JP2006089595A - Build-up resin composition and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a build-up resin composition suitable for production of a cured film with excellent heat resistance and small dielectric loss. <P>SOLUTION: This build-up resin composition comprises an epoxy resin (A), a curing agent (B) for the epoxy resin, a thermoplastic resin (C) and a filler (D), in which the curing agent (B) for the epoxy resin comprises a compound represented by formula (1) (wherein t is 1 or 2, r is 1-15, a plurality of B are a benzene ring or a naphthalene ring which may be substituted by a hydrocarbon or not, R<SP>10</SP>-R<SP>13</SP>are each a hydrogen atom, a 1-10C alkyl group, a 7-20C aralkyl group or a 6-20C aryl group). A vanish comprising the build-up resin composition and an organic solvent is provided. The film for the build-up is obtained using the vanish. A copper foil with a resin is obtained using the vanish. A printed wiring board having a layer of a cured product is composed of the build-up resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition for buildup and its use.

Along with the recent reduction in size and weight of electric and electronic devices, the density of printed wiring boards has been increasing. As one form of such a printed wiring board, a build-up printed wiring board in which conductive circuit layers and insulating layers are alternately laminated and a conductive circuit is formed not only on the surface of the printed wiring board but also inside thereof is known. ing. The insulating layer of this buildup printed wiring board is known to be made of a cured thermosetting film called a buildup film.
An example of a buildup resin composition suitable for this buildup film is composed of an epoxy resin containing a triphenolmethane skeleton as an epoxy resin, a phenol novolac as a curing agent, polyethersulfone as a thermoplastic resin, and silica as a filler. A resin composition for buildup has been proposed (Patent Document 1).
JP 2001-72833 A

  Although the above resin composition for buildup is excellent in heat resistance, the film-like cured product obtained therefrom has a problem that the dielectric loss is not sufficiently small. The objective of this invention is providing the resin composition for buildups suitable for manufacture of the film-like hardened | cured material which is excellent in heat resistance and has a small dielectric loss, and its use.

（式中、ｔは１または２を表し、ｒは１〜１５の平均繰り返し数を表す。複数のＢはそれぞれ同一であっても異なっていてもよく、炭化水素置換もしくは未置換のベンゼン環またはナフタレン環を表す。Ｒ¹⁰〜Ｒ¹³はそれぞれ同一であっても異なっていてもよく、水素原子、炭素数１〜１０のアルキル基、炭素数７〜２０のアラルキル基または炭素数６〜２０のアリール基を表し、Ｒ¹⁰〜Ｒ¹³がそれぞれ複数存在する場合のそれらそれぞれは同一であっても異なっていてもよい。） The present invention includes (A) an epoxy resin, (B) an epoxy resin curing agent, (C) a thermoplastic resin, and (D) a filler, and the epoxy resin curing agent (B) is represented by the following formula (1). The present invention relates to a buildup resin composition, and the present invention relates to a varnish comprising the buildup resin composition and an organic solvent, a buildup film obtained using the varnish, and the varnish. And a printed wiring board having a layer of a cured product of the resin composition for build-up obtained by using the resin composition for build-up.

(In the formula, t represents 1 or 2, r represents an average number of repetitions of 1 to 15. A plurality of B may be the same or different, and each may be a hydrocarbon-substituted or unsubstituted benzene ring or R ^{10 to} R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. Represents an aryl group, and when there are a plurality of R ^{10 to} R ¹³ , each may be the same or different.)

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for buildups which are excellent in heat resistance, and suitable for manufacture of a film-like hardened | cured material with a small dielectric loss, and its use are provided.

Examples of the epoxy resin of component (A) used in the present invention include, for example, phenol novolac epoxy resins, cresol novolac epoxy resins, novolak resins such as biphenyl novolac epoxy resins, bisphenol A epoxy resins, Bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin such as biphenyl type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, aralkyl aromatic type epoxy resin, di Cyclopentadiene phenolic epoxy resins, aromatic bisphenol compounds and / or polyphenolic compound hydrogenated epoxy resins, cyclohexene oxide and other cycloaliphatic epoxy resins, Triethanolamine epoxy various derivatives such as resins. One or two or more epoxy resins can be used.
The epoxy resin which is the component (A) of the present invention is selected from the group consisting of trishydroxyphenylmethane-based epoxy resins, bisphenol-based resins, and aralkyl aromatic epoxy resins in terms of high heat resistance and low dielectric loss. One or more selected are preferable.

  Specific examples of the trishydroxyphenylmethane-based epoxy resins include an epoxy resin represented by the following formula (2).

（式中、ｎは１〜１０の平均繰り返し数を表す。複数あるｉはそれぞれ同一であっても異なっていてもよく、１〜４の整数値を示す。複数あるＲ¹はそれぞれ同一であっても異なってもよく、炭素数１〜１０のアルキル基、炭素数７〜２０のアラルキル基または炭素数６〜２０のアリール基を表し、ｉが２以上の場合、同一環上の複数のＲ¹はそれぞれ同一であっても異なっていてもよい。Ｇｌｙはグリシジル基を示す。）

(In the formula, n represents an average number of repetitions of 1 to 10. Plural i's may be the same or different, and each represents an integer value of 1 to 4. Plural R ^{1 s} are the same. Or an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when i is 2 or more, a plurality of Rs on the same ring ¹ may be the same or different, and Gly represents a glycidyl group.

The alkyl group in R ¹ preferably has 1 to 4 carbon atoms, the aralkyl group preferably has 7 to 10 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, Examples thereof include linear, branched, and alicyclic alkyl groups such as a tert-pentyl group, an n-hexyl group, an iso-hexyl group, a tert-hexyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a diphenylmethyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group. These aralkyl groups and aryl groups may have a substituent such as a methyl group, an ethyl group, a propyl group, or a butyl group.

R ¹ is preferably selected from the group consisting of a hydrogen atom, a methyl group and a tert-butyl group. The softening point of the epoxy resin represented by the general formula (2) is preferably 40 to 100 ° C., more preferably 50 to 50 ° C., from the viewpoint of ensuring embeddability in a conductor circuit and preventing the glass transition temperature from decreasing. 90 ° C.

  Moreover, as a specific example of said bisphenol-type resin, the epoxy resin shown by following formula (3) can be mentioned, for example.

（式中、ｑは０〜１５の平均繰り返し数を表す。Ｒ⁶〜Ｒ⁹はそれぞれ同一であっても異なっていてもよく、水素原子、炭素数１〜１０のアルキル基、炭素数７〜２０のアラルキル基または炭素数６〜２０のアリール基を表し、Ｒ⁶〜Ｒ⁹がそれぞれ複数存在する場合のそれらそれぞれは同一であっても異なっていてもよい。Ｘは単結合を表すか、炭素数１〜１０のアルキレン基、炭素数６〜２０のアリーレン基および炭素数５〜７のシクロアルキレン基からなる群から選ばれる一種の基または二種以上組み合わせてなる基を表す。Ｇｌｙはグリシジル基を示す。）

(In the formula, q represents an average number of repetitions of 0 to 15. R ^{6 to} R ⁹ may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 7 to 7 carbon atoms. 20 represents an aralkyl group or an aryl group having 6 to 20 carbon atoms, and when there are a plurality of R ^{6 to} R ⁹ , they may be the same or different, and X represents a single bond, 1 type of group selected from the group which consists of a C1-C10 alkylene group, a C6-C20 arylene group, and a C5-C7 cycloalkylene group, or the group formed by combining 2 or more types, Gly represents glycidyl. Group.)

The alkyl group in R ^{6 to} R ⁹ preferably has 1 to 4 carbon atoms, the aralkyl group preferably has 7 to 10 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms. 1-4 are preferable, as for carbon number of the alkylene group in said X, 6-10 are preferable, as for carbon number of an arylene group, and carbon number of a cycloalkylene group is 5-6.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, Examples thereof include linear, branched, and alicyclic alkyl groups such as a tert-pentyl group, an n-hexyl group, an iso-hexyl group, a tert-hexyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a diphenylmethyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group. These aralkyl groups and aryl groups may have a substituent such as a methyl group, an ethyl group, a propyl group, or a butyl group.
Examples of the alkylene group include linear and branched hydrocarbon groups such as methylene, dimethylene and isopropylidene groups. Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. These arylene groups may have a substituent such as a methyl group, an ethyl group, a propyl group, or a butyl group. Examples of the cycloalkylene group include a cyclopentylene group and a cyclohexylene group. The group formed by combining two or more kinds from the group consisting of an alkylene group, an arylene group and a cycloalkylene group includes an alkylene group-arylene group, an alkylene group-cycloalkylene group, an alkylene group-arylene group-alkylene group, and an alkylene group-cycloalkylene. Examples include groups such as a group-alkylene group.

R ^{6 to} R ⁹ are preferably each independently a hydrogen atom or a methyl group. X is preferably a single bond, a methylene group or an isopropylidene group. The average number of repetitions q of the epoxy resin represented by the formula (3) is preferably q = 0 to 8 and more preferably q = 0 to 4 from the viewpoint of ensuring embeddability in the conductor circuit.

  Moreover, as a specific example of said aralkyl aromatic epoxy resin, the epoxy resin shown by following formula (4) can be mentioned, for example.

（式中、ｐは１または２を表し、ｍは１〜１５の平均繰り返し数を表す。複数のＡはそれぞれ同一であっても異なっていてもよく、炭化水素置換もしくは未置換のベンゼン環またはナフタレン環を表す。Ｒ²〜Ｒ⁵はそれぞれ同一であっても異なっていてもよく、水素原子、炭素数１〜１０のアルキル基、炭素数６〜２０のアラルキル基または炭素数６〜２０のアリール基を表し、Ｒ²〜Ｒ⁵がそれぞれ複数存在する場合のそれらそれぞれは同一であっても異なっていてもよい。Ｇｌｙはグリシジル基を表す。）

(In the formula, p represents 1 or 2, m represents an average number of repetitions of 1 to 15. A plurality of A may be the same or different, and each may be a hydrocarbon-substituted or unsubstituted benzene ring or R ^{2 to} R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. Represents an aryl group, and when there are a plurality of R ^{2 to} R ⁵ , they may be the same or different, and Gly represents a glycidyl group.)

1-4 are preferable, as for carbon number of the alkyl group in said R < ² > -R < ⁵ >, 7-10 are preferable and, as for carbon number of an aryl group, 6-10 are preferable.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, Examples thereof include linear, branched, and alicyclic alkyl groups such as a tert-pentyl group, an n-hexyl group, an iso-hexyl group, a tert-hexyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a diphenylmethyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group. These aralkyl groups and aryl groups may have a substituent such as a methyl group, an ethyl group, a propyl group, or a butyl group.

The plurality of A are each independently preferably an unsubstituted benzene ring or an unsubstituted naphthalene ring, and particularly preferably an unsubstituted benzene ring. R ^{2 to} R ⁵ are each independently preferably a hydrogen atom or a methyl group. The average number of repetitions m of the epoxy resin represented by the formula (4) is preferably m = 1 to 8, and more preferably m = 1 to 4, from the viewpoint of ensuring embedding property to the conductor circuit.

  The blending ratio of the epoxy resin which is the component (A) used in the present invention is not particularly limited as long as the object of the present invention is achieved, but is usually 1% by weight or more, preferably with respect to the resin component for resin film. Can be appropriately selected from the range of 1 to 80% by weight depending on the relationship with other compounding components.

（式中、ｔは１または２を表し、ｒは１〜１５の平均繰り返し数を表す。複数のＢはそれぞれ同一であっても異なっていてもよく、炭化水素置換もしくは未置換のベンゼン環またはナフタレン環を表す。Ｒ¹⁰〜Ｒ¹³はそれぞれ同一であっても異なっていてもよく、水素原子、炭素数１〜１０のアルキル基、炭素数７〜２０のアラルキル基または炭素数６〜２０のアリール基を表し、Ｒ¹⁰〜Ｒ¹³がそれぞれ複数存在する場合のそれらそれぞれは同一であっても異なっていてもよい。） The epoxy resin curing agent (B) used in the present invention is represented by the following formula (1).

(In the formula, t represents 1 or 2, r represents an average number of repetitions of 1 to 15. A plurality of B may be the same or different, and each may be a hydrocarbon-substituted or unsubstituted benzene ring or R ^{10 to} R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. Represents an aryl group, and when there are a plurality of R ^{10 to} R ¹³ , each may be the same or different.)

The carbon number of the alkyl group in R ^{10 to} R ¹³ is preferably 1 to 4, the carbon number of the aralkyl group is preferably 7 to 10, and the carbon number of the aryl group is preferably 6 to 10.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, Examples thereof include linear, branched, and alicyclic alkyl groups such as a tert-pentyl group, an n-hexyl group, an iso-hexyl group, a tert-hexyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a diphenylmethyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group. These aralkyl groups and aryl groups may have a substituent such as a methyl group, an ethyl group, a propyl group, or a butyl group.

The plurality of B are each independently preferably an unsubstituted benzene ring or an unsubstituted naphthalene ring, and particularly preferably an unsubstituted benzene ring. R ^{10 to} R ¹³ are preferably each independently a hydrogen atom or a methyl group.

（ｓはそれぞれ独立に１〜１５の平均繰り返し単位を表す。）
式（５）で表される硬化剤の軟化点は、導体回路に対する埋め込み性確保、ガラス転移温度低下防止という観点から、軟化点が６０〜１２０℃であることが好ましく、更に好ましくは７５〜１１０℃である。 The epoxy resin curing agent (B) used in the present invention is more preferably a phenol biphenyl aralkyl type resin represented by the following formula (5) or a phenol phenyl aralkyl type resin represented by the formula (6), A phenol biphenyl aralkyl type resin represented by the formula is particularly preferred.

(S each independently represents an average repeating unit of 1 to 15)
The softening point of the curing agent represented by the formula (5) is preferably 60 to 120 ° C., more preferably 75 to 110, from the viewpoints of ensuring embeddability in a conductor circuit and preventing a decrease in glass transition temperature. ° C.

  The blending ratio of the epoxy resin curing agent (B) can be used in any ratio in combination with the epoxy resin, but the blending ratio is usually determined so that the glass transition temperature becomes high, and the epoxy resin (A ) And the epoxy resin curing agent (B) preferably have a hydroxyl group equivalent of 1: 1.

  Examples of the thermoplastic resin which is the component (C) used in the present invention include engineer plastics such as polyphenylene ether, polystyrene and polycarbonate, and super engineer plastics such as polyethersulfone, polysulfone, polyetherimide and polyimide. And polyolefins such as polyethylene and polybutadiene, polyacrylates such as polyacrylate and polymethacrylate, rubbers such as terminal amine and terminal carboxyl group-modified polybutadiene-acrylonitrile rubbers and modified products thereof. Among these, polyethersulfone is more preferable from the viewpoint of toughness and flame retardancy.

  As the polyether sulfone, known polyether sulfones whose molecular ends are halogen atoms, alkoxy groups, and phenolic hydroxyl groups can be used. Among these, polyethersulfone having both phenolic hydroxyl groups at both ends is particularly preferred from the viewpoints of compatibility with the component (A), reactivity, and solvent resistance of the cured product.

  The usage-amount of polyethersulfone is 10-70 weight% normally with respect to the whole resin composition of this invention. If the amount used is too small, the toughness of the cured product may be reduced. If the amount is too large, the processability of the composition may be reduced or the water absorption rate of the cured product may be increased.

  As a method for producing polyethersulfone, a known method can be adopted, and examples of commercially available products include Sumitomo Chemical Co., Ltd., trade name: Sumika Excel, Amoco, trade name: REDEL, etc. Can be mentioned.

  As an example of the filler which is (D) component used for this invention, an organic filler, an inorganic filler, etc. are mentioned, for example. Examples of the organic filler include resin powders such as epoxy resin powder, melamine resin powder, urea resin powder, guanamine resin powder, and polyester resin powder. Moreover, as an inorganic filler, inorganic powders, such as a silica, an alumina, a titanium oxide, can be mentioned, for example. Among these, an inorganic filler is preferable for reducing the thermal expansion coefficient, and silica is particularly preferable among the inorganic fillers from the viewpoint of dielectric properties.

  The filler (D) used in the present invention usually has a maximum particle size in the range of 0.1 to 20 μm, but is preferably in the range of 0.1 to 5 μm, and more preferably 0.1 It is still more preferable if it is in the range of ˜1 μm.

  The content rate of an inorganic filler is 10-80 weight% normally with respect to the whole resin composition. If this content is small, the effect of low water absorption and low coefficient of thermal expansion of the cured product may be reduced. On the other hand, if it is high, laser processability may be reduced. Further, in order to achieve a low thermal expansion coefficient equivalent to that of a general glass cloth base laminate, in the case of silica, it is usually 50% by weight or more, preferably 70% by weight or more.

Moreover, a curing catalyst can be mix | blended with the resin composition for buildups of this invention. Specific examples of such a curing catalyst include organic compounds such as triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, and tri-2-cyanoethylphosphine. Phosphine compounds and tetraphenylborate salts thereof, tributylamine, triethylamine, amines such as 1,8-diazabicyclo (5,4,0) undecene-7, triamylamine, benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide And quaternary ammonium salts such as triethylammonium tetraphenylborate and imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole. The curing catalyst is not limited to these examples, but in the present invention, use of an organic phosphine compound or imidazoles is particularly preferable.
The blending ratio of the curing catalyst can be increased or decreased at an arbitrary ratio so that a desired gel time can be obtained. Usually, it is preferable to mix the composition so that the gel time of the composition is 1 minute to 15 minutes in the temperature range of 80 ° C. to 250 ° C., and the component (A), component (B), component ( It is usually 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, based on the total amount of C).

  You may make the resin composition of this invention contain thermosetting resins other than an epoxy resin component in the range which does not impair the objective of this invention. For example, cyanate resins such as cyanate of bisphenol A, bismaleimides such as diaminodiphenylmethane bismaleimide, diamines such as diaminodiphenylmethane, addition polymers of bismaleimides and diamines, bisvinylbenzyl etherified products of bisphenol A And alkynyl ethers such as dipropargyl etherified products of bisphenol A, polyolefins such as resol resins, vinyl group-containing polyolefin compounds, and the like, but are not limited thereto.

  Furthermore, you may provide photocurability by making the resin composition for buildups of this invention contain acrylates, methacrylates, styrene, etc. as needed.

  In addition, the build-up resin composition of the present invention includes, as necessary, organic flame retardants such as bromo-containing polycarbonate, bromo-containing polyphenylene oxide, bromo-containing polyacrylate, and bromo-containing polystyrene, antimony trioxide, hydroxylated You may contain inorganic flame retardants, such as aluminum and red phosphorus, mold release agents, such as waxes and zinc stearate, surface treatment agents, such as a silane coupling agent.

  The resin composition for buildup of the present invention is suitably used as an insulating material for a buildup method because the cured product is excellent in heat resistance and low dielectric loss. As such an insulating material, for example, a varnish comprising the resin composition for build-up of the present invention and an organic solvent, a film for build-up obtained using this varnish, a copper foil with resin obtained using this varnish Etc.

Said varnish is obtained by mixing the resin composition for buildup of this invention with the organic solvent.
As the organic solvent, γ-butyrolactone, dimethylformamide (DMF), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and the like are usually used.

In addition, the above build-up film is applied to a carrier film such as polyethylene terephthalate using a roll coater or table coater, and the organic solvent is distilled off and semi-cured to build the film with a carrier film. Obtained as an up film. If you peel off the carrier film from this, you can get a build-up film, but with the carrier film attached, the build-up film is already being laminated with copper foil or several layers to build a circuit. A method of use is also possible in which the carrier film is peeled off after being pressure-bonded to the printed wiring board.
The conditions for distilling off and semi-curing the organic solvent are appropriately selected according to the components of the build-up resin composition to be used, the type of solvent, the amount used, and the like. The range is from 30 minutes to 30 minutes.

Also, the copper foil with resin is obtained by applying varnish on the copper foil using a table coater, etc., thinning it, distilling off the organic solvent, and semi-curing, as described above. It can also be obtained by a method in which the surface of the build-up film of the build-up film with a carrier film is pressed against the copper foil and then the carrier film is peeled off.
The conditions for distilling off the organic solvent and semi-curing are appropriately selected according to the components of the build-up resin composition to be used, the type of solvent and the amount used, but usually from 60 ° C to 200 ° C for 1 minute. The range is 30 minutes.

  The insulating layer of the build-up printed wiring board can be obtained by heat-curing the above-described film for build-up or a resin-coated copper foil. The conditions for heat-curing are usually in the range of 60 ° C to 200 ° C for 30 minutes to 5 hours.

  Next, a method for producing a build-up printed wiring board using the above-described film for build-up, copper foil with resin, etc. will be described. As a method for manufacturing the build-up printed wiring board, for example, there are the following methods.

(I) A build-up film is bonded to the core substrate, and is heat-cured to form an insulating layer of the build-up printed wiring board. After this, via formation, wiring layer formation through laser processing, plating process, etc., then build-up printed wiring board is repeated by pasting build-up film on wiring layer again and heat curing How to manufacture.
The condition for laminating the build-up film to the core substrate was as follows: vacuum lamination at 0.05 to 0.5 MPa for 10 seconds to 2 minutes at 80 to 150 ° C. under reduced pressure of 0.1 to 5 hPa, and The pressure is returned to 0.5 to 2 MPa for 20 seconds to 2 minutes at 80 to 150 ° C. and flattened. Thereafter, it is usually cured in a hot air oven at 100 to 200 ° C. for 30 minutes to 5 hours.

(Ii) A varnish is applied onto the core substrate using a roll coater, a table coater or the like, the solvent is distilled off, and then heat-cured to form an insulating layer. After that, after forming vias and wiring layers through laser processing and plating processes, a method of manufacturing a build-up printed wiring board by repeating the steps of applying varnish on the wiring layers and heating and curing.

(Iii) A resin-coated copper foil is bonded onto the core substrate with a vacuum laminator or a vacuum press, followed by heat-curing, then the copper foil is etched to form a circuit, and then the resin-coated copper foil is bonded and heated. A method of manufacturing a build-up printed wiring board by repeating the curing process.
In addition, the conditions for press-bonding and curing the copper foil with resin to the core substrate are usually 1 to 5 ° C./min up to a predetermined temperature selected in the range of 80 to 250 ° C. under reduced pressure of 1 to 10 kPa. Then, when it reaches the predetermined temperature, it is pressure molded at 1 MPa to 10 MPa. Subsequently, it is usually cured for 20 minutes to 300 minutes under reduced pressure and pressure.

  The thickness of the insulating layer for build-up printed wiring boards obtained by the above method is usually in the range of 10 to 300 μm.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.

The components (A) to (D) used in the examples are as follows.
Component (A) Epoxy resin A1: EPPN 502H
(Nippon Kayaku Epoxy Resin, Epoxy Equivalent = 169 g / eq, corresponds to Formula (1))
A2: Epototo YD-128M
(Epoxy resin manufactured by Tohto Kasei, epoxy equivalent = 185 g / eq, corresponding to formula (2))
A3: Epicron 830S
(Epoxy resin manufactured by Dainippon Ink and Chemicals, Epoxy equivalent = 170 g / eq, corresponding to formula (2))
A4: NC-3000
(Nippon Kayaku epoxy resin, epoxy equivalent = 275 g / eq, corresponding to formula (3))

Ｂ６：クレゾールノボラック樹脂
（大日本インキ化学工業製 ＫＡ−１１６０、水酸基当量＝１１０ｇ／ｅｑ；下式に該当）

Ｂ７：液状ポリブタジエンのフェノール変性物
（新日本石油化学製 ＰＰ−７００−３００Ｓ、水酸基当量＝３１７ｇ／ｅｑ） Component (B) Phenol resin-based curing agent B1: Phenol biphenyl aralkyl type resin (Maywa Kasei MEH7851-M, hydroxyl equivalent = 209 g / eq, corresponding to formula (5))
B2: phenol biphenyl aralkyl type resin (MEH7851-H, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent = 216 g / eq, corresponding to formula (5))
B3: phenol biphenyl aralkyl type resin (MEH7851-3H manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent = 230 g / eq, corresponding to formula (5))
B4: Phenolic phenylaralkyl type resin (Maywa Kasei MEH7800-4S, hydroxyl group equivalent = 169 g / eq, corresponding to formula (6))
B5: Phenol novolak resin (Maywa Kasei H-4, hydroxyl equivalent = 105 g / eq; corresponds to the following formula)

B6: Cresol novolac resin (KA-1160, manufactured by Dainippon Ink and Chemicals, hydroxyl equivalent = 110 g / eq; corresponds to the following formula)

B7: Phenol-modified product of liquid polybutadiene (PP-700-300S, manufactured by Shin Nippon Petrochemical Co., Ltd., hydroxyl equivalent = 317 g / eq)

Component (C) Polyethersulfone C1: Terminal phenolic hydroxyl group-type polyethersulfone (Sumitomo Chemical Sumika Excel PES 5003P)

Component (D) Inorganic filler D1: Spherical silica (SFP-20X manufactured by Electrochemical)

  Each component and the organic solvent described in Table 1 were mixed and dispersed in the composition (parts by weight) described in Table 1 to obtain a resin composition for buildup as a mixture (varnish) with the organic solvent.

(1) Production Example of Build-up Film The obtained varnish is applied to a coating thickness of about 130 μm on a 50 μm PET film (Lumirror manufactured by Toray Industries, Inc.) with a film coater (PI-1210 manufactured by Tester Sangyo Co., Ltd.). It was applied to. Then, it dried for 15 to 30 minutes in 80 degreeC oven, and obtained the dry film. The coating thickness after drying was 40-60 μm. The non-volatile content of the coating film measured under the heat treatment conditions at 200 ° C. for 60 minutes was 92 to 98%.

(2) Measuring method of dielectric loss The obtained varnish was applied on a glass plate with a film coater so that the coating thickness was about 80 μm. This glass plate was cured and vacuum dried in a vacuum oven at 160 ° C. for 15 minutes to produce a semi-cured product. The obtained semi-cured product was peeled from the glass plate and further pressure-molded at 180 ° C. for 10 minutes to obtain a tablet-like (thickness: about 1 mm) test piece. The obtained test piece was annealed at 250 ° C./30 minutes, and both sides of the tablet were polished smoothly. Dielectric loss (tan δ) at 1 GHz was measured with an impedance analyzer manufactured by Agilent Corporation at 23 ° C. and 50% RH. The reciprocal of dielectric loss was defined as Q value, and tan δ and Q value are summarized in Table 1.

(3) Measuring method of glass transition temperature A film for buildup was obtained in the same manner as in the film production example for buildup except that the PET film was changed to a polyimide film (Upilex 50S manufactured by Ube Industries). Subsequently, after heat treatment at 180 ° C. for 2 hours, a glass transition temperature was obtained from the measurement data in the second scan in a tensile mode according to JIS C 6481 using a Seiko Instruments thermal analyzer TMA-120. The temperature was raised from 23 ° C. to 200 ° C. at 20 ° C./min (first scan), then cooled to 45 ° C. and heated to 5 ° C./255° C. (second scan). .

Since the resin composition of the present invention has an appropriate melt viscosity, is excellent in build-up processability, and is excellent in storage stability, it is excellent for build-up use. In addition to build-up applications, it can be applied to insulating materials, composite materials, adhesive materials, paint materials, and the like.

Claims (6)

(A) an epoxy resin, (B) an epoxy resin curing agent, (C) a thermoplastic resin and (D) a filler, and the epoxy resin curing agent (B) is represented by the following formula (1) A buildup resin composition.

(In the formula, t represents 1 or 2, r represents an average number of repetitions of 1 to 15. A plurality of B may be the same or different, and each may be a hydrocarbon-substituted or unsubstituted benzene ring or R ^{10 to} R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. Represents an aryl group, and when there are a plurality of R ^{10 to} R ¹³ , each may be the same or different.) The resin composition for buildup according to claim 1, wherein, in the general formula (1), B is an unsubstituted benzene ring or an unsubstituted naphthalene ring, and R ^{10 to} R ¹³ are each independently a hydrogen atom or a methyl group. .   A varnish comprising the resin composition for buildup according to claim 1 or 2 and an organic solvent.   The film for buildup obtained using the varnish of Claim 3.   The copper foil with resin obtained using the varnish of Claim 3. The printed wiring board which has a layer of the hardened | cured material of the resin composition for buildups of Claim 1 or 2.