WO2011145828A2 - Printed circuit board including a dam for underfills, and method for manufacturing same - Google Patents

Printed circuit board including a dam for underfills, and method for manufacturing same Download PDF

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Publication number
WO2011145828A2
WO2011145828A2 PCT/KR2011/003466 KR2011003466W WO2011145828A2 WO 2011145828 A2 WO2011145828 A2 WO 2011145828A2 KR 2011003466 W KR2011003466 W KR 2011003466W WO 2011145828 A2 WO2011145828 A2 WO 2011145828A2
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WO
WIPO (PCT)
Prior art keywords
group
substrate
acid
under
printed circuit
Prior art date
Application number
PCT/KR2011/003466
Other languages
French (fr)
Korean (ko)
Other versions
WO2011145828A3 (en
Inventor
최병주
정우재
최보윤
이광주
정민수
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201180025037.4A priority Critical patent/CN102906867B/en
Priority to US13/699,275 priority patent/US9865480B2/en
Priority to JP2013511100A priority patent/JP2013534714A/en
Priority claimed from KR1020110044011A external-priority patent/KR101450727B1/en
Publication of WO2011145828A2 publication Critical patent/WO2011145828A2/en
Publication of WO2011145828A3 publication Critical patent/WO2011145828A3/en

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    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H—ELECTRICITY
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
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    • H01L2224/27011—Involving a permanent auxiliary member, i.e. a member which is left at least partly in the finished device, e.g. coating, dummy feature
    • H01L2224/27013—Involving a permanent auxiliary member, i.e. a member which is left at least partly in the finished device, e.g. coating, dummy feature for holding or confining the layer connector, e.g. solder flow barrier
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    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
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    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
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    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/818—Bonding techniques
    • H01L2224/81801—Soldering or alloying
    • H01L2224/81815—Reflow soldering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/83007—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector involving a permanent auxiliary member being left in the finished device, e.g. aids for holding or protecting the layer connector during or after the bonding process
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    • H01—ELECTRIC ELEMENTS
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    • H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
    • H01L2224/83102—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus using surface energy, e.g. capillary forces
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    • H01—ELECTRIC ELEMENTS
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    • H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
    • H01L2224/83104—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus by applying pressure, e.g. by injection
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    • H01L2224/92—Specific sequence of method steps
    • H01L2224/921—Connecting a surface with connectors of different types
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    • H01L2224/92122—Sequential connecting processes the first connecting process involving a bump connector
    • H01L2224/92125—Sequential connecting processes the first connecting process involving a bump connector the second connecting process involving a layer connector
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L24/80 - H01L24/90
    • H01L24/92—Specific sequence of method steps
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
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    • H01—ELECTRIC ELEMENTS
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    • H01L2924/013—Alloys
    • H01L2924/014—Solder alloys
    • 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
    • H05K2201/09—Shape and layout
    • H05K2201/09818—Shape or layout details not covered by a single group of H05K2201/09009 - H05K2201/09809
    • H05K2201/09909—Special local insulating pattern, e.g. as dam around component
    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/341—Surface mounted components
    • H05K3/3431—Leadless components
    • H05K3/3436—Leadless components having an array of bottom contacts, e.g. pad grid array or ball grid array components

Definitions

  • Printed circuit board including under-fill dam and method for manufacturing same
  • the present invention relates to a printed circuit board including an under-fill dam and a manufacturing method thereof, and more particularly to a printed circuit board including an under-fill dam using a dry film type solder resist. .
  • the IC mounting method is a direct IC such as surface mount.
  • substrate and packaging using a liquid resin is mainly used (under-fill process).
  • This underfill process is a method for solving the thermal mechanical fatigue problem. Specifically, the inorganic particles are laminated to a polymer material having excellent adhesion such as epoxy resin to have a value close to the thermal expansion coefficient of the solder, and then the chip and the printed circuit. It means the process of filling in the gap between the substrates : The polymer composite material in which the inorganic particles are used at this time is called under-fill.
  • the underfill material generally known is in liquid form, there is a problem that the underfill with high flowability protrudes into an unwanted portion, causing unnecessary contamination or product volume, or making high density mounting difficult.
  • a method of forming a dam called a dam around the device has been used.
  • Previously known dams are mainly formed by a method using a flaky material or a liquid solder resist (for example, Japanese Patent Application Laid-Open No. 1996-325476, etc.) formed by punching, but conventional dam formation by liquid solder resist The method has a large thickness variation to meet the high-density mounting of the IC, There is a problem that the adhesive (liquid encapsulant) leaks, and the dam cannot be formed uniformly when the thickness of the dam becomes minute.
  • a liquid solder resist for example, Japanese Patent Application Laid-Open No. 1996-325476, etc.
  • the present invention is to provide a printed circuit board comprising an under-fill dam having excellent mechanical properties and having a fine and uniform thickness. Moreover, this invention is providing the manufacturing method of the said printed circuit board.
  • the present invention includes an under-fill dam formed along an outer edge of a substrate, wherein the under-fill dam comprises: an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Thermosetting binder resins; And it provides a printed circuit board comprising a dry film solder resist comprising a dried or cured product of the photosensitive resin composition comprising a pigment.
  • the under-fill dam comprises: an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Thermosetting binder resins; And it provides a printed circuit board comprising a dry film solder resist comprising a dried or cured product of the photosensitive resin composition comprising a pigment.
  • the present invention also provides an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Photoinitiators; Thermosetting binder resins; Stacking a dry film comprising a dried or cured product of the photosensitive resin composition comprising an organic solvent and a pigment on a substrate; Exposing a dry film on an outer edge portion of the substrate; And cleaning the exposed dry film.
  • the under-fill dam formed along the outer edge of the substrate, the under-fill dam, acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Thermosetting binder resins; And a dry film solder resist comprising a dried or cured product of the photosensitive resin composition comprising a pigment.
  • an under-fill dam having a very thin and uniform thickness can be formed.
  • the under-fill dam exhibits excellent mechanical properties, it is possible to achieve a certain level of height and strength even with a thin thickness, thereby preventing the leakage of the under-fill material injected or layered on the printed circuit board.
  • the under-fill dam which is formed at the outer edge of the printed circuit board, refers to a structure or a portion of the structure that prevents the leakage of material injected between the substrate and the semiconductor chip in the under-fill process.
  • the printed circuit board may include a substrate, and the under-fill dam may be formed along an outer edge of the substrate.
  • the printed circuit board may include an electrode pad formed on the substrate; A solder bump formed on the electrode pad; And a semiconductor chip flip-chip coupled through the solder bumps. Details of the electrode pad, the solder bumps, and the semiconductor chip are not particularly limited, and a configuration commonly known to be applicable to a printed circuit board may be applied.
  • the under-fill dam is for preventing the leakage of the under-fill material filled between the substrate and the semiconductor chip, and is specifically positioned between the outer edge of the substrate and the outer edge of the semiconductor chip. It serves to prevent the under-fill material from spilling out of the substrate.
  • the under-fill dam may have a height greater than or equal to the distance between the substrate and the semiconductor chip, for example, the under-fill dam formed on the substrate
  • the semiconductor chip may be formed to have the same height as the outermost surface of the semiconductor chip (the surface farthest from the substrate).
  • the under-fill dam may be a variety of colors depending on the color of the pigment or other materials used, for example, may be white, yellow, green, black or red.
  • the detection power is superior to other colors in AOI (Automated Optical Inspection) equipment, which is an optical device, compared to other colors because of the property of reflecting light.
  • AOI Automatic Optical Inspection
  • the under-fill dam may have a different color from the substrate, a solder resist that may be selectively formed on the substrate, or another structure in the printed circuit board. In this way, as the under-fill dam has a different color from the substrate or other solder resist, it is easy to detect and determine the appearance defect.
  • the under-fill dam is formed using a dry film solder resist prepared from a photosensitive resin composition of a specific component, the under-fill dam may have a thickness and uniformity which are not easy to implement by a previously known method. Specifically, the under-fill dam is 10 to 20 ⁇ , preferably 10 to
  • It can have a thickness of 15 ⁇ and the thickness error (difference between the mean value and the maximum / minimum value) can be within 3 / t.
  • the dry film soldering resist manufactured can exhibit the outstanding developability, especially alkali developability, and can easily form a dam with a fine pattern formation or a thin thickness.
  • the cured product of the photosensitive resin composition is a photocured product of the acid-modified oligomer and photopolymerizable monomer; Thermosetting of the acid-modified oligomer and thermosetting binder resin; And pigments.
  • the non-exposed part was developed with an alkaline developer, and the remaining part was thermally cured.
  • a portion of the acid-modified oligomer (eg, carboxyl group (-COOH), etc.) may react to form a crosslinked structure. Accordingly, in the dry film solder resist obtained by using the photosensitive resin composition, each component can form a network structure by crosslinking in the thermosetting or photocuring process, thereby achieving a higher degree of crosslinking. Accordingly, the under-fill formed using the dry film solder resist may have excellent dimensional stability, heat resistance, strength or other mechanical properties.
  • the photosensitive resin composition may include an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Thermosetting binder resins; And a pigment, and may further include a photoinitiator and an organic solvent.
  • the photosensitive resin composition may optionally further include additives such as a thermosetting binder resin curing agent, a thermosetting binder catalyst, a filler, a leveling agent, and the like.
  • additives such as a thermosetting binder resin curing agent, a thermosetting binder catalyst, a filler, a leveling agent, and the like.
  • the photosensitive resin composition includes a carboxyl group (-COOH) and an acid-modified oligomer having a photocurable functional group.
  • acid-modified oligomers can form crosslinks with other components of the resin composition, such as photopolymerizable monomers and / or thermosetting binder resins, by photocuring, and make the resin compositions, including carboxyl groups, have alkali developability. .
  • Such acid-modified oligomers are oligomers having a carboxyl group and a photocurable functional group, for example, a curable functional group having an acrylate group or an unsaturated double bond in the molecule, and all components previously known to be usable in the photocurable resin composition are different.
  • the main chain of the acid-modified ligomer may be a novolac epoxy or polyurethane, and may be used as the acid-modified oligomer having a carboxyl group and an acrylate group introduced into the main chain.
  • the photocurable functional group may preferably be an acrylate group, wherein the acid denaturation
  • An oligomer can be obtained as an oligomer form by copolymerizing the polymerizable monomer which has a carboxyl group, and the monomer containing an acrylate type compound etc. More specifically, specific examples of the acid-modified oligomer usable in the resin composition include the following components.
  • ethylenically unsaturated groups such as vinyl groups, allyl groups, (meth) acryloyl groups, epoxy groups, acid chlorides, and the like, as part of the copolymer of the unsaturated carboxylic acid (a) and the compound (b) having a unsaturated double bond
  • Carboxyl group-containing photosensitive resin obtained by reacting the compound which has a semi-asymmetric group of, for example, glycidyl (meth) acrylate and adding an ethylenically unsaturated group as a pendant;
  • Carboxyl group-containing photosensitive resin obtained by reacting unsaturated carboxylic acid (a) and reacting saturated or unsaturated polybasic anhydride (d), such as phthalic anhydride, tetrahydrophthalic anhydride, and nuxahydrophthalic anhydride, with the produced
  • diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds (k) such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarboxes; Diol compounds such as carbonate polyols, polyether polyols, polyester polys, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adducts, diols, phenolic hydroxyl groups and compounds having alcoholic hydroxyl groups ( carboxyl group-containing urethane resin obtained by addition reaction of m);
  • diisocyanate (j) bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, Obtained by the polyaddition reaction of the (meth) acrylate of bifunctional epoxy resins, such as a biphenol type epoxy resin, or its partial acid anhydride modified substance (II), a carboxyl group-containing dialcohol compound (k), and a diol compound (m) Photosensitive carboxyl group-containing urethane resins;
  • One isocyanate group or one or more isocyanate groups in a molecule such as an equimolar semi-flour of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin (7) or (8).
  • Carboxyl group-containing urethane resin which added the compound which has a (meth) acryloyl group, and was terminal (meth) acrylated;
  • Carboxyl group-containing photosensitive resin obtained by introducing an unsaturated double bond into the reaction product of a bisepoxy compound and bisphenols, and then reacting saturated or unsaturated polybasic anhydride (d);
  • Novolak-type phenol resins alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and / or ethylene carbonate, propylene carbon Saturated or unsaturated polybasic acid in the reaction product obtained by reacting unsaturated monocarboxylic acid (h) with reaction product with cyclic carbonates, such as carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate Carboxyl group-containing photosensitive resin obtained by reacting anhydride (d);
  • the isocyanate group-containing compound used for the resin synthesis is a diisocyanate containing no benzene ring
  • the polyfunctional and bifunctional epoxy resins used for the synthesis of the resins are linear compounds having bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton or bixylenol skeleton, or hydrogenated compounds thereof, the flexibility of DFSR, etc.
  • the acid-modified oligomer components usable preferably can be obtained.
  • the modified product of the resins of the above (7) to (10) is preferable for the bending including the urethane bond in the main chain.
  • the photosensitive resin composition comprises an acid-modified oligomer, 10 to 80 parts by weight 0 /., Preferably 15 to 75 parts by weight 0/0, more preferably from 25 to 65% by weight It may include. If the content of the acid-modified oligomer is too small, developability is lowered, the strength of the film is lowered, if too large, the composition is excessively developed
  • the acid value of the acid-modified oligomer may be 40 to 120 mgKOH / g. If the acid value of the acid-modified oligomer is less than 40 mgKOH / g, alkali development may not be easy. If the acid value is more than 120 mgKOH / g, the exposed portion may be dissolved by a developer, so that the line becomes thinner than necessary. In some cases, it is not preferable because it dissolves and peels off with a developer without distinguishing between the exposed portion and the unexposed portion, which makes it difficult to form a normal resist pattern. Photopolymerizable monomer
  • the photosensitive resin composition may include a photopolymerizable monomer.
  • a photopolymerizable monomer By including such a photopolymerizable monomer, it is possible to form a constant cured product or a crosslinked structure during light irradiation.
  • Such a photopolymerizable monomer may not only impart photocurability to the composition, but may also serve to adjust the viscosity to be suitable for various coating methods or to impart proper solubility in aqueous alkali solution.
  • photopolymerizable monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, or dipentaerythritol pentaacrylate ⁇ :
  • Water-soluble acrylate compounds such as polyethylene glycol diacrylate and polypropylene glycol diacrylate;
  • Polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate or dipentaerythrate;
  • Polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modified product of the hydroxy group-containing acrylate compound;
  • Bisphenol A diglycidyl ether, hydrogenated bisphenol Epoxy acrylate compounds which are (meth) acrylic acid adducts of A diglycidyl ether or phenol novolac epoxy resins;
  • the polyfunctional (meth) acrylate type compound which has two or more (meth) acryloyl groups in 1 molecule is preferable, Pentaerythritol triacrylate- trimethylol propane triacrylate, and dipentaerythrite is especially preferable. Hexaacrylate, caprolactone modified ditrimethylol propane tetraacrylate, etc. are preferable. Moreover, DPEA-12 etc. of Nippon Chemical Co., Ltd. can be used as what is marketed.
  • the photosensitive resin composition may include 1 to 30% by weight of the photopolymerizable monomer described above. When the content of the photopolymerizable monomer is less than 1 weight 0 /., The photocuring may not be divided. If the content exceeds 30 weight 0 /., The film drying property or the physical properties of the film may be reduced. Photoinitiator
  • the photosensitive resin composition may include a photoinitiator.
  • photoinitiators serve to initiate radical photocuring, for example, in the exposed portion of the resin composition.
  • benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and its alkyl ether
  • Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1'dichloroacetophenone, and 4- (lt-butyldioxy-1-methylethyl) acetophenone
  • Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloroanthraquinone
  • Thioxanthones such as 2, 4- dimethyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro thioxanthone
  • Ketals such as acetophenone dimethyl ketal and benzyl dimethyl
  • Irugacure registered trademark
  • acyl phosphine oxides such as Rucillin (trademark) TPO by BASF Corporation and Irgacure 819 by Chivas Specialty Chemical Co., Ltd. can be mentioned as a preferable photoinitiator.
  • oxime ester is mentioned as a preferable photoinitiator.
  • Specific examples of oxime esters include 2- (acetyloxyiminomethyl) thioxanthene-9-one, (1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (0-benzoyloxime ), And (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (7-acetyloxime)).
  • the photosensitive resin composition may include 0.1 to 10% by weight of the photoinitiator, preferably 1 to 5% by weight. When the content of the photoinitiator is too small, the photopolymerization reaction may not occur. If the content is too large, the resolution of the resin composition may be lowered or the reliability of the dry film produced may not be improved.
  • the photosensitive resin composition may also be selected from thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups. It may include a thermosetting binder resin having at least one functional group. Such thermosetting binders may crosslink with acid-modified oligomers and / or photopolymerizable monomers by thermosetting to secure the heat resistance or mechanical properties of a dry film solder resist or an under-fill dam.
  • thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups.
  • It may include a thermosetting binder resin having at least one functional group.
  • Such thermosetting binders may crosslink with acid-modified oligomers and / or photopolymerizable monomers by thermosetting to secure the heat resistance or mechanical properties of a dry film solder resist or an under-fill dam.
  • the thermosetting binder resin may have a softening point of about 70 to 100 ° C, thereby reducing the unevenness during lamination. Low softening points increase the tackiness of the DFSR and high flow rates can deteriorate.
  • a resin having two or more cyclic ether groups and / or cyclic thioether groups hereinafter referred to as cyclic (thio) ether groups
  • a bifunctional epoxy resin may be used.
  • Other diisocyanates or their bifunctional block isocyanates can also be used.
  • thermosetting binder having two or more cyclic (thio) ether groups in the molecule may be a compound having a 3, 4 or 5 membered cyclic ether group, or a cyclic thioether group either or two or more groups of two or more cyclic thioether groups.
  • the thermosetting binder may be a polyfunctional epoxy compound having at least two or more epoxy groups in a molecule, a polyfunctional oxetane compound having at least two or more oxetanyl groups in molecular weight, or episulf having two or more thioether groups in molecular weight. Feed resin and the like.
  • the said polyfunctional epoxy compound it is bisphenol, for example
  • a type epoxy resin hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin Resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group containing epoxy resin, rubber modified epoxy Resins, dicyclopentadiene phenolic epoxy resins, diglycidyl phthalate resins, heterocyclic epoxy resins, tetraglycidyl xylenoylethane resins, silicone-modified epoxy resins, epsilon -caprolactone-modified epoxy resins, and the like.
  • those in which atoms such as phosphorus are introduced into the structure may be used. have.
  • thermosetting these epoxy resins the adhesiveness of a cured film, the solder heat resistance, and the electroless-plating resistance round improve the characteristic.
  • polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxoxtanylmethoxy) methyl] ether, 1,4-bis [( 3-methyl-3-oxetanyl -dihydroxy-20) methyl] benzene, 1, 4-bis-ethyl-3-oxetanyl meteuk City) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, ( 3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) methylmethacrylate or oligomers thereof
  • oxetane alcohol and novolak resin poly (P-hydroxy styrene
  • YDCN-500-80P etc. of Kukdo Chemical Co., Ltd. can be used.
  • the photosensitive resin composition may include 1 to 30% by weight 0 /. Of the thermosetting binder resin. When the content of the thermosetting binder resin is less than 1% by weight, the mechanical properties of the dry film are lowered, and when it exceeds 30% by weight 0 /. Organic solvent
  • the photosensitive resin composition may be commonly used one or more organic solvents to dissolve each component or impart an appropriate viscosity.
  • organic solvents include ketones such as methyl ethyl ketone and cyclonucleanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; 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 monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol mono Glycol ethers such as ethyl ether (cellosolve); Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate,
  • Acetate esters such as dipropylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbyl; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Amides such as dimethylacetamide and dimethylformamide (DMF). These solvents can be used alone or as a mixture of two or more thereof.
  • the photosensitive resin composition may include about 5 to 50 wt% of the organic solvent.
  • the viscosity of the composition may be too large to reduce the coating property, and when the content is too large, the drying may not be good, resulting in deterioration or stickiness of the dry film solder resist sheet. .
  • pigment white 6 phosphorus titanium oxide may be used as a pigment.
  • Titanium oxide used as a white pigment is of rutile type and anatase type. In the case of the anatase type, the whiteness is superior to the rutile type, but since yellowing due to light may occur due to the optical activity, it is preferable to use the rutile type which has a low whiteness but does not have optical activity.
  • pigments include anthraquinone, isoindolinone, condensed azo, and benzimidazolone, for example pigment yellow 108.
  • Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Pigment Yellow 181, Pigment Yellow 193 and the like can be used.
  • Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5 : Solvent Green 20, Solvent Green 28, etc. may be used as the pigment when the color of the under-fill dam is represented as Green. have. However, in the case of a green pigment, since halogen is a problem, a combination of yellow and blue pigments is sometimes used to realize green.
  • carbon black When the color of the under-fill dam is to be expressed in black, carbon black, titanium black, creme oxide, iron oxide, aniline black, and perylene pigments may be used as the pigment.
  • Pigment Red 13 Pigment Red 32, Pigment Red 122, Pigment Red 177 Pigment Red 185, Pigment Red 226, Pigment Red. 246 and the like can be used.
  • the photosensitive resin composition is preferably 0/0, the pigment 0.01-10 increase may comprise from 1 to 5 parts by weight 0/0. If the content of the pigment is too small, visibility, hiding power may be lowered, and if the content is too large, mechanical properties such as heat resistance may be inferior.
  • the photosensitive resin composition may optionally further include the following components in addition to the above-described components.
  • the photosensitive resin composition may optionally further include a thermosetting binder resin curing agent that can increase the degree of curing of the thermosetting binder resin.
  • thermosetting binder resin curing agents include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like.
  • amine compound diaminodiphenylmethane, diethylenetriamine, triethylenetetraamine, diaminodiphenylsulfone, isophoronediamine and the like can be used.
  • Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid, nuxahydrophthalic anhydride, and methyl nucleohydrophthalic anhydride.
  • Examples of the amide compound include dicyandiamide, a diamide of linolenic acid, and a polyamide resin synthesized from ethylenediamine.
  • phenol type compound Polyhydric phenols, such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, a terpene diphenol; Phenol resins obtained by condensation of phenols with aldehydes, ketones or dienes; Phenol resins obtained by polycondensation of phenols, substituted biphenyls, substituted phenyls, and the like; Modified products of phenols and / or phenol resins; Halogenated phenols such as tetrabromobisphenol A and a brominated phenol resin; Other imidazoles, BF3-amine complexes, guanidine derivatives and the like can be used.
  • the photosensitive resin composition may further include 0.01 to 15% by weight of the thermosetting binder resin curing agent. If the content of the thermosetting binder resin curing agent is too small, the effect of increasing the degree of curing of the epoxy resin may be insignificant. If the content is too large, the physical properties of the dry film may be reduced.
  • thermosetting binder resin catalyst can improve the curing rate of the thermosetting binder resin.
  • thermosetting binder catalyst for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) - ⁇ , ⁇ -dimethylbenzylamine, 4-methoxy- ⁇ , ⁇ -dimethylbenzylamine, 4-methyl- ⁇ , ⁇ -dimethylbenzylamine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds such as triphenylphosphine, etc.
  • thermosetting catalyst of an epoxy resin or an oxetane compound may promote reaction of an epoxy group and / or an oxetanyl group, and a carboxyl group, and may be used individually or in mixture of 2 or more types.
  • the compound which also functions as these adhesive imparting agents can be used together with the said thermosetting binder catalyst.
  • the content of the thermosetting binder catalyst may be about 0.3 to 15 weight 0 / .about the total weight of the photosensitive resin composition, in terms of suitable thermosetting.
  • the filler plays a role of improving heat stability, dimensional stability by heat, and resin adhesion. In addition, it also serves as a constitution pigment by reinforcing the color.
  • Inorganic or organic layer fillers may be used as the filler, for example barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina ), Aluminum hydroxide, mica and the like can be used.
  • the content of the filler is preferably from about 5 to 50 parts by weight 0/0 relative to the total weight of the photosensitive resin composition. When used in excess of 50 parts by weight 0/0, it is undesirable high and the viscosity of the composition coating property may be degraded, or the falling down of the degree of cure.
  • the leveling agent serves to remove the popping or craters from the surface when the film is coated.
  • leveling agent examples include silicone, fluorine, and polymer.
  • leveling agent examples include BYK-380N, BYK-307, BYK-378, and BYK-350 of BYK-Chemie GmbH.
  • the content of the leveling agent is 0.05-10 weight 0 /. With respect to the whole increase of the said photosensitive resin composition.
  • the leveling agent is used in less than 0.05 weight 0 / ° , it is unsatisfactory to remove the popping or craters, there is a problem that a lot of bubbles occur when used in excess of 10 weight 0 /.
  • Dispersants serve to improve dispersion stability of fillers and pigments.
  • Dispersing agent Disperbyk-110, Disperbyk-162, Disperbyk-168, etc. of BYK-Chemie GmbH can be used, for example.
  • the content of the dispersant is preferably based on the total amount of photosensitive resin composition is 0.01 to 10 parts by weight 0/0. If the case where the dispersant is 0.01 0/0 is less than two minutes, without being dispersed layer, exceeding 10% by weight, it will affect the heat resistance and reliability.
  • an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Photoinitiators; Thermosetting binder resins; Stacking a dry film comprising a dried or cured product of the photosensitive resin composition comprising an organic solvent and a pigment on a substrate; Exposing a dry film on an outer edge portion of the substrate; And cleaning the exposed dry film.
  • a method of providing a printed circuit board may be provided.
  • an under-fill dam having a very thin and uniform thickness can be formed.
  • the under-fill dam exhibits excellent mechanical properties, it is possible to achieve a certain level of height and strength even with a thin thickness, and is thus injected or layered on a printed circuit board. Outflow of the under-fill material can be prevented, and damage to the under-fill dam or degradation of properties that can be issued on the under-fill process or the semiconductor manufacturing process can be minimized.
  • FIG. 1 is a schematic of a conventional underfill process, where the previously known underfill process includes an alignment and flux dispensing step, a solder bump reflow step, a flux cleaning ( Flux Cleaning step, and the Underfilling step.
  • the under-fill process aligns the chip element 1 on which the solder bumps 2 are formed and the substrate 4 on which the electrode pads 3 are formed, distributes the flux, and then reflows the solder bumps 2. And the flux is cleaned, and then the underfill 5 is filled between the chip element 1 and the substrate 4.
  • FIG. 2 schematically illustrates an under-fill process using an under-fill dam formed by using a dry film including a dried product or a cured product of the photosensitive resin composition described above.
  • the under-fill dam is formed at the outer edge portion of the chip element 1, it is possible to prevent leakage of the under-fill material 5 to be injected.
  • the under-fill dam may be formed by laminating a dry film obtained from the photosensitive resin composition of the specific component described above on a substrate and then undergoing exposure, development and cleaning steps.
  • the under-fill dam the step of preparing a dry film using the photosensitive resin composition; Laminating a dry film between the substrate and the chip element; Exposing the photo mask on the dry film to the desired dam pattern; Developing the dry film after exposure to remove unnecessary portions to form a desired dam pattern; And heat-curing after development to form a dam made of a dry film type solder resist.
  • the specific content about each component contained in the said photosensitive resin composition is as above-mentioned.
  • the coating or coating of the photosensitive resin composition a commonly known coating method such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer coater, gravure coater or spray coater may be used.
  • the drying temperature in the Aubon is preferably about 70 to 110 ° C.
  • the thickness of the photosensitive film formed of the photosensitive resin composition is preferably about 10 to 35 urn.
  • the dry film (the state in which the release film was removed) obtained as mentioned above is laminated
  • a vacuum laminator In the step of laminating the dry film from which the release film is removed, a vacuum laminator, a hot roll laminator, a vacuum press, or the like may be used.
  • Light sources that can be used in the exposing step include ultraviolet (UV) light, electron beams, X-rays, and the like, and the substrate is exposed to light (UV light) having a predetermined wavelength band.
  • the exposure may be selectively exposed with a photo mask, or may be directly pattern exposed with a laser direct exposure machine.
  • the carrier film peels off after exposure. Although exposure amount changes with coating film thickness, 0-1,000 mJ / cuf is preferable.
  • photocuring may occur to form a crosslinking bond between an acid-modified oligomer and a photopolymerizable monomer, and as a result, may not be removed by a subsequent phenomenon.
  • the non-exposed part can maintain the carboxy group as it is, and can be in an alkali developable state.
  • the dry film is developed to remove unnecessary portions to form a desired dam pattern.
  • immersion or spraying is usually used to immerse the developer.
  • an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines is used. After developing with an aqueous alkali solution, the solution is washed with water. By this phenomenon, only the film of the exposed portion may remain.
  • the residue may further be subjected to a post curing step.
  • the heat curing temperature is more than 100 ° C.
  • the cured product of such a photosensitive resin composition includes a photocured product of the acid-modified oligomer and the photopolymerizable monomer; Thermosetting of the acid-modified oligomer and thermosetting binder resin; And pigments.
  • the printed circuit board obtained by the manufacturing method may include an under-fill dam having a thickness of 10 to 20 an, preferably 10 to 15. The thickness error (difference between the average value and the maximum / minimum value) of such an under-fill dam may be within 3 degrees.
  • the method of manufacturing a printed circuit board forming an electrode pad on the substrate; Positioning solder bumps on the electrode pads; And flip chip bonding the semiconductor chip through the solder bumps.
  • the solder bumps may be positioned on the electrode pads while being bonded to the semiconductor chip, or may be firstly installed on the electrode pads and then coupled to the semiconductor chip.
  • the printed circuit board may include an electrode pad formed on the substrate; A solder bump formed on the electrode pad; And a semiconductor chip flip-chip coupled through the solder bumps.
  • the method of manufacturing the printed circuit board may further include injecting an underfill material between the substrate and the semiconductor chip to provide a printed circuit board filled with an under-fill material.
  • a printed circuit board including an under-fill dam having excellent mechanical properties and having a fine and uniform thickness can be provided.
  • FIG. 1 schematically illustrates a conventional underfill process.
  • FIG. 2 schematically shows the underfill process when an under-fill dam is formed on the substrate.
  • Example 3 A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that the prepared photosensitive resin composition was used.
  • Example 3 A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that the prepared photosensitive resin composition was used.
  • CCR-1235 of Nippon Gunpowder as an acid-modified oligomer 35 weight 0 /.
  • DPEA-12 of Kayarad as a photopolymerizable monomer
  • TPO as a photoinitiator
  • EPON- of Nippon Gunpowder as an epoxy resin 1020 to 13 wt. 0/0
  • the epoxy curing agent as dicyandiamide to 0.5 0/0
  • a 0.5 zero filler 2MI as epoxy catalyst by weight of pigment yellow 151.
  • a yellow photosensitive resin composition was prepared using a weight of 0 A and 15% by weight of DMF as a solvent.
  • a dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that the prepared photosensitive resin composition was used.
  • a printed circuit board having the same structure as in Example 1 was manufactured except that an under-fill dam was formed using the liquid solder resist disclosed in Japanese Patent Laid-Open No. 1996-325476.
  • the color of the comparative example is green, whereas in the case of the embodiment may have a variety of colors, such as white.
  • the comparative example is not only thick to form a thickness of about 1 mm and non-uniform due to the thickness variation, in the case of the embodiment can form a dam having a uniform thickness, even very thin dam of 10 to 15 m thickness is uniform It can be formed in thickness.
  • it is difficult to apply the flip chip due to the non-uniform thickness whereas in the embodiment, the thickness is uniform and thin so that the flip chip application is difficult. It is possible.
  • the detection power is lower, while in the embodiment, the detection power is excellent in AOI equipment.

Abstract

The present invention relates to a dam for underfills, which has excellent detectivity. For a dam which is formed in the shape of a fence around a chip to prevent the leakage of underfills filled between a substrate and the chip, a dam for underfills, which is composed of a dry-film-type solder resist, is provided.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
언더 -필용 댐을 포함하는 인쇄 회로 기판 및 이의 제조 방법  Printed circuit board including under-fill dam and method for manufacturing same
【기술분야】  Technical Field
본 발명은 언더 -필용 댐을 포함하는 인쇄 회로 기판 및 이의 제조 방법에 관한 것으로서， 보다 상세하게는 드라이 필름 타입의 솔더 레지스트를 이용한 언더 -필용 댐을 포함하는 인쇄 회로 기판 및 이의 제조 방법에 관한 것이다.  The present invention relates to a printed circuit board including an under-fill dam and a manufacturing method thereof, and more particularly to a printed circuit board including an under-fill dam using a dry film type solder resist. .
【배경기술】  Background Art
직접 회로 (IC)를 중심으로 한 소자의 보호를 위해, 에폭시 수지를 중심으로 각종 수지를 이용한 수지 포장이 행해지고 있고, 근래의 소형화와 경량화에 따라 IC 의 실장 방법은 표면실장이라고 불리는 직접 IC 등의 소자를 기판에 탑재하고 액상 수지를 이용하여 포장하는 방법이 주로 사용되고 있다 (Under-Fill 공정).  In order to protect devices centering on integrated circuits (ICs), resin packaging using various resins has been carried out mainly on epoxy resins. With the recent miniaturization and weight reduction, the IC mounting method is a direct IC such as surface mount. The method of mounting an element on a board | substrate and packaging using a liquid resin is mainly used (under-fill process).
이러한 언더 필 공정은 열적 기계적 피로 문제를 해결하기 위한 방법으로서, 구체적으로 에폭시 수지 등과 같이 접착력이 우수한 고분자 재료에 무기입자를 층진시켜 솔더의 열팽창 계수에 근접한 값을 갖도록 한 후， 이를 칩과 인쇄 회로 기판 사이의 름에 채워 넣어 주는 공정을 의미하며: 이때 사용되는 무기입자가 층진된 고분자 복합재료를 언더 필 (Under- fill)이라고 한다. This underfill process is a method for solving the thermal mechanical fatigue problem. Specifically, the inorganic particles are laminated to a polymer material having excellent adhesion such as epoxy resin to have a value close to the thermal expansion coefficient of the solder, and then the chip and the printed circuit. It means the process of filling in the gap between the substrates : The polymer composite material in which the inorganic particles are used at this time is called under-fill.
일반적으로 알려진 언더 필 재료는 액상 형태이기 때문에, 높은 유동성을 갖는 언더 필이 원하지 않는 부분에 돌출되어 불필요한 오염을 또는 제품 블량을 야기하거나 고밀도의 실장을 어렵게 하는 문제점이 있다. 이러한 문제점을 방지하기 위하여 소자 주위에 댐 (Dam)이라는 을타리를 형성하는 방식이 사용되고 있다.  Since the underfill material generally known is in liquid form, there is a problem that the underfill with high flowability protrudes into an unwanted portion, causing unnecessary contamination or product volume, or making high density mounting difficult. In order to prevent this problem, a method of forming a dam called a dam around the device has been used.
이전에 알려진 댐은 펀칭에 의해 성형된 박편 모양의 재료나 액상 솔더 레지스트 (예를 들어, 일본특허공개 제 1996-325476 호 등)를 이용한 방법으로 주로 형성되고 있으나, 종래 액상 솔더 레지스트에 의한 댐 형성 방식은 IC 의 고밀도 실장에 대웅하기에는 두께의 편차가 크고, 이로 인해 접착제 (액상 봉지제)가 누출되는 문제 등이 있고, 또한 댐의 두께가 단위로 미세화 되는 경우에는 균일하게 댐을 형성할 수 없다. Previously known dams are mainly formed by a method using a flaky material or a liquid solder resist (for example, Japanese Patent Application Laid-Open No. 1996-325476, etc.) formed by punching, but conventional dam formation by liquid solder resist The method has a large thickness variation to meet the high-density mounting of the IC, There is a problem that the adhesive (liquid encapsulant) leaks, and the dam cannot be formed uniformly when the thickness of the dam becomes minute.
이러한 액상 솔더 레지스트를 이용한 댐 형성 방법의 문제를 해결하기 위하여, 드라이 필름 형태의 솔더 레지스트를 사용하는 방법이 제안되었다. 예를 들어， JP1996-097341 또는 US2010-0116534 등의 문헌에 드라이 필름 레지스트를 이용하여 언더 필의 흐름을 방지하기 위한 댐을 제조하는 방법이 제시되어 있다. 그러나, 이전에 알려진 방법에 의하여도 댐의 두께를 미세화하는데 일정한 한계가 있어서 고밀도 집적 회로에 적용하기 어려웠으며, 얇은 두께를 구현하는 경우 일정 수준 이상의 높이를 갖는 댐을 형성할 수 없거나 매우 불균일한 댐이 형성되는 문제점이 있었다. In order to solve the problem of the dam formation method using the liquid solder resist, a method using a dry film type solder resist has been proposed. For example, in JP1996-097341 or US2010-0116534, a method of manufacturing a dam for preventing underfill flow using a dry film resist is disclosed. However, it is difficult to apply it to a high density integrated circuit because there is a certain limit in minimizing the thickness of the dam by the previously known method, and when a thin thickness is realized, a dam having a certain level or more cannot be formed or a very nonuniform dam. There was a problem that is formed.
【발명의 내용】 [Content of invention]
【해결하려는 과제】  [Problem to solve]
본 발명은 우수한 기계적 물성을 가지며 미세하고 균일한 두께를 갖는 언더 -필용 댐을 포함하는 인쇄 회로 기판을 제공하기 위한 것이다. 또한, 본 발명은 상기 인쇄 회로 기판의 제조 방법을 제공하기 위한 것이다.  The present invention is to provide a printed circuit board comprising an under-fill dam having excellent mechanical properties and having a fine and uniform thickness. Moreover, this invention is providing the manufacturing method of the said printed circuit board.
【과제의 해결 수단】  [Measures of problem]
본 발명은, 기판의 외측 테두리를 따라 형성된 언더 -필용 댐을 포함하고, 상기 언더 -필용 댐이, 카르복시기 (-COOH) 및 광경화 가능한 작용기를 갖는 산변성 올리고머; 광중합성 모노머; 열경화성 바인더 수지; 및 안료를 포함하는 감광성 수지 조성물의 건조물 또는 경화물을 포함하는 드라이 필름 솔더 레지스트를 포함하는 인쇄 회로 기판을 제공한다.  The present invention includes an under-fill dam formed along an outer edge of a substrate, wherein the under-fill dam comprises: an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Thermosetting binder resins; And it provides a printed circuit board comprising a dry film solder resist comprising a dried or cured product of the photosensitive resin composition comprising a pigment.
또한, 본 발명은 카르복시기 (-COOH) 및 광경화 가능한 작용기를 갖는 산변성 올리고머; 광중합성 모노머; 광개시제; 열경화성 바인더 수지; 유기 용매 및 안료를 포함하는 감광성 수지 조성물의 건조물 또는 경화물을 포함하는 드라이 필름을 기판 상에 적층하는 단계; 상기 기판의 외측 테두리 부위의 드라이 필름을 노광하는 단계; 및 상기 노광된 드라이 필름을 세정하는 단계를 포함하는 인쇄 회로 기판의 제보 방법을 제공한다.  The present invention also provides an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Photoinitiators; Thermosetting binder resins; Stacking a dry film comprising a dried or cured product of the photosensitive resin composition comprising an organic solvent and a pigment on a substrate; Exposing a dry film on an outer edge portion of the substrate; And cleaning the exposed dry film.
이하 발명의 구체적인 구현예에 따른 인쇄 회로 기판 및 이의 제조 방법에 관하여 보다 구체적으로 설명하기로 한다. 발명의 일 구현예에 따르면， 기판의 외측 테두리를 따라 형성된 언더 -필용 댐을 포함하고, 상기 언더 -필용 댐이, 카르복시기 (-COOH) 및 광경화 가능한 작용기를 갖는 산변성 올리고머; 광중합성 모노머; 열경화성 바인더 수지; 및 안료를 포함하는 감광성 수지 조성물의 건조물 또는 경화물을 포함하는 드라이 필름 솔더 레지스트를 포함하는 인쇄 회로 기판이 .제공될 수 있다. Hereinafter, a printed circuit board and a manufacturing method thereof according to a specific embodiment of the present invention will be described in more detail. According to one embodiment of the invention, the under-fill dam formed along the outer edge of the substrate, the under-fill dam, acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Thermosetting binder resins; And a dry film solder resist comprising a dried or cured product of the photosensitive resin composition comprising a pigment.
상기 특정한 작용기를 갖는 산변성 올리고머， 광중합성 모노머, 열경화성 바인더 수지 등의 성분을 포함하는 감광성 수지 조성물로부터 제조된 드라이 필름 솔더 레지스트를 이용하면, 매우 얇고 균일한 두께를 갖는 언더 -필용 댐을 형성할 수 있다. 특히, 이러한 언더 -필용 댐은 우수한 기계적 물성을 나타내기 때문에 얇은 두께로도 일정 수준 이상의 높이 및 강도를 구현할 수 있으며, 이에 따라 인쇄 회로 기판에 주입 또는 층진되는 언더-필 재료의 유출을 방지할 수 있고, 상기 언더-필 공정 또는 반도체 제조 공정 상에서 발행할 수 있는 언더 -필용 댐의 손상 또는 물성 저하 현상을 최소화할 수 있다. 상기 '언더 -필용 댐，은 인쇄 회로 기판의 외곽 테두리에 형성되어 언더-필 공정에서 기판과 반도체 칩 사이에 주입되는 재료의 유출을 방지하는 구조물 또는 기판 상의 일정 부위를 의마한다.  When using a dry film solder resist prepared from a photosensitive resin composition comprising an acid-modified oligomer having a specific functional group, a photopolymerizable monomer, a thermosetting binder resin, or the like, an under-fill dam having a very thin and uniform thickness can be formed. Can be. In particular, since the under-fill dam exhibits excellent mechanical properties, it is possible to achieve a certain level of height and strength even with a thin thickness, thereby preventing the leakage of the under-fill material injected or layered on the printed circuit board. In addition, it is possible to minimize damage or deterioration of properties of the under-fill dam that may be issued in the under-fill process or the semiconductor manufacturing process. The under-fill dam, which is formed at the outer edge of the printed circuit board, refers to a structure or a portion of the structure that prevents the leakage of material injected between the substrate and the semiconductor chip in the under-fill process.
한편, 상기 인쇄 회로 기판은 기판을 포함하고, 상기 기판의 외측 테두리를 따라서 상술한 언더 -필용 댐이 형성된 형태일 수 있다. 이러한 인쇄 회로 기판은 상기 기판 상에 형성된 전극 패드; 상기 전극 패드 상에 형성된 솔더 범프; 및 상기 솔더 범프를 매개로 플립 칩 결합된 반도체 칩을 포함할 수 있다. 상기 전극 패드, 솔더 범프 및 반도체 칩에 관한 구체적인 내용은 크게 제한되는 것은 아니며， 인쇄 회로 기판에 적용될 수 있는 것으로 통상적으로 알려진 구성을 적용할 수 있다.  The printed circuit board may include a substrate, and the under-fill dam may be formed along an outer edge of the substrate. The printed circuit board may include an electrode pad formed on the substrate; A solder bump formed on the electrode pad; And a semiconductor chip flip-chip coupled through the solder bumps. Details of the electrode pad, the solder bumps, and the semiconductor chip are not particularly limited, and a configuration commonly known to be applicable to a printed circuit board may be applied.
상술한 바와 같이, 상기 언더 -필용 댐은 기판과 반도체 칩 사이에 채워 넣는 언더-필 재료의 누출을 방지하기 위한 것으로서, 구체적으로 상기 기판의 외측 테두리와 반도체 칩의 외측 테두리 사이에 위치하여 주입되는 언더-필 재료가 기판 외부로 유출되는 것을 막는 역할을 한다.  As described above, the under-fill dam is for preventing the leakage of the under-fill material filled between the substrate and the semiconductor chip, and is specifically positioned between the outer edge of the substrate and the outer edge of the semiconductor chip. It serves to prevent the under-fill material from spilling out of the substrate.
이에, 상기 언더 -필용 댐은 기판과 반도체 칩 사이 간격 이상의 높이를 가질 수 있으며, 예를 들어, 상기 기판 상에 형성된 언더 -필용 댐은 상기 반도체 칩의 최외각 일면 (기판으로부터 가장 멀리 있는 면)과 동일한 높이가 되도록 형성될 수 있다. Thus, the under-fill dam may have a height greater than or equal to the distance between the substrate and the semiconductor chip, for example, the under-fill dam formed on the substrate The semiconductor chip may be formed to have the same height as the outermost surface of the semiconductor chip (the surface farthest from the substrate).
한편, 상기 언더 -필용 댐은 사용되는 안료 또는 다른 재료 들의 색상에 따라서 다양한 색상을 될 수 있으며, 예를 들어 백색, 황색， 녹색, 흑색 또는 적색일 수 있다. 특히， 상기 언더 -필용 댐의 색상이 백색 (White)일 경우, 빛을 반사하는 성질 때문에 다른 색상에 비해 광학장비인 AOI(Automated Optical Inspection) 장비에서 검출력이 다른 색깔에 비해 우수하다  On the other hand, the under-fill dam may be a variety of colors depending on the color of the pigment or other materials used, for example, may be white, yellow, green, black or red. In particular, when the color of the under-fill dam is white, the detection power is superior to other colors in AOI (Automated Optical Inspection) equipment, which is an optical device, compared to other colors because of the property of reflecting light.
그리고, 상기 언더 -필용 댐은 상기 기판, 상기 기판 상에 선택적으로 형성될 수 있는 솔더 레지스트 또는 인쇄 회로 기판 내의 다른 구조물과 상이한 색을 가질 수 있다. 이와 같이, 상기 언더 -필용 댐이 기판 또는 다른 솔더레지스트와 다른 색상을 가짐에 따라서, 외관 불량 유무를 용이하게 검출 및 판단할 수 있다.  In addition, the under-fill dam may have a different color from the substrate, a solder resist that may be selectively formed on the substrate, or another structure in the printed circuit board. In this way, as the under-fill dam has a different color from the substrate or other solder resist, it is easy to detect and determine the appearance defect.
상기 언더 -필용 댐은 특정 성분의 감광성 수지 조성물로부터 제조된 드라이 필름 솔더 레지스트를 이용하여 형성되기 때문에, 이전에 알려진 방법에 의하여 구현하기 용이하지 않은 두께 및 균일도를 가질 수 있다. 구체적으로, 상기 언더 -필용 댐은 10 내지 20 μπ, 바람직하게는 10 내지 Since the under-fill dam is formed using a dry film solder resist prepared from a photosensitive resin composition of a specific component, the under-fill dam may have a thickness and uniformity which are not easy to implement by a previously known method. Specifically, the under-fill dam is 10 to 20 μπ, preferably 10 to
15 ^의 두께를 가질 수 있으며， 두께의 오차 (평균값과 최대 /최소값의 차이)가 3/通이내 일 수 있다. It can have a thickness of 15 ^ and the thickness error (difference between the mean value and the maximum / minimum value) can be within 3 / t.
상술한 특정 성분의 감광성 수지 조성물을 사용하는 경우, 제조되는 드라이 필름 솔더 레지스트가 우수한 현상성, 특히 알카리 현상성을 나타낼 수 있어서， 미세 패턴 형성 또는 얇은 두께를 갖는 댐을 용이하게 형성시킬 수 있다.  When using the photosensitive resin composition of the above-mentioned specific component, the dry film soldering resist manufactured can exhibit the outstanding developability, especially alkali developability, and can easily form a dam with a fine pattern formation or a thin thickness.
구체적으로, 상기 감광성 수지 조성물의 경화물은 상기 산변성 올리고머 및 광중합성 모노머의 광경화물; 상기 산변성 올리고머 및 열경화성 바인더 수지의 열경화물; 및 안료를 포함할 수 있다. 상기 감광성 수지 조성물에서는, 조사되는 빛에 의하여 광중합성 모노머와 산변성 올리고머의 감광성 부분 (예를 들어, '-c=c-'등의 이증결합 등)이 반웅하게 되어 가교 구조를 형성할 수 있으며， 추후의 공정에서 알카리 현상액으로 비노광부를 현상하고 남은 부분을 열경화하였을 때 열경화성 바인더 수지와 산변성 올리고머의 일정 부분 (예를 들어, 카르복실 그룹 (-COOH) 등)이 반웅하여 가교구조를 형성할 수 있다. 이에 따라, 상기 감광성 수지 조성물을 사용하여 얻어지는 드라이 필름 솔더 레지스트에서는, 각각의 성분이 열경화 또는 광경화 과정에서 가교 결합에 의한 망상 구조를 형성할 수 있어서, 보다 높은 가교도를 구현할 수 있다. 이에 따라, 상기 드라이 필름 솔더 레지스트를 이용하여 형성된 언더 -필용 은 우수한 치수 안정성, 내열성, 강도 또는 기타 기계적 물성을 가질 수 있다. Specifically, the cured product of the photosensitive resin composition is a photocured product of the acid-modified oligomer and photopolymerizable monomer; Thermosetting of the acid-modified oligomer and thermosetting binder resin; And pigments. In the photosensitive resin composition, the photosensitive portion of the photopolymerizable monomer and the acid-modified oligomer (for example, a binary bond such as '-c = c-', etc.) may be reacted by the irradiated light to form a crosslinked structure. In the subsequent process, the non-exposed part was developed with an alkaline developer, and the remaining part was thermally cured. A portion of the acid-modified oligomer (eg, carboxyl group (-COOH), etc.) may react to form a crosslinked structure. Accordingly, in the dry film solder resist obtained by using the photosensitive resin composition, each component can form a network structure by crosslinking in the thermosetting or photocuring process, thereby achieving a higher degree of crosslinking. Accordingly, the under-fill formed using the dry film solder resist may have excellent dimensional stability, heat resistance, strength or other mechanical properties.
상기 감광성 수지 조성물은 카르복시기 (-COOH) 및 광경화 가능한 작용기를 갖는 산변성 올리고머; 광중합성 모노머; 열경화성 바인더 수지; 및 안료를 포함할 수 있으며， 광개시제 및 유기 용매를 더 포함할 수 있다. 또한, 상기 감광성 수지 조성물은 선택적으로 열경화성 바인더 수지 경화제， 열경화성 바인더 촉매, 필러, 레벨링제 등의 첨가제를 더 포함할 수도 있다. 이하， 상기 감광성 수지 조성물의 각 성분에 관하여 보다 구체적으로 설명하기로 한다. 산변성 올리고머  The photosensitive resin composition may include an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Thermosetting binder resins; And a pigment, and may further include a photoinitiator and an organic solvent. In addition, the photosensitive resin composition may optionally further include additives such as a thermosetting binder resin curing agent, a thermosetting binder catalyst, a filler, a leveling agent, and the like. Hereinafter, each component of the photosensitive resin composition will be described in more detail. Acid-modified oligomer
상기 감광성 수지 조성물은 카르복시기 (-COOH)와， 광경화 가능한 작용기를 갖는 산변성 올리고머를 포함한다. 이러한 산변성 을리고머는 광경화에 의해 수지 조성물의 다른 성분, 즉, 광중합성 모노머 및 /또는 열경화성 바인더 수지와 가교 결합을 형성할 수 있으며， 카르복시기를 포함하여 수지 조성물이 알칼리 현상성을 가질수 있게 한다.  The photosensitive resin composition includes a carboxyl group (-COOH) and an acid-modified oligomer having a photocurable functional group. Such acid-modified oligomers can form crosslinks with other components of the resin composition, such as photopolymerizable monomers and / or thermosetting binder resins, by photocuring, and make the resin compositions, including carboxyl groups, have alkali developability. .
이러한 산변성 올리고머로는 카르복시기와 광경화 가능한 작용기, 예를 들어, 아크릴레이트기나 불포화 이중 결합을 갖는 경화 가능한 작용기를 분자 내에 갖는 올리고머로서, 이전부터 광경화성 수지 조성물에 사용 가능한 것으로 알려진 모든 성분을 별다른 제한 없이 사용할 수 있다. 예를 들어, 이러한 산변성 을리고머의 주쇄는 노볼락 에폭시 또는 폴리우레탄으로 될 수 있고, 이러한 주쇄에 카르복시기와 아크릴레이트기 등이 도입된 산변성 올리고머로서 사용할 수 있다. 상기 광경화 가능한 작용기는 바람직하게는 아크릴레이트기로 될 수 있는데， 이때， 상기 산변성 올리고머는 카르복시기를 갖는 중합 가능한 모노머와, 아크릴레이트계 화합물 등을 포함한 모노머를 공중합하여 올리고머 형태로서 얻을 수 있다. 보다 구체적으로, 상기 수지 조성물에 사용 가능한 산변성 올리고머의 구체적인 예로는 다음과 같은 성분들을 들 수 있다. Such acid-modified oligomers are oligomers having a carboxyl group and a photocurable functional group, for example, a curable functional group having an acrylate group or an unsaturated double bond in the molecule, and all components previously known to be usable in the photocurable resin composition are different. Can be used without limitation. For example, the main chain of the acid-modified ligomer may be a novolac epoxy or polyurethane, and may be used as the acid-modified oligomer having a carboxyl group and an acrylate group introduced into the main chain. The photocurable functional group may preferably be an acrylate group, wherein the acid denaturation An oligomer can be obtained as an oligomer form by copolymerizing the polymerizable monomer which has a carboxyl group, and the monomer containing an acrylate type compound etc. More specifically, specific examples of the acid-modified oligomer usable in the resin composition include the following components.
(1) (메트)아크릴산 등의 불포화 카르복실산 (a)과 스티렌， α- 메틸스티렌, 저급 알킬 (메트)아크릴레아트, 이소부틸렌 등의 불포화 이중 결합을 갖는 화합물 (b)을 공중합시킴으로서 얻어지는 카르복시기 함유 수지; (1) by copolymerizing an unsaturated carboxylic acid ( a ) such as (meth) acrylic acid with a compound (b) having an unsaturated double bond such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, or isobutylene Carboxyl group-containing resin obtained;
(2) 불포화 카르복실산 (a)과 블포화 이중 결합을 갖는 화합물 (b)의 공중합체의 일부에 비닐기， 알릴기, (메트)아크릴로일기 등의 에틸렌성 불포화기와 에폭시기, 산클로라이드 등의 반웅성기를 갖는 화합물, 예를 들어, 글리시딜 (메트)아크릴레이트를 반웅시키고， 에틸렌성 불포화기를 팬던트로서 부가시킴으로서 얻어지는 카르복시기 함유 감광성 수지;  (2) ethylenically unsaturated groups such as vinyl groups, allyl groups, (meth) acryloyl groups, epoxy groups, acid chlorides, and the like, as part of the copolymer of the unsaturated carboxylic acid (a) and the compound (b) having a unsaturated double bond Carboxyl group-containing photosensitive resin obtained by reacting the compound which has a semi-asymmetric group of, for example, glycidyl (meth) acrylate and adding an ethylenically unsaturated group as a pendant;
(3) 글리시딜 (메트)아크릴레이트, α-메틸글리시딜 (메트)아크릴레이트 등의 에폭시기와 불포화 이중 결합을 갖는 화합물 (c)과 불포화 이증 결합을 갖는 화합물 (b)의 공중합체에 불포화 카르복실산 (a)을 반웅시키고, 생성된 2 급의 히드록시기에 무수프탈산, 테트라히드로무수프탈산, 핵사히드로무수프탈산 등의 포화 또는 불포화 다염기산 무수물 (d)을 반응시켜 얻어지는 카르복시기 함유 감광성 수지;  (3) to a copolymer of a compound (c) having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate and a compound (b) having an unsaturated double bond; Carboxyl group-containing photosensitive resin obtained by reacting unsaturated carboxylic acid (a) and reacting saturated or unsaturated polybasic anhydride (d), such as phthalic anhydride, tetrahydrophthalic anhydride, and nuxahydrophthalic anhydride, with the produced | generated secondary hydroxy group;
. (4) 무수 말레산, 무수 이타콘산 등의 불포화 이증 결합을 갖는 산무수물 (e)과 불포화 이중 결합을 갖는 화합물 (b)의 공중합체에 히드록시알킬 (메트)아크릴레이트 등의 1 개의 히드록시기와 1 개 이상의 에틸렌성 불포화 이중 결합을 갖는 화합물 (f)을 반웅시켜 얻어지는 카르복시기 함유 감광성 수지;  . (4) One hydroxy group such as hydroxyalkyl (meth) acrylate in a copolymer of an acid anhydride (e) having an unsaturated double bond such as maleic anhydride and itaconic anhydride and a compound (b) having an unsaturated double bond Carboxyl group-containing photosensitive resin obtained by reacting the compound (f) which has 1 or more ethylenically unsaturated double bond;
(5) 후술하는 바와 같은 분자 중에 2 개 이상의 에폭시기를 갖는 다관능 에폭시 화합물 (g) 또는 다관능 에폭시 화합물의 히드록시기를 추가로 에피클로로히드린으로 에폭시화한 다관능 에폭시 수지의 에폭시기와, (메트)아크릴산 등의 불포화 모노카르복실산 (h)의 카르복시기를 에스테르화 반웅 (전체 에스테르화 또는 부분 에스테르화, 바람직하게는 전체 에스테르화)시키고， 생성된 히드록시기에 추가로 포화 또는 불포화 다염기산 무수물 (d)을 반웅시켜 얻어지는 카르복시기 함유 감광성 화합물; (5) The epoxy group of the polyfunctional epoxy compound (g) which has two or more epoxy groups in the molecule mentioned later, or the polyfunctional epoxy resin in which the hydroxy group of the polyfunctional epoxy compound was further epoxidized with epichlorohydrin, (meth Esterification of carboxyl groups of unsaturated monocarboxylic acids (h) such as acrylic acid (total esterification or partial esterification, preferably Carboxyl group-containing photosensitive compound obtained by esterifying) and reacting saturated or unsaturated polybasic acid anhydride (d) in addition to the resulting hydroxy group;
(6) 불포화 이중 결합을 갖는 화합물 (b)과 글리시딜 (메트)아크릴레이트의 공중합체의 에폭시기에 탄소수 2 내지 17 의 알킬카르복실산, 방향족기 함유 알킬카르복실산 등의 1 분자 중에 1 개의 카르복시기를 갖고， 에틸렌성 불포화 결합을 갖지 않는 유기산 (i)을 반웅시키고, 생성된 2 급의 히드록시기에 포화 또는 불포화 다염기산 무수물 (d)을 반웅시켜 얻어지는 카르복시기 함유 수지;  (6) 1 in 1 molecule of an alkyl carboxylic acid having 2 to 17 carbon atoms, an aromatic group-containing alkyl carboxylic acid, etc., in the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth) acrylate A carboxyl group-containing resin obtained by reacting an organic acid (i) having two carboxyl groups and not having an ethylenically unsaturated bond and reacting a saturated or unsaturated polybasic acid anhydride (d) with the resulting secondary hydroxy group;
(7) 지방족 디이소시아네이트, 분지 지방족 디이소시아네이트， 지환식 디이소시아네이트, 방향족 디이소시아네이트 등의 디이소시아네이트 (j)와， 디메틸올프로피온산, 디메틸올부탄산 등의 카르복시기 함유 디알코올 화합물 (k), 및 폴리카르보네이트계 폴리올, 폴리에테르계 폴리올, 폴리에스테르계 폴리을, 폴리올레핀계 폴리올, 아크릴계 폴리올， 비스페놀 A 계 알킬렌옥시드 부가체 디올， 페놀성 히드록실기 및 알코올성 히드록실기를 갖는 화합물 등의 디올 화합물 (m)의 증부가 반응에 의해 얻어지는 카르복시기 함유 우레탄 수지;  (7) diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds (k) such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarboxes; Diol compounds such as carbonate polyols, polyether polyols, polyester polys, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adducts, diols, phenolic hydroxyl groups and compounds having alcoholic hydroxyl groups ( carboxyl group-containing urethane resin obtained by addition reaction of m);
(8) 디이소시아네이트 (j)와, 비스페놀 A 형 에폭시 수지, 수소 첨가 비스페놀 A 형 에폭시 수지, 브름화 비스페놀 A 형 에폭시 수지， 비스페놀 F 형 에폭시 수지, 비스페놀 S 형 에폭시 수지, 비크실레놀형 에폭시 수지， 비페놀형 에폭시 수지 등의 2 관능 에폭시 수지의 (메트)아크릴레이트 또는 그의 부분산 무수물 변성물 (II), 카르복시기 함유 디알코올 화합물 (k), 및 디올 화합물 (m)의 중부가 반응에 의해 얻어지는 감광성의 카르복시기 함유 우레탄 수지;  (8) diisocyanate (j), bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, Obtained by the polyaddition reaction of the (meth) acrylate of bifunctional epoxy resins, such as a biphenol type epoxy resin, or its partial acid anhydride modified substance (II), a carboxyl group-containing dialcohol compound (k), and a diol compound (m) Photosensitive carboxyl group-containing urethane resins;
(9) 상기 (7) 또는 (8)의 수지의 합성 중에 히드록시알킬 (메트)아크릴레이트 등의 1 개의 히드록시기와 1 개 이상의 에틸렌성 블포화 이중 결합을 갖는 화합물 (f)을 가하여， 말단에 불포화 이중 결합을 도입한 카르복시기 함유 우레탄 수지;  (9) In the synthesis of the resin (7) or (8), a compound (f) having one hydroxy group such as hydroxyalkyl (meth) acrylate and at least one ethylenically unsaturated double bond is added to the terminal, Carboxyl group-containing urethane resin which introduce | transduced unsaturated double bond;
(10) 상기 (7) 또는 (8)의 수지의 합성 중에 이소포론디이소시아네이트와 펜타에리트리를트리아크릴레이트의 등몰 반웅물 등의 분자 내에 1 개의 이소시아네이트기와 1 개 이상의 (메트)아크릴로일기를 갖는 화합물을 가하고, 말단 (메트)아크릴화한 카르복시기 함유 우레탄 수지; (10) One isocyanate group or one or more isocyanate groups in a molecule such as an equimolar semi-flour of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin (7) or (8). Carboxyl group-containing urethane resin which added the compound which has a (meth) acryloyl group, and was terminal (meth) acrylated;
(11) 후술하는 바와 같은 분자 중에 2 개 이상의 옥세탄환을 갖는 다관능 옥세탄 화합물에 불포화 모노카르복실산 (h)을 반웅시켜, 얻어진 변성 옥세탄 화합물 중의 1 급 히드록시기에 대하여 포화 또는 불포화 다염기산 무수물 (d)을 반웅시켜 얻어지는 카르복시기 함유 감광성 수지;  (11) Saturated or unsaturated polybasic anhydrides with respect to the primary hydroxy group in the modified oxetane compound obtained by reacting unsaturated monocarboxylic acid (h) with a polyfunctional oxetane compound having two or more oxetane rings in a molecule as described later. carboxyl group-containing photosensitive resin obtained by reacting (d);
(12) 비스에폭시 화합물과 비스페놀류와의 반웅 생성물에 불포화 이중 결합을 도입하고, 계속해서 포화 또는 불포화 다염기산 무수물 (d)을 반웅시켜 얻어지는 카르복시기 함유 감광성 수지;  (12) Carboxyl group-containing photosensitive resin obtained by introducing an unsaturated double bond into the reaction product of a bisepoxy compound and bisphenols, and then reacting saturated or unsaturated polybasic anhydride (d);
(13) 노볼락형 페놀 수지와， 에틸렌옥시드, 프로필렌옥시드, 부틸렌옥시드， 트리메틸렌옥시드, 테트라히드로푸란, 테트라히드로피란 등의 알킬렌옥시드 및 /또는 에틸렌카르보네이트, 프로필렌카르보네이트, 부틸렌카르보네이트, 2,3-카르보네이트프로필메타크릴레이트 등의 환상 카르보네이트와의 반웅 생성물에 불포화 모노카르복실산 (h)을 반웅시켜， 얻어진 반웅 생성물에 포화 또는 불포화 다염기산 무수물 (d)을 반웅시켜 얻어지는 카르복시기 함유 감광성 수지;  (13) Novolak-type phenol resins, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and / or ethylene carbonate, propylene carbon Saturated or unsaturated polybasic acid in the reaction product obtained by reacting unsaturated monocarboxylic acid (h) with reaction product with cyclic carbonates, such as carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate Carboxyl group-containing photosensitive resin obtained by reacting anhydride (d);
상술한 성분들 증에서도, 상기 (7) 내지 (10)에서, 수지 합성에 이용되는 이소시아네이트기 함유 화합물이 벤젠환을 포함하지 않는 디이소시아네이트로 되는 경우와， 상기 (5) 및 (8) 에서, 수지 합성에 이용되는 다관능 및 2 관능 에폭시 수지가 비스페놀 A 골격, 비스페놀 F 골격, 비페닐 골격 또는 비크실레놀 골격을 갖는 선상 구조의 화합물이나 그 수소 첨가 화합물로 되는 경우, DFSR 의 가요성 등의 측면에서 산변성 을리고머로서 바람직하게 사용 가능한 성분이 얻어질 수 있다. 또한, 다른 측면에서, 상기 (7) 내지 (10)의 수지의 변성물은 주쇄에 우레탄 결합을 포함하여 휘어짐에 대해 바람직하다.  Also in the above-described components, in (7) to (10), when the isocyanate group-containing compound used for the resin synthesis is a diisocyanate containing no benzene ring, and in (5) and (8), In the case where the polyfunctional and bifunctional epoxy resins used for the synthesis of the resins are linear compounds having bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton or bixylenol skeleton, or hydrogenated compounds thereof, the flexibility of DFSR, etc. In terms of the acid-modified oligomer, components usable preferably can be obtained. In addition, in another aspect, the modified product of the resins of the above (7) to (10) is preferable for the bending including the urethane bond in the main chain.
그리고, 상술한 산변성 올리고머로는 상업적으로 입수 가능한 성분을 사용할 수도 있는데, 이러한 성분의 구체적인 예로는 일본화약사의 ZAR- 2000 등을 들 수 있다.  In addition, commercially available components may be used as the acid-modified oligomers described above, and specific examples of such components include ZAR-2000 manufactured by Nippon Chemical Co., Ltd., and the like.
상기 감광성 수지 조성물은 산변성 올리고머 10 내지 80 중량0 /。, 바람직하게는 15 내지 75 중량0 /0， 보다 바람직하게는 25 내지 65 중량 %를 포함할 수 있다. 상기 산변성 올리고머의 함량이 지나치게 작으면 현상성이 떨어지고 필름의 강도가 저하되며, 너무 커지면 조성물이 과도하게 현상될The photosensitive resin composition comprises an acid-modified oligomer, 10 to 80 parts by weight 0 /., Preferably 15 to 75 parts by weight 0/0, more preferably from 25 to 65% by weight It may include. If the content of the acid-modified oligomer is too small, developability is lowered, the strength of the film is lowered, if too large, the composition is excessively developed
•2Γ 아니라 코팅시 균일성이 떨어질 수 있다. • Uniformity may be degraded when coating, not 2Γ.
또한, 상기 산변성 올리고머의 산가는 40 내지 120 mgKOH/g 일 수 있다. 상기 산변성 올리고머의 산가가 40 mgKOH/g 미만이면 알칼리 현상이 용이하지 않을 수 있으며, 상기 산가가 120 mgKOH/g 을 초과하면 현상액에 의하여 노광부가 용해될 수 있기 때문에, 필요 이상으로 선이 얇아지거나 경우에 따라서는 노광부와 미노광부의 구별없이 현상액으로 용해 박리되어 버려 정상적인 레지스트 패턴의 형성이 곤란해지기 때문에 바람직하지 않다. 광중합성 모노머  In addition, the acid value of the acid-modified oligomer may be 40 to 120 mgKOH / g. If the acid value of the acid-modified oligomer is less than 40 mgKOH / g, alkali development may not be easy. If the acid value is more than 120 mgKOH / g, the exposed portion may be dissolved by a developer, so that the line becomes thinner than necessary. In some cases, it is not preferable because it dissolves and peels off with a developer without distinguishing between the exposed portion and the unexposed portion, which makes it difficult to form a normal resist pattern. Photopolymerizable monomer
상기 감광성 수지 조성물은 광중합성 모노머를 포함할 수 있다. 이러한 광중합성 모노머를 포함함에 따라서 광조사시 일정한 경화물 또는 가교 구조를 형성할 수 있다. 이러한 광중합성 모노머는 조성물에 광경화성을 부여할 수 있을 뿐만 아니라, 각종 도포 방법에 적합한 점도로 조정하거나 알칼리 수용액에 대한 적절한 용해성을 부여하는 역할도 할 수 있다.  The photosensitive resin composition may include a photopolymerizable monomer. By including such a photopolymerizable monomer, it is possible to form a constant cured product or a crosslinked structure during light irradiation. Such a photopolymerizable monomer may not only impart photocurability to the composition, but may also serve to adjust the viscosity to be suitable for various coating methods or to impart proper solubility in aqueous alkali solution.
이러한 광중합성 모노머의 구체적인 예로는, 2- 히드록시에틸아크릴레이트, 2-히드록시프로필아크릴레이트, 펜타에리트리를트리아크릴레이트 또는 디펜타에리트리틀펜타아크릴레이트 ττ:  Specific examples of such photopolymerizable monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, or dipentaerythritol pentaacrylate ττ:
"0"의 히드톡시기 함유 아크릴레이트계 화합물; 폴리에틸렌글리콜디아크릴레이트 또는 폴리프로필렌글리콜디아크릴레이트 등의 수용성의 아크릴레이트계 화합물; 트리메틸올프로판트리아크릴레이트, 펜타에리트리틀테트라아크릴레이트 또는 디펜타에리트리를핵사아크릴레이트 등의 다가 알코올의 다관능 폴리에스테르아크릴레이트계 화합물; 트리메틸올프로판, 수소 첨가 비스페놀 Α 등의 다관능 알코올 또는 비스페놀 A, 비페놀 등의 다가 페놀의 에틸렌옥시드 부가물 및 /또는 프로필렌옥시드 부가물의 아크릴레이트계 화합물; 상기 히드록시기 함유 아크릴레이트계 화합물의 이소시아네이트 변성물인 다관능 또는 단관능 폴리우레탄아크릴레이트; 비스페놀 A 디글리시딜에테르, 수소 첨가 비스페놀 A 디글리시딜에테르 또는 페놀 노볼락 에폭시 수지의 (메트)아크릴산 부가물인 에폭시아크릴레이트계 화합물; 카프로락톤 변성 디트리메틸을프로판테트라아크릴레이트, ε-카프로락톤 변성 디펜타에리트리틀의 아크릴레이트, 카프로락톤 변성 히드록시피발산네오펜틸글리콜에스테르디아크릴레이트 등의 카프로락톤 변성의 아크릴레이트계 화합물; 또는 상기 아크릴레이트류에 대웅하는 메타크릴레이트류 등의 감광성 (메트)아크릴레이트 화합물계 화합물을 들 수 있고, 이들을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. A hydroxy compound containing a hydroxy group of "0 " ; Water-soluble acrylate compounds such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; Polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate or dipentaerythrate; Acrylate compounds of ethylene oxide adducts and / or propylene oxide adducts of polyfunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol; Polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modified product of the hydroxy group-containing acrylate compound; Bisphenol A diglycidyl ether, hydrogenated bisphenol Epoxy acrylate compounds which are (meth) acrylic acid adducts of A diglycidyl ether or phenol novolac epoxy resins; Caprolactone modified acrylate compounds such as caprolactone modified ditrimethyl, propane tetraacrylate, acrylate of ε-caprolactone modified dipentaerythritol, and caprolactone modified hydroxy pivalate neopentyl glycol ester diacrylate; Or photosensitive (meth) acrylate compound type compounds, such as methacrylates mentioned to the said acrylate, are mentioned, These can be used individually or in combination of 2 or more types.
이들 중에서도, 1 분자 중에 2 개 이상의 (메트)아크릴로일기를 갖는 다관능 (메트)아크릴레이트계 화합물이 바람직하며, 특히 펜타에리트리를트리아크릴레이트ᅳ 트리메틸올프로판트리아크릴레이트， 디펜타에리트리를헥사아크릴레이트, 카프로락톤 변성 디트리메틸올프로판테트라아크릴레이트 등이 바람직하다. 또한, 시판되고 있는 것으로서, 일본화약사의 DPEA-12 등을 사용할 수 있다.  Among these, the polyfunctional (meth) acrylate type compound which has two or more (meth) acryloyl groups in 1 molecule is preferable, Pentaerythritol triacrylate- trimethylol propane triacrylate, and dipentaerythrite is especially preferable. Hexaacrylate, caprolactone modified ditrimethylol propane tetraacrylate, etc. are preferable. Moreover, DPEA-12 etc. of Nippon Chemical Co., Ltd. can be used as what is marketed.
상기 감광성 수지 조성물은 상술한 광증합성 모노머 1 내지 30 중량%를 포함할 수 있다. 상기 광중합성 모노머의 함량이 1 중량0 /。 미만이면 광경화가 층분하지 않을 수 있고， 상기 함량이 30 중량0 /。를 초과하면 필름 건조성 또는 필름의 물성이 저하될 수 있다. 광개시제 The photosensitive resin composition may include 1 to 30% by weight of the photopolymerizable monomer described above. When the content of the photopolymerizable monomer is less than 1 weight 0 /., The photocuring may not be divided. If the content exceeds 30 weight 0 /., The film drying property or the physical properties of the film may be reduced. Photoinitiator
상기 감광성 수지 조성물은 광개시제를 포함할 수 있다. 이러한 광개시제는, 예를 들어, 수지 조성물의 노광부에서 라디칼 광경화를 개시하는 역할을 한다.  The photosensitive resin composition may include a photoinitiator. Such photoinitiators serve to initiate radical photocuring, for example, in the exposed portion of the resin composition.
이러한 광개시제로서는 공지의 것을 사용할 수 있고, 벤조인, 벤조인메틸에테르, 벤조인에틸에테르 등의 벤조인과 그 알킬에테르류; 아세토페논, 2,2-디메특시 -2-페닐아세토페논， 1,1ᅳ디클로로아세토페논, 4-(l-t- 부틸디옥시 -1-메틸에틸)아세토페논 등의 아세토페논류; 2-메틸안트라퀴논， 2- 아밀안트라퀴논, 2-t-부틸안트라퀴논, 1-클로로안트라퀴논 등의 안트라퀴논류; 2,4-디메틸티오크산톤, 2,4-디이소프로필티오크산톤, 2-클로로티오크산톤 등의 티오크산톤류; 아세토페논디메틸케탈, 벤질디메틸케탈 등의 케탈류; 벤조페논: 4-(l-t-부틸디옥시 -1-메틸에틸)벤조페논, 3,3',4,4'-테트라키스 (t- 부틸디옥시카르보닐)벤조페논 등의 벤조페논류와 같은 물질들을 사용할 수 있다. As such a photoinitiator, a well-known thing can be used and benzoin, such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and its alkyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1'dichloroacetophenone, and 4- (lt-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone : Substances such as benzophenones such as 4- (l- t -butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone Can be used.
또， 2-메틸 -1-[4- (메틸티오)페닐] -2-모르폴리노프로파논 -1,2-벤질 -2- 디메틸아미노 -1-(4-몰포리노페닐) -부탄 -1-온, 2- (디메틸아미노) -2-[(4- 메틸페닐)메틸 ]-1-[4-(4-몰포리닐)페닐] -1-부타논， Ν,Ν- 디메틸아미노아세토페논 (시판품으로서는 치바스페셜리티케미컬사 (현, 치바저팬사) 제품의 이루가큐어 (등록상표) 907， 이루가큐어 369, 이루가큐어 379 등) 등의 α-아미노아세토페논류, 2,4,6- 트리메틸벤조일디페닐호스핀옥사이트, 비스 (2,4,6-트리메틸벤조일) - 페닐포스핀옥사이드， 비스 (2,6-디메록시벤조일 )-2，4,4-트리메틸- 펜틸포스핀옥사이드 (시판품으로서는, BASF 사 제품 루실린 (등록상표) TPO, 치바스페셜리티케미컬사 제품의 이루가큐어 819 등) 등의 아실포스핀옥사이드류가 바람직한 광개시제로서 언급될 수 있다.  In addition, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 -One, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, Ν, Ν- dimethylaminoacetophenone ( As commercially available products, α-aminoacetophenones such as Irugacure (registered trademark) 907, Irugacure 369, Irugacure 379, etc. manufactured by Chiba Specialty Chemical Co., Ltd. (currently Chiba Japan Co., Ltd.), 2,4,6- Trimethylbenzoyldiphenylhospinoxite, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide ( As a commercial item, acyl phosphine oxides, such as Rucillin (trademark) TPO by BASF Corporation and Irgacure 819 by Chivas Specialty Chemical Co., Ltd.), etc. can be mentioned as a preferable photoinitiator.
또, 바람직한 광개시제로서는, 옥심에스테르류를 들 수 있다. 옥심에스테르류의 구체예로서는 2- (아세틸옥시이미노메틸)티오크산텐 -9-온， (1,2-옥탄디온, 1-[4- (페닐티오)페닐] -， 2-(0-벤조일옥심))， (에탄온, 1-[9-에틸 -6-(2- 메틸벤조일) -9H-카르바졸 -3-일] -, 1-(ᄋ-아세틸옥심)) 등을 들 수 있다. 시판품으로서는 치바스페셜리티케미컬사 제품의 GGI-325, 이루가큐어 OXE01 이루가큐어 OXE02, ADE A 사 제품 N-1919, 치바스페셜리티케미컬사의 Darocur TPO 등을 들 수 있다.  Moreover, oxime ester is mentioned as a preferable photoinitiator. Specific examples of oxime esters include 2- (acetyloxyiminomethyl) thioxanthene-9-one, (1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (0-benzoyloxime ), And (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (7-acetyloxime)). Commercially available products include GGI-325 from Chiba Specialty Chemical, Irugacure OXE01 Irgacure OXE02, N-1919 from ADE A, Darocur TPO from Chiba Specialty Chemical, and the like.
상기 감광성 수지 조성물은 상기 광개시제 0.1 내지 10 중량%, 바람직하게는 1 내지 5 중량%를 포함할 수 있다. 상기 광개시제의 함량이 너무 작으면 광중합 반웅이 층분히 일어나지 않을 수 있으며, 상기 함량이 너무 큰 경우 수지 조성물의 해상도가 저하되거나 제조되는 드라이 필름의 신뢰성이 층분하지 않을 수 있다. 열경화성 바인더 수지  The photosensitive resin composition may include 0.1 to 10% by weight of the photoinitiator, preferably 1 to 5% by weight. When the content of the photoinitiator is too small, the photopolymerization reaction may not occur. If the content is too large, the resolution of the resin composition may be lowered or the reliability of the dry film produced may not be improved. Thermosetting binder resin
상기 감광성 수지 조성물은 또한, 열경화 가능한 작용기， 예를 들어, 에폭시기, 옥세타닐기, 환상 에테르기 및 환상 티오 에테르기 중에서 선택된 1 종 이상의 작용기를 갖는 열경화성 바인더 수지를 포함할 수 있다. 이러한 열경화성 바인더는 열경화에 의해 산변성 올리고머 및 /또는 광중합성 모노머와 가교 결합을 형성해 드라이 필름 솔더 레지스트 또는 언더 -필용 댐의 내열성 또는 기계적 물성을 담보할 수 있다. The photosensitive resin composition may also be selected from thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups. It may include a thermosetting binder resin having at least one functional group. Such thermosetting binders may crosslink with acid-modified oligomers and / or photopolymerizable monomers by thermosetting to secure the heat resistance or mechanical properties of a dry film solder resist or an under-fill dam.
상기 열경화성 바인더 수지는 연화점이 약 70 내지 100°C로 될 수 있고， 이를 통해 라미네이션시 요철을 줄일 수 있다. 연화점이 낮을 경우 DFSR의 끈적임 (Tackiness)이 증가하고, 높을 경우 흐름성이 악화될 수 있다. 상기 열경화성 바인더 수지로는, 분자 중에 2 개 이상의 환상 에테르기 및 /또는 환상 티오에테르기 (이하, 환상 (티오)에테르기라고 함)를 갖는 수지를 사용할 수 있고， 또 2 관능성의 에폭시 수지를 사용할 수 있다. 기타 디이소시아네이트나 그의 2 관능성 블록이소시아네이트도 사용할 수 있다.  The thermosetting binder resin may have a softening point of about 70 to 100 ° C, thereby reducing the unevenness during lamination. Low softening points increase the tackiness of the DFSR and high flow rates can deteriorate. As the thermosetting binder resin, a resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule may be used, and a bifunctional epoxy resin may be used. Can be. Other diisocyanates or their bifunctional block isocyanates can also be used.
상기 분자 중에 2 개 이상의 환상 (티오)에테르기를 갖는 열경화성 바인더는 분자 증에 3， 4 또는 5 원환의 환상 에테르기, 또는 환상 티오에테르기 증 어느 한쪽 또는 2 종의 기를 2 개 이상 갖는 화합물로 될 수 있다. 또, 상기 열경화성 바인더는 분자 중에 적어도 2 개 이상의 에폭시기를 갖는 다관능 에폭시 화합물, 분자 증에 적어도 2 개 이상의 옥세타닐기를 갖는 다관능 옥세탄 화합물 또는 분자 증에 2 개 이상의 티오에테르기를 갖는 에피술피드 수지 등으로 될 수 있다.  The thermosetting binder having two or more cyclic (thio) ether groups in the molecule may be a compound having a 3, 4 or 5 membered cyclic ether group, or a cyclic thioether group either or two or more groups of two or more cyclic thioether groups. Can be. The thermosetting binder may be a polyfunctional epoxy compound having at least two or more epoxy groups in a molecule, a polyfunctional oxetane compound having at least two or more oxetanyl groups in molecular weight, or episulf having two or more thioether groups in molecular weight. Feed resin and the like.
상기 다관능 에폭시 화합물의 구체예로서는， 예를 들면 비스페놀 As a specific example of the said polyfunctional epoxy compound, it is bisphenol, for example
A 형 에폭시 수지， 수소 첨가 비스페놀 A 형 에폭시 수지, 브롬화 비스페놀 A 형 에폭시 수지, 비스페놀 F 형 에폭시 수지, 비스페놀 S 형 에폭시 수지, 노볼락형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, N-글리시딜형 에폭시 수지, 비스페놀 A 의 노볼락형 에폭시 수지， 비크실레놀형 에폭시 수지, 비페놀형 에폭시 수지, 킬레이트형 에폭시 수지, 글리옥살형 에폭시 수지, 아미노기 함유 에폭시 수지， 고무 변성 에폭시 수지, 디시클로펜타디엔 페놀릭형 에폭시 수지, 디글리시딜프탈레이트 수지， 헤테로시클릭 에폭시 수지, 테트라글리시딜크실레노일에탄 수지, 실리콘 변성 에폭시 수지, ε -카프로락톤 변성 에폭시 수지 등을 들 수 있다. 또한, 난연성 부여를 위해, 인 등의 원자가 그 구조 중에 도입된 것을 사용할 수도 있다. 이들 에폭시 수지는 열경화함으로써, 경화 피막의 밀착성, 땜납 내열성, 무전해 도금 내성 둥의 특성을 향상시킨다. A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin Resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group containing epoxy resin, rubber modified epoxy Resins, dicyclopentadiene phenolic epoxy resins, diglycidyl phthalate resins, heterocyclic epoxy resins, tetraglycidyl xylenoylethane resins, silicone-modified epoxy resins, epsilon -caprolactone-modified epoxy resins, and the like. . In addition, in order to impart flame retardancy, those in which atoms such as phosphorus are introduced into the structure may be used. have. By thermosetting these epoxy resins, the adhesiveness of a cured film, the solder heat resistance, and the electroless-plating resistance round improve the characteristic.
상기 다관능 옥세탄 화합물로서는 비스 [(3-메틸 -3- 옥세타닐메록시)메틸]에테르, 비스 [ (3 -에틸 - 3 -옥세타닐메톡시)메틸]에테르 , 1 ,4- 비스 [(3-메틸 -3-옥세타닐메톡시)메틸]벤젠, 1,4-비스 에틸 -3- 옥세타닐메특시)메틸]벤젠, (3-메틸 -3-옥세타닐)메틸아크릴레이트, (3-에틸 -3- 옥세타닐)메틸아크릴레이트, (3-메틸 -3-옥세타닐)메틸메타크릴레이트， (3-에틸 -3- 옥세타닐)메틸메타크릴레이트나 이들의 올리고머 또는 공중합체 둥의 다관능 옥세탄류 이외에, 옥세탄 알코올과 노볼락 수지, 폴리 (P-히드록시스티렌), 카르도형 비스페놀류, 카릭스아렌류, 카릭스레졸신아렌류, 또는 실세스퀴옥산 등의 히드록시기를 갖는 수지와의 에테르화물 등을 들 수 있다. 그 밖의, 옥세탄환을 갖는 블포화 모노머와 알킬 (메트)아크릴레이트와의 공중합체 등도 들 수 있다. Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxoxtanylmethoxy) methyl] ether, 1,4-bis [( 3-methyl-3-oxetanyl -dihydroxy-20) methyl] benzene, 1, 4-bis-ethyl-3-oxetanyl meteuk City) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, ( 3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) methylmethacrylate or oligomers thereof In addition to the polyfunctional oxetane of the copolymer, oxetane alcohol and novolak resin, poly (P-hydroxy styrene), cardo type bisphenol, carlix arene, carlix resolcin arene, silsesquioxane, etc. And etherates with a resin having a hydroxyl group. In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate etc. are mentioned.
상기 분자 중에 2개 이상의 환상 티오에테르기를 갖는 화합물로서는, 예를 들면 재팬 에폭시 레진사 제조의 비스페놀 A 형 에피술피드 수지 YL7000 등을 들 수 있다. 또한， 노볼락형 에폭시 수지의 에폭시기의 산소 원자를 황 원자로 대체한 에피술피드 수지 등도 사용할 수 있다.  As a compound which has two or more cyclic thioether group in the said molecule | numerator, bisphenol A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used.
또한, 시판되고 있는 것으로서, 국도화학사의 YDCN-500-80P 등을 사용할 수 있다.  Moreover, as marketed, YDCN-500-80P etc. of Kukdo Chemical Co., Ltd. can be used.
상기 감광성 수지 조성물은 상기 열경화성 바인더 수지 1 내지 30 중량0 /。를 포함할 수 있다. 상기 열경화성 바인더 수지의 함량이 1 중량% 미만인 경우에는 드라이 필름의 기계적 물성이 떨어지게 되고, 30 중량0 /。를 초과할 경우에는 수지 조성물의 현상성이 저하될 수 있다. 유기 용매 The photosensitive resin composition may include 1 to 30% by weight 0 /. Of the thermosetting binder resin. When the content of the thermosetting binder resin is less than 1% by weight, the mechanical properties of the dry film are lowered, and when it exceeds 30% by weight 0 /. Organic solvent
상기 감광성 수지 조성물은 각각의 성분을 용해시키거나 적절한 점도를 부여하기 위해 1개 이상의 유기 용매를 흔용하여 사용할 수 있다. 이러한 유기 용매의 구체적인 예로는， 메틸에틸케톤, 시클로핵사논 등의 케톤류; 를루엔, 크실렌, 테트라메틸벤젠 등의 방향족 탄화수소류; 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노에틸에테르， 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르， 프로필렌글리콜모노에틸에테르, 디프로필렌글리콜디에틸에테르， 트리에틸렌글리콜모노에틸에테르 등의 글리콜에테르류 (셀로솔브); 아세트산에틸, 아세트산부틸, 에틸렌글리콜모노에틸에테르아세테이트, The photosensitive resin composition may be commonly used one or more organic solvents to dissolve each component or impart an appropriate viscosity. Specific examples of such organic solvents include ketones such as methyl ethyl ketone and cyclonucleanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; 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 monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol mono Glycol ethers such as ethyl ether (cellosolve); Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate,
에틸렌글리콜모노부틸에테르아세테이트, Ethylene glycol monobutyl ether acetate,
디에틸렌글리콜모노에틸에테르아세테이트， Diethylene glycol monoethyl ether acetate,
디에틸렌글리콜모노부틸에테르아세테이트, Diethylene glycol monobutyl ether acetate,
프로필렌글리콜모노메틸에테르아세테이트, Propylene glycol monomethyl ether acetate,
디프로필렌글리콜모노메틸에테르아세테이트 등의 아세트산에스테르류; 에탄올, 프로판올, 에틸렌글리콜， 프로필렌글리콜, 카르비를 등의 알코올류; 옥탄， 데칸 등의 지방족 탄화수소; 석유에테르， 석유나프타, 수소 첨가 석유나프타, 용매나프타 등의 석유계 용매; 디메틸아세트아미드, 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; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbyl; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Amides such as dimethylacetamide and dimethylformamide (DMF). These solvents can be used alone or as a mixture of two or more thereof.
상기 감광성 수지 조성물은 상기 유기 용매 약 5 내지 50 중량 %를 포함할 수 있다. 상기 유기 용매의 함량이 너무 작은 경우 조성물의 점도가 지나치게 커져서 코팅성이 저하될 수 있으며, 상기 함량이 너무 큰 경우에는 건조가 잘 되지 않아 드라이 필름 솔더 레지시트의 물성이 저하되거나 끈적임이 증가하게 된다. 안료  The photosensitive resin composition may include about 5 to 50 wt% of the organic solvent. When the content of the organic solvent is too small, the viscosity of the composition may be too large to reduce the coating property, and when the content is too large, the drying may not be good, resulting in deterioration or stickiness of the dry film solder resist sheet. . Pigment
상기 언더 -필용 댐의 색상을 백색 (White)으로 나타내고자 할 경우, 안료로서 피그먼트 화이트 6 인 산화티탄을 사용할 수 있다. 백색 안료로 사용되는 산화티탄은 루틸형과 아나타제형이 있다. 아나타제형의 경우 루틸형에 비해 백색도가 우수하나 광학활성을 가짐으로 인해 광에 의한 황변이 발생할 가능성이 있기 때문에, 백색도는 떨어지나 광학활성을 가지지 않는 루틸형을 사용하는 것이 바람직하다. 상기 언더 -필용 댐의 색상을 황색 (Yellow)으로 나타내고자 할 경우, 안료로는 안트라퀴논계, 이소인돌리논계， 축합 아조계， 벤즈이미다졸론계 등이 있으며, 예를 들어 피그먼트 옐로우 108, 피그먼트 옐로우 147, 피그먼트 옐로우 151, 피그먼트 엘로우 166, 피그먼트 옐로우 181, 피그먼트 옐로우 193 등을 사용할 수 있다. When the color of the under-fill dam is to be represented as white, pigment white 6 phosphorus titanium oxide may be used as a pigment. Titanium oxide used as a white pigment is of rutile type and anatase type. In the case of the anatase type, the whiteness is superior to the rutile type, but since yellowing due to light may occur due to the optical activity, it is preferable to use the rutile type which has a low whiteness but does not have optical activity. When the color of the underfill dam is yellow, pigments include anthraquinone, isoindolinone, condensed azo, and benzimidazolone, for example pigment yellow 108. Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Pigment Yellow 181, Pigment Yellow 193 and the like can be used.
상기 언더 -필용 댐의 색상을 녹색 (Green)으로 나타내고자 할 경우, 안료로는 피그먼트 그린 7， 피그먼트 그린 36, 솔벤트 그린 3, 솔벤트 그린 5: 솔벤트 그린 20, 솔벤트 그린 28 등을 사용할 수 있다. 하지만， 녹색 안료의 경우 할로겐이 문제가 됨으로 인해 녹색을 구현하기 위해 황색과 청색 안료를 적절히 조합하여 사용하기도 한다. Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5 : Solvent Green 20, Solvent Green 28, etc. may be used as the pigment when the color of the under-fill dam is represented as Green. have. However, in the case of a green pigment, since halogen is a problem, a combination of yellow and blue pigments is sometimes used to realize green.
상기 언더 -필용 댐의 색상을 혹색 (Black)으로 나타내고자 할 경우， 안료로서 카본 블랙, 티탄 블랙, 산화 크름, 산화철, 아닐린 블랙, 페릴렌계 안료 등을 사용할 수 있다.  When the color of the under-fill dam is to be expressed in black, carbon black, titanium black, creme oxide, iron oxide, aniline black, and perylene pigments may be used as the pigment.
상기 언더 -필용 댐의 색상을 적색 (Red)으로 나타내고자 할 경우, 피그먼트 레드 13, 피그먼트 레드 32, 피그먼트 레드 122, 피그먼트 레드 177 피그먼트 레드 185， 피그먼트 레드 226， 피그먼트 레드 246 등을 사용할 수 있다.  If the color of the underfill dam is red, Pigment Red 13, Pigment Red 32, Pigment Red 122, Pigment Red 177 Pigment Red 185, Pigment Red 226, Pigment Red. 246 and the like can be used.
상기 감광성 수지 조성물은 상기 안료 0.01 내지 10 증량0 /0, 바람직하게는 1 내지 5 중량0 /0를 포함할 수 있다. 상기 안료의 함량이 너무 작으면, 시인성, 은폐력이 저하될 수 있으며, 상기 함량이 너무 크면 내열성 등의 기계적 물성이 떨어질 수 있다. The photosensitive resin composition is preferably 0/0, the pigment 0.01-10 increase may comprise from 1 to 5 parts by weight 0/0. If the content of the pigment is too small, visibility, hiding power may be lowered, and if the content is too large, mechanical properties such as heat resistance may be inferior.
단, 백색 안료를 사용하는 경우는 백색안료 자체가 필러로서의 역할도 하기 때문에, 다른 무기 필러가 배제되는 대신에， 백색안료의 함량이 감광성 수지 조성물 전체 중량에 대하여 50 중량 % 이내로 사용될 수 있다. 한편, 상기 감광성 수지 조성물은 상술한 성분 이외에도 하기 성분들을 선택적으로 더 포함할 수 있다.  However, in the case of using a white pigment, since the white pigment itself also serves as a filler, the content of the white pigment can be used within 50% by weight based on the total weight of the photosensitive resin composition instead of other inorganic fillers. On the other hand, the photosensitive resin composition may optionally further include the following components in addition to the above-described components.
열경화성 바인더 수지 경화제  Thermosetting Binder Resin Curing Agent
상기 감광성 수지 조성물은 선택적으로 열경화성 바인더 수지의 경화도를 높일 수 있는 열경화성 바인더 수지 경화제를 더 포함할 수 있다. 이러한 열경화성 바인더 수지 경화제의 예로는 아민계 화합물， 산무수물계 화합물, 아미드계 화합물, 페놀계 화합물 등을 들 수 있다. 상기 아민계 화합물로는 디아미노디페닐메탄, 디에틸렌트리아민, 트리에틸렌테트라아민, 디아미노디페닐술폰, 이소포론디아민 등을 사용할 수 있다. 상기 산무수물계 화합물로는 무수 프탈산， 무수 트리멜리트산, 무수피로멜리트산， 무수 말레인산, 테트라히드로 무수 프탈산, 메틸테트라히드로무수프탈산, 무수 메틸나딕산, 핵사히드로무수프탈산, 메틸핵사히드로무수프탈산 등을 사용할 수 있다. 상기 아미드계 화합물로는 디시안디아미드, 리놀렌산의 2 량체와 에틸렌디아민으로부터 합성되는 폴리아미드 수지 등을 사용할 수 있다. 상기 페놀계 화합물로는 비스페놀 A, 비스페놀 F, 비스페놀 S, 플루오렌비스페놀, 테르펜디페놀 등의 다가 페놀류; 페놀류와 알데히드류， 케톤류 또는 디엔류 등의 축합에 의해 수득되는 페놀 수지; 페놀류와 치환 비페닐류, 치환 페닐류 등과의 중축합에 의해 수득되는 페놀 수지; 페놀류 및 /또는 페놀 수지의 변성물; 테트라브로모비스페놀 A, 브름화 페놀 수지 등의 할로겐화 페놀류; 기타 이미다졸류， BF3-아민 착체, 구아니딘 유도체 등을 사용할 수 있다. The photosensitive resin composition may optionally further include a thermosetting binder resin curing agent that can increase the degree of curing of the thermosetting binder resin. Examples of such thermosetting binder resin curing agents include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like. As the amine compound, diaminodiphenylmethane, diethylenetriamine, triethylenetetraamine, diaminodiphenylsulfone, isophoronediamine and the like can be used. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid, nuxahydrophthalic anhydride, and methyl nucleohydrophthalic anhydride. Can be used. Examples of the amide compound include dicyandiamide, a diamide of linolenic acid, and a polyamide resin synthesized from ethylenediamine. As said phenol type compound, Polyhydric phenols, such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, a terpene diphenol; Phenol resins obtained by condensation of phenols with aldehydes, ketones or dienes; Phenol resins obtained by polycondensation of phenols, substituted biphenyls, substituted phenyls, and the like; Modified products of phenols and / or phenol resins; Halogenated phenols such as tetrabromobisphenol A and a brominated phenol resin; Other imidazoles, BF3-amine complexes, guanidine derivatives and the like can be used.
상기 감광성 수지 조성물은 상기 열경화성 바인더 수지 경화제 0.01 내지 15 중량 %를 더 포함할 수 있다. 상기 열경화성 바인더 수지 경화제의 함량이 너무 작으면 에폭시 수지의 경화도를 높이는 효과가 미미할 수 있으며, 상기 함량이 지나치게 크면 드라이 필름의 물성이 저하될 수 있다.  The photosensitive resin composition may further include 0.01 to 15% by weight of the thermosetting binder resin curing agent. If the content of the thermosetting binder resin curing agent is too small, the effect of increasing the degree of curing of the epoxy resin may be insignificant. If the content is too large, the physical properties of the dry film may be reduced.
열경화성 바인더 수지 촉매  Thermosetting Binder Resin Catalyst
열경화성 바인더 수지 촉매는 열경화성 바인더 수지의 경화 속도를 향상시킬 수 있다. ' The thermosetting binder resin catalyst can improve the curing rate of the thermosetting binder resin. '
이러한 열경화성 바인더 촉매로서는， 예를 들면 이미다졸, 2- 메틸이미다졸, 2-에틸이미다졸, 2-에틸 -4-메틸이미다졸, 2-페닐이미다졸, 4- 페닐이미다졸, 1-시아노에틸 -2-페닐이미다졸, 1-(2-시아노에틸) -2-에틸 -4- 메틸이미다졸 등의 이미다졸 유도체; 디시안디아미드， 벤질디메틸아민, 4- (디메틸아미노) -Ν,Ν-디메틸벤질아민, 4-메특시 -Ν,Ν-디메틸벤질아민, 4-메틸 -Ν,Ν- 디메틸벤질아민 등의 아민 화합물; 아디프산 디히드라지드, 세박산 디히드라지드 등의 히드라진 화합물; 트리페닐포스핀 등의 인 화합물 등을 들 수 있다. 또한, 시판되고 있는 것으로서는, 예를 들면 시코쿠 가세이 고교사 제조의 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (모두 이미다졸계 화합물의 상품명), 산아프로사 제조의 U-CAT3503N, UCAT3502T (모두 디메틸아민의 블록이소시아네이트 화합물의 상품명), DBU, DBN,U-CATSA102, U-CAT5002(모두 이환식 아미딘 화합물 및 그의 염) 등을 들 수 있다. 특히 이들에 한정되는 것이 아니고, 에폭시 수지나 옥세탄 화합물의 열경화 촉매， 또는 에폭시기 및 /또는 옥세타닐기와 카르복시기의 반웅을 촉진하는 것일 수 있고, 단독으로 또는 2 종 이상을 흔합하여 사용할 수도 있다. 또한, 구아나민, 아세토구아나민, 벤조구아나민, 멜라민, 2,4-디아미노 -6- 메타크릴로일옥시에틸 -S-트리아진, 2-비닐 -4,6-디아미노 -S-트리아진, 2-비닐 -4,6- 디아미노 -S-트리아진*이소시아누르산 부가물, 2,4-디아미노 -6- 메타크릴로일옥시에틸 -S-트리아진，이소시아누르산 부가물 등의 S-트리아진 유도체를 이용할 수도 있고, 바람직하게는 이들 밀착성 부여제로서도 기능하는 화합물을 상기 열경화성 바인더 촉매와 병용할 수 있다. As such a thermosetting binder catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -Ν, Ν-dimethylbenzylamine, 4-methoxy-Ν, Ν-dimethylbenzylamine, 4-methyl-Ν, Ν-dimethylbenzylamine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds such as triphenylphosphine, etc. Can be mentioned. Moreover, as what is marketed, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all of brand names of imidazole type compounds) by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N and UCAT3502T by San Aprosa (All are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof) and the like. It is not limited to these in particular, It may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or may promote reaction of an epoxy group and / or an oxetanyl group, and a carboxyl group, and may be used individually or in mixture of 2 or more types. . Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tree Azine, 2-vinyl-4,6-diamino-S-triazine * isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which also functions as these adhesive imparting agents can be used together with the said thermosetting binder catalyst.
열경화성 바인더 촉매의 함량은 적절한 열경화성의 측면에서， 상기 감광성 수지 조성물 전체 중량에 대하여 약 0.3 내지 15 중량 0/。로 될 수 있다. The content of the thermosetting binder catalyst may be about 0.3 to 15 weight 0 / .about the total weight of the photosensitive resin composition, in terms of suitable thermosetting.
필러  filler
필러는 내열 안정성, 열에 의한 치수안정성, 수지 접착력을 향상시키는 역할을 한다. 또한， 색상을 보강함으로써 체질안료 역할도 한다. 필러로는 무기 또는 유기 층전제를 사용할 수가 있는데, 예를 들어 황산바륨, 티탄산바륨, 무정형 실리카， 결정성 실리카， 용융 실리카, 구형 실리카, 탈크, 클레이, 탄산마그네슴, 탄산칼슴, 산화알루미늄 (알루미나), 수산화알루미늄， 마이카 등을 사용할 수 있다.  The filler plays a role of improving heat stability, dimensional stability by heat, and resin adhesion. In addition, it also serves as a constitution pigment by reinforcing the color. Inorganic or organic layer fillers may be used as the filler, for example barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina ), Aluminum hydroxide, mica and the like can be used.
필러의 함량은 상기 감광성 수지 조성물 전체 중량에 대하여 약 5 내지 50 중량0 /0인 것이 바람직하다. 50 중량0 /0를 초과하여 사용할 경우에는 조성물의 점도가 높아져서 코팅성이 저하되거나 경화도가 떨어지게 되어 바람직하지 않다. The content of the filler is preferably from about 5 to 50 parts by weight 0/0 relative to the total weight of the photosensitive resin composition. When used in excess of 50 parts by weight 0/0, it is undesirable high and the viscosity of the composition coating property may be degraded, or the falling down of the degree of cure.
레벨링제 레벨링제는 필름 코팅시 표면의 팝핑 (Popping)이나 크레이터 (Crater)를 제거하는 역할을 한다. Leveling agent The leveling agent serves to remove the popping or craters from the surface when the film is coated.
레벨링제로는 실리콘계, 불소계， 고분자계 등을 사용할 수 있으며, 예를 들어 BYK-Chemie GmbH 의 BYK-380N, BYK-307, BYK-378, BYK-350 등을 사용할 수 있다.  Examples of the leveling agent include silicone, fluorine, and polymer. Examples of the leveling agent include BYK-380N, BYK-307, BYK-378, and BYK-350 of BYK-Chemie GmbH.
레벨링제의 함량은 상기 감광성 수지 조성물 전체 증량에 대하여 0.05 내지 10 중량0 /。인 것이 바람직하다. 상기 레벨링제가 0.05 중량0 /。 미만으로 사용할 경우에는 팝핑이나 크레이터를 제거하는데 불층분하며, 10 중량0 /。를 초과하여 사용하게 될 경우 기포가 많이 발생하는 문제가 있다. It is preferable that the content of the leveling agent is 0.05-10 weight 0 /. With respect to the whole increase of the said photosensitive resin composition. When the leveling agent is used in less than 0.05 weight 0 / ° , it is unsatisfactory to remove the popping or craters, there is a problem that a lot of bubbles occur when used in excess of 10 weight 0 /.
분산제  Dispersant
분산제는 필러， 안료 등의 분산 안정성을 향상시키는 역할을 한다. 분산제로는 예를 들어 BYK-Chemie GmbH의 Disperbyk-110, Disperbyk- 162, Disperbyk- 168 등을 사용할 수 있다.  Dispersants serve to improve dispersion stability of fillers and pigments. As a dispersing agent, Disperbyk-110, Disperbyk-162, Disperbyk-168, etc. of BYK-Chemie GmbH can be used, for example.
분산제의 함량은 감광성 수지 조성물 전체 중량에 대하여 0.01 내지 10 중량0 /0인 것이 바람직하다. 상기 분산제가 0.01 중량0 /0 미만일 경우에는 분산이 층분이 되지 않고， 10 중량%를 초과할 경우에는 내열성 및 신뢰성에 영향을 미치게 된다. 한편, 발명의 다른 구현예에 따르면, 카르복시기 (-COOH) 및 광경화 가능한 작용기를 갖는 산변성 을리고머; 광중합성 모노머; 광개시제; 열경화성 바인더 수지; 유기 용매 및 안료를 포함하는 감광성 수지 조성물의 건조물 또는 경화물을 포함하는 드라이 필름을 기판 상에 적층하는 단계; 상기 기판의 외측 테두리 부위의 드라이 필름을 노광하는 단계; 및 상기 노광된 드라이 필름을 세정하는 단계를 포함하는 인쇄 회로 기판의 제보 방법이 제공될 수 있다. The content of the dispersant is preferably based on the total amount of photosensitive resin composition is 0.01 to 10 parts by weight 0/0. If the case where the dispersant is 0.01 0/0 is less than two minutes, without being dispersed layer, exceeding 10% by weight, it will affect the heat resistance and reliability. Meanwhile, according to another embodiment of the present invention, an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Photoinitiators; Thermosetting binder resins; Stacking a dry film comprising a dried or cured product of the photosensitive resin composition comprising an organic solvent and a pigment on a substrate; Exposing a dry film on an outer edge portion of the substrate; And cleaning the exposed dry film. A method of providing a printed circuit board may be provided.
상술한 바와 같이, 상기 특정 성분을 포함하는 감광성 수지 조성물으로부터 얻어진 드라이 필름을 이용하면 매우 얇고 균일한 두께를 갖는 언더 -필용 댐을 형성할 수 있다. 특히, 이러한 언더 -필용 댐은 우수한 기계적 물성을 나타내기 때문에 얇은 두께로도 일정 수준 이상의 높이 및 강도를 구현할 수 있으며， 이에 따라 인쇄 회로 기판에 주입 또는 층진되는 언더-필 재료의 유출을 방지할 수 있고, 상기 언더-필 공정 또는 반도체 제조 공정 상에서 발행할 수 있는 언더 -필용 댐의 손상 또는 물성 저하 현상을 최소화할 수 있다. As described above, when the dry film obtained from the photosensitive resin composition containing the specific component is used, an under-fill dam having a very thin and uniform thickness can be formed. In particular, since the under-fill dam exhibits excellent mechanical properties, it is possible to achieve a certain level of height and strength even with a thin thickness, and is thus injected or layered on a printed circuit board. Outflow of the under-fill material can be prevented, and damage to the under-fill dam or degradation of properties that can be issued on the under-fill process or the semiconductor manufacturing process can be minimized.
도 1 은 통상적인 언더 필 공정을 개략적으로 도시한 것으로, 이전에 알려진 언더-필 공정은， 정렬 및 플릭스 분배 (Alignment and Flux Dispensing) 단계, 솔더 범프 리플로우 (Solder Bump Reflow) 단계， 플럭스 클리닝 (Flux Cleaning) 단계, 및 언더필 (Underfilling) 단계 순으로 진행된다.  1 is a schematic of a conventional underfill process, where the previously known underfill process includes an alignment and flux dispensing step, a solder bump reflow step, a flux cleaning ( Flux Cleaning step, and the Underfilling step.
구체적으로, 언더-필 공정은 솔더 범프 (2)가 형성된 칩 소자 (1)와 전극 패드 (3)가 형성된 기판 (4)을 정렬시킨 후 플럭스를 분배시킨 후， 솔더 범프 (2)를 리플로우시키고, 플럭스를 클리닝한 다음, 칩 소자 (1)와 기판 (4) 사이에 언더 필 (5)을 채워 넣는 방법으로 이루어 질 수 있다.  Specifically, the under-fill process aligns the chip element 1 on which the solder bumps 2 are formed and the substrate 4 on which the electrode pads 3 are formed, distributes the flux, and then reflows the solder bumps 2. And the flux is cleaned, and then the underfill 5 is filled between the chip element 1 and the substrate 4.
도 2 는 상술한 감광성 수지 조성물의 건조물 또는 경화물을 포함하는 드라이 필름을 이용하여 형성된 언더 -필용 댐을 적용한 언더-필 공정을 개략적으로 도시한 것이다. 상기 언더 -필용 댐이 칩 소자 (1) 외측 테두리 부위에 형성됨에 따라서, 주입되는 언더-필 재료 (5)의 누출을 방지할 수 있다.  FIG. 2 schematically illustrates an under-fill process using an under-fill dam formed by using a dry film including a dried product or a cured product of the photosensitive resin composition described above. As the under-fill dam is formed at the outer edge portion of the chip element 1, it is possible to prevent leakage of the under-fill material 5 to be injected.
상기 언더 -필용 댐은 상술한 특정 성분의 감광성 수지 조성물로부터 얻어진 드라이 필름을 기판에 적층한 후， 노광, 현상 및 세정 단계를 거침으로서 형성될 수 있다.  The under-fill dam may be formed by laminating a dry film obtained from the photosensitive resin composition of the specific component described above on a substrate and then undergoing exposure, development and cleaning steps.
구체적으로, 상기 언더 -필용 댐은， 감광성 수지 조성물을 이용하여 드라이 필름을 제조하는 단계; 드라이 필름을 기판과 칩 소자 사이에 적층하는 단계; 원하는 댐 패턴에 대웅하는 포토 마스크를 드라이 필름에 을려놓고 노광하는 단계; 노광 후 드라이 필름을 현상하여 불필요한 부분을 제거하여 원하는 댐 패턴을 형성하는 단계; 및 현상 후 가열 경화하여 드라이 필름 타입의 솔더 레지스트로 이루어진 댐을 완성하는 단계를 통하여 형성될 수 있다.  Specifically, the under-fill dam, the step of preparing a dry film using the photosensitive resin composition; Laminating a dry film between the substrate and the chip element; Exposing the photo mask on the dry film to the desired dam pattern; Developing the dry film after exposure to remove unnecessary portions to form a desired dam pattern; And heat-curing after development to form a dam made of a dry film type solder resist.
상기 감광성 수지 조성물에 포함되는 각각의 성분에 관한 구체적인 내용은 상술한 바와 같다.  The specific content about each component contained in the said photosensitive resin composition is as above-mentioned.
상술한 감광성 수지 조성물을 캐리어 필름에 코팅하는 단계; 상기 캐리어 필름을 오본에 통과시켜 건조시키는 단계; 및 상기 건조물 상에 이형 필름을 적층하는 단계를 통하여, 아래로부터 캐리어 필름, 감광성 필름, 이형 필름으로 구성되는 드라이 필름을 제조할 수 있다. 이때, 캐리어 필름으로는 폴리에틸렌테레프탈레이트 (PET) 등을 사용할 수 있고, 이형 필름으로는 폴리에틸렌 (PE) 등을 사용할 수 있다. Coating the photosensitive resin composition on the carrier film; Passing the carrier film through Aubonn to dry; And release on the dry matter Through the step of laminating the film, it is possible to produce a dry film composed of a carrier film, a photosensitive film, a release film from below. In this case, polyethylene terephthalate (PET) or the like may be used as the carrier film, and polyethylene (PE) or the like may be used as the release film.
상기 감광성 수지 조성물의 도포 또는 코팅에는 콤마 코터， 블레이드 코터, 립 코터, 로드 코터, 스퀴즈 코터, 리버스 코터， 트랜스퍼 를 코터， 그라비아 코터 또는 분무 코터 등의 통상적으로 알려진 도포 방법이 사용될 수 있다. 상기 오본에서의 건조온도는 70 내지 110°C 정도가 바람직하고， 감광성 수지 조성물로 형성되는 감광성 필름의 두께는 10 내지 35 urn 정도가 바람직하다. For the coating or coating of the photosensitive resin composition, a commonly known coating method such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer coater, gravure coater or spray coater may be used. The drying temperature in the Aubon is preferably about 70 to 110 ° C., the thickness of the photosensitive film formed of the photosensitive resin composition is preferably about 10 to 35 urn.
상기 인쇄 회로 기판의 제조 방법에서는, 상기와 같이 얻어진 드라이 필름 (이형 필름이 제거된 상태)을 기판 상에 적층하고, 상기 기판의 외측 테두리 부위에 언더 -필용 댐이 형성될 수 있도록 일정 패턴의 포토 마스크를 이용하여 노광할 수 있다.  In the manufacturing method of the said printed circuit board, the dry film (the state in which the release film was removed) obtained as mentioned above is laminated | stacked on a board | substrate, and the photo of a certain pattern so that the under-fill dam may be formed in the outer edge part of the said board | substrate. It can expose using a mask.
상기 이형 필름이 제거된 드라이 필름의 적층 하는 단계에서는 진공 라미네이터, 핫 롤 라미네이터, 진공 프레스 등을 이용할 수 있다. 상기 노광 단계에서 사용될 수 있는 광원으로는 자외선 (UV), 전자선, X 선 등을 들 수 있으며， 상기 기재를 일정한 파장대를 갖는 광선 (UV 등)으로 노광 (Exposure)한다.  In the step of laminating the dry film from which the release film is removed, a vacuum laminator, a hot roll laminator, a vacuum press, or the like may be used. Light sources that can be used in the exposing step include ultraviolet (UV) light, electron beams, X-rays, and the like, and the substrate is exposed to light (UV light) having a predetermined wavelength band.
상기 노광은 포토 마스크로 선택적으로 노광하거나, 또는 레이저 다이렉트 노광기로 직접 패턴 노광할 수도 있다. 캐리어 필름은 노광 후에 박리한다. 노광량은 도막 두께에 따라 다르나, 0 내지 1,000 mJ/cuf가 바람직하다. 상기 노광을 진행하면， 예를 들어, 노광부에서는 광경화가 일어나 산변성 올리고머와, 광중합성 모노머 등의 가교 결합이 형성될 수 있고, 그 결과 이후의 현상에 의해 제거되지 않는 상태로 될 수 있다. 이에 비해， 비노광부는 카르복시기가 그대로 유지되어, 알칼리 현상 가능한 상태로 될 수 있다.  The exposure may be selectively exposed with a photo mask, or may be directly pattern exposed with a laser direct exposure machine. The carrier film peels off after exposure. Although exposure amount changes with coating film thickness, 0-1,000 mJ / cuf is preferable. When the exposure is performed, for example, in the exposed portion, photocuring may occur to form a crosslinking bond between an acid-modified oligomer and a photopolymerizable monomer, and as a result, may not be removed by a subsequent phenomenon. On the other hand, the non-exposed part can maintain the carboxy group as it is, and can be in an alkali developable state.
상기 노광 단계 이후에는， 상기 드라이 필름을 현상하여 불필요한 부분을 제거하여 원하는 댐 패턴을 형성한다. 노광 후 현상시에는 일반적으로 침지법 혹은 분사법을 사용하여 현상액에 담그게 되는데, 현상액으로는 수산화칼륨， 수산화나트륨， 탄산나트륨, 탄산칼륨, 인산나트륨, 규산나트륨, 암모니아, 아민류 등의 알칼리 수용액을 사용하며, 알칼리 수용액으로 현상 후 물로 세척하게 된다. 이러한 현상에 의해， 노광부의 필름만이 잔류할 수 있다. After the exposure step, the dry film is developed to remove unnecessary portions to form a desired dam pattern. During post-exposure development, immersion or spraying is usually used to immerse the developer. As a developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines is used. After developing with an aqueous alkali solution, the solution is washed with water. By this phenomenon, only the film of the exposed portion may remain.
상기 노광된 드라이 필름을 세정하는 단계 이후에, 잔류물을 가열 경화 (Post Cure)단계를 추가로 적용할 수 있다. 이때, 가열 경화온도는 100 °C 이상이 적당하다.  After the step of cleaning the exposed dry film, the residue may further be subjected to a post curing step. At this time, the heat curing temperature is more than 100 ° C.
상술한 제조 단계, 예를 들어 드라이 필름의 제조 단계, 드라이 필름을 노광하는 단계 또는 세정된 드라이 필름을 가열 경화 (Post Cure)단계 등을 통하여, 상기 감광성 수지 조성물의 건조물 또는 경화물을 포함하는 언더 -필용 댐이 형성될 수 있다. 이러한 감광성 수지 조성물의 경화물은 상기 산변성 을리고머 및 광중합성 모노머의 광경화물; 상기 산변성 올리고머 및 열경화성 바인더 수지의 열경화물; 및 안료를 포함할 수 있다. 상기 제조 방법에 의하여 얻어지는 인쇄 회로 기판에는 상기 10 내지 20 an, 바람직하게는 10 내지 15 의 두께를 갖는 언더 -필용 댐이 포함될 수 있다. 이러한 언더 -필용 댐의 두께 오차 (평균값과 최대 /최소값의 차이)가 3 이내 일 수 있다.  Under containing the dried or cured product of the photosensitive resin composition through the above-described manufacturing step, for example, a manufacturing step of the dry film, exposing the dry film, or post-curing the cleaned dry film. Fill dams may be formed. The cured product of such a photosensitive resin composition includes a photocured product of the acid-modified oligomer and the photopolymerizable monomer; Thermosetting of the acid-modified oligomer and thermosetting binder resin; And pigments. The printed circuit board obtained by the manufacturing method may include an under-fill dam having a thickness of 10 to 20 an, preferably 10 to 15. The thickness error (difference between the average value and the maximum / minimum value) of such an under-fill dam may be within 3 degrees.
한편, 상기 인쇄 회로 기판의 제조 방법은, 상기 기판 상에 전극 패드를 형성하는 단계; 상기 전극 패드 상에 솔더 범프를 위치시키는 단계; 및 반도체 칩올 상기 솔더 범프를 매개로 플립 칩 결합시키는 단계를 더 포함할 수 있다. 상기 솔더 범프는 반도체 칩 상에 결합된 상태로 상기 전극 패드 상에 위치할 수도 있으며, 상기 전극 패드상에 먼저 설치된 이후 상기 반도체 칩과 결합할 수 도 있다.  On the other hand, the method of manufacturing a printed circuit board, forming an electrode pad on the substrate; Positioning solder bumps on the electrode pads; And flip chip bonding the semiconductor chip through the solder bumps. The solder bumps may be positioned on the electrode pads while being bonded to the semiconductor chip, or may be firstly installed on the electrode pads and then coupled to the semiconductor chip.
이에 따라, 상기 인쇄 회로 기판은 상기 기판 상에 형성된 전극 패드; 상기 전극 패드 상에 형성된 솔더 범프; 및 상기 솔더 범프를 매개로 플립 칩 결합된 반도체 칩을 포함할 수 있다.  Accordingly, the printed circuit board may include an electrode pad formed on the substrate; A solder bump formed on the electrode pad; And a semiconductor chip flip-chip coupled through the solder bumps.
또한, 상기 인쇄 회로 기판의 제조 방법은, 상기 기판과 상기 반도체 칩 사이로 언더필 재료를 주입하는 단계를 더 포함하여, 언더-필 재료가 충진된 인쇄 회로 기판을 제공할 수 있다.  The method of manufacturing the printed circuit board may further include injecting an underfill material between the substrate and the semiconductor chip to provide a printed circuit board filled with an under-fill material.
【발명의 효과】 본 발명에 따르면， 우수한 기계적 물성을 가지며 미세하고 균일한 두께를 갖는 언더 -필용 댐을 포함하는 인쇄 회로 기판 및 이의 제조 방법이 제공될 수 있다. 【Effects of the Invention】 According to the present invention, a printed circuit board including an under-fill dam having excellent mechanical properties and having a fine and uniform thickness can be provided.
【도면의 간단한 설명】  [Brief Description of Drawings]
도 1은 통상적인 언더 필 공정을 개략적으로 도시한 것이다.  1 schematically illustrates a conventional underfill process.
도 2 는 기판 상에 언더 -필용 댐이 형성된 경우의 언더 필 공정을 개략적으로 도시한 것이다.  FIG. 2 schematically shows the underfill process when an under-fill dam is formed on the substrate.
【발명의 실시를 위한 구체적인 내용】  [Specific contents for implementation of the 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 invention, but the content of the present invention is not limited by the following examples.
<실시예: 인쇄 회로 기판의 제조 > Example: Fabrication of Printed Circuit Boards
실시예 1  Example 1
(1) 감광성 수지 조성물의 제조  (1) Preparation of Photosensitive Resin Composition
산변성 올리고머로서 일본화약의 CCR-1235 를 35 중량 %, 광중합성 모노머로서 카야라드의 DPEA-12 를 13 중량0 /。, 광개시제로서 TPO 를 3 중량%, 에폭시 수지로서 일본화약의 EOCN-1020 을 13 중량0 /0, 에폭시 경화제로서 디시안디아미드를 0.5 중량0 /0, 에폭시 촉매로서 2MI를 0.5 중량0 A 백색 안료로서 루틸형 산화티탄 (듀폰사 tie pure R-931)을 19 중량0 /0, 레벨링제로서 BYK-380N 을 0.5 중량0 /。, 분산제로서 Disperbyk-110 을 0.5 중량0 /0, 용매로서 DMF 를 15 중량0 /。를 사용하여 백색 감광성 수지 조성물을 제조하였다. 35% by weight of Nippon Kayaku's CCR-1235 as an acid-modified oligomer, 13% by weight of DPEA-12 of Kayarad as a photopolymerizable monomer, 0 /. 13 parts by weight 0/0, 0.5 to dicyandiamide as an epoxy curing agent 0/0, the rutile type titanium oxide to 2MI as epoxy catalyst as 0.5 0 a white pigment (DuPont tie pure R-931) to 19 parts by weight 0/0 , the BYK-380N 0.5 weight 0 /. as a leveling agent, using 15 parts by weight 0 /. the DMF-110 as the Disperbyk 0.5 0/0, the solvent as a dispersant to prepare a photosensitive resin composition is white.
(2) 드라이 필름의 제조  (2) production of dry film
상기 제조된 감광성 수지 조성물을 캐리어 필름으로 PET 에 도포한 후, 75°C의 오븐을 통과시켜 건조시킨 다음， 이형 필름으로 PE 를 적층함으로써, 아래로부터 캐리어 필름, 감광성 필름 (두께 15 ^ηι), 이형 필름으로 구성되는 드라이 필름올 제조하였다. After applying the prepared photosensitive resin composition to the PET with a carrier film, and dried through an oven at 75 ° C, and then laminated PE with a release film, from below, the carrier film, photosensitive film (thickness 15 ^ ηι), A dry filmol composed of a release film was prepared.
(3) 인쇄 회로 기판의 제조 제조된 드라이 필름의 커버 필름을 벗긴 후, 회로가 형성된 기판 위에 감광성 필름층을 진공 적층하였다. 그리고, 원하는 언더 -필용 댐 패턴에 대웅하는 포토 마스크를 드라이 필름에 올려놓고 UV 로 노광한 후, 알칼리 용액으로 현상하고 불필요한 부분을 제거하여 원하는 언더 -필용 댐 패턴을 형성하였다. 그리고, 얻어진 언더 -필용 댐을 가열 경화시킴으로써, 드라이 필름 타입의 솔더 레지스트로 이루어진 댐이 형성된 인쇄 회로 기판을 완성하였다. 실시예 2 (3) manufacture of printed circuit boards After removing the cover film of the manufactured dry film, the photosensitive film layer was vacuum laminated on the board | substrate with a circuit. Then, a photomask that touches the desired under-fill dam pattern was placed on a dry film, exposed to UV, developed with an alkaline solution, and the unnecessary portion was removed to form a desired under-fill dam pattern. And the underfill fill dam obtained was heat-hardened, and the printed circuit board in which the dam which consists of a dry film type soldering resist was formed was completed. Example 2
(1) 감광성 수지 조성물의 제조  (1) Preparation of Photosensitive Resin Composition
산변성 올리고머로서 일본화약의 CCR-1235 를 35 중량0 /0, 광중합성 모노머로서 카야라드의 DPEA-12 를 13 증량%, 광개시제로서 TPO 를 3 중량%, 에폭시 수지로서 일본화약의 EOCN-1020 을 13 중량0 /。, 에폭시 경화제로서 디시안디아미드를 0.5 중량0 /0， 에폭시 촉매로서 2MI를 0.5 중량0 필러로서 BaS04 를 18 중량0 /0, 안료로서 피그먼트 블루 15:3, 피그먼트 엘로우 151 을 각각 0.5 중량0 /0, 레벨링제로서 BYK-380N 을 0.5 중량0 /。, 분산제로서 Disperbyk-110 을 0.5 중량0 /。, 용매로서 DMF 를 15 증량0 /。를 사용하여 녹색 감광성 수지 조성물을 제조하였다. The CCR-1235 of Nippon Kayaku as an acid-modified oligomer 35 parts by weight 0/0, the DPEA-12 of Kaya-Rad as a photopolymerizable monomer 13 increase%, the TPO 3% by weight, as an epoxy resin is used as the photoinitiator to EOCN-1020 of Nippon Kayaku 13 parts by weight 0 / epoxy curing agent of dicyandiamide to 0.5 0/0, as 18 wt. 0/0, the pigment to BaS0 4 as 0.5 0 filler 2MI as epoxy catalyst pigment blue 15 as a: 3, pigment yellow a BYK-380N 151 as each 0.5 0/0, a leveling agent 0.5 0 /., 0.5 0 / a Disperbyk-110 as a dispersant., using a 15 increment 0 /. of DMF as solvent, the green photosensitive resin composition Was prepared.
(2) 드라이 필름의 제조 및 인쇄 회로 기판의 제조  (2) Production of dry film and production of printed circuit board
상기 제조된 감광성 수지 조성물을 사용한 점을 제외하고, 실시예 1과 동일한 방법으로 드라이 필름 및 인쇄 회로 기판을 제조 하였다. 실시예 3  A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that the prepared photosensitive resin composition was used. Example 3
(1) 감광성 수지 조성물의 제조  (1) Preparation of Photosensitive Resin Composition
산변성 올리고머로서 일본화약의 CCR-1235 를 35 중량0 /。, 광중합성 모노머로서 카야라드의 DPEA-12 를 13 중량0 /。, 광개시제로서 TPO 를 3 중량%， 에폭시 수지로서 일본화약의 EOCN-1020 을 13 중량0 /0， 에폭시 경화제로서 디시안디아미드를 0.5 중량0 /0, 에폭시 촉매로서 2MI를 0.5 중량0 필러로서 BaS04를 18 중량0 /0, 안료로서 피그먼트 엘로우 151 을 1.0 중량0 /。, 레벨링제로서 BYK-380N 올 0.5 중량0 /0, 분산제로서 Disperbyk-UO 을 0.5 중량0 A, 용매로서 DMF 를 15 중량 %를 사용하여 황색 감광성 수지 조성물을 제조하였다. CCR-1235 of Nippon Gunpowder as an acid-modified oligomer, 35 weight 0 /. Of DPEA-12 of Kayarad as a photopolymerizable monomer, 13 weight 0 /. Of TPO as a photoinitiator, EPON- of Nippon Gunpowder as an epoxy resin 1020 to 13 wt. 0/0, the epoxy curing agent as dicyandiamide to 0.5 0/0, a 0.5 zero filler 2MI as epoxy catalyst by weight of pigment yellow 151. the BaS0 4 18 parts by weight 0/0, as a pigment, 1.0 0 /., 0.5 to Disperbyk-UO as a dispersant BYK-380N ol 0.5 0/0, as a leveling agent A yellow photosensitive resin composition was prepared using a weight of 0 A and 15% by weight of DMF as a solvent.
(2) 드라이 필름의 제조 및 인쇄 회로 기판의 제조  (2) Production of dry film and production of printed circuit board
상기 제조된 감광성 수지 조성물을 사용한 점을 제외하고, 실시예 1과 동일한 방법으로 드라이 필름 및 인쇄 회로 기판을 제조 하였다.  A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that the prepared photosensitive resin composition was used.
<비교예: 인쇄 회로 기판의 제조 > Comparative Example: Fabrication of Printed Circuit Board
일본 특허 공개 제 1996-325476 호에 개시된 액상 솔더 레지스트를 이용하여 언더 -필용 댐을 형성한 점을 제외하고, 실시예 1 과 동일한 구조의 인쇄 회로 기판을 제조하였다.  A printed circuit board having the same structure as in Example 1 was manufactured except that an under-fill dam was formed using the liquid solder resist disclosed in Japanese Patent Laid-Open No. 1996-325476.
<실험예: 언더 -필용 댐의 물성 측정 > Experimental Example: Measurement of Properties of Underfill Dam
실시예 및 비교예에서 제조한 댐에 대하여, 색상, 두께와 균일도， 플립 칩 적용여부, 및 AOI 장비에서의 검출력을 비교하였으며, 그 결과는 표 1과 같다.  For the dams prepared in Examples and Comparative Examples, color, thickness and uniformity, flip chip application, and detection power in AOI equipment were compared. The results are shown in Table 1.
【표 1】 Table 1
Figure imgf000026_0001
표 1 에서 확인할 수 있는 바와 같이, 비교예의 경우 색상이 녹색인 반면에, 실시예의 경우 백색 등의 다양한 색상을 가질 수 있다. 또한, 비교예의 경우 두께가 1 mm 정도로 두껍게 형성될뿐더러 두께 편차가 심하여 불균일한 반면에, 실시예의 경우 균일한 두께를 갖는 댐을 형성할 수 있고, 10 내지 15 m 두께의 매우 얇은 댐도 균일한 두께로 형성할 수 있다. 또한, 비교예의 경우 두께가 불균일하여 플립 칩을 적용하기가 어려운 반면에， 실시예의 경우 두께가 얇고 균일하여 플립 칩 적용이 가능하다. 또한, 비교예의 경우 색상이 없어서 검출력이 떨어지는 반면에 실시예의 경우 AOI 장비에서 검출력이 우수하다.
Figure imgf000026_0001
As can be seen in Table 1, the color of the comparative example is green, whereas in the case of the embodiment may have a variety of colors, such as white. In addition, in the case of the comparative example is not only thick to form a thickness of about 1 mm and non-uniform due to the thickness variation, in the case of the embodiment can form a dam having a uniform thickness, even very thin dam of 10 to 15 m thickness is uniform It can be formed in thickness. In addition, in the comparative example, it is difficult to apply the flip chip due to the non-uniform thickness, whereas in the embodiment, the thickness is uniform and thin so that the flip chip application is difficult. It is possible. In addition, in the case of the comparative example there is no color, the detection power is lower, while in the embodiment, the detection power is excellent in AOI equipment.
【부호의 설명】 [Explanation of code]
1 칩 소자  1 chip element
2: 솔더 범프  2: solder bump
전극 패드  Electrode pads
기판  Board
언더 필  Under Peel
댐  dam

Claims

【특허청구범위】 [Patent Claims]
【청구항 1]  [Claim 1]
반도체 칩이 형성된 기판의 외측 테두리를 따라 형성된 언더 -필용 댐을 포함하고,  An under-fill dam formed along the outer edge of the substrate on which the semiconductor chip is formed,
상기 언더 -필용 댐이, 카르복시기 (-COOH) 및 광경화 가능한 작용기를 갖는 산변성 을리고머; 광중합성 모노머; 열경화성 바인더 수지; 및 안료를 포함하는 감광성 수지 조성물의 건조물 또는 경화물을 포함하는 드라이 필름 솔더 레지스트를 포함하는 인쇄 회로 기판.  The under-fill dam may include an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Thermosetting binder resins; And a dry film solder resist comprising a dried or cured product of the photosensitive resin composition comprising a pigment.
【청구항 2】 [Claim 2]
제 1항에 있어서,  The method of claim 1,
상기 감광성 수지 조성물의 경화물은 상기 산변성 올리고머 및 광중합성 모노머의 광경화물; 상기 산변성 올리고머 및 열경화성 바인더 수지의 열경화물; 및 안료를 포함하는 인쇄 회로 기판.  The cured product of the photosensitive resin composition is a photocured product of the acid-modified oligomer and the photopolymerizable monomer; Thermosetting of the acid-modified oligomer and thermosetting binder resin; And a pigment comprising a pigment.
【청구항 3】 [Claim 3]
제 1항에 있어서,  The method of claim 1,
상기 기판 상에 형성된 전극 패드; 상기 전극 패드 상에 형성된 솔더 범프; 및 상기 솔더 범프를 매개로 플립 칩 결합된 반도체 칩을 포함하는 인쇄 회로 기판  An electrode pad formed on the substrate; A solder bump formed on the electrode pad; And a semiconductor chip flip-chip coupled through the solder bumps.
【청구항 4】 [Claim 4]
제 1항에 있어서，  The method of claim 1,
상기 언더 -필용 댐은 기판과 반도체 칩 사이에 채워 넣는 언더-필 재료의 누출을 방지하는 인쇄 회로 기판.  And the under-fill dam prevents leakage of under-fill material to fill between the substrate and the semiconductor chip.
【청구항 5】 [Claim 5]
제 3항에 있어서,  The method of claim 3, wherein
상기 언더 -필용 댐은, 상기 기판의 외측 테두리와 반도체 칩의 외측 테두리 사이에 형성되고, 기판과 반도체 칩 사이 간격 이상의 높이를 갖는 인쇄 회로 기판. The under-fill dam is formed between the outer edge of the substrate and the outer edge of the semiconductor chip, A printed circuit board having a height greater than or equal to the gap between the substrate and the semiconductor chip.
【청구항 6】 [Claim 6]
제 1항에 있어서,  The method of claim 1,
상기 언더 -필용 댐이 백색， 황색, 녹색， 혹색 및 적색으로 이루어진 군에서 선택된 1종의 색상을 갖는 인쇄 회로 기판.  The under-fill dam is a printed circuit board having one color selected from the group consisting of white, yellow, green, warm and red.
【청구항 7】 [Claim 7]
제 6항에 있어서,  The method of claim 6,
상기 언더 -필용 댐이 상기 기판 또는 상기 기판 상의 솔더 레지스트와 상이한 색을 갖는 인쇄 회로 기판.  The under-fill dam has a different color than the substrate or solder resist on the substrate.
【청구항 8] [Claim 8]
제 1항에 있어서,  The method of claim 1,
상기 언더 -필용 댐이 10 내지 20 의 두께를 갖는 인쇄 회로 기판.  The under-fill dam has a thickness of 10 to 20.
【청구항 9】 [Claim 9]
제 1 항에 있어서,  The method of claim 1,
상기 산변성 을리고머의 광경화 가능한 작용기는 아크릴레이트기인 인쇄 회로 기판.  The photocurable functional group of the acid-modified oligomer is an acrylate group.
【청구항 10] [Claim 10]
제 1 항에 있어서,  The method of claim 1,
상기 산변성 올리고머는 카르복시기를 갖는 중합 가능한 모노머 및 아크릴레이트계 화합물을 포함하는 모노머의 공증합체인 인쇄 회로 기판.  The acid-modified oligomer is a printed circuit board of the polymerizable monomer having a carboxyl group and a monomer comprising an acrylate compound.
【청구항 11】 [Claim 11]
제 1 항에 있어서,  The method of claim 1,
상기 산변성 올리고머의 산가는 40 내지 120 mgKOH/g 인 인쇄 회로 기판. The acid value of the acid-modified oligomer is 40 to 120 mgKOH / g printed circuit board.
【청구항 12】 [Claim 12]
제 1 항에 있어서,  The method of claim 1,
상기 광중합성 모노머는 히드톡시기 함유 아크릴레이트계 화합물; 수용성 아크릴레이트계 화합물; 다가 알코올의 다관능 폴리에스테르아크릴레이트계 화합물; 다관능 알코을 또는 다가 페놀의 에틸렌옥시드 부가물의 아크릴레이트계 화합물; 다관능 알코올 또는 다가 페놀의 프로필렌옥시드 부가물의 아크릴레이트계 화합물; 다관능 또는 단관능 폴리우레탄아크릴레이트; 에폭시아크릴레이트계 화합물; 카프로락톤 변성의 아크릴레이트계 화합물 및 감광성 (메트)아크릴레이트계 화합물로 이루어진 군에서 선택된 1종 이상의 화-합물을 포함하는 인쇄 회로 기판.  The photopolymerizable monomer may include a hydroxy group-containing acrylate compound; Water-soluble acrylate compounds; Polyfunctional polyester acrylate compound of polyhydric alcohol; Acrylate-based compounds of ethylene oxide adducts of polyfunctional alcohols or polyhydric phenols; Acrylate compounds of propylene oxide adducts of polyfunctional alcohols or polyhydric phenols; Polyfunctional or monofunctional polyurethane acrylates; Epoxy acrylate compounds; A printed circuit board comprising at least one compound-mixture selected from the group consisting of caprolactone-modified acrylate compounds and photosensitive (meth) acrylate compounds.
【청구항 13] [Claim 13]
제 1 항에 있어서,  The method of claim 1,
상기 광개시제는 벤조인과 그 알킬에테르류, 아세토페논류, 안트라퀴논류， 티오크산톤류， 케탈류, 벤조페논류, α-아미노아세토페논류, 아실포스핀옥사이드류 및 옥심에스테르류로 이루어진 군에서 선택된 1 종 이상인 인쇄 회로 기판.  The photoinitiator is a group consisting of benzoin, alkyl ethers thereof, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides, and oxime esters. Printed circuit board is one or more selected from.
【청구항 14] [Claim 14]
제 1 항에 있어서,  The method of claim 1,
상기 열경화성 바인더 수지는 에폭시기, 옥세타닐기， 환상 에테르기 및 환상 티오 에테르기로 이루어진 군에서 선택된 1 종 이상의 작용기가 치환된 화합물을 포함하는 인쇄 회로 기판.  The thermosetting binder resin includes a compound in which at least one functional group selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thio ether group is substituted.
【청구항 15】 [Claim 15]
제 1항에 있어서，  The method of claim 1,
상기 광성 수지 조성물은 광개시제 및 유기 용매를 더 포함하는 인쇄 회뢰 기판. The photoresist composition further comprises a photoinitiator and an organic solvent.
【청구항 16] [Claim 16]
제 15항에 있어서，  The method of claim 15,
상기 감광성 수지 조성물은,  The photosensitive resin composition,
카르복시기 (-COOH) 및 광경화 가능한 작용기를  Carboxyl groups (-COOH) and photocurable functional groups
올리고머 10 내지 80 중량0 /。； Oligomer 10 to 80 weight 0 /.;
광중합성 모노머 1 내지 30 중량0 /0; Photopolymerizable monomer 1 to 30 parts by weight 0/0;
광개시제 0.1 내지 10 중량0 /。； Photoinitiator 0.1 to 10 weight 0 /.;
열경화성 바인더 수지 1 내지 30 중량0 /0; The thermosetting binder resin 1 to 30 parts by weight 0/0;
안료 0.01 내지 10 중량0 /。； 및 Pigment 0.01 to 10 weight 0 /.; And
용매 5 내지 50중량%를 포함하는 인쇄 회로 기판.  Printed circuit board comprising 5 to 50% by weight solvent.
【청구항 17] [Claim 17]
카르복시기 (-COOH) 및 광경화 가능한 작용기를 갖는 산변성 올리고머; 광중합성 모노머; 광개시제; 열경화성 바인더 수지; 유기 용매 및 안료를 포함하는 감광성 수지 조성물의 건조물 또는 경화물을 포함하는 드라이 필름을 기판 상에 적층하는 단계;  Acid-modified oligomers having a carboxyl group (-COOH) and a photocurable functional group; Photopolymerizable monomers; Photoinitiators; Thermosetting binder resins; Stacking a dry film comprising a dried or cured product of the photosensitive resin composition comprising an organic solvent and a pigment on a substrate;
상기 기판의 외측 테두리 부위의 드라이 필름을 노광하는 단계; 및 상기 노광된 드라이 필름을 세정하는 단계를 포함하는 인쇄 희로 기판의 제조 방법.  Exposing a dry film on an outer edge portion of the substrate; And cleaning the exposed dry film.
【청구항 18】 [Claim 18]
제 Π항에 있어서，  The method of claim Π,
상기 기판 상에 전극 패드를 형성하는 단계;  Forming an electrode pad on the substrate;
상기 전극 패드 상에 솔더 범프를 위치시키는 단계; 및  Positioning solder bumps on the electrode pads; And
반도체 칩을 상기 .솔더 범프를 매개로 플립 칩 결합시키는 단계를 더 포함하는 인쇄 회로 기판의 제조 방법.  Flip chip bonding a semiconductor chip through the solder bumps.
【청구항 19】 [Claim 19]
제 18항에 있어서 상기 기판과 상기 반도체 칩 사이로 언더필 재료를 주입하는 단계를 더 포함하는 인쇄 회로 기판의 제조 방법. The method of claim 18 And injecting an underfill material between the substrate and the semiconductor chip.
PCT/KR2011/003466 2010-05-20 2011-05-11 Printed circuit board including a dam for underfills, and method for manufacturing same WO2011145828A2 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0897341A (en) * 1993-11-16 1996-04-12 Mitsui High Tec Inc Manufacture of lead frame for semiconductor device
JP2001159815A (en) * 1999-12-03 2001-06-12 Nippon Kayaku Co Ltd Photosensitive resin composition and photosensitive film using same
JP2004325980A (en) * 2003-04-28 2004-11-18 Kanegafuchi Chem Ind Co Ltd Photosensitive resin composition and photosensitive dry film resist having favorable storage stability, and its use
US20100116534A1 (en) * 2008-11-12 2010-05-13 Samsung Electro-Mechanics Co., Ltd. Printed Circuit Board Having Flow Preventing Dam And Manufacturing Method Thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0897341A (en) * 1993-11-16 1996-04-12 Mitsui High Tec Inc Manufacture of lead frame for semiconductor device
JP2001159815A (en) * 1999-12-03 2001-06-12 Nippon Kayaku Co Ltd Photosensitive resin composition and photosensitive film using same
JP2004325980A (en) * 2003-04-28 2004-11-18 Kanegafuchi Chem Ind Co Ltd Photosensitive resin composition and photosensitive dry film resist having favorable storage stability, and its use
US20100116534A1 (en) * 2008-11-12 2010-05-13 Samsung Electro-Mechanics Co., Ltd. Printed Circuit Board Having Flow Preventing Dam And Manufacturing Method Thereof

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