TW201433599A - Thermosetting resin compositions, resin films in b-stage (semi-cured stage), metal foils, copper-clad boards and multi-layer build-up boards - Google Patents

Abstract

This invention provides an epoxy-based thermosetting resin with a certain degree of bendability and film insulation layer formation properties and reliability and processability no less than halogen-free FR-4 materials. The thermosetting resin composition comprises (a) a liquid epoxy resin, (a2) a solid epoxy resin having a softening point of 125 DEG C or lower, (b) an aromatic diamine compound including a benzoate group and a main chain including polymethylene group, (c) a solvent-soluble polyimide resin having Tg of 200 DEG C or higher and a weight average molecular weight Mw of 50000 or lower, and (d) a phenoxy resin having Tg of 130 DEG C or higher. The total amount of (c) solvent-soluble polyimide resin and (d) phenoxy resin is 15 weight parts or more and 150 weight parts or less, provided that the total amount of (a1) liquid epoxy resin, (a2) solid epoxy resin and (b) aromatic diamine compound is 100 weight parts.

Description

Thermosetting resin composition, B-stage (semi-hardened stage) resin film, metal foil, copper clad laminate, and multilayer build-up substrate Field of invention

The present invention relates to an adhesive, a prepreg, a paint, and the like, and can also be used as a base material for a flexible substrate, a build-up substrate mainly comprising a flexible base material as a core material, and aluminum or the like as a base. A thermosetting resin composition of a metal base substrate, and a B-staged resin film produced using the composition, and coated on a single side of the metal foil, and then B-staged, for example, an adhesive copper foil and copper-clad A foil plate or the like is used for a high-density flexible build-up printed wiring board that can be bent and has high heat resistance, high adhesion strength, and high reliability, and is used for an integrally molded substrate and a heat dissipation substrate. The board can be used for portable devices, LED substrates and module substrates.

Background of the invention

In recent years, there has been a demand for high performance of portable devices and thinning, which is represented by liquid crystal televisions, in addition to thinning and high performance of printed wiring boards and module substrates used in these devices. One Straight, some of them use flexible printed wiring boards.

Conventionally, a material for a flexible substrate having a flexible and non-substrate is usually a ring of a modified material such as a rubber modified with a carboxyl group, a thermoplastic resin, or a phenoxy resin, in addition to a polyimide. An oxyresin-based adhesive is applied to the bonding sheet. These materials are also used on copper clad laminates and cladding. However, these materials generally have low Tg values and are less reliable than rigid materials.

Further, since these adhesives are also excellent in the adhesion strength to the dissimilar materials, they are also used as an adhesive for metal substrate substrates. However, this metal does not contain pure aluminum, and on the following, there is a difficulty in performing anodization of aluminum. Since pure aluminum has excellent bendability, it is suitable for use in a metal base substrate or the like which can be bent.

Therefore, in order to increase the density and thickness of the flexible printed wiring board, it is different from the case where the prepreg, the resin film, and the RCC are used for multilayering and layering of the rigid material, and most of them are double-sided. FPC and double-sided FPC, single-sided FPC and single-sided FPC, or single-sided FPC and double-sided FPC combined to form an example of multi-layering, and through its construction and manufacturing methods, although there are also material properties Improvements are made, but improvements in processability and reliability are not included. Specific examples thereof can be found, for example, in the following Patent Documents 1 to 7. One of the reasons for this is that there is no build-up material equivalent to a resin film, RCC or the like in a rigid substrate.

Further, the applicant of the present invention mainly uses a rigid material in Patent Document 8, and discloses a liquid epoxy resin, a solid epoxy resin, A triazine-modified phenolic novolac resin hardener and a thermosetting resin composition of a solvent-soluble polyimine resin. Further, the applicant of the present invention mainly uses a rigid material, and Patent Document 9 discloses a liquid epoxy resin, a solid epoxy resin, a triazine-modified phenol novolak resin, and a benzoxazine. A resin and a thermosetting resin composition of a phenoxy resin having a Tg value of 120 ° C or higher.

[Previous Technical Literature] [Patent Literature]

Patent Document 1] WO2007/46459

Patent Document 2, Patent No. 4,237,726

[Patent Document 3] Special Opening 2005-126543

[Patent Document 4] Special Opening 2005-347414

[Patent Document 5] Special Opening 2006-299209

[Patent Document 6] Special Opening 2006-179679

[Patent Document 7] Special Opening 2011-40607

[Patent Document 8] Special Opening 2007-224242

[Patent Document 9] Special Opening 2008-037957

Summary of invention

In addition to the copper-clad laminate of all-polyimine, the material is not thinner and lighter in thickness and thickness, and has characteristics and workability that fully meet these requirements as much as possible. Reliable material.

Further, even in a wholly polyimine flexible wiring board, there is currently no suitable material for a build-up material suitable for it.

Therefore, there is no material that satisfies these requirements, especially the flexibility of the material for a flexible substrate, the properties of the thin film insulating layer, and the reliability and processing characteristics of halogen-free FR-4. The epoxy-based flexible substrate material has not yet appeared. The processing characteristics referred to herein are necessary in a high-density package substrate or a build-up substrate, such as laser hole processability, desmear etching, and the like.

In other words, as a material monomer, it is comparable to the prepreg of FR-4 or halogen-free FR-4, and can be used as a flexible substrate without bending. Materials are a must.

An object of the present invention is to provide an epoxy-based thermosetting resin having a certain degree of flexibility and film insulating layering properties, and having reliability and processing characteristics similar to that of halogen-free FR-4.

Further, an object of the present invention is to provide a flexible substrate material using such a thermosetting resin, and to provide a heat-conductive substrate adhesive material having excellent adhesion strength to a metal such as pure aluminum. Further, a high-density flexible build-up printed wiring board, a module substrate, and a heat dissipation substrate using these materials are provided.

The thermosetting resin composition according to the present invention is characterized by comprising (a1) a liquid epoxy resin, (a2) a solid epoxy resin having a softening point of 125 ° C or less, (b) having a benzoate group, and a polymethylene aromatic diamine compound in the main chain, (c) a solvent-soluble polyimine resin having a Tg value of 200 ° C or higher, a weight average molecular weight Mw of 50,000 or less, and (d) a Tg value The phenoxy resin at 130 ° C or higher is measured by the total amount of (a1) the liquid epoxy resin, (a2) the solid epoxy resin, and (b) the aromatic diamine compound in an amount of 100 parts by weight, (c) The total amount of the solvent-soluble polyimine resin and (d) the phenoxy resin is 15 parts by weight or more and 150 parts by weight or less.

Further, the present invention relates to a B-staged resin film produced from the above thermosetting resin composition.

Further, the present invention relates to a metal foil and a copper clad laminate provided with a B-staged resin film.

Further, the present invention relates to a multilayer build-up substrate produced by using the aforementioned thermosetting resin composition as an interlayer insulating material.

Conventionally, in order to improve the flexibility of an epoxy resin, it can be realized by using a phenoxy resin, a thermoplastic resin, a carboxyl group-modified rubber, or the like as a modifying material. However, it is very difficult to achieve the reliability and processability of the halogen-free FR-4 grade by these methods alone.

In the present invention, it has been found that in order to achieve flexibility in the epoxy resin without lowering reliability and workability, it is possible to use a heat-resistant hardener skeleton to have a certain degree of flexibility and to use a specific The phenoxy resin is achieved by means of a soluble polyimine resin.

Further, in order to find out the characteristics of these resins as a resin composition, it has been found that the compatibility state of the resin at the time of hardening has an important effect, and it has been found that the melting of the respective resin components (including the molten state in appearance) can be continuously achieved by selection. occur.

It has further been found that the composition of the present invention basically improves the adhesion properties to the quinone imine film, copper, metal substrate material (especially pure aluminum), etc., and this effect can be achieved by using a benzoate group in combination. The synergistic effect of the aromatic diamine hardener and the soluble polyimine is achieved to achieve the object of the present invention.

Form for implementing the invention

((a1) Liquid epoxy resin and (a2) solid epoxy resin with a softening point below 125 ° C)

In any case, as long as it is an epoxy resin having two or more epoxy propyl groups, it can be appropriately selected according to the purpose. Preferably, the liquid epoxy resin is, for example, a bisphenol A type epoxy resin or a bisphenol F. Epoxy resin, novolac phenol epoxy resin, naphthalene epoxy resin. Further, examples of the solid epoxy resin include a novolac phenol epoxy resin, a biphenyl epoxy resin, a naphthalene epoxy resin, and a dicyclopentadiene epoxy resin. These may be used alone or in combination of two or more.

The softening point of the solid epoxy resin is 125 ° C or less because the Tg value of the phenoxy resin used as the modifying material is limited to Tg 130 ° C or more. The definition of the softening point is difficult to apply to the phenoxy resin of the polymer, and the Tg value has been experimentally confirmed as its substitute property. The purpose is to melt the epoxy resin before the phenoxy resin is melted, so that the hardened resin layer is homogenized.

However, the liquid epoxy resin and the solid epoxy resin are used together because the hardening property is close to the FR-4 resin, and the use of the solid epoxy resin is good, but it is difficult to form a uniform resin composition during hardening. The molten state. Therefore, by using a liquid epoxy resin at a normal temperature to cause the melting to occur continuously, it is to make it possible.

The viscosity of the liquid epoxy resin is preferably 1.0 to 120 Pa s at 25 ° C, and more preferably 1.2 to 100 Pa ‧ . However, this viscosity is defined by the value measured using an E-type viscometer.

Although the softening point of the solid epoxy resin is set to 125 ° C or less, it is preferably 100 ° C or less from the viewpoint of the present invention. However, from the viewpoint of exhibiting the above-described effects of the solid epoxy resin when mixed with a liquid epoxy resin, the softening point is preferably 50 ° C or higher.

The ratio of liquid epoxy resin to solid-state cyclic resin should be determined by the desired characteristics and melting control. For this reason, the most appropriate combination ratio is not necessarily limited. However, when the total amount of the two is 100 parts by weight, the ratio of the liquid epoxy resin is preferably 20 to 50 parts by weight.

((b) an aromatic diamine compound having a benzoate group and a polymethylene group in the main chain)

The aromatic diamine-based curing agent having an ester bond has a good bonding strength with a metal substrate such as a polyimide film or aluminum, and a polymethylene structure is introduced into the skeleton, so that it can simultaneously be used in addition to heat resistance. A certain degree of flexibility is maintained in the epoxy resin skeleton.

Here, the number of methylene groups which the polymethylene group located in the main chain has is preferably 3 or more and 16 or less.

Such a hardener may specifically be exemplified by trimethylene-bis (4-aminobenzoate) [melting point 122 ° C] and poly (tetra/3-methyl four). Methyl ether) bis(4-aminotetramethylene ether)glycol bis(4-aminobenzoate)[liquid], poly-1,4-butanediol double (4-aminobenzoate) (polytetramethylene oxide di-p-aminobenzoate) [melting point 15 to 60 ° C] and the like.

Further, for the same reason as the (a2) solid epoxy resin, the melting point of the hardener is preferably 125 ° C or lower.

In the composition of the present invention, when the total number of epoxy equivalents of the (a1) liquid epoxy resin and the epoxy equivalent of the (a2) solid epoxy resin are 1 in total, (b) the aromatic diamine compound The most suitable amount of use is the active hydrogen equivalent number of 0.95 to 1.50.

Here, the epoxy equivalent number of each epoxy resin is as follows.

The number of epoxy equivalents of each epoxy resin = (weight of each epoxy resin in the composition (solid weight)) / (epoxy equivalent of each epoxy resin)

(b)

The number of active hydrogen equivalents of the aromatic diamine compound is as follows.

(b)

Active hydrogen equivalent number of aromatic diamine compound = (weight of aromatic diamine compound in the composition) / (active hydrogen equivalent of aromatic diamine compound)

When the epoxy equivalent number (total value) of the epoxy resin is 1 time, Since the active hydrogen equivalent number of the aromatic diamine compound is the ratio of the two (the dimensionless amount), it is calculated by the following formula.

(Active hydrogen equivalent number of aromatic diamine compound) / (ring of epoxy resin) Oxygen equivalent number (total value)

((c) Solvent-soluble polyimine resin having a Tg value of 200 ° C or higher and a weight average molecular weight Mw of 50,000 or less)

(c) The solvent-soluble polyimine resin is a polyimine resin which is soluble in an organic solvent used in the production of the composition. (c) The solvent-soluble polyimine resin is suitable for having a high Tg value, a low C.T.E., excellent film physical properties, and excellent adhesion properties. The molecular weight is preferably 50,000 or less by weight average molecular weight (Mw), more preferably 35,000 or less. Further, the weight average molecular weight (Mw) is preferably 20,000 or more, more preferably 25,000 or more.

(c) The solvent-soluble polyimine resin preferably has a phenylindane structure. Further, a fully fluorinated soluble polyimine resin obtained by reacting a diamino trialkyl indane with a tetracarboxylic dianhydride or a derivative thereof is preferred. Here, the diaminotrialkylindan may, for example, be diaminotrimethylindan or diaminotriethylindan, and the derivative of the tetracarboxylic dianhydride may, for example, be benzophenonetetracarboxylic acid anhydride(.

A soluble quinone imine resin obtained by reacting diaminotrimethylphenylindan with benzophenonetetracarboxylic dianhydride is shown in (Formula 1). Further, a soluble quinone imine resin which is obtained by reacting diaminotrimethylphenylindan with tetracarboxylic dianhydride is also suitable.

[Compound 1]

The solvent-soluble polyimine resin, in particular, a resin having a phenylindene structure, has good adhesion strength to copper, bismuth imide film, pure aluminum or the like. Further, since the soluble polyimine resin is added to the resin composition, the purpose of increasing the Tg value can be achieved, and it is more suitable for ensuring the reliability of the FR-4 grade.

The composition of the present invention is basically based on the improvement of the adhesion property to the bismuth imide film, copper, and metal base substrate material (especially pure aluminum), and this action is carried out by containing the benzoate The synergistic effect of the aromatic diamine hardener and the soluble polyimine as a constituent component is produced.

((d) phenoxy resin having a Tg value of 130 ° C or higher)

Here, the phenoxy resin having a Tg value of 130 ° C or higher is defined in order to set the connection reliability to the FR-4 level. In other words, the connectivity of the FR-4 substrate is mostly determined by a thermal cycle test between 125 ° C and -65 ° C. Since the phenoxy resin has a large amount of an epoxy group remaining at its terminal end, it also has a possibility of reacting with a hardener, but it often exhibits a behavior of a plasticizer due to its molecular chain length. Therefore, its Tg value becomes the boundary of viscoelastic behavior. Therefore, a Tg value of 130 ° C or more is a necessary condition for improving connection reliability. In other words, C.T.E., one of the elements of connection reliability, is before and after the Tg value. Will vary greatly, this limit is to mitigate its impact.

The Tg (glass transition temperature) of the phenoxy resin is measured by the DSC method. Although the type of the phenoxy resin is not limited, it is preferable that the resin skeleton is a material such as BPA/BPS type, BP/BPS type, BP type, or BPS type, and has a heat resistant skeleton. Further, the weight average molecular weight Mw of the phenoxy resin is preferably 10,000 or more.

Since it is necessary to uniformly melt at the time of hardening, the Tg value of the phenoxy resin is preferably at most the molding temperature. Although it is not necessary to define the molding temperature, since it is an epoxy resin composition, the molding temperature is usually 180 ° C or lower. In this case, the Tg of the phenoxy resin is preferably 180 ° C or lower.

A commercially available product may be used as the phenoxy resin, and for example, YL6954BH30 (manufactured by JER Corporation, Tg is 130 ° C), ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg is 146 ° C), YX8100BH30 (manufactured by JER Corporation), Tg is 150 ° C) and the like.

Further, since it has been confirmed that a phenoxy resin having a Tg value of 130 ° C or more and the solvent-soluble polyimine resin described above are used in combination, this is because the softening point of the solvent-soluble polyimine resin is high, when hardening ( During the molding process, the resin does not soften during the melting process, and the compatibility with other components is difficult to achieve uniformity. Therefore, it is known that the molding is due to softening, and all the constituent components including the solvent-soluble polyimide resin are in the standard. It will work if it is hardened in a compatible state. Thereby, the hardened physical properties after hardening are made uniform.

Further, the uniform cured product is also effective in improving the processing characteristics. That is, from the conventional resin composition imparting flexibility, In order to greatly improve the unevenness of the laser processing and the unevenness of the roughened surface roughness of the dross surface in the desmear etching process, the reliability is improved.

The total amount of (a1) liquid epoxy resin, (a2) solid epoxy resin, and (b) aromatic diamine compound is 100 parts by weight, (c) solvent-soluble polyimine resin and (d) phenoxy The total amount of the base resins may be selected from the range of 15 parts by weight or more and 150 parts by weight or less. When it is less than 15 parts by weight, since the effect of the adhesive strength and flexibility of the composition is small, 15 parts by weight or more is taken. From this point of view, it is more preferable to take 25 parts by weight or more. On the other hand, when it exceeds 150 parts by weight, the breaking strength of the formed film is lowered, so that it is 150 parts by weight or less, preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and most preferably 30 parts by weight or less. .

(c) The ratio of the solvent-soluble polyimine resin to the (d) phenoxy resin is not particularly limited. However, when the total amount of (c) solvent-soluble polyimide resin and (d) phenoxy resin is 100 parts by weight, all constituent components including the solvent-soluble polyimide resin described above are The amount of the (d) phenoxy resin is preferably 60 parts by weight or more from the viewpoint of (quasi) hardening in a compatible state. Further, from the viewpoint of exerting the action of (c) the solvent-soluble polyimine resin, the amount of the (d) phenoxy resin is preferably 95 parts by weight or less.

((e) filler)

The filler may or may not be added depending on the physical properties required for the composition. Specifically, it is suitable as a filler, and has alumina (thermal conductivity: 32 W/mK), aluminum nitride (thermal conductivity: 150 W/mK), boron nitride (thermal conductivity: 33-55 W/mK), and tantalum nitride (heat conduction). Rate 20W/mK). However, if For the purpose of heat dissipation of the film thickness, cerium oxide (thermal conductivity: 1.3 W/mK) having a low thermal conductivity of a single body, aluminum hydroxide (thermal conductivity: 7.1 W/mK), or the like may be used. The main purpose of the addition of the filler is to improve the thermal conductivity when used as an adhesive for a heat dissipation substrate, and therefore, the selection of these fillers is suitable.

When the total amount of (a1) liquid epoxy resin, (a2) solid epoxy resin, (b) aromatic diamine compound, (c) solvent-soluble polyimide resin, and (d) phenoxy resin is 100 parts by volume, depending on the required physical properties, such as thermal conductivity, determine the amount of (e) filler. In general, the lower limit of the amount of the filler is not particularly limited, but it is preferably 5 parts by volume or more, and more preferably 50 parts by volume or more from the viewpoint of exerting the physical properties of the filler. Further, the amount of the filler is preferably 200 parts by volume or less from the viewpoint of maintaining the physical properties of the composition. In addition, since the heat dissipation characteristics are related to the thermal conductivity and the thickness, it is preferable to add these two factors to determine the amount of addition. Since the organic heat-dissipating material mostly requires a specific thermal conductivity of 2 W/mK or more, from this point of view, the amount of the filler is preferably 100 parts by volume or more.

(additive)

Further, a hardening accelerator may be used in combination in the composition of the present invention as needed. As the hardening accelerator, a general substance such as various imidazoles can be used. It is mainly selected from the viewpoints of reaction speed and use period.

For example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethyl Imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 1-cyanoethyl-2-phenyl- Imidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2 '-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl- S-triazine trimeric isocyanate adduct, 2-phenylimidazole trimer isocyanate adduct, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl 5--5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 4,4'-methylenebis(2-ethyl-5-methylimidazole And TPP and so on.

Further, in order to impart flame retardancy, a flame retardant may be added to the components of the present invention. Halogen-free flame retardants are, condensed phosphates, phosphazenes, polyphosphates, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10) - an oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) derivative, aluminum hydroxide, etc., but there is no particular limitation.

The solvent which can be used in the thermosetting resin composition of the present invention is not particularly limited, but a high boiling point solvent such as NMP (N-methylpyrrolidone) or γ-butyrolactone, and cyclohexanone or MEK (A) are combined. Among the base ethyl ketones and the like, a low boiling point solvent is particularly suitable. Further, DMF (dimethylformamide) and DMAC (dimethylacetamide) can be exemplified.

A resin film can be obtained by subjecting the thermosetting resin composition of the present invention to a B-stage. That is, the resin composition of the present invention described above can be diluted with a suitable mixed organic solvent to form a varnish, and if necessary, coated on a release-coated poly-pair by a die coater or the like. On the ethylene phthalate film (PET film), the so-called dry A conventional method of drying produces a B-state thermosetting resin film. The B stage refers to a state in which the resin composition is semi-hardened.

Further, the thermosetting resin composition of the present invention can be applied onto a metal foil to produce a metal foil with an adhesive. This metal foil can be exemplified by a copper foil or an aluminum foil having a roughened surface, and a copper foil is particularly suitable.

The resin film and the RCC of the present invention can also be used as a HDI material having a laminated core plate of a rigid core material or an FPC core material, and can be used for a printed wiring board having a non-through-perforation of a laser hole or the like.

Example

Hereinafter, the present invention will be further described by way of examples.

(Example 1)

98 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), and 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 126 parts by weight 250P (polytetra-methylene oxide-di-o-aminobenzoate, manufactured by IHARA CHEMICAL INDUSTRY CO., LTD., melting point 60 ° C), 100 Parts by weight of soluble polyimide resin Q-VR-X0163 (manufactured by PI Institute of Technology, Tg value: 246 ° C, resin solid content: 20% by weight), 303 parts by weight of phenoxy resin ERF-001M30 (Nippon Steel A mixture of HCA having a Tg value of 146 ° C and a resin solid content of 30% by weight and 18 parts by weight of HCA was adjusted to a resin varnish having a resin solid content of 40% by weight.

(Example 2)

111 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, epoxide equivalent 188), and 167 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 92 parts by weight of CUA-4 (trimethylene-bis(4-aminobenzoate), melting point 122 ° C, IHARA CHEMICAL INDUSTRY CO., LTD.), 100 parts by weight of soluble polyimide resin Q-VR-X0163 (manufactured by PI Institute of Technology, Tg value: 246 ° C, resin solid content: 20% by weight), and 303 parts by weight of phenoxy resin ERF A mixture of -001 M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg value: 146 ° C, resin solid content: 30% by weight) and 18 parts by weight of HCA, and adjusted to have a resin solid content of 40% by weight of a resin varnish.

(Example 3)

98 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), and 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 126 parts by weight 250P (poly-1,4-butanediol bis(4-aminobenzoate), manufactured by IHARA CHEMICAL INDUSTRY CO., LTD., melting point 60 ° C), 100 parts by weight of soluble polyimide resin Q- VR-X0163 (manufactured by PI Institute of Technology, Tg value: 246 ° C, resin solid content: 20% by weight), 303 parts by weight of phenoxy resin YL6954BH30 (manufactured by JER, Tg value: 130 ° C, resin solid content: 30% by weight) A mixture of 18 parts by weight of HCA was adjusted to have a resin solid content of 40% by weight of a resin varnish.

(Example 4)

98 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), and 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 126 parts by weight 250P (poly-1,4-butanediol bis(4-aminobenzoate), manufactured by IHARA CHEMICAL INDUSTRY CO., LTD., melting point 60 ° C), 100 parts by weight of soluble polyimide resin Q- VR-X0163 (manufactured by PI Institute of Technology, Tg value: 246 ° C, resin solid content: 20% by weight), 303 parts by weight of phenoxy resin YX8100BH30 (manufactured by JER, Tg value: 150 ° C, resin solid content: 30% by weight) A mixture of 18 parts by weight of HCA was adjusted to have a resin solid content of 40% by weight of a resin varnish.

(Example 5)

98 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), and 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 126 parts by weight 250P (poly-1,4-butanediol bis(4-aminobenzoate), manufactured by IHARA CHEMICAL INDUSTRY CO., LTD., melting point 60 ° C), 100 parts by weight of soluble polyimide resin Q- VR-X0163 (manufactured by PI Institute of Technology, Tg value: 246 ° C, resin solid content: 20% by weight), 303 parts by weight of phenoxy resin YX8100BH30 (manufactured by JER, Tg value: 150 ° C, resin solid content: 30% by weight) A mixture of 18 parts by weight of HCA and 1600 parts by weight of the surface-treated spherical alumina was adjusted to have a resin solid content of 75% by weight of a resin varnish.

(Comparative Example 1)

103 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, epoxide equivalent 188), and 155 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Made by Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 112 parts by weight of BAPP (2,2-bis[4-(4-aminophenoxy)phenyl]propane (2,2-bis[4] -(4-aminophenoxy)phenyl]propane), manufactured by Wakayama Seika Chemical Co., Ltd., melting point 128 ° C), 100 parts by weight of soluble polyimide resin Q-VR-X0163 (manufactured by PI Technology Research Institute, Tg value 246 °C, resin solid content 20% by weight), 303 parts by weight of phenoxy resin ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg value 146 ° C, resin solid content 30% by weight), and 18 parts by weight of HCA mixture And adjusted to a resin solid content of 40% by weight of resin varnish.

(Comparative Example 2)

97 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), 145 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Manufactured by Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 213 parts by weight of melamine-modified phenolic novolac resin LA-7054 (manufactured by Dainippon Ink and Chemicals Co., Ltd., hydroxyl value 125, resin solid content 60 weight %), 100 parts by weight of soluble polyimine resin Q-VR-X0163 (manufactured by PI Institute of Technology, Tg value: 246 ° C, resin solid content: 20% by weight), and 303 parts by weight of phenoxy resin ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg value 146 ° C, resin solid content 30% by weight), 18 parts by weight of HCA mixture, and adjusted to resin The solid form is divided into 40% by weight of resin varnish.

(Comparative Example 3)

Formulated from 237 parts by weight of cresol novolac type epoxy resin N-695 (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 215, softening point: 98 ° C), 134 parts by weight 250P (poly-1,4-butanediol bis(4-aminobenzoate), manufactured by IHARA CHEMICAL INDUSTRY CO., LTD., melting point 60 ° C), 100 parts by weight of soluble polyimide resin Q- VR-X0163 (manufactured by PI Technology Co., Ltd., Tg value: 246 ° C, resin solid content: 20% by weight), 303 parts by weight of phenoxy resin ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg value: 146 ° C, resin solid) A mixture of 30% by weight and 18 parts by weight of HCA was adjusted to have a resin solid content of 40% by weight of a resin varnish.

(Comparative Example 4)

98 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), and 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 126 parts by weight 250P (poly-1,4-butanediol bis(4-aminobenzoate), manufactured by IHARA CHEMICAL INDUSTRY CO., LTD., melting point 60 ° C), 370 parts by weight of phenoxy resin YX8100BH30 (JER Corporation A mixture of HCA having a Tg value of 150 ° C and a resin solid content of 30% by weight and 18 parts by weight of HCA was adjusted to have a resin solid content of 40% by weight of a resin varnish.

(Comparative Example 5)

97 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), 145 parts by weight Dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink Chemical Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 213 parts by weight of melamine-modified phenolic novolac resin LA-7054 (Great Japan Manufactured by Ink Chemical Industry Co., Ltd., having a hydroxyl value of 125, a resin solid content of 60% by weight, and 111 parts by weight of a acrylonitrile-butadiene rubber, NIPOL 1072 (manufactured by Nippon Zeon Co., Ltd.), A mixture of 18 parts by weight of HCA was adjusted to a resin solid content of 40% by weight of a resin varnish.

(Comparative Example 6)

97 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), 145 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Manufactured by Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 213 parts by weight of melamine-modified phenolic novolac resin LA-7054 (manufactured by Dainippon Ink and Chemicals Co., Ltd., hydroxyl value 125, resin solid content 60 weight %), a mixture of 111 parts by weight of a phenoxy resin YP-55 (manufactured by Tohto Kasei Co., Ltd., Tg value: 84 ° C) and 18 parts by weight of HCA, and adjusted to a resin varnish having a resin solid content of 40% by weight.

(Comparative Example 7)

97 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 188), 145 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Daily ink) Manufactured by Chemical Industry Co., Ltd., epoxy equivalent 283, softening point 83 ° C), 213 parts by weight of melamine-modified phenolic novolac resin LA-7054 (manufactured by Dainippon Ink and Chemicals Co., Ltd., hydroxyl value 125, resin solid content 60 weight %), 100 parts by weight of soluble Polyimine resin Q-VR-X0163 (manufactured by PI Technology Co., Ltd., Tg value: 246 ° C, resin solid content: 20% by weight), and 303 parts by weight of phenoxy resin YX8100BH30 (manufactured by JER, Tg value: 150 ° C) A resin solid content of 30% by weight), 18 parts by weight of HCA, and 1600 parts by weight of a mixture of surface-treated spherical alumina, and adjusted to a resin solid content of 75% by weight of a resin varnish.

The sample containing the filler and the sample containing the rubber in the resin varnish of each of the above examples were well dispersed by a three-roller. This was applied to a 25 μm polyethylene terephthalate film (PET film) subjected to release treatment by an extrusion coater, and dried at a temperature of 120 ° C to obtain a heat of B state having a thickness of 51 μm. Curable resin film (A). The volatiles were adjusted to 0.5 wt%. Further, a laminated polyethylene film (PE film) is used as a protective film. This was superposed on a 18 μm surface-free copper foil, and sent to a vacuum press for heating at 180 ° C × 120 minutes, 1 MPa, and pressurization (vacuum 5 Torr). (formed product (1))

The same treatment was carried out, and it was superposed on the copper foil with the pins, and it was sent to a vacuum press and heated at 180 ° C for 120 minutes under a condition of 1 MPa and pressurized (with a vacuum of 5 torr). (formed object (2))

On the one hand, a circuit and a through hole are formed on a 25 μm thick full-polyimide copper-clad laminate (copper foil 18 μm), and after the conductor is subjected to black copper oxide treatment, the protective film is peeled off from the film (A) on both sides. Lamination of processing on this surface. Further, after the copper foil was laminated on both sides, it was fed into a vacuum press and heated under the conditions of 180 ° C × 90 minutes and 1 MPa, and pressurized (vacuum degree 1 torr). After cooling and taking out, a blind hole of a predetermined aperture was formed by a CO ₂ laser in a conformal mask method.

The surface is roughened by a permanganate degumming solution, and the residual resin inside the bottom of the hole is also dissolved and removed. A 0.5 μm electroless copper plating layer and a 20 μm electrolytic plating copper plating layer were formed thereon, and post-heat treatment was performed at 180 ° C for 30 minutes. A circuit was formed thereon, and a 4-layer build-up multilayer printed wiring board (PWB (I)) having a single layer of one layer was formed.

The parameters of the above examples are shown in Tables 1 and 2. In addition, the evaluation results of the characteristics of each example are shown in Tables 3 and 4.

Further, PWB (II) in Table 2 is a test pattern substrate of JPCA-HD01 manufactured in accordance with the manufacturing method of PWB (I).

PWB (II): A test pattern substrate of JPCA-HD01 manufactured in accordance with the manufacturing method of PWB (I).

*1) Replace the copper foil of the molded product (2) with AL1060

*2) Replacing the copper foil of the molded article (2) with a polyimide film

Reliability: According to the JPCA-BU01 measurement.

(a) Thermal shock test: 125 ° C × 30 min ← → - 65 ° C × 30 min (1 cycle)

(b) High temperature and high humidity bias test: 85 ° C × 85% RH, DC = 30 V (but measured in the tank)

Laser processability: aperture after CO ₂ laser processing, top aperture / bottom aperture, determined from the amount of resin remaining in the bottom of the hole.

In addition to the slag etchability: it is determined from the amount of residual resin after the removal of the permanganic acid and the surface roughness and the uniformity of the rough surface.

As described above, according to the present invention, it is possible to use a high-density thin-layer build-up printed wiring board for a high-density flexible build-up printed wiring board which is bendable and has high heat resistance, high adhesion strength, and high reliability. The use or heat dissipation substrate can be used, and the obtained printed wiring board can be used for portable devices, LED substrates, and the like.

In addition, as a reference, the reliability of the sample prepared from the FR-4 substrate ‧ FR-4 resin is known as "(a) > 500" "(b) > 1,000", and Embodiments of the invention are equivalent.

Claims (7)

A thermosetting resin composition characterized by comprising (a1) a liquid epoxy resin, (a2) a solid epoxy resin having a softening point of 125 ° C or less, (b) having a benzoate group and a polycondensation on a main chain a methylene aromatic diamine compound, (c) a solvent-soluble polyimine resin having a Tg value of 200 ° C or higher, a weight average molecular weight Mw of 50,000 or less, and (d) a phenoxy resin having a Tg value of 130 ° C or higher, And when the total amount of the liquid epoxy resin (a1), the solid epoxy resin (a2), and the aromatic diamine compound (b) is 100 parts by weight, (c) the solvent-soluble polyimine resin The total amount of the phenoxy resin to (d) is 15 parts by weight or more and 150 parts by weight or less. The composition according to claim 1, wherein the solvent-soluble polyimine resin is a fully ruthenium-soluble soluble polyimide resin having a phenylindene structure. The composition according to claim 1 or 2, further comprising (e) a filler, wherein the (e) filler is selected from the group consisting of alumina, aluminum nitride, boron nitride, cerium oxide, and hydroxide. One or more materials of the group consisting of aluminum. A B-staged resin film is produced from the composition described in any one of claims 1 to 3. A metal foil having a B-staged resin film described in claim 4 of the patent application. A copper-clad board is a B-stage of the fourth paragraph of the patent application scope. The resin film is formed by hardening a copper foil. A multilayer build-up substrate comprising an interlayer insulating material formed of the thermosetting resin composition according to any one of claims 1 to 3.