KR20160041788A - Dry film, cured product and printed wiring board - Google Patents

Abstract

(Problems to be Solved) A dry film having excellent heat resistance, low warpage and crack resistance of a cured product, excellent releasability from a carrier film, and having a resin layer for suppressing cracking and powder dropping, And to provide a printed wiring board having a cargo.
A dry film having a resin layer containing a thermosetting resin component, at least one of a curing agent and a curing accelerator, a maleimide compound, a filler, and at least two kinds of solvents, wherein the at least two kinds of solvents All have a boiling point of 100 占 폚 or more and a boiling point of 5 占 폚 or more.

Description

DRY FILM, CURED PRODUCT AND PRINTED WIRING BOARD BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

TECHNICAL FIELD The present invention relates to a dry film, a cured product and a printed wiring board. More particularly, the present invention relates to a dry film, a cured product, and a printed wiring board which are excellent in heat resistance, low warpage and crack resistance of a cured product, A cured product obtained by curing a resin layer of the dry film, and a printed wiring board comprising the cured product.

BACKGROUND ART [0002] In recent years, as a manufacturing method of a multilayer printed wiring board, a build-up manufacturing technique in which a resin insulating layer and a conductor layer are alternately stacked on a conductor layer of an inner circuit board has attracted attention. For example, an epoxy resin composition is applied to a circuit-formed inner-layer circuit board, and after heating and curing, a roughened surface is formed on the surface by a roughening agent and the conductor layer is subjected to plating (Refer to Patent Document 1 and Patent Document 2). Further, a multilayer printed wiring board production method in which an adhesive sheet of an epoxy resin composition is laminated on a circuit-formed inner-layer circuit board, followed by heating and curing, forming a roughened surface on the surface by a coagulating agent, and forming a conductor layer by plating (See Patent Document 3).

An example of a method of forming a layer structure of a multilayer printed wiring board by a conventional build-up method will be described with reference to Fig. 1. First, an inner layer conductor pattern 3 and a resin insulating layer 4 are formed on both surfaces of an insulating substrate 1, The outer layer conductor pattern 8 is formed on both sides of the laminated substrate X on which the resin layer 9 is formed and an insulating resin composition such as an epoxy resin composition is applied thereon by coating or the like and is thermally cured to form the resin insulating layer 9 do. Subsequently, after appropriately forming the through-hole 21 and the like, a conductor layer is formed on the surface of the resin insulating layer 9 by electroless plating or the like, and then a predetermined circuit pattern is formed on the conductor layer So that the outermost conductor pattern 10 can be formed.

As a method for forming a resin insulating layer (hereinafter referred to as an interlayer insulating layer) to be formed between layers in a multilayer printed wiring board, a thermosetting resin composition such as an epoxy resin composition is coated on a film There is used a method in which a dry film having a resin layer obtained by coating and drying is thermally cured after lamination.

Japanese Patent Application Laid-Open No. 7-304931 (claims) Japanese Patent Application Laid-Open No. 7-304933 (claims) Japanese Patent Application Laid-Open No. 2010-1403 (claims)

As one of the thermosetting resin components to be blended in a dry film, a liquid epoxy resin is used (for example, Patent Document 3). When a liquid epoxy resin is contained, the adhesion of the dry film is excellent, and cracks and powder do not fall off. However, when a liquid epoxy resin is contained, there is a problem that when the carrier film is peeled from the resin layer, the resin layer adheres to the carrier film and part or all of the resin film peels off. Further, since the glass transition temperature (Tg) of the cured product is lowered by the inclusion of the liquid epoxy resin, there is a problem that sufficient heat resistance can not be obtained. In addition, there is also a problem that warping occurs during mounting.

In addition, as the performance of electronic devices has become higher, there has been a demand for a long-term reliability in a printed wiring board, and a dry film having a resin layer capable of forming a cured product having excellent crack resistance has been demanded.

Therefore, an object of the present invention is to provide a dry film having excellent heat resistance, low warpage and crack resistance of a cured product, excellent releasability of a carrier film, and a resin layer for suppressing cracking and dropout, A cured product obtained by curing a cured product, and a printed wiring board comprising the cured product.

The inventors of the present invention have conducted intensive studies in view of the above, and as a result, discovered that the above problems can be solved by combining a maleimide compound and two kinds of solvents having a boiling point of 100 캜 or more and a different boiling point. .

That is, the dry film of the present invention is a dry film having a resin layer containing a thermosetting resin component, at least one of a curing agent and a curing accelerator, a maleimide compound, a filler, and at least two kinds of solvents, Both of the two solvents are characterized in that their boiling point is 100 DEG C or more and their boiling point is 5 DEG C or more.

In the dry film of the present invention, the residual content of the solvent is preferably 0.1 to 4% by weight or less based on the whole amount of the resin layer of the dry film containing the solvent.

The dry film of the present invention is characterized in that the at least two kinds of solvents are at least one selected from the group consisting of N, N-dimethylformamide, toluene, methoxypropanol, methylisobutylketone, cyclohexanone and aromatic hydrocarbons having 8 or more carbon atoms Two kinds are preferable.

In the dry film of the present invention, it is preferable that the curing agent includes at least one of a phenol resin, a cyanate ester resin and an active ester resin having a triazine structure.

The dry film of the present invention preferably contains an epoxy compound as the above-mentioned thermosetting resin component.

The dry film of the present invention is preferably for producing a printed wiring board.

The cured product of the present invention is characterized by being obtained by curing the resin layer of the dry film.

The printed wiring board of the present invention is characterized by comprising the cured product.

INDUSTRIAL APPLICABILITY According to the present invention, there can be provided a dry film having excellent heat resistance, low warpage and crack resistance of a cured product, excellent releasability from a carrier film and having a resin layer inhibiting cracking and dropout, A cured product obtained by curing, and a printed wiring board comprising the cured product.

1 is a partial cross-sectional view showing a schematic structure of a multilayer printed wiring board manufactured by a conventional build-up method.
2 is a schematic side view showing two test tubes used for liquid phase determination of an epoxy resin.

The dry film of the present invention is a dry film having a resin layer containing a thermosetting resin component, at least one of a curing agent and a curing accelerator, a filler, a maleimide compound and at least two kinds of solvents, All of the solvents have a boiling point of 100 ° C or higher and a boiling point of 5 ° C or higher. The boiling point is, for example, 5 to 130 占 폚.

If only a solvent having a boiling point of less than 100 占 폚 is used, the resin layer of the dry film becomes excessively dry, resulting in poor flexibility and breakage or powder falling off.

On the other hand, when only one solvent having a boiling point of 100 ° C or higher is used, or when a solvent having a boiling point difference of less than 5 ° C is used, the solvent remains excessively even if dried, so that the resin layer is peeled off Therefore, the peelability is deteriorated. In addition, bubbles are easily generated, and it is difficult to form a flat resin layer. Further, if the drying is carried out at a high temperature to reduce the residual solvent, the thermosetting proceeds excessively despite the drying step.

However, when two kinds of solvents having a boiling point of 100 占 폚 or higher and a boiling point different from 5 占 폚 or higher are mixed, a dry film having a resin layer excellent in peeling property with a carrier film and suppressing cracking and dropout of the powder can be obtained .

In addition, the dry film of the present invention has a resin layer having a high glass transition temperature (Tg) of the cured product and excellent heat resistance and crack resistance, while retaining the flexibility of the dry film by containing the maleimide compound in the resin layer. In addition, the cured product of the resin layer has less warpage of the substrate, which is generated at the time of mounting the semiconductor chip, and is also excellent in low bending property. That is, it is possible to reduce warpage at a high temperature, which is a time of mounting a semiconductor chip.

Each component of the resin layer of the dry film of the present invention will be described below.

[Thermosetting resin component]

The resin layer of the dry film of the present invention contains a thermosetting resin component. The thermosetting resin component is a resin having a functional group capable of curing reaction by heat. The thermosetting resin component is not particularly limited, and an epoxy compound, a polyfunctional oxetane compound, a compound having two or more thioether groups in the molecule, that is, an episulfide resin, and the like can be used.

The epoxy compound is a compound having an epoxy group, and all conventionally known epoxy compounds can be used. A bifunctional epoxy compound having two epoxy groups in the molecule, and a polyfunctional epoxy compound having a large number of epoxy groups in the molecule. Further, it may be a hydrogenated bifunctional epoxy compound.

Examples of the epoxy compound include, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, Type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, alicyclic epoxy resin, aliphatic type epoxy resin, Chain epoxy resin, phosphorus-containing epoxy resin, anthracene-type epoxy resin, norbornene-type epoxy resin, adamantane-type epoxy resin, fluorene-type epoxy resin, aminophenol type epoxy resin, aminocresol type epoxy resin, . These epoxy resins may be used alone or in combination of two or more.

The epoxy compound may be a solid epoxy resin, a semi-solid epoxy resin, or a liquid epoxy resin. In the present specification, the solid epoxy resin refers to an epoxy resin which is solid at 40 占 폚, and the semi-solid epoxy resin refers to an epoxy resin which is solid at 20 占 폚 and liquid at 40 占 폚, ≪ / RTI >

The determination of the liquid phase shall be made in accordance with the "Method for Confirmation of Liquid Phase" of Attachment 2 of the Ordinance on the Testing and Characteristics of Dangerous Goods (1989 Self-Government Ordinance No. 1).

(1) Device

Constant temperature bath:

A stirrer, a heater, a thermometer, a thermostat (capable of temperature control at a temperature of 占 .0 占 폚), and a depth of 150 mm or more is used.

In the determination of the epoxy resin used in the later-described examples, all of 22 liters of tap water were mixed with a low-temperature constant-temperature water bath (type BU300) and a charging-type thermostatting thermometer (type BF500) manufactured by Yamato Kagaku Co., (Type BF500) to the set temperature (20 ° C or 40 ° C), set the water temperature to the set temperature ± 0.1 ° C, and then turn on the thermometer (type BF500) But it can be used as long as it is possible to perform the same adjustment.

examiner:

As shown in Fig. 2, the test tube is made of a plain cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, mark lines 31 and 32 are provided at points of 55 mm and 85 mm from the base, respectively, And a rubber stopper 33b having a hole for inserting and supporting a thermometer in the center are provided at the entrance of the test tube with the same size as the test tube 30a for liquid phase determination sealed with the rubber stopper 33a, And a temperature measuring test tube 30b in which a thermometer 34 is inserted into the rubber stopper 33b is used. Hereinafter, a table line at a height of 55 mm is referred to as " A line " and a table line at a height of 85 mm from the base is referred to as a " B line ".

As the thermometer 34, a temperature range of 0 to 50 占 폚 is to be measured, while a thermometer 34 (SOP-58 scale range: 20 to 50 占 폚) specified in JIS B7410 (1982) Anything that can be done.

(2) Procedure for conducting tests

A sample left to stand for 24 hours or more under atmospheric pressure at a temperature of 20 ± 5 ° C was placed in a liquid phase determination test tube 30a shown in Figure 2 (a) and a test tube 30b for temperature measurement shown in Figure 2 (b) Put them up to line A, respectively. The two test tubes 30a and 30b are placed upright in the low-temperature and constant-temperature water bath so that the line B is below the water surface. The lower end of the thermometer should be 30 mm below the A line.

After the sample temperature reaches the set temperature ± 0.1 ° C, the sample remains unchanged for 10 minutes. After 10 minutes, the test tube 30a for liquid phase determination was taken out from the low-temperature constant-temperature water bath and immediately dropped horizontally on a horizontal test bench. The time at which the tip of the liquid surface in the test tube moved from line A to line B was measured with a stop- Record. The sample is judged to be a liquid phase when the measured time is within 90 seconds at the set temperature, and a solid phase when it exceeds 90 seconds.

Examples of the solid epoxy resin include naphthalene type epoxy resins such as HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (tetra naphthalene type epoxy resin) manufactured by DIC, NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Epoxy resin; EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. and epoxides (trisphenol type epoxy resin) of condensates of aromatic aldehydes having a phenolic hydroxyl group; Dicyclopentadiene aralkyl type epoxy resins such as Epiclon HP-7200H (multifunctional solid epoxy resin containing dicyclopentadiene skeleton) manufactured by DIC Corporation; Biphenylaralkyl type epoxy resins such as NC-3000H manufactured by Nippon Kayaku Co., Ltd. (polyfunctional solid epoxy resin containing biphenyl skeleton); Biphenyl / phenol novolak type epoxy resins such as NC-3000L manufactured by Nippon Kayaku Co., Ltd.; Novolak type epoxy resins such as Epiclon N660 manufactured by DIC Corporation, Epiclon N690, and EOCN-104S manufactured by Nippon Kayaku Co., Ltd.; Biphenyl-type epoxy resins such as YX-4000 manufactured by Mitsubishi Chemical Corporation; A phosphorus-containing epoxy resin such as TX0712 made by Shin-Tetsu Sumitomo Chemical; Tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Kagaku Kogyo Co., Ltd., and the like.

As the semi-solid epoxy resin, Epiclon 860, Epiclon 900-IM, Epiclon EXA-4816, Epiclon EXA-4822 manufactured by DIC, Araldite AER280 manufactured by Asahi Shiba Co., Bisphenol A type epoxy resins such as jER834 and jER872 manufactured by Epoxy Resin, and ELA-134 manufactured by Sumitomo Chemical Co., Ltd.; Naphthalene-type epoxy resins such as Epiclon HP-4032 manufactured by DIC Corporation; And phenol novolak type epoxy resins such as Epiclon N-740 manufactured by DIC Corporation.

Examples of the liquid epoxy resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, Epoxy resins, and alicyclic epoxy resins.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, , Poly (p-hydroxystyrene), cardo-type bisphenols, calixarene, calix resorcinarene or silsesquioxane, as well as polyfunctional oxetanes such as an oligomer or copolymer of oxetane alcohol and novolak resin, And etherified with a resin having a hydroxyl group such as quinoxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the episulfide resin include a bisphenol A type episulfide resin and the like. An episulfide resin in which an oxygen atom of an epoxy group of an epoxy resin is substituted with a sulfur atom can also be used by using a similar synthesis method.

The thermosetting resin component is preferably an epoxy compound. Further, at least one of a solid epoxy resin and a semi-solid epoxy resin is preferable because a cured product having a high glass transition temperature (Tg) and excellent crack resistance can be obtained. Among them, a semi-solid epoxy resin is more preferable in that it is excellent in flexibility and can form a resin layer having excellent physical properties of a cured product. As the epoxy compound, an aromatic epoxy resin is preferable from the viewpoints of favorable physical properties of a cured product and the like. Among them, a naphthalene type epoxy compound and a biphenyl type epoxy compound are more preferable. In this specification, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in its molecule.

The thermosetting resin component may be used alone or in combination of two or more. The blending amount of the thermosetting resin component is preferably 10 to 50% by weight, more preferably 10 to 40% by weight, and even more preferably 10 to 35% by weight, based on the whole amount of the resin layer of the dry film excluding the solvent. When the liquid epoxy resin is blended, the blending amount of the liquid epoxy resin is preferably 0 to 45% by weight based on the total weight of the thermosetting resin component in order to improve the handleability such as peelability of the carrier film, More preferably 30% by weight, and particularly preferably 0% by weight to 5% by weight.

[Curing agent]

The resin layer of the dry film of the present invention may contain a curing agent. Examples of the curing agent include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, and active ester resins. The curing agent may be used alone or in combination of two or more.

Examples of the phenol resin include polyphenylene ether resins, phenol novolac resins, alkylphenol novolac resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, cresol / naphthol resins , Polyvinyl phenols, phenol / naphthol resins, phenol resins having a biphenyl structure, phenol resins having an? -Naphthol structure, cresol novolac resins having a triazine structure, and phenol novolac resins having a triazine structure Which may be used singly or in combination of two or more.

Among the phenol resins, phenol resins having a triazine structure such as a cresol novolac resin having a triazine structure and a phenol novolac resin having a triazine structure have a better glass transition temperature (Tg) of a cured product of the resin layer desirable. When a phenol resin having a triazine structure is used, it is preferable to use a cresol novolac resin, a dicyclopentadiene-type phenol resin, a phenol novolak resin, a biphenyl structure, and the like in order to further improve the water absorbability of the cured product of the resin layer And other curing agents such as a cyanate ester resin and an active ester resin are preferably used in combination.

The polycarboxylic acid and its acid anhydride are compounds having two or more carboxyl groups in one molecule and an acid anhydride thereof, and examples thereof include copolymers of (meth) acrylic acid, copolymers of maleic anhydride, condensates of dibasic acids , And resins having a carboxylic acid terminal such as a carboxylic acid terminal imide resin.

The cyanate ester resin is a compound having two or more cyanate ester groups (-OCN) in one molecule. As the cyanate ester resin, conventionally known ones can be used. Examples of the cyanate ester resin include phenol novolak type cyanate ester resins, alkylphenol novolak type cyanate ester resins, dicyclopentadiene type cyanate ester resins, bisphenol A type cyanate ester resins, bisphenol F type cyanate ester resins Naphthoate ester resin, and bisphenol S type cyanate ester resin. In addition, some of the prepolymer may be triarylated. The cyanate ester resin is preferable because a glass transition temperature (Tg) becomes better and a cured product of a resin layer excellent in water absorption is obtained.

The active ester resin is a resin having at least two active ester groups in one molecule. The active ester resin can be generally obtained by a condensation reaction of a carboxylic acid compound and a hydroxy compound. Among them, an active ester resin obtained by using a phenol compound or a naphthol compound as a hydroxy compound is preferable. Examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, , Catechol,? -Naphthol,? -Naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone , Tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolak, and the like. The active ester resin is preferable because a glass transition temperature (Tg) becomes better and a cured product of a resin layer excellent in absorbability is obtained.

As the curing agent, an alicyclic olefin polymer may also be used. As a specific example of the production method of the alicyclic olefin polymer, there can be mentioned (1) a method of polymerizing an alicyclic olefin having a carboxyl group and / or a carboxylic acid anhydride group (hereinafter referred to as "carboxyl group etc.") together with other monomers , (2) a method of hydrogenating an aromatic ring portion of a (co) polymer obtained by polymerizing an aromatic olefin having a carboxyl group or the like together with other monomers as necessary, (3) a method of reacting an alicyclic olefin having no carboxyl group, (4) a method of hydrogenating an aromatic ring portion of a copolymer obtained by copolymerizing an aromatic olefin having no carboxyl group or the like and a monomer having a carboxyl group, etc., (5) a method of hydrogenating an alicyclic (6) a method of introducing a compound having a carboxyl group or the like into an olefin polymer by a modification reaction, or And a method of converting a carboxylic acid ester group of the alicyclic olefin polymer having a carboxylic acid ester group thus obtained into a carboxyl group by hydrolysis or the like.

Among the curing agents, a phenol resin, a cyanate ester resin, an active ester resin and an alicyclic olefin polymer are preferable, and a phenol resin, a cyanate ester resin and an active ester resin having a triazine structure are more preferable.

Two or more kinds of curing agents may be used in combination. For example, a combination of a cyanate ester resin and an active ester resin may be used, or a combination of a cyanate ester resin, an active ester resin and a phenol resin may be used. By combining a phenol resin, adhesion with a circuit can be improved.

The curing agent preferably has a ratio such that the ratio of the functional group capable of thermosetting reaction such as an epoxy group of the thermosetting resin component and the functional group in the curing agent reacting with the functional group becomes 0.2 to 2 (equivalent ratio) capable of functional / thermosetting reaction of the curing agent . ≪ / RTI > By setting the functional group (equivalent ratio) capable of a functional group / thermosetting reaction of the curing agent within the above range, it is possible to prevent the surface of the film from blurring in the desmearing step. More preferably, the functional group capable of reacting with the functional group / thermosetting reaction of the curing agent (equivalent ratio) is 0.2 to 1.5, and more preferably the functional group (equivalence ratio) of the functional group / thermosetting reaction of the curing agent is 0.3 to 1.0.

[Maleimide compound]

The resin layer of the dry film of the present invention contains a maleimide compound. The maleimide compound is a compound having a maleimide skeleton, and all conventionally known ones can be used. The maleimide compound is preferably one having at least two maleimide skeletons, and may be selected from the group consisting of N, N'-1,3-phenylene dimaleimide, N, N'-1,4-phenylenedimaleimide, N, N'- Bis (maleimide) ethane, 1,6-bismaleimide hexane, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 2, Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl (4-methylphenyl) Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethane maleimide and oligomers thereof, And at least one of the diamine condensates having a mid skeleton is more preferable. The oligomer is an oligomer obtained by condensing a maleimide compound as a monomer in the maleimide compound described above. The maleimide compounds may be used alone or in combination of two or more.

Among the maleimide compounds, at least one of condensates of phenylmethane maleimide and bismaleimide oligomers is more preferable. The bismaleimide oligomer is preferably an oligomer obtained by condensation of phenylmethane bismaleimide and 4,4-diaminodiphenylmethane. Commercially available condensates of phenylmethane maleimide include BMI-2300 available from Yamato Kasei Co., Ltd. Examples of commercial products of bismaleimide oligomers include DAIMAID-100H manufactured by Yamato Kasei Co., Ltd.

Further, the maleimide compound is preferably a maleimide compound represented by the following general formula (I).

In the general formula (I), R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom or an organic group, and n represents an integer of 0 to 1. In the general formula (I), R ¹ to R ³ are preferably a hydrogen atom.

The maleimide compound is preferably a mixture of the maleimide compound represented by the general formula (I). Further, since the solubility of the mixture is high and the coefficient of linear expansion of the cured product of the resin layer is further lowered, the average value of n in the formula (I) of the mixture is more preferably 0.1 to 1. The larger the average value of n, the higher the solubility of the mixture. In the case of a mixture of maleimide compounds having an average value of n of 0.1 to 1, it is possible to form a cured product having a high glass transition temperature (Tg) even by thermosetting a resin layer of a dry film at a low temperature and using a thin substrate having low heat resistance .

The blending amount of the maleimide compound is preferably 2 to 50% by weight based on the whole amount of the resin layer of the dry film excluding the solvent and the filler. If it is 2% by weight or more, the coefficient of linear expansion of the cured product becomes low, and the glass transition temperature (Tg) of the cured product becomes higher. More preferably 10% by weight or more. When the content is 50% by weight or less, the breaking strength is increased.

[Filler]

The resin layer of the dry film of the present invention contains a filler. By containing the filler, the thermal characteristics of the dry film can be improved by aligning the thermal strength with the conductor layer such as copper around the insulating layer. As the filler, all known inorganic fillers and organic fillers can be used, and although not limited to specific ones, inorganic fillers that suppress curing shrinkage of the coating film and contribute to improvement in properties such as adhesion and hardness are preferable. Examples of inorganic fillers include extender pigments such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, Metal powders such as silver, copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold and platinum. Among these inorganic fillers, silica and barium sulfate which are difficult to be immersed by the roughening liquid are preferable, and spherical silica is particularly preferable because of its small specific gravity, its high proportion in the composition and its low thermal expansion.

The filler may be a filler having an average linear thermal expansion coefficient of 300 ppb / 占 폚 or less between 30 占 폚 and 150 占 폚. Specific examples of such a filler include glass fillers such as titanium dopes, zirconium phosphate fillers, cordierite fillers, silicon oxide fillers, zirconium tungstate fillers having an average linear thermal expansion coefficient of 300 ppb / Based filler, and manganese nitride-based filler. As commercial products of titanium doped glass fillers, "AZ Filler" available from Asahi Glass Co., Ltd., "ZWP" available from Public Material Co., Ltd. as a commercially available product of zirconium phosphate filler, DL7400 " manufactured by Nippon Denkigaras Co., Ltd., and the like.

As the filler, a filler having a negative thermal expansion coefficient may also be used. Examples of such fillers include zirconium phosphate (Ultaia series manufactured by Do A Kose Co.), zirconium tungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ , ZWP), LaCu ₃ Fe ₄ O ₁₂ Bi _{1 - x} Ln _x NiO ₃ (Ln = La, Nd, Eu, Dy, perovskite structure oxide), Al ₂ O _{3 (} perovskite structure oxide) · TiO ₂ (manufactured by AGC Ceramics Co., Ltd.), Li ₂ O · Al ₂ O ₃ · nSiO ₂ (Na, Ca _0.5 , Mg _0.5 , K) _x [Al _x Si _{12 - x} O ₂₄ ] 16H ₂ O) , LiAlSiO ₄ , PbTiO ₃ , Sc ₂ W ₃ O ₁₂ , Lu ₂ W ₃ O ₁₂ , ZrW ₂ O ₈ , Mn ₃ XN (X = Cu-Sn, Zn-Sn and the like).

The average particle diameter of the filler is preferably 3 占 퐉 or less, more preferably 1 占 퐉 or less. The average particle diameter can be obtained by a laser diffraction particle diameter distribution measuring apparatus.

The blending amount of the filler is preferably 1 to 90% by weight, more preferably 10 to 90% by weight, and still more preferably 30 to 80% by weight, based on the whole amount of the resin layer of the dry film excluding the solvent. When the blending amount of the filler is 1% by weight or more, thermal expansion can be suppressed and the heat resistance can be further improved. On the other hand, when it is 90% by weight or less, the hardness of the cured product is improved and the occurrence of cracks can be further suppressed.

When the blending amount of the filler is 60 wt% or more based on the entire amount of the resin layer of the dry film excluding the solvent, a cured product having a low water absorption property can be obtained even though it contains a maleimide compound. By increasing the blending amount of the filler in this way, the coefficient of linear expansion is low, and the glass transition temperature (Tg), the reduction of the warping of the substrate, and the suppression of the occurrence of cracks become better. More preferably 60 to 90% by weight, and still more preferably 60 to 80% by weight.

[solvent]

The resin layer of the dry film of the present invention contains two kinds of solvents having a boiling point of 100 占 폚 or higher and a boiling point different by 5 占 폚 or higher. The solvent is not particularly limited and conventionally known solvents having a boiling point of 100 占 폚 or higher can be used. In the present invention, when there is a width at the boiling point of the solvent, the boiling point is the extreme point or the end point at the time of distillation.

Examples of the solvent having a boiling point of 100 占 폚 or more include methoxy propanol such as isobutyl alcohol, toluene, methyl isobutyl ketone, n-butanol, butyl acetate and 2-methoxypropanol, isobutyl acetate, tetrachlorethylene, ethylene glycol monomethyl ether , Methyl butyl ketone, isopentyl alcohol, ethylene glycol monoethyl ether, N, N-dimethylformamide (DMF), ethylene glycol monoethyl ether acetate, turpentine oil, cyclohexanone, ethylene glycol monobutyl ether, And lactones.

Examples of the solvent having a boiling point of 100 ° C or higher include xylene, petroleum naphtha, Maruzen Sekiyu Kagaku Suazol 1000 (having 8 to 10 carbon atoms in the high boiling point aromatic hydrocarbon), Swazol 1500 (high boiling point aromatic hydrocarbon) (High boiling point aromatic hydrocarbon), Solvesso 150 (having 10 to 11 carbon atoms, high boiling point aromatic hydrocarbon), Solvent # 100, Solvent # 150, Shell Chemical Co., Ltd. manufactured by Yuasa Osaka Hatsubai Co., (A major component of aromatic hydrocarbons having 9 carbon atoms), and Ipzol 150 (main component of aromatic hydrocarbons having 10 carbon atoms), and the like. The high boiling point aromatic hydrocarbon preferably contains an aromatic component at 99% by volume or more. It is preferable that each of the benzene, toluene and xylene as the high-boiling aromatic hydrocarbon is less than 0.01% by volume.

The resin layer of the dry film of the present invention may contain three or more kinds of solvents having a boiling point of 100 ° C or more, in which case the boiling points of the two kinds of solvents should be different. Among the solvents having a boiling point of 100 占 폚 or higher, solvents having a boiling point of 100 to 230 占 폚 are preferable, and solvents having 100 to 220 占 폚 are more preferable. When the boiling point is 230 占 폚 or lower, the solvent hardly remains in the resin layer of the dry film after the thermal curing or the annealing treatment. More preferably, the solvent is toluene, N, N-dimethylformamide, methoxypropanol, methyl isobutyl ketone, cyclohexanone, petroleum naphtha, and aromatic hydrocarbons having 8 or more carbon atoms. Among these, a combination of toluene and cyclohexane, a combination of toluene and methyl isobutyl ketone, and a combination of cyclohexanone and methyl isobutyl ketone are more preferable.

The blending amount of the solvent before drying is preferably 10 to 150 parts by weight, more preferably 25 to 100 parts by weight with respect to 100 parts by weight of the resin layer of the dry film from which the solvent has been removed. When the blending amount of the solvent is 10 parts by weight or more, the solubility is improved and the amount of the residual solvent is easily adjusted. On the other hand, when the amount is 150 parts by weight or less, the thickness of the resin layer can be easily controlled.

The amount of the solvent after drying, that is, the ratio of the residual content of the solvent is preferably 0.1 to 4% by weight, more preferably 0.3 to 3% by weight, based on the whole amount of the resin layer of the dry film containing the solvent.

The resin layer of the dry film of the present invention may contain a solvent having a boiling point of less than 100 占 폚. Examples of the solvent having a boiling point of less than 100 占 폚 include diethyl ether, carbon disulfide, acetone, chloroform, methanol, n-hexane, ethyl acetate, 1,1,1-trichloroethane, carbon tetrachloride, methyl ethyl ketone, isopropyl alcohol, trichloro Ethylene, isopropyl acetate and the like.

(Polymer resin)

The resin layer of the dry film of the present invention preferably contains a polymer resin because the flexibility of the dry film and the crack resistance of the cured product of the resin layer of the dry film become better. As the polymer resin, it is preferable to use the following thermoplastic resin and rubber-like particles.

(Thermoplastic resin)

The resin layer of the dry film of the present invention may further contain a thermoplastic resin in order to improve the mechanical strength of the resulting cured coating film. The thermoplastic resin is preferably soluble in a solvent. When it is soluble in a solvent, the flexibility of the dry film is improved, and generation of cracks and dropout of the powder can be suppressed.

Examples of the thermoplastic resin include a thermoplastic polyhydroxypolyether resin, a phenoxy resin which is a condensation product of epichlorohydrin and various bifunctional phenol compounds, or a hydroxyl group of a hydroxy ether moiety existing in the skeleton thereof, using various acid anhydrides or acid chlorides A polyvinyl acetal resin, a polyamide resin, a polyamide-imide resin, a block copolymer, and the like. The thermoplastic resin may be used alone or in combination of two or more.

The polyvinyl acetal resin is obtained, for example, by acetalizing a polyvinyl alcohol resin with an aldehyde. Examples of the aldehyde include, but are not limited to, formaldehyde, acetaldehyde, propionaldehyde, and butylaldehyde.

Specific examples of the phenoxy resin include FX280, FX293, and YX8100, YX6954, YL7213 and YL7218 manufactured by Mitsubishi Chemical Corporation. Specific examples of the polyvinyl acetal resin include Slak KS series manufactured by Sekisui Chemical Co., Ltd., KS5000 series manufactured by Hitachi Chemical Co., Ltd., BP series manufactured by Hitachi Chemical Co., Ltd., BP series manufactured by Hitachi Chemical Co., Ltd., and KS9000 series manufactured by Hitachi Kasei Kogyo Co., .

When the thermoplastic polyhydroxypolyether resin has a fluorene skeleton, it has a high glass transition point and is excellent in heat resistance, so that a low coefficient of thermal expansion due to a semi-solid or solid epoxy resin is maintained and the glass transition point thereof is maintained , And the resulting cured coating has a low coefficient of thermal expansion and a high glass transition point in balance.

In addition, since the thermoplastic polyhydroxypolyether resin has a hydroxyl group, it exhibits good adhesion to a substrate and a conductor, and the obtained cured film is hardly dipped by the coagulant, but the coagulating liquid in the form of an aqueous solution, The filler on the surface of the cured coating is liable to be detached by the coarsening treatment, and it is easy to form a good roughened surface.

As the thermoplastic resin, a block copolymer may also be used. The block copolymer refers to a copolymer having a molecular structure in which two or more kinds of polymers having different properties are linked by a covalent bond to form a long chain.

As the block copolymer, an A-B-A type or an A-B-A 'type block copolymer is preferable. Among the ABA type and AB-A 'type block copolymers, it is preferable that the central B is a soft block, the glass transition temperature (Tg) is low, preferably less than 0 ° C, It is preferable that the polymer is composed of polymer units having a high temperature (Tg), preferably at least 0 占 폚. The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC).

Also, among ABA type and AB-A 'type block copolymers, A or A' includes a polymer unit having a Tg of 50 ° C or higher and B is a block including a polymer unit having a glass transition temperature (Tg) Copolymers are more preferred.

Among the A-B-A type and the A-B-A'-type block copolymers, it is preferable that A or A 'has high compatibility with the thermosetting resin component, and B has low compatibility with the thermosetting resin component. As described above, it is considered that a structure specific to a matrix is likely to be exhibited by forming a block copolymer in which blocks at both ends are common to a matrix and a central block is a block copolymer in a matrix.

Among the thermoplastic resins, phenoxy resins, polyvinyl acetal resins, thermoplastic polyhydroxy polyether resins having fluorene skeleton, and block copolymers are preferred.

The blending amount of the thermoplastic resin is 1 to 20% by weight, preferably 1 to 10% by weight based on the whole resin layer excluding the solvent. If the blending amount of the thermoplastic resin is out of the above range, it is difficult to obtain a uniform roughened state.

(Rubber-like particles)

The resin layer of the dry film of the present invention may further contain rubber-like particles if necessary. Examples of such rubber-like particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl-modified polybutadiene rubber, acrylonitrile modified with a carboxyl group or hydroxyl group Butadiene rubber, crosslinked rubber particles thereof, and core-shell-type rubber particles. These may be used singly or in combination of two or more. These rubber-like particles are added in order to improve the flexibility of the resulting cured coating, to improve crack resistance, or to enable surface roughening treatment with an oxidizing agent to improve the adhesion strength with the copper foil and the like.

The average particle diameter of the rubber-like particles is preferably in the range of 0.005 to 1 mu m, more preferably in the range of 0.2 to 1 mu m. The average particle diameter of the rubber-like particles in the present invention can be measured using a dynamic light scattering method. For example, rubber-like particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber-like particles is prepared on the basis of weight by using FPRA-1000 (manufactured by Otsuka Chemical Co., Ltd.) The average particle size can be measured.

The blended amount of the rubber-like particles is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the whole resin layer excluding the solvent. When it is 0.5% by weight or more, crack resistance is obtained and the adhesion strength with the conductor pattern and the like can be improved. When it is 10% by weight or less, the CTE is lowered and the glass transition temperature (Tg) is increased to improve the curing property.

[Curing accelerator]

The resin layer of the dry film of the present invention may contain a curing accelerator. The curing accelerator promotes the thermosetting reaction and is used to further improve properties such as adhesion, chemical resistance and heat resistance. Specific examples of such curing accelerators include imidazoles and derivatives thereof; Guanamine such as acetoguanamine and benzoguanamine; Polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazide; Organic acid salts and / or epoxy adducts thereof; Amine complexes of boron trifluoride; Triazine derived products such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine; (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetra (dimethylaminophenol), N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, Amines such as methyl guanidine and m-aminophenol; Polyphenols such as polyvinyl phenol, polyvinyl phenol bromide, phenol novolac, and alkylphenol novolak; Organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; Phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, and hexadecyl tributylphosphonium chloride; Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; The polybasic acid anhydride; Photo cationic polymerization catalysts such as diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, and 2,4,6-triphenylthiopyrylium hexafluorophosphate; Styrene-maleic anhydride resin; Condensation reaction products of phenyl isocyanate and dimethyl amine, equimolar reaction products of organic polyisocyanates such as tolylene diisocyanate and isophorone diisocyanate with dimethylamine, metal catalysts, and other known curing accelerators. Of the curing accelerators, phosphonium salts are preferred because BHAST resistance is obtained.

The curing accelerator may be used alone or in combination of two or more. The use of a curing accelerator is not essential, but when curing is to be particularly promoted, the curing accelerator may be used in an amount of preferably 0.01 to 5 parts by weight based on 100 parts by weight of the thermosetting resin component.

In the case of the metal catalyst, the amount is preferably 10 to 550 ppm, more preferably 25 to 200 ppm in terms of metal, based on 100 parts by weight of the thermosetting resin component.

(coloring agent)

The resin layer of the dry film of the present invention may contain a coloring agent. When the dry film of the present invention is used for forming a surface layer of a solder resist layer or the like by containing a colorant, the hiding power of a circuit or the like can be enhanced. As the coloring agent, known coloring agents such as red, blue, green, yellow, white and black can be used, and any of pigments, dyes and pigments may be used. Specifically, a color index (published by C.I., The Society of Dyers and Colors) is appended. However, it is preferable that the colorant is a halogen-free colorant from the viewpoint of environmental load reduction and human impact.

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. As the blue colorant, there are a metal substituted or unsubstituted phthalocyanine type or anthraquinone type, and a pigment type is classified into a pigment. Examples of the green colorant include phthalocyanine-based, anthraquinone-based, and perylene-based pigments, which are metal-substituted or unsubstituted. Examples of the yellow colorant include a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, and an anthraquinone system. Examples of the white colorant include titanium oxide such as rutile type and anatase type. Examples of the black colorant include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, Molybdenum, and bismuth sulfide. For the purpose of adjusting other color tones, a coloring agent such as violet, orange, or brown may be added.

The colorant may be used alone or in combination of two or more. The blending amount of the colorant is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight based on the whole resin layer excluding the solvent.

(Other components)

If necessary, the resin layer of the dry film of the present invention may contain a conventional thickening agent such as asbestos, orthovan, benton, and fine silica, a defoaming agent such as a silicone type, a fluorine type or a high molecular type, and / or a leveling agent such as a thiazole type, , Adhesion promoters such as silane coupling agents, flame retardants, titanate-based, and aluminum-based additives.

The dry film of the present invention can be produced by applying and drying a thermosetting resin composition for forming a resin layer on a carrier film, laminating a protective film if necessary, and forming a dried film. Here, the thermosetting composition includes at least one of a thermosetting resin component, at least one of a curing agent and a curing accelerator, a maleimide compound, a filler, and at least two kinds of solvents, And the boiling point is different by 5 占 폚 or more.

Examples of the material of the carrier film include polyolefins such as polyethylene, polypropylene (PP) and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polyimide, furthermore, And metal foil of the same kind. In addition to the mud treatment and the corona treatment, the carrier film may be subjected to release treatment. The thickness of the carrier film is suitably 8 to 60 탆.

As the material of the protective film, the same materials as those used for the carrier film can be used, and suitably PET or PP. The thickness of the protective film is suitably 5 to 50 占 퐉.

As a coating method of the thermosetting resin composition, known methods such as a screen printing method and the like can be used. As the volatile drying method, a known method using a hot air circulation type drying furnace or the like can be used.

The printed wiring board of the present invention comprises a cured product obtained by curing the dry film of the present invention. The manufacturing method thereof will be described below, but the present invention is not limited thereto.

In the cured product of the present invention, the protective film is peeled off from the dry film of the present invention, and the dry film of the present invention is laminated on the inner-layer circuit board on which the circuit is formed. Thereafter, the mixture is cured in an oven or cured by hot plate press to obtain a cured product of the present invention.

The laminate or hot plate press method in the above process is preferable because the fine unevenness due to the inner layer circuit is dissolved when heated and melted and is hardened as it is to finally obtain a multilayer plate having a flat surface state. Further, when the base material on which the inner layer circuit is formed and the dry film of the present invention are laminated or hot plate pressed, a copper foil or a circuit formed substrate may be laminated at the same time.

After the thermosetting resin composition is laminated on the circuit board, the resin layer is thermally cured to form the insulating layer on the circuit board. The conditions of the thermosetting may be appropriately selected depending on the kind and content of the resin component in the resin layer, but preferably 20 to 180 minutes at 150 to 220 deg. C, more preferably 30 to 120 minutes at 160 to 210 deg. Lt; / RTI > Further, by adhering the carrier film without peeling, it is possible to prevent foreign matter such as dust and dust from adhering.

The thus obtained substrate is drilled with a semiconductor laser such as a CO ₂ laser or a UV-YAG laser or a drill. The hole may be either a through hole (through hole) for conducting the inside and outside of the substrate, or a partial hole (conformal via) for connection between the resin layer and the resin layer It is possible. The carrier film may be peeled off either before or after laser processing. When the carrier film is peeled off before the laser machining, the machining diameter as the designed value of the mask diameter (aperture diameter) of the laser is easily obtained, and since there is no carrier film, the resin layer can be processed with low output. On the other hand, when the carrier film is peeled off after laser processing, it is possible to suppress debris (resin fragment) generated at the time of processing and damage to the resin layer surface caused by laser light.

After the hole is drilled, it is possible to remove the residue (smear) existing on the inner wall or the bottom of the hole and to form a rough surface on the surface in order to develop an anchor effect of the conductor layer (metal plating layer formed thereafter) For the purpose, the solution is simultaneously carried out with a harmful liquid containing an oxidizing agent such as a desmear liquid (harming agent) or a permanganate, a dichromate, ozone, hydrogen peroxide / sulfuric acid or nitric acid. When the smear removal is performed in the state that the carrier film is adhered, the damage of the surface of the resin layer due to desmear can be suppressed.

Subsequently, a circuit is formed by a subtractive method, a semi-edible method, or the like after forming a hole in which the residue is removed by a desmear solution or a film surface of a cured product which has generated a fine uneven rough surface. In either method, after the electroless plating or the electrolytic plating, or both the platings are performed, a heat treatment called annealing at about 80 to 180 DEG C for about 10 to 60 minutes is performed for the purpose of stress relief and strength enhancement .

As the metal plating used here, copper, tin, solder, nickel and the like are not particularly limited and a plurality of combinations may be used. It is also possible to substitute metal sputter instead of the plating used here.

The dry film of the present invention can be suitably used in the production of printed wiring boards. In particular, it can be suitably used for forming a permanent insulating layer of a printed wiring board such as an interlayer insulating layer, a solder resist layer, or a coverlay. By using the dry film of the present invention, wiring boards can be formed by bonding wires. It can also be suitably used as a sealing resin for a semiconductor chip.

[Example]

Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples and Test Examples of the present invention, but it goes without saying that the present invention is not limited to the following Examples. In the following, " part " and "% " are by weight unless otherwise specified.

(Examples 1 to 30 and Comparative Examples 1 to 4)

Each component was compounded by the formulations shown in Tables 1 to 5 below, kneaded and dispersed, and adjusted to have a viscosity of 0.5 to 20 dPa 占 퐏 (rotational viscometer 5 rpm, 25 占 폚). Subsequently, the film was applied to a carrier film (PET film; Lumirror 38R75 manufactured by Toray Co., Ltd., thickness: 38 mu m) so that the film thickness of the dry film was 40 mu m after drying using a bar coater. Subsequently, the dried film was dried in a hot air circulation type drying furnace to obtain a dried coating film having a thermosetting resin layer on one side. The drying conditions were dried at the time and temperature indicated in the table. Subsequently, a protective film was laminated on the resin layer to obtain a dry film.

* 1: Biphenyl / phenol novolak type epoxy resin (epoxy equivalence 280 to 290 g / eq; solid type, softening point 70 ° C, manufactured by Nippon Kayaku Co., Ltd.)

* 2: naphthalene type epoxy resin (epoxy equivalence 145 to 157 g / eq; semi-solid type, manufactured by DIC)

* 3: Liquid BPA type and BPF type epoxy resin (epoxy equivalent weight 160 to 170 g / eq; liquid phase) manufactured by Shin-Tetsu Sumitomo Chemical Co.,

* 4: Polyphenylene ether resin (PPO manufactured by SABIC Innovative Plastic Co., Ltd., hydroxyl equivalent: 850 g / eq)

* 5: phenol novolac resin (manufactured by Meiwa Chemical Industries, Ltd., hydroxyl equivalent: 104 to 108 g / eq; softening point: 82 to 86 ° C)

* 6: Phenol novolak resin (biphenyl skeleton-containing phenol novolak resin, manufactured by Meiwa Chemical Industries, Ltd., hydroxyl equivalent: 201 to 220 g / eq; softening point:

* 7: Triazine-containing cresol novolak resin (DIC, hydroxyl equivalence: 151 g / eq; nitrogen content: 18%)

* 8: Phenol novolac resin containing triazine (manufactured by DIC; hydroxyl equivalent weight: 125 g / eq; nitrogen content: 12%)

* 9: Active ester resin (manufactured by DIC; active ester equivalent: 223 g / eq)

* 10: Active ester resin (active ester equivalent: 223 g / eq; softening point: 152 캜)

* 11: Bisphenol A dicyanate (Lonza Japan; cyanate equivalent: 232 g / eq)

* 12: phenol novolak type polyfunctional cyanate ester (manufactured by Lonza Japan; cyanate equivalent 124 g / eq)

* 13: Condensation product of phenylmethane maleimide (manufactured by Yamato Kasei Kogyo Co., softening point: 70 to 145 ° C)

* 14: 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (available from Yamato Kasei Kogyo Co., Ltd., softening point 160 to 170 ° C)

* 15: Synthesis of 2,2'-bis- [4- (4-maleimidophenoxy) phenyl] propane (manufactured by K.K.

* 16: spherical silica (manufactured by Admatechs; average particle diameter: 0.5 m)

* 17: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.)

* 18: Phosphonium salt (manufactured by Hokko Sankyo)

* 19: 4-Aminopyridine (manufactured by Koegaku Kogyo Co., Ltd.)

* 20: zinc naphthenate (II) mineral spirit (zinc content 8% by Wako Pure Chemical Industries, Ltd.)

* 21: Phenoxy resin (glass transition temperature: 130 占 폚, manufactured by Mitsubishi Chemical)

* 22: Polyvinylacetacetal (available from Sekisui Chemical Co., Ltd., glass transition temperature: 107 占 폚)

* 23: core-shell rubber particles (manufactured by Aika Kogyo Co., Ltd.)

* 24: Toluene (boiling point: 110 ° C)

* 25: methyl isobutyl ketone (boiling point: 116 DEG C)

* 26: 2-Methoxypropanol (boiling point 118 캜)

* 27: Cyclohexanone (boiling point: 150 ° C)

* 28: N, N-Dimethylformamide (boiling point: 153 占 폚)

* 29: Zephol 150 (boiling point: 184 to 205 ° C)

* 30: Methyl ethyl ketone (boiling point: 79.5 DEG C)

* 31: Hexane (boiling point: 69 占 폚)

The dry films of Examples 1 to 30 and Comparative Examples 1 to 4 were evaluated by the following evaluation methods. The evaluation results are shown in Tables 6 to 10.

≪ Measurement of Residual Content (%) of Organic Solvent in Dry Film >

After removing the carrier film and the protective film from the dry film of each of the examples and the comparative example, about 1.2 g of the resin layer was sampled and placed in a container having a hermetic stopper, and the mass of the collected resin layer was precisely weighed (W). To the vessel was added one drop of ethyl 3-ethoxypropionate as an internal standard substance with a pipette, and the mass (We) thereof was precisely weighed. Then, 5 ml of acetone was added by a hole pipette to seal the cap, and the container was sufficiently shaken to dissolve the resin layer. Subsequently, this solution was filtered with a filter having a scale of 0.5 mu m, and the composition of the filtrate was analyzed by gas chromatography (TRACEGCULTRA, manufactured by Thermo Fisher Scientific Company). The mass of the organic solvent relative to 1 g of the internal standard substance (Ws). From these, the residual content of the organic solvent was calculated according to the following formula.

Residual content (mass%) of organic solvent = (We x Ws / W) x 100

From the residual content, the ease of adjustment of the residual content of the organic solvent in the dry film was evaluated by the following evaluation criteria.

The measurement conditions in the gas chromatography are as follows. Column: DB-1MS (30 m x 0.25 mm) manufactured by Agilent Technologies, detector: MS (ITQ 900), carrier gas: helium, injector temperature: 300 캜, detector temperature: 230 캜, The sample was held at an initial temperature of 50 ° C and 50 ° C for 2 minutes after the sample was injected. The sample was heated to 300 ° C at 10 ° C / min, reached 300 ° C, and held for 10 minutes.

?: 0.3 to 2.5%

O: not less than 2.5% and not more than 3.0%

?: Not less than 0.1% and not more than 0.3%, or not less than 3.0% and not more than 4.0%

X: 0.1 to 4.0% other

≪ Flexibility of dry film (bending test) >

A cylindrical mandrel bending test machine manufactured by BYK-Gardner (Gardner) was used to comply with JIS K5600-5-1 (ISO1519), and a mandrel test was conducted in which the cracks of the dry films and the peeling from the carrier film of the respective Examples and Comparative Examples The flexibility of the dry film was evaluated. The evaluation criteria are as follows. When the flexibility of the dry film is good, the flexibility of the resin layer is high, and cracks and powder dropout can be suppressed.

&Amp; cir & & cir &: No cracks in the resin layer, dropout of the resin and peeling of the carrier film occurred at a diameter of 2 mm or less.

?: No cracks in the resin layer, dropout of the resin, or peeling of the carrier film occurred within the range of more than 2 mm and less than 5 mm.

?: Cracks of the resin layer, powder dropout and peeling of the carrier film occurred in a range of more than 2 mm and less than 5 mm.

X: Cracks in the resin layer, powder dropout and peeling of the carrier film occurred at a diameter of 5 mm or more.

<Bubble residue>

The dry film of each of the examples and comparative examples was peeled off from the protective film, and then the conductor thickness of copper of 35 mu m and L (line: wiring width) / S (thickness of the wiring) was measured using a batch type vacuum laminator MVLP- (Space: gap width) = 100/100 mu m. 5 kgf / cm &lt; 2 &gt;, 80 DEG C for 1 minute, and 1 Torr, and then leveled by a hot plate press at 10 kgf / cm2 at 80 DEG C for 1 minute. After lamination, air was drawn into the boundary between the lines and spaces to check whether 20 voids were formed in the resin layer. The evaluation criteria are as follows. When the resin layer is sticky, that is, when the peelability of the following carrier film is poor, air bubbles are drawn between the resin layer and the comb pattern, and voids are increased. In this case, cracks tend to occur.

○: No void was confirmed.

?: One to four voids were confirmed.

X: At least five voids were found.

<Peelability of Carrier Film>

The dry film of each of the examples and the comparative example was laminated under the same conditions as the test of the residual bubbles, the carrier film was peeled off, and whether or not the resin composition derived from the resin layer adhered to the carrier film was visually judged. The evaluation criteria are as follows.

&Amp; cir &amp;: No resin composition is adhered to the carrier film, and the surface of the resin surface is favorably dried.

?: No resin composition was attached to the carrier film.

?: A little resin composition adhered to the carrier film.

X: A large amount of resin composition adhered to the carrier film.

<Compatibility of maleimide compound, epoxy resin and solvent>

The solubility of the epoxy resin and the maleimide compound in each of the examples and comparative examples in a solvent and the compatibility of the resins with each other were examined as follows.

The epoxy resin, maleimide compound and solvent used in each of the examples and comparative examples were compounded at the same ratios as in the table. Subsequently, the mixture was heated and dissolved at a temperature lower than the boiling point of each component while stirring.

The mixture of the resin and the solvent was dissolved by heating, and then cooled to room temperature to prepare a film having a thickness of 1 mm. The produced film was observed with an optical microscope at 25 times, and it was confirmed whether or not the solids were precipitated in the range of 1 cm x 1 cm.

?: No coarse particles of 20 占 퐉 or more were observed at all.

X: At least one coarse particle of 20 탆 or more is observed.

<DSC measurement>

The protective film of each dry film of each of the examples and the comparative example was peeled off and 10 mg of the resin layer was cut out and weighed in a dedicated aluminum pan and immediately exposed to a temperature of 30 to 300 占 폚 in a DSC-6200 manufactured by Seiko Instruments Inc. at a heating rate of 5 占 폚 / And DSC measurement was carried out for each of them. For each of them, an exothermic peak temperature was confirmed from the obtained DSC chart.

○: All exothermic peak temperatures are below 190 ° C.

Δ: The first exothermic peak is less than 190 ° C., and the second exothermic peak is more than 190 ° C.

&Lt; Glass transition temperature (Tg) and thermal expansion coefficient (CTE (alpha 1))>

The protective film was peeled off on the glossy surface side (copper foil) of the GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.) of the dry films of the examples and the comparative examples and the copper foil Lt; / RTI &gt; Subsequently, the resin layer was cured at 220 DEG C for 60 minutes in a hot air circulation type drying furnace. For the composition not containing the maleimide compound described in the comparative example, the resin layer was cured at 180 DEG C for 60 minutes. Thereafter, the cured product was peeled off from the copper foil, and then the sample was cut at a measurement size (size of 3 mm x 10 mm) and supplied to TMA6100 manufactured by Seiko Instruments. The TMA measurement was carried out two times in succession at a heating rate of 5 g from the room temperature at a heating rate of 10 캜 / min. The intersection of the two tangent lines having different thermal expansion coefficients at the second time was regarded as the glass transition temperature (Tg) and the thermal expansion coefficient (CTE (alpha 1)) in the region below Tg. It can be said that the higher the Tg, the higher the heat resistance.

Evaluation of glass transition temperature (Tg)

◎ ◎: Tg is over 250 ℃.

?: Tg is 220 ° C or more and less than 250 ° C.

?: Tg of 200 占 폚 or more and less than 220 占 폚.

占 Tg less than 200 占 폚.

Evaluation of thermal expansion coefficient (CTE (? 1))

?: Less than 15 ppm.

?: 15 ppm or more and less than 20 ppm.

<Measurement of Absorption Rate>

The dry film of each of the Examples and Comparative Examples was cured by the same method as described in the above-mentioned <Glass Transition Temperature (Tg) and Thermal Expansion Coefficient (CTE (? 1))>. Thereafter, the cured product was peeled from the copper foil, and then the sample was cut at a measurement size (size of 50 mm x 50 mm), followed by drying at 100 ° C for 2 hours to completely remove water, Were measured. Thereafter, the sample was immersed in distilled water maintained at 23 占 폚 占 2 占 폚, and the mass (W2) after 24 hours was measured. The water absorption was obtained by (W2-W1) / W1 100 (%).

◎ ◎: less than 0.3%.

◎: 0.3% or more and less than 0.7%.

○: 0.7% or more and less than 1.4%.

X: 1.4% or more.

&Lt; Circuit concealment >

(MCL-E-679FGR, manufactured by Hitachi Kasei Kogyo Co., Ltd.) having a thickness of 400 mm x 300 mm x 0.8 mm thick on which a conductive layer having a copper thickness of 10 mu m was formed as a circuit board, , Manufactured by Mack Co., Ltd.) to form a profile corresponding to a copper etching amount of 1 占 퐉. The dry film of each of the examples and comparative examples was applied onto the copper-clad laminate by means of a batch type vacuum laminator MVLP-500 (manufactured by Meikis Co., Ltd.) at 5 kgf / cm 2 at 80 ° C for 1 minute, 1 &lt; / RTI &gt; Torr. Thereafter, the carrier film was peeled off, heated in a hot-air circulation type drying furnace, and the resin layer was cured to form a cured film, thereby preparing a substrate for evaluation. At this time, the composition containing the maleimide compound was cured at 220 占 폚 for 60 minutes and for the composition not containing it at 180 占 폚 for 60 minutes. With respect to each substrate for evaluation, discoloration of the copper circuit from the cured film was visually confirmed, and the concealability of the circuit was evaluated.

⊚: discoloration is not confirmed.

○: Very slight discoloration was confirmed.

&Lt; Evaluation of bending of substrate &

Etching equivalent to 1 占 퐉 was carried out using CK-8101 manufactured by Mack Co., Ltd. as a pretreatment on a copper plate (thickness of copper on one side = 20 占 퐉, MCL-E-679FGR, Hitachi Chemical Co., Ltd.) having a total thickness of 100 占 퐉 and a size of 200 占 200 mm . Subsequently, the dry films of Examples and Comparative Examples were laminated on the front and back sides of the transverse plate. Subsequently, the carrier film was peeled off, and the resin layer was cured in a hot-air circulation type drying furnace to obtain a substrate having a thermosetting resin composition on the front and back sides of the substrate. At this time, the composition containing the maleimide compound was cured at 220 占 폚 for 60 minutes and for the composition not containing it at 180 占 폚 for 60 minutes.

Thereafter, laser vias having a top diameter of 65 占 퐉 and a bottom diameter of 50 占 퐉 were formed on one surface of the substrate with a ViaMechanics CO ₂ laser: LC-2K 212. The processing area of the laser was 50 × 50 mm as one unit, and about 10,000 holes were formed on one side. Subsequently, as a cleaning of the laser via, the wafer was swelled with a chemical liquid for sap: SAP Securinganth SAP manufactured by Atotech for 5 minutes at 60 ° C, 20 minutes at permanganic acid at 80 ° C, and 5 minutes at 40 ° C for 5 minutes. Cleaning was carried out. Subsequently, plating was carried out using a commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel 0.5 탆 and gold plating 0.03 탆, and gold plating was applied to the bottom of the laser via.

The obtained substrate was cut into a laser via processing area of 50 x 50 mm. Subsequently, on the surface on which the via was formed, an echo solder ball (φ0.1 to 0.25 mm) manufactured by Senju Gijuku Co., Ltd., and silicon beads of φ100 μm as a gap retaining material were dumped (TEG chip, size 20 × 20 mm × 1 mmt) In a mounting area of 20 x 20 mm. The mounting area was approximately the center of the 50 x 50 mm substrate.

Thereafter, a dummy chip was mounted on the area where the solder balls were arranged, and the substrate was subjected to a reflow treatment once at a surface temperature of 260 占 폚 to obtain a substrate having a flexural evaluation. In the method of evaluating warpage, the obtained substrate was precisely cut to a diagonal line of 50 x 50 mm, and the difference between the greatest value and the smallest value in the cross section of the diagonal area was defined as the deflection.

?: The warping amount of the substrate is less than 100 占 퐉.

?: The deflection amount of the substrate is not less than 100 占 퐉 and less than 200 占 퐉.

X: The deflection amount of the substrate is 200 m or more.

<Cooling / Heating Cycle (Suppressing Cracks)>

The dry films of each of the Examples and Comparative Examples were laminated on the copper layer of the copper clad laminate under the conditions of 5 kgf / cm 2, 80 ° C, 1 minute, and 1 Torr using a batch vacuum laminator MVLP-500 (manufactured by Meikisha Co., Ltd.). Thereafter, the carrier film was peeled off and heated in a hot-air circulation type drying furnace to cure the resin layer. At this time, the composition containing the maleimide compound was cured at 220 占 폚 for 60 minutes and for the composition not containing it at 180 占 폚 for 60 minutes.

Thereafter, vias were formed using a CO ₂ laser processing machine (manufactured by Hitachi Biomekanix Co., Ltd.) so as to have a top diameter of 65 μm and a bottom diameter of 50 μm.

Subsequently, treatment was carried out in the order of commercially available wet permanganic acid dismear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.) and electrolytic copper plating treatment, A thickness of 25 탆, and a copper plating treatment so as to fill the via portion. Subsequently, curing was carried out in a hot-air circulation type drying furnace to obtain a test substrate on which a completely cured copper plating treatment was carried out. The obtained test substrate was heated for 30 minutes at -65 占 폚 and for 30 minutes at 150 占 폚, and thermal history was applied. After the lapse of 2000 and 3000 cycles, in order to observe the state of the via bottom or the wall surface by an optical microscope, the center portion of the via was cut and polished by a precision cutter to observe the cross-sectional state. The evaluation criteria were as follows. The number of observed vias was 100 holes.

◎ ◎: No cracks in both 2000 and 3000 cycles.

&Amp; cir &amp;: No crack occurred in the 2000 cycle. One or two cracks occur in 3000 cycles.

?: No crack occurred in 2000 cycles. 3 to 5 cracks occur in 3000 cycles.

X: Crack occurred in 2000 cycles.

* 32: When the carrier film was peeled off after lamination, a large amount of the resin derived from the resin layer adhered to the carrier film, so that the characteristic test could not be conducted.

* 33: Since the dry film after drying had no flexibility, and the powder was separated and cracked, the test could not be conducted.

The results shown in Tables 6 to 10 show that the dry films of Examples 1 to 30 exhibit excellent heat resistance, low warpage and crack resistance, excellent peelability from the carrier film, It is possible to obtain a resin layer which suppresses the adhesion of the resin.

On the other hand, the dry film of Comparative Example 1 containing two kinds or more of solvents but containing only one solvent having a boiling point of 100 ° C or higher, and the solvent having a boiling point of 100 ° C or higher, It can be understood that the dry film has poor peelability of the carrier film and can not withstand the use as a dry film because a large amount of the resin layer is peeled off when the carrier film is peeled off. In addition, since the resin layers of the dry films of Comparative Examples 1 and 3 were sticky, bubble remained when laminated to the substrate.

The dry film of Comparative Example 2 containing only a solvent having a boiling point of less than 100 占 폚 as a solvent was excellent in peelability of the carrier film but had no flexibility in the resin layer and cracks and dropout of the powder occurred.

The dry film of Comparative Example 4 containing no maleimide compound had low heat resistance and poor crack resistance of the cured product. Also, the warp of the substrate was large.

1 insulating substrate
3 inner conductor pattern
3a connection part
4, 9 resin insulating layer
8 outer layer conductor pattern
10 outermost layer conductor pattern
20 Through Hole
21 Through Hole Holes
22 Connection section
30a Test tube for liquid determination
30b Test tube for temperature measurement
31 Line (A line)
32 Mark line (line B)
33a, 33b Rubber plug
34 Thermometers
X laminated substrate

Claims (8)

A dry film having a resin layer containing a thermosetting resin component, at least one of a curing agent and a curing accelerator, a maleimide compound, a filler, and at least two kinds of solvents,
Wherein the at least two kinds of solvents all have a boiling point of 100 캜 or higher and a boiling point of 5 캜 or higher. The dry film according to claim 1, wherein the ratio of the residual content of the solvent is 0.1 to 4% by weight based on the whole amount of the resin layer of the dry film containing the solvent. The method according to claim 1, wherein the at least two solvents are at least two solvents selected from the group consisting of N, N-dimethylformamide, toluene, methoxypropanol, methylisobutylketone, cyclohexanone, and aromatic hydrocarbons having a carbon number of 8 or more Lt; / RTI &gt; film. The dry film according to claim 1, wherein the curing agent comprises at least one of a phenol resin, a cyanate ester resin and an active ester resin having a triazine structure. The dry film according to claim 1, wherein the dry film contains an epoxy compound as the thermosetting resin component. The dry film according to any one of claims 1 to 5, which is for producing a printed wiring board. A cured product obtained by curing a resin layer of the dry film according to any one of claims 1 to 6. A printed wiring board comprising the cured product according to claim 7.

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