WO2013165211A1 - Novel polyamic acid, photosensitive resin composition, dry film and circuit board - Google Patents

Novel polyamic acid, photosensitive resin composition, dry film and circuit board Download PDF

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Publication number
WO2013165211A1
WO2013165211A1 PCT/KR2013/003864 KR2013003864W WO2013165211A1 WO 2013165211 A1 WO2013165211 A1 WO 2013165211A1 KR 2013003864 W KR2013003864 W KR 2013003864W WO 2013165211 A1 WO2013165211 A1 WO 2013165211A1
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WIPO (PCT)
Prior art keywords
formula
group
polyamic acid
resin composition
photosensitive resin
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PCT/KR2013/003864
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French (fr)
Korean (ko)
Inventor
김정학
경유진
김희정
이광주
Original Assignee
주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US14/115,201 priority Critical patent/US9410017B2/en
Priority to JP2014523883A priority patent/JP5788096B2/en
Priority to CN201380001007.9A priority patent/CN103502313B/en
Priority claimed from KR1020130049734A external-priority patent/KR101595457B1/en
Publication of WO2013165211A1 publication Critical patent/WO2013165211A1/en

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    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/0387—Polyamides or polyimides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

Definitions

  • Novel polyamic acid, photosensitive resin composition, dry film and circuit board Novel polyamic acid, photosensitive resin composition, dry film and circuit board
  • the present invention relates to a novel polyamic acid, a photosensitive resin composition, a dry film and a circuit board. More specifically, a novel polyamic acid, a photosensitive resin composition capable of providing a photosensitive material that satisfies excellent flexibility and low stiffness properties and exhibits excellent heat resistance and plating resistance, a dry film obtained from the photosensitive resin composition, and It relates to a circuit board comprising a dry film.
  • Solder resist solder Resist, or protective film
  • solder Resist is a circuit surface protection film formed on the outermost layer of the printed circuit board, and the improvement of precision is strongly required in accordance with the tendency of miniaturization of the printed wiring board.
  • a photosensitive protective film for a circuit board (Photo imageable coverlay) has been used for the purpose of miniaturizing a circuit pattern and improving positional accuracy in a photolithography process using a photosensitive resin composition.
  • a photosensitive protective film for a circuit board is thermally compressed by pressing a liquid or film-type photosensitive resin composition on a circuit of a copper clad laminate (CCL), UV exposure according to a pattern, developing with a developer, washing with water, drying and thermosetting. Manufactured through the process, it is possible to precisely drill the fine holes required to connect the circuit to the desired position.
  • the former soldering resist for circuit boards was obtained from the photosensitive resin composition which added the acrylate to the epoxy resin.
  • a conventional photosensitive resin composition has insufficient flame retardancy, or has low heat resistance after curing, so that the resin discolors when soldered and is separated from the circuit, or does not have flexibility and flex resistance.
  • There was a problem such as that it could not be, so that it could not be applied to the photosensitive protective film for circuit boards.
  • a brid-containing aromatic compound or antimony Although a method of additionally adding compounds and the like has been used, the added substance has a problem of generating dioxin upon combustion or adversely affecting the human body in itself, and it is difficult to satisfy recently strengthened environmental regulations. .
  • polyimide and its precursor are used as a base film of a printed circuit board, a highly integrated semiconductor device, or a cover film for a highly integrated multilayer wiring board based on excellent durability, heat resistance, flame retardancy, mechanical and electrical properties, etc. Since the problem of a film can be supplemented or solved, the demand for polyimide photosensitive resin is high recently. However, despite these demands, there are some technical obstacles to the material of the polyimide photosensitive circuit protective film.
  • the polyimide when used as a photosensitive resin, it is used in the form of a polyamic acid, which is a precursor of polyimide, which is advantageous for molding.
  • polyimide of the polyamic acid is required to have high silver of 350 ° C. or higher. Therefore, when polyimide is formed by coating or film-forming on a circuit pattern in the form of polyamic acid and performing polyimide through a thermosetting process, copper circuits that are weak to heat may be oxidized and deteriorated.
  • a certain level of molecular weight is required.
  • the present invention is to provide a novel polyamic acid.
  • the present invention provides a photosensitive material that satisfies excellent flexibility and low stiffness characteristics and exhibits excellent heat resistance and plating resistance. It is for providing the photosensitive resin composition which can be obtained.
  • this invention is for providing the dry film obtained from the said photosensitive resin composition.
  • this invention is providing the circuit board containing the said dry film.
  • the present invention provides a polyamic acid comprising repeating units of a particular structure.
  • the present invention is a polymer resin containing the polyamic acid; Crosslinking agents; Organic solvents; And it provides the photosensitive resin composition containing a photoinitiator.
  • this invention provides the dry film containing the hardened
  • the present invention provides a circuit board including the dry film.
  • Ttaron polyamic acid a photosensitive resin composition on the concrete implementation of the following invention, will be described in more detail with respect to the substrate as a dry film, and time.
  • a polyamic acid including the repeating unit of Formula 1 may be provided.
  • 3 ⁇ 4 is a tetravalent organic group
  • 3 ⁇ 4 is a trivalent or tetravalent organic group including an aromatic ring
  • n is an integer of 0 or 1
  • ⁇ and P 2 may be the same or different from each other, It is an organic functional group containing an imidazolyl group.
  • Newly reacted polyamic acid comprising the repeating unit of Formula 1
  • Resin composition allows curing at low temperatures
  • a photosensitive material can be provided.
  • 3 ⁇ 4 is trivalent or tetravalent including an aromatic ring.
  • Polyimide prepared from the polyamic acid according to containing the aryl group
  • the polymer compound may have better heat resistance
  • Chemical Formula 1 3 ⁇ 4 is the following Chemical Formula 11 to
  • One tetravalent organic group selected from the group consisting of 15 or
  • One bonding point can be formed at all possible positions (or elements).
  • ⁇ is a direct bond, -0-, -CO-, -S-, -S0 2 ⁇ , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-,- C00-, — (CH 2 ) nl — , — 0 (CH 2 ) n 2 , or — 0C 0 (CH 2 ) tl 3 0C 0 ⁇ where nl, n 2 and n 3 are each an integer from 1 to 10.
  • Y 2 and ⁇ 3 may be the same as or different from each other, and a direct bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3) 2 -, -C0NH- , -CO coming, eu (CH 2) nl -, -0 (CH 2) n2 is 0-, or -0C0 (CH 2) n3 0C0-, wherein nl, n2 and n3 is an integer of 1-10, respectively.
  • Y 4 , ⁇ 5 and ⁇ 6 may be the same as or different from each other, and a direct bond, —O, —CO—, —S—, —SO 2 —, —C (CH 3 ) 2 —, ⁇ C (CF 3 ) 2- , -C0NH-,-C00-, — (CH 2 ) nl ⁇ , -0 (CH 2 ) n2 0-, or -0C0 (CH 2 ) n3 0C0-, wherein nl, n2 And n3 are each an integer of 1 to 10.
  • Yi is a direct bond, -0—, -CO-, -S-, -S0 2- , -C (CH 3 ) 2 —, -C (CF 3 ) 2- . -CONH-, -C00-,-(C ⁇ —, -0 (CH 2 ) n2 0-, or -0C0 (CH 2 ) n3 0C0-, wherein nl, n2 and n3 are each an integer from 1 to 10 .
  • Y 2 and ⁇ 3 may be the same as or different from each other, and a direct bond, -0- ⁇ -CO-, -S-, -S0 2 —, -C (CH 3 ) 2- , ⁇ C (CF 3 ) 2- , -C0NH-, -C00-,-
  • Y 4 , ⁇ 5 and ⁇ 6 may be the same as or different from each other, and a direct bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-,-COCK-(CH 2 ) n i-, -0 (CH 2 ) n2 0-, or — 0C0 (CH 2 ) n3 0C0—, wherein nl, n2 and n3 are the integers of 1-10, respectively.
  • ⁇ and P 2 may be the same as or different from each other, and may be an organic functional group including an imidazolyl group.
  • the imidazole compound has anti-corrosion function, increases adhesion to metals, enhances copper foil adhesion effect, and acts as a catalyst for imidation reaction of polyamic acid, thereby curing at low temperature during photosensitive material production. Can play a role in making things happen.
  • the results of the inventors of the present invention when the imidazole compound is added to the photosensitive resin composition and the like in the form of a single molecule and used, the compatibility with the fuliamic acid is not good. It may be disproportionately or unevenly dispersed in the composition or the like, thereby making it difficult to ensure uniform physical properties of the photosensitive material manufactured or causing partial contamination of a circuit board or the like.
  • the present inventors have solved the problem of compatibility with polyamic acid or dispersibility in the photosensitive resin composition by introducing an imidazolyl group into the branches of the polyamic acid polymer, and the polyamic acid into which the imidazolyl group is introduced.
  • the polymer can be cured with high efficiency at low temperatures, maintains high adhesion with metals such as copper foil, and can achieve excellent plating resistance by implementing excellent corrosion protection.
  • a material such as a more homogeneous photosensitive resin composition and a dry film having uniform and excellent physical properties
  • the photosensitive resin composition and the material obtained therefrom may have high adhesion, excellent bendability, good lead heat resistance, relatively low coefficient of thermal expansion, high high temperature moisture resistance, high elasticity and excellent acid plating resistance.
  • Each of p L and p 2 may include a carbonyl group (carbonyl groLip) and include a functional group having an imidazolyl group bonded to the terminal thereof.
  • Pi and P 2 are each preferably a functional group represented by Formula 2 below.
  • ⁇ is '
  • a is 0 or 1
  • 3 ⁇ 4 is a linear or branched alkylene group having 1 to 10 carbon atoms
  • b is 0 or 1
  • Y is an imidazolyl group unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms.
  • an "alkylene group” refers to a divalent functional group derived from a linear or branched alkane.
  • Y may be a functional group of the formula 51 to 53.
  • R 51 , R 52 , R53 and 4 may be the same as or different from each other, and each represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and * denotes a bonding point in the functional group.
  • 3 ⁇ 4 may be a tetravalent organic group, but the type of the tetravalent organic group to be applied is not particularly limited, but it is one tetravalent organic group selected from the group consisting of the following Chemical Formulas 21 to 35: desirable.
  • ⁇ is a single bond, —0-, -CO-, -S-, -S0 2 -,-C (CH 3 ) 2 —, -C (CF 3 ) 2- , -C0NH-,- COCK-(CH 2 ) n ⁇ , -0 (CH 2 ) n 2 0-, or-0C0 (CH 2 ) n3 0C0—, wherein nl, n2 and n3 are each an integer from 1 to 10.
  • Y 2 and ⁇ 3 may be the same as or different from each other, and each single bond, -0-, -CO-, -S-, -S0 2- , — C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -COO—,-
  • nl -, -0 (CH 2) n2 is 0-, or -0C0 (CH 2) n3 0C0-, wherein nl, n2 and n3 is an integer of 1 to 10, respectively.
  • ⁇ 4 , ⁇ 5 and ⁇ 6 may be the same as or different from each other, and each of a single bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -CO,-(CH 2 ) n i-, -0 (CH 2 ) n2 0-, or -0C0 (CH 2 ) n3 0C ()-, Nl, n2 and n3 are each an integer of 1 to 10.
  • the polyamic acid is general in addition to the repeat unit of the formula Repeating unit of the polyamic acid, -er may further include a repeating unit of the formula (3).
  • X 3 is a tetravalent organic group, is a divalent organic group.
  • the type of the tetravalent organic group that can be applied to 3 ⁇ 4 is not particularly limited, but each tetravalent organic group selected from the group consisting of Chemical Formulas 21 to 35 is preferably applied.
  • the repeating unit of the formula (3), when the polyamic acid containing the polyimide is preferably having a structure or properties that the glass transition temperature is 250 ° C or less from the viewpoint of compatibility with the optical crosslinking agent.
  • divalent organic group usable above is not particularly limited, but it is preferable to use one divalent functional group independently selected from the group consisting of the following Chemical Formulas 60 to 68, respectively.
  • In Formula 61 is a single bond, -0-, -co-, -S-, -so 2- , C (CH 3 ) 2- . ⁇ C (CF 3 ) 2- , -CONH—, ⁇ CO, — (CH 2 ) nl --0 (CH 2 ) n2 0- -0CH2-C (CH 3 ) i CH 2 O-or a C00 (CH 2) n3 0C0-, the eu nl n2 and n3 is an integer from to 10, respectively.
  • L 2 and L 3 may be the same as or different from each other, and each single bond, -0—, -CO—, -S-, -S0 2- , ⁇ C (CH 3 ) 2- , -C (CF 3) 2 -, -C0NH- , -C00-, - (CH 2) nl -, -0 (CH 2) n2 0-, -0CH 2 -C (CH 3) 2-CH 2 0- or - 0C0 (CH 2 ) n3 0C0-, wherein nl, n2 and n3 are each an integer from 1 to 10.
  • L 4 , L 5, and L 6 may be the same as or different from each other, and each of a single bond, -E, -CO, -S-, -S0 2- , -C (CH 3 ) 2 -,- C (CF 3 ) 2- , -C0NH-,-C00-,-(CH 2 ) ni-, -0 (CH 2 ) n 2 0-, -0CH 2 -C (CH 3 ) 2 -CH 2 0- or -0C0 (CH 2 ) n3 0C, wherein nl, n2 and n3 are each an integer from 1 to 10.
  • ⁇ is alkylene or arylene having 2 to 8 carbon atoms and R 2 Is alkylene having 2 to 8 carbon atoms, a and b are each 0 or 1, and c is an integer of 1 to 21.
  • R u , R 12 , R 13, and R 14 may be the same as or different from each other, and are each an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 15 and R 16 are each 1 carbon atom. It is a linear or branched alkylene group of 20, (pi) is an integer of 1 or more, n is an integer of 0 or more.
  • the polyamic acid is 0.1 to 50 mol% of the repeating unit of Formula 1; And it may include 50 to 99.9 mol% of the repeating unit of Formula 3.
  • the polyamic acid is 0.3 to 30 mol% of the repeating unit of Formula 1; And 70 to 99.7 niol% of the repeating unit of Formula 3 above. And, more preferably, 0.5 to 10niol% of the repeating unit of Formula 1; And it may include 90 to 99.5 mol% of the repeating unit of Formula 3.
  • the heat resistance, copper foil adhesion and plating resistance of the photosensitive material obtained using the polyamic acid may appear, and when the content is too large, compatibility with other photosensitive materials This may be reduced or a sharp increase in viscosity, thereby lowering the workability or physical properties, and may lower the developability and flexibility.
  • the polyamic acid may have a weight average molecular weight of 5,000 to 200,000, preferably a weight average molecular weight of 8,000 to 50,000.
  • the molecular weight of the polyamic acid is too small, if it is difficult to properly implement the role of the photosensitive resin composition as the base resin, if the molecular weight of the polyamic acid is too large, compatibility with other materials included in the photosensitive resin composition may be lowered. .
  • the polyamic acid including the repeating unit of Formula 1 may be prepared by applying a conventional organic synthesis method known in the art.
  • the polyamic acid may be prepared by dissolving a diamine compound represented by Chemical Formula 4 and a diamine compound represented by Chemical Formula 5 in a solvent, and adding tetracarboxylic acid dianhydride to this solution. have.
  • X 2 is the same as described above with respect to 3 ⁇ 4 of Chemical Formula 1 The same may be applied, and R 2 , a, b and Y may be applied in the same manner as described above in Chemical Formula 2.
  • Examples of the diamine compound of Chemical Formula 5 include p-PDA (p-phenylenediamine), m-PDA (m-phenylenediamine), 4,4'-0DA (4,4'-oxydianiline), 3, 4'-0DA (3,4'-oxydianiline), BAPP (2,2-bis (4- [4-aminophenoxy] -phenyl) propane), APB-N (l, 3-bis (3- Aminophenoxy) benzene), TPE-R (1,3-bis (4-aminophenoxy) benzene), TPE-Q (1,4-bis (4-aminophenoxy) benzene), and m—BAPS ( 2,2-bis (4- [3 'aminophenoxy] phenyl) sulfone) and the like, but are not limited thereto.
  • p-PDA p-phenylenediamine
  • m-PDA m-phenylenediamine
  • tetracarboxylic acid dianhydride a compound represented by the following Chemical Formula 6 may be used.
  • 3 ⁇ 4 is a tetravalent organic group
  • 3 ⁇ 4 may be a tetravalent organic group
  • the kind of usable tetravalent organic group is not limited to a large one, but one selected from the group consisting of the following Chemical Formulas 21 to 35 It is preferable that tetravalent organic group is applied. More details are as described above.
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride, 3,3 ', 4,4'—biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic Rick dianhydride, 4,4'—oxydiphthalic anhydride, 4,4'— (4'4'-isopropylbiphenoxy) biphthalic Anhydride, 2,2'-bis— (3,4-dicarboxylphenyl) hexafluoropropane dianhydride and TMEG (ethylene glycol bis (anhydro- trimellitate)) Although it can use, it is not limited to these.
  • the reaction of the polyfunctional aliphatic amine compound, the diamine compound and the tetracarboxylic dianhydride is usually carried out about 24 hours starting from the reaction at 0 to 5 ° C until the reaction is completed in the temperature range of 10 to 40 ° C. It is preferable. At this time, the sum of the diamine compound of Formula 4 and the diamine compound of Formula 5: tetracarboxylic dianhydride is preferably 1: 0.9 to 1: 1.1.
  • the molecular weight of the polyamic acid to be produced is out of the appropriate range, and thus the mechanical properties of the polyamic acid or polyimide obtained And the like may be degraded.
  • the solvent used in the preparation of the polyamic acid is N-methylpyrrolidinone (N-methylpyrrolidinone; NMP).
  • NMP N-methylpyrrolidinone
  • ⁇ ⁇ - dimethylacetamide ( ⁇ , N-d i thy 1 acet am i de; DMAc), tetrahydrofuran (THF),! ⁇ dimethylformamide ⁇ ⁇ diniethylforniamide; DMF), dimethylsulfoxide (DMS0).
  • NMP N-methylpyrrolidinone
  • ⁇ ⁇ - dimethylacetamide
  • THF tetrahydrofuran
  • THF tetrahydrofuran
  • DMF dimethylformamide
  • DMF dimethylsulfoxide
  • One or more selected from the group consisting of cyclohexane, acetonitrile, and combinations thereof may be used, but is not limited thereto.
  • the inventors of the present invention when using the photosensitive resin composition to which the novel polyamic acid containing the repeating unit of the formula (1) is applied, can be cured at a low degree of silver to provide stability of the process and convenience in process operation, and excellent flexibility And low stiffness characteristics Experiments confirmed that it can provide a photosensitive material that can implement excellent mechanical properties and high developability, such as excellent heat resistance and plating resistance, excellent copper foil adhesion, and completed the invention.
  • novel polyamic acid including the repeating unit of Formula 1 are as described above.
  • the photocrosslinking agent may be used without any limitation as long as it is known to be commonly used in the photosensitive resin composition, but it is preferable to use a (meth) acrylate compound including a carbon-to-carbon double bond.
  • (meth) acrylate means acrylate or methacrylate.
  • the (meth) acrylate-based compound including the carbon-to-carbon double bond not only exhibits high compatibility with the polyamic acid, but also is included in the photosensitive resin composition to enable high developability and excellent photosensitivity to an alkali solution.
  • the photosensitive resin composition to which the (meth) acrylate-based compound including the carbon-to-carbon double bond is applied when processed into a dry film, the modulus is lowered during heat processing and the fluidity is imparted during thermal lamination, thereby providing a pattern having irregularities. Filling properties can be improved, thereby enabling a thermal lamination process even at a relatively low temperature.
  • Examples of the (meth) acrylate-based compound containing a carbon-to-carbon double bond, which can be used as the photocrosslinking agent, are not particularly limited.
  • Polyester acrylate urethane acrylate, pentaerythri (tetra) (meth) acrylate, etc. are mentioned, You may use these in mixture of 2 or more types.
  • NK ligomers EA-1010 and EA-6310 of Shinnakamura Chemical which are commercially available products, EA-1020, EA-6320, EA-6340, Ebecryl 600, ZAA-205 of Nippon Kayaku Co., ZFA-266H etc. can also be used.
  • the photocrosslinking agent preferably includes a part of the compound represented by the following Chemical Formula 7.
  • R1 is an aromatic having two or more benzene rings in the molecule
  • R2 is an ethylene oxide or propylene oxide group
  • R3 is a hydrogen or methyl group
  • 0 and p are each an integer of 2 or more and o + p value is 50 It may be an integer below, preferably an integer below 30.
  • Examples of the compound belonging to Formula 7 include bisphenols such as A—BPE-10, A-BPE 20, A-BPE-30, BPE-500, BPE-900, Shin-Nakamura Chemical Co.
  • Specific examples of the compound include ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide-propylene oxide modified bisphenol A di (meth) acrylate, and ethylene oxide.
  • the photopolymerization initiator may include an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or a mixture thereof.
  • photopolymerization initiator examples include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1— (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4 -(2-hydroxyethoxy) -phenyl- (2-hydroxy-2- propyl) ketone, 1-hydroxycyclonucleophenylphenyl ketone, benzoinmethyl ether, benzoinethyl ether, benzoin isobutyl ether, benzo Inbutyl ether, 2, 2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propane-1-one, 2-benzyl 2-dimethyl Acetofe such as amino-1- (4-morpholinophenyl) -butane-1-silver or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one Acetophenone compounds;
  • an organic solvent may be used for the purpose of dissolving the components of the photosensitive resin composition and imparting an appropriate level of viscosity for applying the composition.
  • the organic solvent may be used without any limitation as long as it is known to be used in the photosensitive resin composition.
  • ketones such as methyl ethyl ketone and cyclonucleanone; Toluene, xylene.
  • Aromatic hydrocarbons such as tetramethyl benzene, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol Glycol ethers (cellosolve) such as monomethyl ether, propyl tenglycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate,
  • Acetate esters such as dipropylene glycol monomethyl ether acetate; Ethane, protubes, alcohols such as ethylene glycol, propylene glycol and carbitle; Aliphatic hydrocarbons such as octane and decane; Petroleum ether. Petroleum naphtha. Petroleum solvents such as hydrogenated petroleum naphtha and solvent naphtha; Amides, such as dimethyl acetamide (DMAc) and dimethylformamide (DMF), etc. are mentioned. These solvents can be used alone or as a mixture of two or more thereof.
  • DMAc dimethyl acetamide
  • DMF dimethylformamide
  • Solid content concentration of the polymer resin containing the polyamic acid may be appropriately selected in consideration of the physical properties of the final product, for example, dry film, etc., prepared from the molecular weight, viscosity, volatility, and the like of the polyamic acid including the repeating unit of Formula 1 have.
  • the solid content concentration of the polymer resin may be 15 to 90% by weight based on the total weight of the photosensitive resin composition.
  • the amount of the photocrosslinking agent may be 10 to 200 parts by weight based on 100 parts by weight of the polyamic acid solids in the photosensitive resin composition. If the content of the photocrosslinking agent is too small, the developing characteristics and pattern fillability of the photosensitive material to be manufactured may be lowered. If the content is too large, the mechanical properties of the film including heat resistance lowering and cutting resistance may be lowered.
  • the content of the photopolymerization initiator may be 0.1 to 10 parts by weight based on 100 parts by weight of the polyamic acid solids in the photosensitive resin composition. If the content of the photopolymerization initiator is too small, the photocuring participation of the photopolymerization initiator is lowered. If the content is too large, the physical properties of the film prepared from the photosensitive resin composition may decrease due to radicals that do not participate in curing.
  • the organic solvent may be used as the organic solvent is easy to dissolve the polyamic acid, photocrosslinking agent, photopolymerization initiator or optionally additional additives, a solvent that can be easily dried in particular during the coating process is preferred.
  • the content of the organic solvent may be 100 to 1000 parts by weight based on 100 parts by weight of the polyamic acid solids in the photosensitive resin composition. In the case where the content of the organic solvent is too small, the viscosity of the photosensitive resin composition may be excessively high, thereby decreasing the coating property. When the content is too high, the drying of the photosensitive resin composition may not be easy. And the like may be degraded.
  • the photosensitive resin composition may further include a thermal crosslinking agent, a curing accelerator, a photocrosslinking sensitizer, a curing accelerator, a phosphorus-based flame retardant, an antifoaming agent, a leveling agent, a gel inhibitor, or a mixture thereof.
  • a thermal crosslinking agent e.g., a thermal crosslinking agent, a curing accelerator, a photocrosslinking sensitizer, a curing accelerator, a phosphorus-based flame retardant, an antifoaming agent, a leveling agent, a gel inhibitor, or a mixture thereof.
  • Such additives may be used without limitation as long as they are known to be used in the photosensitive resin composition, and may be used in an appropriate amount in consideration of physical properties of the photosensitive resin composition or the film obtained therefrom.
  • a dry film including a cured product or a dried product of the photosensitive resin composition may be provided.
  • a photosensitive material can be provided that satisfies low stiffness properties and exhibits excellent heat resistance and plating resistance.
  • the dry film means a film form obtained by drying the photosensitive resin composition or a film form in which the photosensitive resin composition is photocured or thermoset.
  • the cured product may include a crosslinked semi-aqua product of a polyimide and a photocrosslinker including a repeating unit represented by Chemical Formula 1-1.
  • Xi is a tetravalent organic group
  • X 2 is a trivalent or tetravalent organic group including an aromatic ring
  • n is an integer of 0 or 1
  • P 2 may be the same or different from each other
  • an organic functional group containing an imidazolyl group More specifically, in Formula 1-1, may be one tetravalent organic group selected from the group consisting of Formula 11 to 15, or may be one trivalent organic group selected from the group consisting of Formula 16 to 20.
  • Chemical Formula 1-1 may be a tetravalent organic group, and the type of tetravalent organic group to which it may be applied is not particularly limited, but it is preferably one tetravalent organic group selected from the group consisting of Chemical Formulas 21 to 35. Do.
  • Pi and P 2 are each preferably a functional group represented by Formula 2 below.
  • ⁇ is ,
  • a is 0 or 1
  • R 2 is a straight or branched chain alkylene group having 1 to 10 carbon atoms
  • b is 0 or 1
  • Y is an imidazolyl group unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms. to be.
  • Y may be a functional group of Formula 1 Equation 51 to 53.
  • the said dry film can be manufactured by apply
  • the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, poly Polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride, vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene
  • the plastic film of the is mentioned.
  • the composite material which consists of these 2 or more types can also be used,
  • the polyethylene terephthalate film excellent in the light transmittance is especially preferable.
  • the thickness of the support is preferably 5 to 150 / ⁇ , more preferably 10 to 50.
  • the coating method of the photosensitive resin composition is not particularly limited, and for example, a spray method, a coating method, a rotary coating method, a slit coating method, an extrusion coating method, a curtain coating method, a die coating method, a wire bar coating method or a knife coating method Law and the like can be used. Drying of the photosensitive resin composition is preferably carried out for 30 seconds to 15 minutes at 60 to 100 ° C, depending on each component or type of organic solvent, and content ratio.
  • the film thickness of the dry film after drying and hardening is 5-95, More preferably, it is 10-50. If the film thickness of the dry film is 5 m or less, the insulation is not good, and if it exceeds 95, the resolution may be lowered.
  • the dry film may be used in a protective film for a circuit board, a base film of a circuit board, an insulating layer of a circuit board, an interlayer insulating film of a semiconductor, or a solder resist. Meanwhile, according to another embodiment of the present invention, a circuit board including the dry film may be provided.
  • the circuit board may include a multilayer printed wiring board, a fusible circuit board, or a flexible circuit board.
  • the dry film may be used in a circuit board, and the dry film may be used as a protective film for a circuit board, a base film of a circuit board, an insulating layer of a circuit board, an interlayer insulating film or a solder resist of a semiconductor, and the like.
  • the dry film included in the circuit board is meant to include a dry film or a workpiece of the dry film, for example, a workpiece or a light reflection material laminated on a predetermined substrate.
  • the dry film is pre-laminated at a temperature of 20 to 50 ° C. by a method such as flat pressing or pressing on the circuit forming surface, vacuum lamination at 60 to 90 to obtain a photosensitive film. Can be formed.
  • the dry film is capable of forming a pattern by exposing using a photomask to form a fine configuration or a fine width line.
  • the exposure amount can be appropriately adjusted according to the type of light source used for UV exposure and the thickness of the film film, for example, 100 to 1200 ni / cuf is preferable, and 100 to 500 m / cuf is more preferable.
  • the active light rays examples include electron beams, ultraviolet rays, X-rays, and the like, and preferably ultraviolet rays.
  • a light source that can be used a high pressure mercury lamp, a low pressure mercury lamp or a halogen lamp can be used as the light source.
  • a spray method is generally used.
  • the photosensitive resin composition is developed using an aqueous alkali solution such as an aqueous sodium carbonate solution and washed with water. Then, when the plymic acid is changed to polyimide according to the pattern obtained by development through the heat treatment process, the heating Treatment silver may be between 100 and 25 CTC required for imidization.
  • the heating temperature is effective to continuously increase the temperature over 2 to 4 steps with an appropriate temperature profile, but may be cured at a constant temperature in some cases.
  • novel polyamic acid A photosensitive resin composition capable of providing a photosensitive material that satisfies excellent flexibility and low stiffness characteristics and exhibits excellent heat resistance and plating resistance; A dry film obtained from the photosensitive resin composition and a circuit board including the dry film may be provided.
  • the photosensitive resin composition and the material obtained therefrom have high adhesion, excellent bendability, excellent lead heat resistance, It can have a relatively low coefficient of thermal expansion, high temperature moisture resistance, high elasticity and excellent acid plating resistance.
  • NMP N-methylpyridone
  • each component was mixed on the basis of the beating ratio (part by weight) of the solid content to obtain a photosensitive resin composition.
  • EA-1020 Epoxy (meth) acrylate compound containing two or more hydroxyl groups (manufactured by Shin-Nakamori Chemical Co., Ltd.)
  • DPEA-12 Nucleoacrylate of E0-modified dipentaerythrates (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • 1651 and 1819 are Igacure 651 and Igacure 819 as photopolymerization initiators, respectively.
  • each of the photosensitive resin composition solutions obtained by the said Example and the comparative example was apply
  • the polyethylene protective film Teamapoly Co., Ltd. product, brand name: NF-
  • Example 1 Performance Evaluation of Dry Films According to Examples and Comparative Examples>
  • the dry films prepared in Examples and Comparative Examples were placed on a copper foil surface of a 2CCL product having a pattern formed thereon, and then, using a MEIK MVLP-500 vacuum laminator. Vacuum was applied at 20 ° C. for 20 seconds, and vacuum lamination was performed at a pressure of 0.6 Mpa for 40 seconds.
  • UV irradiation with a light amount of 400mJ / cm 2 spray development for 1 minute in an aqueous solution of sodium carbonate at 1%, curing for 90 minutes in an oven at 160 ° C., and then performing physical property evaluation as follows. The results are shown in Table 2 below.
  • Experimental Example 1 Circuit Fillability
  • the electroless nickel / gold plating properties were tested using the dry films prepared in Examples and Comparative Examples, and immersion or peeling was observed visually after the electroless nickel / gold plating. As a result, when there is no liquid penetration or peeling observed after the electroless nickel / gold plating, it is "0K", and when there is liquid penetration or peeling which is observed by the naked eye after electroless nickel / gold plating. Indicated by "NG” is shown in Table 2.
  • the dry film obtained by using the photosensitive resin compositions of the above Examples and Comparative Examples shows similar 'post-lamination filling' or 'developing (35 ° C)' at the same thickness, Of the above embodiment It was confirmed that the dry film prepared by using the photosensitive resin composition had higher adhesion, better bendability, better lead heat resistance, relatively lower coefficient of thermal expansion, higher high temperature moisture resistance, higher elasticity and excellent acid plating resistance than the comparative example.

Abstract

The present invention relates to: a novel polyamic acid in which imidazole is introduced to polymer chains; a photosensitive resin composition containing the polyamic acid which can provide a photosensitive material satisfying the characteristics of excellent flexibility and low stiffness, and has excellent heat resistance and coating resistance; a dry film obtained from the photosensitive resin composition; and a circuit board including the dry film.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
신규한 폴리아믹산, 감광성 수지 조성물, 드라이 필름 및 회로 기판 【기술분야】  Novel polyamic acid, photosensitive resin composition, dry film and circuit board
본 발명은 신규한 폴리아믹산, 감광성 수지 조성물, 드라이 필름 및 회로 기판에 관한 것이다. 보다 상세하게는 신규한 폴리아믹산, 우수한 유연성과 낮은 강성 (low stiffness) 특성을 만족시키고 우수한 내열성 및 내도금성을 나타내는 감광성 재료를 제공할 수 있는 감광성 수지 조성물， 상기 감광성 수지 조성물로부터 얻어지는 드라이 필름 및 상기 드라이 필름을 포함하는 회로 기판에 관한 것이다.  The present invention relates to a novel polyamic acid, a photosensitive resin composition, a dry film and a circuit board. More specifically, a novel polyamic acid, a photosensitive resin composition capable of providing a photosensitive material that satisfies excellent flexibility and low stiffness properties and exhibits excellent heat resistance and plating resistance, a dry film obtained from the photosensitive resin composition, and It relates to a circuit board comprising a dry film.
【발명의 배경이 되는 기술】  [Technique to become background of invention]
솔더 레지스트 (Solder Resist, 또는 보호필름)는 프린트 기판의 최외층에 형성되는 회로면 ^ 보호막으로서， 최근 프린트 배선판의 세밀화 경향에 따라 정밀도 향상이 강하게 요구되고 있다. 이에 따라, 최근에는 감광성 수지 조성물을 이용한 포토리쏘그래피 공정으로 회로패턴의 미세화 및 위치 정밀도를 향상시키는 목적으로 회로 기판용 감광성 보호 필름 (Photo imageable coverlay)을 사용하고 있다. 일반적으로， 회로 기판용 감광성 보호 필름은 액상 또는 필름 형태의 감광성 수지 조성물을 CCL( Copper Clad Laminate)의 회로상에 열 압착하고, 패턴에 따라 UV 노광한 후 현상액으로 현상하고 수세 건조한 후 열경화하는 과정을 통하여 제조되며, 원하는 위치에 회로를 연결하는데 필요한 미세 구멍을 정밀하게 뚫을 수 있다.  Solder resist (Solder Resist, or protective film) is a circuit surface protection film formed on the outermost layer of the printed circuit board, and the improvement of precision is strongly required in accordance with the tendency of miniaturization of the printed wiring board. Accordingly, in recent years, a photosensitive protective film for a circuit board (Photo imageable coverlay) has been used for the purpose of miniaturizing a circuit pattern and improving positional accuracy in a photolithography process using a photosensitive resin composition. In general, a photosensitive protective film for a circuit board is thermally compressed by pressing a liquid or film-type photosensitive resin composition on a circuit of a copper clad laminate (CCL), UV exposure according to a pattern, developing with a developer, washing with water, drying and thermosetting. Manufactured through the process, it is possible to precisely drill the fine holes required to connect the circuit to the desired position.
이전의 회로 기판용 솔더 레지스트는 에폭시 수지에 아크릴레이트를 첨가한 감광성 수지 조성물로부터 얻어졌다. 그런데， 이러한 종래의 감광성 수지 조성물은 난연 특성이 충분하지 못하거나， 경화 후의 내열성이 낮아서 남땜시 수지가 변색되고 회로에서 분리되거나, 가요성과 내굴곡성이 층분하지 못하여 반복 접지가 요구되는 부분에는 적용할 수 없는 등의 문제를 가지고 있어서， 회로 기판용 감광성 보호 필름으로 적용하기에 층분하지 못하였다. 이에 따라, 이전의 감광성 수지 조성물의 난연 특성 또는 내열 특성을 향상시키기 위하여 브틈 함유 방향족 화합물 또는 안티몬 화합물류 등을 추가로 첨가하는 방법이 사용되었으나, 상기 첨가되는 물질은 연소시에 다이옥신을 발생시키거나 그 자체로 인체에 유해한 영향을 끼치고, 최근 강화되는 환경 관련 규제를 층족시키기 어려운 문제점을 가지고 있었다. The former soldering resist for circuit boards was obtained from the photosensitive resin composition which added the acrylate to the epoxy resin. However, such a conventional photosensitive resin composition has insufficient flame retardancy, or has low heat resistance after curing, so that the resin discolors when soldered and is separated from the circuit, or does not have flexibility and flex resistance. There was a problem such as that it could not be, so that it could not be applied to the photosensitive protective film for circuit boards. Accordingly, in order to improve the flame retardant properties or heat resistance properties of the previous photosensitive resin composition, a brid-containing aromatic compound or antimony Although a method of additionally adding compounds and the like has been used, the added substance has a problem of generating dioxin upon combustion or adversely affecting the human body in itself, and it is difficult to satisfy recently strengthened environmental regulations. .
이에 따라, 우수한 내열성， 난연성, 굴곡성 및 절연 신뢰성을 확보하면서도 친환경적이고 인체에 무해한 감광성 수지 조성물에 대한 요구가 있어 왔으며 , 최근에는 폴리이미드 또는 그 전구체를 활발히 사용되고 있다. 구체적으로, 폴리이미드 및 그 전구체는 우수한 내구성과 내열성, 난연성, 기계적 및 전기적 특성 등을 바탕으로 인쇄 회로기판의 베이스 필름， 고집적 반도체 장치 또는 고집적 다층 배선 기판용 커버 필름으로 사용되고 있는데, 기존의 감광성 보호 필름의 문제점을 보완 또는 해결할 수 있어서 최근 폴리이미드 감광성 수지에 대한 요구가 높다. 그러나 이러한 주위의 요구에도 불구하고 폴리이미드 감광성 회로 보호막의 소재로 하는 데는 몇 가지 기술적인 장애가 있다.  Accordingly, there has been a demand for an environmentally friendly and harmless photosensitive resin composition while securing excellent heat resistance, flame retardancy, flexibility, and insulation reliability, and recently, polyimides or precursors thereof are actively used. Specifically, polyimide and its precursor are used as a base film of a printed circuit board, a highly integrated semiconductor device, or a cover film for a highly integrated multilayer wiring board based on excellent durability, heat resistance, flame retardancy, mechanical and electrical properties, etc. Since the problem of a film can be supplemented or solved, the demand for polyimide photosensitive resin is high recently. However, despite these demands, there are some technical obstacles to the material of the polyimide photosensitive circuit protective film.
구체적으로, 폴리이미드를 감광성 수지로 사용할 경우 성형에 유리한 폴리이미드의 전구체인 폴리아믹산 형태로 사용하게 되는데, 이러한 경우 폴리아믹산을 폴리이미드화 시키는데， 350°C 이상의 고은이 요구된다. 따라서, 폴리아믹산 형태로 회로 패턴 상에 도포 혹은 필름 상태로 접합하여 열경화 과정을 통하여 폴리이미드화 시킬 경우 열에 약한 동회로가 산화 및 열화하는 문제점이 발생할 수 있으므로 바람직하지 않다. 또한， 폴리이미드의 성질을 제대로 구현하기 위해서는 일정수준의 분자량이 요구되는데， 분자량이 커지면 다른 물질과의 상용성이 저하될 뿐만 아니라 약알칼리 수용액에서 현상성을 구현하기가 어렵고, 모들러스가 높아져 빈공간의 채움성이 저하되어 감광성 보호필름으로서 폴리이미드 소재의 회로 보호막 개발에 한계가 되어왔다. Specifically, when the polyimide is used as a photosensitive resin, it is used in the form of a polyamic acid, which is a precursor of polyimide, which is advantageous for molding. In this case, polyimide of the polyamic acid is required to have high silver of 350 ° C. or higher. Therefore, when polyimide is formed by coating or film-forming on a circuit pattern in the form of polyamic acid and performing polyimide through a thermosetting process, copper circuits that are weak to heat may be oxidized and deteriorated. In addition, in order to properly implement the properties of the polyimide, a certain level of molecular weight is required. As the molecular weight increases, the compatibility with other materials decreases, and developability in a weak alkali aqueous solution is difficult, and the modulus becomes high. The filling of space is deteriorated and it has become a limit to the development of the circuit protective film of polyimide material as a photosensitive protective film.
【발명의 내용】  [Content of invention]
【해결하고자 하는 과제】  Problem to be solved
본 발명은 신규한 폴리아믹산을 제공하기 위한 것이다.  The present invention is to provide a novel polyamic acid.
또한, 본 발명은 우수한 유연성과 낮은 강성 (low stiffness) 특성을 만족시키고 우수한 내열성 및 내도금성을 나타내는 감광성 재료를 제공할 수 있는 감광성 수지 조성물을 제공하기 위한 것이다. In addition, the present invention provides a photosensitive material that satisfies excellent flexibility and low stiffness characteristics and exhibits excellent heat resistance and plating resistance. It is for providing the photosensitive resin composition which can be obtained.
또한, 본 발명은 상기 감광성 수지 조성물로부터 얻어지는 드라이 필름을 제공하기 위한 것이다.  Moreover, this invention is for providing the dry film obtained from the said photosensitive resin composition.
또한， 본 발명은 상기 드라이 필름을 포함하는 회로 기판을 제공하기 위한 것이다.  Moreover, this invention is providing the circuit board containing the said dry film.
【과제의 해결 수단】  [Measures of problem]
본 발명은 특정 구조의 반복 단위를 포함하는 폴리아믹산을 제공한다. 또한， 본 발명은 상기 폴리아믹산을 포함하는 고분자 수지 ; 가교제; 유기 용매; 및 광중합 개시제를 포함하는 감광성 수지 조성물을 제공한다. 또한 , 본 발명은 상기 감광성 수지 조성물의 경화물을 포함하는 드라이 필름을 제공한다.  The present invention provides a polyamic acid comprising repeating units of a particular structure. In addition, the present invention is a polymer resin containing the polyamic acid; Crosslinking agents; Organic solvents; And it provides the photosensitive resin composition containing a photoinitiator. Moreover, this invention provides the dry film containing the hardened | cured material of the said photosensitive resin composition.
또한, 본 발명은 상기 드라이 필름을 포함하는 회로기판을 제공한다. 이하 발명의 구체적인 구현예에 따론 폴리아믹산， 감광성 수지 조성물, 드라이 필름 및 회'로 기판에 관하여 보다 상세하게 설명하기로 한다. 발명의 일 구현예에 따르면， 상기 화학식 1의 반복 단위 포함하는 폴리아믹산이 제공될 수 있다. In addition, the present invention provides a circuit board including the dry film. Ttaron polyamic acid, a photosensitive resin composition on the concrete implementation of the following invention, will be described in more detail with respect to the substrate as a dry film, and time. According to one embodiment of the invention, a polyamic acid including the repeating unit of Formula 1 may be provided.
[화학식 1]  [Formula 1]
Figure imgf000004_0001
Figure imgf000004_0001
상기 화학식 1에서, ¾ 은 4가의 유기기이고, ¾ 는 방향족 고리를 포함하는 3가 또는 4가의 유기기이고， n은 0 또는 1인 정수이고， ^ 및 P2는 서로 같거나 다를 수 있으며, 이미다졸일기 (imidazolyl group)를 포함하는 유기 작용기이다. 본 발명자들은， 이미다졸일기가 치환된 특정한 디아민과 In Formula 1, ¾ is a tetravalent organic group, ¾ is a trivalent or tetravalent organic group including an aromatic ring, n is an integer of 0 or 1, ^ and P 2 may be the same or different from each other, It is an organic functional group containing an imidazolyl group. The present inventors, and the specific diamine substituted imidazolyl group
테트라카르복실산 이무수물 (tetracarboxylic acid dianhydr ide)을 Tetracarboxylic acid dianhydride
반웅시킴으로서 상기 화학식 1의 반복 단위를 포함하는 폴리아믹산을 새로이 Newly reacted polyamic acid comprising the repeating unit of Formula 1
합성해내었다. 후술하는 감광성 수지 조성물에 관한 내용에 나타난 바와 Synthesized. As shown in the contents about the photosensitive resin composition mentioned later
같이, 상기 화학식 1의 반복 단위를 포함하는 폴리아믹산을 적용한 감광성 Likewise, photosensitive to which a polyamic acid including the repeating unit of Formula 1 is applied
수지 조성물을 사용하면， 낮은 온도에서 경화가 가능하여 공정의 안정성 및 Resin composition allows curing at low temperatures
공정 작업상의 편리성을 제공할 수 있으며， 우수한 유연성과 낮은 강성 (low It can provide the convenience of process operation and has excellent flexibility and low rigidity.
stiffness) 특성을 만족시키고 우수한 내열성 및 내도금성을 나타내는 stiffness) characteristics and excellent heat resistance and plating resistance
감광성 재료를 제공할 수 있다. A photosensitive material can be provided.
상기 화학식 1에서， ¾는 방향족 고리를 포함하는 3가 또는 4가의  In Chemical Formula 1, ¾ is trivalent or tetravalent including an aromatic ring.
유기기일 수 있는데 ¾가 방향족 고리， 예를 들어 탄소수 6 내지 20의 Organic group, wherein ¾ is an aromatic ring, e.g.
아릴기를 포함함에 따라서， 상기 폴리아믹산으로부터 제조되는 폴리이미드 Polyimide prepared from the polyamic acid according to containing the aryl group
또는 고분자 화합물은 보다 우수한 내열성올 가질 수 있으며， 높은 Or the polymer compound may have better heat resistance,
유연성과 낮은 강성 (low stiffness) 특성을 확보할 수 있다. Flexibility and low stiffness can be achieved.
바람직하게는, 상기 화학식 1에서， 상기 ¾는 하기 화학식 11 내지  Preferably, in Chemical Formula 1, ¾ is the following Chemical Formula 11 to
15로 이루어진 군에서 선택된 하나의 4가 유기기이거나, 하기 화학식 16  One tetravalent organic group selected from the group consisting of 15 or
내지 20으로 이루어진 군에서 선택된 하나의 3가 유기기일 수 있다. 이때, ¬가 3가의 유기기인 경우， 상기 n은 0이다. 하기 화학식 11 내지 20에서， It may be one trivalent organic group selected from the group consisting of 20 to. At this time, when ¬ is a trivalent organic group, n is 0. In Chemical Formulas 11 to 20,
방향족고리의 내부에서 외부로 향한 선 (line)은 방향족고리에서 치환 Lines from inside to outside of the aromatic ring are substituted in the aromatic ring
가능한 모든 위치 (또는 원소)에서 하나의 결합 (bonding point)이 형성될 수 One bonding point can be formed at all possible positions (or elements).
있음을 의미한다. It means that there is.
[화학식 11]  [Formula 11]
Figure imgf000005_0001
Figure imgf000005_0001
[화학식 12]
Figure imgf000006_0001
[Formula 12]
Figure imgf000006_0001
상기 화학식 12에서， ^ 은 직접결합, -0-， -CO-, -S-, -S02ᅳ， - C(CH3)2-, -C(CF3)2-, -C0NH-, -C00-, — (CH2)nl -， — 0(CH2)n2으， 또는 - 0C0(CH2)tl30C0-이고ᅳ 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Formula 12, ^ is a direct bond, -0-, -CO-, -S-, -S0 2 ᅳ, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-,- C00-, — (CH 2 ) nl — ， — 0 (CH 2 ) n 2 , or — 0C 0 (CH 2 ) tl 3 0C 0 − where nl, n 2 and n 3 are each an integer from 1 to 10.
[화학식 13]  [Formula 13]
Figure imgf000006_0002
Figure imgf000006_0002
상기 화학식 13에서， Y2 및 Υ3는 서로 같거나 다를 수 있으며, 각각 직접결합, -0-， -CO-, -S-, -S02-, -C(CH3)2-, -C(CF3)2-, -C0NH-, -CO으， ᅳ (CH2)nl -, -0(CH2)n20-, 또는 -0C0(CH2)n30C0—이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Chemical Formula 13, Y 2 and Υ 3 may be the same as or different from each other, and a direct bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3) 2 -, -C0NH- , -CO coming, eu (CH 2) nl -, -0 (CH 2) n2 is 0-, or -0C0 (CH 2) n3 0C0-, wherein nl, n2 and n3 is an integer of 1-10, respectively.
[화학식 14]  [Formula 14]
Figure imgf000006_0003
Figure imgf000006_0003
상기 화학식 14에서， Y4, Υ5 및 Υ6는 서로 같거나 다를 수 있으며， 각각 직접결합， ―으, -CO-, -S-, -SO2-, -C(CH3)2-, ᅳ C(CF3)2-, -C0NH-, - C00-, — (CH2)nl―， -0(CH2)n20-, 또는 -0C0(CH2)n30C0-이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Chemical Formula 14, Y 4 , Υ 5 and Υ 6 may be the same as or different from each other, and a direct bond, —O, —CO—, —S—, —SO 2 —, —C (CH 3 ) 2 —, ᅳ C (CF 3 ) 2- , -C0NH-,-C00-, — (CH 2 ) nl ―, -0 (CH 2 ) n2 0-, or -0C0 (CH 2 ) n3 0C0-, wherein nl, n2 And n3 are each an integer of 1 to 10.
[화학식 15]
Figure imgf000007_0001
[Formula 15]
Figure imgf000007_0001
[화학식 16]  [Formula 16]
Figure imgf000007_0002
Figure imgf000007_0002
[화학식 17]  [Formula 17]
Figure imgf000007_0003
Figure imgf000007_0003
상기 화학식 17에서, Yi 은 직접결합， -0—， -CO-, -S-, -S02-, - C(CH3)2— , -C(CF3)2-. -CONH-, -C00-, -(C^ —, -0(CH2)n20-, 또는 - 0C0(CH2)n30C0-이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Formula 17, Yi is a direct bond, -0—, -CO-, -S-, -S0 2- , -C (CH 3 ) 2 —, -C (CF 3 ) 2- . -CONH-, -C00-,-(C ^ —, -0 (CH 2 ) n2 0-, or -0C0 (CH 2 ) n3 0C0-, wherein nl, n2 and n3 are each an integer from 1 to 10 .
[화학식 18]  [Formula 18]
Figure imgf000007_0004
Figure imgf000007_0004
상기 화학식 18에서, Y2 및 Υ3는 서로 같거나 다를 수 있으며, 각각 직접결합， -0-ᅳ -CO-, -S-, -S02— , -C(CH3)2-, ᅳ C(CF3)2-, -C0NH-, -C00-, -In Formula 18, Y 2 and Υ 3 may be the same as or different from each other, and a direct bond, -0- ᅳ -CO-, -S-, -S0 2 —, -C (CH 3 ) 2- , ᅳ C (CF 3 ) 2- , -C0NH-, -C00-,-
(CH2)nr, -0(CH2)n20-, 또는 -0C0(CH2)n30C0-이고， 상기 nl, n2 및 η3는 각각 1 내지 10의 정수이다. (CH 2) nr, -0 ( CH 2) n2 0-, or -0C0 (CH 2) n3 and 0C0-, wherein nl, n2 and η3 is an integer of 1 to 10, respectively.
[화학식 19]
Figure imgf000008_0001
[Formula 19]
Figure imgf000008_0001
상기 화학식 19에서， Y4, Υ5 및 Υ6는 서로 같거나 다를 수 있으며， 각각 직접결합， -0-, -CO-, -S-, -S02-, -C(CH3)2-, -C(CF3)2-, -C0NH-, - COCK -(CH2)ni-, -0(CH2)n20-, 또는 — 0C0(CH2)n30C0—이고， 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Formula 19, Y 4 , Υ 5 and Υ 6 may be the same as or different from each other, and a direct bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-,-COCK-(CH 2 ) n i-, -0 (CH 2 ) n2 0-, or — 0C0 (CH 2 ) n3 0C0—, wherein nl, n2 and n3 are the integers of 1-10, respectively.
[화학식 20]  [Formula 20]
Figure imgf000008_0002
한편， 상술한 바와 같이 , 상기 화학식 1에서, ^ 및 P2는 서로 같거나 다를 수 있으며, 이미다졸일기 (imidazolyl)를 포함하는 유기 작용기일 수 있다.
Figure imgf000008_0002
Meanwhile, as described above, in Formula 1, ^ and P 2 may be the same as or different from each other, and may be an organic functional group including an imidazolyl group.
이미다졸류 화합물은 부식 방지 기능이 있으며 , 금속과의 접착력을 증가시키는 역할을 하여 동박 접착 효과를 높일 수 있고, 폴리아믹산의 이미드화반응의 촉매 역할을 할 수 있어서 감광성 재료 제조시에 저온에서 경화가 일어날 수 있게 하는 역할을 할 수 있다.  The imidazole compound has anti-corrosion function, increases adhesion to metals, enhances copper foil adhesion effect, and acts as a catalyst for imidation reaction of polyamic acid, thereby curing at low temperature during photosensitive material production. Can play a role in making things happen.
다만, 본 발명자들의 연구 결과, 이미다졸류 화합물을 단분자의 형태로 감광성 수지 조성물 등에 첨가하여 사용하는 경우 풀리아믹산과의 상용성이 좋지 않아서. 조성물 등에서 불균칙하게 또는 불균일하게 분산될 수 있으며, 이에 따라 제조되는 감광성 재료의 균일한 물성을 확보하기 어렵게 하거나, 회로 기판 등에 부분적인 오염을 야기시킬 수 있다.  However, the results of the inventors of the present invention, when the imidazole compound is added to the photosensitive resin composition and the like in the form of a single molecule and used, the compatibility with the fuliamic acid is not good. It may be disproportionately or unevenly dispersed in the composition or the like, thereby making it difficult to ensure uniform physical properties of the photosensitive material manufactured or causing partial contamination of a circuit board or the like.
이에 본 발명자들은, 이미다졸일기를 폴리아믹산 고분자의 가지에 도입하여 폴리아믹산과의 상용성이나 감광성 수지 조성물 내에서의 분산성 등에 대한 문제를 해결하였으며, 상기 이미다졸일기가 도입된 폴리아믹산 고분자을 사용하면 저온에서 높은 효율로 경화가 가능하며 동박 등의 금속과도 높은 접착력을 유지할 수 있고 탁월한 부식 방지 기능을 구현하여 우수한 내도금성을 구현할 수 있다는 점을 실험을 통하여 확인하였다. The present inventors have solved the problem of compatibility with polyamic acid or dispersibility in the photosensitive resin composition by introducing an imidazolyl group into the branches of the polyamic acid polymer, and the polyamic acid into which the imidazolyl group is introduced. Experiments confirmed that the polymer can be cured with high efficiency at low temperatures, maintains high adhesion with metals such as copper foil, and can achieve excellent plating resistance by implementing excellent corrosion protection.
상기 일 구현예의 플리아믹산을 사용하면, 이미다졸류 화합물을 첨가제의 형태로 감광성 수지 조성물 등에 첨가하여 사용하는 경우에 비하여, 보다 균질한 감광성 수지 조성물 및 균일하고 우수한 물성을 갖는 드라이 필름 등의 재료를 제공할 수 있으며， 이러한 감광성 수지 조성물 및 이로부터 얻어지는 재료는 높은 접착력， 우수한 굴곡성, 우수한 납내열성， 상대적으로 낮은 열팽창계수, 높은 고온 내습성， 높은 탄성 및 우수산 내도금성을 가질 수 있다.  When the plymic acid of the above embodiment is used, compared to the case where the imidazole compound is added to the photosensitive resin composition or the like in the form of an additive, a material such as a more homogeneous photosensitive resin composition and a dry film having uniform and excellent physical properties The photosensitive resin composition and the material obtained therefrom may have high adhesion, excellent bendability, good lead heat resistance, relatively low coefficient of thermal expansion, high high temperature moisture resistance, high elasticity and excellent acid plating resistance.
상기 pL 및 p2 각각이 카보닐기 (carbonyl groLip)을 포함하고 말단에 이미다졸일기가 결합된 작용기를 포함할 수 있다. Each of p L and p 2 may include a carbonyl group (carbonyl groLip) and include a functional group having an imidazolyl group bonded to the terminal thereof.
구체적으로, 상기 화학식 1에서 상기 Pi 및 P2는 각각 하기 화학식 2의 작용기인 것이 바람직하다. Specifically, in Formula 1, Pi and P 2 are each preferably a functional group represented by Formula 2 below.
[화학식 2]  [Formula 2]
—(R^-(R2)b— 상기 화학식 2에서， ^은
Figure imgf000009_0001
' ，
Figure imgf000009_0002
이고， a는 0 또는 1이고, ¾는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬렌기이고, b는 0 또는 1이고， Y는 탄소수 1내지 3의 알킬기로 치환 또는 비치환된 이미다졸일기이다. 본 명세서에서 '알킬렌기'는 직쇄 또는 분지쇄의 알케인 (alkane)으로부터 유도된 2가의 작용기를 의미한다. — (R ^-(R 2 ) b— In Formula 2, ^ is
Figure imgf000009_0001
' ,
Figure imgf000009_0002
And a is 0 or 1, ¾ is a linear or branched alkylene group having 1 to 10 carbon atoms, b is 0 or 1, and Y is an imidazolyl group unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms. . As used herein, an "alkylene group" refers to a divalent functional group derived from a linear or branched alkane.
그리고, 상기 Y는 하기 화학식 51 내지 53의 작용기일 수 있다.  And, Y may be a functional group of the formula 51 to 53.
[화학식 51] [Formula 51]
Figure imgf000010_0001
Figure imgf000010_0001
[화학식 52]  [Formula 52]
Figure imgf000010_0002
Figure imgf000010_0002
[화학식 53]  [Formula 53]
Figure imgf000010_0003
Figure imgf000010_0003
상기 화학식 51 내지 53에서, R51, R52, R53 및 4는 서로 같거나 다를 수 있으며, 각각 수소 또는 탄소수 1 내지 3의 알킬기 이고, *는 작용기에서의 결합점 (bonding point)올 의미한다. In Chemical Formulas 51 to 53, R 51 , R 52 , R53 and 4 may be the same as or different from each other, and each represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and * denotes a bonding point in the functional group.
한편， 상기 화학식 1에서, ¾은 4가의 유기기 일 수 있으며， 적용될 수 있는 4가 유기기의 종류가 크게 한정되는 것은 아니나, 하기 화학식 21 내지 35로 이루어진 군에서 선택된 하나의 4가 유기기인 것이 바람직하다.  Meanwhile, in Chemical Formula 1, ¾ may be a tetravalent organic group, but the type of the tetravalent organic group to be applied is not particularly limited, but it is one tetravalent organic group selected from the group consisting of the following Chemical Formulas 21 to 35: desirable.
[화학식 21]  [Formula 21]
Figure imgf000010_0004
[화학식 22]
Figure imgf000010_0004
[Formula 22]
Figure imgf000011_0001
Figure imgf000011_0001
상기 화학식 22에서, ΥΊ 은 단일결합， —0-, -CO-, -S -， -S02-, - C(CH3)2— , -C(CF3)2-, -C0NH-, -COCK -(CH2)n厂, -0(CH2)n20-, 또는 - 0C0(CH2)n30C0—이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Formula 22, ΥΊ is a single bond, —0-, -CO-, -S-, -S0 2 -,-C (CH 3 ) 2 —, -C (CF 3 ) 2- , -C0NH-,- COCK-(CH 2 ) n厂, -0 (CH 2 ) n 2 0-, or-0C0 (CH 2 ) n3 0C0—, wherein nl, n2 and n3 are each an integer from 1 to 10.
[화학식 23]  [Formula 23]
Figure imgf000011_0002
Figure imgf000011_0002
상기 화학식 23에서， Y2 및 Υ3는 서로 같거나 다를 수 있으며， 각각 단일결합, -0-, -CO-, -S-, -S02-, — C(CH3)2-, -C(CF3)2-, -C0NH-, -COO—, -In Chemical Formula 23, Y 2 and Υ 3 may be the same as or different from each other, and each single bond, -0-, -CO-, -S-, -S0 2- , — C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -COO—,-
(CH2)nl -, -0(CH2)n20-, 또는 -0C0(CH2)n30C0—이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. (CH 2) nl -, -0 (CH 2) n2 is 0-, or -0C0 (CH 2) n3 0C0-, wherein nl, n2 and n3 is an integer of 1 to 10, respectively.
[화학식 24]  [Formula 24]
Figure imgf000011_0003
Figure imgf000011_0003
상기 화학식 24에서 Υ4, Υ5 및 Υ6는 서로 같거나 다를 수 있으며, 각각 단일결합, -0-， -CO-, -S-, -S02-, -C(CH3)2-, -C(CF3)2-, -C0NH-, - CO으， -(CH2)ni-, -0(CH2)n20-, 또는 -0C0(CH2)n30C()-이고， 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Formula 24, Υ 4 , Υ 5 and Υ 6 may be the same as or different from each other, and each of a single bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -CO,-(CH 2 ) n i-, -0 (CH 2 ) n2 0-, or -0C0 (CH 2 ) n3 0C ()-, Nl, n2 and n3 are each an integer of 1 to 10.
[화학식 25]  [Formula 25]
Figure imgf000011_0004
[화학식 26]
Figure imgf000011_0004
[Formula 26]
Figure imgf000012_0001
Figure imgf000012_0001
[화학식 27]  [Formula 27]
Figure imgf000012_0002
Figure imgf000012_0002
상기 화학식 26
Figure imgf000012_0003
작용기에서의 결합점 (bonding point)을 의미한다. Formula 26
Figure imgf000012_0003
It means the bonding point in the functional group.
[화학식 28]  [Formula 28]
Figure imgf000012_0004
Figure imgf000012_0004
[화학식 29]
Figure imgf000012_0005
[Formula 29]
Figure imgf000012_0005
[화학식 30] [Formula 30]
Figure imgf000013_0001
한편, 상기 폴리아믹산은 상기 화학식의 반복 단위 이외로 일반적인 폴리아믹산의 반복 단위， -어 하기 화학식 3의 반복 단위를 더 포함할 수 있다.
Figure imgf000013_0001
On the other hand, the polyamic acid is general in addition to the repeat unit of the formula Repeating unit of the polyamic acid, -er may further include a repeating unit of the formula (3).
[화학식 3]  [Formula 3]
Figure imgf000014_0001
Figure imgf000014_0001
상기 화학식 3에서， X3은 4가의 유기기이고, 는 2가의 유기기이다. 상기 ¾에 적용될 수 있는 4가 유기기의 종류가 크게 한정되는 것은 아니나， 각각 독립적으로 상기 화학식 21 내지 35로 이루어진 군에서 선택된 하나의 4가 유기기가 적용되는 것이 바람직하다. 그리고， 상기 화학식 3의 반복 단위는, 이를 포함하는 폴리아믹산이 폴리이미드화 되었을 때 유리 전이 온도가 250°C 이하가 되는 구조 또는 특성을 갖는 것이 광가교제와 상용성 측면에서 바람직하다. In Formula 3, X 3 is a tetravalent organic group, is a divalent organic group. The type of the tetravalent organic group that can be applied to ¾ is not particularly limited, but each tetravalent organic group selected from the group consisting of Chemical Formulas 21 to 35 is preferably applied. In addition, the repeating unit of the formula (3), when the polyamic acid containing the polyimide is preferably having a structure or properties that the glass transition temperature is 250 ° C or less from the viewpoint of compatibility with the optical crosslinking agent.
또한， 상기 에 사용 가능한 2가의 유기기에도 별 다른 제한이 있는 것은 아니나， 각각 독립적으로 하기 화학식 60 내지 화학식 68로 이루어진 군에서 선택된 하나의 2가 작용기를 사용하는 것이 바람직하다.  In addition, the divalent organic group usable above is not particularly limited, but it is preferable to use one divalent functional group independently selected from the group consisting of the following Chemical Formulas 60 to 68, respectively.
[화학식 60]  [Formula 60]
[화학식 61] [Formula 61]
Figure imgf000014_0002
Figure imgf000014_0002
상기 화학식 61에서, 은 단일결합， -0-, -co-, -S -， -so2-, C(CH3)2-. ᅳ C(CF3)2-, -CONH—, ᅳ CO으, — (CH2)nl- -0(CH2)n20- -0CH2-C(CH3)i CH20- 또는 C00(CH2)n30C0-이고, 상기 nlᅳ n2 및 n3는 각각 내지 10의 정수이다. In Formula 61, is a single bond, -0-, -co-, -S-, -so 2- , C (CH 3 ) 2- . ᅳ C (CF 3 ) 2- , -CONH—, ᅳ CO, — (CH 2 ) nl --0 (CH 2 ) n2 0- -0CH2-C (CH 3 ) i CH 2 O-or a C00 (CH 2) n3 0C0-, the eu nl n2 and n3 is an integer from to 10, respectively.
[화학식 62]  [Formula 62]
Figure imgf000015_0001
Figure imgf000015_0001
상기 화학식 62에서， L2 및 L3는 서로 같거나 다를 수 있으며, 각각 단일결합, -0—， -CO-, -S-, -S02-, ᅳ C(CH3)2-, -C(CF3)2-, -C0NH-, -C00-, - (CH2)nl-, -0(CH2)n20-, -0CH2-C(CH3)2-CH20- 또는 -0C0(CH2)n30C0-이고， 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Chemical Formula 62, L 2 and L 3 may be the same as or different from each other, and each single bond, -0—, -CO—, -S-, -S0 2- , ᅳ C (CH 3 ) 2- , -C (CF 3) 2 -, -C0NH- , -C00-, - (CH 2) nl -, -0 (CH 2) n2 0-, -0CH 2 -C (CH 3) 2-CH 2 0- or - 0C0 (CH 2 ) n3 0C0-, wherein nl, n2 and n3 are each an integer from 1 to 10.
[화학식 63]  [Formula 63]
Figure imgf000015_0002
Figure imgf000015_0002
상기 화학식 63에서, L4, L5 및 L6는 서로 같거나 다를 수 있으며, 각각 단일결합, -으, -CO, -S-, -S02-, -C(CH3)2-, -C(CF3)2-, -C0NH-, - C00-, -(CH2)ni-, -0(CH2)n20-, -0CH2-C(CH3)2-CH20- 또는 -0C0(CH2)n30C으이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이다. In Chemical Formula 63, L 4 , L 5, and L 6 may be the same as or different from each other, and each of a single bond, -E, -CO, -S-, -S0 2- , -C (CH 3 ) 2 -,- C (CF 3 ) 2- , -C0NH-,-C00-,-(CH 2 ) ni-, -0 (CH 2 ) n 2 0-, -0CH 2 -C (CH 3 ) 2 -CH 2 0- or -0C0 (CH 2 ) n3 0C, wherein nl, n2 and n3 are each an integer from 1 to 10.
[화학식 64]
Figure imgf000015_0003
[Formula 64]
Figure imgf000015_0003
[화학식 65]  [Formula 65]
Figure imgf000015_0004
[화학식 66]
Figure imgf000015_0004
[Formula 66]
Figure imgf000016_0001
Figure imgf000016_0001
상기 화학식 64, 65 및 66에서， *는 결합 지점을 의미한다.  In Chemical Formulas 64, 65 and 66, * means a bonding point.
[화학식 67]  [Formula 67]
0 0  0 0
-ᅳ (Ri )τᅳ" ( C ½ᅳ (O R2)— 0~~ ( C r -" ( Ri)r— 상기 화학식 67에서， ^은 탄소수 2 내지 8의 알킬렌 또는 아릴렌이고 R2는 탄소수 2 내지 8의 알킬렌이고， a,b는 각각 0 또는 1이고， c는 1 내지 21의 정수이다. -ᅳ (Ri) τ ᅳ "(C ½ ᅳ (OR 2 ) — 0 ~~ (C r-" (Ri) r— In formula 67, ^ is alkylene or arylene having 2 to 8 carbon atoms and R 2 Is alkylene having 2 to 8 carbon atoms, a and b are each 0 or 1, and c is an integer of 1 to 21.
[화학식 68]  [Formula 68]
Figure imgf000016_0002
Figure imgf000016_0002
상기 화학식 68에서， Ru, R12, R13 및 R14 는 서로 같거나 다를 수 있으며, 각각 탄소수 1 내지 5의 알킬기 또는 탄소수 6 내지 10의 아릴기이며, R15 및 R16 은 각각 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬렌기이며 , πι은 1 이상의 정수이고， n은 0이상의 정수이다. In Chemical Formula 68, R u , R 12 , R 13, and R 14 may be the same as or different from each other, and are each an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 15 and R 16 are each 1 carbon atom. It is a linear or branched alkylene group of 20, (pi) is an integer of 1 or more, n is an integer of 0 or more.
한편, 상기 폴리아믹산은 상기 화학식 1의 반복 단위 0.1 내지 50mol%; 및 상기 화학식 3의 반복 단위 50 내지 99.9 mol%를 포함할 수 있다. 바람직하게는, 상기 폴리아믹산은 상기 화학식 1의 반복 단위 0.3 내지 30mol%; 및 상기 화학식 3의 반복 단위 70 내지 99.7 niol%를 포함할 수 있으며， 보다 바람직하게는 상기 화학식 1의 반복 단위 0.5 내지 10niol%; 및 상기 화학식 3의 반복 단위 90 내지 99.5 mol%를 포함할 수 있다. 상기 화학식 1의 반복 단위의 함량이 너무 작은 경우, 상기 폴리아믹산을 이용하여 얻어지는 감광성 재료의 내열성， 동박 접착력 및 내도금성의 저하가 나타날 수 있고， 상기 함량이 너무 큰 경우 다른 감광성 재료와의 상용성이 저하되거나 점도의 급격한 상승이 나타날 수 있으며， 이에 따라 작업성 또는 물성이 저하될 수 있고, 현상성 및 유연성이 저하될 수 있다. 한편, 상기 폴리아믹산은 5,000 내지 200, 000의 중량평균분자량， 바람직하게는 8,000 내지 50,000 의 중량평균분자량을 가질 수 있다. 상기 폴리아믹산의 분자량이 너무 작으면, 감광성 수지 조성물의 베이스 수지로서의 역할을 제대로 구현하기 어려우면, 폴리아믹산의 분자량이 너무 크면, 감광성 수지 조성물에 포함되는 다른 물질과의 상용성이 저하될 수 있다. On the other hand, the polyamic acid is 0.1 to 50 mol% of the repeating unit of Formula 1; And it may include 50 to 99.9 mol% of the repeating unit of Formula 3. Preferably, the polyamic acid is 0.3 to 30 mol% of the repeating unit of Formula 1; And 70 to 99.7 niol% of the repeating unit of Formula 3 above. And, more preferably, 0.5 to 10niol% of the repeating unit of Formula 1; And it may include 90 to 99.5 mol% of the repeating unit of Formula 3. When the content of the repeating unit of Formula 1 is too small, the heat resistance, copper foil adhesion and plating resistance of the photosensitive material obtained using the polyamic acid may appear, and when the content is too large, compatibility with other photosensitive materials This may be reduced or a sharp increase in viscosity, thereby lowering the workability or physical properties, and may lower the developability and flexibility. On the other hand, the polyamic acid may have a weight average molecular weight of 5,000 to 200,000, preferably a weight average molecular weight of 8,000 to 50,000. If the molecular weight of the polyamic acid is too small, if it is difficult to properly implement the role of the photosensitive resin composition as the base resin, if the molecular weight of the polyamic acid is too large, compatibility with other materials included in the photosensitive resin composition may be lowered. .
한편, 상기 화학식 1의 반복 단위를 포함하는 폴리아믹산은 당 기술분야에 알려져 있는 통상적인 유기 합성 방법을 적용하여 제조할 수 있다. 예를 들어， 상기 폴리아믹산은 하기 화학식 4의 디아민 화합물과 화학식 5의 디아민 화합물을 용매에 용해시키고, 이 용액에 테트라카르복실산 이무수물 (tetracarboxylic acid dianhydr ide)을 첨가한 후 반웅시켜 제조할 수 있다.  Meanwhile, the polyamic acid including the repeating unit of Formula 1 may be prepared by applying a conventional organic synthesis method known in the art. For example, the polyamic acid may be prepared by dissolving a diamine compound represented by Chemical Formula 4 and a diamine compound represented by Chemical Formula 5 in a solvent, and adding tetracarboxylic acid dianhydride to this solution. have.
[화학식 4]  [Formula 4]
2)b— Y
Figure imgf000017_0001
2) b— Y
Figure imgf000017_0001
상기 화학식 4에서, X2는 상기 화학식 1의 ¾에 관하여 상술한 내용과 동일하게 적용할 수 있으며, 상기 ， R2, a, b 및 Y는 각각 상기 화학식 2에서 상술한 내용과 동일하게 적용할 수 있다. In Chemical Formula 4, X 2 is the same as described above with respect to ¾ of Chemical Formula 1 The same may be applied, and R 2 , a, b and Y may be applied in the same manner as described above in Chemical Formula 2.
[화학식 5]  [Formula 5]
NH2-X4-NH2  NH2-X4-NH2
상기 화학식 5에서, 는 2가의 유기기로서， 이에 사용 가능한 2가의 유기기에도 별 다른 제한이 있는 것은 아니며, 구체적인 예는 상술한 바와 같다.  In Formula 5, is a divalent organic group, there is no particular limitation on the divalent organic group that can be used, specific examples are as described above.
상기 화학식 5의 디아민 화합물의 예로， p-PDA(p-페닐렌디아민), m- PDA(m-페닐렌디아민), 4,4'-0DA(4,4'-옥시디아닐린)， 3,4'-0DA(3,4'- 옥시디아닐린), BAPP(2,2-비스 (4-[4-아미노페녹시] -페닐)프로판), APB- N(l, 3—비스 (3-아미노페녹시)벤젠), TPE-R(1,3-비스 (4-아미노페녹시)벤젠), TPE-Q(1,4-비스 (4-아미노페녹시)벤젠), 및 m— BAPS(2,2-비스 (4-[3ᅳ 아미노페녹시]페닐)설폰) 등이 있으나， 이들에 한정되는 것은 아니다.  Examples of the diamine compound of Chemical Formula 5 include p-PDA (p-phenylenediamine), m-PDA (m-phenylenediamine), 4,4'-0DA (4,4'-oxydianiline), 3, 4'-0DA (3,4'-oxydianiline), BAPP (2,2-bis (4- [4-aminophenoxy] -phenyl) propane), APB-N (l, 3-bis (3- Aminophenoxy) benzene), TPE-R (1,3-bis (4-aminophenoxy) benzene), TPE-Q (1,4-bis (4-aminophenoxy) benzene), and m—BAPS ( 2,2-bis (4- [3 'aminophenoxy] phenyl) sulfone) and the like, but are not limited thereto.
상기 테트라카르복실산 이무수물 (tetracarboxylic acid dianhydride)로는 하기 화학식 6의 화합물을 사용할 수 있다.  As the tetracarboxylic acid dianhydride, a compound represented by the following Chemical Formula 6 may be used.
[화학식 6]  [Formula 6]
Figure imgf000018_0001
Figure imgf000018_0001
상기 화학식 6에서, ¾은 4가 유기기이고， 상기 ¾은 4가 유기기일 수 있으며, 사용 가능한 4가 유기기의 종류가 크게 한정되는 것은 아니나， 하기 화학식 21 내지 35로 이루어진 군에서 선택된 하나의 4가 유기기가 적용되는 것이 바람직하다. 보다 구체적인 내용은 상술한 바와 같다.  In Chemical Formula 6, ¾ is a tetravalent organic group, ¾ may be a tetravalent organic group, and the kind of usable tetravalent organic group is not limited to a large one, but one selected from the group consisting of the following Chemical Formulas 21 to 35 It is preferable that tetravalent organic group is applied. More details are as described above.
상기 테트라카르복실산 이무수물의 구체적인 예로, 피로멜리틱 디안하이드라이드， 3,3' ,4,4'—바이페닐테트라카복실릭 디안하이드라이드, 3,3' ,4, 4'-벤조페논테트라카복실릭 디안하이드라이드, 4，4'—옥시다이프탈릭 안하이드라이드， 4,4'— (4ᅳ 4'-이소프로필바이페녹시)바이프탈릭 안하이드라이드， 2,2'-bis— (3，4-디카복실페닐) 헥사플루오로프로판 디안하이드라이드 및 TMEG (에틸렌 글리콜 비스 (안하이드로- 트리멜리테이트)로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있으나, 이들에 한정되는 것은 아니다. Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'—biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic Rick dianhydride, 4,4'—oxydiphthalic anhydride, 4,4'— (4'4'-isopropylbiphenoxy) biphthalic Anhydride, 2,2'-bis— (3,4-dicarboxylphenyl) hexafluoropropane dianhydride and TMEG (ethylene glycol bis (anhydro- trimellitate)) Although it can use, it is not limited to these.
상기 다관능 지방족 아민 화합물, 상기 디아민 화합물 및 테트라카르복실산 이무수물의 반웅은 0 내지 5 °C에서 반웅을 시작하여 10 내지 40 °C의 온도 범위에서 반웅이 완결 될 때까지 통상 24 시간 전후로 수행하는 것이 바람직하다. 이때, 상기 화학식 4의 디아민 화합물 및 화학식 5의 디아민 화합물의 합: 테트라카르복실산 이무수물의 흔합 몰비는 1:0.9 내지 1:1.1 인 것이 바람직하다. 만일 상기 디아민 화합물들의 합: 테트라카르복실산 이무수물의 몰비가 1:0.9 내지 1:1.1 를 벗어나는 경우에는 제조되는 폴리아믹산의 분자량이 적정 범위를 벗어나게 되고, 이에 따라 얻어지는 폴리아믹산 또는 폴리이미드의 기계적 물성 등이 저하될 수 있다. The reaction of the polyfunctional aliphatic amine compound, the diamine compound and the tetracarboxylic dianhydride is usually carried out about 24 hours starting from the reaction at 0 to 5 ° C until the reaction is completed in the temperature range of 10 to 40 ° C. It is preferable. At this time, the sum of the diamine compound of Formula 4 and the diamine compound of Formula 5: tetracarboxylic dianhydride is preferably 1: 0.9 to 1: 1.1. If the molar ratio of the sum of the diamine compounds: tetracarboxylic dianhydride is 1: 0.9 to 1: 1.1, the molecular weight of the polyamic acid to be produced is out of the appropriate range, and thus the mechanical properties of the polyamic acid or polyimide obtained And the like may be degraded.
상기 폴리아믹산의 제조 단계에서 사용되는 용매로는 N- 메틸피를리디논 (N-methylpyrrolidinone; NMP). Ν,Ν- 디메틸아세트아미드 ( Ν , N-d i me thy 1 acet am i de； DMAc ) , 테트라히드로퓨란 (tetrahydrofuran; THF), ！^ ᅳ디메틸포름아미드 ^ᅳ diniethylforniamide; DMF), 디메틸설폭시드 (dimethylsulfoxide; DMS0) . 시클로핵산 (cyclohexane), 아세토니트릴 (acetonitri le) 및 이들의 흔합물로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있으나， 이들에 한정되는 것은 아니다. 한편, 발명의 다른 구현예에 따르면， 상기 신규한 폴리아믹산을 포함하는 고분자 수지; 광가교제; 유기 용매; 및 광중합 개시제를 포함하는 감광성 수지 조성물이 제공될 수 있다.  The solvent used in the preparation of the polyamic acid is N-methylpyrrolidinone (N-methylpyrrolidinone; NMP). Ν, Ν- dimethylacetamide (Ν, N-d i thy 1 acet am i de; DMAc), tetrahydrofuran (THF),！ ^ dimethylformamide ^ ᅳ diniethylforniamide; DMF), dimethylsulfoxide (DMS0). One or more selected from the group consisting of cyclohexane, acetonitrile, and combinations thereof may be used, but is not limited thereto. On the other hand, according to another embodiment of the invention, a polymer resin containing the novel polyamic acid; Photocrosslinking agents; Organic solvents; And the photosensitive resin composition containing a photoinitiator can be provided.
본 발명자들은, 상기 화학식 1의 반복 단위를 포함하는 신규한 폴리아믹산을 적용한 감광성 수지 조성물을 사용하면， 낮은 은도에서 경화가 가능하여 공정의 안정성 및 공정 작업상의 편리성을 제공할 수 있으며, 우수한 유연성과 낮은 강성 (low stiffness) 특성을 만족시키고 우수한 내열성 및 내도금성, 우수한 동박접착력 등의 우수한 기계적 물성과 높은 현상성을 구현할 수 있는 감광성 재료를 제공할 수 있다는 점을 실험을 통하여 확인하고 발명을 완성하였다. The inventors of the present invention, when using the photosensitive resin composition to which the novel polyamic acid containing the repeating unit of the formula (1) is applied, can be cured at a low degree of silver to provide stability of the process and convenience in process operation, and excellent flexibility And low stiffness characteristics Experiments confirmed that it can provide a photosensitive material that can implement excellent mechanical properties and high developability, such as excellent heat resistance and plating resistance, excellent copper foil adhesion, and completed the invention.
상기 화학식 1의 반복 단위를 포함하는 신규한 폴리아믹산에 관한 구체적인 내용은 상술한 바와 같다.  Details of the novel polyamic acid including the repeating unit of Formula 1 are as described above.
상기 광가교제로는 감광성 수지 조성물에 통상적으로 사용 가능한 것으로 알려진 것이면 별 다른 제한 없이 사용할 수 있으나， 탄소간 이중결합을 포함하는 (메타)아크릴레이트계 화합물을 사용하는 것이 바람직하다. 본 명세서에서， 별다른 정의가 없는 한 (메타)아크릴레이트는 아크릴레이트 또는 메타크릴레이트를 의미한다.  The photocrosslinking agent may be used without any limitation as long as it is known to be commonly used in the photosensitive resin composition, but it is preferable to use a (meth) acrylate compound including a carbon-to-carbon double bond. In the present specification, unless otherwise defined, (meth) acrylate means acrylate or methacrylate.
상기 탄소간 이중결합을 포함하는 (메타)아크릴레이트계 화합물은 폴리아믹산과 높은 상용성을 나타낼 뿐 만 아니라, 감광성 수지 조성물에 포함되어 알카리 용액에 대한 높은 현상성과 우수한 감광성을 구현할 수 있게 한다. 또한, 이러한 탄소간 이중결합을 포함하는 (메타)아크릴레이트계 화합물을 적용한 감광성 수지 조성물은 드라이 필름으로 가공되었을 때, 열 가공 시 모들러스가 내려가고 열 라미네이션 시 유동성이 부여되어 요철이 있는 패턴의 채움성을 향상시킬 수 있고， 이에 따라, 비교적 낮은 온도에서도 열라미네이션 공정이 가능해진다.  The (meth) acrylate-based compound including the carbon-to-carbon double bond not only exhibits high compatibility with the polyamic acid, but also is included in the photosensitive resin composition to enable high developability and excellent photosensitivity to an alkali solution. In addition, the photosensitive resin composition to which the (meth) acrylate-based compound including the carbon-to-carbon double bond is applied, when processed into a dry film, the modulus is lowered during heat processing and the fluidity is imparted during thermal lamination, thereby providing a pattern having irregularities. Filling properties can be improved, thereby enabling a thermal lamination process even at a relatively low temperature.
상기 광가교제로 사용 가능한， 탄소간 이중결합을 포함하는 (메타)아크릴레이트계 화합물의 예는 크게 한정되는 것은 아니나， 예를 들어, 2-에틸핵실 (메타)아크릴레이트， 2ᅳ히드록시에틸 (메타)아크릴레이트， 2-히드록시프로필 (메타)아크릴레이트， 2ᅳ히드록시 아크릴레이트, 페녹시에틸아크릴레이트， 2-히드록시부틸 (메타)아크릴레이트, 스테아릴아크릴레이트， 라우릴아크릴레이트， 글리시딜 (메타)아크릴레이트, 트라이에틸렌글리콜디아크릴레이트， 1，3_부탄디을 디아크릴레이트， 디에틸렌글리콜 디아크릴레이트, 네오펜틸글리콜 디아크릴레이트， 1,6- 핵산디을 디아크릴레이트， 3-메틸 -1,5-펜탄디올 디아크릴레이트, 2-부틸 -2- 에틸 -1,3—프로관디올 아크릴레이트, 1,9ᅳ노난디올 디아크릴레이트, 1,6- 핵산디올 에폭시 아크릴레이트， 펜타에리스리를트리 (메타)아크릴레이트， 트리메티롤프로판트리 (메타)아크릴레이트， 페닐글리시딜에스터 아크릴레이트 (예를 들어 일본화약 R-128H), 1,6-헥산디올 에폭시 아크릴레이트 (예를 들어， 일본화약 Kayarad R-167), 트리스 (히드록시에틸 (메타)아크릴로일)이소시아누레이트， Examples of the (meth) acrylate-based compound containing a carbon-to-carbon double bond, which can be used as the photocrosslinking agent, are not particularly limited. For example, 2-ethylnuclear (meth) acrylate and 2'hydroxyethyl ( Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2'hydroxy acrylate, phenoxyethyl acrylate, 2-hydroxybutyl (meth) acrylate, stearyl acrylate, lauryl acrylate, Glycidyl (meth) acrylate, triethylene glycol diacrylate, 1,2-butanedi diacrylate, diethylene glycol diacrylate, neopentylglycol diacrylate, 1,6- nucleic acid diacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-butyl-2-ethyl-1,3—propanediol acrylate, 1,9 ᅳ nonanediol diacrylate, 1,6-nucleic acid diol epoxy acrylic Rate ， Pentaerythritol tri (meth) acrylate ， Trimetholpropane tri (meth) acrylate ， Phenylglycidyl ester Acrylate (e.g. Nippon Kayaku R-128H), 1,6-hexanediol epoxy acrylate (e.g. Nippon Kayarad R-167), Tris (hydroxyethyl (meth) acryloyl) Rate
폴리에스테르아크릴레이트 우레탄 아크릴레이트， 펜타에리스를테트라 (메타)아크릴레이트 등을 들 수 있으며， 이들을 2종 이상 흔합하여 사용할 수도 있다. 또한， 상기 화합물 이외로 상용 제품인 신나카무라 화학의 NK 을리고머 EA-1010, EA-6310 등이나， EA-1020, EA- 6320， EA-6340 등이나, Ebecryl 600， 일본화약사의 ZAA-205, ZFA-266H 등을 사용할 수도 있다. Polyester acrylate urethane acrylate, pentaerythri (tetra) (meth) acrylate, etc. are mentioned, You may use these in mixture of 2 or more types. In addition to the above compounds, NK ligomers EA-1010 and EA-6310 of Shinnakamura Chemical, which are commercially available products, EA-1020, EA-6320, EA-6340, Ebecryl 600, ZAA-205 of Nippon Kayaku Co., ZFA-266H etc. can also be used.
상기 감광성 수지 조성물 또는 이로부터 얻어지는 제품의 유연성 또는 굴곡성의 확보 측면에서， 상기 광가교제는 하기 화학식 7의 화합물을 일부 포함하는 것이 바람직하다.  In view of securing flexibility or flexibility of the photosensitive resin composition or a product obtained therefrom, the photocrosslinking agent preferably includes a part of the compound represented by the following Chemical Formula 7.
[화학식 7]  [Formula 7]
Figure imgf000021_0001
Figure imgf000021_0001
상기 화학식 7에서, R1은 분자 내에 벤젠고리를 둘 이상 가지는 방향족이고， R2는 에틸렌옥사이드 혹은 프로필렌옥사이드기이며， R3는 수소 혹은 메틸기이고， 0과 p는 각각 2 이상의 정수이며 o+p 값은 50 이하의 정수， 바람직하게는 30이하의 정수일 수 있다.  In Formula 7, R1 is an aromatic having two or more benzene rings in the molecule, R2 is an ethylene oxide or propylene oxide group, R3 is a hydrogen or methyl group, 0 and p are each an integer of 2 or more and o + p value is 50 It may be an integer below, preferably an integer below 30.
상기 화학식 7에 속하는 화합물의 예로는, NK Ester의 A— BPE-10, A- BPE 20， A-BPE-30, BPE-500, BPE-900, 신나카무라 화학제 혹은 공영사 등의 비스페놀 (bisphenol)A E0 변성 메타 (아크릴레이트)， 비스페놀 (bisphenol )F E0 변성 메타 (아크릴레이트)， P0 변성 메타 (아크릴레이트), 그리고 스토머 (Stomer)사의 SR-480, S -602, C으 542등을 들 수 있으며 , 구체적인 화합물로는 에틸렌옥사이드변성 비스페놀 A 디 (메타)아크릴레이트， 프로필렌옥사이드변성 비스페놀 A 디 (메타)아크릴레이트， 에틸렌옥사이드- 프로필렌옥사이드변성 비스페놀 A 디 (메타)아크릴레이트， 에틸렌옥사이드변성 비스페놀 F 디 (메타)아크릴레이트， 프로필렌옥사이드변성 비스페놀 F 디 (메타)아크릴레이트, 에틸렌옥사이드- 프로필렌옥사이드변성 비스페놀 F 디 (메타)아크릴레이트 등을 들 수 있다. 한편, 상기 광중합 개시제는 아세토페논계 화합물， 비이미다졸계 화합물， 트리아진계 화합물, 옥심계 화합물 또는 이들의 흔합물올 포함할 수 있다. Examples of the compound belonging to Formula 7 include bisphenols such as A—BPE-10, A-BPE 20, A-BPE-30, BPE-500, BPE-900, Shin-Nakamura Chemical Co. A E0 modified meta (acrylate), bisphenol F E0 modified meta (acrylate), P0 modified meta (acrylate), and Stormer's SR-480, S-602, C 542, etc. Specific examples of the compound include ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide-propylene oxide modified bisphenol A di (meth) acrylate, and ethylene oxide. Modified bisphenol F di (meth) acrylate ， Propylene oxide modified bisphenol F di (meth) acrylate, ethylene oxide propylene oxide modified bisphenol F di (meth) acrylate, and the like. The photopolymerization initiator may include an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or a mixture thereof.
상기 광중합 개시제의 구체적인 예로， 2-히드톡시 -2-메틸 -1- 페닐프로판 -1-온， 1— (4-이소프로필페닐) -2-히드록시 -2-메틸프로판 -1—온, 4- (2-히드록시에톡시 ) -페닐— (2-히드톡시 -2-프로필 )케톤 , 1- 히드록시시클로핵실페닐케톤, 벤조인메틸 에테르, 벤조인에틸 에테르, 벤조인이소부틸 에테르， 벤조인부틸 에테르， 2, 2-디메톡시 -2- 페닐아세토페논, 2-메틸 -(4-메틸티오)페닐 -2-몰폴리노 -1-프로판 -1-온, 2- 벤질ᅳ 2-디메틸아미노 -1-(4-몰폴리노페닐) -부탄 -1-은, 또는 2-메틸 -1-[4- (메틸티오)페닐] -2-몰폴리노프로판 -1-온 등의 아세토페논계 (acetophenone) 화합물;  Specific examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1— (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4 -(2-hydroxyethoxy) -phenyl- (2-hydroxy-2- propyl) ketone, 1-hydroxycyclonucleophenylphenyl ketone, benzoinmethyl ether, benzoinethyl ether, benzoin isobutyl ether, benzo Inbutyl ether, 2, 2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propane-1-one, 2-benzyl 2-dimethyl Acetofe such as amino-1- (4-morpholinophenyl) -butane-1-silver or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one Acetophenone compounds;
2,2-비스 (2-클로로페닐) -4,4'，5，5'-테트라페닐 비이미다졸, 2,2'- 비스 (0—클로로페닐) -4,4' ,5,5'—테트라키스 (3,4,5-트리메록시페닐 ) -1,2'- 비이미다졸, 2, 2'-비스 (2, 3-디클로로페닐 )-4,4' ,5, 5'-테트라페닐 비이미다졸, 또는 2,2'-비스(0-클로로페닐)-4，4，5，5'—테트라페닐-1,2'- 비이미다졸 등의 비이미다졸계 (biimidazole) 화합물:  2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (0—chlorophenyl) -4,4', 5,5 ' —Tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5, 5'- Biimidazole compounds such as tetraphenyl biimidazole or 2,2'-bis (0-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole :
3—{4-[2,4—비스 (트리클로로메틸 )-s—트리아진 -6- 일]페닐티오}프로피오닉 산, 1,1,1，3,3,3-핵사플로로이소프로필-3-{4-[2，4- 비스 (트리클로로메틸) -S-트리아진 -6-일]페닐티오}프로피오네이트, 에틸 -2- {4-[2，4-비스 (트리클로로메틸) -S-트리아진 -6-일]페닐티오}아세테이트, 2- 에폭시에틸— 2-{4-[2，4-비스 (트리클로로메틸) -S-트리아진 -6- 일]페닐티오}아세테이트， 시클로핵실 -2-{4-[2,4-비스 (트리클로로메틸) -S- 트리아진 -6-일]페닐티오}아세테이트, 벤질 -2-{4-[2，4- 비스 (트리클로로메틸) -S-트리아진 -6-일]페닐티오}아세테이트, 3-{클로로 -4- [2, 4ᅳ비스 (트리클로로메틸) -S-트리아진— 6-일]페닐티오}프로피오닉 산， 3- {4-[2,4-비스 (트리클로로메틸) -S-트리아진— 6-일]페닐티오}프로피온아미드, 2, 4-비스 (트리클로로메틸) -6-p-메톡시스티릴 -S-트리아진, 2,4- 비스 (트리클로로메틸) -6— (l-p-디메틸아미노페닐) -1,3,ᅳ부타디에닐 -s- 트리아진， 또는 2-트리클로로메틸 -4-아미노—6-p-메톡시스티릴 -S-트리아진 등의 트리아진계 화합물; 및 일본 시바사의 CGI-242, CGI-124 등의 옥심계 화합물 등을 들 수 있다. 3— {4- [2,4—bis (trichloromethyl) -s—triazine-6-yl] phenylthio} propionic acid, 1,1,1,3,3,3-nuxafluoroisopropyl -3- {4- [2,4-bis (trichloromethyl) -S-triazin-6-yl] phenylthio} propionate, ethyl-2- {4- [2,4-bis (trichloro Methyl) -S-triazine-6-yl] phenylthio} acetate, 2-epoxyethyl— 2- {4- [2,4-bis (trichloromethyl) -S-triazine-6-yl] phenylthio } Acetate, cyclonuxyl-2- {4- [2,4-bis (trichloromethyl) -S-triazine-6-yl] phenylthio} acetate, benzyl-2- {4- [2,4-bis (Trichloromethyl) -S-triazine-6-yl] phenylthio} acetate, 3- {chloro-4- [2,4bisbis (trichloromethyl) -S-triazine— 6-yl] phenylthio } Propionic acid, 3- {4- [2,4-bis (trichloromethyl) -S-triazine- 6-yl] phenylthio} propionamide, 2,4-bis (trichloromethyl) -6- p-methoxystyryl-S-triazine, 2,4- Bis (trichloromethyl) -6— (lp-dimethylaminophenyl) -1,3, butadienyl-s-triazine, or 2-trichloromethyl-4-amino—6-p-methoxystyryl Triazine compounds such as -S-triazine; And oxime compounds such as CGI-242 and CGI-124 from Shiba, Japan.
상기 감광성 수지 조 물은 감광성 수지 조성물의 성분을 용해시키고, 또한 조성물을 도포하기에 적절한 정도의 점도를 부여하는 목적으로 유기 용매가 사용될 수 있다. 상기 유기 용매로는 감광성 수지 조성물에 사용될 수 있는 것으로 알려진 것이면 별 다른 제한 없이 사용할 수 있다. 예를 들어， 메틸에틸케톤, 시클로핵사논 등의 케톤류; 를루엔, 크실렌. 테트라메틸밴젠 등의 방향족 탄화수소류 : 에틸렌글리콜모노에틸에테르 , 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노부틸에테르 , 디에틸렌글리콜모노에틸에테르 , 디에틸렌글리콜모노메틸에테르， 디에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르， 프로필텐글리콜모노에틸에테르， 디프로필렌글리콜디에틸에테르， 트리에틸렌글리콜모노에틸에테르 등의 글리콜에테르류 (셀로솔브); 아세트산에틸 , 아세트산부틸， 에틸렌글리콜모노에틸에테르아세테이트， 에틸렌글리콜모노부틸에테르아세테이트，  As the photosensitive resin composition, an organic solvent may be used for the purpose of dissolving the components of the photosensitive resin composition and imparting an appropriate level of viscosity for applying the composition. The organic solvent may be used without any limitation as long as it is known to be used in the photosensitive resin composition. For example, ketones, such as methyl ethyl ketone and cyclonucleanone; Toluene, xylene. Aromatic hydrocarbons, such as tetramethyl benzene, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol Glycol ethers (cellosolve) such as monomethyl ether, propyl tenglycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate,
디에틸렌글리콜모노에틸에테르아세테이트 , Diethylene glycol monoethyl ether acetate,
디프로필렌글리콜모노메틸에테르아세테이트 등의 아세트산에스테르류; 에탄을, 프로관을, 에틸렌글리콜, 프로필렌글리콜， 카르비틀 등의 알코을류; 옥탄, 데칸 등의 지방족 탄화수소; 석유에테르. 석유나프타. 수소 첨가 석유나프타, 용매나프타 등의 석유계 용제; 디메틸아세트아미드 (DMAc), 디메틸포름아미드 (DMF) 등의 아미드류 등을 들 수 있다. 이들 용매는 단독으로 또는 2종 이상의 흔합물로서 사용할 수 있다. Acetate esters, such as dipropylene glycol monomethyl ether acetate; Ethane, protubes, alcohols such as ethylene glycol, propylene glycol and carbitle; Aliphatic hydrocarbons such as octane and decane; Petroleum ether. Petroleum naphtha. Petroleum solvents such as hydrogenated petroleum naphtha and solvent naphtha; Amides, such as dimethyl acetamide (DMAc) and dimethylformamide (DMF), etc. are mentioned. These solvents can be used alone or as a mixture of two or more thereof.
상기 폴리아믹산을 포함하는 고분자 수지의 고형분 농도는 상기 화학식 1의 반복단위를 포함하는 폴리아믹산의 분자량， 점성， 휘발성 등과 제조되는 최종 제품, 예를 들어 드라이 필름 등의 물성을 고려하여 적절히 선택될 수 있다. 바람직하게는, 상기 고분자 수지의 고형분 농도는 감광성 수지 조성물 중 총 중량에 대하여 15 내지 90 중량 %일 수 있다. 그리고， 상기 광가교제의 함량은 상기 감광성 수지 조성물 중 폴리아믹산 고형분 100중량부에 대하여 10 내지 200중량부일 수 있다. 상기 광가교제의 함량이 너무 작으면 제조되는 감광성 재료의 현상 특성 및 패턴 채움성이 저하될 수 있고, 상기 함량이 너무 크면 내열성의 저하 및 내절성을 포함하는 필름의 기계적 특성이 저하될 수 있다. Solid content concentration of the polymer resin containing the polyamic acid may be appropriately selected in consideration of the physical properties of the final product, for example, dry film, etc., prepared from the molecular weight, viscosity, volatility, and the like of the polyamic acid including the repeating unit of Formula 1 have. Preferably, the solid content concentration of the polymer resin may be 15 to 90% by weight based on the total weight of the photosensitive resin composition. The amount of the photocrosslinking agent may be 10 to 200 parts by weight based on 100 parts by weight of the polyamic acid solids in the photosensitive resin composition. If the content of the photocrosslinking agent is too small, the developing characteristics and pattern fillability of the photosensitive material to be manufactured may be lowered. If the content is too large, the mechanical properties of the film including heat resistance lowering and cutting resistance may be lowered.
상기 광중합 개시제의 함량은 상기 감광성 수지 조성물 중 폴리아믹산 고형분 100중량부에 대하여 0.1 내지 10중량부일 수 있다. 상기 광중합 개시제의 함량이 너무 작으면 광중합 개시제의 광경화 참여도가 떨어지며， 상기 함량이 너무 커지면 경화에 참여하지 못한 라디칼로 인하여 감광성 수지 조성물로부터 제조된 필름의 물성이 저하될 수 있다.  The content of the photopolymerization initiator may be 0.1 to 10 parts by weight based on 100 parts by weight of the polyamic acid solids in the photosensitive resin composition. If the content of the photopolymerization initiator is too small, the photocuring participation of the photopolymerization initiator is lowered. If the content is too large, the physical properties of the film prepared from the photosensitive resin composition may decrease due to radicals that do not participate in curing.
상기 유기 용매는 유기 용매는 상기 폴리아믹산, 광가교제， 광중합 개시제 또는 선택적으로 추가의 첨가제들을 용해하기 쉬운 것으로 사용할 수 있으며， 특별히 코팅 공정시 쉽게 건조될 수 있는 용매가 바람직하다. 상기 유기 용매의 함량은 상기 감광성 수지 조성물 중 폴리아믹산 고형분 100중량부에 대하여 100 내지 1000 중량부일 수 있다. 상기 유기 용매의 함량이 너무 작은 경우에는 감광성 수지 조성물의 점도를 지나치게 높아져서 코팅성이 저하될 수 있으며, 상기 함량이 너무 높은 경우 감광성 수지 조성물의 건조가 용이하지 않을 수 있으며, 제조되는 필름의 기계적 물성 등이 저하될 수 있다.  The organic solvent may be used as the organic solvent is easy to dissolve the polyamic acid, photocrosslinking agent, photopolymerization initiator or optionally additional additives, a solvent that can be easily dried in particular during the coating process is preferred. The content of the organic solvent may be 100 to 1000 parts by weight based on 100 parts by weight of the polyamic acid solids in the photosensitive resin composition. In the case where the content of the organic solvent is too small, the viscosity of the photosensitive resin composition may be excessively high, thereby decreasing the coating property. When the content is too high, the drying of the photosensitive resin composition may not be easy. And the like may be degraded.
한편, 상기 감광성 수지 조성물은 열가교제， 경화 촉진제, 광가교 증감제， 경화 촉진제， 인계 난연제, 소포제， 레벨링제, 겔 방지제 또는 이들의 흔합물을 더 포함할 수 있다. 이러한 첨가제로는 감광성 수지 조성물에 사용될 수 있는 것으로 알려진 것이면 별 다른 제한 없이 사용할 수 있으며, 제조되는 감광성 수지 조성물 또는 이로부터 얻어지는 필름의 물성 등을 고려하여 적절한 양으로 사용할 수 있다. 한편, 발명의 다른 구현예에 따르면， 상기 감광성 수지 조성물의 경화물 또는 건조물을 포함하는 드라이 필름이 제공될 수 있다.  Meanwhile, the photosensitive resin composition may further include a thermal crosslinking agent, a curing accelerator, a photocrosslinking sensitizer, a curing accelerator, a phosphorus-based flame retardant, an antifoaming agent, a leveling agent, a gel inhibitor, or a mixture thereof. Such additives may be used without limitation as long as they are known to be used in the photosensitive resin composition, and may be used in an appropriate amount in consideration of physical properties of the photosensitive resin composition or the film obtained therefrom. On the other hand, according to another embodiment of the present invention, a dry film including a cured product or a dried product of the photosensitive resin composition may be provided.
상술한 바와 같이, 상기 화학식 1의 반복 단위를 포함하는 폴리 아믹산이 적용된 감광성 수지 조성물을 이용하면， 우수한 유연성과 낮은 강성 (low stiffness) 특성을 만족시키고 우수한 내열성 및 내도금성을 나타내는 감광성 재료가 제공될 수 있다. As described above, using the photosensitive resin composition to which the polyamic acid including the repeating unit of Formula 1 is applied, excellent flexibility and low A photosensitive material can be provided that satisfies low stiffness properties and exhibits excellent heat resistance and plating resistance.
구체적으로, 상기 드라이 필름은 상기 감광성 수지 조성물이 건조되어 얻어진 필름상 또는 상기 감광성 수지 조성물이 광경화되거나 열경화물된 필름상을 의미한다. 그리고, 이러한 경화물은 하기 화학식 1- 1의 반복단위를 포함하는 폴리이미드와 광가교제의 가교 반웅물을 포함할 수 있다.  Specifically, the dry film means a film form obtained by drying the photosensitive resin composition or a film form in which the photosensitive resin composition is photocured or thermoset. In addition, the cured product may include a crosslinked semi-aqua product of a polyimide and a photocrosslinker including a repeating unit represented by Chemical Formula 1-1.
[화학식 1-1]  [Formula 1-1]
Figure imgf000025_0001
Figure imgf000025_0001
상기 화학식 1-1에서, Xi 은 4가의 유기기이고, X2 는 방향족 고리를 포함하는 3가 또는 4가의 유기기이고, n은 0 또는 1인 정수이고， 및 P2는 서로 같거나 다를 수 있으며， 이미다졸일기를 포함하는 유기 작용기이다. 보다 구체적으로, 상기 화학식 1-1에서, 상기 는 상기 화학식 11 내지 15로 이루어진 군에서 선택된 하나의 4가 유기기이거나, 상기 화학식 16 내지 20으로 이루어진 군에서 선택된 하나의 3가 유기기일 수 있다. In Formula 1-1, Xi is a tetravalent organic group, X 2 is a trivalent or tetravalent organic group including an aromatic ring, n is an integer of 0 or 1, and P 2 may be the same or different from each other And an organic functional group containing an imidazolyl group. More specifically, in Formula 1-1, may be one tetravalent organic group selected from the group consisting of Formula 11 to 15, or may be one trivalent organic group selected from the group consisting of Formula 16 to 20.
상기 화학식 1-1에서, 은 4가의 유기기 일 수 있으며, 적용될 수 있는 4가 유기기의 종류가 크게 한정되는 것은 아니나， 상기 화학식 21 내지 35로 이루어진 군에서 선택된 하나의 4가 유기기인 것이 바람직하다. 또한, 상기 화학식 1-1에서 상기 Pi 및 P2는 각각 하기 화학식 2의 작용기인 것이 바람직하다. In Chemical Formula 1-1, may be a tetravalent organic group, and the type of tetravalent organic group to which it may be applied is not particularly limited, but it is preferably one tetravalent organic group selected from the group consisting of Chemical Formulas 21 to 35. Do. In addition, in Formula 1-1, Pi and P 2 are each preferably a functional group represented by Formula 2 below.
[화학식 2]  [Formula 2]
— ( i)a-( 2)b— Y 상기 화학식 2에서， ^은
Figure imgf000025_0002
, ,
Figure imgf000026_0001
이고, a는 0 또는 1이고, R2는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬렌기이고， b는 0 또는 1이고, Y는 탄소수 1내지 3의 알킬기로 치환 또는 비치환된 이미다졸일기이다. 그리고， 상기 Y는 상기 화헉1식 51 내지 53의 작용기일 수 있다. — (I) a- ( 2 ) b— Y In Formula 2, ^ is
Figure imgf000025_0002
,,
Figure imgf000026_0001
And a is 0 or 1, R 2 is a straight or branched chain alkylene group having 1 to 10 carbon atoms, b is 0 or 1, and Y is an imidazolyl group unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms. to be. And, Y may be a functional group of Formula 1 Equation 51 to 53.
상기 드라이 필름은 지지체 상에 감광성 수지 조성물을 공지의 방법으로 도포하고 건조하는 것에 의해 제조할 수 있다. 상기 지지체는 감광성 수지 조성물층을 박리할 수 있고， 또한 광의 투과성이 양호한 것이 바람직하다. 또한, 표면의 평활성이 양호한 것이 바람직하다.  The said dry film can be manufactured by apply | coating and drying a photosensitive resin composition on a support body by a well-known method. It is preferable that the said support body can peel the photosensitive resin composition layer, and the light transmittance is favorable. Moreover, it is preferable that surface smoothness is favorable.
상기 지지체의 구체적인 예로서, 폴리에틸렌테레프탈레이트， 폴리에틸렌나프탈레이트 , 폴리프로필렌, 폴리에틸렌， 3초산 셀를로오스， 2초산 셀를로오스, 폴리 (메타)아크릴산 알킬에스테르, 폴리 (메타)아크릴산 에스테르공중합체, 폴리염화비닐, 폴리비닐알콜， 폴리카보네이트, 폴리스티렌, 셀로판, 폴리염화비닐리덴 공중합체， 폴리아미드, 폴리이미드, 염화비닐，초산비닐 공중합체, 폴리테트라플루오로에틸렌, 및 폴리트리플루오로에틸렌 등의 각종의 플라스틱 필름을 들 수 있다. 또한 이들의 2종 이상으로 이루어지는 복합재료도 사용할 수 있으며, 광투과성이 우수한 폴리에틸렌테레프탈레이트 필름이 특히 바람직하다. 상기 지지체의 두께는 5 내지 150/ΛΙΙ가 바람직하며， 10 내지 50 이 더욱 바람직하다.  Specific examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, poly Polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride, vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene The plastic film of the is mentioned. Moreover, the composite material which consists of these 2 or more types can also be used, The polyethylene terephthalate film excellent in the light transmittance is especially preferable. The thickness of the support is preferably 5 to 150 / ΛΙΙ, more preferably 10 to 50.
상기 감광성 수지 조성물의 도포방법은 특별히 한정되지 않고， 예를들어 스프레이법, 를코팅법， 회전도포법, 슬릿코팅법， 압출코팅법， 커튼코팅법, 다이코팅법, 와이어바코팅법 또는 나이프코팅법 등의 방법을 사용할 수 있다. 상기 감광성 수지 조성물의 건조는 각 구성 성분이나 유기 용매의 종류， 및 함량비에 따라 다르지만 60 내지 100°C에서 30초 내지 15분간 수행하는 것이 바람직하다. The coating method of the photosensitive resin composition is not particularly limited, and for example, a spray method, a coating method, a rotary coating method, a slit coating method, an extrusion coating method, a curtain coating method, a die coating method, a wire bar coating method or a knife coating method Law and the like can be used. Drying of the photosensitive resin composition is preferably carried out for 30 seconds to 15 minutes at 60 to 100 ° C, depending on each component or type of organic solvent, and content ratio.
건조 및 경화 후의 드라이 필름의 막 두께가 5 내지 95 , 더욱 바람직하게는 10 내지 50 이다. 상기 드라이 필름의 막 두께가 5 m 이하이면 절연성이 좋지 못하며, 95 를 초과하면 해상도가 저하 될 수 있다. 상기 드라이 필름은 회로 기판용 보호 필름， 회로 기판의 베이스 필름, 회로 기판의 절연층, 반도체의 층간 절연막 또는 솔더 레지스트에 사용될 수 있다. 한편, 발명의 또 다른 하나의 구현예에 따르면, 상기 드라이 필름을 포함하는 회로 기판이 제공될 수 있다. The film thickness of the dry film after drying and hardening is 5-95, More preferably, it is 10-50. If the film thickness of the dry film is 5 m or less, the insulation is not good, and if it exceeds 95, the resolution may be lowered. The dry film may be used in a protective film for a circuit board, a base film of a circuit board, an insulating layer of a circuit board, an interlayer insulating film of a semiconductor, or a solder resist. Meanwhile, according to another embodiment of the present invention, a circuit board including the dry film may be provided.
상기 회로 기판은 다층 프린트 배선판 , 가용성 회로기판 또는 연성 회로기판을 포함할 수 있다. 상술한 바와 같이, 상기 드라이 필름은 회로 기판에서, 드라이 필름은 회로 기판용 보호 필름， 회로 기판의 베이스 필름, 회로 기판의 절연층， 반도체의 층간 절연막 또는 솔더 레지스트 등으로 사용될 수 있다.  The circuit board may include a multilayer printed wiring board, a fusible circuit board, or a flexible circuit board. As described above, the dry film may be used in a circuit board, and the dry film may be used as a protective film for a circuit board, a base film of a circuit board, an insulating layer of a circuit board, an interlayer insulating film or a solder resist of a semiconductor, and the like.
상기 회로 기판에 포함되는 드라이 필름은 드라이 필름 또는 드라이 필름의 가공물, 예를 들어 일정한 기판에 라미네이션 (lamination)된 가공물 또는 광반웅물 등을 포함하는 의미이다.  The dry film included in the circuit board is meant to include a dry film or a workpiece of the dry film, for example, a workpiece or a light reflection material laminated on a predetermined substrate.
상기 드라이 필름을 회로 형성면 위에 평면 압착 또는 를 압착 등의 방법으로 20 내지 50°C의 온도에서 프리—라미네이션 (pre-lainination)한 후， 60 내지 90t에서 진공 라미네이션 (vacumn lamination) 하여 감광성 피막을 형성할 수 있다. After the dry film is pre-laminated at a temperature of 20 to 50 ° C. by a method such as flat pressing or pressing on the circuit forming surface, vacuum lamination at 60 to 90 to obtain a photosensitive film. Can be formed.
또한， 상기 드라이 필름은 미세 구성이나 미세 폭 라인을 형성하기 위하여 포토마스크를 이용하여 노광함으로서 패턴의 형성이 가능하다. 노광량은 UV 노광에 사용되는 광원의 종류과 필름 막의 두께에 따라 적절히 조절될 수 있으며， 예를 들어 100 내지 1200 ni/cuf가 바람직하고, 100 내지 500 m/cuf가 더욱 바람직하다.  In addition, the dry film is capable of forming a pattern by exposing using a photomask to form a fine configuration or a fine width line. The exposure amount can be appropriately adjusted according to the type of light source used for UV exposure and the thickness of the film film, for example, 100 to 1200 ni / cuf is preferable, and 100 to 500 m / cuf is more preferable.
사용 가능한 활성 광선으로는 전자선, 자외선, X-ray 등이 있으며, 바람직하게는 자외선을 사용할 수 있다. 그리고, 사용 가능한 광원으로는 고압 수은등, 저압 수은등 또는 할로겐 램프 등을 광원으로 사용할 수 있다. 노광 후 현상시에는 일반적으로 스프레이법을 사용하게 되몌 상기 감광성 수지 조성물은 탄산 나트륨 수용액 등의 알칼리 수용액을 사용하여 현상하고, 물로 세척하게 된다. 그후, 가열 처리 과정을 통하여 현상에 의해 얻어진 패턴에 따라 플리아믹산이 폴리이미드로 변하게 되면， 가열 처리 은도는 이미드화에 필요한 100 내지 25CTC일 수 있다. 이때 가열 온도는 적절한 온도 프로파일을 가지고 2 내지 4단계에 걸쳐 연속적으로 승온하는 것이 효과적이나, 경우에 따라 일정한 온도에서 경화할 수 도 있다. 상술한 단계를 통하여 다층 프린트 배선판, 가용성 회로기판 또는 연성 회로기판 등을 얻을 수 있다. Examples of the active light rays that can be used include electron beams, ultraviolet rays, X-rays, and the like, and preferably ultraviolet rays. As a light source that can be used, a high pressure mercury lamp, a low pressure mercury lamp or a halogen lamp can be used as the light source. In the post-exposure development, a spray method is generally used. The photosensitive resin composition is developed using an aqueous alkali solution such as an aqueous sodium carbonate solution and washed with water. Then, when the plymic acid is changed to polyimide according to the pattern obtained by development through the heat treatment process, the heating Treatment silver may be between 100 and 25 CTC required for imidization. At this time, the heating temperature is effective to continuously increase the temperature over 2 to 4 steps with an appropriate temperature profile, but may be cured at a constant temperature in some cases. Through the above-described steps, a multilayer printed wiring board, a fusible circuit board or a flexible circuit board can be obtained.
【발명의 효과】  【Effects of the Invention】
본 발명에 따르면, 신규한 폴리아믹산; 우수한 유연성과 낮은 강성 (low stiffness) 특성을 만족시키고 우수한 내열성 및 내도금성을 나타내는 감광성 재료를 제공할 수 있는 감광성 수지 조성물; 상기 감광성 수지 조성물로부터 얻어지는 드라이 필름 및 상기 드라이 필름을 포함하는 회로 기판을 제공될 수 있다.  According to the invention, novel polyamic acid; A photosensitive resin composition capable of providing a photosensitive material that satisfies excellent flexibility and low stiffness characteristics and exhibits excellent heat resistance and plating resistance; A dry film obtained from the photosensitive resin composition and a circuit board including the dry film may be provided.
상기 폴리아믹산을 이용하면 보다 균질한 감광성 수지 조성물 및 균일하고 우수한 물성을 갖는 드라이 필름 등의 재료를 제공할 수 있으며， 이러한 감광성 수지 조성물 및 이로부터 얻어지는 재료는 높은 접착력， 우수한 굴곡성, 우수한 납내열성, 상대적으로 낮은 열팽창계수， 높은 고온 내습성, 높은 탄성 및 우수산 내도금성을 가질 수 있다.  By using the polyamic acid, it is possible to provide a more homogeneous photosensitive resin composition and a material such as a dry film having uniform and excellent physical properties. The photosensitive resin composition and the material obtained therefrom have high adhesion, excellent bendability, excellent lead heat resistance, It can have a relatively low coefficient of thermal expansion, high temperature moisture resistance, high elasticity and excellent acid plating resistance.
【발명을 실시하기 위한 구체적인 내용】  [Specific contents to carry out invention]
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐， 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다.  The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the present invention, the content of the present invention is not limited by the following examples.
<합성예: (3, 5-디아미노페닐) (1H-이미다졸 -1-일)메타논의 합성 > Synthesis Example: Synthesis of (3,5-diaminophenyl) (1H-imidazol-1-yl) methanone
1. (3, 5-디니트로페닐) (1H-이미다졸 -1일)메타논의 합성 -하기 반웅식 1의 화합물 A  1.Synthesis of (3,5-dinitrophenyl) (1H-imidazol-1-yl) methanone-Compound A of Banung Formula 1
교반기를 설치한 3구 등근 바닥 플라스크에 N-메틸피를리돈 (NMP)용매 N-methylpyridone (NMP) solvent in a three-necked back-bottom flask equipped with a stirrer
300g, 3, 5-디니트로벤조산 100g과 이미다졸 32. lg, Ν,Ν'- 디시클로핵실카보이미드 97.5g을 넣고 균일하게 교반하였다. 이 용액을 70°C에서 12시간 동안 교반하여 반웅을 진행하였다. 이후, 반응의 종료를 확인한 후, 에틸아세테이트 용매 800g을 넣고, 10¾ 염산 용액 10g을 넣고， 10분간 교반하였다. 이후 수세 과정을 거쳐， 염과 N-메틸피롤리돈을 제거하고 감압증류를 통하여 화합물 A를 얻었다. 100 g of 300 g, 3, 5-dinitrobenzoic acid and 32. lg of imidazole and 97.5 g of Ν, Ν'-dicyclonucleosilcarbodiimide were added and stirred uniformly. The solution was stirred at 70 ° C. for 12 hours to proceed reaction. Then, after confirming the completion of the reaction, 800 g of ethyl acetate solvent was added, 10 g of 10¾ hydrochloric acid solution was added thereto, and the mixture was stirred for 10 minutes. After washing with water, salt and N-methylpyrrolidone Compound A was obtained by distillation under reduced pressure.
2. (3, 5-디아미노페닐) (1H-이미다졸 -1-일)메타논의 합성 2. Synthesis of (3,5-diaminophenyl) (1H-imidazol-1-yl) methanone
상기에서 얻어진 화합물 A 100g을 메틸렌 클로라이드 용액 300g에 용해시키고 팔라듐차콜 10g을 넣은 후 3기압의 수소 분위기 하에서 12시간 교반하였다. 이후 반웅의 종료를 확인한 후, 팔라듐차콜을 감압 필터를 통하여 제거한 후 최종 결과물 (3,5-디아미노페닐)(111-이미다졸-1- 일)메타논을 얻었다. 상기 합성 과정을 하기 반응식 1의 단계를 통하여 이루어졌다  100 g of the compound A obtained above was dissolved in 300 g of methylene chloride solution, 10 g of palladium charcoal was added, and the mixture was stirred for 12 hours under a hydrogen atmosphere of 3 atm. After confirming the completion of reaction, the palladium char was removed through a reduced pressure filter to obtain a final product (3,5-diaminophenyl) (111-imidazol-1-yl) methanone. The synthesis process was carried out through the steps of Scheme 1 below.
[반웅식 1]  [Banungsik 1]
Figure imgf000029_0001
Figure imgf000029_0001
A DPI  A DPI
<제조예: 폴리아믹산의 제조 > Preparation Example: Production of Polyamic Acid
[제조예 1] 폴리아믹산 (PM1)의 제조  Preparation Example 1 Preparation of Polyamic Acid (PM1)
온도계， 교반기 및 질소흡입구와 분말투입구 (powder dispensing funnel)를 설치한 4구 등근 바닥 플라스크에 질소를 흘려 보내면서， 4,4'- 옥시디프탈릭 안하이드라이드 (ODPA) 38g을 를루엔과 디메틸아세트아마이드가 3:7의 중량비로 흔합된 용매 150g에 분산시켰다. 이후 4，4'-옥시디아닐린(4,4'-00/) 23.2g과 상기 합성예에서 얻어진 DPIM 2.59g을 용액에 교반하여 완전히 용해시키고， 24시간 동안 교반하여 폴리아믹산 바니시를 얻었다. 이 바니시 용액의 고형분은 30wt%이며， 점도는 실온에서 3,400cps였다. [제조예 2] 폴리아믹산 (PAA2)의 제조 38 g of 4,4'- oxydiphthalic anhydride (ODPA) was poured into a four-necked back-bottomed flask equipped with a thermometer, agitator, nitrogen inlet, and powder dispensing funnel. The amide was dispersed in 150 g of the mixed solvent in a weight ratio of 3: 7. Thereafter, 23.2 g of 4,4'-oxydianiline (4,4'-00 /) and 2.59 g of DPIM obtained in the above synthesis example were stirred in a solution to completely dissolve and stirred for 24 hours to obtain a polyamic acid varnish. Solid content of this varnish solution was 30 wt%, and the viscosity was 3,400 cps at room temperature. Preparation Example 2 Preparation of Polyamic Acid (PAA2)
온도계， 교반기 및 질소흡입구와 분말투입구 (powder dispensing funnel)를 설치한 4구 등근 바닥 플라스크에 질소를 홀려 보내면서， 4，4'- 옥시디프탈릭 안하이드라이드 (ODPA) 38g을 틀루엔과 디메틸아세트아마이드가 3 :7의 중량비로 흔합된 용매 149g에 분산시켰다. 이후 4,4'-옥시디아닐린(4，4'-00/ ) 20.6g과 상기 합성예에서 얻어진 DPIM 5.19g을 용액에 교반하여 완전히 용해시키고, 24시간 동안 교반하여 폴리아믹산 바니시를 얻었다. 이 바니시 용액의 고형분은 30wt%이며， 점도는 실온에서 3,600cps였다.  38 g of 4,4'- oxydiphthalic anhydride (ODPA) was injected into a four-necked back-bottomed flask equipped with a thermometer, stirrer, nitrogen inlet and powder dispensing funnel, and toluene and dimethylacetate. The amide was dispersed in 149 g of the mixed solvent in a weight ratio of 3: 7. Thereafter, 20.6 g of 4,4'-oxydianiline (4,4'-00 /) and 5.19 g of DPIM obtained in the above synthesis example were stirred in a solution to completely dissolve and stirred for 24 hours to obtain a polyamic acid varnish. Solid content of this varnish solution was 30 wt%, and the viscosity was 3,600 cps at room temperature.
[제조예 3] 폴리아믹산 (PM3)의 제조 Preparation Example 3 Preparation of Polyamic Acid (PM3)
온도계， 교반기 및 질소홉입구와 분말투입구 (powder dispensing funnel)를 설치한 4구 등근 바닥 플라스크에 질소를 홀려 보내면서， 4，4'- 옥시디프탈릭 안하이드라이드 (ODPA) 38g을 틀루엔과 디메틸아세트아마이드가 3:7의 중량비로 흔합된 용매 149g에 분산시켰다. 이후 4,4'-옥시디아닐린(4，4'-( ^ 25.8g을 반웅 용액에 교반하여 완전히 용해시키고, 24시간 동안 교반하여 폴리아믹산 바니시를 얻었다. 이 바니시 용액의 고형분은 30wt%이며， 점도는 실온에서 3,100cps였다.  38 g of 4,4'- oxydiphthalic anhydride (ODPA) was injected into a four-necked back-bottomed flask equipped with a thermometer, stirrer, nitrogen inlet and powder dispensing funnel, toluene and dimethyl Acetamide was dispersed in 149 g of mixed solvent in a weight ratio of 3: 7. Thereafter, 4,4'-oxydianiline (4,4 '-(^ 25.8 g) was completely dissolved by stirring in a reaction solution, and stirred for 24 hours to obtain a polyamic acid varnish. The solid content of the varnish solution was 30 wt%, The viscosity was 3100 cps at room temperature.
<실시예 및 비교예: 감광성 수지 조성물의 제조 > <Examples and Comparative Examples: Preparation of Photosensitive Resin Composition>
[실시예 1 및 실시예 2]  Example 1 and Example 2
상기 제조예 1 및 2에서 얻어진 폴리아믹산 바니시 100증량부 (고형분기준)에 대하여， 표 1에 기재된 바와 같이 각 성분을 고형분의 배항비 (중량부)를 기준으로 흔합하여 감광성 수지 조성물을 얻었다.  With respect to 100 parts by weight of the polyamic acid varnish (solid content basis) obtained in Production Examples 1 and 2 above, as shown in Table 1, each component was mixed on the basis of the beating ratio (part by weight) of the solid content to obtain a photosensitive resin composition.
[비교예 1] Comparative Example 1
상기 제조예 3에서 얻어진 폴리아믹산 바니시 100증량부 (고형분기준)에 대하여, 표 1에 기재된 바와 같이 각 성분을 흔합하여 고형분의 배항비 (중량부)를 기준으로 감광성
Figure imgf000031_0001
With respect to 100 parts by weight of the polyamic acid varnish (solid content basis) obtained in Preparation Example 3, each component was prepared as shown in Table 1 below. Photosensitivity on the basis of the beating ratio (parts by weight) of solids
Figure imgf000031_0001
얻었다. Got it.
【표 1】 Table 1
감광성 수지 조성물의 조성 Composition of the photosensitive resin composition
Figure imgf000031_0002
Figure imgf000031_0002
나카무라 화학공업주식희사 제품， ΕΟΓ7) Nakamura Chemical Co., Ltd., ΕΟΓ7)
2) EA-1020: 2개 이상의 수산기를 함유하는 에폭시 (메타)크릴레이트계 화합물 (신 나카무리 화학공업주식회사 제품)  2) EA-1020: Epoxy (meth) acrylate compound containing two or more hydroxyl groups (manufactured by Shin-Nakamori Chemical Co., Ltd.)
3) DPEA-12: E0-변성 디펜타에리트리를 핵사아크릴레이트 (신 나카무라 화학공업주식회사 제품)  3) DPEA-12: Nucleoacrylate of E0-modified dipentaerythrates (manufactured by Shin-Nakamura Chemical Co., Ltd.)
4) GP0-303: 프로폭시레이티화 글리세린 트리아크릴레이트 (신나카무라 화학공업주식회사 제품， n=3) 4) GP0-303: Propoxylated Glycerine Triacrylate (Shin-Nakamura Chemical Co., Ltd., n = 3)
5) 1651 및 1819는 광중합 개시제로서 각각 Igacure 651 및 Igacure 819이다.  5) 1651 and 1819 are Igacure 651 and Igacure 819 as photopolymerization initiators, respectively.
6) 1，2,4-트리아졸은 알드리치사 제품을 사용하였다.  6) 1,2,4-triazole was used by Aldrich.
[시편의 제작] [Production of Psalms]
그리고， 상기 실시예 및 비교예에서 얻어진 감광성 수지 조성물 용액 각각을 의 두께의 폴리에틸렌테레프탈레이드 필름 (테이진듀폰 (주) 제품)의 기재 필름 상에 균일하게 도포하였다. 그리고， 75°C의 열풍 대류식 건조기를 사용하여 상기 도포된 조성물을 건조하고, 건조 후의 막의 두께가 38/ 인 감광성 수지 조성물층을 형성하였다. 이후， 상기 형성된 감광성 수지 조성물층 상에 폴리에틸렌 보호 필름 (타마폴리 (주) 제품， 상품명: NF- 15)를 를 가압에 의하여 적층하여， 감광성 엘리먼트를 얻었다. And each of the photosensitive resin composition solutions obtained by the said Example and the comparative example was apply | coated uniformly on the base film of the polyethylene terephthalate film (made by Teijin Dupont) of thickness. Then, the coated composition was dried using a hot air convection dryer at 75 ° C., and a photosensitive resin composition layer having a thickness of 38 / y after drying was formed. Thereafter, the polyethylene protective film (Tamapoly Co., Ltd. product, brand name: NF-) on the formed photosensitive resin composition layer 15) was laminated by pressing to obtain a photosensitive element.
<실험예: 실시예 및 비교예에 따른 드라이 필름의 성능 평가 > 실시예 및 비교예에서 제조한 드라이 필름을 패턴이 형성된 2CCL 제품의 동박면 위에 두고， MEIKI 사의 MVLP-500 진공 라미네이터를 이용하여 70°C에서 20초간 진공을 가하여， 40초간 0.6Mpa의 압력으로 진공 라미네이션을 진행하였다. 이를 400mJ/cm2의 광량으로 UV 조사하고， 1 %의 탄산나트륨 수용액에서 1분간 분무 현상한 뒤, 160°C의 질소 분위기 하의 오븐에서 90분간 경화한 뒤， 하기와 같은 방법으로 물성 평가를 진행하여, 그 결과를 하기 표 2에 기재하였다. 실험예 1: 회로 채움성 <Experimental Example: Performance Evaluation of Dry Films According to Examples and Comparative Examples> The dry films prepared in Examples and Comparative Examples were placed on a copper foil surface of a 2CCL product having a pattern formed thereon, and then, using a MEIK MVLP-500 vacuum laminator. Vacuum was applied at 20 ° C. for 20 seconds, and vacuum lamination was performed at a pressure of 0.6 Mpa for 40 seconds. UV irradiation with a light amount of 400mJ / cm 2 , spray development for 1 minute in an aqueous solution of sodium carbonate at 1%, curing for 90 minutes in an oven at 160 ° C., and then performing physical property evaluation as follows. The results are shown in Table 2 below. Experimental Example 1: Circuit Fillability
진공 라미네이션 (온도: 7(rc, 압력: 0.7Mpa, 진공시간: 20초， 가압시간: 40초)을 수행한 후 드라이 필름 o 갖는 회로에서의 채움성을 평가하였다. 실험예 2: 현상성  After vacuum lamination (temperature: 7 (rc, pressure: 0.7Mpa, vacuum time: 20 seconds, pressurization time: 40 seconds) was performed, the filling property in the circuit having a dry film o was evaluated.
실시예 및 비교예에서 제조된 시편을, 350 mJ/cm2으로 노광하고, 35°C의 1 %의 탄산나트륨 수용액으로 분무 현상한 뒤에 L/S=50 m/50/im 피치로 현상이 가능한지 확인하였다. 현상성 평가결과를 하기 표 1에 나타내었으며, 현상이 가능한 경우 'Ό", 현상이 불가능한 경우 "X"로 표시하였다. 실험예 3: 접착력 (바둑판무늬별) The specimens prepared in Examples and Comparative Examples were exposed to 350 mJ / cm 2 , spray-developed with a 35% aqueous solution of sodium carbonate at 35 ° C., and then checked for development at a pitch of L / S = 50 m / 50 / im. It was. The developability evaluation results are shown in Table 1 below, and when the development is possible, '현상', and when the development is not possible, are indicated by “X.” Experimental Example 3: Adhesive force (by checkerboard pattern)
2CCL 제품의 동박면 위에 일련의 과정으로 얻어진 감광성 수지 조성물의 최종 경화막의 접착 강도를 J IS K5400에 따라 바둑판 무늬 테이프법으로 평가하였다 (붙어있는 개수 / 초기 개수) 실험예 4: 접착력  The adhesive strength of the final cured film of the photosensitive resin composition obtained by a series of processes on the copper foil surface of 2CCL products was evaluated by the checkered tape method according to J IS K5400 (the number of stuck / initial number) Experimental Example 4: Adhesive force
동박면 위에 일련의 과정으로 얻어진 감광성 수지 조성물의 최종 경화막의 접착 강도를 J IS K5404에 따라 필 (Peel)로 측정하였다. 실험예 5: 휘어짐량 (Curl, 2CCL) 평가 Final of photosensitive resin composition obtained by a series of processes on copper foil surface The adhesive strength of the cured film was measured by Peel according to J IS K5404. Experimental Example 5: Evaluation of Curvature (Curl, 2CCL)
2CCL 제품의 등박면 위에 일련의 과정으로 얻어진 감광성 수지 조성물의 최종 경화막을 200隱 *200隱의 필름으로 자르고 직각으로 세웠을 때 얻어지는 굴곡 반경을 측정하였다. 실험예 6: 고은내습성 (내 PCT성) 측정  The bending radius obtained when the final cured film of the photosensitive resin composition obtained by a series of processes on the isoclinic surface of 2CCL product was cut into the film of 200 mm * 200 mm, and stood at right angles. Experimental Example 6: Measurement of High Silver Moisture Resistance (PCT Resistance)
2CCL 제품의 동박면 위에 일련의 과정으로 얻어진 감광성 수지 조성물의 최종 경화막을 고온 및 고습 조건 (120t:, 100%RH)하에서 5시간 동안 방치하고 경화막의 변색 및 계면에서의 팽창 현상 발생 유무를 관찰하였다. 실험예 7. 납내열성 평가  The final cured film of the photosensitive resin composition obtained by a series of processes on the copper foil surface of 2CCL product was left under high temperature and high humidity conditions (120t :, 100% RH) for 5 hours, and the discoloration of the cured film and the presence of the expansion phenomenon at the interface were observed. . Experimental Example 7 Evaluation of Lead Heat Resistance
288±5°C와 300±5°C인 납조에 드라이 필름면이 위로 가도록 하여Place the dry film side up in a lead bath at 288 ± 5 ° C and 300 ± 5 ° C.
10초 동안 플로팅한 후， 드라이. 필름의 이상여부 (필름의 박리나 변형이 있는지)를 육안으로 관찰하였다. 온도별 납내열성 결과를 하기 표 1에 나타내었으며, 각각의 온도의 납조 안에서 육안으로 관찰되는 필름의 박리나 변형이 없는 경우, 'Ό", 박리나 변성이 발생한 경우 "X"로 표시하였다. 실험예 8. 굴곡성 After plotting for 10 seconds, dry. Abnormality of the film (such as peeling or deformation of the film) was visually observed. The lead heat resistance results for each temperature are shown in Table 1 below, and when there is no peeling or deformation of the film visually observed in the lead bath at each temperature, 'Ό' is indicated and 'X' when peeling or deformation occurs. Example 8. Flexibility
L/S=100/ i/100mi인 FCCL패턴 위에 드라이 필름을 진공 라이네이션 하여 노광, 현상， 경화한 후, MIT방법 (0.38R, 500g load)으로 굴곡성을 측정하였다 (JIS C6471). 실험예 9. 열팽창계수  After drying, vacuum drying and curing the dry film on the FCCL pattern of L / S = 100 / i / 100mi, the flexibility was measured by the MIT method (0.38R, 500g load) (JIS C6471). Experimental Example 9. Coefficient of Thermal Expansion
실시예 및 비교예에서 제조된 드라이 필름을 이용하여 5mm*20mm의 strip 형태로 만든 뒤 TMA( Thermo— Mechanical Analysis)를 이용하여 Tg 이하 (αΐ)와 Tg 이상 (α2)에서의 열팽창계수를 측정하여, 그 결과를 하기 표 2 에 나타내었다. 실험예 10. 강성 (stiffness) Using the dry film prepared in Examples and Comparative Examples to form a strip of 5mm * 20mm and then the coefficient of thermal expansion at Tg (αΐ) and Tg or more (α2) by using TMA (Thermo—Mechanical Analysis) Doing the results Table 2 shows. Experimental Example 10. Stiffness
L/S=l隱 /1隱 인 FCCL 패턴 (구리배선 잔존율 50%) 위에 상기 실시예 및 비교예에서 제조된 드라이 필름을 진공 라미네이션 한 후에， 노광， 현상 및 경화하였다. 그리고， 둘레길이 lOcni의 loop 형태로 만들어 loop 직경이 2cm 일 때의 힘을 UTM 만능시험기를 이용하여 측정하였다 (Ν/πι). 실험예 11. 내도금성  The dry films prepared in Examples and Comparative Examples above were vacuum-laminated on an FCCL pattern (50% copper wiring residual ratio) of L / S = l 隱 / 1 隱, followed by exposure, development, and curing. In addition, the circumferential length lOcni was made into a loop shape and the force at the loop diameter of 2 cm was measured using a UTM universal testing machine (Ν / πι). Experimental Example 11. Plating Resistance
실시예 및 비교예에서 제조된 드라이 필름을 이용하여 무전해 니켈 /금도금성을 실험하였으며， 무전해 니켈 /금도금 후 액침투나 박리 등을 육안으로 관찰하였다. 그 결과, 무전해 니켈 /금도금 후, 육안으로 관찰되는 액침투나 박리 등이 없는 경우 "0K"로， 무전해 니켈 /금도금 후， 육안으로 관찰되는 액침투나 박리 등이 있는 경우. "NG"로 표시하여 표 2에 나타내었다.  The electroless nickel / gold plating properties were tested using the dry films prepared in Examples and Comparative Examples, and immersion or peeling was observed visually after the electroless nickel / gold plating. As a result, when there is no liquid penetration or peeling observed after the electroless nickel / gold plating, it is "0K", and when there is liquid penetration or peeling which is observed by the naked eye after electroless nickel / gold plating. Indicated by "NG" is shown in Table 2.
【표 2】Table 2
Figure imgf000034_0001
상기 표 2에 나타난 바와 같이, 상기 실시예 및 비교예의 감광성 수지 조성물을 이용하여 얻어진 드라이 필름은 동일한 두께에서 유사한 '라미네시션 후 채움성 '이나 '현상성 (35°C)'을 나타내지만, 상기 실시예의 감광성 수지 조성물을 이용하여 제조된 드라이 필름이 비교예의 경우보다 높은 접착력 , 우수한 굴곡성， 우수한 납내열성 , 상대적으로 낮은 열팽창계수， 높은 고온 내습성, 높은 탄성 및 우수산 내도금성을 갖는다는 점이 확인되었다.
Figure imgf000034_0001
As shown in Table 2, the dry film obtained by using the photosensitive resin compositions of the above Examples and Comparative Examples shows similar 'post-lamination filling' or 'developing (35 ° C)' at the same thickness, Of the above embodiment It was confirmed that the dry film prepared by using the photosensitive resin composition had higher adhesion, better bendability, better lead heat resistance, relatively lower coefficient of thermal expansion, higher high temperature moisture resistance, higher elasticity and excellent acid plating resistance than the comparative example.

Claims

【특허청구범위】 [Patent Claims]
【청구항 1】  [Claim 1]
하기 화학식 1의 반복 단위를 포함하는 폴리아믹산:  A polyamic acid comprising a repeating unit of formula
[화학식 1]  [Formula 1]
Figure imgf000036_0001
Figure imgf000036_0001
상기 화학식 에서，  In the above formula,
Xi 은 4가의 유기기이고，  Xi is a tetravalent organic group,
X 는 방향족 고리를 포함하는 3가 또는 4가의 유기기이고， n은 0 또는 1인 정수이고,  X is a trivalent or tetravalent organic group containing an aromatic ring, n is an integer of 0 or 1,
Pi 및 ^는 서로 같거나 다를 수 있으며， 이미다졸일기를 포함하는 유 7 작용기이다. And Pi ^ may be the same or different from each other, an organic functional group 7, which comprises the imidazole group.
【청구항 2】 [Claim 2]
제 1항에 있어서,  The method of claim 1,
상기 ¾ 는 하기 화학식 11 내지 15로 이루어진 군에서 선택된 하나의 4가 유기기이거나,  ¾ is one tetravalent organic group selected from the group consisting of Formulas 11 to 15,
하기 화학식 16 내지 20으로 이루어진 군에서 선택된 하나의 3가 유기기인 폴리아믹산:  A polyamic acid which is one trivalent organic group selected from the group consisting of the following Chemical Formulas 16 to 20:
[화학식 11]  [Formula 11]
Figure imgf000036_0002
Figure imgf000036_0002
[화학식 12]
Figure imgf000037_0001
[Formula 12]
Figure imgf000037_0001
상기 화학식 12에서, 은 직접결합, -0-, -CO-, -S -， -S02-, C(CH3)2-, -C(CF3)2-, -C0NH-, -COO—, -(CH2)nl -, -0(CH2)n20—， 또는 0C0(CH2)n30C0—이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이고, In Chemical Formula 12, is a direct bond, -0-, -CO-, -S-, -S0 2- , C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -COO— , -, and -0 (CH 2) n2 0-, or 0C0 (CH 2) n3 0C0-, and wherein nl, n2 and n3 is an integer from 1 to 10, - (CH 2) nl
[화학식 13]  [Formula 13]
Figure imgf000037_0002
Figure imgf000037_0002
상기 화학식 13에서, Y2 및 Υ3는 서로 같거나 다를 수 있으며， 각각 직접결합, -0-, -CO-, -S-, -S02-, -C(CH3)2-, -C(CF3)2-, -C0NH-, -C00-, -In Chemical Formula 13, Y 2 and Υ 3 may be the same as or different from each other, and a direct bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -C00-,-
(CH )ni-, -0(CH2)n2( 또는 -0C0(CH2)n30C0—이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이고， (CH) ni-, -0 (CH 2 ) n2 (or -0C0 (CH 2 ) n3 0C0—, wherein nl, n2 and n3 are each an integer of 1 to 10,
[화학식 14]  [Formula 14]
Figure imgf000037_0003
Figure imgf000037_0003
상기 화학식 14에서， Y4, Υ5 및 Υ6는 서로 같거나 다를 수 있으며 , 각각 직접결합, -0-, -CO-, -S -， -S02-, -C(CH3)2-, -C(CF3)2-. -C0NH-, - COCK -(CH2)ni-, —0(CH2)n20-, 또는 — 0C0(CH2)n30C0-이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이고, In Formula 14, Y 4 , Υ 5 and Υ 6 may be the same as or different from each other, and a direct bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- . -C0NH-,-COCK-(CH 2 ) n i-, —0 (CH 2 ) n2 0-, or — 0C0 (CH 2 ) n3 0C0-, wherein nl, n2 and n3 are each an integer from 1 to 10 ego,
[화학식 15] [Formula 15]
Figure imgf000038_0001
Figure imgf000038_0001
상기 화학식 17에서， 은 직접결합， -0-, -CO—， -S-, -S02-, - C(CH3)2-, -C(CF3)2-, -C0NH-, -C00-, _(CH2)nl―, -0(CH2)n20_, 또는 - 0C0(CH2)n30C0-이고， 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이고, In Formula 17, is a direct bond, -0-, -CO—, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -C00 -, _ (CH 2) nl - , and 0C0 (CH 2) n3 0C0-, and wherein nl, n2 and n3 is an integer from 1 to 10, -, -0 (CH 2) n2 0_, or
[화학식 18]  [Formula 18]
Figure imgf000038_0002
Figure imgf000038_0002
상기 화학식 18에서, Y2 및 Υ3는 서로 같거나 다를 수 있으며 , 각각 직접결합, -0-, -CO—, -S-, -S02-, ᅳ C(CH3)2—， — C(CF3)2-, -C0NH -， -C00-, - (CH2)nr, -0(CH2)n20-, 또는 -0C0(CH2)n30C0—이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이고, In Chemical Formula 18, Y 2 and Υ 3 may be the same as or different from each other, and a direct bond, -0-, -CO—, -S-, -S0 2- , ᅳ C (CH 3 ) 2 — ， — C (CF 3 ) 2- , -C0NH-, -C00-,-(CH 2 ) nr, -0 (CH 2 ) n2 0-, or -0C0 (CH 2 ) n3 0C0—, wherein nl, n2 and n3 Are each an integer of 1 to 10,
[화학식 19]
Figure imgf000039_0001
[Formula 19]
Figure imgf000039_0001
상기 화학식 19에서， Y4, Υ5 및 Υ6는 서로 같거나 다를 수 있으며， 각각 직접결합, -0—, -CO-, -S-, -S02-, -C(CH3)2—， -C(CF3)2-, -C0NH-, - COCK — (CH2)nl―, -0(CH2)n20-, 또는 -0C0(CH2)n30C()-이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이고, In Formula 19, Y 4 , Υ 5 and Υ 6 may be the same as or different from each other, and a direct bond, -0—, -CO-, -S-, -S0 2- , -C (CH 3 ) 2 — , -C (CF 3) 2 - , -C0NH-, - COCK - (CH 2) nl -, -0 (CH 2) n2 0-, or -0C0 (CH 2) n3 0C ( ) - , and wherein nl , n2 and n3 are each an integer of 1 to 10,
[화학식 20]  [Formula 20]
Figure imgf000039_0002
Figure imgf000039_0002
【청구항 3】 [Claim 3]
제 1항에 있어서，  The method of claim 1,
상기 ！ 및 p2 각각이 카보닐기 (carbonyl group)을 포함하고 말단에 이미다졸일기가 결합된 작용기를 포함하는， 폴리아믹산. The polyamic acid, wherein each of！ and p 2 includes a carbonyl group and a functional group bonded to an imidazolyl group at its terminal.
【청구항 4】 [Claim 4]
저 U항에 있어서,  In that U term,
상기 및 P2는 각각 하기 화학식 2의 작용기인 폴리아믹산:  Wherein and P2 are each a polyamic acid which is a functional group of the formula:
[화학식 2]  [Formula 2]
— ( i)a-( 2)b— Y - (i) a - (2 ) b- Y
상기 화학식 2에서,  In Chemical Formula 2,
또는
Figure imgf000039_0003
a는 0 또는 1이고, or
Figure imgf000039_0003
a is 0 or 1,
R2는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬렌기이고， b는 0 또는 1이고, R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms, b is 0 or 1,
Y는 탄소수 1내지 3의 알킬기로 치환 또는 비치환된 이미다졸일기이다ᅳ  Y is an imidazolyl group unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms.
【청구항 5] [Claim 5]
제 1항에 있어서，  The method of claim 1,
상기 Xi 는 하기 화학식 21 내지 35로 이루어진 군에서 선택된 하나의 4가 유기기인 폴리아믹산:  The Xi is a polyamic acid which is one tetravalent organic group selected from the group consisting of Formulas 21 to 35:
[화학식 21]  [Formula 21]
Figure imgf000040_0001
Figure imgf000040_0001
상기 화학식 22에서， ^ 은 단일결합， — 0-， -CO-, -S-, -S02-, - C(CH3)2-, -C(CF3)2-, -C0NH-, -C00-, -(CH2)nl -, -0(CH2)n20-, 또는 - 0C0(CH2)n30C0-이고, 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이고， In Formula 22, ^ is a single bond, — 0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-,- and 0C0 (CH 2) n3 0C0-, and wherein nl, n2 and n3 is an integer from 1 to 10, - C00-, - (CH 2 ) nl -, -0 (CH 2) n2 0-, or
[화학식 23]  [Formula 23]
Figure imgf000040_0002
Figure imgf000040_0002
상기 화학식 23에서， Y2 및 Υ3는 서로 같거나 다를 수 있으며， 각각 단일결합， — 0—， -CO-, -S-, -S02-, -C(CH3)2-, -C(CF3)2-, -C0NH-, -C00-, -In Formula 23, Y 2 And Υ 3 It may be the same or different from each other, each a single bond, — 0—, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -C00-,-
(CH2)n厂, -0(CH2)n20-, 또는 -0C0(CH2)n30C0-이고, 상기 nl, n2 및 η3는 각각 1 내지 10의 정수이고, [화학식 24] (CH 2 ) n厂, -0 ( CH 2 ) n2 0-, or -0C0 (CH 2 ) n3 0C0-, wherein nl, n2 and η3 are each an integer from 1 to 10, [Formula 24]
Figure imgf000041_0001
Figure imgf000041_0001
상기 화학식 24에서， Y4, Υ5 및 Υ6는 서로 같거나 다를 수 있으며, 각각 단일결합， -0—， -CO-, -S-, -S02-, -C(CH3)2-, — C(CF3)2— , -C0NH-, - C00-, — (CH2)nl -， -0(CH2)n20-, 또는 -0C0(CH2)n30C0—이고， 상기 nl, n2 및 n3는 각각 1 내지 10의 정수이고， In Formula 24, Y 4 , Υ 5 and Υ 6 may be the same as or different from each other, and each of a single bond, -0—, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , - C (CF 3) 2 -, -C0NH-, - C00-, - (CH 2) nl -, -0 (CH 2) n2 is 0-, or -0C0 (CH 2) n3 0C0-, wherein nl , n2 and n3 are each an integer of 1 to 10,
[화학식 25]  [Formula 25]
Figure imgf000041_0002
상기 화학식 26 및 27에서， *는 작용기에서의 결합점 (bondi point)을 의미하며，
Figure imgf000042_0001
Figure imgf000041_0002
In Chemical Formulas 26 and 27, * means a bond point in the functional group,
Figure imgf000042_0001
[화학식 30] [Formula 30]
Figure imgf000042_0002
Figure imgf000042_0002
[화학식 31]
Figure imgf000042_0003
[Formula 31]
Figure imgf000042_0003
[화학식 33]
Figure imgf000043_0001
[Formula 33]
Figure imgf000043_0001
[화학식 34] [Formula 34]
Figure imgf000043_0002
Figure imgf000043_0002
[화학식 35]
Figure imgf000043_0003
[Formula 35]
Figure imgf000043_0003
【청구항 6】 [Claim 6]
제 1항에 있어서,  The method of claim 1,
하기 화학식 3의 반복 단위를 더 포함하는 폴리아믹산: [화학식 3]
Figure imgf000043_0004
A polyamic acid further comprising a repeating unit of Formula 3:
Figure imgf000043_0004
상기 화학식 3에서，  In Chemical Formula 3,
¾은 4가의 유기기이고, 는 2가의 유기기이다. 【청구항 7】  ¾ is a tetravalent organic group and is a divalent organic group. [Claim 7]
저) 6항에 있어서,  I) according to claim 6,
상기 화학식 1의 반복 단위 0.1 내지 50mol%: 및 상기 화학식 3의 반복 단위 50 내지 99.9 mol%를 포함하는 폴리아믹산. 0.1 to 50 mol% of the repeating unit of Formula 1: And Polyamic acid containing 50 to 99.9 mol% of the repeating unit of Formula 3.
【청구항 8】 [Claim 8]
제 1항에 있어서，  The method of claim 1,
중량평균분자량이 5,000 내지 200， 000인 폴리아믹산.  Polyamic acid having a weight average molecular weight of 5,000 to 200, 000.
【청구항 9】 [Claim 9]
제 1항의 폴리아믹산을 포함하는 고분자 수지; 광가교제; 유기 용매; 및 광증합 개시제를 포함하는 감광성 수지 조성물.  A polymer resin comprising the polyamic acid of claim 1; Photocrosslinking agents; Organic solvents; And a photopolymerization initiator.
【청구항 10] [Claim 10]
제 9항에 있어서,  The method of claim 9,
상기 광가교제는 탄소간 이중결합을 포함하는 (메타)아크릴레이트계 화합물을 포함하는 감광성 수지 조성물.  The photocrosslinking agent is a photosensitive resin composition comprising a (meth) acrylate compound containing a carbon-to-carbon double bond.
【청구항 11】 [Claim 11]
제 9항에 있어서,  The method of claim 9,
상기 광증합 개시제는 아세토페논계 화합물, 비이미다졸계 화합물， 트리아진계 화합물 및 옥심계 화합물로 이루어진 군에서 선택된 1종 이상의 화합물을 포함하는 감광성 수지 조성물  The photoinitiator is a photosensitive resin composition comprising at least one compound selected from the group consisting of acetophenone compounds, biimidazole compounds, triazine compounds and oxime compounds
【청구항 12】 [Claim 12]
제 9항에 있어서，  The method of claim 9,
상기 고분자 수지의 고형분 농도는 감광성 수지 조성물 증 총 증량에 대하여 15 내지 90 중량 %인 감광성 수지 조성물.  Solid content concentration of the polymer resin is 15 to 90% by weight based on the total increase in the photosensitive resin composition.
【청구항 13] [Claim 13]
제 9항에 있어서,  The method of claim 9,
열가교제， 경화 촉진제, 광가교 증감제, 경화 촉진제， 인계 난연제， 소포제, 레벨링제 및 겔 방지제로 이루어진 군에서 선택된 1종 이상의 첨가제를 더 포함하는 감광성 수지 조성물. At least one selected from the group consisting of thermal crosslinking agents, curing accelerators, photocrosslinking sensitizers, curing accelerators, phosphorus-based flame retardants, antifoaming agents, leveling agents and gel inhibitors The photosensitive resin composition further containing an additive.
【청구항 14】 [Claim 14]
저 19항의 감광성 수지 조성물의 경화물을 포함하
Figure imgf000045_0001
Including the hardened | cured material of the photosensitive resin composition of Claim 19
Figure imgf000045_0001
【청구항 15] [Claim 15]
제 14항에 있어서，  The method of claim 14,
상기 경화물은, 하기 화학식 1-1의 반복 단위를 포함하는 폴리아믹산과 광가교제의 가교 반웅물을 포함하는 드라이 필름:  The cured product, a dry film comprising a cross-linked semi-aungmul of a polyamic acid and an optical crosslinking agent comprising a repeating unit of the formula 1-1:
[화학식 1-1]  [Formula 1-1]
Figure imgf000045_0002
Figure imgf000045_0002
상기 화학식 1-1에서,  In Chemical Formula 1-1,
Xj 은 4가의 유기기이고，  Xj is a tetravalent organic group,
X2 는 방향족 고리를 포함하는 3가 또는 4가의 유기기이고， n은 0 또는 1인 정수이고， X 2 is a trivalent or tetravalent organic group containing an aromatic ring, n is an integer of 0 or 1,
Pi 및 P2는 서로 같거나 다를 수 있으며， 이미다졸일기를 포함하는 유기 작용기이다. Pi and P 2 may be the same as or different from each other, and are organic functional groups including an imidazolyl group.
【청구항 16】 [Claim 16]
제 14항에 있어서,  The method of claim 14,
회로 기판용 보호 필름, 회로 기판의 베이스 필름， 회로 기판의 절연층， 반도체의 층간 절연막 또는 솔더 레지스트에 사용되는 드라이 필름  Dry film used for the protective film for a circuit board, the base film of a circuit board, the insulating layer of a circuit board, the interlayer insulation film of a semiconductor, or a soldering resist.
【청구항 17】 [Claim 17]
제 14항의 드라이 필름을 포함하는 회로기판. 2013/165211 A circuit board comprising the dry film of claim 14. 2013/165211
【청구항 18】 [Claim 18]
제 17항에 있어서,  The method of claim 17,
상기 회로기판은 다층 프린트 배선판, 가용성 회로기판 또는 연성 회로기판인 회로기판.  The circuit board is a multilayer printed wiring board, a fusible circuit board or a flexible circuit board.
PCT/KR2013/003864 2012-05-03 2013-05-03 Novel polyamic acid, photosensitive resin composition, dry film and circuit board WO2013165211A1 (en)

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