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WO2016060237A1 - Structure stratifiée, film sec, et carte de câblage imprimé souple - Google Patents

Structure stratifiée, film sec, et carte de câblage imprimé souple Download PDF

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Publication number
WO2016060237A1
WO2016060237A1 PCT/JP2015/079291 JP2015079291W WO2016060237A1 WO 2016060237 A1 WO2016060237 A1 WO 2016060237A1 JP 2015079291 W JP2015079291 W JP 2015079291W WO 2016060237 A1 WO2016060237 A1 WO 2016060237A1
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WIPO (PCT)
Prior art keywords
resin layer
resin
wiring board
printed wiring
flexible printed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/079291
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English (en)
Japanese (ja)
Inventor
宮部　英和
亮 林
悠斗 小田桐
直之 小池
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Filing date
Publication date
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Priority to CN201580055810.XA priority Critical patent/CN106796402B/zh
Priority to JP2016554131A priority patent/JP6578295B2/ja
Priority to KR1020177013163A priority patent/KR101998002B1/ko
Publication of WO2016060237A1 publication Critical patent/WO2016060237A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a laminated structure useful as an insulating film of a flexible printed wiring board, a dry film, and a flexible printed wiring board.
  • the mounting part (non-bent part) has a mixed mounting process using a photosensitive resin composition that is excellent in electrical insulation and solder heat resistance and can be finely processed. Widely adopted.
  • a cover lay based on polyimide is not suitable for fine wiring because it requires processing by die punching. Therefore, it is necessary to partially use an alkali developing type photosensitive resin composition (solder resist) that can be processed by photolithography in a chip mounting portion that requires fine wiring.
  • solvent resist alkali developing type photosensitive resin composition
  • JP-A-62-263692 Japanese Patent Laid-Open No. 63-110224
  • the conventional flexible printed wiring board manufacturing process has to employ a mixed mounting process of bonding the coverlay and forming the solder resist, which is inferior in cost and workability. It was.
  • an object of the present invention is to provide a laminated structure, a dry film, which is excellent in flexibility and suitable for a batch forming process of an insulating film of a flexible printed wiring board, particularly a bent portion (bent portion) and a mounting portion (non-bent portion), And it is providing the flexible printed wiring board which has the hardened
  • the laminated structure of the present invention is a laminated structure having a resin layer (A) and a resin layer (B) laminated on the flexible printed wiring board via the resin layer (A),
  • the resin layer (B) is composed of a photosensitive thermosetting resin composition containing an alkali-soluble resin, a photopolymerization initiator, and a heat-reactive compound, and the resin layer (A) is an alkali-soluble resin.
  • an alkali development type resin composition containing no photopolymerization initiator.
  • the resin layer (A) is made of a resin composition further containing a polymerization inhibitor.
  • the laminated structure of the present invention can be used for at least one of a bent portion and a non-bent portion of a flexible printed wiring board, and among the cover lay, solder resist, and interlayer insulating material of the flexible printed wiring board It can be used for at least one of the applications.
  • the dry film of the present invention is characterized in that at least one surface of the laminated structure of the present invention is supported or protected by the film.
  • the flexible printed wiring board of the present invention comprises an insulating layer formed by forming a layer of the laminated structure of the present invention on a flexible printed wiring board, patterning by light irradiation, and forming the pattern in a batch with a developer. It is characterized by having a film.
  • the flexible printed wiring board of the present invention is formed by sequentially forming the resin layer (A) and the resin layer (B) without using the laminated structure according to the present invention, and then patterning by light irradiation.
  • the pattern may be collectively formed with a developer.
  • the “pattern” means a patterned cured product, that is, an insulating film.
  • a laminated structure, a dry film which is excellent in flexibility and suitable for a batch forming process of an insulating film of a flexible printed wiring board, particularly a bent portion (bent portion) and a mounting portion (non-bent portion), and It is possible to realize a flexible printed wiring board having the cured product as a protective film, for example, a cover lay or a solder resist.
  • the laminated structure of the present invention has a resin layer (A) and a resin layer (B) laminated on the flexible printed wiring board via the resin layer (A), and the resin layer (B) And a photosensitive thermosetting resin composition containing an alkali-soluble resin, a photopolymerization initiator, and a heat-reactive compound, and the resin layer (A) contains an alkali-soluble resin and a heat-reactive compound. It consists of an alkali developing resin composition that does not contain a polymerization initiator.
  • Such a laminated structure of the present invention has a resin layer (A) and a resin layer (B) in this order on a flexible printed wiring board in which a copper circuit is formed on a flexible substrate, and an upper resin layer ( B) is made of a photosensitive thermosetting resin composition that can be patterned by light irradiation, and the resin layer (B) and the resin layer (A) can form a pattern collectively by development. .
  • the resin layer (A) on the printed wiring board side does not contain a photopolymerization initiator and cannot be patterned by a single layer.
  • active species such as radicals generated from the photopolymerization initiator contained in the layer (B) into the resin layer (A) directly below, both layers can be patterned simultaneously.
  • a printed wiring board manufacturing method including a PEB (POST EXPOSURE BAKE) process the effect is remarkable due to thermal diffusion of the active species.
  • the photopolymerization initiator when the photopolymerization initiator is contained in the resin layer (A) on the printed wiring board side, the photopolymerization initiator itself has a property of absorbing light, so that the photopolymerization initiator increases toward the deep part. Although the polymerization initiating ability is lowered and the photoreactivity in the deep part is lowered, it tends to be undercut, and high-definition pattern formation has been difficult, but the upper resin layer in the laminated structure of the present invention The present inventors considered that such a problem can be improved by the influence of the diffusion of the active species from (B).
  • the resin layer (A) does not contain a photopolymerization initiator, and as a result, it is possible to form a pattern with excellent deep curability without undercut.
  • the reason is not clear, but the diffusion of the active species occurs in areas other than the exposed area due to the influence of the interface. There was a new problem that so-called halation is likely to occur near the interface between A) and the resin layer (B).
  • the alkali-developable resin composition constituting the resin layer (A) includes an alkali-soluble resin that contains at least one functional group of phenolic hydroxyl group and carboxyl group and can be developed with an alkali solution, and thermal reactivity. It is sufficient if the composition contains a compound and does not contain a photopolymerization initiator.
  • the alkali-soluble resin include compounds having a phenolic hydroxyl group, compounds having a carboxyl group, compounds having a phenolic hydroxyl group and a carboxyl group, and known and commonly used resins are used.
  • the present invention contains a carboxyl group-containing resin or a carboxyl group-containing photosensitive resin, a compound having an ethylenically unsaturated bond, and a heat-reactive compound, which has been conventionally used as a solder resist composition, including a compound having a carboxyl group. And a resin composition containing no photopolymerization initiator.
  • carboxyl group-containing resin or the carboxyl group-containing photosensitive resin and the compound having an ethylenically unsaturated bond known and commonly used compounds are used, and as the thermally reactive compound, a cyclic (thio) ether is used.
  • a cyclic (thio) ether is used as the thermally reactive compound.
  • Known and conventional compounds having a functional group capable of undergoing a curing reaction by heat, such as a group are used.
  • a polymerization inhibitor into the alkali developing resin composition constituting the resin layer (A).
  • a polymerization inhibitor it is possible to minimize the influence of exposure, suppress the influence of heat in the PEB process, and stabilize the opening shape. In this case, the problem of poor curing in the deep portion does not occur. Therefore, by blending the polymerization inhibitor into the alkali developing resin composition constituting the resin layer (A), it is possible to achieve both stabilization of the opening shape and good deep part curability.
  • polymerization inhibitor a known and usual polymerization inhibitor can be used.
  • Polymerization inhibitors include phenothiazine, hydroquinone, N-phenylnaphthylamine, chloranil, pyrogallol, benzoquinone, t-butylcatechol, hydroquinone, methylhydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, naphthoquinone, 4-methoxy- Examples thereof include 1-naphthol, 2-hydroxy 1,4-naphthoquinone, phosphorus-containing compounds having a phenolic hydroxyl group, and nitrosamine compounds. These polymerization inhibitors may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the polymerization inhibitor is preferably 0.01 to 100 parts by mass, and more preferably 0.03 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • the photosensitive thermosetting resin composition constituting the resin layer (B) includes an alkali-soluble resin, a photopolymerization initiator, and a thermoreactive compound.
  • an alkali-soluble resin known and conventional resins similar to the resin layer (A) can be used, but an alkali-soluble resin having an imide ring which is superior in characteristics such as flex resistance and heat resistance is preferable. Can be used.
  • a heat-reactive compound the well-known and usual thing similar to the said resin layer (A) can be used.
  • the alkali-soluble resin having an imide ring has at least one alkali-soluble group out of phenolic hydroxyl group and carboxyl group and an imide ring.
  • a known and usual method can be used for introducing the imide ring into the alkali-soluble resin. Examples thereof include a resin obtained by reacting a carboxylic anhydride component with an amine component and / or an isocyanate component. The imidization may be performed by thermal imidization or chemical imidization, and these may be performed in combination.
  • examples of the carboxylic acid anhydride component include tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, but are not limited to these acid anhydrides, and acid anhydrides that react with amino groups or isocyanate groups. Any compound having a physical group and a carboxyl group can be used, including derivatives thereof. These carboxylic anhydride components may be used alone or in combination.
  • amine component examples include diamines such as aliphatic diamines and aromatic diamines, polyvalent amines such as aliphatic polyether amines, diamines having carboxylic acids, and diamines having phenolic hydroxyl groups. It is not limited to. These amine components may be used alone or in combination.
  • Diisocyanates such as aromatic diisocyanates and their isomers and multimers, aliphatic diisocyanates, alicyclic diisocyanates and their isomers, and other general-purpose diisocyanates can be used as the isocyanate component. It is not limited. These isocyanate components may be used alone or in combination.
  • the alkali-soluble resin having an imide ring as described above may have an amide bond.
  • This may be a polyamideimide obtained by reacting an imidized product having a carboxyl group, an isocyanate and a carboxylic acid anhydride, or may be due to other reactions.
  • you may have the coupling
  • an organic solvent is not particularly limited as long as it is a solvent that does not react with the carboxylic acid anhydrides, amines, and isocyanates that are raw materials and that dissolves these raw materials, and the structure is not particularly limited.
  • aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and ⁇ -butyrolactone are preferred because of the high solubility of the raw materials.
  • An alkali-soluble resin having at least one alkali-soluble group and imide ring among phenolic hydroxyl groups and carboxyl groups as described above has an acid value of 20 to 200 mgKOH / g in order to cope with the photolithography process. And more preferably 60 to 150 mgKOH / g.
  • the acid value is 20 mgKOH / g or more, the solubility in alkali increases, the developability becomes good, and further, the degree of crosslinking with the thermosetting component after light irradiation becomes high, so that sufficient development contrast is obtained. be able to.
  • the molecular weight of the alkali-soluble resin is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000, considering developability and cured coating film characteristics.
  • the molecular weight is 1,000 or more, sufficient development resistance and cured properties can be obtained after exposure and PEB.
  • the molecular weight is 100,000 or less, alkali solubility increases and developability improves.
  • Photopolymerization initiator As the photopolymerization initiator used in the resin layer (B), known and conventional ones can be used. For example, benzoin compounds, acylphosphine oxide compounds, acetophenone compounds, ⁇ -aminoacetophenone compounds, oxime ester compounds, thioxanthone System compounds and the like.
  • a photopolymerization initiator that also has a function as a photobase generator is suitable.
  • a photopolymerization initiator and a photobase generator may be used in combination.
  • a photopolymerization initiator that also functions as a photobase generator is a polymer that undergoes a polymerization reaction of a thermoreactive compound, which will be described later, when the molecular structure is changed by light irradiation such as ultraviolet light or visible light, or when the molecule is cleaved. It is a compound that produces one or more basic substances that can function as a catalyst. Examples of basic substances include secondary amines and tertiary amines. Examples of the photopolymerization initiator having a function as a photobase generator include ⁇ -aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, and N-acylated aromatics.
  • oxime ester compounds and ⁇ -aminoacetophenone compounds are preferable, and oxime ester compounds are more preferable.
  • oxime ester compounds those having two or more nitrogen atoms are particularly preferable.
  • the ⁇ -aminoacetophenone compound is not particularly limited as long as it has a benzoin ether bond in the molecule and is cleaved within the molecule when irradiated with light to produce a basic substance (amine) that exhibits a curing catalytic action.
  • any compound that generates a basic substance by light irradiation can be used.
  • photopolymerization initiators may be used singly or in combination of two or more.
  • the blending amount of the photopolymerization initiator in the resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.3 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • the development resistance contrast of the light irradiated part / non-irradiated part can be favorably obtained.
  • cured material characteristic improves.
  • the following components can be blended as necessary.
  • Polymer resin As the polymer resin, known and commonly used ones can be blended for the purpose of improving the flexibility and dryness of the touch of the resulting cured product.
  • examples of such polymer resins include cellulose-based, polyester-based, phenoxy resin-based polymers, polyvinyl acetal-based, polyvinyl butyral-based, polyamide-based, polyamide-imide-based binder polymers, block copolymers, and elastomers. This polymer resin may be used individually by 1 type, and may use 2 or more types together.
  • An inorganic filler can be mix
  • examples of such inorganic fillers include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, Neuburg Sicilius Earth etc. are mentioned.
  • Colorant As the colorant, known and commonly used colorants such as red, blue, green, yellow, white and black can be blended, and any of pigments, dyes and pigments may be used.
  • Organic solvent can be mix
  • organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.
  • Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.
  • components such as a mercapto compound, an adhesion promoter, an antioxidant, and an ultraviolet absorber can be further blended.
  • a mercapto compound such as a mercapto compound, an adhesion promoter, an antioxidant, and an ultraviolet absorber can be further blended.
  • known and commonly used ones can be used.
  • known and commonly used thickeners such as finely divided silica, hydrotalcite, organic bentonite, montmorillonite, defoamers and / or leveling agents such as silicones, fluorines and polymers, silane coupling agents, rust inhibitors
  • Known and conventional additives such as can be blended.
  • the laminated structure of the present invention is excellent in flexibility, it can be used for at least one of a bent portion and a non-bent portion of a flexible printed wiring board. It can be used as an application of at least one of a resist and an interlayer insulating material.
  • the laminated structure of the present invention according to the configuration as described above is preferably used as a dry film having at least one surface supported or protected by a film.
  • the dry film of the present invention can be produced as follows. That is, first, on the carrier film (support film), the composition constituting the resin layer (B) and the resin layer (A) is diluted with an organic solvent and adjusted to an appropriate viscosity. Apply sequentially by a known method such as a coater. Thereafter, the film is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes, whereby a dry film comprising the resin layer (B) and the resin layer (A) can be formed on the carrier film. A peelable cover film (protective film) can be further laminated on the dry film for the purpose of preventing dust from adhering to the surface of the film. As the carrier film and the cover film, conventionally known plastic films can be used as appropriate. When the cover film is peeled off, the adhesive force between the resin layer and the carrier film may be smaller. preferable.
  • the thicknesses of the carrier film and the cover film are not particularly limited, but are generally appropriately selected within the range of 10 to 150 ⁇ m.
  • the manufacture of a flexible printed wiring board using the laminated structure of the present invention can be performed according to the procedure shown in the process diagram of FIG. That is, a step of forming the layer of the laminated structure of the present invention on the flexible wiring board on which the conductor circuit is formed (lamination step), and a step of irradiating the layer of the laminated structure with active energy rays in a pattern (exposure step)
  • the manufacturing method includes a step (developing step) of forming a layer of the patterned laminated structure at once by alkali developing the layer of the laminated structure.
  • further photocuring and heat curing post-cure process
  • the manufacture of the flexible printed wiring board using the laminated structure of the present invention can also be performed according to the procedure shown in the process diagram of FIG. That is, a step of forming the layer of the laminated structure of the present invention on the flexible wiring board on which the conductor circuit is formed (lamination step), and a step of irradiating the layer of the laminated structure with active energy rays in a pattern (exposure step)
  • lamination step a step of forming the layer of the laminated structure of the present invention on the flexible wiring board on which the conductor circuit is formed
  • exposure step a step of irradiating the layer of the laminated structure with active energy rays in a pattern
  • the step of heating the layer of the laminated structure heating (PEB) step), and the step of forming the layer of the patterned laminated structure at once by developing the layer of the laminated structure with alkali (developing step)
  • PEB heating
  • developing step a manufacturing method containing.
  • each process shown in FIG. 1 or FIG. 2 is demonstrated in detail.
  • a resin layer 3 (resin layer (A)) made of an alkali-developable resin composition containing an alkali-soluble resin and the like is formed on the flexible printed wiring board 1 on which the conductor circuit 2 is formed, and on the resin layer 3.
  • a resin layer 4 (resin layer (B)) made of a photosensitive thermosetting resin composition containing an alkali-soluble resin or the like.
  • each resin layer constituting the laminated structure forms, for example, the resin layers 3 and 4 by sequentially applying and drying the resin composition constituting the resin layers 3 and 4 on the wiring board 1.
  • the resin composition that forms the resin layers 3 and 4 may be formed by laminating the resin composition in the form of a two-layer dry film on the wiring board 1.
  • the method for applying the resin composition to the wiring board may be a known method such as a blade coater, a lip coater, a comma coater, or a film coater.
  • the drying method is a method using a hot-air circulation type drying furnace, IR furnace, hot plate, convection oven, etc., equipped with a heat source of the heating method by steam, and the hot air in the dryer is counter-contacted and supported by the nozzle
  • a known method such as a method of spraying on the body may be used.
  • the photopolymerization initiator contained in the resin layer 4 is activated into a negative pattern by irradiation with active energy rays, and the exposed portion is cured.
  • the exposure machine a direct drawing apparatus, an exposure machine equipped with a metal halide lamp, or the like can be used.
  • the patterned exposure mask is a negative mask.
  • the active energy ray used for exposure laser light or scattered light having a maximum wavelength in the range of 350 to 450 nm is preferably used. By setting the maximum wavelength within this range, the photopolymerization initiator can be activated efficiently.
  • the exposure amount varies depending on the film thickness and the like, but can usually be set to 100 to 1500 mJ / cm 2 .
  • the exposed portion is cured by heating the resin layer.
  • a base generated in the exposure step of the resin layer (B) made of a composition using a photopolymerization initiator having a function as a photobase generator or a combination of a photopolymerization initiator and a photobase generator is used.
  • the resin layer (B) can be cured to a deep part.
  • the heating temperature is, for example, 80 to 140 ° C.
  • the heating time is, for example, 2 to 140 minutes.
  • the curing of the resin composition in the present invention is, for example, a ring-opening reaction of an epoxy resin by a thermal reaction, distortion and curing shrinkage can be suppressed as compared with a case where curing proceeds by a photoradical reaction.
  • the unexposed portion is removed by alkali development to form a negative patterned insulating film, particularly a cover lay and a solder resist.
  • the developing method can be a known method such as dipping.
  • the developer include sodium carbonate, potassium carbonate, potassium hydroxide, amines, imidazoles such as 2-methylimidazole, alkaline aqueous solutions such as tetramethylammonium hydroxide aqueous solution (TMAH), or a mixed solution thereof. Can be used.
  • the resin layer is completely thermoset to obtain a highly reliable coating film.
  • the heating temperature is, for example, 140 ° C. to 180 ° C.
  • the heating time is, for example, 20 to 120 minutes. Further, light irradiation may be performed before or after the post cure.
  • ⁇ Synthesis Example 1 Synthesis Example of Polyamideimide Resin Solution> 3.8 g of 3,5-diaminobenzoic acid, 2,2′-bis [4- (4-aminophenoxy) in a separable three-necked flask equipped with a stirrer, nitrogen inlet tube, fractional ring, and cooling ring 6.98 g of phenyl] propane, 8.21 g of Jeffamine XTJ-542 (manufactured by Huntsman, molecular weight 10225.64) and 86.49 g of ⁇ -butyrolactone were charged at room temperature and dissolved.
  • the obtained imidized product solution was charged with 9.61 g of trimellitic anhydride and 17.45 g of trimethylhexamethylene diisocyanate and stirred at a temperature of 160 ° C. for 32 hours.
  • a polyamideimide resin solution (PAI-1) having a carboxyl group was obtained.
  • the acid value of the obtained resin (solid content) was 83.1 mgKOH, and Mw was 4300.
  • Examples 1 to 6 Comparative Examples 1 to 4
  • the materials described in Examples and Comparative Examples were respectively blended, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a resin composition constituting each resin layer. .
  • the values in the table are parts by mass of the solid content.
  • each resin composition was applied so that the film thickness after drying was 10 ⁇ m. Then, it dried at 90 degreeC / 30 minutes with the hot-air circulation type drying furnace, and formed the resin layer (B) which consists of a resin composition.
  • ⁇ Minimum remaining line width> Each of the obtained laminated structures was exposed at 500 mJ / cm 2 using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp.
  • the PEB process was performed at 90 ° C. for 30 minutes, and then development (30 ° C., 0.2 MPa, 1 mass% Na 2 CO 3 aqueous solution) was performed in 60 seconds.
  • a pattern was drawn and heat cured at 150 ° C. for 60 minutes to obtain a cured coating film.
  • the minimum remaining line width of the obtained cured coating film was counted using an optical microscope adjusted to 200 times. The smaller the minimum remaining line width, the better the deep curability.
  • the surface on which the resin composition was applied was placed on the outside, bent around a core rod having a diameter of 2 mm, and the presence or absence of discoloration and crack generation was evaluated.
  • a case where no discoloration or crack occurred in the bent portion was indicated by “ ⁇ ”, a case where discoloration occurred and no crack occurred, “ ⁇ ”, and a case where crack occurred, ⁇ .
  • each of the obtained laminated structures is 500 mJ / cm 2 through a negative mask in which an opening having a diameter of about 2 mm to 5 mm is formed on copper. Exposed. Thereafter, in Examples 3 to 6 and Comparative Examples 3 and 4, the PEB process was performed at 90 ° C. for 30 minutes, and then development (30 ° C., 0.2 MPa, 1 mass% Na 2 CO 3 aqueous solution) was performed in 60 seconds. The cured laminated structure was obtained by thermosetting at 150 ° C. for 60 minutes. The obtained cured laminated structure was immersed in a solder bath heated to 260 ° C.
  • each example is superior in sensitivity and deep curability as compared with the laminated structure of each comparative example. It is.
  • the photopolymerization initiator absorbs light, so that deep curability cannot be obtained, and fine lines are dropped during development. End up.
  • Examples 7 to 12, Comparative Example 5 In accordance with the composition described in the following table, the materials described in Examples and Comparative Examples were respectively compounded, premixed with a stirrer, and then kneaded with a three-roll mill, thereby forming a resin composition constituting each resin layer.
  • the resin layer (A) and the resin layer (B) were formed in the same manner as in Example 1 above. Unless otherwise specified, the values in the table are parts by mass of the solid content.
  • ⁇ Resolution (opening size and minimum remaining line width)> Each of the obtained laminated structures was exposed at 500 mJ / cm 2 using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp.
  • the exposure pattern was a pattern for drawing a line having a width of 30/40/50/60/70/80/90/100 ⁇ m and a pattern for opening an opening of 300 ⁇ m. Then, after performing a PEB process at 90 ° C. for 30 minutes, development (30 ° C., 0.2 MPa, 1 mass% Na 2 CO 3 aqueous solution) is performed in 60 seconds to draw a pattern, and heat curing is performed at 150 ° C. ⁇ 60 minutes. A cured coating film was obtained.
  • the minimum remaining line width was counted using an optical microscope adjusted to 200 times, the opening size (design value 300 ⁇ m) was measured, and the opening shape was photographed. The smaller the minimum remaining line width, the better the deep curability. The results are shown in the table below and in FIGS. 3 (a) to (i), respectively.
  • LUCIRIN TPO acylphosphine oxide photopolymerization initiator, manufactured by BASF Japan
  • QS-30 4-methoxy-1-naphthol (manufactured by Kawasaki Chemical Industry Co., Ltd.) * 13)
  • HCA-HQ Phenolic hydroxyl group-containing phosphorus compound (manufactured by Sanko Co., Ltd.)
  • Example 7 to 12 The laminated structures of Examples 7 to 12 in which the polymerization inhibitor was blended in the resin layer (A) had less halation, a stable opening shape, and a minimum residual line width of 30 ⁇ m.
  • Example 6 having the same composition as Example 12 except that the polymerization inhibitor was not blended was evaluated for the opening size and gold plating resistance, the minimum residual line width was 30 ⁇ m, but the halation There was a small opening size of 240 ⁇ m.
  • Comparative Example 5 a photopolymerization initiator is used for the resin layer (A), and halation is prevented to some extent. However, the resistance to gold plating is poor, and the minimum line width and the opening size are sufficient. It was not a thing.

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  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : une structure stratifiée et un film sec ayant une excellente souplesse et utilisable en tant que film isolant d'une carte de circuit imprimé souple, notamment pour un processus de formation collective d'une partie coudée (partie courbée) et d'une partie de montage (partie non courbée) ; et une carte de circuit imprimé souple comportant en tant que film protecteur un produit durci dudit film sec. L'invention concerne une structure stratifiée ayant une couche de résine (A) et une couche de résine (B) qui est stratifiée sur la carte de circuit imprimé souple, la couche de résine (A) étant interposée entre celles-ci. La couche de résine (B) comprend une composition de résine thermodurcissable photosensible comprenant une résine soluble dans les alcalis, un initiateur de photopolymérisation et un composé réagissant à la chaleur, et la couche de résine (A) comprend une composition de résine développable en milieu alcalin comprenant une résine soluble dans les alcalis et un composé réagissant à la chaleur mais ne comprenant pas d'initiateur de photopolymérisation.
PCT/JP2015/079291 2014-10-16 2015-10-16 Structure stratifiée, film sec, et carte de câblage imprimé souple Ceased WO2016060237A1 (fr)

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CN201580055810.XA CN106796402B (zh) 2014-10-16 2015-10-16 层叠结构体、干膜以及柔性印刷电路板
JP2016554131A JP6578295B2 (ja) 2014-10-16 2015-10-16 積層構造体、ドライフィルムおよびフレキシブルプリント配線板
KR1020177013163A KR101998002B1 (ko) 2014-10-16 2015-10-16 적층 구조체, 드라이 필름 및 플렉시블 프린트 배선판

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JP (1) JP6578295B2 (fr)
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JP2022062573A (ja) * 2020-10-08 2022-04-20 太陽インキ製造株式会社 感光性積層樹脂構造体、ドライフィルム、硬化物および電子部品
WO2022211122A1 (fr) * 2021-03-31 2022-10-06 太陽インキ製造株式会社 Structure stratifiée, film sec, produit durci et composant électronique
WO2022211121A1 (fr) * 2021-03-31 2022-10-06 太陽インキ製造株式会社 Structure stratifiée, film sec, produit durci et composant électronique
WO2025120861A1 (fr) * 2023-12-08 2025-06-12 株式会社レゾナック Procédé de fabrication de dispositif à semi-conducteur
US12381138B2 (en) 2018-09-10 2025-08-05 AT&SAustria Technologie &Systemtechnik Aktiengesellschaft Component carrier with a photoimageable dielectric layer and a structured conductive layer being used as a mask for selectively exposing the photoimageable dielectric layer with electromagnetic radiation

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WO2016143580A1 (fr) * 2015-03-06 2016-09-15 東レ株式会社 Composition de résine photosensible et composant électronique
KR102372882B1 (ko) 2016-06-29 2022-03-08 코오롱인더스트리 주식회사 드라이 필름 포토레지스트용 감광성 수지 조성물
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WO2018155188A1 (fr) * 2017-02-21 2018-08-30 日本ゼオン株式会社 Composition de résine photosensible
JP7127635B2 (ja) 2017-02-21 2022-08-30 日本ゼオン株式会社 感光性樹脂組成物
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KR20180111607A (ko) * 2017-03-31 2018-10-11 다이요 잉키 세이조 가부시키가이샤 경화성 수지 조성물, 적층 구조체, 그의 경화물 및 전자 부품
CN108693702A (zh) * 2017-03-31 2018-10-23 太阳油墨制造株式会社 固化性树脂组合物、层叠结构体、其固化物和电子部件
JP2018172533A (ja) * 2017-03-31 2018-11-08 太陽インキ製造株式会社 硬化性樹脂組成物、積層構造体、その硬化物、および電子部品
KR102457058B1 (ko) * 2017-03-31 2022-10-21 다이요 잉키 세이조 가부시키가이샤 경화성 수지 조성물, 적층 구조체, 그의 경화물 및 전자 부품
JP2019001967A (ja) * 2017-06-20 2019-01-10 太陽インキ製造株式会社 硬化性樹脂組成物、積層構造体、その硬化物および電子部品
KR20200027969A (ko) * 2017-07-10 2020-03-13 다이요 잉키 세이조 가부시키가이샤 적층 구조체, 드라이 필름 및 플렉시블 프린트 배선판
JP2019015913A (ja) * 2017-07-10 2019-01-31 太陽インキ製造株式会社 積層構造体、ドライフィルムおよびフレキシブルプリント配線板
WO2019012986A1 (fr) * 2017-07-10 2019-01-17 太陽インキ製造株式会社 Structure multicouche, film sec et panneau de câblage imprimé souple
KR102580790B1 (ko) * 2017-07-10 2023-09-20 다이요 홀딩스 가부시키가이샤 적층 구조체, 드라이 필름 및 플렉시블 프린트 배선판
US12381138B2 (en) 2018-09-10 2025-08-05 AT&SAustria Technologie &Systemtechnik Aktiengesellschaft Component carrier with a photoimageable dielectric layer and a structured conductive layer being used as a mask for selectively exposing the photoimageable dielectric layer with electromagnetic radiation
US11140768B2 (en) 2019-04-10 2021-10-05 At&S Austria Technologie & Systemtechnik Aktiengesellschaft Component carrier with high passive intermodulation performance
JP2022062573A (ja) * 2020-10-08 2022-04-20 太陽インキ製造株式会社 感光性積層樹脂構造体、ドライフィルム、硬化物および電子部品
WO2022211122A1 (fr) * 2021-03-31 2022-10-06 太陽インキ製造株式会社 Structure stratifiée, film sec, produit durci et composant électronique
WO2022211121A1 (fr) * 2021-03-31 2022-10-06 太陽インキ製造株式会社 Structure stratifiée, film sec, produit durci et composant électronique
WO2025120861A1 (fr) * 2023-12-08 2025-06-12 株式会社レゾナック Procédé de fabrication de dispositif à semi-conducteur

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CN106796402B (zh) 2020-09-08
TW201630732A (zh) 2016-09-01
CN106796402A (zh) 2017-05-31
KR101998002B1 (ko) 2019-07-08
JP6578295B2 (ja) 2019-09-18
KR20170070187A (ko) 2017-06-21
JPWO2016060237A1 (ja) 2017-04-27
TWI688475B (zh) 2020-03-21

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