JP2016113608A - Curable resin composition, dry film, cured article and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having properly adjusted thermal expansion coefficient without deteriorating long term reliability such as flexibility as a film or laser processability, cold heat cycle resistance or the like of a cured film, a dry film, a cured article and a printed wiring board using the same.SOLUTION: There is provided a curable resin composition containing a filler having thermal expansion coefficient of minus value, a curable resin and at least two kinds of solvents, where the at least two kinds of solvents have the boiling point of 100°C or more and 5°C or more different. There are provided a dry film, a cured article and a printed wiring board using the same.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a curable resin composition (hereinafter also simply referred to as “composition”), a dry film, a cured product, and a printed wiring board, and more specifically, curability having a reduced coefficient of thermal expansion without impairing other performances. The present invention relates to a resin composition, a dry film, a cured product, and a printed wiring board.

  In recent years, as a method for manufacturing 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, a multilayer printed wiring board in which an epoxy resin composition is applied to a circuit-formed inner layer circuit board, heat-cured, a roughened surface is formed on the surface with a roughening agent, and a conductor layer is formed by plating The manufacturing method of this is proposed. There has also been proposed a method for producing a multilayer printed wiring board in which a conductive layer is formed after laminating an adhesive sheet of an epoxy resin composition on a circuit-formed inner layer circuit board and heat-curing. A resin composition applied to the production of such a multilayer printed wiring board is disclosed in Patent Document 1, for example.

  Here, an example of a method for forming a layer structure of a multilayer printed wiring board by a conventional build-up method will be described with reference to FIG. First, the outer layer conductor pattern 8 as the conductor layer is formed on both surfaces of the laminated substrate X in which the inner layer conductor pattern 3 as the conductor layer and the resin insulating layer 4 are formed in advance on both surfaces of the insulating substrate 1, and on that, An insulating resin composition such as an epoxy resin composition is provided by coating or the like, and is cured by heating to form the resin insulating layer 9. Next, after appropriately providing 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 according to a conventional method. The outermost conductor pattern 10 can be formed. In the figure, reference numeral 3a denotes a connection portion, 20 denotes a through hole as a conductor layer, and 22 denotes a connection portion.

JP 2010-1403 A (Claims)

  Since heating is essential in the production process of a printed wiring board, the resin composition for an interlayer insulating layer has a coefficient of thermal expansion (CTE) that is as close as possible to a substrate or the like serving as a base. It is desirable. Conventionally, the CTE is decreased and adjusted by blending a filler in the resin composition, but when the filler content is increased, the blended amount of the resin in the composition is relatively reduced. Therefore, the long-term reliability such as flexibility when used as a film, laser processability of a cured film, and heat cycle resistance (also referred to as TCT) is lowered, which is a problem.

  Accordingly, an object of the present invention is to provide a curable resin composition in which a coefficient of thermal expansion is appropriately adjusted without impairing long-term reliability such as flexibility, laser processability, and thermal cycle resistance as a film, and a dry film using the same. It is in providing a hardened | cured material and a printed wiring board.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a filler having a negative coefficient of thermal expansion, unlike silica that has been generally used in the past. It came to complete.

That is, the curable resin composition of the present invention includes a filler having a negative coefficient of thermal expansion, a curable resin, and at least two solvents.
Each of the at least two solvents has a boiling point of 100 ° C. or higher and a boiling point of 5 ° C. or higher.

In the composition of this invention, it is preferable that the true specific gravity of the said filler is 2.5-4.0 g / cm < ³ >. Moreover, the composition of this invention is used suitably for manufacture of a printed wiring board. In particular, the composition of the present invention has a difference in thermal expansion coefficient between a cured product obtained from the curable resin composition and a conductor layer of the printed wiring board or a wafer layer of a semiconductor chip mounted on the printed wiring board. Is preferably within 15 ppm / ° C. In other words, the difference in thermal expansion coefficient between the conductor layer and the cured product is preferably 15 ppm / ° C. or less, or the difference in thermal expansion coefficient between the wafer layer and the cured product is preferably 15 ppm / ° C. or less.

  The dry film of the present invention has a resin layer obtained by drying the curable resin composition of the present invention on the film.

  The cured product of the present invention is characterized in that the curable resin composition of the present invention or the resin layer of the dry film of the present invention is cured.

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

  According to the present invention, a curable resin composition in which the coefficient of thermal expansion is appropriately adjusted without impairing long-term reliability such as flexibility as a film, laser processability of a cured film, and thermal cycle resistance, and the like were used. It has become possible to realize dry films, cured products and printed wiring boards.

It is a fragmentary sectional view which shows schematic structure of the multilayer printed wiring board produced by the conventional buildup method. It is an expanded partial sectional view which shows the printed wiring board by which the chip | tip was flip-chip connected. It is a schematic side view which shows the two test tubes used for the liquid determination of the epoxy resin.

Hereinafter, embodiments of the present invention will be described in detail.
The curable resin composition of the present invention includes a filler having a negative coefficient of thermal expansion, a curable resin, and at least two types of solvents, both of which have a boiling point of 100 ° C. or higher. In addition, the boiling point is different by 5 ° C. or more.

  In the present invention, unlike conventional general-purpose silica and the like, the filler having a negative coefficient of thermal expansion is used, so that the composition can be reduced even if the blending amount of the filler in the composition is relatively small. It becomes easy to lower the CTE of an object. Therefore, since the compounding amount of the resin in the composition can be relatively increased, the flexibility of the film is not impaired by sufficiently exhibiting the characteristics of the resin, that is, excellent in handling properties, A curable resin composition having good long-term reliability such as laser processability as a cured film and thermal cycle resistance can be obtained. In addition, the difference between the coefficient of thermal expansion of the cured product and the coefficient of thermal expansion of the conductor layer or wafer layer of the printed wiring board can be within 15 ppm / ° C., and when the composition is used for the production of a printed wiring board. Since it is considered that the expansion amount of the composition and the conductor layer or the wafer layer becomes substantially the same during heating such as reflow in the manufacturing process, the generation of cracks between these layers can be suppressed, and the reliability of the substrate can be suppressed. Can be improved.

  Here, the thermal expansion coefficient of the cured product is substantially constant at a temperature lower than the glass transition temperature Tg of the cured product, but increases rapidly due to molecular motion above the glass transition temperature Tg. Therefore, in the present invention, the thermal expansion coefficient α1 below the glass transition temperature (Tg) is used as the thermal expansion coefficient of the cured product. In the present invention, since the problem is not the absolute value of the thermal expansion coefficient of the cured product, but the thermal expansion coefficient between the cured product and the conductor layer or the wafer layer, α1 is used as the thermal expansion coefficient of the cured product, By defining the difference in coefficient of thermal expansion with the conductor layer or wafer layer to be small, for example, it is possible to suppress the difference in coefficient of thermal expansion at the temperature at the time of solder mounting, and to obtain the effects such as crack suppression. Become.

  Moreover, when forming a dry film using the composition of this invention, two types of solvents whose boiling point is 100 degreeC or more and whose boiling point differs 5 degreeC or more are used as a solvent. Thereby, it becomes possible to obtain a dry film excellent in flexibility. The difference in boiling points is preferably 10 ° C. or higher, more preferably 20 ° C. or higher. In addition, in this specification, when the boiling point of a solvent has a width | variety, let the boiling point be the initial boiling point-end point of distillation.

  Next, each component of the curable resin composition of this invention is demonstrated. In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

[Curable resin]
The curable resin composition of the present invention contains a curable resin. The curable resin used in the present invention is a thermosetting resin or a photocurable resin, and may be a mixture thereof.

(Thermosetting resin)
The thermosetting resin is a resin having a functional group that can be cured by heat. The thermosetting resin is not particularly limited, and is an epoxy compound, an oxetane compound, a compound having two or more thioether groups in the molecule, that is, an amino resin such as an episulfide resin, a melamine resin, a benzoguanamine resin, a melamine derivative, or a benzoguanamine derivative. , Blocked isocyanate compounds, cyclocarbonate compounds, bismaleimides, carbodiimides, and the like may be used, and these may be used in combination.

  The epoxy compound is a compound having an epoxy group, and any conventionally known one can be used. A bifunctional epoxy compound having two epoxy groups in the molecule, a polyfunctional epoxy compound having many epoxy groups in the molecule. Etc. In addition, a hydrogenated bifunctional epoxy compound may be used.

  Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, and cresol novolak type. Epoxy resin, bisphenol A novolak 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 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 Resin, amino cresol type epoxy resin, alkylphenol type epoxy resin or the like is used. These epoxy resins can 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. Here, in this specification, solid epoxy resin refers to an epoxy resin that is solid at 40 ° C., and semi-solid epoxy resin refers to an epoxy resin that is solid at 20 ° C. and liquid at 40 ° C., The liquid epoxy resin refers to an epoxy resin that is liquid at 20 ° C.

The determination of the liquid state can be performed in accordance with the second “liquid confirmation method” of the ministerial ordinance on the test and properties of hazardous materials (Ministry of Local Government Ordinance No. 1 of 1989).
(1) Equipment constant temperature water bath:
A thing equipped with a stirrer, a heater, a thermometer, and an automatic temperature controller (with temperature control at ± 0.1 ° C.) having a depth of 150 mm or more is used.
In the determination of the epoxy resin used in the examples described later, all use a combination of a low-temperature thermostatic water tank (model BU300) manufactured by Yamato Scientific Co., Ltd. and a thermostat (model BF500) of a charging type thermostatic apparatus (model BF500). Is put into a low temperature constant temperature water bath (model BU300), the thermomate (model BF500) assembled to this is turned on and set to a set temperature (20 ° C or 40 ° C), and the water temperature is set to a set temperature ± 0.1 ° C. Although fine adjustment was performed with a thermomate (model BF500), any apparatus capable of the same adjustment can be used.

Test tube:
As shown in FIG. 3, the test tube is made of a flat bottom cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, and marked lines 31 and 32 are respectively provided at heights of 55 mm and 85 mm from the tube bottom. The test tube 30a for liquid judgment with the test tube 30a sealed with a rubber plug 33a is the same size as that of the test tube 30a. The rubber plug 33b is similarly provided with a marked line and a hole for inserting and supporting a thermometer in the center. A test tube 30b for temperature measurement in which the mouth of the test tube is sealed and a thermometer 34 is inserted into the rubber plug 33b is used. Hereinafter, a marked line having a height of 55 mm from the tube bottom is referred to as “A line”, and a marked line having a height of 85 mm from the tube bottom is referred to as “B line”.
As the thermometer 34, the one for freezing point measurement (SOP-58 scale range 20-50 ° C) specified in JIS B7410 (1982) "Petroleum test glass thermometer" is used, but the temperature is 0-50 ° C. It is sufficient if the range can be measured.

(2) Test procedure The liquid test tube 30a shown in FIG. 3 (a) and the temperature measurement test shown in FIG. 3 (b) were prepared for 24 hours or more at atmospheric pressure of 20 ± 5 ° C. Insert up to line A in each tube 30b. The two test tubes 30a and 30b are left standing in a low temperature constant temperature water tank so that the line B is below the water surface. The thermometer has its lower end 30 mm below the A line.
The state is maintained as it is for 10 minutes after the sample temperature reaches the set temperature ± 0.1 ° C. Ten minutes later, the test tube 30a for liquid judgment is taken out of the low-temperature water bath and immediately tilted horizontally on a horizontal test stand, and the time when the tip of the liquid level in the test tube has moved from the A line to the B line is measured with a stopwatch. Measure and record. A sample is determined to be liquid when the measured temperature is 90 seconds or less at a set temperature, and solid when it exceeds 90 seconds.

  As the solid epoxy resin, HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC, NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd. Naphthalene-type epoxy resins such as EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Epoxidized products (trisphenol-type epoxy resins) of condensation products of phenols and aromatic aldehydes having a phenolic hydroxyl group; Dicyclopentadiene aralkyl epoxy resin such as Epiklon HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; biphenyl aralkyl such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Type Epoxy Resin; biphenyl / phenol novolak type epoxy resin such as NC-3000L manufactured by Nippon Kayaku; novolak type epoxy resin such as Epicron N660 and Epicron N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku; YX- manufactured by Mitsubishi Chemical Corporation Biphenyl type epoxy resin such as 4000; Phosphorus-containing epoxy resin such as TX0712 manufactured by Nippon Steel & Sumikin Chemical Co .; Tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Industries, Ltd.

  Semi-solid epoxy resins include DIC Corporation Epicron 860, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Asahi Ciba Araldite AER280, Toto Kasei Epoto YD-134, Japan Epoxy Resin Corporation jER834. , JER872, bisphenol A type epoxy resin such as ELA-134 manufactured by Sumitomo Chemical Co., Ltd .; naphthalene type epoxy resin such as Epicron HP-4032 manufactured by DIC; phenol novolak type epoxy resin such as Epicron N-740 manufactured by DIC It is done.

  Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin And alicyclic epoxy resins.

  Next, oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, Poly (p-hydroxystyrene), cardo bisphenol S, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the episulfide resin include bisphenol A type episulfide resin. In addition, an episulfide resin or the like in which the oxygen atom of the epoxy group of the epoxy resin is replaced with a sulfur atom can be used by using a similar synthesis method.

  In the present invention, an epoxy compound is preferably used as the thermosetting resin. Furthermore, since a cured product having a high glass transition temperature (Tg) and excellent crack resistance can be obtained, it is preferably at least one of a solid epoxy resin and a semi-solid epoxy resin. As the epoxy compound, an aromatic epoxy resin is preferable from the viewpoint of preferable physical properties of the cured product, and among them, a naphthalene type epoxy compound and a biphenyl type epoxy compound are more preferable. In the present specification, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in the molecule.

  A thermosetting resin can be used individually by 1 type or in combination of 2 or more types. When using 2 or more types of thermosetting resins together, it is preferable that the total amount of a semi-solid epoxy compound and a solid epoxy compound is 10-55 mass% in conversion of solid content on the basis of the total amount of the composition. More preferably, it is 50 mass%, and it is further more preferable that it is 20-45 mass%. Further, the blending amount of the liquid epoxy resin is preferably 20% by mass or less and preferably 15% by mass or less based on the total amount of the composition from the viewpoint of not excessively reducing the glass transition temperature (Tg) of the cured product. Is more preferable, and it is further more preferable that it is 10 mass% or less.

(Photo-curing resin)
Next, the photocurable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation. In particular, in the present invention, the resin has one or more ethylenically unsaturated bonds. A compound is preferably used.

  As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used. Among these, examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.

  As the photopolymerizable vinyl monomer, known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylate (Meth) acrylamides such as luamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; alcohols such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Xylalkylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol Alkylene polyol poly (meth) acrylates such as propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxy Polyoxyalkylene glycol poly (methyl) such as trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) acrylate ) Acrylates; poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate It is done. These can be used alone or in combination of two or more according to the required properties.

  When the composition of the present invention is an alkali development type photosensitive resin composition, a carboxyl group-containing resin is preferably used as the curable resin. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, and may or may not have an aromatic ring. As the carboxyl group-containing resin, a resin having an epoxy resin as a starting material, a resin having a phenol compound as a starting material, a resin having a urethane structure, a resin having a copolymer structure, and a resin having an imide structure are preferable. A phenolic hydroxyl group-containing resin may be used as the curable resin.

  Specific examples of the carboxyl group-containing resin that can be used in the composition of the present invention include the following compounds (any of oligomers and polymers).

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.

  (5) During the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.

  (6) During the synthesis of the resin of the above (2) or (4), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (7) Photosensitivity obtained by reacting polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride to the hydroxyl group present in the side chain Carboxyl group-containing resin.

  (8) A photosensitive carboxyl group obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl group Containing resin.

  (9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

  (10) Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

  (11) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

  (12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.

  (13) One epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above A photosensitive carboxyl group-containing resin obtained by adding a compound having a group.

  Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

  The acid value of the carboxyl group-containing resin is desirably in the range of 20 to 2000 mgKOH / g, and more preferably in the range of 40 to 1800 mgKOH / g. When it is in the range of 20 to 2000 mg KOH / g, adhesion of the coating film is obtained, alkali development is facilitated, dissolution of the exposed area by the developer is suppressed, and the line does not fade more than necessary and is normal. This is preferable because the resist pattern can be easily drawn.

  Moreover, although the weight average molecular weight of carboxyl group-containing resin used by this invention changes with resin frame | skeletons, the range of 2,000-150,000 is preferable. Within this range, tack-free performance is good, the moisture resistance of the coated film after exposure is good, and film loss is less likely to occur during development. Further, when the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is improved. More preferably, it is 5,000-100,000. The weight average molecular weight can be measured by gel permeation chromatography.

[Filler]
As the filler having a negative thermal expansion coefficient used in the present invention, a filler having a large absolute value of the thermal expansion coefficient is preferable because the CTE of the cured product can be reduced with a small amount of blend, and in particular, the linear expansion coefficient. However, a filler of −0.1 × 10 ⁻⁶ / ° C. or lower, more preferably −0.3 × 10 ⁻⁶ / ° C. or lower is preferable. Specifically, for example, zirconium phosphate (Ultea series manufactured by Toagosei Co., Ltd.), zirconium tungstate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ , ZWP), LaCu ₃ Fe ₄ O ₁₂ ( A-site ordered perovskite structure oxide, see Table 2010/101153), Bi _1-x Ln _x NiO ₃ (Ln = La, Nd, Eu, Dy, perovskite structure oxide), Al ₂ O ₃ .TiO ₂ (Rotec manufactured by AGC Ceramics Co., Ltd.), Li ₂ O.Al ₂ O ₃ .nSiO ₂ β-spodumene solid solution (Neoceram manufactured by Nippon Electric Glass Co., Ltd.), faujasite; Na, Ca _{0.5 , Mg 0.5, K) x [} Al x Si 12-x O 24] · 16H 2 O), LiAlSiO 4, PbT _{O 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 , etc.) and the like. Among them, zirconium phosphate and zirconium tungstate phosphate are easily available, and zirconium phosphate having a large absolute value of thermal expansion coefficient and a small true specific gravity is particularly preferable.

Moreover, as said filler used in this invention, that whose true specific gravity is 2.5-4.0 g / cm < ³ > is preferable. By using a filler with a small specific gravity, it is possible to mix with a smaller mass with respect to the volume occupied in the composition. Therefore, the CTE as a composition is equivalent with a small amount compared to a filler with a large specific gravity. It can be reduced to a certain extent, which is preferable. Furthermore, it is preferable that the filler has a smaller average particle diameter (median diameter) because laser workability is improved.

  Further, in the present invention, when the composition is used for production of a printed wiring board, the difference between the thermal expansion coefficient of the cured product of the composition and the thermal expansion coefficient of the conductor layer or wafer layer of the printed wiring board is It is preferably within 15 ppm / ° C. More preferably, it is within 10 ppm / ° C., more preferably within 5 ppm / ° C., and the difference is preferably closer to zero. Here, as a conductor layer, for example, copper (17 ppm / ° C.), silver (19 ppm / ° C.), gold (14 ppm / ° C.), lead solder: Sn—Pb (24 ppm / ° C.), lead free solder: Sn—Ag -Cu (21 ppm / ° C), Sn-Zn-Al (24 ppm / ° C), Sn-Bi-Ag (15 ppm / ° C), as a wafer layer, for example, a silicon wafer (3 ppm / ° C), a sapphire wafer (6- 10 ppm / ° C.), GaP (gallium phosphide) wafer (6 ppm / ° C.), GaAs (gallium arsenide) wafer (7 ppm / ° C.), InP (indium phosphide) wafer (5 ppm / ° C.), GaN (gallium nitride) wafer (2 ppm / ° C.), germanium (6 ppm / ° C.), silicon carbide (7 ppm / ° C.) (the value in the parentheses is the coefficient of thermal expansion)That is, the cured product obtained from the composition of the present invention is any one of copper, silver, gold, lead solder, lead-free solder, silicon, sapphire, GaP, GaAs, InP, GaN, germanium, and silicon carbide. The difference in thermal expansion coefficient from the seed is preferably within 15 ppm / ° C.

  As a compounding quantity of the said filler in the composition of this invention, it is preferable that it is 25-90 mass% on a composition whole quantity basis, It is more preferable that it is 30-90 mass%, It is 35-85 mass%. More preferably. By making the compounding quantity of a filler into the said range, favorable crack resistance can be obtained, ensuring desired low CTE as a composition. The present invention is characterized in that the CTE can be reduced as much as or more than the conventional amount by using an amount smaller than the conventional filler blending amount.

  In the present invention, a conventional filler having a positive thermal expansion coefficient may be used in combination with the filler having a negative thermal expansion coefficient. Examples of fillers having a positive coefficient of thermal expansion include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, water Examples include aluminum oxide, silicon nitride, and aluminum nitride.

[Curing agent]
In the composition of the present invention, when a thermosetting resin is used, a curing agent can be further added. Examples of the curing agent include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, and active ester resins. A hardening | curing agent can be used individually by 1 type or in combination of 2 or more types.

  Examples of the phenol resin include phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, cresol / naphthol resin, polyvinylphenols, phenol / naphthol resin. Conventionally known ones such as an α-naphthol skeleton-containing phenol resin and a triazine-containing cresol novolak resin can be used singly or in combination of two or more.

  The polycarboxylic acid and acid anhydride thereof are compounds having two or more carboxyl groups in one molecule and acid anhydrides thereof. For example, (meth) acrylic acid copolymer, maleic anhydride copolymer Resin 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. Any conventionally known cyanate ester resins can be used. Examples of the cyanate ester resin include phenol novolac type cyanate ester resin, alkylphenol novolak type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type cyanate ester resin. Is mentioned. Further, it may be a prepolymer partially triazine.

  The active ester resin is a resin having two or more active ester groups in one molecule. The active ester resin can generally be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Among these, an active ester compound obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferable. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like.

  Moreover, you may use an alicyclic olefin polymer as a hardening | curing agent. Specific examples of the method for producing an alicyclic olefin polymer include (1) an alicyclic olefin having a carboxyl group and / or a carboxylic acid anhydride group (hereinafter referred to as “carboxyl group etc.”) as necessary. (2) The aromatic ring portion of the (co) polymer obtained by polymerizing an aromatic olefin having a carboxyl group or the like with another monomer as necessary. (3) a method of copolymerizing an alicyclic olefin having no carboxyl group and a monomer having a carboxyl group, (4) an aromatic olefin having no carboxyl group, and a carboxyl group A method of hydrogenating an aromatic ring portion of a copolymer obtained by copolymerizing with a monomer having, for example, (5) an alicyclic olefin polymer having no carboxyl group or the like having a carboxyl group or the like. Or a carboxylic acid ester group of an alicyclic olefin polymer having a carboxylic acid ester group obtained as described in (1) to (5) above, for example, The method etc. which convert to a carboxyl group by decomposition | disassembly etc. are mentioned.

  Among the curing agents, phenol resin, active ester resin, and cyanate ester resin are preferable.

  In the curing agent, the ratio of the functional group capable of thermosetting reaction such as epoxy group of the thermosetting resin and the functional group in the curing agent that reacts with the functional group is the functional group of the curing agent / thermosetting reaction. It is preferable to mix | blend in the ratio which becomes the functional group (equivalent ratio) = 0.2-2. By setting the functional group of the curing agent / functional group capable of thermosetting reaction (equivalent ratio) within the above range, roughening of the surface of the cured film in the desmear process can be prevented. More preferably, the functional group of the curing agent / functional group capable of thermal curing reaction (equivalent ratio) = 0.3 to 1.0.

[Curing accelerator]
In the composition of the present invention, when a thermosetting resin is used, a curing accelerator can be blended together with the curing agent or alone. The curing accelerator is for accelerating the thermosetting reaction, and is used for further improving properties such as adhesion, chemical resistance, and heat resistance. Specific examples of such curing accelerators include imidazole and derivatives thereof; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, Polyamines such as melamine and polybasic hydrazides; organic acid salts and / or epoxy adducts thereof; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4- Triazine derivatives such as diamino-6-xylyl-S-triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) Amines such as lamin, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac; tributylphosphine, tri Organic phosphines such as phenylphosphine and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; benzyltrimethylammonium chloride and phenyltributylammonium chloride Quaternary ammonium salts such as polybasic acid anhydrides; diphenyliodonium tetrafluoroboroate, triphenyl Photocationic polymerization catalyst such as sulfonium hexafluoroantimonate and 2,4,6-triphenylthiopyrylium hexafluorophosphate; styrene-maleic anhydride resin; equimolar reaction product of phenyl isocyanate and dimethylamine, tolylene diisocyanate, Conventionally known curing accelerators such as an equimolar reaction product of an organic polyisocyanate such as isophorone diisocyanate and dimethylamine, and a metal catalyst can be used. Among the curing accelerators, phosphonium salts are preferred because BHAST resistance is obtained. A hardening accelerator can be used individually by 1 type or in mixture of 2 or more types.

  Although the use of a curing accelerator is not essential, particularly when it is desired to accelerate curing, it is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the thermosetting resin It can be used in the range. Moreover, in the case of a metal catalyst, 10-550 ppm is preferable at metal conversion with respect to 100 mass parts of thermosetting resins, and 25-200 ppm is more preferable.

[Photopolymerization initiator]
In the composition of the present invention, when a photocurable resin is used, it is preferable to further add a photopolymerization initiator. Any photopolymerization initiator can be used as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.

  Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenyl Monoacylphosphine oxides such as phosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1-hydroxy-cyclohexylphenylketone, 1- [4- (2 -Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -Benzyl] phenyl} -2-methyl-propan-1-one, hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, Benzoins such as benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bis Benzophenones such as diethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Loacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1 (manufactured by BASF Japan Ltd., IRGACURE 369), 2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1- Acetophenones such as butanone and N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl Thioxaton and other thioxa Tones; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; acetophenone dimethyl ketal, benzyldimethyl Ketals such as ketals; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- ( Phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) Oxime such as Steles; bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl)- Titanocenes such as bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobuty Examples include nitrile and tetramethylthiuram disulfide, and among them, acetophenones can be preferably used. Any of the above photopolymerization initiators may be used alone or in combination of two or more.

  The blending amount of the photopolymerization initiator is preferably 0.01 to 30 parts by mass and more preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the photocurable resin in terms of solid content. By blending the photopolymerization initiator within this range, the photocurability on copper becomes sufficient, the curability of the paint film becomes good, the paint film properties such as chemical resistance are improved, and the deep part curability. Will also improve.

[Thermoplastic resin (polymer resin)]
In order to improve the mechanical strength of the obtained cured film, a thermoplastic resin can be further blended with the composition of the present invention. As the thermoplastic resin, use is made of thermoplastic polyhydroxy polyether resin, phenoxy resin which is a condensate of epichlorohydrin and various bifunctional phenolic compounds, or hydroxyl group of hydroxy ether part present in the skeleton, and various acid anhydrides and acid chlorides. And esterified phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamideimide resin, block copolymer and the like. A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  Among the above, when the thermoplastic polyhydroxypolyether resin has a fluorene skeleton, it has a high glass transition point and is excellent in heat resistance. Therefore, while maintaining a low coefficient of thermal expansion due to a semi-solid or solid epoxy resin, the glass The cured film obtained by maintaining the transition point has a low thermal expansion coefficient and a high glass transition point in a well-balanced manner. In addition, since the thermoplastic polyhydroxy polyether resin has a hydroxyl group, it exhibits good adhesion to the substrate and the conductor, and the cured film obtained is hardly affected by the roughening agent, but the aqueous solution is roughened. Since the liquid easily penetrates into the interface between the cured film and the filler, the roughening treatment makes it easy for the filler on the surface of the cured film to come off, and it becomes easy to form a good roughened surface.

  The polyvinyl acetal resin is obtained, for example, by acetalizing a polyvinyl alcohol resin with an aldehyde. The aldehyde is not particularly limited, and for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, benzaldehyde, 2-methylbenzaldehyde, 3- Examples include methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde, and the like, butyraldehyde is preferable.

  Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Tohto Kasei Co., Ltd., YX8100, YX6954, YL6954, and YL6974 manufactured by Mitsubishi Chemical Corporation. As specific examples of the polyvinyl acetal resin, the SEREC KS series manufactured by Sekisui Chemical Co., Ltd., as the polyamide resin, the KS5000 series manufactured by Hitachi Chemical Co., Ltd., the BP series manufactured by Nippon Kayaku Co., Ltd., and the polyamideimide resin KS9000 series manufactured by Hitachi Chemical Co., Ltd.

  A block copolymer may be used as the thermoplastic resin. The block copolymer is a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by a covalent bond to form a long chain.

  The block copolymer is preferably an ABA type or AB-A 'type block copolymer. Of the ABA type and ABA 'type block copolymers, the central B is a soft block and has a low glass transition temperature (Tg), preferably less than 0 ° C. In which A or A ′ is a hard block and has a high glass transition temperature (Tg), preferably composed of polymer units of 0 ° C. or higher. The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC). Further, among the ABA type and ABA type block copolymers, A or A ′ is composed of polymer units having a Tg of 50 ° C. or higher, and B has a Tg of −20 ° C. or lower. More preferred is a block copolymer comprising a certain polymer unit. Further, among the ABA type and ABA 'type block copolymers, those in which A or A' is highly compatible with the thermosetting resin are preferable, and B is the thermosetting resin. Those having low compatibility with are preferable. Thus, it is considered that a specific structure in the matrix can be easily shown by using a block copolymer in which the blocks at both ends are compatible with the matrix and the central block is incompatible with the matrix.

  Among the thermoplastic resins, phenoxy resin, polyvinyl acetal resin, thermoplastic polyhydroxy polyether resin having a fluorene skeleton, and a block copolymer are preferable.

  1-20 mass parts is preferable with respect to 100 mass parts of curable resin, and, as for the compounding quantity of a thermoplastic resin, 1-10 mass parts is more preferable. When the blending amount of the thermoplastic resin is within the above range, a uniform roughened surface state can be easily obtained.

[Rubber particles]
Furthermore, rubbery particles can be blended in the composition of the present invention as necessary. Since the composition of the present invention includes a resin having a positive CTE value and a filler having a negative CTE value, it is considered that the internal stress increases when the temperature changes. Thus, the effect of relieving internal stress can be obtained. Further, by blending rubber-like particles, the effect of improving the flexibility of the resulting cured film, enabling surface roughening treatment with an oxidizing agent, and improving the adhesion strength with copper foil or the like can be obtained.

  Examples of such rubber-like particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl group-modified polybutadiene rubber, acrylonitrile butadiene rubber modified with a carboxyl group or a hydroxyl group, and These crosslinked rubber particles, core-shell type rubber particles, and the like can be mentioned, and one kind can be used alone or two or more kinds can be used in combination. The core-shell type rubber particle is a particle having a core-shell structure in which a core layer made of a rubbery polymer is coated with a shell layer of a glassy polymer, and a rubbery polymer between the core layer made of a glassy polymer and the shell layer. Examples thereof include particles having an intermediate layer.

  The average particle size of the rubber-like particles is preferably in the range of 0.005 to 1 μm, and more preferably in the range of 0.2 to 1 μm. 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, etc., and using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.), the particle size distribution of the rubber-like particles is created on a mass basis and the median diameter is The average particle size can be measured.

  The compounding amount of the rubber-like particles is preferably 0.5 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the curable resin. By blending rubber particles in the above range, it is possible to achieve low CTE while improving crack resistance and adhesion strength with conductor patterns, etc., and further improve the curing characteristics by increasing the glass transition temperature (Tg). can do.

[Other ingredients]
If necessary, the composition of the present invention may further contain other conventionally known additives. Other additives include, for example, conventionally known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, asbestos, olben, benton, fine Conventionally known thickeners such as silica powder, defoamers and / or leveling agents such as silicones, fluorines, and polymers, adhesion imparting agents such as thiazoles, triazoles, and silane coupling agents, flame retardants , Titanate-based and aluminum-based additives.

[solvent]
In the composition of the present invention, a solvent can be used for preparing the composition, adjusting the viscosity for application to a substrate or carrier film, forming a resin layer of a dry film, and the like. It does not specifically limit as a kind of solvent, A conventionally well-known solvent can be used. Moreover, the compounding quantity of a solvent is not limited.

  Solvents having a boiling point of less than 100 ° C. include diethyl ether, carbon disulfide, acetone, chloroform, methanol, n-hexane, ethyl acetate, 1,1,1-trichloroethane, carbon tetrachloride, methyl ethyl ketone, isopropyl alcohol, trichloroethylene, acetic acid. And isopropyl.

  Examples of the solvent having a boiling point of 100 ° C. or higher include alcohol solvents such as isobutyl alcohol, n-butanol and 2-methoxypropanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether (DPM), isopentyl alcohol, Ether solvents such as ethylene glycol monoethyl ether, ester solvents such as butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ketone solvents such as cyclohexanone and methyl isobutyl ketone (MIBK), tetrachloroethylene N, N-dimethylformamide, turpentine oil and the like.

  Examples of the solvent having a boiling point of 100 ° C. or higher include toluene, xylene, petroleum naphtha, SWAZOL 1000 (carbon number 8 to 10: high boiling aromatic hydrocarbon) manufactured by Maruzen Petrochemical Co., Ltd., and SWAZOL 1500 (high boiling aromatic carbonization). Hydrogen), Solvesso 100 (carbon number 9-10: high-boiling aromatic hydrocarbons), Standard Petroleum Osaka Sales Office, Solvesso 150 (carbon number 10-11: high-boiling aromatic hydrocarbons), Solvent #, Sankyo Chemical Co., Ltd. 100, Solvent # 150, Shellzol A100, Shellzol A150 manufactured by Shell Chemicals Japan, Ipsol 100 manufactured by Idemitsu Kosan Co., Ltd. (mainly an aromatic hydrocarbon having 9 carbon atoms), No. 150 Ipsol (aromatic having 10 carbon atoms) Aromatic solvents such as hydrocarbon as a main component) are also included. The high-boiling aromatic hydrocarbon preferably contains 99% by volume or more of an aromatic component. Moreover, it is preferable that each of high-boiling aromatic hydrocarbons is less than 0.01% by volume of benzene, toluene and xylene.

  When forming a dry film using the composition of this invention, you may mix | blend 3 or more types of solvents with a boiling point of 100 degreeC or more in a composition, In this case, any one of 3 or more types of solvents. Any solvent may be used as long as the two solvents have different boiling points. Among solvents having a boiling point of 100 ° C. or higher, solvents having a boiling point of 100 to 230 ° C. are preferable, and solvents having a boiling point of 100 to 220 ° C. are more preferable. When the boiling point is 230 ° C. or less, the solvent almost remains in the resin layer of the dry film after the thermosetting or annealing treatment.

  As the solvent used in the present invention, toluene, N, N-dimethylformamide, cyclohexanone, aromatic hydrocarbon having 8 or more carbon atoms, MIBK, DPM, propylene glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl acetate, Further, diethylene glycol monoethyl ether acetate is more preferable, and in particular, when a dry film is formed, a combination of cyclohexanone and MIBK is more preferable.

  Moreover, when forming a dry film using the composition of this invention, the compounding quantity of the solvent after drying, ie, the ratio of the residual content of a solvent, is 0.00 on the resin layer whole quantity basis of the dry film containing a solvent. It is preferable that it is 1-4 mass%, and it is more preferable that it is 0.3-3 mass%. By making the ratio of the residual content of the solvent within the above range, it is possible to improve the releasability, reduce the residual of bubbles and suppress the generation of cracks while suppressing the cracking and powder falling of the dry film. It will be a thing.

[Dry film]
The dry film of the present invention can be produced by applying the composition of the present invention on a carrier film and drying to form a resin layer as a dry coating film. A protective film can be laminated on the resin layer as necessary.

  As a material of the carrier film, polyethylene terephthalate (PET) or the like can be preferably used. The thickness of the carrier film is preferably 8 to 60 μm. Moreover, as a material of a protective film, the thing similar to what is used for a carrier film can be used, Preferably it is PET or polypropylene (PP). The thickness of the protective film is preferably 5 to 50 μm. In the present invention, a resin layer may be formed by applying and drying the composition of the present invention on the protective film, and a carrier film may be laminated on the surface. That is, as a film to which the composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a protective film may be used.

  Here, as a coating method of the composition, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, or the like can be used. Further, as a volatile drying method, a hot air circulation drying furnace, an IR (infrared ray) furnace, a hot plate, a convection oven, or the like equipped with a heat source of an air heating method using steam can be used.

[Hardened products and printed wiring boards]
The cured product of the present invention is obtained by curing the resin layer of the composition or dry film of the present invention, and the printed wiring board of the present invention comprises the cured product of the present invention. Although the manufacturing method is demonstrated below, it is not limited to this.

  The form of the composition of the present invention may be provided as a coating material whose viscosity is appropriately adjusted, or as described above, a dry film obtained by applying the composition onto a supporting base film and drying the solvent. Good. Moreover, it is good also as a prepreg sheet | seat which apply | coated and / or impregnated the sheet-like fibrous base materials, such as a glass cloth, glass, and an aramid nonwoven fabric, and was semi-hardened. Examples of the supporting base film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonates and polyimides, and metal foils such as release paper, copper foil, and aluminum foil. Note that the support base film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  The coating material, dry film, or prepreg using the composition of the present invention is directly coated on the inner layer circuit board on which the circuit is formed and dried or cured, or the dry film is laminated by heating to be integrally formed. Then, it may be cured in an oven or a hot plate press, or by light irradiation. In the case of a prepreg, a method of stacking on an inner layer circuit board, sandwiching it with a metal plate via a release film, and pressurizing and heating can be used.

  Among the above steps, the method of laminating or hot plate pressing is preferable because the fine unevenness caused by the inner layer circuit is eliminated when heated and melted and is cured as it is, so that a multilayer plate having a flat surface state can be finally obtained. Moreover, when laminating or hot plate pressing the base material on which the inner layer circuit is formed and the film or prepreg of the composition of the present invention, the copper foil or the base material on which the circuit is formed can be simultaneously laminated.

A hole is made in the substrate thus obtained with a semiconductor laser such as a CO ₂ laser or a UV-YAG laser or a drill. The hole is a through hole (through hole) that is intended to connect the front and back of the substrate, but it is also a partial hole (conformal via) that is intended to connect the inner layer circuit and the circuit on the surface of the interlayer insulating layer. either will do.

  After drilling, in order to remove the residue (smear) present on the inner wall and bottom of the hole and to develop an anchor effect with the conductor layer (the metal plating layer to be formed thereafter), a rough surface with fine irregularities For the purpose of forming a chemical surface, use a commercially available desmear liquid (roughening agent) or a roughening liquid containing an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid or nitric acid. Process simultaneously.

  Next, a circuit is formed by a subtractive method, a semi-additive method, or the like after forming a hole from which a residue has been removed with a desmear liquid or a film surface having a fine uneven rough surface. In either method, after electroless plating or electrolytic plating, or after both plating, a heat treatment called annealing at about 80 to 180 ° C. for about 10 to 60 minutes for the purpose of removing stress from the metal and improving the strength. May be applied.

  As metal plating used here, there is no restriction | limiting in particular, such as copper, tin, solder, nickel, etc., It can also be used in multiple combination. Further, instead of the plating used here, metal sputtering or the like can be used instead.

  The composition of this invention can be used suitably for manufacture of a printed wiring board, and can be used suitably especially for formation of insulating layers of printed wiring boards, such as an interlayer insulation layer and a soldering resist. You may form a wiring board by bonding a wiring together using the composition of this invention. It can also be suitably used as a sealing resin for semiconductor chips. The composition of the present invention is useful in, for example, smartphones and personal computers.

  FIG. 2 is an enlarged partial cross-sectional view of a printed wiring board in which chips are flip-chip connected. In the printed wiring board shown in the figure, a thermosetting resin composition layer 43 and a photocurable resin composition layer 44 are laminated in order from the substrate surface side on the surface of the substrate 41 on which the conductor pattern 42 is formed. Yes. A solder ball 50 is provided on the component mounting portion 42a exposed by patterning after curing the thermosetting resin composition 43 and the photocurable resin composition layer 44, and the bumps 52 provided on the chip 51 and In this manner, the chip 51 is flip-chip connected to form a flip chip mounting substrate 53a. In addition, the code | symbol 46 in a figure shows a groove-shaped dam.

  In the case of the printed wiring board shown in FIG. 2, the difference in thermal expansion coefficient between the cured products 43 and 44 to which the curable resin composition of the present invention can be applied and the conductor layer (copper) 42 is within 15 ppm, or Similarly, the difference in thermal expansion coefficient between the cured products 43 and 44 and the wafer layer included in the chip 51 is preferably within 15 ppm.

Hereinafter, the present invention will be described in more detail with reference to examples.
<Preparation of curable resin composition>
In accordance with the formulation described in Table 2 to Table 4 below, 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 curable resin composition. did. The compounding quantity in a table | surface shows a mass part. Table 1 below shows the physical property values of the fillers used. In addition, the true specific gravity of each compounding component other than the filler was 1.1 g / cm ^{3 in the} calculation.

<Preparation of dry coating film using liquid composition>
A double-sided printed wiring board having a copper thickness of 15 μm and a circuit formed thereon having a thickness of 0.4 mm was prepared, and pre-processing was performed using a Mec CZ-8100. Then, using a roll coater (Furness), the curable resin compositions of Examples 1 to 5, 7 to 15 and Comparative Examples 1, 2, and 4 were dried on the printed wiring board that had been pretreated. The coating was adjusted to 20 μm. Then, it dried at 80 degreeC / 30min, and obtained the dry coating film.

<Production of dry film>
The curable resin compositions of Example 6 and Comparative Example 3 were kneaded and dispersed, and the amount of solvent was adjusted so that the viscosity was 0.5 to 20 dPa · s (rotary viscometer 5 rpm, 25 ° C.). Using a coater, the resin layer was applied to a carrier film (PET film; Lumirror 38R75 manufactured by Toray Industries, Inc., 38 μm thick) so that the film thickness would be 40 μm after drying. Next, it is dried for 5 to 10 minutes at 70 to 120 ° C. (average 100 ° C.) so that the residual solvent of the resin layer becomes 1.0 to 1.5% by mass in a hot-air circulating drying oven, A resin layer was formed.

<Method for producing printed wiring board having cured film>
The dried coating films and the resin layers of the above Examples and Comparative Examples were cured by three types of curing methods of “thermosetting”, “light / thermosetting”, and “PEB (post exposure bake)”, respectively. In the items of “curing method” in the following Tables 5 to 7, the cured methods are described. Below, each hardening method is described.

(Curing method "Thermosetting")
About the dry coating films of Examples 1-5, 7-9, 12-15 and Comparative Examples 1 and 4, they were thermally cured at 170 ° C./60 min in a hot air circulating drying oven to cure the dry coating films. .

For Example 6 and Comparative Example 3, first, using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.), a treatment agent (CZ-8100 + CL-8300, manufactured by MEC) was applied to the copper-clad laminate. A profile corresponding to a copper etching amount of 1 μm was formed by performing pretreatment using the same. Next, the resin layer of the dry film was laminated on the copper under the conditions of 5 kgf / cm ² , 80 ° C., 1 minute, 1 Torr. Thereafter, the carrier film was peeled off, and the resin layer was cured by heating at 180 ° C. for 30 minutes in a hot air circulation type drying furnace.

(Curing method “PEB”)
About the dry coating film of Example 10, the soldering resist pattern was exposed at 500 mJ / cm < ² > through the negative film using the exposure apparatus mounted with a high pressure mercury lamp (short arc lamp). Next, after peeling off the carrier film, heat treatment (PEB treatment) was performed at 100 ° C. for 30 minutes in a hot air circulation type drying furnace. The obtained printed wiring board was immersed in a mixed aqueous solution of 3% by mass TMAH (tetramethylammonium hydroxide) at 35 ° C. and 5% by mass ethanolamine for 3 minutes and developed to obtain a patterned resist. . Furthermore, ultraviolet irradiation was performed with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by ORC, and then heat treatment was performed at 170 ° C. for 60 minutes in a hot-air circulating drying furnace to cure the dried coating film. .

(Curing method "light / thermosetting")
For the dried coating film of Example 11 and Comparative Example 2, the solder resist pattern was exposed at 200 mJ / cm ² using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) through a negative film, and then the carrier film was peeled off. Thereafter, a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 Pa to obtain a patterned resist. Next, this printed wiring board is irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1 J / cm ² , and then subjected to heat treatment at 150 ° C. for 60 minutes using a hot air circulation type drying furnace to cure the dried coating film. It was.

  The composition of each example and comparative example was evaluated according to the following. The results are also shown in Tables 5 to 7 below.

1. <Glass transition temperature (Tg) and coefficient of thermal expansion (CTE (α1))>
After the cured film formed on the printed wiring board was peeled off from the copper foil, a sample was cut into a measurement size (3 mm × 10 mm size), and measurement was performed using TMA6100 manufactured by Seiko Instruments Inc. In the TMA measurement, the sample was heated from room temperature at a heating rate of 10 ° C./min at a test load of 5 g and measured twice continuously. The intersection of two tangents having different thermal expansion coefficients in the second round was taken as the glass transition temperature (Tg), and the average thermal expansion coefficient (CTE (α1)) from 30 ° C. to 100 ° C. in the region below Tg was evaluated. The results were evaluated according to the following, with the difference from the thermal expansion coefficient (17 ppm) of copper. In addition, about Example 15, it evaluated according to the following by the difference with the thermal expansion coefficient (3 ppm) of a silicon wafer.
◎◎ ... The difference is within 5ppm.
A: The difference is more than 5 ppm and within 10 ppm.
○: The difference is more than 10 ppm to within 15 ppm.
Δ: Difference is more than 15 ppm to within 20 ppm.
× ・ ・ ・ The difference is more than 20ppm

2. <Laser workability>
Using a CO ₂ laser processing machine (manufactured by Hitachi Via Mechanics), vias are formed on the cured film formed on the printed wiring board so that the top diameter is 65 μm and the bottom diameter is 50 μm, and the laser workability is evaluated as follows. did. The via formation conditions are as follows.
Aperture (mask diameter): 3.1 mm / Pulse width: 20 μsec / Output: 2 W / Frequency: 5 kHz / Number of shots: Burst 3 shots ◎: Difference from the target machining diameter is less than ± 2 μm and the machining hole wall is Smooth state.
A: The difference from the target processing diameter is less than ± 2 μm, but some unevenness is observed on the processing hole wall.
○: The difference from the target processing diameter is less than ± 2 μm, but the processing hole wall is uneven.
Δ: The difference from the target processing diameter is ± 2 μm or more and less than 5 μm.
X: The difference from the target processing diameter is ± 5 μm or more.

3. <Desmear resistance>
Assuming desmear treatment for the printed wiring board after laser processing, roughening solution (Swelling Dip Securigans P (swelling), Concentrate Compact CP, manufactured by Atotech Japan Co., Ltd.), which is an oxidizer solution (Oxidation), reduction solution securigant P (neutralization)) were used in the order of swelling 60 ° C. × 5 minutes, oxidation 80 ° C. × 20 minutes, neutralization 40 ° C. × 5 minutes. About the obtained printed wiring board, each surface roughness Ra was measured with laser microscope VK-8500 (Keyence Corporation, measurement magnification 2000 times, Z-axis direction measurement pitch 10 nm). The Ra value was an average value of 10 points in the entire measurement range. The desmear resistance was evaluated according to the following value according to the value of the surface roughness (Ra value).
A: Surface roughness Ra after permanganate desmear is less than 0.1 μm.
○: Surface roughness Ra after permanganate desmear is 0.1 μm or more and 0.3 μm or less.

4). <TCT (cooling cycle (crack suppression evaluation))>
TCT processing was performed on the printed wiring subjected to laser via and desmear processing. Specifically, a thermal history was added to the printed wiring board with 30 minutes at -65 ° C and 30 minutes at 150 ° C as one cycle. After 2000 cycles, in order to observe the state of the via bottom and the wall surface with an optical microscope, the via center was cut and polished with a precision cutting machine, and the cross-sectional state was observed. Evaluation was performed according to the following. The number of observation vias was 100 holes.
A: No cracking occurred.
A: Crack occurrence rate is less than 5%.
○: Crack occurrence rate is less than 5 to 10%.
Δ: Crack occurrence rate is less than 10 to 20%.
X: Crack occurrence rate of 20% or more.

5. <Warpage (Substrate warpage after curing)>
Using a CZ-8101 made by MEC as a pretreatment on a copper-clad plate (copper thickness on one side = 20 μm, MCL-E-679FGR, manufactured by Hitachi Chemical Co., Ltd.) having a total thickness of 100 μm and a size of 50 × 50 mm, 1 μm Substantial etching was performed. A cured film was formed on this copper-clad board by the above method to obtain a printed wiring board. The warpage evaluation method was carried out in accordance with the following, by precisely cutting the obtained substrate with a diagonal line of 50 × 50 mm, and using the difference between the largest value and the smallest value in the cross section of the diagonal area as the amount of warpage.
A: The amount of warpage of the substrate is less than 10 mm.
A: The amount of warpage of the substrate is 10 mm or more and less than 15 mm.
○: The amount of warpage of the substrate is 15 mm or more and less than 20 mm.
X: The amount of warping of the substrate is 20 mm or more.

6). <Undercut>
For Examples 10 and 11 and Comparative Example 2 which are light / thermosetting compositions, undercuts were also evaluated as described below.
On a copper-clad plate having a copper thickness of 15 μm, a CZ-8101 process manufactured by MEC was performed as a pretreatment, and an etching process corresponding to 0.5 μm was performed. Next, in accordance with the preparation method of the curing method “light / thermosetting” in the above-mentioned item of preparation of the cured substrate, using the compositions of Examples 10 and 11 and Comparative Example 2, a patterned resist (L / S = 50/50 μm, a linear pattern). About the obtained printed wiring board, it cut | disconnected so that it might become perpendicular | vertical with respect to a line using a precision cutting machine, and the cross-sectional length of the line of a surface layer part and a deep part was measured using the optical microscope. The evaluation criteria are as follows.
A: The difference in cross-sectional length between the surface layer portion and the deep portion line is 0 μm or more and less than 5 μm.
○: The difference in cross-sectional length between the surface layer portion and the deep portion line is 5 μm or more and less than 8 μm.
X: The difference of the cross-sectional length of the surface layer part and the deep part line is 8 micrometers or more.

7). <Flexibility of dry film (bending test)>
About the dry film of Example 6 and Comparative Example 3, the softness | flexibility was also evaluated as follows.
In accordance with JIS K5600-5-1 (ISO 1519), using a cylindrical mandrel bending tester manufactured by BYK-Gardner, cracking of the dry film of Example 6 and Comparative Example 3 and peeling from the carrier film start to occur. The softness of the dry film was evaluated from the minimum diameter of the mandrel. The evaluation criteria are as follows. When the flexibility of the dry film is good, the flexibility of the resin layer is high and cracking and powder falling can be suppressed.
O: φ 1 mm, no cracking of the resin layer and no peeling of the carrier film, and no powder falling off of the resin layer.
(Triangle | delta): The crack of the resin layer, powder fall, and peeling of the carrier film generate | occur | produced with the diameter of (phi) 2-5 mm.

8). <Water absorption rate>
After the cured film formed on the printed wiring board is peeled off from the copper foil, a sample is cut into a measurement size (50 mm × 50 mm size) and dried at 100 ° C. for 2 hours to completely remove moisture. The mass (W1) was measured with a balance. Then, the sample was immersed in distilled water controlled at 23 ° C. ± 2 ° C., and the mass (W2) after 24 hours was measured. The water absorption was determined by (W2-W1) / W1 × 100 (%). The evaluation criteria are as follows.
A: Less than 0.3%.
A: 0.3% or more and less than 0.7%.
○: 0.7% or more and less than 1.4%.
Δ: 1.4% or more.

＊１）（株）アドマテック製、シリカＳｉＯ_２
＊２〜４）東亜合成（株）製，ウルテアシリーズ
＊５）リン酸タングステン酸ジルコニウム

* 1) Silica SiO ₂ manufactured by Admatech Co., Ltd.
* 2-4) ULEA series, manufactured by Toa Gosei Co., Ltd. * 5) Zirconium tungstate phosphate

＊６）ＺＦＲ−１１２４：日本化薬（株）製（ビスフェノールＦ構造の多官能エポキシ樹脂を使用した感光性カルボキシル基含有樹脂，固形分６３質量％，樹脂としての酸価は１０２ｍｇＫＯＨ／ｇ）
＊７）ＥＭＧ−１０１５：ＤＩＣ（株）製（カルボキシル基含有ポリイミド樹脂、溶液酸価：８６３ｍｇＫＯＨ／ｇ、固形分５０質量％、固形分酸価１７２６ｍｇＫＯＨ／ｇ）
＊８）ＡＤＣＰ：トリシクロデカンジメタノールジアクリレート（新中村化学工業（株）製 Ａ−ＤＣＰ）
＊９）エピクロンＮ−８７０：ＤＩＣ（株）製（ビスフェノールＡノボラック型エポキシ樹脂、エポキシ当量２０５ｇ／ｅｑ、軟化点７０℃、分子量１６００）
＊１０）ＨＰ−７２００：ＤＩＣ（株）製（ジシクロペンタジエン型エポキシ樹脂，エポキシ当量２５０〜２８０ｇ／ｅｑ；軟化点５７〜６８℃）
＊１１）ＨＰ−４０３２：ＤＩＣ（株）製（ナフタレン型エポキシ樹脂，エポキシ当量１３５〜１６５ｇ／ｅｑ；半固体）
＊１２）ＪＥＲ８２８：三菱化学（株）製（ビスフェノールＡ型エポキシ樹脂，エポキシ当量１８４〜１９４ｇ／ｅｑ、液状）
＊１３）ＪＥＲ８０７：三菱化学（株）製（ビスフェノールＡ型エポキシ樹脂，エポキシ当量１６０〜１７５ｇ／ｅｑ、液状）
＊１４）ＨＦ−１Ｍ：明和化成（株）製（フェノールノボラック樹脂）
＊１５）ＨＰＣ−８０００：ＤＩＣ（株）製（活性エステル樹脂）
＊１６）ＰＴ３０：ロンザジャパン社製（フェノールノボラック型多官能シアネート樹脂）
＊１７）Ｉｒｇ３６９：ＢＡＳＦジャパン（株）製（ＩＲＧＡＣＵＲＥ３６９，２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１）
＊１８）ＤＰＨＡ：日本化薬（株）製（ジペンタエリスリトールヘキサアクリレート，ＫＡＹＡＲＡＤ ＤＰＨＡ）
＊１９）２Ｅ４ＭＺ：２−エチル−４−メチルイミダゾール
＊２０）４ＡＰｙ：広栄化学工業（株）製（４−ジメチルアミノピリジン）
＊２１）ＮａｐＺｎ（ＩＩ）：ナフテン酸亜鉛（ＩＩ）
＊２２）ＹＸ−６９５４：三菱化学（株）製（フェノキシ樹脂）
＊２３）ＢＹＫ−３５２：ビックケミー社製（レベリング剤）（アクリル系表面張力調整剤）
＊２４）ＫＢＭ−４０３：信越化学（株）製（トリメトキシエポキシシラン）
＊２５）シクロヘキサノン（沸点１５５．６５℃）
＊２６）ジプロピレングリコールモノメチルエーテル（沸点１９０℃）
＊２７）イプゾール１５０：出光興産（株）製（芳香族系高沸点溶剤，沸点１８４〜２０５℃）
＊２８）メチルイソブチルケトン（沸点１１６℃）

* 6) ZFR-1124: manufactured by Nippon Kayaku Co., Ltd. (photosensitive carboxyl group-containing resin using a polyfunctional epoxy resin having a bisphenol F structure, solid content 63 mass%, acid value as resin is 102 mgKOH / g)
* 7) EMG-1015: manufactured by DIC Corporation (carboxyl group-containing polyimide resin, solution acid value: 863 mg KOH / g, solid content 50 mass%, solid content acid value 1726 mg KOH / g)
* 8) ADCP: Tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 9) Epicron N-870: manufactured by DIC Corporation (bisphenol A novolac type epoxy resin, epoxy equivalent 205 g / eq, softening point 70 ° C., molecular weight 1600)
* 10) HP-7200: manufactured by DIC Corporation (dicyclopentadiene type epoxy resin, epoxy equivalent 250-280 g / eq; softening point 57-68 ° C.)
* 11) HP-4032: manufactured by DIC Corporation (Naphthalene type epoxy resin, epoxy equivalent of 135 to 165 g / eq; semi-solid)
* 12) JER828: manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent of 184 to 194 g / eq, liquid)
* 13) JER807: manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent of 160 to 175 g / eq, liquid)
* 14) HF-1M: Meiwa Kasei Co., Ltd. (phenol novolac resin)
* 15) HPC-8000: manufactured by DIC Corporation (active ester resin)
* 16) PT30: Lonza Japan Co., Ltd. (phenol novolac type polyfunctional cyanate resin)
* 17) Irg369: manufactured by BASF Japan Ltd. (IRGACURE369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1)
* 18) DPHA: Nippon Kayaku Co., Ltd. (dipentaerythritol hexaacrylate, KAYARAD DPHA)
* 19) 2E4MZ: 2-ethyl-4-methylimidazole * 20) 4APy: Guangei Chemical Industry Co., Ltd. (4-dimethylaminopyridine)
* 21) NapZn (II): zinc naphthenate (II)
* 22) YX-6594: Mitsubishi Chemical Corporation (phenoxy resin)
* 23) BYK-352: manufactured by Big Chemie (leveling agent) (acrylic surface tension adjusting agent)
* 24) KBM-403: Shin-Etsu Chemical Co., Ltd. (trimethoxyepoxysilane)
* 25) Cyclohexanone (boiling point 155.65 ° C)
* 26) Dipropylene glycol monomethyl ether (boiling point 190 ° C)
* 27) Ipsol 150: manufactured by Idemitsu Kosan Co., Ltd. (aromatic high-boiling solvent, boiling point 184-205 ° C.)
* 28) Methyl isobutyl ketone (boiling point 116 ° C)

  As shown in the above table, a filler having a negative coefficient of thermal expansion is blended, each of which contains at least two solvents having boiling points of 100 ° C. or higher and different in boiling points of 5 ° C. or higher, and cured. In each example using a composition in which the difference between the thermal expansion coefficient of the product and the thermal expansion coefficient of copper constituting the conductor layer is within 15 ppm / ° C., flexibility as a film, workability of a cured film, etc. As for various performances, it was confirmed that good performance was obtained. Further, from comparison between Example 1 and Examples 4, 5, and 12, it can be seen that the lower the specific gravity, the higher the CTE reduction effect and the better.

  On the other hand, for each Comparative Example in which only a filler having a positive coefficient of thermal expansion was blended, in Comparative Examples 1 and 2, since the amount of filler was small, CTE was high, TCT and warpage were deteriorated, and photocurability was obtained. In Comparative Example 2, the undercut was further deteriorated. Moreover, in the comparative example 3 about a dry film, a softness | flexibility deteriorated, and in the comparative example 4 with too much filler amount, laser workability and TCT deteriorated.

DESCRIPTION OF SYMBOLS 1 Insulation board | substrate 3 Inner layer conductor pattern 3a as a conductor layer Connection part 4, 9 Resin insulation layer 8 Outer layer conductor pattern as a conductor layer 10 Outermost layer conductor pattern as a conductor layer 20 Through hole 21 as a conductor layer Through hole hole 22 Connection Part 30a Test tube for liquid determination 30b Test tube for temperature measurement 31 Mark (A line)
32 Mark (B line)
33a, 33b Rubber plug 34 Thermometer 41 Substrate 42 Conductor pattern 42a as conductor layer Component mounting portion 43 Thermosetting resin composition layer 44 as cured product Photocurable resin composition layer 46 as cured product Groove-shaped dam 50 Solder ball 51 Chip 52 Bump 53a Flip chip mounting substrate X Multilayer substrate

Claims (7)

Including a filler having a negative coefficient of thermal expansion, a curable resin, and at least two solvents,
The curable resin composition characterized in that the at least two kinds of solvents each have a boiling point of 100 ° C or higher and a boiling point of 5 ° C or higher. The curable resin composition according to claim 1, wherein the true specific gravity of the filler is 2.5 to 4.0 g / cm ³ .   The curable resin composition of Claim 1 or 2 used for manufacture of a printed wiring board.   The difference in thermal expansion coefficient between the cured product obtained from the curable resin composition and the conductor layer of the printed wiring board or the wafer layer of the semiconductor chip mounted on the printed wiring board is within 15 ppm / ° C. Item 4. A curable resin composition according to Item 3.   It has a resin layer which dried the curable resin composition as described in any one of Claims 1-4 on a film, The dry film characterized by the above-mentioned.   Hardened | cured material which hardened | cured the resin layer of the curable resin composition as described in any one of Claims 1-4 or the dry film of Claim 5.   A printed wiring board comprising the cured product according to claim 6.

Images