeation chromatography using polystyrene as a standard substance, and is measured by a method based on JIS K 7252-1 (published in 2008).
  • the organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention contains a diamine compound represented by the following general formula (1) as a reaction component at the time of synthesis. Thereby, the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved. Further, the coefficient of thermal expansion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound can be effectively improved.
  • any one of R 1 ⁇ R 4 are preferably either R 1 or R 3, particularly preferably is R 3, aromatic groups having 6 to 10 carbon atoms, 6 carbon atoms It is selected from a phenoxy group having a phenoxy group of about 10 and a benzyl group having 6 to 10 carbon atoms and a benzyloxy group having 6 to 10 carbon atoms, and the other groups R 1 to R 4 are hydrogen atoms.
  • the aromatic group having 6 to 10 carbon atoms includes a phenyl group, a trill group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a diethylphenyl group, a propylphenyl group, a butylphenyl group, a fluorophenyl group, and a pentafluorophenyl group.
  • Examples of the phenoxy group having 6 to 10 carbon atoms include a methylphenoxy group, an ethylphenoxy group, a propylphenoxy group, a dimethylphenoxy group, a diethylphenoxy group, a methoxyphenoxy group, an ethoxyphenoxy group and a dimethoxyphenoxy group.
  • Examples of the benzyl group having 6 to 10 carbon atoms include a benzyl group, a methylbenzyl group, an ethylbenzyl group, a propylbenzyl group, a dimethylbenzyl group, a methoxybenzyl group, an ethoxybenzyl group and a methoxybenzyl group.
  • the methylbenzyloxy group includes a benzyloxy group, a betylbenzyloxy group, an ethylbenzyloxy group, a propylbenzyloxy group, a dimethylbenzyloxy group, a methoxybenzyloxy group and an ethoxy.
  • Examples include the benzyloxy group.
  • an aromatic group having 6 to 10 carbon atoms is more preferable, and a phenyl group, a tolyl group, a methylphenyl group, and the like.
  • a dimethylphenyl group, an ethylphenyl group and a diethylphenyl group are more preferable, and a phenyl group is particularly preferable.
  • the constituent ratio of the diamine compound represented by the above general formula (1) is 15 mol parts or more and 60 mol parts. It is preferably 18 mol parts or more, and more preferably 55 mol parts or less.
  • the effect of the diamine compound represented by the above-mentioned general formula (1) can be further improved.
  • the adhesion of the cured product formed by using the colored resin composition of the present invention to the polyimide film substrate can be further improved.
  • the organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention contains a diamine compound having at least one of a carboxyl group and a hydroxyl group as a reaction component at the time of synthesis.
  • the diamine compound having at least one of a carboxyl group and a hydroxyl group is represented by the following general formula (2).
  • R 5 is a divalent organic group or a single bond
  • n is an integer of 1 to 10, preferably 1 to 5.
  • R 6 is independently selected from COOH or OH
  • o is an integer of 0 to 4
  • the diamine compound represented by the general formula (2) has at least one R 6 .
  • the following compounds are mentioned as a particularly preferable embodiment of the diamine compound having at least one of a carboxyl group and a hydroxyl group represented by the general formula (2).
  • the diamine compound having at least one of a carboxyl group and a hydroxyl group is represented by the following general formula (3).
  • R 5 is a divalent organic group or a single bond
  • p is an integer of 1 to 4.
  • the following compounds are mentioned as a particularly preferable embodiment of the diamine compound having at least one of a carboxyl group and a hydroxyl group represented by the general formula (3).
  • the constituent ratio of the diamine compound having at least one of a carboxyl group and a hydroxyl group is 30 mol parts or more and 85 mol parts or less. It is more preferably 33 mol parts or more and 60 mol parts or less, and further preferably 35 mol parts or more and 45 mol parts or less.
  • the organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention contains a diamine compound having a siloxane bond as a reaction component during synthesis. Thereby, the adhesiveness of the cured product formed by using the colored resin composition of the present invention to the polyimide film base material can be effectively improved.
  • the diamine compound having a siloxane bond is represented by the following general formula (4).
  • R 7 to R 12 are alkyl groups or phenyl groups.
  • an alkyl group is preferable, and the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6. It is more preferably 1 to 3.
  • q and r are independently selected from integers of 1 to 10. From the viewpoint of polymerization reactivity, it is preferably 1 to 6, and more preferably 1 to 3.
  • s is selected from an integer from 0 to 10. From the viewpoint of polymerization reactivity, it is preferably 0 to 6, and more preferably 0 to 2.
  • the constituent ratio of the diamine compound having a siloxane bond is preferably 30 mol parts or more and 60 mol parts or less. , 35 mol parts or more, more preferably 55 mol parts or less.
  • the organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention can be used as a reaction component during synthesis, and examples of the acid anhydride include pyromellitic anhydride, 2,2'-bis [4- (3).
  • the organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention may contain other reaction components as reaction components at the time of synthesis as long as the characteristics of the present invention are not impaired.
  • Other polymerization components include 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, and bis.
  • the organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention can be synthesized by a conventionally known method. Specifically, it can be obtained by reacting a diamine compound with an acid anhydride to obtain a polyimide precursor (polyamic acid), and then performing a cyclization dehydration reaction to convert it into a polyimide compound.
  • a polyimide precursor polyamic acid
  • the synthesis of the organic solvent-soluble polyimide compound can be carried out in an organic solvent described later.
  • an imidization catalyst may be used, for example, methylamine, ethylamine, trimethylamine, triethylamine, propylamine, tripropylamine, butylamine, tributylamine, tert-butylamine, hexylamine, triethanolamine, etc.
  • N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidin, N-ethylpyrrolidin, aniline, benzylamine, toluidine, trichloroaniline, pyridine, colidin, lutidine, picolin, quinoline, isoquinolin , Valerolactone and the like can be used.
  • an azeotropic dehydrating agent such as toluene, xylene, or ethylcyclohexane
  • an acid catalyst such as acetic anhydride, propionic anhydride, butyric anhydride, and benzoic anhydride
  • a sealing agent such as benzoic acid, phthalic anhydride, or hydrogenated phthalic anhydride can be used.
  • the colored resin composition of the present invention contains at least one colorant.
  • the colorant may be a pigment or a dye, but a pigment is preferable from the viewpoint of heat resistance and light resistance of the cured product formed by the colored resin composition of the present invention.
  • the pigment may be an organic pigment or an inorganic pigment. Further, the pigment and the dye may be used in combination.
  • the colorant is not particularly limited, and a conventionally known colorant can be appropriately used. However, a shielding portion provided with an organic EL display device or the like on a cured product formed by the colored resin composition of the present invention.
  • a black colorant or a white colorant When applied to, it is preferable to use a black colorant or a white colorant.
  • the black colorant include carbon black, iron tetraoxide, titanium oxide, copper manganese black, copper chromium black and cobalt black, cyanine black and aniline black.
  • the black colorant also includes a colorant obtained by mixing a plurality of colorants to make them black.
  • the white colorant include titanium oxide, barium carbonate, zirconium oxide, calcium carbonate, zinc white, antimony white and zinc sulfide.
  • the content of the colorant in the colored resin composition is preferably 80 parts by mass or more and 200 parts by mass or less, preferably 100% by mass or more, with respect to 100 parts by mass of the organic solvent-soluble polyimide compound constituting the colored resin composition. , 150% by mass or less is more preferable.
  • the colored resin composition of the present invention can obtain excellent handleability in the coating step, and the cured product formed after heating can be obtained. , It is possible to provide a shielding property applied to a shielding portion provided in an organic EL display device or the like.
  • organic solvent for example, a lactone-based organic solvent, an ester-based organic solvent, an ether-based organic solvent, a ketone-based organic solvent, an alcohol-based organic solvent, and the like can be used. Among these, a lactone-based organic solvent and an ester-based organic solvent can be used. Organic solvents are preferred.
  • the lactone-based organic solvent is preferably ⁇ -butyrolactone, and the ester-based organic solvent is preferably an aromatic carboxylic acid ester, more preferably alkyl benzoate, and particularly preferably methyl benzoate or ethyl benzoate.
  • Such an organic solvent can satisfactorily dissolve the organic solvent-soluble polyimide compound contained in the colored resin composition of the present invention, and the interface between the cured product formed by the colored resin composition and the polyimide film base material. It is possible to prevent the whitening phenomenon caused by the erosion of the organic solvent. In addition, the storage stability of the colored resin composition and the continuous printability in screen printing can be effectively improved.
  • the colored resin composition of the present invention may contain two or more kinds of organic solvents.
  • the content of the organic solvent in the colored resin composition is preferably 210 parts by mass or more and 550 parts by mass or less, and 250 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the organic solvent-soluble polyimide compound. Is preferable.
  • the organic solvent-soluble polyimide compound can be satisfactorily dissolved and the moldability of the colored resin composition of the present invention can be improved. it can.
  • the colored resin composition of the present invention may contain an antifoaming agent.
  • the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and fluorine compound.
  • the content of the defoaming agent in the colored resin composition is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.
  • the colored resin composition may contain a polyimide compound other than the organic solvent-soluble polyimide compound and a precursor (polyamic acid) of the organic solvent-soluble polyimide compound as long as the characteristics of the present invention are not impaired.
  • the colored resin composition comprises a pigment dispersant, a thickener, an oxygen remover, a fluorescent whitening agent, a surfactant, an antioxidant, a plasticizer, a flame retardant, and an antistatic agent.
  • Additives such as inhibitors, leveling agents, and antibacterial agents can be included.
  • the cured product of the present invention is formed by using the above-mentioned colored resin composition, and has high adhesion to a polyimide film base material.
  • the shape of the cured product is not particularly limited, and it is preferable to change the shape as appropriate depending on the intended use.
  • a film-shaped cured product can be used.
  • the coefficient of thermal expansion of the cured product is preferably less than 50 ppm / ° C.
  • the coefficient of thermal expansion of the cured product is such that the cured product is subjected to a thermomechanical analyzer (manufactured by TA Instruments Japan, TMA'Q400) at a temperature rise temperature of 10 ° C./min at room temperature to 370 ° C. Refers to the average coefficient of thermal expansion from 500 ° C to 250 ° C.
  • the cured product of the present invention can be produced by applying a colored resin composition on a substrate such as a polyimide film and drying it.
  • a coating method of the colored resin composition include a screen printing method, a gravure printing method, a spin coating method, an inkjet method, a spray coating method, a slit coating method, a dispenser coating method, a dropping method, and the like.
  • the screen printing method is particularly preferable because the shape of the coating film can be easily formed.
  • the drying temperature of the colored resin composition is preferably 80 to 200 ° C., which can prevent discoloration of the coating film made of the colored resin composition.
  • the laminate of the present invention is characterized by including a polyimide film base material and a layer made of a cured product formed by using the colored resin composition.
  • the thickness of the polyimide film base material is preferably 10 ⁇ m or more and 120 ⁇ m or less, and preferably 20 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the layer made of the cured product formed by using the colored resin composition is preferably 1 ⁇ m or more and 500 ⁇ m or less, and preferably 3 ⁇ m or more and 20 ⁇ m or less.
  • Carboxyphenoxy) propanoic acid dianhydride] (BPADA) 15.61 g (30 mmol), methyl benzoate 94.64 g, pyridine 0.47 g (6 mmol), toluene 10 g, and in a nitrogen atmosphere at 180 ° C.
  • a solution of 20% by mass of polyimide compound A was obtained by reacting for 4 hours while removing toluene from the system on the way. No precipitation of the synthesized polyimide compound A was observed in this polyimide solution.
  • the composition ratios of PHBAAB, MBAA and BPADA in the polyimide compound A are as shown in Table 1.
  • the weight average molecular weight of the polyimide compound A was measured in accordance with JIS K 7252-1 (issued in 2008) and found to be 48,000.
  • a polyimide solution containing polyimide compound A and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition A of the present invention.
  • Example 2 Synthesis of polyimide compound B
  • PHBAAB 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
  • 6FAP 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
  • polyimide compound B A solution of 20% by weight of polyimide compound B was obtained by reacting with the mixture for 4 hours. No precipitation of the synthesized polyimide compound B was observed in this polyimide solution.
  • the composition ratios of PHBAAB, 6FAP and BPADA in the polyimide compound B are as shown in Table 1. The weight average molecular weight of the polyimide compound B was measured and found to be 48,000.
  • a polyimide solution containing polyimide compound B and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition B of the present invention.
  • Example 3 Synthesis of polyimide compound C
  • PHBAAB 4.57 g (15 mmol)
  • 3,5-diaminobenzoic acid (DABz) 2.28 g (15 mmol)
  • BPADA 15.61 g in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer.
  • (30 mmol) 94.64 g of methylbenzoate, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added and reacted at 180 ° C. under a nitrogen atmosphere for 4 hours while removing toluene from the system.
  • a 20 wt% solution of the polyimide compound C was obtained.
  • composition ratios of PHBAAB, DABz and BPADA in the polyimide compound C are as shown in Table 1. Moreover, when the weight average molecular weight of the polyimide compound C was measured, it was 43,000.
  • a polyimide solution containing polyimide compound C and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition C of the present invention.
  • Example 4 Synthesis of polyimide compound D
  • PHBAAB 4.57 g (15 mmol)
  • PAM-E 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • a polyimide solution of 20% by weight of the polyimide compound D was obtained by reacting with the mixture for 4 hours. No precipitation of the synthesized polyimide compound was observed in this polyimide solution.
  • the composition ratios of PHBAAB, PAM-E and BPADA in the polyimide compound D are as shown in Table 1. Moreover, when the weight average molecular weight of the polyimide compound D was measured, it was 38,000.
  • the polyimide compound D, the methyl benzoate polyimide solution, carbon black, and the defoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition D of the present invention.
  • Example 5 Synthesis of polyimide compound E
  • ODPA 4'-oxydiphthalic acid anhydride
  • the composition ratios of PHBAAB, MBAA, PAM-E and ODPA in the polyimide compound E are as shown in Table 1.
  • the weight average molecular weight of the polyimide compound E was measured and found to be 39,000.
  • a polyimide solution containing a polyimide compound E and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition E of the present invention.
  • composition ratios of PHBAAB, 6FAP, PAM-E and ODPA in the polyimide compound F are as shown in Table 1.
  • the weight average molecular weight of the polyimide compound F was measured and found to be 43,000.
  • a polyimide solution containing a polyimide compound F and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition F of the present invention.
  • Example 7 Synthesis of polyimide compound G
  • 94.64 g, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added and reacted at 180 ° C. under a nitrogen atmosphere for 4 hours while removing toluene from the system on the way to obtain 20% by weight of the polyimide compound G.
  • a solution was obtained.
  • composition ratios of PHBAAB, 6FAP, DABz and ODPA in the polyimide compound G are as shown in Table 1. Moreover, when the weight average molecular weight of the polyimide compound G was measured, it was 43,000.
  • a polyimide solution containing a polyimide compound G and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition G of the present invention.
  • a polyimide solution containing a polyimide compound b and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain a colored resin composition b.
  • Adhesion evaluation >> A polyimide film (manufactured by Koron Co., Ltd.) having a thickness of 50 ⁇ m was prepared. The colored resin compositions obtained in the above Examples and Comparative Examples were applied to the surface of this polyimide film and dried by heating at 100 ° C. to form a cured film. The adhesion of the cured film was confirmed in accordance with JIS K 5600-5-6. Specifically, a single-edged blade is used to make 100-square grid-like cuts in the cured film at 1 mm intervals, then "cellotape” (registered trademark) is attached, and then the cellophane tape (registered trademark) is peeled off.
  • cellotape registered trademark
  • the cured film prepared in the above adhesion evaluation was cut into a test piece having a length of 100 mm, a width of 100 mm, and a thickness of 15 ⁇ m.
  • the coefficient of linear thermal expansion of this test piece was measured using a thermomechanical analyzer (manufactured by TA Instruments Japan, TMA'Q400). Specifically, after mounting the test piece on a thermomechanical analyzer, measurements were taken from room temperature to 370 ° C. under a nitrogen atmosphere (nitrogen flow rate: 100 mL / min) at a heating rate of 10 ° C./min. Next, the average coefficient of linear thermal expansion in the range of 50 ° C. to 250 ° C. was calculated and evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 3. (Evaluation criteria) ⁇ : The average coefficient of linear thermal expansion was less than 50 ppm / ° C. X: The average coefficient of linear thermal expansion was 50 ppm / ° C. or higher.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Le problème décrit par la présente invention est de fournir : une composition de résine colorée qui comprend un composé de polyimide qui est hautement soluble dans un solvant organique et à partir duquel un produit durci ayant une excellente adhérence à un substrat de film de polyimide peut être formé ; et un produit durci formé à l'aide de ladite composition de résine colorée. La solution selon la présente invention porte sur une composition de résine colorée qui comprend (A) un composé de polyimide soluble dans un solvant organique, (B) un colorant et (C) un solvant organique, la composition de résine colorée étant caractérisée en ce que le composé de polyimide soluble dans un solvant organique (A) est obtenu par imidisation d'un précurseur de polyimide composé de composants de réaction comprenant : (A-1) un composé de diamine représenté par la formule générale (1) ; (A2) un composé de diamine ayant un groupe carboxyle et/ou un groupe hydroxyle, et/ou un composé de diamine ayant une liaison siloxane ; et (A-3) un anhydride d'acide.
PCT/JP2019/031565 2019-08-09 2019-08-09 Composition de résine colorée, produit durci et stratifié Ceased WO2021028960A1 (fr)

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PCT/JP2020/029613 WO2021029243A1 (fr) 2019-08-09 2020-08-03 Composition de résine colorée, produit durci et stratifié
TW109126668A TW202120593A (zh) 2019-08-09 2020-08-06 著色樹脂組成物、硬化物及層合體

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JP2021187934A (ja) * 2020-05-28 2021-12-13 太陽ホールディングス株式会社 ポリアミド酸、ポリイミド及びポリイミドフィルム
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WO2023080059A1 (fr) * 2021-11-04 2023-05-11 第一工業製薬株式会社 Dispersion de nanotubes de carbone, composition liquide de revêtement d'électrode l'utilisant, électrode et batterie rechargeable au lithium-ion
JP2023069043A (ja) * 2021-11-04 2023-05-18 第一工業製薬株式会社 カーボンナノチューブの分散体、並びにそれを用いた電極用塗工液組成物、電極及びリチウムイオン２次電池
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CN115820084A (zh) * 2022-12-22 2023-03-21 湖南大麓科技有限公司 一种高强度防腐管道加固复合材料及其制备方法
CN115820084B (zh) * 2022-12-22 2024-03-29 湖南大麓科技有限公司 一种高强度防腐管道加固复合材料及其制备方法

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